CA1133810A - Temperature indicating compositions of matter - Google Patents

Abstract

ABSTRACT
Novel and stable compositions of matter are disclosed which change color sharply upon a transition from a liquid state to a solid state or from a solid state to a liquid state, which change of state is at substantially a predetermined temperature corresponding with a temperature to be measured.
The constituents of the novel compositions of matter comprise:
1. a solvent (I) consisting of a single substance or a mixture of substances and adapted to change from a solid state at substantially a predetermined temperature to a liquid state and 2. an indicator system (II) consisting of one or more substances different from (I), characterized in that (a) (II) is soluble in (I) when the latter is in the liquid phase, and (b) (II) changes color visible to the naked eye when (I) passes from the solid to the liquid phase or from the liquid to the solid phase.

Description

113~810 The invention relates to the field of temperature-indicating compositions and devices therefor, and in particular, the sub-fields of disposable thermometers and compositions of matter which change characteristics with change in phases ~or use in disposa~le thermometers.
For many years the conventional mercury thermometer has ~een the pri~ary temperature-ind;cating device which has ~een used in clinical applications f~r the measurement of temperature in the human body and other animal bodies, and for the measure-- 1~33810 ment of tem~erature of gases, liquids, and even solids in commer-cial and industrial ap~lications. ,iowever, as will be readily discerned by the observer, this ty~e of ther~ometer has numerous disadvantages inherent in the nature of mercury, a poisonous sub-S s~ance to humans and other animals, and construction or themercury thermometer with the place~lent of mercury ~itnin fragile glass. First, in clinical a~plications involving humans and other ani~als, several minutes, usually at least three, are required to obtain a meaningful temperature reading. Second, once used, the conventional ~ercury theri~ometer because of its extraordinar~ expense must ~e sterilized before th.e next clinical i~o~e B aPplication. S~lcn sterilization and resterilization often ~4~--substantial labor costs, whether in hospitals, physician~' offices, homes, or in the rield. Third, in hospital use, inevit-1~ able hu~an error in the sterili~a~ion of ther~ome~ers presentsthe ever-occurring substantial prooa~ilities of outbreaks of contagious diseases such as hepatitis. Fourtn, the breakaDle nature o~ the mercury ther~ometer is an ever-present dan~er when consi~ering the ?oisonous nature of mercury, especially in the ~0 presence of children. Fiftn, in industrial aPplications, espec-iallv involving the determination of r latively hi~h temperatures in vessels located in Dlants and re~ineries, t~e user must ~ cc~ss~Je ordinarily reach into -inexces3~1e places to locate the tner-mometer, and oecause of the extreme difference ~etween said

2~ relatively high temperat~res and the outside am~ient temperature, readings from conventional thermojr,eters are often in extren~e error secondO after the withdrawal of the mercury thermometer.

Accordingly, for many years ~ersons have attem~tea to construct an inexpensive cevlce of mixtures or materials or any

3~ kind which ~ould chan~e in some characteristic visi~le to ~he i~33810 naked eye at substantially the temperature to ~e measured so that the inconveniences of the conventional mercury thermometer could be avoided. For instance, Ramsden in British Pat. No. '3540 (1897) provided a ~iece of paper, celluloid, metal or other suitable material which would be (1) coated with, or (2) formed with a hollow or recess containing a substance, mixture ~J
material ~hich would change in opacity at the temperature ror the indication of which the appliance is intended to be used (see page 1, lines 24-38; page 5, lines 23-45 of '3640). Ramsden 1~ desired a substance or material (see page 2, lines 9-23) that would change in color at the Dredetermined temperature, bu~ did not indicate any in his specification; he only indicated several substances, generally fatty acids, which would change in opacity or change from being opaque to trans?arent upon change in Dhases from soli.1 to liquid or vice versa ~see page ~, lines 11-18), so that indicator layers, dyes, etc., would have to be emPloyed in the device.
~fter P.amsden, the Qrt primarily pursued only those heat-sensitive suostances which would change from being opaque to 2U trans~arent at the phase interf~ce in devices (hereinafter described as "oDaque thermometers") that would employ indicator layers having dyes that would only ~e apparent -,Jhen the heat-sensitive substance had changed from opa~ue to transparent~would mix with the heat-sensitl~e comDounds ~pon a change in ~hases.
For exam~le, ~.S. Pat. ~o. 3,175,401 issued to Geld.macher ~19~5) descri~es a thermometer ~ith several cavities, each containing a different thermall~y-indicating composition melting at a different te~perature range. Each o the thernally in~icating com~ositions em~loye~ by Geldmacher is normally opaque helow a certain tem~er-ature and trans~arent a~ove a cerLain temperature, simila~ ~o - li338~0 Ramsden's compositions of matter. The temperature indication is o~tained by a complete cnange of state of the thermally res~on-sive material in each cavity. Furthermore, as ~any as forty to fifty different chemical compounds would be necessary to cover the desired numan clinical temDerature range of 96~F to 10~F, so that reldmacher's device was ~rohibitively ex~ensive to manu-facture for mas~ consumer ~se; li~;ewise, tne availa~ility of these compounds at 0.2F or 0.1C increments was not disclosed.
~ notner type of temperature indicating device was disclosed in U.S. Dat. I`10. 3,~55,590 (1953) to ~luth, et al. The 1~ teachin~ describes a thermometer which is disposable after a single a~plication and does not employ mercury as the thermally responsive substance. Rather, Kluth, et al, employed mixtures of certain of the even series of saturated fatty acids, ~perhaps3 suggested by the Ramsden materials on Page 3, lines 11-18 of lS '3640), to wit, myristic acid, palmitic acid and lauric acid for inaication of temperature of the human body ~ithin plus or minus 1/2DF. gain, as in Geldmacher, the device o~ Kluth ~easure~ and indicated temperature by a complete chan~e oF state of the thermally-res~onsive material in each cavity. Although the use 2~ of Kluth's thermometer obviated some o the deficiences of the conventiol~al mercury t~ermometer, its a~plication was limitea to tem~erature measurements in the range OL about 9~F to about lOl~F, and the ~ccuracy was restricted explicitly in Kl~th ~o plus or minus 1~2~F, thus ~recluding Kluth from u~e for ~,ore precise temperature measurements and replacement of the con-ventional mercury thermometer. As a practical matter, such Kluth instruments di~ not provi-3e accurate clinical information regarding the temperature sf the human or animal ~od~ during a period of fever when the tempera~ure was fre~uentl~ a~ove 1~

1~33~10 h~ n B as the nunl~ body is often (102F - 105F) during high fevers Another difficulty with the Kluth thermo,-neter was that an accurate tem~erature deter~ ation really ce~ende~ on a complete change of state of tne soli~ solution e.nploved as the thermally-responsive naterial. Whil~ Kluth intended for each cavitv in his thermometer to have three stages of melting (each stage repre-sented an indication of plus or .-ninus l/2F), some experience by the user was necessary in order to determine which stage a cavity w~r~
was in if it ~a3 melting. More probably, i~ the cavity respond-ing to the closest tem~erature of the human or animal body to be measured did not completely change state, certain nuclea~ior.
sites remained in the cavity so that the cavity ra~idly solia-ified, causing an inaccurate measurement as withdra~al of the ther,nometer ~tas followed by quick solidification of the cavities only partially liauified or containing a~preciable nucleation sites because of impurities, etc. The com,?lete change of state necessary, i.e., from opaque solid to translucent liquid, in addition to the inherent 1/2F inaccuracy and the 101F limit-ation of the device made the Kluth ther~ometer inadequate to replace the conventional mercury thermometer (admitted by Xluth in Column 2, lines 70-73 and Column 3, lines 1-~ of U.~. Pat.
~o. 3,465,5~0).
Still another type of thermometer was described ~y ~inklestein in U.S. Pat. ~`7O. 3,521,4~9 (1970). The temDerature indication in this type of ther~lorneter is ~ased upon the flow of a melted material fro~ so-called "holding compartTnent" into a adsor ben1 so-called "flos/-inducing receivin~ element" such as the ~sor~e~
material, by a capillary action (see Col~n 1, lines 61-72 or:
'~g). ~s in the Geldmacher patent, however, tem~erature inai-cation ~as realizeù ~y the use of numerous differellt therndlly - 113~3810 res~onsive chesnical com~ounds, each underyoing a complete change of state at a different predetermined temperature with a corres-ponding change from opa~ue to trans~arency. It was obvious once again that witn thQ er,lployment of an~ "classical" ~nateriaI
changing from opaque ~o transluscent at the phase change, some indicator c,~e or material at the bottom o~ a cavity would have to be placed in ~rder to indicate rea~ily to the observer the change in state of the composition of matter indicatiny the tem~erature to be determined. See also Crites U.S. Pat. ~o. 3,580,079 (1971) 1~ which required the transparent state of the telnperature respon-sive material to be of the sa.-ne index of refraction of a rough-ened window in order to optically smooth the window.
As the search con~inued for a disposable clinical thermometer to rePlace the conventional mercury thermometer, Weinstein and Sa~i in U,S. Pat. No. 3.631,720 disclosed a speciEic device em~loying a carrier sneet (11 in '720) with a ~lurality of individual temperature-inAicating elements distrib!~Qd over at least one surface of the carrier sheet in the form of a grid with the elements buried in a corresDonding nu~ber of cavities (located between the sheet 11 and surfaces 20~ and lOA), each element 12 having an o~a~ue layer coverins an _ indicator element 2~. Upon meltiny of tne coatings 22 in '72~, the indicator material 20 would be expvsed to the observer. The dra~ac~ of '72~ was that the manufacturer of a multilaye.ed 2~ device as s~own in Figure 4 of '72~ with a "s~ndwich" indicator means 2V in temperature-indicating ele~ents 12 became expensive.
In U.S. Pat. ~o. 3,946,612 (lY76) to Sagi and ~einstein, the s~ecilication disclosed tne use of a heat con-ducting carrier having a plurality of spaced cavities with a 3~ corres~onding plurality of so7 id solutions each comnrising an --- 113~3810 organic layer of at least two different organic che.nicals (ortho-chloronitro~romobenzene and ortho-bromonitrobromobenzene) in varied com~osition ratios deposited in said cavities that would turn from opaque to clear upon a change in phase from solid to liquid. ~his or~anic layer ~9 in '612) formed a sandwich for an .
indicator layer ~13 in 1612) between it and a masking or opaque layer (15 in a multilayered device similar to U.~. Pat. No.
3.665,770). When the cavit~ of Fisure 2 of '612 ~as heated to a ~redetermined temperature, the composition of matter would change lG from a solid to a liquid state, permeating the indicator 13 and forcing a dye into the opaque layer to change the color of aaid opaque layer to the color of the dye. Several problems were presented in the construction of the '612 multilayered device:
first, such a device with three internal layers in the cavity and two transparent external layers was hard to manufacture and very ex~ensive. Second, sometimes the organic com~osition would not totally change frorn liqui~ to solid, so that nucleation sites remained in the organic layer 9; hence, resolidification quickly occurred u2on withdrawal of the thermometer, and not all the dye was forced into the up~er or opaque layer 15. Thi~d, because of the size of the layers, it was someti~nes hard to visualize the change in color when only some of the dye ~as transferred into ~ opa ~,4e the previously ~t~q~- layer. For otner exam~les of "opaque"
ther.~o,~eters, see K~ele, U.S. Pat. ~o 3,859,~6 (with "su;oercoolable" inorganic co~,~ounds, column 4, lines 5G-~4~;
~oconti, U.S. Pat. No. 2,92~,791 (d-~es employed with solve~ts of ~rable I); Gignilliat II~, U.S. Pat. No. 3,43G,491 (physical movement of heat-sensitive solvent u~on melting into "absorbent backing" layer with different color, col~.mn 7, lines 54-53~;
3Q ~osz~ows~ .S. Pat. 7O. 3, 785,3j6 (metnll sterate); Godse~, 1~33810 Jr., ~.S. Pat. No. 3,9~0,581 ("nucleating" agents to limit or reduce undercooling); ~7ahl, et al, ~.S. Pat. ~o. 3,G02,385; Fryar U.S. Pat. No. 3,597,976; Lang, U.S. Pat. No. 3,677,0~8 ("spacer layer" between indicator layer and heat-sensitive material);
Pickett, U.S. Pat. No. 3,704,985 (ortho-chloronitrobenzene:
ortho-bromonitrohenzene heat-sensitive material, ~ui no "space layer"); Chadha, ~.S. Pat. No. 3,712,141 ("space layer");
Pic~ett, U.S. Pat. No. 3,76S,243 ("self-firing thermometer" with exothermic reaction between heat-sensitive material and dye);
Godsey, U.S. Pat. ~o. 3,774,450 ("frangible" spacer layer to be crushed before ap~lication); Pickett, U.S. Pat. No. 3,826,141;
Ayres, U.S. Pat. No. 3,922,917 (avoids "cover" layer by means of crushable dome); Pecorella, U.S. Pat. No. 3,929,021; Chadha, U.S.
Pat. ~o. 3,956,153; Sagi, U.S. Pat. No. 3,835,9~0, Keele, U~S.
Pat. No. 3,a59,8s6; Sagi et al, U.S. Des. 238,661 (1976); ~ollen, U.S. Pat. 3,8~5,523; Chilton, U.S. Pat. 3,998,098; and Pickett, U.S. Pat. No. 3,871,232.
'rhe phenomena of undercooling encountered with various heat responsive materials in passing from liquid to solid is taught in Chadha, U.S. Pat. 3,956,153 to ~e minimized by incor-poration of predetermined amounts of a regenerative nucleating age.~t partially or who~ly soluble in some degr~e in the heat responsive materials.
Another form of device in another art and n~t to be confused with the "~ure" thermometer (this is used only or measurement of temperature3 is the "time-tem~erature" thermometer or "time-tem~erature" watch which indicates by inteqration of time and temperature a ~roperty of a substance (such as deterioration of meat due to elevated tem~erature). For exai~le, Chaoman in ~.S. Pat. ~o. 2,195,395 teaches the measurement of the thermal abuse of frozen food by indicating whether or not a chemical reaction has proceeded past a certain point through a measurement of the change in pH, using a dye in water. A major advance in such an art was Larsson, U.S. Pat. No. 3,946,611, ~herein paraformaldehyde 19 in FIGURE 2 decomposes at a rate which is a function of temperature to ?roduce formaldehyde gas that permeats through me~lbrane 22 to contact a wick means 18 which contains hydroxyamine hydrochloride and a dye and low volatile acid. After an accumulation of time the HCl lowers the B Cha~
pH of wick means 18 so that the dye and wick changes color (see Example 3). The color change does not indicate a change in color upon change in phases of a solvent. See also Gessler, U.S. Pat.
No. 3,065,083 describing a time-temperature indicator to indicate the presence of fatty acids for frozen food packages; U.S. Pat.
No. 3,437,07~ to Campbell; and U~S. Pat. No. 3,479,877 to Allen Still another type of device in still another art and not to be confused with the "Pure" thermorneter is a device ernploying "liquid crystals" -- a "liquid" which, although turning color in a specific range of temperatures (usually in a range o 1-1/2~F - 2F an~ no better than 1/2~F) because of a change in 2a orientation of the liquid, is not suitable for thermometry because the "li~uid" is incapable of supercooling, therefore resolution at better than l/2F is diff~cult and the dev~ce mu~t be read immediately upon withdrawing the "liquid crystal" device from the subject. ~xamples of "liquid crystal" devices and sprays and related technology are Sanford, U.S. Pat. No.
3,633,425; Flam, U.S. Pat. No. 3,661,142 (accuracy only ~ithin 2C); Par~er, U.S. Pat. No. 3,898,354; Suzuki, U.S. Pat. No.
3,974,317; and Davis, U.S. Pat. 3,619,254.
A state of he art method for depositing ~recisely _ - 11338~

metere~l quantities of liquid on a small surface is reveale~ in Pickett et al, U.S. Pat. 3,810,779.
Ja?anese Patent Applications 47-34735 and 50-105555 B which show, respectively, compositions (l) comprising a dye and an acid with a polymeric material, and (2) a dye, an acidic compound, and a solvent ~hich change colors although not at the melting ?oint of the solvent.
Some abbreviated attempts have been made to find substances that would change color upon change in phases for use in ther~nometers, but none have been able to overcome the combined problems of emPloying many different unrelated compounds, accidental overheating, etc. For example, Jennings in U.S. Pat.
No~ 2,261,473 combines certain cognizable, organic dyes (page 2.
column 2, lines 13-28) ~"7ith certain solvents (page 2, column 1, lines 56-60) wherein the change in pH changes the color of the d~res, but needs, like Kluth, 45 or 50 different comDositions over a range such as the human clinical range. A major advance in the art is Renbaum, U.S. Pat. No. 3,700,603 wherein no solvent system is em~loyed, but the organic moieties ("electron donors" and "electron acceptors") do change color uL>on change in p'nases (see Table I, columns 5 and 6). However, because P~enbaum ap~arentl~,r did not atteml~t to find a suitable solven. system for his electron donor-accelptor pairs, a numi~er of different parts would be needed for almost any temperature range to be determined, e.g., the same Problems as Kluth appeared. See also E~ammond, U.S. Pat. No. 3,376,504, who also does not use a solvent over a range of temperatures.
,~n inex~ensive ~isposat~le thermometer was needed and intensely desired in the thermometer industry which would be easily constructe.i and have materials which would chan~e some 113:~81~

characteristics visible to the naked eye but not rea~i1y susceptible to ~uic'~ reverslbility upon withdrawal from the source ~hose temperature was to be meas~red. If one could ~rovide a chemical substance that would change in color in and of itself upon cnange in Phases, the use of dyes in indicator layers would be eliminated. Likewise, a disposable thermometer was needed to magnify the presence of an indicator layer in cases involving "classical" substances that changed only from opaq~e to transparent upon change in Phase from solid to liquid.

In an unpublished and short memorandum of June, 1~ ~ by a scientist not associated with the 2resent inventors working in-the field of disposable thermometry (who was attempting to develoo a reversible thermometer through a color change of a dye by use of molten thermometer cnemicals instead of solid thermometer chemicals) a curious phenomenom was revealed. By mixing ethyl red and bromothymol blue toget~er in a "thermometer chemical", he found out that a "very obvious color change" took ~lace when ~elting and freezing of the mixture occurred. When 2~ the chemical solidified, the color changed to yellow-oran~e. The reaction appeared to him to be co~pletely reversible. Screening tests with available dyes and indicators ap~arently showed the scientist that bromophenol blue and bromocresol purple could ~e su~stituted for ~romothylnol ~lu2. Similar structures without the ~ ph lf q J~ in 25 ~ bromine ~toms did not wor~; e.g., thymol blue, cresol htalein, f3J,~1 4 ~P ;~) thymol Dhtalein. The scientist also aDoarently found tAat suitable structures for replacement of ethvl red included crysta]
violet, Dara rosaniline base, para rosaniline acetate, new fuchsin, basic fuchsin and 8-hydroxy~uinoline. Tne me~o stated 3G that the ~-hydroxyq~inoline, althou~h not a c3~Ie or indicator, /~ --1133~10 served as a substitute by allowing the bromo compound to change from yellow to blue-green from solid to liquid form. The scientist reported that the indicating compounds were then tried in various solid solvent systems, and that the color change only took place in aromatic systems such as naphthalene, 2-ethoxybenz-R naph-th~
'~~ amide, thymol and 2-n~pthol. Aliphatic compounds such as 2-chloroacetamide and sorbitol did not exhibit color changes.
The report concluded with a statement that imidazole was too strongly basic to exhibit any change since the indicators went to the basic state and remained there.
The present inventors learned of this abandoned attempt about eighteen months later than the date of the memorandum through a technology-transfer agreement and amongst other attempts by different methods (use of metal complexes, different solutions of cations, etc ) to obtain an inexpensive disposable ~and possibly reversible) thermometer, performed the identical experiments as perceived by reading the short memorandum. The color change dîd not work for the desired disposable thermometer applications in these experiments because (1~ a broad melting point was experienced and, as the memorandum did not indicate in what proportion the components were to be mixed, ~2) much experi-mentation had to be performed to adjust the ratios of the first and second types of c~mpounds mentioned above for any color ~33810 change to occur. Even after the present inventors found the correct ratios of "Group I" to "Group II" type materials relative to each other, the broad melting range still presented a seemingly unsurmountable Droblem. The unpublished memo above did not mention any phenomena of the "Group III" compounds listed below.
Surprisingly, when the Grou~ I and Group II co~ponents were mixed in a certain ratio found by the inventors and wer2 added to the com~osition (at a total weight of about 0.05%), and when the solvent (ortho-chloronitrobenzene and ortho-bromonitro-benzene) was employed in a composition almost entirely free of nucleating agents (impurities, especially less than 0.1 weight percent), a sharp and narrow melting range (or "point"~ with a sharp color change was discovered for the composition, which at the same time exhibited the desired color change ~ith change in phases and a remarkable color stability in the liauid upon heating, ~resu.~ably due to some type of undercooling effect, i.e., upon withdra~al from the source o the tem~erature to be measured, the materials were not rea~ily susceptible to refreezing and color reversibility. The exact mecnanism for this sharp color cnange ~henolnena iD unknown and only theories have been postulated.

German Patent Application 27,15,752 (published October 2S 27, 1977) discloses, inter alia, the use of an ionic reaction between the solvent mfxture ~for example, n-octadecane/
n-eicosane) upon meltins to ionize a pair of color producing reagents ~for example methyl red and acid clay). ~ore specifically, the color si~nal in 27,15,752 is develo~ed b~
physically separating two reactive components which are later ~-1~33810 unite<i at a visually accessible site by the action of the flo~ of the liauid phase of the temperature sensitive composition. The authors describe that this may be accomplished by applying each réagent on se~arate sides of a bibulum or by dissolving one reagent in the melting su~stance an~ applying each reagent in the melting substance and applying the other to the bibulum. The German reference is seen as no more pertinent than U.S. Pat.
3,712,141 (Chadha).
Suzuki et al in U.S. Pat. 4,015,591 teaches the manu-facture of a com?osition of matter having thermal color respon-sive characteristics ~adapted for effecting vanapuncture in the human body3 and comprising an entantiotro~ic cholesteric liquid crystalline phase materia~, and at least two oil-soluble dyes dissolved in the material in a total dye concentration of 0.01-1.0 weight percent of the com~osition and with the dyes togetherabsorbing light of substantially all wave lengths wit'nin the range.

'.~

113;~810 Novel and stable temperature indicating compositions are provided for use in a number of different types of disposable thermometers for measuring the temperature of human and other animal bodies, and for other temperature measurement applications in industry as well. Furthermore, the application of these novel chemical compositions are not limited to use in clinical or industrial applications induced by temperature changes, but may be extended to other indication or measuring systems in which the color change described can be used to indicate a liquid to solid or solid to liquid phase change in a non-polar solvent or weakly polar solvent induced by pressure, radiation, electromotive forces or other kinetic energy sources.
According to the invention, there is provided a reversible indicator composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid stage to a liquid state and capable of being supercooled for at least several minutes consisting essentially of:
(1) an inert solvent lI3 consisting of a single substance or a mixture of substances capable of changing from a solid state to a liquid state at substantially a predetermined temperature, and (2) an indicator system ~II) consisting of one or more substances different from said solvent (I), characterized in that (a) said indicator system (II) is soluble in said solvent (I) when the latter is in the li~uid state, and (b) said indicator system (II) changes color visible to the naked eye when said solvent (I) passes from the solid state to the liquid state or from the liquid state to the solid state, said indicator system (II) exhibiting a sharp color change upon transition of said solvent (I) from the liquid state to the solid state or from the solid state to the liquid state, said composition capable of being supercooled for at least several minutes and said color change being reversible.
The invention also provides a temperature-indicating device comprising a heat conducting carrier having one or more spaced regions defined therein to determine a like number of predetermined temperatures in a predetermined temperature range, said spaced regions containing a like number of different compositions of matter therein, each a solid solution, said carrier having a transparent cover sheet means in sealing -engagement therewith, and with a single solid solution being deposited in each of said regions and being associated with a single one of said predetermined temperatures, each composition of material exhibiting a sharp color change upon transition from a solid state to a liquid state, capable of being supercooled for at least several minutes, and substantially free of impurities, consisting essentially of:
(a) a solvent adapted to change from a solid at substantially the predetermined temperature to a liquid state;
and (b) an effective amount of one or more suitable moieties dissolved in and inert towards said solvent to form a solid solution when the composition is in the solid state, and adapted to change the color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved, and selected from one of the groups consisting of:
(l) one or more of a ~roup III body or compounds consisting of pinacyanol iodide, quinaldine red, l,l'-diethyl-2,2'-cyanine iodide, pinacyanol chloride, thionin, methylene blue, cresol red, chlorophenol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, Toluidin Blue O , Orasol Orange RLNTM, Orasol Navy BlueTM, Irgalith Red PRTM, Fat Red BSTM, Xylene Cyanol FFTM, Rhodamine 6G , Rhodamine B

-15a-` ~33~0 Irgalith Magenta TCBTM, Irgalite pink TYNCTM, Toluidine Blue O, Savinyl Green BTM, Savinyl Blue RSTM, purpurin, 3,3'-diethyl-thiadicarbocyanine iodide, cryptocyanine, Dicyanine ATM, Merocyanine 540TM, 4-(p-ethoxyphenylazo)-m-phenylene diamine monohydrochloride, Yellow Orange STM, Chrysoidin GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue RTM, Pyronin GTM, gallein, Erythrosin Yellow BlendTM, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphosphine oTM, acriflavine, acridine orange, rhoduline violet, Alizarin Cyanin 2RTM, Alizarin RED STM, alcannin, Aurantia, Direct Green GTM, Fast Red Salt 3GLTM, Fast Blue Salt BBTM, Fast Garnet Salt GBCTM, Carta Yellow G 180 o/oTM, murexide, Savinyl Blue GLSTM, Irgalith Blue GLSMTM, phthalocyanine, Di Amingreen BTM, Alizarin Blue S, Celliton Blue ExtraTM, neocyanine, Janus Green, dimethyl yellow, Fast Yellow, Methyl red sodium salt, Alizarin yellow R M, Eriochrome Black T M, Chromotrope 2R M, Ponceau 6R , Brillîant Ponceau G/R/2RTM, chromolan yellow, Sudan Red BTM, Bismarck brown GTM, Fat BlackTM, Resorcin BrownTM, Benzofast pink 2BLTM, Oil Red EGNTM, Euroglaucine, Fuchsin NB , parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin B , fluorescein sodium salt, Rhodamine B base , Eosin Scarlet, Eosin YellowishTM, Erythrosin extra bluish, 4,5-dibromofluor-escein, ethyleosin, PhloxineTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-ethyl pyridinium iodide, ethyl red, neutral red iodide, nigrosine, savinyl blue B M, Orasol Blue BLN , Safranin O , Azocarnun GTM, Phenosafranine, Azocarmine BXTM, Solophenyl Brilliant Blue BL , Nile Blue A , gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/C , Blue VIF Organol Alizarin, Nitrofast Green GSB M, quinalizarine, Oil Blue NT , Solvay purple, Ciba BlueTM, Indigo syntheticTM, Chromophtal Bordeaux RS M, Acid Alizarin Red B , 5-Aminofluorescein, Rose -15b-113~810 BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, Cresyl violet, 4,4'-Bis(dimethylamino)-benzylhydrol, Zinc Phthalocyanine, Sudan IIITM, Pyronin y M, Toluylene Blue cresyl violet perchlorate, Mendola's Blue M, Phosphine Dye, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-l-naphthyl-amine, 4-(4-~imethylamino-1-naphthylazo)-3-methoxy-benzene sulfonic acid, Bindschedler's GreenTM, p-(p-dimethyl-aminophenylazo)benzoic acid;
(2) a binary mixture of (A) one or more of a Group I body of compounds soluble in said solvent consisting of the halogenated sulfonphthaleins and the organic acids having a pK
of less than or about four; and (B) one or more of a Group II body of compounds con-sisting of the aminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines;
with the proviso that if the Group II compounds consist solely of one or more aminotriphenylmethanes or their soluble salts, then the Group I compound must be selected from one or more of the group consisting of oxalic acid, suitable soluble sulfonic acids, the tetrahalogenated sulfonphthaleins, and the other soluble organic acids having a pKl of less than or about 2, and wherein the weight ratio of the Group I body of compounds to the Group II boay of compounds is more than or about 3 to 1;
and (33 one or more of the aforesaid Group III body of compounds with one or more of the Group I or Group II bodies of compounds.

~ ' -15C-~13~8~0 The constituents of the novel compositions of matter substantially free of impurities most preferably comprise (a) a suitable inert solvent (i.e., stable and in which Group I-III
moieties are soluble, and generally aromatic hydrocarbons) adapted to change from a solid state at substantially a predeter-mined temperature to a liquid state, and (b) an effective amount (generally ahout 0.005 to about 0.5 percent pre~erably about 0.025 to about 0.05 percent by weight) of (l) one or more Grou?
III cornpounds (pinacyanol iodide, quinaldine red, l,l'-diethyl-2, 2'-cyanine iodide, pinacyanol chloride, thionin, methylene blue, cresol red, chloro~henol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, toluidin blue O, Orasol Orange RLN~, Orasol Navy ~lue~, Ir~alith Red PR~, Fat Red BS~, mcthyl violct, Xylene Cyanol FF'~, Rhodamine 6G'~, Irgalith Magenta TC~, Irgalith PinX TYNC~, roluidin blue O~, Savinyl Green B~, Savinyl Blue RS~, purpurin, 3,3'-diet~ylthiadicarbocyani.ne iodide, cryptocyanine, Dicyanine A'~, Merocyanine 540~, 4-(p-ethoxyphenylazo)-m-~henylene diamine monohydrochloride, Yellow Orange S'~, Chrysoidin G~, fuchsin, aurintricar~oxylic aci~
(a~lnoniu.~n salt), Victoria Blue R'~, Pyronin G'~, gallein ~,I.1v~L~
Erythrosin Yellowish Blend~, chloro?henol blue, bro~lophenol blue, bromocresol ~ur~le, Coriphosphine O'~, acriflavine, acridine orange, r~oduline violet, Alizarin cyanin 2~'~, Alizarin Red S~, alcannin, Aurantia~, Direct Green G'~, Fast Red Salt 3GL'~, Fast Blue ~Salt ~B~, ~ast Garnet Salt GBC'~, Carta Yellow G 1~0 o/o, xid~
Savinyl Blue G~S~, Ir~alith alue GLS.I~, ohthalocyanine, Di ATnin~reen B~, Alizarin Blue S'~, Celliton ~lue ~xtra~, Janus Green, dimethyl yellow, Fast Yellow, .~ethi~l red sodium salt, Ali~arin yellow R'~, Eriochron~e l~lack 'l~, Chro~otrope 2R'~, Ponceau 6R~, Brilliant Ponceau G/R/2R~, chro!nolan ye~low, Sudan Reo B~, i:~3~ 0 Bismarck brcwn G , Fat BlackTM, Resorcin Brown , Benzofast pink 2BLTM, Oil Red EGNTM, Euroglaucine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluores oe in sodium salt, Rhodamune B baseTM, Eosinscarlet, Eosin Yellcwish Erythrosin extrabluish, 4,5-dibrom3 fluores oe in, ethyleosin, Phloxine, Cyanovin BTM, chlorocresol green, pinacyanol b m mide, 2-(p-dimethylaminostyryl)-1-1-ethyl pyridinium iodide, ethyl red, nigrosine, savinyl blue BTM, Orasol Blue BLNTM, Safranin o Azocar.nun GTM, Phenosafranine, Azocarmine BXTM, Solophenyl Brilliant Blue BL , Nile Blue A , gallocyanine, gallanine blue, oe lestine blue, methylene green, Azure A~B/C , Blue VIF Organol Alizarin, Nitrofast Green GSBTM, quinalizarine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo syntheticTM, Chroncphtal Bordeaux RS , acid Alizarin Red B , 5-kminoflourescein, Rose B ngal , Martius Yellow , Chicago Blue 6B , Alcian Blue 8G~
cresyl violet, 4,4'Bis(dimethylamino)benzylhydrol, Zinc Pthalo-cyanine, Sudan IIITM, Pyronin yTM~ Toluylene Blue , Cresyl Violet perchlorate, Mendola's BlueTM, 3,3'-diethylthiadicarbocyanine iodide, Phosphine DyeTM, NitronTM, Cresyl violet acetate, Ceres Orange R , 4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamlno-l-naphthylazo)-3-methoxybenzene sulfonic a d d, Bindschedler's GreenTM, and p-(p-dimethylamino phenylazo) benzoic acid and neocyanine) or in the alte m ative, (2) a similarly small a~DUnt of one or more of a Group I bcdy of compounds consisting of the halogenated sulfon-phthaleins and organic acids having a pK of less than about fcur, together with one or more of a Group II body of compounds consist-ing of the aminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines (with the proviso that if the Group II compounds consist solely of one or more aminotriphenylmethanes or their soluble salts, then Group I must be selected from one or more of the group consisting of oxalic acid, suitable soluble sulfonic acids, tne tetrahalogen-ated sulfonphthaleins and the other known soluble organic acids S ~ having a pKl of about 2 or less~ dissolved in the above-mentioned suitable solvents. Examples of Group I compounds suitable for use in this invention are one or more of the group consisting of oxalic acid, maleic acid, dichloroacetic acid, trichloroacetic acid, naphthalene sulfonic acid, benzenesulfonic acid, chloro-anilic acid, bromophenol blue, bromothymol blue, chlorophenolred, bromochlorophenol blue, bromocresol green, 3,4,5,6-tetra-bromophenolsulfonphthalein, bromophenol red, chlorophenol blue, bromocresol purple, 2,4-dinitrobenzenesulphonic acid, and chlorocresol green. ~xam~les of Grou~ II comPounds suitable for use in this invention are ethyl red, crystal violet, pararosan-iline, pararosaniline acetate, oasic fuchsin, ~-hydroxyquinoline, ethyl violet, brilliant green, pinacyanol chloride, and 3,3'-diethylthlodicarbocyanine. Preferable combinations of Group I
and Group II compounds when Group III cornpounds are not employed are: (1) brornsphenol blue: basic fuchsin; (2) chlorophenol blue:
ethyl red; (3) chlorophenol red: ethyl red; (4J bromophenol red:
ethyl red; and (5) bromochlorophenol blue: brilliant green. If a Group III compound is not employed, the weight ratio of the Group I to Group II compound is more than or about 3 to 1. A
Group III compound in an e~fective amount may be used alone or together ~ith any small amount (preferably less than about 0.5 percent) of Group I and/or Group II conpound.
A most preferable solvent system for use in measurinc3 temperatures in the hu.nan clinical termperature ran(3e is that of ~33810 ortho-bromonitrobenzene and ortho-chloronitrobenzene (OBNB:OCNB) wh~rein tne ratio of ortho-bromonitrobenze to ortho-chloronitro-benzene varies ~rom about 5~.2:43.8 to about 96.0:4.0, which, when in use with a~nroxim~tely 0.05 percent by weight of Group I-III compounds yields an accurate system for measurement of temperatures from ~.0F to 1~F. The ~B~B:OCI~B solvent system also allows the temperature to be measured within the range of 96F to 105F within 0.2F or 0.1C.
~The invention also contemplates a novel temperature-lG indicating device comprising (a) a flat or gradually curved heat-conductinq carrier having one or more regions defined ther-in, preferably cavities, to determine a like number of predetermined temperatures at temperatures separated by a constant increment in a predetermined te~perature range by means of a like number of different thermally-responsive compositions of matter, each cavity associated with one of the predetermined temperatures and each substantially without impurities, (b) if the ncvel compositions of our invention are not employed, an indicator means located at the bottom of each said cavities, (c) a trans?arent means in sealing engagement ,7ith a carrier means above each cavity and overlying each of said cavities to form an enclosure for each cavity between the walls of the cavity and the transparent means, and (d) one of said compositions of matter adapted to change from a solid to a liquid at substantially the ~redetermined te,nperature associated with said cavity, and in addition, substantially filling the cavity exce~t for a substantially s~herical void within said cavity and composition of matter. The novel tem~erature indicator device does not contemplate the necessity of employing the novel temperclture-indicating compositions of inatter, but can, in the alternative.

- 113381~

em~lo~ the "classical" compositions of matter (compositions other than our novel cosnpositions ~hich generally change from opaque to transparent with a corresPonding change in phase at a predetermined temperature). On the other hand, if the novel com~ositions of matter are employed, the indicator means in the novel temperature-indicating device may be elininated. The invention contemplates use of the novel device for ordinary opaque thermometers where the entire backing material is colored, or when a cover layer of bibulum paper is employed, or when numerals are employed at the bottom of void spaces.
In one as~ect, this invention contemplates providing t~ermally-sensitive compositions which undergo a cnange of state, i.~., frosn solid to liquid, at ~recisely preaetermined tes~peratures with a corres?onding change of color visible to the naked eye; such temperature-sensiti~e compositions being solid solutions of certain organic compounds to be hereinafter described.
In another aspect, the present invention is concerned with providing solid solutions ~hich undergo a change of state rapidly over a very narrow temperature ran~e, e.g., within an accuracy of 1/10C, OL in the alternative, witnin an accuracy of 2/10F, so that the solid solutions may be employed for a measurement of temperature ~ithin a predetersnined te~perature range, for example, the clinical range of 96~ to 105F or 35.5C
to 40.4DC. An example of a device is a disk with three void B spaces di~ec~ed t~2ra3 three novel compositions melting at different temperatures ~hich might (a) be placed on a baby's abdomen to detect fever or (b) be placed on a ~erson's forehead to detect a like fever. Such an example has obvious advantages 0 in the detection of malignant hyperthermia; see ~erida ;~.
_ 2-1~33810 Dilworth, "THE IMPO~TAN OE OF CHAN OE S IN BODY TEMPERAIURE INPAEDIATR1C suRGæ~y ~ND ANAESTHESIA", Anaesthesia and Intensive Care, Vol. l, No. 6 (November 1973) 480 et seq.
Another aspect of this invention is directed to the use of an indicating system associated with the novel compositions of matter so as to obtain a rapid visual indication of the change of state of such material, and hen oe , the temperature of the test sub-ject.
Furthermore, another aspect of this invention is directed toward the provision of novel ccmpositions of matter which may be applied to other indication or measuring systems other than tempera-ture measuring systems such as those suggested or taught by our invention in which the color change described can be used to indic-ate a liquid-to-solid or solid-to-liquid change, preferably in a nonpolar solvent or weakly polar solvent induced by pressure, radia-tion, electromDtive for oe s, or other kinetic energy s oe s.
In yet another aspect, the invention is directed tcward the provision of a novel temperature-indicating devi oe suitable as a disposable therm~meter, in which each temperature-sensitive ccm-position of ~atter used is substantially free of impurities so that said oomposition of matter upan oomplete melting has few nucleation sites and is not oonducive to resolidification, i.e., the tempera-ture-sensitive oomposition of matter has the property of stable undercooling and will remain liquid for at least several minutes up to several hours when subjected to a surrounding temperature that is somewhat belcw the freezing point of the ccmposition.
In yet still another aspect, the present invention is directed toward the prcvision of a novel temperature-indicating ~ ~-device (comprising a flat or gradually curved heat conducting carrier means with one or ,~ore cavities therein and a transParent means in sealing engagement with said carrier means above tne cavity) for use of so-called "classical" temperature-sensitive materials, e.g., compositions of matter commonly employed in disposable thermometers which cnange from opaque to become transparent upon a change in phase from solid to liquid, through the use of a substantially s~herical void within said cavity containing tne composition of matter deter~ining the temPerature to be indicated to magnify the presence of an indicator layer at the bottom of said cavity.
Finally, while other aspects of our invention will-become apparent from the detailed description thereof, infra, the overall object of our invention is to provide generally use~ul 15 ~ improvements in change-of-state thermometers.
The details of the invention pertaining to the novel temperature-indicating device will become more evident from the detailed description to follow with reference to the appended drawings:
FIGURE 1 depicts a liquidous curve of a solid solution of ortho-chloronitrobenzene and ortho-bromonitrobenzene for the human clinical range of tem?eratures. Irhe bands defined by the dash lines in this diagram, greatly exaggerated,re~resent the limit of accuracy of te~perature measurements of this invention, i.e., plus or minus 1/10C or approximately plus or minus 2/10F~
The band is shown in substantially exaggerated width (forty or fifty maqnitude) in order to facilitate this illu~tration;

FIGUR~ 2 is a partial plan view from the horizontal of a flat Gr gradually curved novel heat conducting carrier having a cavity defined therein, ~hich cavity form~ an enclosure for a li33810 temperature-sensitive "classical" composition of matter therein when such cavity is covered by a transparent cover sheet means in sealing engagement with the carrier means overlying the heat-conducting carrier means and above the cavity; the figure also 5 B depicts a substantially spherical cavity inside ~ the temperature-sensitive composition of matter;
FIGURE 3 is a vertical section taken along line 3-3 of FIGURE 2; it is the partial ~lan view of t~e cavity when taken from the overhead of t'ne cavity of FIGU~E 2 when a painted material is at the bottom of said cavity in an indicator means;
FIGURE ~ is a vertical section taken along line 4-4 of FIGURE 2; it is a ~artial ?lan view taken from the overhead of the cavity of FIGURE 2 when a painted material is magnified due to a spherical cavity in the "classical" composition, when said composition of matter has nelted;
~I~URE 5 is a ~artial overhead plan view of a thermometer over part of the human clinical range of tem~eratures em~odyin~ tne princit21es of this invention in degrees Celsius;
~I~URE ~ is a ?artial overnead plan view of a thermometer over the human clinical tem~erature ran~e em~odying - the principles of this invention ~hen in degr~es E'arcnhcit-, FIGURE 7 is a vie~7 of a thermometer with 10F
increments when using the novel com~ositions of ~,atter of this invention in a commercial a??lication;
FIGi~RE ~ is a ~lan view or a tem~erature-indicating device fro~ the horizontal (iogether ~7ith a plan view from the vertical of a la~el on said aevice) using th2 novel com?ositions of ,matter of t'nis invention for indication OL a tem~erature exceeding a ~redetermined safe limit. The details of tne a~ove figures wiil De ~iscussea, lnrra;

-~3--~33810 FIGURE 9 is a cut-a~a~ three-dimensional view from a skewed angle of a thermometer comprising a heat-conducting carrier means with a grid of cavities thereon, enclosed in a case so that only a handle of the heat-conducting carrier means protrudes;
FIGU~E 10 is another three-dimensional view from the same skewed angle as FIGURE 9 of the thermometer when removed from the case of ~IGURE 9, exce~t that it reveals a clinical temperature scale from 96.0F to 104.8F in the form of a grid of cavities in the heat-conducting carrier means;
FIGURE 11 is a partial plan horizontal view taken along line 11-11 in FIGURE 10, revealing several cavities in tne heat-conducting carrier means, each surrounded by a transparent cover sheet means and a bottom transparent bottom plate means;
FIGU~E 12 is a plan view of a flat temperature-indicating d~vice from the vertical without the use of a case, comprising a heat-conducting carrier means with a grid of cavities thereon; and FIGURE 13 is a plan horizontal view ta~en along line 13-13 in FIGURE 12 revealing the heat-conducting carrier means, cavities within, transparent cover sheet ,~eans, and a ~ottom plate means.
FIGU~F 1A is a plan view ta~en from the vertical of a transparent su~port ~ember for a disp~sable clinical thernometer either OL FI~URE 10 or FIGUR2S 12-13.
FIGU~E 15 is a plan vi~w taken from the vertical of the transoarent supDort member of FIGVRE 14, except in sealing engagement, with a disposa~le thermometer sucn as that shown in FIGUR~ 10 with a ~'ahrenheit scale from 96.0 degrees ~ahrenheit to 104.~ degrees Fahrenheit graduated in 0.2 degrees Fahrenheit Z~_ ~3;3810 increments.
FIGURE 16 is a plan view taken from the vertical of the trans?arent support member of FIGURE 14, except in sealing engagement with a disposable thermometer, such as that shown in 5 FIGURE 10, but with a Centigrade scale from 35.5 degrees Centigrade to 40.4 degrees Centigrade graduated in ~.1 degrees Centigrade increments.
Figure 17 is a partial Plan view from th~ horizontal of a flat or gradually curved novel heat-conducting carrier having a cavity defined therein, where a cover layer is bonaed to a carrier layer by a pressure-sensitive adhesive layer comprised of polyisobutylene (PIB).
Figure 18 is a partial plan view from the horizontal like Figure 17 except using an additional layer of PIB adjacent to the lower edges of the cavity.
Throughout the Detailed ~escri~tion below, the terms "novel thermally-responsive substance", "novel thermally-responsiv~ material", "novel temperature-indicating compositions of mat~er", "novel temDerature-sensitivP solid solutions", "novel temperature-indicating solid solutions", and "novel solid solutions", or variations thereof, are used interchangeably to denote the same novel materials of our invention. Otherwise, the term "compositions of matter" or "classical compositions of matter" are used interchangeably to denote compounds which change only from being opaque to transparent with a corresponding change from the solid to liquid state, or vice versa.

1. Novel Compositions of ~;latter It has now been discovered unex~ectedly that certain :, ,~ , . .
! , . , , ' ,~30,0 organic compounds (to be described hereinafter) form novel solid solutions which undergo a change in state from solid to liquid at precise and predetermined temperatures with a corresponding change in color visible to the naked eye, and likewise, from liquid solutions which undergo a change in state from liquid to solid at precise and predetermined te-,nperatures with a corresponding change in color visible to the naked eye. The term "solid solution" is well known and usually refers to a homogenous solution of one solid in anotlner. The novel solid solutions contemplated in the present invention are composed of two or B more, preferably three or four~different organic compounds .Yith varying pro~ortions of at least two compounds which form a solvent for the solution. Each novel solid solution undergoes a rapid chan~e of state at a ~recise and predetermine~ temperature or substantially thereaoouts. By a "change in color visible to the naked eye" of a sourc~ ~7e mean a change in the wavelength of luminous flux of light (from the source distributing or reflecting such energy in the region of the Zlectromagnetic Spectrum from about 3900 Angstrom unit~ to about 7600 Angstrom units before or after the change, or ~referably both) visible to a ~erson of normal vision and eyesight wherein the intensity of the lui~inous flux surrounding the source is more than or about 5 lumens ~er square foot (ft-c). In most instances, this cnange in the wavelength oE luminous flux to the e~e will be at least about 175 Angstro~ns, and ~referably at least about S00 Angstroms.
Preferaoly, when a small but effective amount (general-ly a weight fraction from about 0.005 to 0.2 weight percentum, and generally about 0.05 weight percentum of the entire cornpo-sition, but the o~timum ma~ be more or less upon experimentation, depending on the Grou~ I-III comDounds selected and the solvent 1' !l Iselected, up until both phases ap~ear ~lar'~, a~pear the same ,,color, or the melting point becomes too broad for the use desir~d-~ latitude for experimentation is present her~) of one ~ or more of Group III compounds: pinacyanol iodide, l,l'-diethyl-,.2-2'-cyanine iodide, quinaldine red, pinacyanol chloride, ,thionin, Inethylene blue, cresol red, chlorophenol red, neutral ired iodide, neutral red chloride, crystal violet, acridin orange, ¦Orasol Orange RLN~, Orasol Navy Blue~, Irgalith Red PR~, Fat Red B I BS~, mcth~ viole~, Xylene Cyanol FF~, Rhodamine B, Rhodamine ¦6G~, Irgalith Magenta TC~I~, Irgalith Pink TYNC~, Toluidin Blue ~, Savinyl Green B, Savinyl Blue RS'~, ~urpurin, 3,3'-diethyl-~thiadicarhocyanine iodide, cryptocyanine, Dicyanine A~, M~ro~yanine 54~, 4-(p-et'noxvphenylazo)-~,-phenylene diamine l! monohydrochloride, Yellow Orange S~, Chrysoidin G'~, fuchsin, ¦!aurintricarboxylic acid (amnloni~lm salt), Victoria Blue R~, ! Pyronin G~, gallein hlo~.in-~, Eryt'nrosin Yellowish Blend'~, chlorophenol blue, bromophenol blue, bro.~ocresol pur~le, Coriphosphine O'~, acriflavine, acridine orange, rhoduline violet, 'Alizarin cyanin 2R~, Alizarin Red S'~, alcannin, Aurantia~, ~irect ~0 ~ Green G~, Fast Re~ ~alt 3GL'~, Fast 31ue 5alt ~B~, F~st Garnet ~u r ~x; de ~ Salt GBC'~, Carta Yello~ G 18U o/o,~Savinyl Blue GLS~, Irgalit~
~Blue G~SM'~, phthalocyanine, Di Amingreen B'~, Alizarin Blue S, I'lCelliton Blue Extra ~, neocyanin~, Janus Green~, dimethyl yellow, ¦IFast Yell~w, Methyl red sodium sa~t, Alizarin yellow R~, 1~ Eriochrome black T~, Chromotrope 2R~, Ponceau 6R~, ~rilliant ~Ponceau G/R/2R~, chromolan yellow, Sudan Red B~, Bismarc~ brown G~, Fat Black'~, Resorcin Brown'~, Benzofast pink 2BL~, Oil Red ,EGNT~, Euroglaucine, Fuchsin NB'~, ~arafuchsin, Patent ~lue~, I~Irgalith Blue TNC'~, Phloxin B'~, fluorescein sodium salt, ' Rhodamine a base'~, Eosinscarlet, Eosin Yello~7ish'~, Erytnrosin ~ extrabluish, 41~ dibromofluorescein, ethyl~osin, ~hloxine'^, ! , .

Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethyl-aminostyryl)-l-ethyl pyridinium iodide, ethyl red, nigrosine, savinyl blue BTM, Orasol Blue BLNTM, & franin oTM, Azocarnun GTM, Phenosafranine, Azocarmine BX M, Solophenyl Brilliant Blue BL
Nile Blue A M, gallocyanine, gallamine blue, oe lestine blue, methylene green, Azure A/B/CTM, Blue VIF M arganol , Alizarin, Nitrofast Green GSB , qulnalizarine, Oil Blue N , Solvay purple, Ciba Blue M, Indigo syntheticTM, Chromophtal Bordeaux RSTM, Acid Alizarin Red BTM, 5-Aminofloures oe in, Rose BengalTM, Martius Yellow , Chicago Blue 6B , Alcian Blue 8GXTM, cresyl violet,

4,4'Bis(dLmethylamino)benzylhydrol, Zinc Pthalocyanine, Sudan IIITM, Pyronin yTM~ Toluylene BlueTM, Cresyl Violet perchlorate, Mendola's Bl~e M, 3,3'~diethylthiadicarbocyanine iodide, Phosphine DyeTM, NitronTM, cresyl violet a oe tate, Ceres Orange R , 4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamino-l-naphthylazo-3imethoxybenzene sulfonic acid, Bindschedler's GreenTM, and p-(p-dimethylaminophenyl-azo)benzoic acid, or one of the other organic moieties to be des-criked (one or more Group I ccn}oondb with one or more Group II comr pounds) is combined with a suitable solvent, for example, a pure mixture of ortho-chloronitrobenzene and ortho-bromDnitrobenzene for use in clinical applications, the temperature of tlle change of state of a number of solid solutions with a corresponding change in color may be accomplished at approximately l/lo& or 2/10F inter-vals, i.e., a change of state of one novel te~perature-sensitive ccmposition of matter at a temperature 1/10 C or 1/5 F different from the temperature of chance in state of another novel composi-tion of matter in an adjacent region containing another proportion of the same organic moieties in ortho-chloronitrobenzene and ortho-bromonitrobenzene.

~ T
, ,~.~

3~aQ

Thus, for example, in human clinical a~plications where temper-~l ature measurements in the range of 96F to 105F (or from 35.5C
to 40.5C) are usually desired, 45 to 50 different solid solu-tions (differing in their percentage compositions but otherwise made from the same two components~ will provide all of the necessary temperature cJradations at increments of 2/10F, i.e., 96.0, 96.2, 96.4, etc., up and including 104.~F, or in the alternative, 35.5, 35.6, 35.7, up and including 40.4C. The ¦~ solution of ortho-chloronitrobenzen~ and ortho-bromonitrobenzene, l,l when the ortho-~romonitrobenzene varies from 56.2 ~eight percent ¦¦ to 96.0 weight percent, provides an excellent starting mixture ¦l for determination of temperatures in the human clinical tem~er-¦l ature range. ~lsuallv the addition of the Group I-III organic - !I moieties (hereinafter sometimes "organic moieties") consisting of 15 1¦ a small but effective percentage of one or more of the aforesaid ¦ Group III compounds, or a combination of one or more Group I com-1~ pounds ~ith one or more Group II comPounds affects th~e 1~ temperature curve in FIGJRE 1 by only a small increment ~ or d~, ~1 which is substantially constant along the entire curve. Regard-2~ less of the solvent system selected for a gi~en pred~ter!nined temperatur~ range, it is necess~ry t'nat the organic moieties i selected for the color chan~e constitute a sm,all but effective ¦~ amount of moieties, e.g., at least that amount sufficient to !~ provoke a color change visi~le to the na~ed eye, anQ preferably 25 ll up to a saturated solution of Grou? I-III orcanic moieties, and 1, most preferably about 0.0~5 to about 0.2 weight percent of an " inert, preferably arom~tic solvent constituents, constituting the re~aining b~lance of the rnixture. The ~,roup I - Group III
moieties may in some instances exceed ().2 weignt percentum as ;, :
,~ long as the melting point remains sharp an~ both phase~ are not ,, .

' 29 ~33810 so dar~ as to eliminate a color change visible to the naked eye.
If too s!nall an amount of organic moieties is employed, the colors and the color change are too faint under weak light; if too large an amount is em~loyed, the colors are too dark and the color change is harder to visualize and there is a possibility th~t the shar~ness of the melting point will affected. It-is also noted that the organic moieties and suitable solvent to De described should be substantially free of impurities; generally, such impurities should be ke~t less than three tenths of one percent of the entire composition. Su~ersaturated solutions are not preferred for reasons to be enumerated below.
-- It ~ust be emphasized from t~e outset that once a pro-2osed solvent system has been selected (consisting of one or more compounds) for the tem~erature(s) to be aetermined, the com-pound(s) of the system must be tested for the Grou~ I-III
moieties for stability (i.e., inertness) and Grou~ I-III moieties are soluble in the compound(s) of the solvent. This inust be done by routine testing, within the skill of tnose in the art. Only after the solvent system compound(s) are shown to dissolve the Group I-III moieties and be inert towards them, can such a solvent system be suitable for our invention.
While sometimes under ~ortuitous circumstances the solvent syste~n may consist of only one compound, in most instances (as those skilled in the art ~7ill appr2ciate) the temperature to be determined will not readily be obtainable without mixing two or mor2 organic comoounds for the solvent system. E~ence, for a temperature-indicating device, two or more related organic compound constituents in the solvent are esPec-ially helpful for neasuring forty or more temperatures locat2d at regular incre~ents.

,0 It is apparent from the foregoing description that the selection of one or more inert solvents towards the organic moie-ties for use in the novel composition of matter requires judicious and careful scrutiny, sin oe not all organic compounds are useful for this purpose and many may fall outside a desired temperature range. A suitable solvent may be any solvent which is inert to-wards the organic moieties and in which the organic moieties are soluble while the solvent is in the liq~id phase. In some in-stances, simple alcohols and other organic substan oe s may be suit-able (see Table 3) rather than aromatic ocmpounds. The organic ocmr pounds which are particularly adapted for the formations of solid solutions which can serve a novel temperature-indicating oomposition in acoordan oe with the present invention are generally those which are aromatic weakly polar (e.g., oompounds which are immiscible in water and have a dielectric constant less than about 35) or moder-ately pol æ aromatic organic ocmpounds, as well as the requirements of organic moiety solublity and inertness towards the organic moie-ties. Thus, it has been disaovered that weakly polar or moderately polar aromatic organic ccmpcunrs, which have analogous chemical structures (e.g., analogs, hcmologs and optical isomers), have sub-stantially the same molecular volume or have similar crystalline structures (e.g., isomorphous) and which form the novel solid solu-tions useful for the puLpose of this invention, are especially use-ful for solvent system constituents in preparing a grid of novel oompositions of matter to be used in predetermined temperature range for the determination of a temperature falling within said range. In addition, it is preferable that the solvent solutions have a linear or a substantially linear temperature composition liquidous cuxve, particularly over the desired tem~erature range k:-¦i5uch as, for e~ampl~, over the human clinical temperature range. .Exemplary wea~ly ~301ar or non~olar ~romatic solvents are ortho-chloronitrobenz~ne, ortho-bromotlitrobenzene, naphthalene, ,2-ethoxyhenzamide, l-thymol, 2-naphthol, ortho-iodonitrobenzene, ,meta-iodonitro~3enzene, ~3ara-iodonitrobenzene, para-chloronitro- .
~ d;bro~o n ~'~ro~e~ze3~
B,b~nzene, ~3.et.à-33romonitrobenzene, par~-di-biornon.i~ob~n~e-ne and , i!para-toluic acid. It must be em~hasized, of course, that a I
suitable solvent useful for one selection o organic moieties may j l¦not be useful for another, and that an operable solvent at one , ~ltemperature range may not work at a different range. It is recommended that for a given temperature to be measured, one may i start his investigation for the appropriate temperature(s) to be ersninel a .r,~itabl~ solvent sy..tem .s~lect~d ~om com~ol~nds f~om the following:
~ ~R ~.
15 ~ ~y~r- or weakly polar aromatic compounds, i.e.r!
jli.e., compounds having a dielectric constant of less than about i,i35;
(2) water; or Il (3) aronatic and aliphatic co~pounds other than (1)-20 (2) which are ger-~,an~ to the tem~eratures to be deterMined, and which are "inert" to the Group I-III dyes.
The constituents of the novel compositions of matter comprise: ' gin~læ
Il (1) a solvent (I) consisting o~ a singel substance or a ~

! mlxture of substances and adaote~ to chan~e from a solid state at i ¦'substantially a predetermin~d tem3~3erature to a li~uia state and 3 (2) an indicator system ~II) consistin~J of one or more ¦

' su~stances di~ferent from (I), characterized in that 'l (a) (II) is soluble in (I) when the latte~r is in the liquid p}-ase, .and ~338SO

Il . I
i' t 1 (b) (II) changes color visible to the naked eye I' when (I) passes from the solid to the liquid j !, I phase or from the licuid to the solid phase.
,jlt is well within the range of kno~ledge of those skilled in the !

5 ~ l~art to find for a given tem~erature ranye to~measured and for ?
, color change desired (choosing from the various Grou~ I-III
,compounds) a suitable solvent, i.e., one which is in toward the ¦Group I-III compounds and for which the latter i~ solu'~le in the ¦liquid phase in said solvent.
i The solid solutions made frorn ortho-chloronitrobenzene and ortho-bromonitrobenzene have been found to be most preferable l¦for use in temperature measurements in the clinical range withi~ l ¦Ithe ~C~resa~d ~c~lracy. Of co~Jrs~, as 't will be readi~ under-!lstood by those skilled in the art, any t-~o or more aromatic ¦I solvents as defineJabove in which the organic moieties to be !Idescribed below are coluble, stable and inert, may be employed ,l,for thermometers if adaptable to the temperature range to be tested, and if ca~able tocJether of forming a homoyenous solid ,Isolution.
l' Preferably the novel composition of matter cor,sists ¦ essentiaily of:
(A) a suitable solvent ada~ted to change from a ~I solid state at a ~redetermined temperature ¦~ to a liquid state, and ll ~ne 25 j~ (B3 an eCfective amount of ~ or more suitable ¦l organic moieties soluble in said solvent in ¦I tne liquid state and ada~ted to c'nanye the ~, color of the comoo~ition visi~le to the 1' naked eye upon the change of state of the Ii 1, 33 j~ solvent at substantially the predetermined temperature and selected from one or more of the group consisting of (1) a group ~ body of single compounds consistin~ of the cYy ~ n~ class of dyes, suitable dyes from the follo~in~
r~ m on o ~zo D classes: nomoaz~, diazo, triar~l-methane, xanthene, sulphonephthalein, ~! acridul, guinoline, -zine, oxazine, 10 ¦, thia~ine, anthraquinone, indigold, and ¦l, the following individual com~ounds:
Aurantia~, Orasol orange RLN~, Diamin en ~, nirect green G~, ~ast Red Il salt 3 GL~, Fast blue salt BB'~, Fast 15 1' Garnet salt GBCI~, Carta Yellow G 180 l o/o'~ lurexide, Savinyl blue GLS, Irgalith blue GLS~ , Phthalocyanin~ and Alcannin, : (2) mixtures of:
2~ (a) one or more organic ~cid CGI~-pounds, having a pK of les~ than i about four, and ,l (3) mixtures oE

!~ (a) one or more organic acids having 25 ' a pK of less than ahout 2 and ~j (b) one or more acid ~y~s or acid indicators (4) mixtures of (a) one or more organic acid co!n~ounds ~, having a pK of less than about 4 and , 3 33810 ~ .

(b) one or more members of the group ¦~ I body of colnpounds, , (5) mixtures of jl (a) one or more basic dyes or basic .
5 ,~ indicators and (b) one or more members of the grou~
I body of co~pounds,

(6) mixtures of .
(a) one or more dyes having a molec- -~ ular structure containing a i lactone grouPr and ll (b) one or more acids having a pK of I, a b o u t 8 t o a b o u t 1 2 .
¦IThe compounds mentioned in group ~ are classified according to jl the Colour Index, 3rd Edition (1971), puhlis~ed by the Society o, Dyers and Colourists, Great Britain and Conn's Biological Stains ¦

! (9th ed 1977).
~j Suitahle monoazo dyes are: 4-(p-Etho~y~henylazo)-m-,, phenylene-diamine monohydrochloride, Orasol Navy Blue~, Organol . Orange, Jar.us Green~, Irgalith red P4R, Dimet~yl yellow, Fast , Yellow, ~thyl red sodium salt, ~lizarin ~ello~ R'~, ~riochrome j' Blac~ T, Chrol.lotro~e 2~, Ponceau 5R, Yellow Orange S'~, Brilliant Ponceau 5~, Chrysolidin G", Eriochro~e blac'c A, Ben~yl orange, Il Brilliant Ponceau G/R/2R~ and chrol~olan yellow.
I Suita~le disazo dyes are: Fat red as~, Sudan Red B~, 1 Bismarck 3rown G~, Fat Black', Resorcin ~rown'~, ~enzofas~ Pin~ 2 ¦l ~L'~ and Oil Red EG~
Suitable triarylmethane dyes are: ~letnyl violet,, Xylene cyanol FF~, Eri.oglaucine , Fuc~xin NBr~, Fuchsin, ~, .
, 35 .; 1, 11;~3810 Parafuchsin, Aurintricarboxylic acid ammonium salt, Patent Blue, Victoria blue R'~, Crystal violet and Irgalith Blue TNC~.
Suitable xanthene dyes are: Phloxin B, Fluorescein sodium salt, Rhodamine B'~, Rhodamine B ~ase, Rhodamine ~G~, Pyronin G, Irgalith Magenta TCB~, Irgalith pink TYNC'~, Eosin Scarlet~, Eosin Yellowish, Erythrosin extra bluish~, 4'5'-Dibrom-ofluorescein, Ethyl eosin, Gallein, Phloxinel~, Erythrosin yellowish 31end'U and Cyanosin ~
The suitable sulphonephthaleins are: cresol red, chlorophenol red, chlorophenol blue, bromo~henol blue, bromo-cresol purple and chlorocresol green.
The suitable acridine dyes are: Corisphos~hine O'~, Acriflavine and acridine orange.
The suitable quinoline dyes are: pinacyanol chloride, pinacyanol bromide, pinacyanol iodide, ~uinaldine red, crypto-cyanine, l,l'-Diethyl-2,2'-cyanine iodide, 2-(p-Di~ethylamino-styryl)-l-ethyl-~yridinium iodide, 3,3'-Diethylthia~icarbocyanine iodide, ethyl red, Dicyanine A, Merocyanine 540~ and Neocyanine'~.
The suitable azine dyes are: ~leutral red chloride, Neutral red iodide, Nigrosine~, Savinyl blue ~'~, Orasol blue BLn'~, Safranin O'~, Azocarmin G'~, Phenosafranine~, Azocarmine ~X'~
and Rhoduline violet.
The suitable oxazine dyes are: Solo~henyl 3rilliant Blue 3L'r, Nile blue A~, Gallocyanine~, Gallamine blue~ and Celestine blue.
The suitable dyes are: Methylene blue, Thionin, Toluidine ~lue ~, Metnylene Green an(l Azure A/B/C'r.
The suitable anthraquinone dyes are: Savinyl Green B'~, Savinyl Blue RS, D+C Green 6'~, Blue VIF Organol'~, Alizarin, Alizarin Cyanin 2RI~, Celllton Blue Extral~, Alizarin Blue S'~, -3~-~ 338~0 Nitro Fast .,reen GSB, Alizarin red S, Chinalizarin, Oil blue N, Solvay purple~ and Purpurin'~.
The suitable indigoid dyes are: Ciba Blue~, Indigo Synt'netic~, Chromophtal Bordeaux RS~ and Thioindigo red.
Instead of one or more group I compounds, to be used in the novel composition of matter, mixtures can be employed.
The group of organic acidic compounds with a pK less than about four generally consists of organic acids and/or the B su/~ on~th ql~ ;nS
halogenated sulphon-ephthalein~, which are soluble in the selected solvent, when the latter is in the liquid state. Examples of these acids include oxalic acid, maleic acid, dichloroac~tic na~ hth 4 J~r~e acid,-tricnloroacetic acid, 2-naph~halinc-sulphonic acid, chloro-anilic acid, bromophenol blue, bromothymol blue, chlorophenol red, brolnochlorophenol blue, bromocresol green, 3,4,5,6-tetra-bro~op~en~ Oh p~ le;n brol"ophenolsul~lonephtll~leil" bromophenol red, chlorocresol green, chloroph2nol blue, brol~locresol ~urPle and 2,4-dinitro-benzenesulphonic acid.
The grou~ of basic dyes or basic indicators are gener-ally the aminotriphenyl methanes, also known as the triaryl ~eth-anes, or their soluble salts, 8-hydroxyc~uinoline and the quin-oline dyes, preferably the cyanines. Examples are: basic fuchsin, pinacyanol iodide, pinacyanol chloride, pinacyanol bromide, 2-p-(dimethylaminostyryl)-1-ethyl-pyridinium iodide, crystal violet, cryptocyanir,e, dicyanine A, 3,3'-diethylthiacar-bocyanine iodide, 1,1'-diethyl-2,2'-cyanine iodide, ethyl red, quinaldine red, ethyl violet, brilliant green, pararosaniline, pararosaniline acetate, 8-hydroxy-quinoline, l-ethyl~yridinium iodide and 5-(p-dimethylaminobenzilidine) rhodanine.
Preferably the weight of the acid compounds is about three or more times the weight o~ the hasic co~?ounds.
--3 ~_ ~ 0 The above-mentioned pK values refer to the ~X values as measured in water. Generally it is preferred that the pK of the acidic cor~ound is lower than the corresponding pK value of the basic compound. Prefera~ly the acid compounds have a p~ value less than about four and the basic cornpounds have a pK value less than about 5.
It should be noted that when the basic compound consists solely of one or more aminotriphenylmethanes or their soluble salts, the acid compound must'be selected from the group consisting of tetrahalogenated sulphonphthaleins and the other organic acids having a pK of less than about 2.
Preferred combinations of acidic compounds having a pK
less than about 4 and basic dyes or basic indicators are brorno-h S trf 3 phenol blue/basic ~fucnsn, chlorophenol blue/ethyl red and tri-lS chloroacetic acid/3,3'-diethylthiadicarbocyanine iodide.
Mixtures of one or more organic acids having a ~K less than about 2 and one or more acid dyes or acid indicators, used in the nc~el composition of ~atter, change color when the solvent ~asses from the solid into the liquid pnase or reversed. In this combination the acid dyes used are prefera'vly halogenated S Ll I ~ o nf~ h ~ nS
sul~h~ncDhthalcin_.
Mixtures of one or more organic dyes, having a molec-ular structure containing a lactone grou~ and one or more acids having a PK of about 8 to about 12, used in a solvent also change color when the solvent passes from the solid phase into the liquid phase or reversed. In that combination the preferred compounds are crystal violet lactone and one or more of acids such as phenol, bisphenol A, pyrocathechol or 3 nitrophenol.
The novel compositions of matter most ~referably com-prise o (a) a suitahle inert solvent as described above ada~tea _ 3L~ _ 3381~ ~ ' .~. .

~to change from a solid state to a liquid state at substantially i ithe predetermined temperature and [b) one or more organ~c .
I moieties soluhle in said solvent and adapted to change color upon j,the change in state of the solvent at suhstantially the pre-l~detérmined temperature when so dissolved, and selected from:
jj (1) one or more Group III colnpounds consisting o~: , !I pinacyanol iodide, quinaldine red, 1,1'-diethyl-2,2l- i B I cyanine iodide, pinacyanol chloride, thionin, methyl-ene blue, cresol red, chlorophenol red, neutral red~
iodi~e, neutral red chloride, crystal viole~, acridin ¦ orange, toluidin blue O, Orasol Orange RLN~, Orasol Navy Blue~, Irgalith Red PR'~, Fat Red BS'~, methyl il vio.le~, X~lene C~.~n~~ F.~ h~d~ e B~, Rho~.mi.ne ~, 6G~, Irgalith MagenLa TCB'~, Irgalith Pin~ TY~Cl~, ¦, Toluidin Blue Ol~, Savinyl Green B~, Savinyl Blue RS'~, ! purpurin, 3,3'-diethylthiadicarbocyanine iodide, ¦I cryptocyanine, Dicyanine A, merocyanine 540, ¦~ 4-(p-ethoxyphenylazo)- m-pher.ylene diamine ¦l monohydroch.loride, Yello~ Orange S'~, Chrysoidan G~, 20 ~I fuchsin, Aurintricarboxylic acid (ammonium salt), 1 Victoria Blue R~, Pyronin G'~, ~allein phl~xine, Ij ¦~ Erythrosin Yellow Blend~, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphos2hine ~, O~ acriflavine, acri~ine oran~e, rhoduline violet, 25 11 Alizarin cyanin 2~'~, Alizarin ~ed S'~, alcannin, Aurantia, Direct Green G'~, Fas~ Red Salt 3GL~, Fast Blue Salt ~B~, Fast Garnet Salt GBC , Carta Yellot~7 G
180 o/o'~, murexide, Savinyl Blu~ GLS'n, ~rqalith Blue ,I GLSrl'~, phthal~cyanine, Di Arningr~en B~, Alizarin ~lue 30 , S~, Celliton Blue ~tra,~neocyanine, Janus Gree~n~, - ~' dimethyl. yellow., Fast Yello.~ e~h~l red sodium s~t, - 3q-;-~ ~,338,0 Alizarin yellow R M, Eriochrome black TTM, Chromotrope 2RT , Pon oe au 6RT , Brilliant Pon oe au G/R~2RTM, Chrom~lan yellcw, Su~an Red B , Bismarck bro~n G M, Fat BlackTM, Resorcin Brcwn Banzofast pink 2BLT , Oil Red EGNTM, Euroglaucine, Fuchsin NB
parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin B M, fluores oe in sodium salt, Rhodamine B baseTM, Eosinscarlet~ Eosin YellcwishTM, Erythrosin extra bluish, 4~s-dibromD fluores oe in, ethyleosin, PhloxineTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-1-ethyl pyridinium iodide, ethyl red, neutral red, iodide, nigrosine, & vinyl Blue BTM, Orasol Blue BLN M, & franin oTM, Azocarnun GTM, Phenosafranine, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM, Nile Blue ATM, gallocyanine, gallamine blue, oe lestine blue, methylene green, Azure A/B/C M, Blue VIF Organol M, Alizarin, Nitrofast Green GSB
quinalizarine, Oil Blue N , Solvay Purple , Ciba Blue , Indigo synthetic M, ChromDphtal Bordeaux RSTM, Thiorifolex M, Acid Aliz æ in Red BTM, 5-aminofloures oe in, Ro~e BengalTM, Mbrtius Yellow , Chicago Blue 6B , Alcian Blue 86X , cresyl violet, 4,4'Bis(dimethylamLno) benzylhydrol, Zinc Pthalocyanine, Sudan IIITM, Pyro m n yT , Toluylene Blue M, cresyl violet perchlorate, Mendola's BlueTM, 3,3'-diethylthiadicarb~cyanine iodidb, Phosphine Dye , Nitron , cresyl violet a oe tate, oe res orange RTM, 4-phanyl-azo-l-naphthyl-amine, 4-(4-Dimethylamino-l-naphthylazo)-3-methoxy-benzene sulfonic acid, Bindschedler's GreenTM, and p-(p-dimethyl-aminophenylazo)benzoic acid (hereinafterwards referred to ~`

1~ 810 coh poun d s o r ~roclp ~
B as th~ Group III cor~pound3 or or GLVU~ III organic moieties), or (2) a binary mixture of:
(A) one or more of a Grou? I ~ody of com-pounds (hereinafterwards referred to as the Group I compounds) consisting of (a) the organic acids, which when inserted in the solvent system at conditions other than supersaturation will yield a color chanye visible to the naked eye, and also have a pK
of less than about four and (b) the halogenated sulfonphthaleins; and (~) one or more of a Group II body of compounds (hereinafter~ards referred to ~s the Group II compounds) consisting of the amino-tripnenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines, wit.; the proviso that if no ~roup III compound is present and if the Grou2 II compoun~s consist solely of one or more aminotri~henylmethanes or their soluble salts, then the Group I com~ound must be selected from one or more of the group consisting of oxalic acid, suitable sulfonic acids and the tetrahalogenated sulfonphthaleins, and other organic acids having a pKl of about or less than 2.
Of course, the ?rimary application of the instant invention is where the change in stato of the novel cornposition of matter is induced by temperature forces for use in a 'emperature-indicating device. ~y "suitable sulfonic acids" we rnean sulfonic acids soluDle in the selected solvent; these .nay be, ~or exanple, ~33810 benzene sulfonic acid, napnthalene sulfonic acid, toluene sulfonic acid, anthracene sulfonic acid, etc., depending on the solvent.
One of the requisites of our invention is that each novel composition have the property of su~ercooling. We require that if and only if a given composition reaches one hundred percent liquid after melting, will that liquid remain liquid for more than several seconds when withdrawn from the source whose temperature is to be measured; less than one hundred percent melting ~ill cause the composition to return instantaneously to its solid state when the composition is withdrawn from the above-mentioned source. It is only by these means that a commercially useful composition for disposable thermometry can measurably advarlce the state of the art. We have found, sur~risingly, that the best method of obtaining the "undercooling property" in each of our novel compositions of matter is to render them substantially free of impurities to the extent stated below, aithough doubtlessly the undercooling effect can be made through different alternative mecnanisms--for example, several organic solvents exist for the Group I-III compounds (high molecular weight aliphatic alcohols) which become suddenly very iscous ~ee~ in their liquid state close to solidification, so that they possess the undercooling pro~erty despite the presence of some impurities, i.e., these compounds form glasses. ~ence, this limited number of solvents ~r~ equivalent to the ~eneral solvents used in our invention which are substantially free from impurities.
The novel composition should therefore be substantially free from impurities, i.e., they should have few impurities that are soluble in the novel compositions of matter (generally which 4~

may not exceed about 0.3 percent), and have few solid foreign sub-stan oe s that react with the novel cQmpositiQn or that might induce instantaneous resolidification after melting (i.e. immediate revers-ibility). Impurities are defined as any substance other than the Group I-III moieties and the suitable solvents and may be soluble or insoluble, but exclude suitable nucleating agents used in an effective am~unt. Generally, if these soluble substances are less than about 0.3 weight peroe nt of the entire composition, the de-sired undercooling effect will not be altered. Too great an am~unt of soluble impurity results in a broad melting point for a given CQmposition or separation of the Group I-Group III moiety(s) from the suitable solvent. Cn the o~her hand, a very small amcunt of a soluble impurity inert to the composition (generally less than about 0.3 peroe nt) may act in the same desirous manner as the re-d ted insoluble suitable nucleating agents. If the weight per-oe ntum of these soluble substan oe s is less than about 0.1 weight per oe nt, the desired undercooling effect will alm~st always be ob, served. It ~st be noted that any insoluble ~oreign substan oe chemically inert to the oombinatian of the Group I-Gro~p III moie-ties and tne suitable solvent may be utilized as a suitable nucleat-ing agent so long as the foreign substan oe does not indu oe instant-aneous resolidification at temperatures just bel3w the melting point. Examples of suitable insoluble nucleating agents are given below (most preferably talc) and are e~ployed in an effective amount to promDte resolidification of the novel oompositiQn at a predetermLned gradient below the melting point so long as absorE-tiQn of the Group I - Group III m~ieties by the nucleat ng agent is within an acceptable range. Tbo great an a~LUnt of nucleating agent results in unac oe ptable absorpticn of the Group I-III moie-ties by the nucleating ~33~0 agent, and removal of the otherwise occurring change in color visible to the naked eye. ~enerally, the upper limit of suitable insoluble nucleating agent varies from 0.1 to 10 weight percent of the composition, depending upon the suitable nucleating agent, suitable solvent, and Grou~ I-III moiety(s) selected. For example, in an OCNB-OBNB system with ~.05 weight percent pinacyanol iodide, an effective amount of talc (as a suitable nucleating agent) is preferably from about 0.01 to about 1.5 weight percent of tAe entire com?osition (and even up to in some circu~stances ten percent and higher), depending on the gradient between melting point and recrystallization temperature selected.
'~e have found 0.1 percent to be most preferable and that high concentrations may affect the color change for a particular system. If toG great an amount of talc is used (over about two ~ercent), in a pinacyanol iodide/OCN~-OB~B system, the composition is always blue whether in a liquid or solid state.
Hence, as will be recognized by one skilled in the art, a suit-able nuc;eating agent may consist of (1) any insoluble foreign sùbstance inert to the Grou~ I-III moieties and the suitable solvents, so long as the forei~n substance does not induce instantaneous solidification, or (2) a substance soluble in and inert to the com~osition, but limited to less than about 0.3 weight perc*nt of the composition.
phe~enan An interesting ~hcnomcna exhibited by the novel compo-sitions is illustrated by the exam?le o~ a composition essent-ially consistin~ o~ pinacyanol iodide (ac 0 035 weight percent) in ortho-bro:nonitrobenzene:ortho-chloronitrobenzene (75:25) solvent. In the liquid ?hase this com?osition is blue, and in the solid ?hase appears rose~tan. However, if the composition is chilled to a very low tem~erature at a very high rate of cooling _ y~

'`' ii~3810 initially, the color of the solid appears purple. As the oomposi-tion is all~wed to warm to roam temperature, the color changes fram purple to rose/-an, requiring about 3-5 minutes for the color to be-come rose/tan. (Similar phenomena have been observea with other novel co~positions containing other Group III mDieties or other Group I plus Group II combinations.
nlring solidification of the oomposition the chlorophenol red is ooncentrated in the remaining liquid part of the solvent.
When the solidification has been completed the solid has a ni oe red oolor. Microsoopic investigation of the solid composition shows that the chlorophenol red particles have been substantially separ-ated from the soluent crystals. In our opinion the intra-molecul æ
re æ rangement of a sultone group, when the chlorophenol red is dis-solued in the liquid soluent, into a quino~e structure, when the chlorophenol red is sPparated, is responsible for this oolor change.
When the indicator system comprises more than one compon-ent, the color change often will be caused by chemical reactions be-tween the indicator compounds.
W~y pinacyanol iodide changes its color upon being separ-ated fL~- the soluent col pounds is not fully understood at this time.
~he color change may be caused by an intermolecular inter-action between the pinacyanol ion and the counter ion. It is most likely that the pinacyanol icdide crystals, being formed upon separation of the soluent, oonsist of a stack structure with oolumns of positive aye ions ana negative ccunter ions. Such a structure might give raise to a drastic change in rescn3n oe as cam-pared with the unpPrturbed state of dissolved pinacyanol iodide.
X

li33810 Another example of an especially preferred group I
compound is chloroPhenol red at a concentration of about 0.05 percent by mass. ~hen dissolved in a solvent such as OCNB/OB~B, di~enzofurane, para-toluic acid and other halogen nitrobenzenes, the liquid composition has a yellow color.
As enumerated above, in the absence of one or more Group III compounds to be used for the organic moieties in the solvent system, one or more of a Group I body of compounds must be employed together with one or more of a Group II body of compounds. The Group I body of compounds generally consist of (a) the organic acids, which when lnserted in the solvent system (at conditions other than supersaturation) will yield a color change visible to the naked eye, and have a pK of less than about four, and (b) the halogenated sulfonphthaleins which are soluble in ne selected ~,~eakly polar or nonpolar aromatic solvent described above. Preferably, the ~roup I compound has a pX of between zero and three, and most preferably between about zero and abou_ two. Examples of this Group I body of compounds include oxalic acid, naphthalenesulfonic acid, trichloroacetic acid, broMophenol blue, brornothymol blue, cnlorophenol red, bromochlorophenol blue, bromocresol green, 3,4,5,6~tetrabrom~-phenol sulfonphthalein, bromophenol red, and chlorocresol green.
Some compo-lnds, such as maleic acid, will wor~ if soluble in the predetermined solvent system employed if the correct Group II
compound is chosen.
These first groups of com~ounds, which are generally the halogenated sulfonphthaleins, are derivatives of the sulfon-phthaleins, to wit, phenol blue, cresol red and phenol red. It may be observed that the halogenated sulfonphthaleins are different from the basic or unsubstituteci sulfon?ht.haleins in the ~.~3810 follo~ing ways: first, the unsubstituted compounds are diprotic acid/base indicators, each having pK values of (1) a pKl of about 2 and (2) a PK2 f about 7 to about 9. The halogenated derivatives show only one pK which is much lower than the PK2 f the unsubsti-tuted sulfonphthalein.
Examples of Group II compounds include ethyl red, crystal violet, pararosaniline ~or "para Rosaniline Base"), pararosaniline -acetate (or "para Rosaniline acetate"), basic fuchsin, 8-hydroxy-quinoline, ethyl violet, brilliant green, pinacyanol chloride, and 3,3-diethylthiodicarbocyanine iodide. The Group I compounds are preferably selected from the group consisting of bromophenol blue, bromochlorophenol blue, and bromothymol blue. One will .
1~33810 notice that the secon~ group of compourlds generally consist of dyes which have basic nitrogen grou~s either as substituent amines or in heterocyclic rings. In general, the addition of one or ~ore of the first group of compounds along with the second group of compounds to a solution of the ~reviously described nonpolar or weakly Dolar aromatic solvent(s) such as ortho-chloronitrobenzene and ortho-bromonitroDenzene solutions will provide a color difference between the solia and licuid ~hases of the aromatic solvent. It is preferred that the total weight of the Group I and Grou~ II compounds be about 0.025 to about 0.05 total weight percent of the entire weight of the no~el compositions of matter. It is advised that the melting point of the Group III or Group I and Group II moieties ~e more than the melting point of the solvent system. It is preferred that the melting point of each of the Group I and Group II constituents be substantially more than the melting point of the solvent syste~n selected, and it is much preferred that these Group I and Gr~up II compounds melt at more than sixty degrees above the mielting point of the solvent system. A basic requirement is that at least one of tne ~roup I and Grouv II compounds reflects or absorbs light in the visible area of the spectrum on or belo~ the melting point of the solvent system or, in the alterna~ive, on or above the melting point of the solvent system, or both, in different colors so that a change in color is visible to the naked eye. It is also Preferred that the Group I compounds weish three or more times the weight of the Grou,~ II compounds. While 0.05 weight ~ercent of the total of the Group I and Group II

compounds or ~roup III compound(s) is most preferred, any effective amount from the smallest for ~hich the cnange in color 3~ is visible to the naked eye u?on change in phases is satlstactory, and certainly no more than the solublity limits of the ~roup I and Group II compounds (or Group III compound(s)) in the solvent system at the melting ~oint of the solvent system.
Too great an amount of Group I-III organic moieties renders the compositions o~tained darker than necessary so that the color change is harder to detect; li~ewise, the melting point might also ~e affected. A supersaturated solution of GrouD I and Group II compounds (or Group III com~ound(s)) in the solvent system, is not ~referred, since Grouo I-III compounds are substantially mor-~ expensive tnan the solvent system constituents and~excess of them will be extravagant. ~ny pressure may be employed i~ nal~in~ or in using the novel composition(s) of matter in a tem~erature-indicating ~evice so long as the solvent does not generate a sllbstantial vapor in the application for the compositio.. If a Group III compound is not employed, it is preferred that the Grou~ I co~r)ound have a lesser pKl and PK
value than the corresponding pK values of t'ne Group II compound.
Preferab , the ~,roup II compound should have a pKl value of less than about 5, and the Group I compound should have a pKl of less than about 4.
As it will be appreciated by those skilled in the art, it is possible with the disclosure given a~ove to comhine almost any ~roup I compound of indicated ~K, whicn is soluble in the solvent system selected, (a solvent system of ortho-bromonitro-benzene: ortho-chloronitrobenzene, for example) and a colnplementary acid base inaterial from Jroup II and generate practically any desired change in color. rrhe considerations for those skilled in the art will be (1) the selection of Group III

and/or Group I and Group II compound(s) which yield a satisfactory change in predetermine(3 colors; (2) tnat these `-` ~33810 oompounds are soluble in the solvent syst~n in the liquid state;
(3) that the solvent system be properly determined for the tempera-ture range desired; (4) that the Group I and/or Group II cc~pounds (or Group III ccmpounds) be soluble in the desired syst~n, and (5) if pertinent, that one oompound of the Group I ccmpounds react as a strong acid against one or more of the Gr~up II ocmpounds in the solvent system.
As it will be reccgnized by those skilled in the art, one may employ oombinations of m~re than one Group III m~iety, or a com~
bination of a Group III mDiety and a Group I moiety, or a oombina-tion of a Group II m~iety and Group III moiety, or m~re than one Group I mDiety with m~re than one Group II mDiety to obtain oolor shifts generally not found in a single syst~n, e.g., a mixture of pinacyanol iodide and quinaldine red (two Group III oompounds) yields a tan solid and deep dark purple liquid. There are s e in-stan oe s where two Group I compounds may be operable where one acts as an acid relative to the other e.g., (1) naphthalenesulfonic acid an,d one or more of (2) bromochlorophenol blue, chlorophenol blue, or bromocresol purple.
We have disoovered that, as an alternative of using one or m~re of the Group II compounds with one or m~re of the Group I
compounds, one may select one of the aforesaid Grcup III oompounds with (or preferably) in place of a oo~bination of one or more Group I compounds and one or mDre Group II oorpownds. A caveat and pro-viso must be stated: in absen oe of a Group III oompound one m~lst employ one or more Group I oo~pound~ with one or more Group II ocm~
pounds; if the Group II compounds CQnsist solely of one or more aminotriphenylnethanes or their soluble salts, then the Group I com-pound must be frvm one or more of the group oonsisting of oxalic acid, suitable sulfonic acids, tetrahalogenated sulfonphthalelns, a~d other soluble strong organic acids having a pKl of about or less than 2.

- il33810 Further, in a OCNB/OBNB system not employing oxalic acid which utilizes a Group I and Group II compound for exam~le, bromochlorophenol blue and quinaldine red, a unique color change was obtained as follows: in the liquid phase, the bromochloro-S ~henol blue (Group I) takes a proton from the quinaldine red, sothat the quinaldine red takes on its characteristic basic red color (which is characteristic of the latter compound dye between a pH of 2 and 13); on the other hand, in the solid ~hase, the bromochlorophenol blue protonates the quinaldine red and is yellow, at the same time quinaldine red is în its acid form and is colorless. ~ence, the solid phase is colored by the 5roup I
dye in its yellow form. Thus, the color of the liquid solution was red. Also, in a novel ~C~/OBN~ composition employing a Group I and Group II compound, and with bromophenol blue as the lS Group I com~ound, and ethyl red as the Grou~ II cor.lpound in its acid form having no color whatsoever in the solid phase of the solvent. Thus, the solid took on the ycllow coloration of the bromphenol blue. On the other hand, in the li~uid form, the bromophenol blue is diluted in the solvent and the ethyl red becomes the red color characteristic of the dye at a higher p~.
Another example of a Group I compound and a Group II
compound is bromo~henol blue and ~asic fuchsin. In the solid form, the basic fuchsin behaved as if it were at a very low pH
and was in a form which has a green color ~etween its pKl and pl~2. This green color of basic fuchsin at very low pH is a little known fact, but can easily be demonstrated in an~
laboratory with common reagents. In the liquid form, however, the bro-nophenol blue is yellow. The basic fuchsin was not in its first acid forJn and became red. Thus, the color of the liquid was red~ -~ith this disclosure, one skilled in the art will more appreciate the results to be enumerated below in Exa;nples 1-5 anc~
in lable II.

~33810 As will be appreciated by those in the art, generally the color of the liquid is the saMe or similar to the color of the Group II colnpound or Group III compound when dissolved in the liquid phase of most of the suitable solvents employed.
Similarly, crystal violet, which is a pH indicator having a pKl of approximately 1, forms, in combination with oxalic acid and dissolved in the OC~L~B/OBN~ solution, a blue liquid and a yellow solid.
We have also found as well that (1) quinaldine red (a Group III compound) which has a pKl of approximately l.b; (2) ethyl violet, which has a pKl of about 1.2; and (3) brilliant green,~which has a pKl of about 1.4, all react in solutions witn B naphthalenesulfonic acid to form different colored solid,then liquid~hases.
As as alternative to the above for Group I - Group II
combinations, when the Group I material is other than a simple acid, and is a "dye" compound (such as bromophenol blue), in addition to the Group I's behavior as an acid, there may be formed in the com~osition aggregates, mixed Polymers, and the like, which cause what is referred to in the literature as "metachromisrn" or "rnetachromacy". "Metachromacy" is that pro~erty of a substance which is expressed as a change in color (according to the wavelength of the light in which it is viewed) due to an outside force. "~letachromacy" is rnainly attributed to tilat color change phenomena when a dye is brought together with certain "tissue" molecules (lilacrornolecules, e.g., solid ~aterials such as heparin, polysaccharides). Certain organic dyestuffs, however, are characterized by different colors when dissolved in inert solvents, which is describea as "solvatocnromism". See HAC~H'S C~EMICAL DICTIONARY 421 (4th ed~ 1969). The literature is full of articles attempting to give some explanation of metachromacy (and "solvatochromism" ) apparently caused by increasing dye concentration in the liquid phase, adding salts, or lowering the dielectric constan~ of the solvent from medium to low values. Thus the literature spea~s of salt-induced metachromism (increase in the concentration of salt), dye-induced metachromism (increase in concentration of dye ) and dielectric-induced metachromism (decrease in the dielectric constant of the medium). The concept of metachromacy in the art was studied as a theory (definition), generally with little practical application other than the coloring of tissue. See the classic article by ~.
B. McKay and P. J. Hillson, "Metachromatic Behavior of Dyes in Solution", .1 TRANS. FAP~ADAY SOC. 1800-1810 (1965); also Such as C. Guhaniyogi and Groja M. Mandal, "Studies on Intramolecular Association of Salt Groups in Polyrners Following their Bind ing with a t~etachromatic Dye", 175 DIE ~!~KROMOLEKt~LARE CHEMIE 823-831 (1974); Eryl D. Owen, et al, "Metachromic Interactions Between Azo and Tri~henylmethane Dyes in .~queous Solution", 25 J. APP.
CL1~ BIOTECHNOL 211- ~19 ( 1975 ); M. K. Pal and ;1an ju Chaduri, "Condutometric Titrations of Anionic Polyelectrolytes with ~letachromatic Dyes and Ef fects of Organic Solvents", 133 DI
M~K~OMOLEKULA~iE CEI~IIE 151-lbU (1970); Ger. Pat. 2,327,723 (1973) to Pilot Ink Co.; A. Van Dormael, "Solvatochromism, Tautochromi srn, and MetachroMism", 31 INDUSTRIE~ C~IMIQUE BELGE 1-9 (~lo. 1, 1966); ~. Scheibe, "Uber Metachromasie" 35 ~ALETTE 2~-34 ( 1970 ); k. B. McKay and ~. J. Hillson, "t~letachro!natic Behavior of Dyes in Solvents of ~igh Dielectric Constant: the Anomoly of Water", 53 TRANS . EARADA'~ SOC . 777~781 (1967 ); a fascinatin~

"''-` ~33810 study by Medini Kanta Pal and ~axwell Schubert, '!Simple and Compound ~letachromasia", 67 J. PHYS. CHE~. 1821 et seq (1963), ;~1. K. Pal and Sudhir Rumar Ash, "Metachromasia of Basic Dyes Induced ~y Mercuric Chloride II", 7~ J. PHYS. CHEM. 536-540 (No. 5, 1974); Yamaokak et al, 'IDiffuse Reflectance Spectra of ~;letachromatic Dyes --Existence of a Long r~avelength ~and in Solid States", 78 J. PE~YS. CHEM. 1040 (No. 10, 1974); CO~N'S BIOLOGICAL
STAINS 2-58 (9th ed. 1977); von F. Feichtmayr, et al, "Einflu~
der Dielectric Eigenschaften von Losun~Jsmitteln and Substraten auf die Lichtabsorption and die Photoc~lemische Verhatten von Kationischen Farbstoffen" (Losurgsmittel) OPTISCHE ANZC;;`J~G
ORGANISCHE SYSTE~IE VERLAG CHEiVlI2 1966 (~est Germany) 357-374-(1964(?)); L. I~icharelis and S. Granick, "Metachromasy of Basic Dyestuffs", 67 JACS 1212 (1945); and ~. J. H~ llson and R. B. McKay "~letachro~asy" 210 ~IATIlRE 296-297 (1966); Paddy, J .F ., rlETAcHRo~lA~y OF DYES IN ~OL[lTI~r~, CHFi~ OL. BIOL.
INTE~CELL. I~ATRIX ADVA~I. STUDY IINST. 1969: 1007-31 (England). See also Ja2anese s~pecifications 47-34735 and 50-105555.
Indeed, it wou]d ap?ear from the combined definition of Hac3ch and Hillson/~lcKay that the phenomena of our invention ~ay not fall within the definition of "metachromacy" (or even solvatochro nacy) let alone relying on metachromacy as a complete "mechanism" for understanding the phenomena of our invention.
Perhaps the closest article with a description of similar ?henomena (components dissolved in a solvent changing color u~on change in phases is P. R. E~ammond and L. A. Burkardt, "Electron ~cceptor - Electron Donor Interactions. XV. Examination of Sone ~7eak Charge - Transfer Interactions and tlle Phenomenon of Thermachromism in these Systems", 74 J. E;~IYS. CHE~I. 639 (~o. 3, 197~)). A nurnber of pairs of non-dye donors and acce~>tors are ~33810 listed at page ~42 in solvents such as dichloror,~ethane, cyclo-hexane, and n-nexane. "Thermochromasy" is the change in color of a com~osition due to a change in temperature. See also Ja?anese 75 - / 5 ~ 555, 7~ - ~a~,o ~o ~ patent applications 75-105,554; 75,105,555i 7.,107,040 by Norikaya ~akasuji, et al (1975). Even Hammond/Burkardt, however, fail to give any explanation as far as single compounds (such as those in Group III) which exhibit the novel phenomena of our invention~ ~

~33~

-Concerning the relationshiP bet~een structure and use in the Group I-Group II com~inations, the types of grouping that give rise to pll-dependent color changes in Vie~l of tne disclosure herein will ~e well known to those in the art since compounds of this type are used as indicators. Indeed, all the examples cited here are typical indicator dyes, combined with an acid. In order to obtain a color change on melting, it is necessary to choose an - acid-dye combination in which proton transfer occurs on passage from solid to solution. Probably almost any pH indicator could be used in this connection in combination with a suitable acid.
10As described above, the Group III compound.s operate by showing a color change in their o~n right, between the crystal and solution in the thermo~eter solvent. ~rhe exalr?les cited ,, ~,, ~33sao herein are generally, witn small exception, the "cyanin-tyve"
dyes, conjuqated with odd-conjuaated nydrocarDon anions. Dyes of this type, in ~articular the cationic ones, are kno~n to those in the art to show color changes ~ith concentration and solvent changes and also when combined with biological materials ("~etacnromatism", above). It now seems fairly clear that these changes are mostly due to association of the dye into polymers, the flat dye ions being stacked together like a ~ack o cards.
The interactions between the ground and excited states of individual dye ions leads to a s?litting o~ the lowest transition. Ot the resulting spectrurn of transitions, all exce~t that of nighest energy are forbidden, so the effect is a hypsochromic shift. Similar effects are well known to those in related arts in organic crystals (Davidson effect). For the polymerizat;on of the dye ions to be ~ossible, the interactions between them must be strong enough to overcome their ,nutual coulombic repulsions. This can be so only if the ions are large (so that ~_he coulombic repulsion is minimal) and if they can approach closely so that the molecular orbitals (MOS) of different ions can overlap. For this to happen, we believe that it is essential that the ions be ~lanar and free from bulky obstructing grou~s. These conditions are ~let well by the organic dyes themselves, which show dramatic color changes with concentration in suitable solvents, and also by a variety of other cationic dyes. Other equivalent anionic dyes should be equally able to sho~ similar effec~s though fe~"er exam~les are known to us.

il338~0 An example of an especially preferred Group III oompound is pinacyanol iodide at a ooncentration of 0.025-0.05 percent by weight. When dissolved in an O~NB/OENB solvent, the liquid oomposi-tion is an eye-appealing brilliant blue. During solidification at room temperature of the O~NB/OCNB solvent, the pinacyanol iodide be-oomes increasingly concentrated in the oorrespondingly decreasing proportion of liquid. m e pinacyanol iodide increases in concentra-tion to the point that when solidification of the co~position is co~plete, the pinacyanol iodide, because of (1) decreasing attrac-tion to the solid OENB/OCNB solvent, and (2) its apparent metra-dhrcmatir-type behavior, is isolated in small particles around the crystalline structure of the OENB/OCNB solvent and from the view of an observer turns the oolor of the entire oomposition to an attrac-tive r~se. When the solidifying ocmpositian is seen by any form of microsoopy, the beads of pinacyanol iodide particles appear quickly on the surface of the crystalline solvent in an aggregate. ~hen Group I and Group II materials are employed (without the presen oe of a Grw p III material), a similar pheno~ena is seen when viewed by microsoopy at about tw~ hundred to six hundred power.
The method preferably employed in designLng a series of oc~positions of matter for use in a temperature-indicating devi oe or thermometer is as follows: first, two or more weakly pol~r or mDderately polar aromatic solvent constituents (that are inert to-ward the chosen Group I-III organic moieties) which have melting points that most closely oontain the predetermined temperature range desired to be tested are selected, e.g., one of the melting points of the tw~ oonstituents must be equal or lower (preferably slightly lower) than the lowest temperature of the range, and the other oonstituent must be equal or higher (preferably slightly higher) than the highest temperature of the range. Preferably, tw~

analogous chemical structures (e.g., analogs, homologs and r - li33810 optical isomers) having substantially the same molecular volume or having tne same crystalline structure (e.g., isomorphous) are selected if they border the temperature range to be tested. The temPerature range is divided up into increments, usually no smaller than 2/10F or l/10C over the temperature range to be tested. Then, a liquidous curve of the melting point as a function of temperature is constructed for the solid solution of the solvent constituents, herein for example, ortho-chloronitro-benzene and ortho-bromonitrobenzene as in FI~UR~ l, over the temperature range to oe tested. In FIGURE l it will be noted that the band, exaggerated about 40 or 50 times, is defined by the dash lines and 1 on either side of the liquidous curve in the diagram and represents in an exaggerated manner the limit of accuracy of temperature measurements, i.e., aDproximately 1/10C
lS or 2/10F. It is desired that the percentage of organic moieties (Group I and Group II compounds, or one or more GrouP III com-pounas) be of a very small weight fraction of the total novel composition of matter in that when the organic moiety(s) is added to the solvent system as tne melting ~oint of the curve is affected by a shift toward a higher or lower temperature for a given proportion of solvent constituents. Usually about 0.05 weight percent moieties (Group I and ~roup II compounds or Group B III compound(s))shifts the temperature curve in a uniforl-n manner less than about 0.5C (~ or ~' in Figure l) in one direction or the other over the entire length of the curve. 8y keeping the weight fraction of organic moieties in the solvent s~steln con-stant, one car. determine ~ or ~' in a curve such as FIGURE 1 and adjust the curve to com~ensate for the difference in melting point caused b~ the addition of the moieties. The ternperature scale such as in FIGURE 1 is then divided into the suitable -5~-increment size, for example, 0.2F or 0.1C in hulllan clinic~l use, so that the number of novel compositions of .-natter necessary for the temperature range is determined. These are marked on the ordinate or temperature scale from which the same number of abscissas or mol/weight fractions of one of the solvents may be determined for each of the temPeratures incrementally located in the range. For example, if one selects a temperature range of 96.0F to 105F and one also desires tlle increment of temperature as 0.2F, one would divide a chart such as FIG~RE 1 into forty-five ordinates (96.0F, 96.2~,.. 104.8F).
In preferable o~eration, the disposable thermomete. forthe clinical temperature as is shown in FIGURES 12-13 is so constructed with about 0.025 weight percent pinacyanol iodide, and the remaining nalance of the composition (except for B nucl~q~iny ,.ucela~ing agents, if any) ortho-chloronitrobenzene and ortho-bromonitrobenzene in the proportions shown in FIGURE 1, except that the temperatures are adjusted to be about 0.3C high (increment "~") for the entire curve (even after ~ or L ~ has been determined) between 96F and 104.8F, since the user of the 2~ disposable thermometer is only instructed to insert the thermometer for at least about fcrty-five seconds to aoout one minute in the mouth (see spatula portion "F" of FI~URE 12) under the tongue as far bac~ as possible ~and a-ljacent, to but on the inside of the lower teeth, ~ith the tongue on top of the thermometer portion "F"). After the stioulated time~ the user re.-noves the thermometer fron the .nouth and the temperature corresPonding to the last blue dot is read by the user although the temperature that ~ould have been required to turn the ~ocket froln liquid to solid over an infinte period is about 0.3~C less than tne tem,?erature of the mouth. Of course, the 'a can be _ ~0_ ad~usted lower, say, to about 0.2C, if the user is instructed to spend a longer period of time with the thermometer in place, or visa versa. ~n example of such a thermometer is the TEMPA-~OT~
READY-5TRI~ Single Use Sterile rhermometer, by the Inro-Chem Division of Akzona Inc. (distributed by Organon Inc., a subsidiary of ~kzona I-nc.).
Ignoring the effect of the organic moieties Group I-III
of such a temperature curve for the purposes of this paragraph, one would then determine for any given temperatur2 in the range of the novel composition of matter by first determining the proportion of solvent constituents such as ortho-bromonitro-benzene to ortho-chloronitrobenzene. For example, using Table I
listed below, for 100F one would select a solvent system of 77.3 weight percent ortho-bromonitrobenzene and 22.7 weight percent ortho-chloronitrobenzene, if one chose to ignore the effects E or E ' of the organic moieties Group I-III on the melting point curve such as that listed in FIGURE 1.
Of course, it is preferred that the weight percellt of organic moieties be ~ept to a slight amount such as under 0.05 percent, so that a curve ~=f (temperature) or ~'=f (temperature) could be constructed similar to FIGUR~ l with a uniform temperature effect of the organic moieties on the liquidous curve.

_ 6 ~ -COMPOSITION IL~ WEIGHT PERCEN~ OF PURE OC~B-OBNB
A P PRO~ I L`l AT E
,~ELT~NG TE'~IPE~ATURE ORTHOBROMO- O~THOCL-ILORO-F ~IITRO~ENZENE NITROBENZENE

96.0 56.2 43.8 96.2 57,5 42.5 96.4 58.~ 41.2 96.6 60.1 39.9 0 96.~ 61.3 38.7 97.0 62.5 37.5 97.2 63.5 3&.5 97.4 64.5 35.5 97.6 ~5.5 34.5 9/.~ 6~.5 33.S
98.0 67.5 32.5 98.2 b8.5 31.5 9~.4 69.5 30.~
9~.6 70.5 29.5 2~ 9~.8 71.5 2~.5 g9.0 72.5 27.5 99.2 73.5 26.5 99.4 74,5 25.5 99.6 75.5 24.5 99O~ 76.4 23.6 00.0 77.3 22.7 0~.2 7~.1 21.9 ~33~10 10~.4 7Y.0 21.0 100.6 79.9 20.1 10~.~ 80.8 19.2 101.0 81.7 18.3 101.2 82.6 17.4 101.4 ~3.5 16.5 101.6 ~4.3 15.7 101.8 a5.1 14.9 ld2.0 85.9 14.1 102.2 86.7 13.3 102.4 8/.5 12.5 102.6 8~.2 11.8 102.8 88.9 11.1 103.0 ~9.6 10.4 lS 103.2 90.3 9,7 103.4 gl .0 9.0 103.~ 91.7 8.3 103.~ 92.4 7.6 104.~ 93.1 6.9 104.2 93. ~ ~ .2 104.4 9~.5 ~.5 104.6 95.2 4.
10~.8 g~,o 4.0 _ 63_ 1~33810 on oe the organic moieties Group III compounds and/or Group I and Group II oompounds are determined for the desired color change, they are added to a liquid mixture of the solvent constitu-ents for the predetermined temperature and mixed, preferably by any suitable industrial mechanical mixlng means known to those in the art until a substantially oomplete dissolution has been obtained.
After the solvent weight fractions have been determined and the novel ocmposition of matter formed for each of the incre-ment temperatures to be tested, a suitable temperature-indicating device is constructed such as the novel devi oe described below hav-ing a plurality of temperature-sensitive xegions, preferably having cavities in a heat-conductive carrier such as aluminum wherein each novel composition of matter corresponding to one of the pre-selected points along the temperature curve fills one of the regions, prefer-ably a cavity, in the heat conductive carrier devioe . A method and apparatus for depositing precisely metered quantities of a tempera-ture-sensitive oo~position of matter on a surfa oe is taught by Pickett, et al, United States Patent No. 3,810,779 (1974), and the techniques of that patent are incorporated herein as m~ch as copied verbatim. A preferable devi oe for sealing a heat-sensitive trans-parent oover sheet means in vacuumrsealing engage~ent with an aluminum heat-~uL,ductive carrier ovex cavities in the carrier is the Wehb Model No. 2 machine manufactured by Bio-Medical Sciences, Inc., in Fairfield, New Jersey.
Besides use in disposable oral thermcmeters, the novel ccmpositions of our invention may be employed for the detection of averheating in engLnes, for the detection of leaks from steam ~33810 tr~ps (the indicator may be ~laced on an uninsulated piece of pipe just below the steam trap), for the detection of high temperatures in the surroundings of computers, home furnaces and appliances, as well as on packages for foods, forehead, skin and rectal tem~erature indicators.
As a preferred embodiment, we have found that film B forming materials such as gelatin, polyvinyl alcohol, and water-soluble cellulose derivatives are good barriers for containing s~all particles or droplets of the novel comPositions of ~atter of our invention, especially the compositions wherein OCNB/OB~
is the solvent. After this form of microencapsulation, a dry granular material is formed that is easily adaptable to various machinery processes. A ty~ical microencapsulated novel c~mpo-sition would ~e an OC~B/OBNB solution containing 0.035 weight 1~ percent pinacyanol iodide surrounded by a layer of gelatin coacervated with acacia and fixed with ylutaraldehyde. The use of these microencarsulated novel compositions ~Jould per~it application to te~perature-sensin-~ devices with more ~lexi~ility.
For example, the microencap~ulated novel com~ositions ~ay be formulated into a pressur~-sensitive adhesive from w~ic~ a lemperature indicating ta3e could ~e ma-~e. Microer.ca~sulate~
n~v~l compositions could be incor~orated into printing Dres~es to ~ermit ten~erature sensing r~gions of unlimited geo.~tr~
including temperature-responsive messayes.
2. Novel Te~Perature-In~icating Device In FIGU~tE 2, a nove~ te~peratur2-indicatGr device is disc~osed com?rising a ~lat, gra-3ual~y curved, ~r su~stantiall~
curvilinear heat-conducting carrier means ha~iny one or more s~aced cavities r3efined tnerein to deterl~ine a ~ike numbfr ~
_ G~

-~33~

predetermined tem~eratures in a tQm~erature range by means or a aOS;~ nS
like number of different tnermally-res~onsive composiLiu~. of matter. ~ach of the predetermined temperatures is associated witn a composition of matter that is substantially without imourities, and may or may not he the novel compositions of matter stated above, but a composition of matter which does change from an opaque form when solid to a transparent liquid upon melting. The novel tem~erature-indicating device co,~prises (1) a flat, gradually curved, or substantially curvilinear heat-conducting carrier with one or rnore cavities indented therein; (2) (in the absence of em~loying the novel compositions of matter o~ this invention) an indicator means located at the bottom of each of said cavities; (3) a transparent cover sheet means in sealing engagement witn the carrier means above and overlying each of said cavities to form an enclosure between the walls of the cavity and the transparent cover sheet .~eans; and (4) a composition of matter which substantially fills the cavity and is ada~ted to change rom a solid tc) a liqui~ at substantially the predetermined temperature associated with said cavity, except f~r a substantially spherical void in the composition of matter between the bottom of the cavity and the transparent c~vef sAeet ~neans.
~ eferring to FIGUR~ 2, one will notice that colorant 1 fills the ~ttom of a cavity ''A'' in a flat heat-conducting carrier means 2 of width ~ which m2ans is s~bstantially ~illed ~ith a "classical" so~id solution 5. The cavity 'A' is covered by a transparent cover s'~eet means 4 which ~its in sealing engagement with heat-conductin~ carrier means 2 immediately surrounding cavity 'A" and covering the so'id solution ~ filling cavity ''A''. Within solid solution ~ is a substantially s~herical cavity 3 which has a diameter 1~ only slightly smaller than the width 12 of the cavitY minus the small width 11 of the colorant r ~ ,'e r ~e a~s l. In the preferred embodiment shown in FIGURE 2, the~cavity is in the shape of a trapezoid rotated around its axis, having a large diameter 8 at the top o the cavity and a smaller diametex 9 at the bottom of the cavity. The width 7 of the transparent film 4 is preerably substantially equal to the ~7idth 6 of the heat-conducting carrier means 2. While the exact dimensions (6,7,8,9,1l,l2) of a cavity in items such as those in FIGURE 2 vary with the solvent system employed, the materials selected, and the composition of matter which is predetermined (whether or not one of the novel co~positions of matter described a30v~ or a classical comPosition of matter which changes from opaque to transparent with chanye in phases from solid to li~uid), it is well to de,cribe a device employing ortho-chloronitrobenzene and ortho-bromonitrobenzene recently constructed.
Referring again to FIG'~RE 2, the heat conducting carrier ,means 2 i5 an aluminu~ foil of Wi~CIl 6 o a~2roximately 0.003 inches (naturally, the heat-conductin~ carrier rneans 2 must be a material "hich has a high thermal conductivity and relatively large surface area of contact with the test subject and ~e of minimum thickness, while preservin~ its structural integrity, in order to permit rapid conduction of heat into the cavity such as shown in ~IGU~E 2. Where aluminum is used, its thickness may vary from about 0.0~1 inches to about 0.004 inches.
In any event, the selection of such heat-conductive carrier means is well ~ithin the 3snowledge of those s'silled in the art and needs no further elaboration). Tn a particularly effective embodiment, the heat-conductive carrier means 2 is always 3~ preferably constitut~d of aluminum or allo~s thereof Wil ich _ G ?-transfer heat in an effective manner. In the alte m ative, the heat oontraction carrier means may be made of plastic. Thereby, the carrier is provided with the ne oe ssary strength to serve as the main structural support, while at the same time providing rapid and uniform temperature distribution throughout the thermometer devi oe .
As a consequence, the time required for taking te~perature is sub~
stantially diminished. The depth 12 of cavity "A" in FIGURE 2 is selected to be preferably 0.004 inches, with the upper horizontal width 9 being appro~imately 0.035 inches. The width 7 of the trans-parent film is approximately 0.001 inches, the letter being a painted letter on the bottom of the cavity "A". As implied in FIGURE 2, a layer 11 of colorant material (paint is stamFed onto the bottom of each cavity "A" of a visible material that may be somewhat absorbed into the ocmposition of matter or solid solution 5 upon melting of the " d assical" solid solution 5 to make the colorant material more visible (See FIGURE 9). m e transparent film cover means 4 may be polypropylene, M~lar~M, (polyethylene terephthalate) nitro oe llulose, polyvinyl chloride, etc. In FIGURE
2, the transparent film cover means 4 is preferably a heat-sensi-tive material and is a coextruded film of Nylon 6~ ~nanufactured by the Allied Chemical Cc~pany) and Surlyn 1652R (manufactured by E. I.
duPont deNemours & Company) which filn is produced by Pierson Industries Incorporated that is subsequently la~Qnated to polypropy-lene by the Millprint Company of Milwauhee, Wisccnsin.
~n each cavity "A", such as that shown in FIGURE 2, one of the predetermined compositions of matter that is assoc-ated with a predetermined melting point is poured into the ca~ity, filling approximately ~0~ of said cavity. After partial ~i~ling of each cavity "A" with a particular oc~position of matter (here OCNB:O~B) associated with a temperature to be measured ~here ~33~10 between 9o.0F an(l 104.RF), transparent filJn 4 is ?ut in sealing engagement ~ith aluminum foil 2 through the use of a machine such as the ~ebb r~od~l 2~50. 2 manufactured by aio-Medical Sciences Inc.
of Fairfield, New Jersey. E3ecause of the surface tension ~ro-duced in the cavity "A", a substantially spherical void 3 isformed in the cavity ''A" which retains its character even upon melting of the com?osition of snatter. This cavity acts as a magnifying device for the observer from above to see the color-ant 1 which Inay or may not be absorbed or partially absorbed into the comDosition of matter u~on melting from the solid. As will be recognized by those skilled in the art, small deviations could be ~nade in ratios of the widths 6 through 12, or alternatively, the ratios coul~ be maintained for different sized s~stems (e.g., by multiplying distances 6 through 12 by a uniform but different constant) ~Jithout su~stantially affecting the results of the invention.
FI5URES 3 and 4 are taken from sectional views [lines 3-3 and ~-4] of FI~URE 2 sho~Jn as the osbserver ~ould see tnem froin above the cavity ''A'' of FIGURE 2; FIGUR~ 3 is a view o~
cavity "A" when empty of the cc,mposition o~ matter (8 in FIGURE 3 or 1 in FIGURE 23, whi~e FI~URE 4 shows a cavity illed witn the "classical" composition of matter after the "classical" compo-sition of matter has melted as~d is transparent, so that the observer has the ap~arent observation that the colorant 9 fills 2~ tAe entire ~ottc,m of ts~e cavity "A", and in this case, partially absorbed throu~hout the cavity "A" When the cavity "A" has been filled ~ith the colnposition o~ matter 5, an<l the composition of rnatter is a solid solution prior to its ~elting, the opa~ue char-acteristic of the composition of snatter cos,~pletely obscures sight of the co~orant 1 at the botto~ of the cavity "A". Eience, only _G~--when the CO~T~poSition of macter has melted can one see the colorant 1 at the bottom of the cavity "A" or throughout the cavity "A". It is necessary that the Jnelting substance or compo-sition of matter 5 in FI~RE 2 be of such purity in nature that upon meltiny com- ~letely, it has the ~roperty of "stable under-cooling", or simply "undercooling" known to those skilled in the art, i.e., that it has the property that after liquifying u~on cooling at ambiellt tem~era~ure '~elow the free7ing point of the composition of matter, it will remain liquid for several hours.
It has been f~und that ir the coin~osition or matter has the concentration of impurities indicated above, then it will ~iave such a property of stable undercooling.
If the novel comPositions of matter described above are used (instead of "classical" compositions that change only from o~aque to transparent upon a corres~onding chanye from solid to liquid) the layer of colorant 1 ~ay be eliminated.
FIGURES 5 and 6, respectively, present a partial Plan view from above and the side of one embodi.nent of the invention showing a heat-conducti~ carrier mean~ "C" of a thermometer in a Celsius s~ystem (one sub-grid showing cavities associated with 35.5C to 37.9C only), and a plan view Crom above a simil3r F~hrenhe~;~
B means of the same chemical ther~ometer in a ~a.~.,l,~it system in a particularly ef~ective em~o~iment of the invention, to wit, a rectan~ular grid is ~ormed (pre.erably havi~ two sub-grids of 35.5C to 37.9C and 38.0C to 40 4C for the Celsius type and ~a h r~ ~ h e~
96.0F to 59.8F and 100.0F to 104.8F for the-R~e~}~- s~stem3 ~herein eacn cavity 13 employs a construction as in F~G~R~ 2 and is clearly associated with a temperature to be determined ~ithin the range of temperatures to be tested through markings located on the side oE the grid. ~n F~G~XES 5 and ~, one ~ill notice ~33810 tnat as eacn cavity 13 employs the same colorant (1 of FIGURE 2).
so t~at upon a completion of a test for the thermometer ~ithin the predetermined temperature range, one or ~ore cavities having com~ositions of matter in the liquid phase will clearly be distinguished from the remaining cavities havin~ compositions of matt~r in the solid ~nase.
FIGURE 7 indicates a scheme for testing temperatures of intervals of 10F using the novel co~n~ositions of matter described above (which turns from orange 103 to red 104, for exaMple, on meltin~) ~7herein the necessity for colorant materials 1 of FIGURE 2 is eliminated. Here in FIGU~E 7, transparent cover plate means 101 is in sealing engagement, preferably vacuum sealing engagement, with the neat cond~cting carrier means 10 and each of the ~eripheries of the six cavities shown. It will readily be ~ppreciated by those s'~illed in the art that the novel compositions of matter can be used not only in the novel temperature-indicating device shown in ~IGUR2 2, but in other configur^,tions as well, such as FIGU~E 8, wherein a single cavity is em~loyed with the same novel co)nposition of matter of FIGURE 7 (that has already changed to red upon melting) to determine whether or not a material in storage has exceeded a safe tem~erature.
~ eferring again to FIGU~ 2, in the case of employing one or more "classical" com~osition~s3 of matter, the colorant or dye layer 1 ~ay contain a dyestuff which is responsive to the change in the ~hysical state o~ the com~osition of matter 5. ~rhe colorant 1 ~nay be a "dye layer", or layer constructed of a material im~reynate~ with a dyestuf~. Examples of dyestuffs suitable ~or indicator materials are tne halogenated nitro-~enzenes s~c~ as ~rocein- Scarlett SS~ and ~olynal ~lue~, ~oth _ 7~--manuEactured by the Allied Chemical Corporation, and both stable over long periods of time. As the composition of ~atter 5 under~oes initial melting, tne dye layer 1 becomes wetted, resulting in the substantially instantaneous mi3ration of dye from layer 1 to the entire body of the composition of matter 5.
~owever, it may be necessary onl~ to einr~loy colorant materials 1 ~hich are merely paints at the bottom of cavity ''A'', preferably that are blue or black. The greater the intensity of the visible change of appearance in the composition of matter 5 through the employment of a su~stantially spnerical void s2ace 3 and dark colorant layer 1, the greater the ease in reading the ther,~ometer cavity. In one preferred em~odiment, the change in appearance of the "classical" composition of matter 5 wnen seen from above, sucn as in FIGURE 9, is from white to intense blue usiny a painted indicator layer having the latter color.
Tne operation of the thermometer of FIGU~E S (or FIGURE
6) is as follows: viewing FIGURE 5 with cavities substantially constructed as in FIGUR2 2, the remote part of the handle portion "~" (not sho~n in FIGURE 5, but 35 in FIG~RF 9) in FIGU~ 5 is held between tne ~ingers, and ~ortion "C" ~ith cavities 13 is inserted into the mouth and preferably held under the tongue for a relatively short period, to wit, approximately thirty seconds to one minute. During this time, all of the compositions of matter of the various cavities 13 which have melting points below the temperature in the mouth will melt, revealing tne colorant 1 in each of said cavities to indicate a change in color ~isible to the na~ed eye. ~ecause of the purit~ in ~ature of the melting compositions of matter, such th~t they have a property o~ stable undercooling ~or at least se~eral MinuteS, the user may sim~y withdraw the thermometer of FIGU~ES 5 and ~ and c~early see via ~ ,7~Z_ 38~0 the grid shown thereon his temperature to the increment of precision chosen, to wit, 0.2F or 0.1C. Preferably, the colorant 1 for each of the cavities 13 in FIGURE 5 is of the sam~
color, and all of.the cavities are filled by OC~B/OBNB
S com?ositions of matter having melting points se~arated by equal increments of 0.2F or 0.1C whose constituents have been selected from a graph such as FIGURE 1. FIGURES 9 and 10 display in another ~referrPd ein~odiment in three dimensions from a s~ewed angle a flat heat-conducting carrier means 37, here aluminum, f a h re, n h e ;-f 10 V with cavities 36 (such as shown in FIGURE 2) in a-Farcnhcit grid (as FIGURE 6) from ~6.0F to 104.8F connected to a plastic (prefera~ly polystyrene, poly~ropylene, or polyethylene) handle 35. Until used, the carrier means 37 fits co~fortably inside a case (~referably made of the same materials as the handle 35) 32 and by ~eans of a roller 33 which exerts leverage downward against carrier means 37 and a layer of paper, plastic, or other retaining Ineans 31 to prevent the carrier means 37 from being removed ~ccidentally from case 32 unless a deliberate force is exerted on handle 35 to accomplish such removal. Although not 2~ sno-~n in FIGURE 9, the end of the carrier means 37 (which is most ad3acent to ~andle 34) is fitted with locking means so as to m~e a vacuum-sealing engagement between said carrier means 37 and case 32 until a deli~erate force of suEficient magnitude brea~s the locking ~eans. Also, the handle 35 may ~e notched so as to f~rm indentures 34 therein for a ~irmer gri~ ~y the user who desires to remove the carrier means 37 from the case 32.
In FI~URE 1~, once again a transparent cover sheet means 39 in the form of a plastic transparent sneet or plastic transparent cover means fits in sealing engagement, ~referably ~ vacuu.r. sealing engagernent, siith the carrier means 37 overl~ing - ~3 _ 11.3381~

and above cavities 36 and in sealing engagernent with each of the peripheries of said cavities.
FIGURE 11 shows a hori~ontal section along line 11-11 of FIGURE 10; it is a partial plan view o~ several cavities having indicator means 38 in the form o~ a paint. Transparent cover sheet means 39 is in sealing engagement with aluminum heat conducting carrier means 37 and is in sealing engagement with each o the peripheries of the cavities; a similar bottom plate means 40 fits in sealing engagement with heat conducting carrier means 37 and is in sealins engagement ~ith each of the peri-pheries of t'ne cavities; a similar bottom plate means 40 fi-~ in sealing engagement with heat conducting carrier means 37 so as to present the thermometer as a flat surface. The bottom plate means 40 is pro-~ided to aid the carrier means 37 in preserving lS structural inte~rity and is co-extensive with the entire surface o~ carrier ,~eans 37, and has a thickness from about 0.001 inches to about 0.004 inches.
In FIGU~E~ 12 and 13, another ~referred embodiment of the invention is disclosed for measuring temperatures at 0.2F
increments from 96.0F to 104.8F, combining the novel composi-tions of matter of this invention (pre~erably ocNa:o3i3a/pina cyanol iodide3 ~rith the novel cavlties of FIGURE 2, only ~ithout the necessity of an indicator layer. Unlike the ei-nbodiment shown in FIGURE 9 and 10, the em~odiment realized in FIGU~ES 12 ana 13 does not have a case, and therefore is less ex~ensive to manu~acture.
FIGURE 12 displays a ~lan view o~ the substantially ~lat oral te~perature indicating device as seen rom above.
Again, the Lherlnoi~eter hds an aluminum heat conaucting carrier means 44 (of ~idth 47 in FIGU~E 12) which acts not only as a main - ~33810 structural body ~f support, but at the same time provides rapid and uniform temperature distribution throughout the spatula portion ''F'' (having width 54 containing grid ''G'' of a plurality of cavities (each of diamPter 57 and s~aced center-to-center ~ith each neighbor along a horizontal "x" axis or vertical "y" axis in FIGU~E 12 at a distance 52 apart) of FIGURE 2, each cavity with th~ novel composition of matter and each associated with a predetermined temperature to be measured at 0.2~F increments from 96.0F to 104.8~, and each novel composition of matter substantially s~herical void within said cavity. "Spatula"
portion "5" of the device of FIGUR2 12 is rounded for safety so that some distance 56 is maintained between t~e most ~orward row of cavities and the edge of the device. It may sbe observed by those skilled in the art that if "classical" compositions of matter are employed in lieu of our novel compositions of matter, that each cavity will necessary employ an indicator layer such as layer 1 of FI5U~E 2.
Again in FIGURE 12, one will note that the aluminum heat-con~ucting carrier means is covered above for the entire handle "E" portion of the thermometer device ~y a to~ plastic layer 42 of ~Jidth 54, preferaoly ma~e out of a plastic such as polystyrene, polypropylene, or polyethylene. ~n FI~U~ 13 a hottom p~ate means 46 of width 49 extends along the entire ~ength 53 of the ther.~ometer device The top layer 42 terminates upon entering the s~atula portion "F" of the thermometer device, revealing grid "G" of cavities, dar~ mar~ings ~pre~erably blue or black-painte~ 45 indicating the ~redetersnined temperat~sre to be measure~ for each cavity, and a heat-sensitive t~ans~Jarent ~ilm cover means ~3 o~ width 50, which as before is most pre~erab1y a 0 coextruded film of ~ylon 6~ and Surlyn ~652~ ~rDd~sced by Pierson - 75 ~

- ```

Indu~tries Incorporated that is subsequently laminated to poly-pro~ylene by the Mill?rint Com~any, or in the alternative, simply ,~ylar, poly~ro?ylrene, nitrocellulose, ~olyvinyl chloride, etc.
The heat-sensitive transparent film cover means 43, as in FIGURE
12, is in sealing engagement with the carrier means 44 above, and is overlying ~ach of said cavities to form an enclosure between the ~alls o~ each cavity and the trans~arent cover sheet means 43. It is important the the film cover means 43 be in tight vacuum- sealing engagement with the peri~hery of the carrier means 44 with each cavity to avoid loss of the com~ositions of matter within each cavity. For that reason, as well as for a?pearances, some minimal di~tance 55 is maint~ined between a leadin~ edge of a row of cavities and the edge of the thermometer device. Pre~erably, the heat-sensitive trans~arent film cover means 43 colsists of bands that cover only the immediate area surrounding the cavities to avoid undue manufacturing expense.
(In FIGURE 13, the transparent film cover means is shown in two bands, er-ch of width 51 which covers the two rows of cavities), although it will be obvious to one skilled in the art that the heat-sensitive transparent filtr~ cover means could cover the entire spatula portion "~" of the device ~he heat-sensitive trans~arent film cover means 43 ~,ay be put in sealing enga~ement witn aluminum carrier means 44 throu~h the use of a machine such as ~e~o M~odel ~o 2 manufactured by ~io-~edical Sciences, Inc., of Fairfield, New Jersey.
Also in F~G~E 12, it will be recognized that the handle ''E'' has been stamped from below so as to ma~e the de~ice realize t~o ridges, ribs, or abutments 41a that ~rotru~e from ahove t~e carrier means 44 by some nominal ~istance which is ap~roximately the same as width 47 of carrier means 44, lik~-~ise, _ 7 C -^

the c3evice realizes two cavities 41b in carrier means 44 that parallel the ridges 41a. As will be appreciated by those skilled in the art, although the distances shown in FIGURES 12 and 13 can be readily adjusted with respect to one another or in proportion (widths 47, 43, 49, 50, 51, 52, 53, 54, 55, 56, 57, and 58 can be multiplied ~y difEerent constants) it is ~ell to describe a device for measuring numan temperatures in the range of 96.~F to 104.8F that we recently constructed, employing ortho-chloro-nitrobenzene and ortho-bro,~onitrobenzene in a solvent system with ~inacyanol iodide in the amount of 0.035% ~y weight to form a thermometer ~ith the novel compositions of matter of this inv~nt-ion, which is the best mode of our invention and which is market-ed by Organon Inc., (West Orange, Ne-~ Jersey) under the trademark ~t~PA DOT XEADY STRI~ eferring again to FI~URE 12, the ther-mometer nas a width 54 of about 0.345 inches at the ~idest portion of handle ''E'' and has the same width 54 of a~out 0.34~
inches in the spatula portion ''F" of the ther~ometer. The cav-ities each have a diameter 57 of about 0.039 inches and each cavity has a depth of about ~.005 inches, and is s~aced from eacn neignbor on a horizontal "x" axis or vertical "y" axis by a dist-ance _ of 0.015 incnes. T:ne top and bottom ro~s of cavities are o~ a distance 55 of about 0.~39 inches frol~l the leading edges, respectively, of the thermometer, and have a center line on the right-hand column which is a distance 56 of about ~.193 inches from the ti~ or tne rounded edge of the spatudl "G" portion of the thermometer. In FIGURE 13, taken alGng line 13-13 of EIG~RE
12, it will be appreciated that the oral thermometer device nas an overall length of 4 250 inches, and consists of an alu~inum heat conducting carrier means 44 having ~n overall length of 4.250 inches and a depth 47 of about 0.003 incnes. Th2 aluminum

- 7 ~ _ ~ r` 1~1 ~810 heat oonducting carrier means 44 is oovered on the handle portion ''E'' of the thermometer by a polypropylene or polystyrene layer of thickness 48 of about 0.003 inches; the r~rrier means also is in engagement with a polypropylene or polystrene bottom plate means 46 of width 49 of about 0.003 inches that tra~erses the entire length of the thermometer. Two bands of heat-sensitive material (coex-truded film of Nylon 6TM and Surlyn 1652~M subsequently laminated to polypropylene~ oo~er the two sub-grids (100F to 104 8F and 96.0F to 99.8F) and are each of width 51 of apprDximately 0.300 inches along the "x" axis and of depth 50-of frcm about 0.003 to about 0.005 inches.
As previcusly stated, grid ''G" in Figure 12 consists of two sub-grids, cne from 96.0F to 99.8F and the second fno~ 100F
to 104.8F. In this pattern, the cavities are arranged in rows along the longitudinal axis of the thermometer. Althcugh the two su~grids selected were merely for convenien oe , o~e large grid could have been selected for the devi oe. The group associated with the lower temperature value is positicned more distantly from the thermomet~r handle while the grcup associated with the higher temperature value is positioned nearer to the thermometer handle.
The temperature scale utilized (Fahrenheit or Celsius) and the de-sired range of measurements and temperature increments will quite obviously deternine the exact number of cavities and therefore rows.
Although not shown, a thermometer similar to that shown in FIGU Æ S 12 and 13 cGuld be oonstru~ted where~y the bottcm plate means (46 in FIGU Æ 13~ oculd ~e remDved fro~ spatula portion ''F'' of the devi oe , and each of the cavities allowed to protLude entirely through the carrier ~fans (44 in Figures 12 and 13); a ~Dtt~m heat-sensiti~e and transparent fi~m c~er means cc~ld ~e pla oe d in sea~-ing engagement wqth the carrier means and the Eeripheries of each -7~-~, ` ~13:~10 of the cavities so that one could observe the change in color of the novel co~positions of matter if the latter were employed. ~lso, it is obvious to one skilled in the art that ribs 41a in FIGURE 12 are not necessary; indeed, many minor changes in the device shown in FIGURES 12 and 13 cculd be made without departing from the spirit of the invention. As a preferred embodiment, ribs 41a ~ay be re-moved as in actual practice (TEMPA- ~ READY-STRIP disposable clinical ther~Lmeter of Organon Inc., W~st Orange, New Jersey).
~he spherical void of FIGURE 2 is not required for the entxlL~nent of FIGURES 12-13 when novel compositions are employed.
FIGURE 14 is a plan view of a elongated monolithic sup-port member (preferably transparent) for a disposable clinical thermcmeter such as depicted in FIGUgE 10 or in FIGURES 12-13. The support m~mber is preferably made of highly translucent p~ly-propylene, although it will readily be notioed b,y one skilled in the art that the support member could, in the alternative, be con-structed of any suitable malleable, soft material form so as to support the thermcmeter, yet flexible enough to avoid damaging delicate tissue of the user. The support member is intended specifically for rectal administration of the thermometer, such as for infants and the elderly or others who might otherwise not be capable of re oe iving oral administratian prcperly. The member can also ~e used for admlnistration in any ~ody cavity indicative of the temperature of the ~cdy and of sufficient dimensiQns to ac oe pt the me~ber.
Referring to FIGURE 14 as before and now also FIGURES
~5-1~, it will be appanent that FIGU~ES 14-16 are taken frc~ the vertical, and re particularly, that FIGU~E 15 depicts in plan view the translu oe nt support me~ber, ex oe pt in sealing engagement 3~ with a disposable thermometer as shown in FIGU~E 10 wi~ a Fahrenheit scale frYm 96.0 to 104.8 degrees Fahrenheit with 0.2 -degrees Fahrenheit increments. FIGU~E 16 is identical to FIGURE
15, except utilizing a Centigrade scale from 35.5 degrees Centigrade to 40.4 degrees Centigrade with il-crements of 0.1 degrees Centigrade. Body 61 of the member acts as a bridge ~et~een the sections "H" and "I", which are adapted to fit comforta~ly spatula portion ''F'' and handle portion 42 of the disposable thermometer of FIGURE 12, res~ectively, in sealing engagement. Section "I" comprises a handle portion 64 with a ridge or i~dentation 63 as seen from above and facing the user in FIGUR~ 14 and above but away from the user in FIGURES 15-16, i.e. as if the member of FIGURE 14 was merely rotated on its axis 1~0~ to receive the r'ahrenheit thermolneter of FI&U~E lS or the Centigra~e thermo.neter of FIGU~E 16. ~icge 63 continues into body 61 as rid~e ~r indentation 62 ~nich traverses the entire support mer,~er on both sides of the mem~er into section "H". rl'he ridge is of suf L icient width (~bout 1 c~) to accept the ther-moneter comforta~ly and to alleviate the problem of cutting during insertion into the ~ody cavity, and is of sucn a tolerance that the disposable ther~omet~r of ~IC7UPE 10 or 12 snaps securely 2~ into fitting engagement with the mem~er. ~ne spat~la tip 65 of section '"~" is ro~Jnded smoothly, as are exterior edges of the me~er, in order to avoid damage to delica~e tissue u~on adminlstration of the thermometer. Spatula ~ortion ''H'' is suitaDl~ constructed to have a window or vacancy so that the grid oF the the-rmometer such as grid ''G'' of FIGURE 10 is clear~y see~
upon removal from the source by the user.
As a most -~ref.^-rred embodiment, and referring again to FIGU~ES 14, 15 and 16 displ.ay a rectal adar~ter including forward section "~-I" and rearward section ''I'. For~ard section "H"
includes su~stantially solid ti? 65 which i- the leading edge of ~ ~0-the rectal adapter during insertion into the rectum. Tip 65 is a partially flattened conical shape for comfort during insertion.
The inside bottom portion 64 of the rectal adapter receives the bottom portion 42 of thermometer of FI~URE 12. The thermometer is adapted to be snap-fitted into the adapter by means of lips 62 and 63 which extend about a portion of the periphery of the ada?ter. As can be seen, lip 62 extends outwardly from the bottom surface of the adapter and inwardly towards its longi-tudinal axis. The rearward portion 12 of the adapter further includes a handle receiving portion 63 for the receiving handle 42 of tne thermometer. Other embodiments of disposable _ner-mometers do not utilize a handle and thus handle receiving portion 16 would act as a handle itself or could be eliminated.
Again referring to FIGUR~S 15 and 16, the forward section "~5" of the ada~ter furtner includes an open wirJdow portion which is adapted to ~ n with thermally-respon~ive tem-~erature in~icating portion of the thermometer o~ ~IGURES l2 and 13. This window is in effect a hole punched through the adapter for providing improved thermal contact for temperature indicatin~ i~ortion of the thermo~eter and its immediate environmen~.
FIGURE 14 also shows the thermometer of FIGU~E 12 snap-fitted into a recta~ adapter with the top side of the indicating portion ~acing the user and partially covered ~y an open window sho~n in ~ection "13". FIGU~E 15 also shows t~e rectal adapter with the temperature indicating portion of the ther,~ometer l ex~osing ~oc~ets directly to its surrounding environment through the open window in Section "~". The use of the tnermometers of the ~rior art with prior art rectal ada"ter, did not permit the ~ottom side of the thermo~eter thermally-rec;ponsive Inaterial to Oa/ _ ~338~0 be exposed to the environment. That is, the pockets such as 43 of FIGU~ES 12 and 13 rested ayainst the poly~ropylene material on the inside bottom layer of the prior art rectal adapter. Since the rectal adapter of the prior art was normally made of a p7astic, such as ~oly?ropylene, and since these plastic .materials are therinal insulators, it was found that the thermometer, when used with the prior art rectal adapter, registered lower than a mercury and glass thermometer. Furthermore, clinical studies have shown that the use of the disposable thermometers ~ith the prior art rectal adapter did not "fire", that is, some of the dots between the highest te~erature dot fired and some lower temperature dots did not even register, thus providing a confused reading to the ooserver. Further.nore, if the indicating portion of the thermometer was inserted face down into the prior art adaDter, the thermosneter could be read only by removing it from the ada~ter. The instant adapter exposes both sides of the thermally-responsive portion of the disposa~le thermometer to its immediate environment by providing an open window in the rectal adapter tnermally-responsive portion of the thermometer greatly improving the accuracy and response time of the tnermorneter. It has been sho~n by experiment that rectal temperatures ta~en using the improved rectal adapter/disposab7e thermometer comDination provides the same temperature readings as a 3-minute glass and mercury thermometer reading. The disposable thermometer, 2~ however, provided the reading within 1-~/2 to 2 minutes. Further-more, experiments showed no tendency for the dis?osable ther-mometer to register "no fires", or skips, as did the thermometer used with a ?rior art rectal adapter. 8ecause of the window, the thermometer may ~e easily read without removing it froin the 3~ recta~ adapter even if the thermometer has its indicating portion 1~338~0 face down in the adapter. ThuS, the window in tne improved rectal ada~ter orovides a dual function of improved thermal transfer characteristics and ease of reading for the thermometer.
As stat~d 2reviously, one of the problems ~ith the prior art ada~ter is incorrect low thermometer readinc3s due to the fact that the adaoter may be made of plastic insulators with the ther~al conductivities listed below:
polypropylene 2.8 x 10~4cal-cm/sec/cm2/C
polyethylene8-12 x 10-4 " " " "
polyvinylchloride 3-4 x 10-4 " " " "
polycarbonate4.6 x 10-4 " " " "

pol~styrene1-3 x 10-4 " " " "
a p ~ a n ~ s B Thus an operable ada~ter utilizing policent'~
invention may be made from the same or similar materials enabling correct thermomet:er readings.
From the foregoing description of the ada~ter, it would be apparent that many modifications may be made therein. For e~am~le, the thermometer of FIGURE 12 may be placed into the ada~ter with eitner the pockets 22 facing up or down. It is thererore intended that such modifications shall be covered by the appended claims.
In still another embodiment to this invention, we nave found that one ~nay ad~ an additional and effective amount of a soluble suitable nucleating agent, here a small amount of anthraquinone, to the existing nove1 co~,positions of t'nis invention (or just to "classical" compositions of .natter which will change from o~ac~ue to transparent u~on a chan~e ~rom solid to the liquid state, or vice versa) which li~its the a:nount of ur.dercoolincJ that the novel -conlp~ition of matter ~or even "claàsical" compositions of matter) can ex~erience. Prev-ously, ~ 3 _ (Chadha, United States Patent 3,956,153) those skilled in the art employed anthraquinone in a "saturated" am~unt (e.g., from about 0.7~ by weight to 0.9% by weight) in disposable thermometers in order to assure that the disposable thermLmeter (such as one employ-in OCNB:o8WB systems, such as shown in Table I) did not beccme molten prior to time of usage because of accidental or inadvertent melting due to high storage or shipp~ng temperatures (see United States Patent No. 3,980,581). However, we have disco~ered unexpect-edly that anthraquinone may be employed in an effective amDunt, which is a somewhat lower content, e.g., fram about 0.01 to about 0.4% by weight in order to allow the user to induce resolidifica-tion of the termometer at a predetenmined controlled temperature below the melting point of the novel (or "classical") ccmposition of matter. In this manner, the thermometer can utilize the under-cooling principle to indicate accurately for a substantial period of time a temperature upon withdrawal of a heat-conducting carrier means oantaining a grid of cavities from the mouth, and also be regenerated or made reusable by placing the thermometer (e.g., the heat-oonducting carrier with the grid of cavities) in cold water ~e.g., 32F - 40F) or another convenient low temçerature medium which would lower its temperature to a point where nucleation sites would be formed in the supercooled liquid ca~sing a spont~neous solidification of the novel (or "classical") oompositions of matter, with its indicator additives. At that tIme, the thermLmeter would change from its liquid phase oolor (for example, red in the case of a OCN~BNB system with chlorophenol ~lue and ethyl red) ~ack to its solid phase color Iyellow). This embodiment would ma~e the novel temperature-indicating devi oe of our invention, whether employing the novel ocmpcsiticns of matter of the "Classical" comr ~1338~10 positions of matter with the indicator means being a painted layer, etc., capable of multiple uses, thus representing a substantial advancement in the technology of chemical thermometry. For ex-amples of other suitable nucleating agents, see United States Patent 3,980,581, columns 5 and 6 and especially column 6, lines 26-49 listing equivalent alternatives to anthraquinone.
As a much preferred en~xxliment, from about 0.01 weight peroe nt to about 1.0 weight percent of an insoluble nucleating agent, talc (Talcum Powder, USP, Mg2(Si4010(0H)2), which may be ob-ta m ed from Whittaker, Clark & ~aniels Co., South Plainfield, New Jersey. (#399 Magnesium Silicate), may be employed in the novel compositions of matter as a means to control the temperature of resolidificatiQn in a pinacyanol iodide/OCNB-C~NB system adapted for clinical use with the 0.1 weight percent talc addition, regenera-tion or recrystallization occurs at about -6 & . Inter alia, potas-sium ethyl sulfate or potassium ~yrosulfate in effective amLunts are suitable alternatives to talc; see United States Patent 3,980,581, of which Col. 6, lines 7-49 are inoorporated herein. It must be noted that some routine experimentation is necessary to determine whether or not a nucleating agent is inert, i.e., whether or not it will affect the change in color upon change in phases of the novel ocmpositions of matter For example, some nu leating agents such as hydroxylamine hydrochloride act as a strong acid and will decolorize the dye porticn of the ocmpOsitiQn; for example, a pinacyanol iodide/0CNE,OBNB ccmposition 0thers, Floricil, ~or ex-ample, will ~orm a pigment "la~e" ("laking") within the dye and Yender the no~el compositions inapera~le. Okher po~ential nuc~eat-ing agents, such as potassium aoe tate or sodium tet~borate contain substantial ~, - li33810 quantities of water which when released upon crystallization will deactivate some of our novel compounds oy dissolving and partitioning the dye (for example bromochlorophenol blue) in the aqueous phase. Also, the water may affect the melting point of the solvent.
We have found that about a preferable amount o~ 0.1 weight percent of the recited talc in a composition of 0.035 weight Dercent pinacyanol iodide and the balance OCNB/OB~
(contained within a package o SURLYs~1652 by ~. I. duPont deNemours & Company, and aluminu~)will raise the temperature of recrystallization from -4~C to about -6C.
As an alternate to the nucleating agents mentioned above, the surface of the heat-conducting carrier may be treated by anodizing lanodic oxidation) or chemical passivation to create n~cleating ;,ites. The anodizing ?rocedure may be carried out in e.g. sul~huric aci~ or phos?horic acid or under other circum-stances as will be known to those skilled in the art. Chemical passiva~ion of the surface may ~e carried out by an etcning procedure in 2~ sodium hydroxide, a subsequent treatment with la~ nitric arid and washiny with ~ater.
In yet another perferred embodiment of the invention, and as an alternative of em~loyin~ a su~stantially spherical void of FIGU~E 2, one may employ a circular layer of suita~le absor~-ent bi~ulous material, which may be loaded ~ith tne novel compo-sitio~(s) of matter, and that substantially fills no~ only thespace of the solution ~, but also the void space 3, and is isnpregnated s~ith the novel compositions of ratter of the instant in-~ention. Viewed fron1 above, as in r~U~.E 5, each of ~he DOc~e~S 13 a~oear to be a fully colored dot which i5 surPrisir,gly as easy, if not easier, for the user to read as tne ~oc~ets of ~133810 FIGURE 2 employing a substantially spherical void spa oe . Of course, the bibulous material must be inert to the phenomena of the novel compositions of matter upon changing phase. One material which has been found to be especially suitable is E. I. duPont deNemDurs &
Company, spun-bonded polyolefin TYUEKTM. Other suitable materials may include aggregated inorganic pow~ers, glass fiber paper, ordinaLy oe llulosic paper, or other permeable polymeric material An ~ ;tional advantage of employing a bibulous material is that in case of accidental rupture of transparent film cover means 43 (FIGURE 13) by the user, for example, by the teeth, the bibulous material would prevent spillage of the liquid contents on the sur-rcundings. Another advantage of the emplcyment of bibulous mate-rial is that instead of relying on the expertise of a skilled operator to meter the am~unt of liquid novel compositions to each cavity through the careful adjustment of many variables of a fill-ing machine such as that depicted in United States Patent 3,810,779 (such as hydrostatic head, flow rates, cycle time, a~d interfacial tensi~n) can be eliminated sin oe the capacity of the bibulum is pre-determined for the size of the cavity and material employed. m us, the open end of the filling system will contact the bibulum ~when previously installed in place in the cavity) and liquid will con-tact the bibulum and liquid will quickly saturate the bi~ulum;
dri~en by the capillary attraction of the liquid to the b~u~um, the flow will stop when saturation is reached. A still further advantage of the invention is that it provides for flexibility in the geometry of the display-symbols, such as ~etters and num~ers, of other than dot or grid geomet~y, w~ich be 3uxtaposed (~s shown in EIGURES ~ a~d 12) or messages constructed from the novel ccmposi-tion(s) loaded on the bi~ulum.

Another preferred temperature indicating devi oe consists of a layer of an absorbent material (bibulum) in which the novel composition of matter has been absorbed and which is surrounded by two transparent cover sheets in a sealing engagement with each other.
Another type of operation can be developed for applica-tion to suitable devi oe s. m e novel Gc~position can be loaded onto a web of bibulum, solidified and the pro oe ssed (e.g. by die cutting for example) into various devi oe s simplifying manufacturing and re-ducing capital costs even further as the necessity for hot liquid loading of the novel compositions into the cavities is eliminated.
It is noted that if the duPont SUR~ ~ 1652 sealing layer aforementioned is repla oe d by a suitable structure ccmprising poly-isobutylene (PIB by BASF, B-15 ~ , then the novel liquid oomposi-tions inside each cavity sometimes renEins pooled in a "dot" con-figuration instead of a "donut" or ring display of FIGURE 2. It is believed that this phencmena is different from that phenomena ob-served when SURL ~ 1652 is emplcyed, because the interfacial ten-sian of the novel liquid composition (here pinacyanol iodide of about 0.025-0.05 weight per oe nt/O~NB~OBNB as before~ to the SURL ~
1652 is very low while the interfacial tension of the novel composi-tion to PIB is extremely high. ThermLdynamics predicts that when materials are liquid and are physically free to move about, they will occu~y the lowest energy config~ration Hen oe , i~ SURL ~
1~52 or other SU~L ~ adhesives are employed in the clinical thermc-meter of FIGURES 12-13 with the novel compositions, the lowest energy oonfigura~on is with the ncvel composition drawn against the SURL ~ , and particul æ ly in the region ~here the SUR~ ~ for~s a narrow capillary wi~h the circumference of the alun~nu~ base (44 -1~33810 of FIGURE 13). With PIB adhesives (by BASF, B-15 ~ it is believed that the novel composition is "repelled" by the surface of the adhe-sive (compared to the alumunum base 44) and instead remains spread against the aluminum with which it has a lower interfacial tension.
Furtherm~re, we have found, unexpectedly, that a bibulous material raises the resolidification temperature of the composi-tions of matter (when in a supercooled state~ to a level higher th~n heretofore experien oe d by solid inorganic nucleating agents.
m erefore, by employing ~ or other suitable bibulous materials, an easily regeneratable thermometer (placing the fired thermameter into a refrigerator at about 40F) of a design substantially simil æ to that shown in FIGU~ES 12-13 can be produced. Otherwise, without the use of the bibulous material, temperatures of -40F to -50F are needed to regenerate a fired thernometer. In this manner, thermometers which have "fired" because of excessive heat in tran-sit or storage ~ay be salvaged easily. BibuloNs materials have been used for the determinaticn of glucose and other substan oe s in liquids; United States Patent 4,059,407.
A further advantage of a bibulous ff t is that the bibulum may be used as a carrier for the inclusion of other hard-to-handle materials such as finely pcwdered insoluble nucleating agents.
Thus, i~ talc is e~ployed as a nucleating agent, it may be first loaded onto the bibulum. Such loading can ke acccmplished ~y pass-ing the web through a dispersion of powder and then by evaporating the solvent. Bibulum material can ~e punched in predetermined oDn~
figuration; the punched bibulum can carry predetermined quantity of the nucleating agent to each and eve~y cavity o~ the thermcmeter _~9_ ~,, pocket(s) or other devi oe employing the novel compositions of matter.
Many items of commerce are subject to degradation or destruction by exoe ssively high temperatures, and as recited before, single-use clinical thermcmeters employing the novel compositions of matter of the instant invention are no exception, especially when a nucleating agent is not employed. Exposure of the clinical thermometers abo~e 96F will cause them to "fire", i.e. to record the exposed temperature and become unusable for further temçerature measurement unless an effective method of recrystallization is employed. If no nucleating agent is employed in a cooposition hav-ing ocNB/oeNB as a solvent, means to lower the temperature of the thermameter from -40 & to -50C will be ne oe ssary, which means is sometimes unavailable to the ll~Pr. qypically, products such as clinical thermLmeters are shielde~ from adverse effects of high shipping and storage te~peratures through heavy insulated shipping cartons containing ice (solid water) as refrigerant - a method which has obvious shortoom m gs.
We have discovered, unexpectedly, that protective packag-ing of heat labile goods can be greatly improved by using oe rtain salts, notably scdium sulfate decahydrate, e g. Glauber's salt, as the refrigerant. Glauber's salt acts as a refrigerant as follcws:
the melting point of Glauber's salt is 32.28 & . The TEMPA-~EADY-S~IP~M begins to indicate temperature at 35.2 &. When qEMPA- ~ ~EA~Y-ST~IP thermometers are pac~aged with Glauber's salt and expose~ to high temperatures, for example 50 &, the temperature ~f the pac~age rises unti~ it reac~es 32.28C. At that temperature the Glauber's salt ~egins to melt and absorb heat (energy) at a capacity of about 54 cal/gra~. m e ~-- ~

~acka~e ~ill remain at a~out 3~C until the salt has been consumeci.
Ice, on the other hand, can only De loa~ed into the oacka~e imme~iately before anticipated thermal abuse since it will melt an~ lose its refrigeration capacities in storage at normal .em~erature (i.e. appro~in:ately 70F).
A curther advantage of t~e invention over com-.nonly uaed r~frigeration relates to its abllity to preserve the yOods ~or extended ~erio~s o ti~e. Irhe rate oc ther~al conauctivity throu~h any material, including insulation, is directly ~ropGr-tlonal to the difference in temoerature on eit;rler siae of tre Mat~rial or insulation. ~hen ice is used as refrigerant in an exposure to 100CF the difrerence in te.~Derature is o8F since ice ~erforms .~o.st of its refrigeration during melting at 32F. ~ith ~lauber's _31t, however, th~ difrerence in ternperature is only 10.4F (100F-~9.6F). Thus, the ra~e of heat flo-Y~ YJitr.
~lauDerls salt is less than l/o the rate of heat clow with ice as refri~er-nt. The result of tne aicferences in tern~erature and heat of rusion oetween Glauber's ~alt and ice is that one ?ound of Glau~er's salt ~!Jil~ preserve ~he goods in t.~e pac'sage as well as 4.~ ~ounds of ice during ex2osure to lG~~.
For the application of preserving sin~le-use ther.~ometers sodiu~ sulfate decahydrate or calcium chloride hexahydrate ~re ~ell suited, otne~ thermally l~bile soods or a~pl cations may re~uire alternate saits or co.~1~0unds. The refri~erant should be selected as or,e having a meltin~ ~oint 3-5C below the labile tem~erature. Tne amGunt of refriyerant is dependent u~on the thickness oi: insulation and surface area/volume ratio of the pac~age, tne amount o~ ti~.e and the 3~ temperature or which tne ~oods n~ed ?rotection. An exa~?1e o~

L~

~133810 another usahie salt is sodium metaphospate trinydrate (e.g.
Knorre's salt) which melts at 53C and can be used to protect things la~ile at 57~C. There are many more examples of usable inor~anic compounds (e.g. Potassium iron (III) sulfate .24H20, MP = 28C) but organic com~oun~s ~ay be substituted. Thus, Glauber's salt may be re~laced with o-chloronitro~enzene in the a~plication with single-use thermometers.
It is desirable to Dac~age the novel refrigerant as with the classical reErigerant, ice. The novel refri~erant may be sealed in a flexible polypropylene plastic bag or closed in a rigid container. The purpose of such a pac~age is to ?r_,ent contamination and moisture exchange to take place as well as to prevent the molten refrigerant from contaminating the goods being thermally shielded.
While the use of the above "novel refrigerants" has many advantages, there are some ~inor ~roblems. First, unless cast into a solid block, the novel refrigerants are generally formless powders which can be diIficult to handle. Further, upon melting, they form liquids which are Free to flo-~ into new ~eo~etrics ~ithin their container, if flexible.
We have found that these novel pro'~lems can be overcome by absor~in~ t~e molten novel refrigerant into a ~ibulous material such as open cell foam, ~aper, natural or synthetic sponge and the like, sealed to exclude contamination and, for hydrated salts, water va~or exchange ~y enclosing the struct~re in a ~lexible ~lastic bag, for example.
The novel refriyerant so ~ac~aged, is easv to handle, retains its shape when the refrigerant is molten and prevents the refrigerant from ~a~giny from its intenc3ed location within the ~ac~age.

,7 ,q 1~3810 An exalnple of SIJC~ a packa~e~ novel refrigerant is so~ium sulfate ~ecanydrat~ a~sorbe~ into a Dlock of open cell F ~ r m ~ d e pnenol-rormaldelly~J~' foam and contained in a 2olyethylene bag closed by heat sealin~. When placed in an insulated container, the novel r2frigerant bloc~ ~rotects the contents froln ex~osure to hign temoerature in the sa.~e fashion as the unsu~ported ~la~ber's salt.
L~S a preferable examPle of containing dis~osaDle thermorneters as depicted in FIGUR~S 12-13 ~ith the novel compositions of matter (sucn as ~inacyanol iodide/OCiYB-Oa~a) one may shi? and store aoout two thousand thermo.,ieters in a standard cardboard box of outer di.~ensions 9-3/4 inches wide by 13--5/8 inches long by 15-1/2 inches high (top and bottom ~-3/4 inches by 13-5/~ inches; two sides 9-3/4 inches by 15-1/2 inches; two sides 13-5/~ inc~es Dy 15-1/2 inches~, by placing in the 'DOX square pieces (preferably six3 of close cell polyurethane foa~ of 1-1/2 inches thickness adja~ent to tne sides, to.?, and botto.~ of the box and ~lacing the aforementioned ~oly~roDy1ene-wrap~ed squares of souiui-n sulfate aecahydrate (thickness of about 1/2 inch to 1 incn) insi~e the polyurethane foam. Pieces of sucn a container are easy to manuracture ana assemble.
It ~ilust be notea that a ~referred method of individ-ually wrap~iny the thermometer of F~GUR~S 12-13 is ~y wrap~iny them in an envelo~e Ihere 1-1/3 incnes ~iae by 4-ll/16 inches 2~ long) o~ bleached ~aper sealed on the ed~es by a suitable contact aahesive ~nO~,Jn to those in the art. Such envelopes are readily available at a reasonable cost from ~10dern Packagin~ ~nc., ~ount ~3011y, ~ew 3ersey. More eiaborate i~lethods of in(~ividually wrap-~in~ tne tnermometers are available, e.~ .S. Pat ~,&3~

incor~orated-ne~ n, but are not ne~essary i the above ?re-- 9~

cautions are taken foL- shi~in~ an~ storing (using ti~e Glauber's salt, etc., ~hen am~ient temperature is above 96Y and otnerwise preventin~ exposure to t~mperat~res abovP ~6F).
~n one preferred emDo~iment the transparent cover sheet San~ tne heat conducting carrier means or the above FIGURES 1-16 are ~referably conded together hy means of a layer of a Pressure Bsensitive adhesive w'nich entirely or substantially c0.-2sists of polyisobutylene, as sho~n in FI5U~ES 1~-19' ~lore speci~icallv, a temperature~ dicating device 10neat-conducting carrier l~a~ be em~loyed having one or more spac~d re~ions derined therein to determine a li~e number of ored--~er-mined tem~eratures in a predetermined te~erature range, with a li~e numher of different compositions of matter defined therein, contained b~ a transparent cover sheet means in sealiny enga~e-15ment with the carrier, and with a single composition of matter being deposited in each of said regions and being associated tJith a single one oL ~aid ,redeterrnine~ tem~eratures wh~rein tne com~ositiona of ~natter used are tne novel co-~positions of ~natter of this nvention ~nd wher~in tne tran~arent cover sneet means 2~an~ tqe ~2eat-conducting carrier are sealed tv each other by .~eans of an a~hesive ~ayer of a ~ressure-sensitive a~'nesive wnich entirely or substantially consistJ of ~olyi~obutylene.
In a~ition, lr. a similar wa~i polyiso~ut~1ene ~,a~ ~e used as an adr2eJive in any temoerature-indicating device co.~lPrising:
(a) a heat-conducting carrier ;neans ~rovided ~itn one or more cavities at least one of ~"hicn cavities is ille~ with an indicator means an~ a classical comPosition of matter ~Jhicn melts at a ?rede~er-30mined te~n2erature and is con~osed of~ (ni~ture o ,7 ~

li33810 ortno-cnloronitroDenzene and ortho-broJnonitro-benzene, and (b) a transparent cover sheet in sealing engagement with the carrier ~eans overlying each of said cavitles.
~rom tne United States Patent Specification 3,002 ~5, B temperature-indicating devices are known in which use is made of low-tem~erature oonding adhesive, such as an e oxy resin or a pressure-sensitive adhesive substance havin~ a basis of rea~onS
silicones. ~or various rcason-7 sucn as insufficiQnt resistance to the chemicals used, release of low-molecular constituents, a f~ec~
which detrimentally affcct3 durability t2mperature indication and reproducibility, and the fact that they are insufficiently imoervious to chemicals, said adhesives have ~een found to be unsuitable.
It is preferred that t;le ~olyisobutylene used as 2ressure-sensitive adhesive should have an average molecular weight in the range of 50 000 to 5 000 ~()0, more particularly 150 ûO0 to ~ ~00 00~.
A very favora~le com~ination of a~hesive strengtl~ and resistance to the cne.~nicals ~resent in the cavities is obtainea l~ ~ne adhesive layer consists of a ~ixture o 3~-70% by ~eight of ?olyisobutvlene havins an average r~olecular ~eight of 70 000 to lOO V~Q and 70-30% by weight o~ ~lyisobutylene having an average molecular weight o~ l,O~O,OO'j to 3,500,000. ~t is ~referred that sai~ mixture shoul~ consist of practically eaual parts by wei~ht of the res~ective cons~it~ents.
Ihe adhesion bet~een carrier layer and ~2ressure-sensitive a~hesive can still ~e ~urther im~roved in various wavs.
3~ Such impr~vement is o~tained if t~.e Carrier layer consists OL-~ ~5 ~3~8tO

alulninum foil having an etcnea surface. Impro-ve,~ent of the adhesive strength can also ~e realize~ by making use of a carrier layer of aluminum foil coated with a polyisobutylene surface layer ap21ied from a sol~tion in an organic solvent~
The adhesion between carrier layer and pressure-sensitive adhesive oan still be further im~roved in various ways.
Such imProvement is o~tained if the carrier layer consists of aluminum foil h2ving an etch2d surface. I,~provement of the adhesive strength can also ~e realized by ~.aking use of a carrier layer of aluminurn foil coated witn a ~olyisobutylene surface layer ap~lied from a solution in an or~anic solvent.
~s exarnple of a suitable solvent hexane may be mentioned. It is preferred that such a s~rface layer should have a thickness of 2-10 microrneters. It is preferred that the polyiso~utylene used for such a surface layer should have an average molecular wei~ht in tne range of 2,000,000 to 3,500,0G0.
The use of a carrier layer having a surface thus modified rnakes it po~sible to obtain good a~hesive strengtn also when erlployiny polyisooutylene ~.avin~ a relatively nig~ molecular 2~ weight. A carrier layer coated with a surface layer o polyiso-but~ylene is therefore ?referably used i the carrier layer is bo~ded to the trans~arent cover layer ~y rne~ns of a ~ressure-sensitive adnesive layer of polyisooutyl~ne having an average molecular weight in the range of 2,000,~00 to 3,500,00~.
The ~ressure-sensitive adhesive to ~e used accorQing to the invention can be a?~lid as thin layer to one s1de of tae film rnaterial used ~s trans~arent cover layer, for instance ~olyester fil~. This may De done from a solution in, or instance, hexane or fro,n t'ne melt. The thicl~ness of the adnesive la~er thus ;~

formed ia as a rule 10-100 lnicro~eters and prererably 20-60 micrometers.
The pol~Iisobutylene-coated side of the trans~arent cover layer is brought into contact with the carrier layer on the side ~7here the cavit~es to he closed off are positioned, and bonded to it under pressure ~7ithout the temperature being increased. The ~onding pressure applied is generally in the ran~e of 1 to 50 kg/cm2.
Various types of polyisobutylene are suita~le to be used for this pur~ose. It i5 2referred that tne average molec-ular weight of the ~olyisobutylene should be in the ranj- of 50,000 to 5,V00,000. By average molecular weignt is to be under-stood tne viscosity average molecular weignt. This is calculated from the intrinsic viscosity, which in its turn is determined lS frorn the rate of flow of a solution havin~ a concentration of 1 g/dl in isoc~ane through the ca~illary of an Ubbeloh~e viscometer a~ a temperature of 20C.
For the calculation, the following forMula is used:

En] = nsp/C = 3.06 x 10-4 y ~1 0 65 2~ v 1 + 0.31 n wnere:
~n} = intrinsic viscosity nSp= t/t - 1 = s~ecific viscosity t = rate of flGw of the solution, correcte~ in accordance ~itn ~agen,~acn-Couette to = rate of flow of the solvent, corrected in accordance with ~ayenbach-Coliette c = concentration of t~le solution in ~/dl ~v = avera~e s~,olecular wei~ht ,~ I

rhe ?olyisobutylene used has a good resistance to the chemical SuDStances present in the cavities, does not influence their melting point, and hardly absorbs chemical substances and does not allo~ the passage thereof.
SIn FIGU~ 17 the cover layer 66 is bonded to the carrier layer 67 by an adhesive layer 68. This adhesive layer 68 consists of a ~ressure-sensitive adhesive ~hi~h is entirely or substantially of polyisobutylene and can be aoplied to the carrier layer 67 without the ~elt tem~erature of the tenperature-10sensitive composition 69 in the cavities ~ein~ exceeded.
In FIGUR~ 18 tne carrier layer h7 is stlll pro ~ded with a sur~ace layer 70 of polyisobutylene. The la~ter serves to improve the adhesion between the pressure-sensitive ~olyiso--~ff~ of the adhesive layer ~8, consisting essentially of 15~olyisobutylene, and the material of the carrier layer o7. The surface layer 70 is generally obtained by providing the carrier layer material with a tnin coat of a solution of ~olyisobltylene in an organic solvent, e.g. hexane, and subsequently allowir,g the solvent to ~vaporate. The temperature-sensitive co~osition o9 20in FI~1]RES 17 and 13 is prefera~ly selected ~-ro~ the novel compositions OL matter of tnis invention. ~,~hen the temperature-sensitive composition 69 is a classical co~POSition o~ ~atter it is used together with an indicator means ~not sho~n in ~IGUl~iS 17 and 153), ~nich nay be any indicator means kno~n in the art, e.~.
25a layer of paint located at the bottol.~ of the cavity, a dye dispersed in the temperature-sensitive com~osition or an inai-cator layer of absoribent material located above the temDerature-sensitive co~position.
Alt'nougn the invention nas been descri~ed ~ich reifer-30ence to specific em~odiments above, r.umerous variations and ~ q~

-,~odi~ications will becoine evident to tnose skille~ in tne art, without deDarting from the scope and spirit of the invention as B described above~definea in the appended claims, and as shown in tne following examples:
. . 5 EXAi~PL~ 1 About 1.25 grams of pinacyanol iodide ~as mixed and dis.solved in a 100 ml beaker by mechanical stirring means in a solvent system of 24.99g of a mixture of ortho-bromonitrobenzene 1~ and ortho-chloronitro3enzene (75% of the solvent systeln was com?osed of ortno-bromonitro- ~en~ene and 25~ ~Ja~ con~osed of ortho-chloronitro~enzene). Ttle 0.05% pinacyanol iodide content could be deter~ined accurately by means of a i~lettler~ balance ~herein 0.01259 of DinaCyanOl iodide was placed on top of paper lS wei~hin~ ~.2426g to obtain tlle objective of a total ~.2551g. The pinacyanol iodide was mixed in the beaker with the 24.99g of ort~o-bromonitrobenzene: ortho- chloronitrov~nzene solution at from about 4j~C to a~out 6~C to o~tain a uniform novel co.npo-sition of matter. This liquid .Jas allo~ed to cool, and at about 3~.V~C -~ith artificial nucleation the liquid solution c~anged from a blu2 color to a solid solution ,Jhicn ,Jas lig.ht brown rose.
This example demonstrates that a novel co.,(~osition of matter employing a Grou? III com?ound Ot pinacyanol iodide without the presence o 2 Group I or Group II compound may alone change color in a transition from a liquid to a solid state. It ~as found tnat upon heatin-~ up the solid solution back into the li~uid phase, that tne solution turned ~ro~: a li<Jht bro-~n back to its or~-~inal blue form.

~ ~q ~33$1~ . -EXAi~5~LE 2 In tne same manner as ~xample 1, a lO.Og solu~ion of 0.05~ chloro~henol blue ~a Grou~ I and Group III material) and ethyl red (a Grou~ II material), wherein the chlorophenol hlue weighed 0.00375g and the ethyl r~d weighe~ 0.00125g, were added to a liquid solution of ortno-brorr~onitro~er~zene:ortho-clnloro-nitrobenzene of 9.995g wherein the ra.io of the ortho-bromo-nitrobenzene to the ortho-chloronitrooenzene in the 9~995g solvent system was 3:1 by weight. The 0.00375~ of chlorophenol l blue and 0.00125g of ethyl red were added simultaneously to the ,~ ortho-bromonitro~enzene: ortho-chloronitrobenzene solution at il from about 40C to about 60C. The li~uid solution had a red ., ~L~
~lor that ch~nged ~37.5C to a y~llo~-orange olor in the solid state immediately at the change in state. Upon heating, the yellow soli~ solution turned at 3~.04C Dack to its original red color. This exam~le demonstrates that a combination of a Grou~ I co~pound and a Grou~ II compound ~or a novel co~position of matter in a ~uit~ble weakly polar aromatic solvent syst~ will c~ange color u~on a corres~onding chan~e frol~ a liquid to a solid 2() state or vice versa.

~X~i~3P~E 3 In the same manner as ~xample 1, a 0.05% so7ution of ethyl red (a Group II compound) consisting of 0.005a o~ ethyl red ~ was ~ixe~ at from a~out 40C to a~o~t ~C in a solution composed of 75~s ortho-bromonitrobenzene and 25o ortno-chloronitrobenzene wherein the ortho-brornonitrobenzen2 and ortho-chlo~onitro~enzene weighed a total of 9.9g~. No Gro~? I ~at~rial was added to the ~ instant solution. The li~uid at 4~C wa ?urple in col~r ~ut u~on solidifyin-j at 3~.04~C with the aid o arti~icial nu~leat-ion remained in its original ~rple form for several c~ay~. Likewlse B ~oo - 1133~3~0 u?on re'neating, the purple solid solution turned back into a ~urple liauid ~t 38.04C. This example demonstrates that a Group II materiai in and of itself without the presence of a Group III
material will not undergo the desired color change without a Group I material with the corresponding change in phases, and therefore, a Grou? II material alone will not suffice for one of our novel compositions of matter. (One notes that the phenomena observed herein is inconsistent with the compl~ment or the theory pro~osed by R. B. McKay and P. J. ~illson, "Metachromatic ~ehavior of 3yes in Solution", 61 TRAE~SAC11IO~S OF FARADA-~ SOCIETY
1800 (1965).

In this exam21e, in the sa~e manner as Exâ~ple 1, a solution of 0.~5~ bro)~c~hlorophenol blue and pinacyanol chloride ~a Group ~2 ml~t~re.
II/Group III compound)~where the ratio o~ broin~chloro-phenol blue to pinacyanol chloride was 5:1 (0.0042g ~romochloro-phenol blue was emPloyed to 0.0008g ~inacyanol chlori~3e with 9.9995g of a solvent solution com~osed of 75~ ortho-bromonitro-~enzene ana ?5 ortho-chloronitrobenzene). 7~ain, by the use of a .~lettler'~
balance, the weight of the bromochloropnenol blue and ~inacyano~
chloride could be accurately determined after ~lacin~ these ~aterials on pieces of pa~er weighirlg 0.2517g and ~.2457g, res~ectively. The 0.(3042g ~romochloropneno1 blue and 0.(30~38g pinacyanol chloride was added at from 40C to 60~C to the ortho-~romonitro~enzene:ortho-chloronitrobenzene solution in a 1(30 ml beaker and stirred `~y mechanical stirring means. The qreenish-blue li~uid solution was a1lowed to cool fro~ 40C to it~
solidi.ication point at about 38.04C, wnereby it change-3 with ~0 the aid of artificial nl~cleation instantlv to a yellowish-green ~ .

solid fonm. This example demonstrates clearly that another Group I
compcund, bromcchlorophenol blue, is suitable for use in the making of a ncvel com~osition of matter when taken into a solvent mixture with a Group II/Group III compound, pinacyanol chloride, and will change color upon a corresponding change in state.

In the same manner as the pre oe ding Examples, a lOg solu-tion of 0.05% by weight bromochlorophenol blue (0.005g by MettlerTM
balan oe) was added to a 25:75 weight ratio ortho-chloronitrobenzene:
ortho-bromonitrobenzene of 9.995g, at a temperature from about 40 &
to about 60C. The liquid solution at 40 & was yellow, and was allowed to oool slowly to its solidification point at about 38.04 & .
Upon solidification, the material remained yellow in its solid state. Upan reheating, there was no change in oolor visible to the naked eye. This example demonstrates that a Group I co~pound taken alone without a Group II or III compound will not bring forth the desired color change results at the change in phases from a liquid state to a solid state.

A solution of abcut 0.05 mass % of chlorophenol red in dibenzofurane was prepared by adding the chlorophenol red to liquid dibenzofurane at 95 & . After dissolution of the chlorophenol red a yellow liquid was obtained. After this liquid had keen coDlRd to about 87 &, it began to solidify and when the solidification was complete a red colored solid was obtained. Upon heating the red solid, it changed back into a yellow liquid. This example demon-strates the use of a group I and group III member dissolved ~33~10 ir~ a heterocyclic solvent to obt~in a color change while p~ssing from the liquid state to the solid state, or conversely.
, EXA~5P~E 7 5 ' In the same manner as ~xample I, a solution o 0.037 n~ss ~ na~nth~lenesulE~nonic aci~ and 0.013 ~ass ~ or ethyl violet was pre~ared in a mixture of ortho ~ nitro~enzene and ortho-, chloronitrobenzene (mass ratio 3:1). Whereas the liquid solution was gre~n, the solid solution obtained by artificial nucleation l, at 38C was yello~. Upon neating the com~osition to its melting point a gre2n li~uia was obtained. This example dernonstrates , that the co~bination of an acid ~7it~ p~ of less than about 2 and , an ~mino-triphenylmetl-a~ dye wil3 chan~e color ~7hile ~A~Sin~
Il from the liquid state to the solid state, or co~ver~ely.
15 ',, XAl~IP.',L~ ~ , This e~air,~ile del,lonstrates the u~e of a colr~bination of a dy~ having a rnolecular structure containing a lactone group and an acic3 having a pK of ~bout ~ to about 12. In the s~ne way as 2~ , described in EY.a~e 1, a compos-tion of matter ~as pr--pare3 by disso3ving 0.05 mass % phenol in a mi~ture of ortho-~ro.~lonitro- ;
c ~ Jo ro n ~ ro b~ n ze ne B~ ben~ene and ortho-chronoitro~cn~cne (mass ratio 3:1~. The liquid ~, solution was yello~J, and turned blue whe;l it had co.npletely 1, solidified at 37.5C ~y artificial nuclea~ion. ~i~on heatin~ the 25 ~' composition it became yello~ ayaisl. Z
, i s ~XA~IPLE 9 This examrSle deals wit~i a dye falling ~>eyond the sco~e ~ of this invention. In the same ~ay c--lS descri~;ed in ~xar,lpie I, a solution was prepared of Fast Blue Salt B in a m xtu~ of ortho-, ~1338~0 bromonitrobenzene and ortho-chloronitrobenzene (mass ratio 3:1).
The color of the liquid was yellow and did not change after complete crystallization of the solvent.

EXAMP~E lO
This exam~le gives dyes tested for their suitability as a Group III member in various solvents at different concentra-r~ ~
~ tions. The results are given in Table ~H~.

lOUnless otherwise indicated, each of the cases 1-117 in the following Table 2 employs a solvent system of 75 weight percent ortho-chloronitro- benzene: 25 weight percent ortho-bromonitrobenzene, with about 0.05 weight percent of indicated Group I, Grou? II, Grou~ III or other organic compounds. The 15solution o~ each case was prepared in a similar manner as ~xample 1.

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l . ., - 1~33810 Example 11 This example gives combinations tested for color change in various solvents and at different combinations. These combi-nations include:
S (a) mixtures of Group III moieties;
(b) mixtures of acids having a pK less than about four and basic dyes or basic indicators;
(c) mixtures of organic acids havin ~ a pK less than about two and acidic dyes or acidic indicators;
(d) mixtures of Group III moieties and organic acidic compounds with a pK less than about 4i (e) mixtures of Group III moieties and basic dyes or basic indicators; and (f) mixtures of a dye having a molecular structure containina a lactone dye and acids.
B The results are given in Table ffl .

-- ~33~10 3 3 . 3 ~:
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r~; ~ O ~ a~
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1:~33810 .~
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--- 1133~:10 Example 13 The ~ollowing Table 5 lists results of various compositions con-trasting quick ~instantaneous) versus slow (using ambient temperature) cool-ing of liquids on color change:

~; .
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c ~ ~ ~ ~ ~ ~
V ~ ; I U~ ~ - h ~ O u~ -' m ~ v~ ~-3~
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8 ~ 3 D ~ ~ O~ ~ ~73 ; 3 o~ ~
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a~ o,~ o_l o,~ o,~ o,~ ~o,~ ,~
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S O O V t~; ~ S., ~t~~ V O C ~ O V~) O O
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!
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ri) o In ~n Ln Ln ~n rn Ln v~ o m o In o Lt`l O n o rn o ~ o ~i ~ v In o o Ln o o Ln o o In o oLn o oIn o o ~n o o I; a~ O fi; ... ... ... ... ... ... ... I
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-,. _ ~33810 Example 14 The following dyes in Table 6 were ra ~ y mixed in the tw~ sol-vents lauric acid and l-hexadecanol and observed for oolor changes:

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These d~es with the exception of those marked totally soluble were Eound to ~e partially soluble in both solvents Therefore any colors recorded were not necessarily the true color of the dye in the solvent in Proportional amounts.
Those dyes that were com~letely insoluble in both solvents were:
1. 2,2' - (4,~'-Bi~henylene)-bis/2-hy-~roxy-4,4'-1norphol/n ;~
di.~ethyl mor~holinuim ~ro~,ide~ (~ast. 9762) enatein (stain) (East. 8594) napJ.th;
10 B 3. ~-~ydrox~-7-(6-sulfo-2-ma~hthi(az~)-5-auinoline-sulfonic ~cid ~isodium Salt (~ast. ~644) The only dye t'~at ,howed a si~nificant color c~an~e was P.ose Bingal (East. C2245~ in Lauric Acid. Dilutions of this solution ~ere made and the followin~ results were observed:
Color Ccm~ound Solvent% Conc. Li~suid Fast Slow Beng4J
~ose Bin~J~lLauric Acid 0.5 red-brown rose rose (East.C2245) 0.05 lt. Deach pink pink ~0 0,OG5 cl-,-ar ~Ihite wnite ` 1133810 ~ o _ _ _ _ ____ ~ ~ ,_ ~ ~

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~1338~0 r ~xample 15 This examDle de~onstrates the use of insolu~le nucle-ating agents in a t~m~erature-indicating device in order to render the com?osition of matter recrystallizable at a S predetermined temperature.
A number of cavities formed in an aluminium carrier layer were filled with a mixture of ortho-bromonitrobenzene and ort~o-cnloronitrobenzene ~mass ratio 3:1), containing 0.025 mass ~ of ?inacyanol iodide to whic-h different amounts of nucleating agen~s had been added The cavities thus filled were provided B T/n witn a heat-sensitive trans?arent Surlyn~1552 film (E.I. DuPont de ;~Jen.ours & ComJany) laminated to a polyester film ~elinex ICI).
After recrystallization of the chemicals at -40C, the indica~in~ levice was heated for on~ hour at about 55~C (imita-tion of storage at hig.~ tem~er~tures).
The indicating device ~as cooled at -5C and the percenta~;? of cavities in which tne mixture has recrystallized was deter~ined.
In a second series the indicatin~ device containing recr~stallized mixtures~ was heated in a water bath For 45 secon~s -iust aoove the melting Point of the che~icals (abt. 38C) in order to i.~itate a measurement of the temperature of tne human body.
Then the indicating device "as cooled to room te~nner-ature an~ the ~e-rcentag~ of cavities in which the chemicals ~ -crystal7 i7ec'~ as deter~rlined.
For com?arison cavities ~ere filled with t;he sa.ne 03;~/O('~i~J l"ixture containi].g 0.025 mass ~i pinac~anol iodide hut without nucleatin~ agen~s.
k~ - /9/_ -' 1133810 The results are presented in Table 7.
It appears that whereas the ~;tion of a nucleating agent favor-ably influen oe s the recrystallization at -6 &, it d oe s not affect the under-oooling at r~om ~emperature.
Example 16 m is Example dem~nstrates the use of a pretreated aluminium carrier layex for rendering the oomposition of matter recrystallizable at a predeter-m ed temperature. An aluminium carrier layer provided with cavities was passivated by cleaning the aluminium with acetone, pickling in a 2~ solution of sodium hydroxide, subsequent pickling in 10% nitric acid and immersion in boiling water for 5 minutes. m e cavities were filled with a mixture of ortho-chloronitrobenzene and ortho-brcmDnitrobenzene (m~ss ratio 1:3) oontain-ing 0.025 mass % of pinacyanol iodide. The filled cavities were further treated as described in Example IX. For oomparison, cavities formed in un-treated aluminium were filled with the above-mentioned ~lxture and treated in a similar way.
The results are given in Table 7A.
Table 7A
~ Recrystallized after cooling to Treatment room tençerature for -6C (ocoling time) 15 min (after heating after heating to to 38qC~ 55C

none 2 30 (10 min) 46 ~60 m~n) passivaticn about ~ 100 (30 min~

It appears that the passivation of the alum~nium carrier layer favorably influen oe s recrystallization at -6 C.
~xample 17 A transparent polyester film (Melinex , supplied by ICI pro~vided with an adhesive layer of polyisbbutylene is pressed together with an --lg2--a aluminium layer foil. As a measure of the adhesive strength is taken, the foroe in g/cm which is requlred to peel the polyester film off the aluminium foil at a rate of 30 cm/minute. This foroe should be at least about 150 g/cm.
The influence on the magnitude of the peeling force has been investigated of the nature of the aluninium surface (rough, sm~oth, etched), the type of polyisobutylene (m~lecular weight, mixture) and bonding pressure (5 and 50 kg/cm ).
The polyisobutylene types used have been obtained from BASF, Ludwigshafen, W. Germany and are marketed und2r the trade name Oppanol. m e results are listed in Table 9.
Table 9 Peeling force in g/cm . _ .
Pretrea~ ~ of PIBl PIB2 PIB3 PIB4 PIB5 aluninium foil A B A B A B A B A B

RDugh surface l)550 600 400 600 100 150 20 20 400 450 SmDoth surface 600 600 600 600 150 200 100 130 400 450 etched:
Rough surfa oe 2) 600 600 600 600 100 240 40 120 - -SmDoth surface 600 600 600 600 250 330 200 300 coated:
~Dugh surface 3)400 400 400 400 400 400 400 400 Smooth surfaoe 300 300 300 300 300 300 300 300 - -A = used bondinq for oe 5 kg/cm2 B = used ~anding for oe 50 kg/om2 .~.

~133810 r 1) rouqh sur~ace: rr.echanic~lly rou~n~netl;
2) etched: ~retreatment witn a solution of sodium metasilicatt~ in water;
3) coac~d: surface layer Oppanol B 150, thicknt-ss Su.
S
PIBl: Op~anol B15, average mol. wt. 77-92.103;
PIB2~ anol D30~1~ average mol. ~t. about 140.103î
PIB3: O~anol ~50, average mol. wt. 34G-4~0.103;
PIB4: O~?anol P,150, average mol. -~t. 2.3-3.3.10~;
10 PI~5: ini~ture of O?panol B15/~150 (1 : 1).

- Exam~le 1~
Of Dol~isohutylene the perma~ility is investigated for the cnemicals used in the temperature indicating device. Polyiso-butylene films are formed from a solution disPosed on Paper. 'l'he filr..s thu~ obtained are made into bags of ar~out 50 c~ which are filled with 2.5 grams of a mi~ture of ortho-chloronitrobenzene - and ortho-bromonitrobenzerle (weight ratio 62 : 3~j and sealed.
.~fter beiny ~,Jeighed, the ~ags are stored at 32~C in a roo~ with air circulation and after differf-nt periods ~'ne loss of weic~'nt is deterr~ned.
The results are su~marized in Table 10.

Ta~le 10 Sa~(~le Loss of ~ei~h~ in rr.~/h/~/c.,~2 PI~l 0.12 PI~2 f).l4 ~-~ PI~3 0.17 Slrl~n 1552 ~control) 1.~, - ~33810 The d~signation~ 2I~l, PIa2 and PIB3 have the same meaninq as in ~xample XV For comnarison, mention is ~ade of the r2sult obtained :~ith a film (thickness about 45 ~ ) of an iono-~;2 ' 7'~
V meric adhesive Surlyn 1652. It apDears that the volyisobutylene sa~Dles are far less ~er~eable than the iono~eric adnesive.
~xamDle 19 Cavities for~.ed in an aluminium carrier layer are fille~ with mix~ures of ortho-chloronitrobenzene and ortho-~romonitr~benzene and sealed ~ith a cover l~yer of polyester film provided with a polyisobutylene adhesive layer. The test objects th-~s obtained are stored at 20C and 3~C and examined un~er a stereo micro~coPe to establisn whether the chemicals dissolve in the adhesiv~ layer, disanPear from their cavities or become ~ id.
~.~ser~ations ~ere taken for 40 days. The results are given in Tahle 11.
~able 11 Sam~le Observations PIBl After a few days viscous de~Grr~ation o the ql ur- layer occurs at 20C.

~o leaking away or diss~lving of the chemicals after 40 days at 32C.
PIB2 ditto.

PIB3 After a few days sli~3~t viscous defortr.ation of tne po1~iso~utyle.ne occurs at 2-3C. At the end of the observation period so~le le~king a,~ay of cnemicals as a resuit of the ~olyiso~u~ylene beco~nin~ detacned from t he al um i n i um .

PI~4 ~fter 40 days at 32C no fiscous deforrtlation occurs.
~o leakinq away or ~issolvinq o chcmicals in thsse ol~ces where tne adhesion bet~een alu,~inium and rjoly-s~utylene has heen maintained. Ir. a few ~laces the ~olyiaonut~Jlene la~er ha5 ;~econe dctached from the alu,~inium and cnemicals ha~Je leaked away there.

_ / 7~

381~
r Fro~ this table it a~pears that the chemlcals neither leak away nor dissolve, ~rovided that the adhesion to the aluminiu;n foil is kept up High mol2cular ~ei~ht polyisobutylene (PI~4) is the S least liable to viscous deformation.
~xamDle 20 -In this example the reproduci~ility of the tem~erature indication is demonstrated. A number of cavities formed in an aluminium carrier layer are filled witn a series of mixtures of ortno-chloronitrobenzene, ortho-bromoitrobenzene and 0.1~ by weight of orasol blue 3L~ (solvent blue 49), whose Ine :inq temperatures ?rogressively increase by 0.1C. The cavities thus filled are covered with Whatman chromatograDhy paper No. 1 and rn1 subse~uently sealed with a polyester film (i`'~elinex) provided with a ~ressure-sensitive adhesive layer of polyisobutylene~ The ~olyisobutylene used is a mixture of equal ~arts of O~anol B15 (average ~olecular weight 77,~0G - 92,000) and O~anol B100 (avera~e molecular weight 1.08 ~ 1.46 x 106). The test o~jects arl stored ~t 23~C and after 3, 7 and lO ~eeks, respectively, ~laced in a water bath of a ~articular tem~erature to ~,easure tne tem~erature at ~hich discoloration of the indicator layer taices place.
The results o~taine~ a5 dvera~e values of the 4 tzmpe~ature indicatin~ devices are list--d ir. T~ble 12 _able ~2 Te~m~erat U re d t ~Jhich discolor tion oc-ur~ (~C) t~fter 0 ~7Peks 36.4() 3 J~ 3O.~5 7 ~ee'-s 36.48 ~ P~S 36.50 ,o~

~1338~0 r It a?pears that the temperature indication as a ~;n\ .
B function of-hm~ does not or hardly undergo any change.

~xamDle 21 (com~arative) A numb2r of known adhesives ~ith which an adhesive la~er car be for~ed at room temperatur~ are exanined in the way described in Example XIX. The aluminium foil used has previously been etched. ~ro~n tne results sum~arized in Table 13 it appears l~ that of the adhesiv2s examined, wr3ich all fall beyond the scope of the ~resent invention, none are suitable to be used for the ~resent purDose envisaged.

-~ ~9~

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~3810 f Su~pliers of dyes used irl our invention:
~astman Xodak (E.K.) Rochester, ~ew York acridine yellow .Azure Ar~, B'~ and C'~, 4,4'bis(2-amino-1-naphthyl-azo) -2,2'-stilbene disulfonic acid, 4,4'-bis(4-amino-1-naphthyl-azo) -2 2'-stilbene disulfonic acid, quinaldine red, Chlorasol alack E'~, 4,5'-di~r~mofluorescein, 1,1-diethyl-2,2'-cyanine iodide, 5-(p-dimet'n~laminohenzylidine) rhodamine, p-(p-dimethy-ben~olc ac;C( lamino~ilenylazo)-bcnLnoi-e aci~sodium salt, 4-(4-di~ethylamino-l-na?hthylazo)-3-~,ethoxybenzene-sulfonic acid, 2-(~-di~ethyl-a~inostyryl)-l-ethyl-~yrioiiniu~ ioaide, 4-lp-ethoxy~nenylazo)-bis- phenylenediamine monohydrochloride, Eth~yl Eosin'~, Gallein'~, Methylene Violet'~, Na~hthol ~'~llow S'~, liile Blue A'~ -l~erck 6100 ~arnstadt, W Germany -acridine Gran~e, Alizarine Yellow GG'~, Aiizarine Yellow R'~, alizarine sulfonic acid sodium salt, alkali ~lue, amaranth, auramine, aurintricar~oxylic acid ammoniu~ salt, ~zarcar.~nine B'~, benzyl orange, 3riliiant Cre~yl Blue'~, Calcor.'~, chloro~henol red, Diamine Green B'~, fast yeliow, Eriochrome Cyanine P~ vans Blue~ hloxine, fuchsin, fucnsin ~IP,'~, yeilo~ orange S'~, cresol red, curcumin, methyl green, rnet'n~l red so~ium salt, murexide, Oran~e GG~, Patent ~lue V~, Poncea~ 6R, R'noda~,ine B'~, Rhodamine 6G~, safranin, Salicyl 'i'~llo~ , T~,io~lavir.e ~C~3~, thi~nin, Try~an Bl ue ~

;~atheson, Cole~.an & P,ell ~:.C.& B.) 3O~ ~5, E. Ruthfrfor~, ,i. J.

acridine red, Alizarine Bl ue Bl ck B'', Aniline YellcJw'~, ~nthra~1uinone 'Jiolet ~ , Benzo Fas' Pi.-.~. 2 BL~, Benzi~?ururin 4B'~, ~u1noline yellow (s?irit soluDlf-), Chroz"o~.~n rellor"
Croceln .Scarlet iOi~, 3B'~, fast ~ellow, Fd',t Green G'', Fa t Grecr r ~CE"~, Erichrome Black A'~, Frythro5in Yellowish Blend'~, etnyl-violet, methyl violet l~ase, '~a~hthalene Green V~, Oil Red EGN~, Patent Blue'~, ~onceau G, ~, 2R~, Ponceau 3R'~, prussian blue, resorsin brown, Victoria Blue R~

ICI~ - K&K 121 Express St , Plainview, New York acridlavine, Alizarine ~rilliant Blue BS'~, alizarine viridin, ameth~st violet, Bindschedler's Green~, Capri Blue'~, celestine ~lue, china yellow, ciba blue, Coricr,ospni.~e O~, Cyanosin B~, diamond black, Eriochrome Blue SE'~, 4-phenylazo-1-naphthylamine, phenylene blue, gallamine blue, Gallocyanine'~, induline~ (alcohol or wa'L~r soluble), Iris Blue, magdala red, neutral red (io~i~e), neutral violet, new green, Oil ~lue N~, proflavine, resazurin, rho~uline violet, rivanol, solway ~urole, Thioindigo Red'~, Viola~ine 3B", Acid Aliz~rine Llue BB~

Fluka, C~-g470 Buchs, Switzerland allzarlne, aurankia, azo~hloxine, Azocar~ine g'~, ~is~.arck brown 5'~, Bismarck Brown P~'~, brilliar.t green, ~uinalizarin, quinoline y~llow, Chromazurol S', Chro~otro?e 2~, Chrysoidine ~
Chrysoidine R'~, dichlorofluorescein, Fa.s~ Vi~let Salt, osin Yellowish, ~osin Scarlet, ~riochrome ~lue Black 3'~, Eriochrome 2ed B'~ 'rythrosin Extra ~luish~, Indigo S~Jnthetic'~, induline (~ater soluble), ~ight Green SF yellowi.,'n'~, ~ethylene green, .~a~hthol Blue Black B'~, 2-nitroso-1-r,apt.thol, 1-nitroso-2-naphthol, Orange 1~, Oran~e II'~, Orange '~'~, ?arauchsine, Ponceau BS'~, ~onceau S'~, Pyronin G, qu~rcetin dih~ rat*, Scarle~ R'~, Si~A~lS, Sudan III'~, Thiazine ~ed '~)~, Fat ~lack, '~ictoria ~lue ~
~iater biue, acld fucr.sin, ~ast .Red ',a~t -~C an~ and 3GL'~ ~ F!ast Blue Salt B~ and ~, Fast Garnet Salt GaC'~

~opkins ~ ~,Jilliams (H&'~3 St. Cro~s Street, London, England Ali~arine Blue S , Alizarin~ Cyanine 2R'~, alkanin, Anthracene Bl~e 2X~, anthr?~urpurin, brazilin~ Chromotrope 2R'~, purpurin, rosolic acid Carl Roth, Postfach ~109~0, D-7500 Karlsrube, W. Germany auercltrin dih~drate BaXer, Postbus 1, Deventer, Netherlands Alizarin ~ed S~, ~lkali ~lue 6B~, bromo~henol hlue, ~romocresol green, bromocresol pur~le, Eriochrome Black T'~, ~nenosaEranin, hematoxyline, indigo carmine, metanil yellow, methylene hlue, ~eth~l oran~e, NaPhthol Green B'~, neutral red (chloride), Oil Red O~, Orar.~e IV~, Rho~amine B base~, Sudan III'~, Tropaeolin O~, Xylene Cya~.~l FF'~, congo red Y. D. Towers & Co. Liverpaol, England ~,alach~te yr~en ~erva, IieidelDerg, r~. Gerinany Tol~llc!lne ~lue 0~

Sand~,z, Basle, Switzerlanc Artisil Ve!low F-L'~, Carta Yello~ G ld~ o/o'~, Sandorin Bordeaux 2RLl~, .Sandorin ~reen GLS , Sandorin ~ 15t B1,~, Savinyl ~lue B~, Savinyl Blue GLS'~, Savinyl Blue ~S'~, ~Savinyl Green Bl~, Savinyl Red BLS~, Sa~in~ ire P.ed 3 GL5~, Solar l~r-~oise ~lue GGL 16 o/o I. G. rar~en Frank~urt ~ l., ',er.n~ny Rose Bengal'~, tartrazin 11338~0 Hollida~ Fr~nkfurt A.M. Germany .
brllliant ?onceau SR

BASF Ludwigshafen, W Germany Celliton Blue ~xtra~, Celliton Fast Blue FFG~, Sudan red G'~

aayer Leverkusen, ~ Germany Ceres Blue R~, Ceres Yellow 31~, Ceres Orange ~, Ceres Red B'~

Konin~lyke ~har~aceutische Fabriek, Stationswig 39/41, ~eppel, ~1etherlands cochenille Ciba-Geigy, ~asle, S-nitzerland Cro~o~htha; Blue h3R~, Cromophthal Boroleaux RS~, Cro~noPhthol Red A38~, Irgalith Blue GLS~I~, Irgalit~ Blue T~C", Irgalith Green BLN~, Ir~alith Green DBN~, Irgalith Magenta TC73~, Irgalith Xed P4R , Irgalith Pink TYNC~, Irgalith Violet ~IC~, Orasol Blue BL~, Orasol Blue 2GLN~, Orasol ~rilliant Blue GN', Orasol Navy Blue 2RB , Orasol Orange RL~3", Orasol ~ed G~, Solo?nenyl ~rilliant ~ e ~L~, Solo~henyl ~e~ 3BL~, ';olophenyl Turquois ~lue G~L~, Terasil Yellow 2GW'~

American Cyanamid ~ound ~rook, ~1ew Jersey D & C Green 6 Ciba T Basle, S~itzerlan~
~eorlene blue 5G~

~;L G 3 .,."- ~

Amsterdalnsche Clininefabrick (A.C.F.) Amsterdam, Netherlands Dimethyl yellow, crystal violet, methyl violet, Tropaeolin 00 Geig~ Basle, Switzerland Eriochrome Azurol 2.~

British Dru~ Hou;es (~.D.H.) Poole, Dorset, England Erloglaucine, Janus Green, morin, Titanium Yellow ~dward Gurr, 42 U~per Richmond Rd., London, England nigrosine, Sudan Red 7B'~

Sandoz, ~asle, Switzerland Nitro Fast Blue 3GDB'~, Nitro Fast Green GSB-, Fat Red BS'~

Ugine Kuhl~ann, Paris, France ~r~anol ~lue VIFYN~, Organol Yello~ G~, Organol Orange 2R'~

l-liscellaneous brilliant yeliow cryptocyanine*
phloxine ~*
fluourescein sodium salt ~prepared fro,~ Merck fluoresceir) phthal~cyani,.e*

These dyes may be obtained through local supDliers, including Eastman l~odak.

~ Y

1~338~0 ~xam~le 22 In a further oreférred embodiment for the clinical thermometers of the invention, one of tne novel compositions of matter is solidified, ground to a very fine powder, and dispersed in a solution of polymer resin. A prefera~le polymer resin is polyvinyl alcohol.
The polymer resin is selected based upon (1) compat-ability with the novel tem~erature-indicating composition of matter. and (2) by the non-solubility of tn~ temperature sensing comPosition of ~.atter in either tne resin or the solvent for tne resin ~11 components of the novel temperature-indicating compo-sition of ~atter must be insoluble in the resin an~ in the resin and solvent. A pre~erred example is a system which uses poly-viny~ alcohol for the polyrner resins ~"ater as a solvent, and a novel com~sition ~f matter consisting of ortho-brornonitro-benzene/ortno-chloronitrobenzene solid solution with pinacyanol iodide added to the ortho~brom,onitrobenzene and ortho-cnloro-nitrobenzene as hereinbefore descri~ed.
For some ~Pplications it is desirable to have a temp-2V eraturG-indicatiny com~osition which is easily reversihle. Such a reversible com~osition nature can ne obtained by mixin~ a suit-able nucleating ayent preferabl~ talc, I,Jit~i the novel com~?o-sition of matter hefcre solidifying and grinding, or by dispersing ~h~ nucleating agent in t.ne resin solution separately from t;.e novel composition of rnatter particles.
For sorne applications sucn as human clinical tem;?er-toqf~ rt';, ature ta~ing it is desira~le to prevent the p~tcnt's s~liva frorndissolving the polyvinyl alcohGl or other ~ater-soluble polymer resin. ~his can ~e accol,~lished b~ a~?~lyin~ a layer of ?ressure 3U sensitive col-n-?osition packages Gr ;~ ap?ly,ng a s2par2te c~ating of ~sl~,T!er resin ~"hich is not ~ater soluble.

~338~

In any event, the dis~ersed solution is de~osited on an aluminum or plastic backing sheet, which may or may not have pockets, after which the water of the solution is evaporated, leaving a wat~r-solu~le mass of polymer with dispersed novel com~osition of matter particles therewithin.
The advantages of using such a novel cornposition temp-erature sensin~ packag~ ~re as follows: first, the display in a cavity such as Figure 7 is, from above, a full circle of color, but also the ~ispersed solution can ~e ~plied in other geom-e,~ryS
etr~'_ to form messages, words, numbers and the like. Another advantage is that the system is v~ry insusce?tible to nucle~-ion occurrlng in the su?ercooled liquid. This is because within each dot of a ~atrix thermometer there are thousands of small pools of super-cooled liquid, each one se~arate from the other. A
nucieation ev~nt occurring in one pool of che~ical does not qf,e~
^offcc~ tne other Pools of chemical. 'rhus the indication of tem?erature is much more stable and controllable than in those syste~s which utilize one large pool of novel com~osition of matter ~or each point on the matrix of the tnermometer.
In order to utilize these novel col~osition of matter packages to construct the thermomete~r, it is necessary to provide a means for de~ositing very smal7 quantities of tnis ~aterial onto the backing. Suc;~, a system ~ is curre~tly used in the~-mometer machines known to those in the art. Such a system for a~?lying t~e dispersed solution to a te~late having cavities such as backinq 44 of Figure 12 consists of a syringe pump such as a Sage model 371 syringe (Sage instru~ents Inc., ~i~. of Orion Research Cor~., Cam~ridge, ~ass.) pum~,. Tr,e output of the syringe PUI~ is directed througn tu,~ing to a fil} nead as ~reviously descri~ed. Tne Sa~e syringe pumD ou~put rate is adjusted by changing gears motor speed, etc., until the output of the pump equals the uptake of the backing material. In operation, the flow of the material w w ld be CDntinUOUs and at the fill tip a small droplet of material would begin to form at the start of each cycle. The droplet would grow in size, but would be smaller in size than would be required for gravity acting upon the droplet to cause the drops to fall off. As the filling cycle oontinues, the filling head is brought very close to the backing material and the growing droplet touches the backing material, wets the backing material, and the fluid flcws off the pin. Ihe fill cycle continues as the head is raised away fram the backing material and the growth of a new droplet begins to take place on each fill pin.
~xample 23 In yet another preferred emixxlbnent, a polymeric resLn, generally a water-soluble polymeric resin, is applied as a coating film to the top of pockets ~58 of Figure 13) which have already been partially filled with the novel oompositions of matter. The thermL-meter is then allowed to stand until all the solvent has evaporated away. As a further preferred enbcdUrl~lt, a oovering pressure sensi-tive adhesive tape can be applied on top of the coating.
The preferred p~lymer material for casting upon the thermD-meter is a water soluble polymer such as polyvinyl alcohol (99 to 100% hydrolized). The sol~ent for polyvinyl alcohol is water. A
second preferred polymer resin is p~lyiscbutyl~ne cast from a solu-tion of aliphatic hydrocarbon solvent.
The covering pressure sensitive adhesi~e tape can be a polyisobuty~ene c~ated polyester or the like or Perma oe l's J-T~r s-t-' 91~'~ (l'ne ~eL-macel Co New Brunswick, N. J., a division of Johnson St ,Johnson). rhe ~ressure sensitive adhesive tape covering ~rovides additional strength and durability protecting tne coating covering t~le film from disrtl~tion and abrasion. Also S in applications for human clinical thermo~etry, the covering layer of pr2ssure sensitive adhesive ta~e prevents the water soluble resins such as polyvinyl alcohol~ frorn dissolving in the ~atient's saliva or in the ~ater used in test bath apparatus.
It has also been founa that such a tnermometer has vastly improved regenerative ~roperties t"hen a nucleating agent for the no-~el com?osition of matter is added to tne soiut~ n of coating re~sin. Thus, then the novel composition of matter is ~;nqrya n o ¦
e~x~ iodide dissolved in ortho-brornonitrobenzene:orthQ-chloronitrobenzene solid solutions, the nucleating agent talc (~hitta~er, Clark & Daniels, South ~lainfield, N. J. ~g9 - magnesium silicate) is added to the solution of the coating resin hefore a~plication to the thermometer. The tnermometers made i~
thls fashion ~lill sho~l colnplete recrystallization t~ithin 18 hours at 0C 'rhermometers constructed as ~bo~e hut withoi~t addition of talc -~ill haJe only about 25~ of the ?oc~ets recrystallized within 18 hours at 0C.

r~ ~

s f _ ~xamplc~ 24 r The tollowing Table gives further results o~
poss 1ble ~;rou~ 11 I com~?ounds:

~ c C a) ~ 0 3 C a) ~ C a o -~ ~ o 3 ~
Q 5 a) D ~t OCl ~ aJ ~ aJ ::1 o ~ n ~ ~
o ~c ~ s~ s ~ n ~ s ~1 ~ n - ~ ~ c c ~ o c ~ o ~ ~ ~ l ~ ~
3 Q. ~ ~. a~ ~ 3 S ~ Y ~
u~ ~Q' ~' Ch ~,,, SJ ~ ~ D ~1 ~ ~ 54 31 0 ~:) 9 C1J ~I D

a C
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C ~1 5 ~ C S~ 0 3 5 ~1 :J C
'~~ ~~ 5 Q~ n ~ o ~ .~ C
h ~ ~ ~ a) I _ Sl 9 D
O O ~S ~ h S ~) n S: ~ h ~
--I O';4 aJ rJ) ~) U~ ~ 3 3 a) aJ tn ~ ~ a~ aJ QJ
O ' ~~1 ~ C ~ o C
C~OJ 3 ~ aJ aJ a) ~ D~ 3 C ~ ~ ~ ~ ,~ O a) ~ CL.

C C
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C~-~ JJ OC v o Q
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C C
rls o ~ ~ u~
r~ ,~ ~ o ~ o In O '~ O U~ ~ U O .. ~ O
C vu~ o o 1~ o ~u~ o C~i .~ o ~ Lt o ~ .~ o o ~ o o o r;5 , .... ... ... ... ... ... ...
o o o o o o ~ o ~ o c o o ~ O ~ O O

V ~ ~ ~ ~ '^ 3: ~3 C Z Z Z Z Z Z Z
J r ~ J J
:~G ~ O,--O ~ O ~ O _~ O-- O--;~3Z Z Z Z Z ;~: Z

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c~ ~ x x v ~ c ~

~33810 ~ 3 _.
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r~~ aJ O ~ 3 3 3 ~ ~ 3 ~

Q, h aJ C~
h 3 3 S S
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O O Q~ ~ 3 _~ o h <IJ a~ l ~ O o 3 O V .~ c;- C
U aJ (rJ S-l ,Y ~ h 5 ~ ~ 5 3-~1 3 3 1~ C 5 ~ ~ O ~ ~ ~ ~L Ql ~ ~ ~ R~

G) ~J
3 G) , ,--( Ç --~ 5 n G) G) C) GJ aJ
Ul C 3 Ll 5 GJ 5 GJC 5 q) a) ~ ~5)~ 5 -1 5aJ ~1 ~ .C
n n ~ n ~ aJ n O GJ I~J n n S~
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5' ~ C ~ ~ a~ ~~ '~ ~ ~f :~ 3~ G) ~a) o G) -~ y ~ 10 ~5 ~ O ~ ~~ SJ hGJ ~ ~1 v~ ~ ~o ~ ~ns~ CQ~ cn o u er C C
O u~ .n~ L,'~ Lr~ ~ u~
tJ ~ o u~ o~ oLr> o ~ ~lr> ou~ o~ ~
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o ~ ~ ~ .~ m ~ t3 ~C~
u) ~; ~ z z z :z ~ m m m m m O O O C~ O O
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mrJ ~ r~oo 000 000 000 000 V

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Claims (229)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A reversible indicator composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state and capable of being supercooled for at least several minutes consisting essentially of:
(1) an inert solvent (I) consisting of a single substance or a mixture of substances capable of changing from a solid state to a liquid state at substantially a predetermined temperature, and (2) an indicator system (II) consisting of one or more substances different from said solvent (I), characterized in that (a) said indicator system (II) is soluble in said solvent (I) when the latter is in the liquid state, and (b) said indicator system (II) changes color visible to the naked eye when said solvent (I) passes from the solid state to the liquid state or from the liquid state to the solid state, said indicator system (II) exhibiting a sharp color change upon transistion of said solvent (I) from the liquid state to the solid state or from the solid state to the liquid state, said composition capable of being supercooled for at least several minutes and said color change being reversible.

2. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state, capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in a solid state, consisting essentially of:

(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of an indicator material selected from the group consisting of pinacyanol iodide, thionin, methylene blue, cresol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, Orasol Orange RLNTM, Orasol Navy BlueTM, Irgalith Red PRTM, Fat Red BSTM, Xylene Cyanol FFTM, Rhodamine BTM, Rhodamine 6GTM, Irgalith Magenta TCBTM, Irgalith Pink TYNCTM, Toluidene Blue OTM, Savinyl Green BTM, Savinyl Blue RSTM, purpurin, 3,3'-diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine ATM, Merocyanine 540TM, 4-(p-ethoxyphenylazo)-m-phenylene diamine hydrochloride, Yellow Orange STM, Chrysoidan GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue RTM, Pyronin GTM, gallein, Erythrosin Yellow BlendTM, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphosphine OTM, acriflavine, acridine orange, rhoduline violet, Alizarin Cyanine 2RTM, Alizarin Red STM, alcannin, Aurantia, Direct Green GTM, Fast Salt Red 3GLTM, Fast Salt Blue BBTM, Fast Garnet Salt GBCTM, Carta Yellow G 180 0/0TM, murexide,Savinyl Blue GLSTM, Irgalith Blue GLSMTM, phthalocyanine, Di Amingreen BTM, Alizarin Blue STM, Celliton Blue Extra TM, neocyanine,Janus GreenTM, dimethyl yellow, Fast YellowTM, methyl red sodium salt, Alizarin Yellow RTM, Eriochrome Black TTM, Chromotrope 2RTM, Ponceau 6RTM, Brilliant Ponceau G/R/2RTM, chromolan yellow, Sudan Red BTM, Bismark brown GTM, Fat BlackTM, Resorcin BrownTM, Benzofast Pink 2BLTM, Oil Red EGNTM, Euroglaucine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluorescein sodium salt, Rhodamine B baseTM, Eosin Scarlet, Eosin Yellowish, Erythrosin extra bluish, 4,5-dibromofluorescein, ethyleosin, PhloxinTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-ethylpyridinium iodide, ethyl red, nigrosine, Savinyl Blue BTM, Orasol Blue BLNTM, Safranin OTM, Azocarnum GTM, Phenosafranine M, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM, Nile Blue ATM, gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/CTM, Blue VIF OrganolTM, Alizarin, Nitrofast Green GSBTM, quinalizarine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo SyntheticTM, Chromophthal Bordeau RSTM, Acid Alizarin Red BTM, 5-aminofluorescein, Rose BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, cresyl violet, 4,4-bis(dimethylamino)-benzhydrol, zinc phthalocyanine, Sudan IIITM, Pyronin yTM, Toluylene BlueTM, cresyl violet perchlorate, Mendola's BlueTM, Phosphine Dye, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-1-naphthyl-amine, 4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene sulfonic acid, Bindschedler's GreenTM, and p-[p-dimethylaminophenylazo)-benzoic acid dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

3. A composition of matter substantially free of impurities, consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrohenzene and ortho-bromonitrobenzene having a proportion of ortho-chloronitrohenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0;and (b) an effective amount of an indicator material selected from the group consisting of pinacyanol iodide, thionin, methylene blue, cresol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, Orasol Orange RLNTM, Orasol Navy BlueTM, Irgalith Red PRTM, Fat Red BSTM, Yylene Cyanol FFTM, Rhodamine BTM, Rhodamine 6GTM, Irgalith Magenta TCBT , Irgalith Pink TYNCTM, Toluidene Blue OTM, Savinyl Green BTM, Savinyl Blue RSTM, purpurin, 3,3'-diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine ATM, Merocyanine 540TM, 4-(p-ethoxyphenylazo)-m-phenylene diamine hydrochloride, Yellow Orange STM, chrysoidan GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue RTM, Pyronin GTM, gallein, Erythrosin Yellow BlendTM, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphosphine OTM, acriflavine, acridine orange, rhoduline violet, Alizarin Cyanine 2RTM, Alizarin Red STM, alcannin, Aurantia, Direct Green GTM, Fast Salt Red 3GLTM, Fast Salt Blue BBTM, Fast Garnet Salt GBCTM, Carta Yellow G 180 0/0TM, murexide, Savinyl Blue GLSTM, Irgalith Blue GLSMTM,phthalocyanine, Di Amingreen BTM, Alizarin Blue STM, Celliton Blue ExtraTM, neocyanine, Janus GreenTM, dimethyl yellow, Fast YellowTM, methyl red sodium salt, Alizarin Yellow RTM, Eriochrome Black TTM, Chromotrope 2RTM, Ponceau 6RTM, Brilliant Ponceau G/R/2RTM, chromolan yellow, Sudan Red BTM, Bismark Brown GTM, Fat BlackTM, Resorcin BrownTM, Benzofast Pink 2BLTM, Oil Red EGNTM, Euroglancine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluorescein sodium salt, Rhodamine B baseTM, Eosin Scarlet, Eosin Yellowish, Erythrosin extra bluish, 4,5-dibromofluorescein, ethyleosin, PhloxinTM, Cyanovin BTM, chlorocresol green,pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-ethylpyridinium iodide, ethyl red, nigrosine, Savinyl Blue BTM, Orasol Blue BLNTM, Safranin OTM, Azocarnum GTM, PhenosafranineTM, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM, Nile Blue ATM, gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/CTM, Blue VIF OrganolTM Alizarin, Nitrofast Green GSBTM, quinalizarine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo SyntheticTM, Chromophthal Bordeau RSTM, Acid Allzarin Red BTM, 5-aminofluorescein, Rose BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, cresyl violet, 4,4-bis(dimethylamino) -benzhydrol, zinc phthalocyanine, Sudan IIITM , Pyronin YTM, Toluylene BlueTM, cresyl violet perchlorate, Mendola's Blue Phosphine Dye, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-1-naphthylamine, 4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene sulfonic acid, Bindschedler's GreenTM, and p-(p-dimethylaminophenylazo)-benzoic acid dissolved in and inert towards said solvent mixture (a) and adapted to change color of the composition visible to the naked eye upon the change in state from a solid state to a liquid state at a predetermined temperature.

4. The composition of claim 2 or claim 3 wherein said indicator material is pinacyanol iodide.

5. The composition of claim 2 or claim 3 wherein said indicator material is thionin.

6. The composition of claim 2 or claim 3 wherein said indicator material is methylene blue.

7. The composition of claim 2 or claim 3 wherein said indicator material is cresol red.

8. The composition of claim 2 or claim 3 wherein said indicator material is neutral red iodide.

9. The composition of claim 2 or claim 3 wherein said indicator material is neutral red chloride.

10. The composition of claim 2 or claim 3 wherein said indicator material is crystal violet.

11. The composition of claim 2 or claim 3 wherein said indicator material is acridin orange.

12. The composition of claim 2 or claim 3 wherein said indicator material is Orasol Orange RLNTM.

13. The composition of claim 2 or claim 3 wherein said indicator material is Orasol Navy BlueTM.

14. The composition of claim 2 or claim 3 wherein said indicator material is Irgalith Red PRTM.

15. The composition of claim 2 or claim 3 wherein said indicator material is Fat Red BSTM

16. The composition of claim 2 or claim 3 wherein said indicator material is Xylene Cyanol FFTM.

17. The composition of claim 2 or claim 3 wherein said indicator material is Rhodamine BTM.

18. The composition of claim 2 or claim 3 wherein said indicator material is Rhodamine 6GTM.

19. The composition of claim 2 or claim 3 wherein said indicator material is Irgalith Magenta TCBTM.

20. The composition of claim 2 or claim 3 wherein said indicator material is Irgalith Pink TYNCTM.

21. The composition of claim 2 or claim 3 wherein said.
indicator material is Toluidene Blue OTM,

22. A composition of matter exhibiting a sharp color change upon transition from a liquid state to solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of one or more suitable organic moieties dissolved in and inert towards said solvent to form a solid solution when the composition is in the solid state, and adapted to change the color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved, and selected from one of the groups consisting of:
(1) one or more of a Group III body of compounds consisting of pinacyanol iodide, l,l'-diethyl-2,2'-cyanine iodide, quinaldine red, pinacyanol chloride, thionin, methylene blue, cresol red, chlorophenol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, Orasol Orange RLNTM, Orasol Navy BlueTM,Irgalith Red PRTM, Fat Red BSTM, Xylene cyanol FFTM, Rhodamine BTM, Rhodamine 6GTM, Irgalith Magenta TCBTM, Irgalith Pink TYNCTM, Toluidine Blue OTM, Savinyl Green BTM, Savinyl Blue RSTM , purpurin, 3,3'-diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine ATM, Merocyanine 540 M, 4-(p-ethoxyphenylazo)-m-phenylene diamine monohydrochloride, Yellow Orange STM, Chrysodian GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue RTM, Pyronin GTM, gallein, Erythrosin Yellow BlendTM, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphosphine OTM, acriflavine, acridine orange, rhoduline violet, Alizarin cyanin 2RTM, Alizarin Red STM
alcannin, Aurantia, Direct Green GTM, Fast Red Salt 3GLTM, Fast Blue Salt BBTM, Fast Garnet Salt GBCTM, Carta Yellow G
180 o/oTM, Murexide, Savinyl Blue GLSTM, Irgalith Blue GLSMTM, phthalocyanine, Di Amingreen BTM, Alizarin Blue S, Celliton Blue ExtraTM, neocyanine, Janus GreenTM, dimethyl yellow, Fast YellowTM, methyl red sodium salt, Alizarin Yellow RTM, Eriochrome Black TM, Chromotrope 2RTM, Ponceau 6RTM, Brilliant Ponceau G/R/2R/TM, chromolan yellow, Sudan Red BTM, Bismarck brown GTM, Fat Black TM, Resorcin Brown TM, Benzofast Pink 2BLTM
Oil Red EGNTM, Euroglaucine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluorescein sodium salt, Rhodamine B baseTM, Eosin Scarlet, Eosin Yellowish Erythrosin extra bluish, 4,5-dibromofluorescein, ethyleosin, PhloxineTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethylaminostyryl)-1-ethyl pyridinium iodide, ethyl red, nigrosine, Savinyl Blue BTM, Orasol Blue BLNTM, Safranin OTM, Azocarnum GTM, PhenosafranineTM, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM, Nile Blue ATM, gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/C
Blue VIF OrganolTM, Alizarin, Nitrofast Green GSBTM, quinalizar-ine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo syntheticTM, Chromophtal Bordeaux RSTM, Acid Alizarin Red BTM, 5-amino-fluorescein, Rose BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, cresyl violet, 4,4'Bis(dimethylamino)benzyl-hydrol, zinc Phthalocyanine, Sudan III M, Pyronin Y
Toluylene BlueTM, cresyl violet perchlorate, Mendola's Blue Phosphine Dye, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamino-l-naphthylazo)-3-methoxybenzene sulfonic acid, Bindschedler's GreenTM, and p-(p-dimethylaminophenylazo)benzoic acid;
(2) a binary mixture of (A) one or more of a Group I body of compounds soluble in said solvent consisting of the halogenated sulfon-phthaleins and the organic acids having a pK1 less than about four; and (B) one or more of a Group II body of compounds consisting of the aminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines;
wherein the weight ratio of the Group I body of compounds to the Group II body of compounds is more than or about 3 to 1 and with the proviso that if the Group II compounds consist solely of one or more aminotriphenylmethanes or their soluble salts, then the Group I compound must be selected from one or more of the group consisting of oxalic acid, suitable soluble sulfonic acids, and the tetrahalogenated sulfonphthaleins, and the other organic acids having a pK1 of less than or about 2; and (3) one or more of the aforesaid Group III body of compounds with one or more of the Group I or Group II bodies of compounds.

23. The composition of matter recited in claim 22 wherein the change in state is induced by temperature forces for use in a temperature-indicating device.

24. The composition of matter recited in claim 23 wherein (a) the Group I body of compounds are one or more of the group consisting of oxalic acid, bromophenol blue, bromothymol blue, chlorophenyl red, bromochlorophenol blue, bromocresol green, 3,4,5,6-tetrabromophenolsulfonphthalein, 2-naphthalenesulfonic acid, trichloroacetic acid, chloroanilic acid, bromophenol red, and chlorocresol green and (b) the Group II body of compounds are one or more of the group consisting of 5(p-dimethylamino benzilidine) rhodanine, ethyl red, crystal violet, pararosaniline, pararosaniline acetate, 3-ethyl-2-[5-(3-ethyl-2-benzothiazolinyli-dene)-1,3-pentadienyl]-benzothiazolium iodide, basic fuchsin, 8-hydroxyquinoline, ethyl violet, brilliant green, dicyanine A, pinacyanol chloride, 2-(p-dimethylaminostyryl)-1-ethyl-pyridinium iodide, 3,3'-diethylthiodicarbocyanine iodide, and cryptocyanine.

25. The composition of matter recited in claim 24 wherein the weight percentage of organic moieties soluble in the solvent is from about 0.025 to about 0.05% of the weight of the solvent and said soluble organic moieties.

26. The composition of matter recited in claim 24 wherein the predetermined temperature is from about 96°F. to about 105°F.

27. The composition of matter recited in claim 24 wherein the solvent is selected from one or more of the group consisting of ortho-chloronitrobenzene, orthobromonitrobenzene, 1-thymol, 2-naphthol, 2-ethoxybenzamide, and naphthalene.

28. The composition of matter recited in claim 24 wherein the solvent is a binary mixture of orthochloronitrobenzene and ortho- bromonitrobenzene having a proportion of ortho-chloronitrobenzene to orthobromonitrobenzene of about 43.8:56.2 to about 4.0:96Ø

29. The composition of matter recited in claim 24 wherein the group I compounds consist of the halogenated sulfonphthaleins having a pK1 of about 2 and a PK2 of about 7 to about 9.

30. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of chlorophenol blue and ethyl red dissolved in an inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

31. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurit-ies, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of bromochlorophenol blue and ethyl violet dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved.

32. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state on from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of bromophenol blue and basic fuchsin dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved

33. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:

(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of bromophenol red and brilliant green dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

34. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of bromochlorophenol blue and pinacyanol chloride dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

35. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of 3,3'-diethylthi-adicarbocyanine iodide and bromocresol purple dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

36. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of 3,3'-diethylthi-adicarbocyanine iodide and bromophenol blue dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

37. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of pinacyanol chloride and 3,4,5,6-tetrabromophenolsulfonphthalein dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

38, A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of pinacyanol chloride and bromocresol purple dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

39. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of ethyl red and bromochlorophenol blue dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

40. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of pinacyanol chloride and chlorocresol green dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

41. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of pinacyanol iodide dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

42. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:

(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of quinaldine red dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

43. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurit-ies, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of 1,1'-diethy.-2,2'-cyanine iodide dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

44. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to liquid state; and (b) an effective amount of a mixture of bromophenol blue and ethyl red dissolved in and inert toward. said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

45. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of chlorophenol red dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

46. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of ethyl red and 3,4,5,6-tetrabromophenolsulfonphthalein dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

47 A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of ethyl red and bromophenol red dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

48 The composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of ethyl red and bromocresol purple dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved

49. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially, of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of crystal violet and bromophenol blue dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

50. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of bromochlorophenol blue and brilliant green dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

51. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:

(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of naphthalene sulfonic acid and ethyl violet dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

52. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of naphthalene sulfonic acid and crystal violet dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

53. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of naphthalene sulfonic acid and ethyl red dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved.

54. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of trichloroacetic acid and cryptocyanine dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

55. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid stat or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of trichloroacetic acid and ethyl violet dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

56. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of 3-ethyl-2-[5-(3-ethyl-2-benzothiazolinylidene)-1,3-pentadienyl ]-benzothiazolium iodide and trichloroacetic acid dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

57. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of chloroanilic acid and basic fuchsin dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved.

58. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of chlorophenol red and dicyanine A dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

59. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of chlorophenol red and cryptocyanine dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved.

60. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:

(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of bromochlorophenol blue and dicyanine A dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

61. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state;
and (b) an effective amount of a mixture of 5-p-dimethylamino-benzylidine rhodanine and dicyanine A dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

62. A composition of matter exhibiting a sharp color change upon transition from a liquid state to a solid state or from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, to form a solid solution when the composition is in the solid state, consisting essentially of:
(a) a solvent adapted to change from a solid state at substantially a predetermined temperature to a liquid state; and (b) an effective amount of a mixture of 5-p-dimethylamino-benzylidine rhodanine and cryptocyanine dissolved in and inert towards said solvent and adapted to change color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved.

63. A temperature-indicating device comprising a heat conducting carrier having one or more spaced regions defined therein to determine a like number of predetermined temperatures in a predetermined temperature range, said spaced regions con-taining a like number of different compositions of matter therein, each a solid solution, said carrier having a transparent cover sheet means in sealing engagement therewith, and with a single solid solution being deposited in each of said regions and being associated with a single one of said pre-determined temperatures, each composition of material exhibiting a sharp color change upon transition from a solid state to a liquid state, capable of being supercooled for at least several minutes, and substantially free of impurities, consisting essentially of:
(a) a solvent adapted to change from a solid at substantially the predetermined temperature to a liquid state; and (b) an effective amount of one or more suitable moieties dissolved in and inert towards said solvent to form a solid solution when the composition is in the solid state, and adapted to change the color of the composition visible to the naked eye upon the change in state at substantially the pre-determined temperature when so dissolved, and selected from one of the groups consisting of:

(1) one or more of a Group III body of compounds consisting of pinacyanol iodide, quinaldine red, l,l'-diethyl-2,2'-cyanine iodide, pinacyanol chloride, thionin, methylene blue, cresol red, chlorophenol red, neutral red iodide, neutral red chloride, crystal violet, acridin orange, Toluidin Blue OTM, Orasol Orange RLNTM, Orasol Navy BlueTM, Irgalith Red PRTM, Fat Red BSTM, Xylene Cyanol FFTM, Rhodamine 6GTM, Rhodamine BTM, Irgalith Magenta TCBTM, Irgalite pink TYNCTM, Toluidine Blue O, Savinyl Green BTM, Savinyl Blue RSTM, purpurin, 3,3'-diethyl-thiadicarbocyanine iodide, cryptocyanine, Dicyanine A M, Merocyanine 540TM, 4-(p-ethoxyphenylazo)-m-phenylene diamine monohydrochloride, Yellow Orange STM, Chrysoidin GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue R
Pyronin GTM, gallein, Erythrosin Yellow Blend M, chlorophenol blue, bromophenol blue, bromocresol purple, Coriphosphine O
acriflavine, acridine orange, rhoduline violet, Alizarin Cyanin 2RTM, Alizarin Red STM, alcannin, Aurantia, Direct Green GTM, Fast Red Salt 3GLTM, Fast Blue Salt BBTM, Fast Garnet Salt GBCTM, Carta Yellow G 180 o/oTM , murexide, Savinyl Blue GLSTM, Irgalith Blue GLSMTM, phthalocyanine, Di Amingreen BTM, Alizarin Blue S, Celliton Blue ExtraTM, neocyanine, Janus Green, dimethyl yellow, Fast Yellow, Methyl red sodium salt, Alizarin yellow RTM, Eriochrome Black TTM, Chromotrope 2RTM, Ponceau 6RTM, Brilliant Ponceau G/R/2RTM, chromolan yellow, Sudan Red BTM, Bismarck brown GTM, Fat Black TM, Resorcin Brown TM, Benzofast pink 2BLTM, Oil Red EGNTM, Euroglaucine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluorescein sodium salt, Rhodamine B base TM, Eosin Scarlet, Eosin YellowishTM, Erythrosin extra bluish, 4,5-dibromofluor-escein, ethyleosin, PhloxineTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-dimethylaminostyryl)-ethyl pyridinium iodide, ethyl red, neutral red iodide, nigrosine, savinyl blue BTM, Orasol Blue BLNTM, Safranin OTM, Azocarnun GTM, Phenosafranine, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM , Nile Blue ATM, gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/CTM, Blue VIF OrganolTM, Alizarin, Nitrofast Green GSBTM, quinalizarine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo syntheticTM, Chromophtal Bordeaux RSTM, Acid Alizarin Red BTM, 5-Aminofluorescein, Rose BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, Cresyl violet, 4,4'-Bis(dimethylamino)-benzylhydrol, Zinc Phthalocyanine, Sudan IIITM, Pyronin YTM, Toluylene Blue M, cresyl violet perchlorate, Mendola's BlueTM, Phosphine Dye, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamino-1-naphthylazo)-3-methoxy-benzene sulfonic acid, Bindschedler's GreenTM, p-(p-dimethyl-aminophenylazo)benzoic acid;
(2) a binary mixture of (A) one or more of a Group I body of compounds soluble in said solvent consisting of the halogenated sulfonphthaleins and the organic acids having a pK1 of less than or about four; and (B) one or more of a Group II body of compounds con-sisting of the aminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines;
with the proviso that if the Group II compounds consist solely of one or more aminotriphenylmethanes or their soluble salts, then the group I compound must be selected from one or more of the group consisting of oxalic acid, suitable soluble sulfonic acids, the tetrahalogenated sulfonphthaleins, and the other soluble organic acids having a pK1 of less than or about 2, and wherein the weight ratio of the Group I body of compounds to the Group II body of compounds is more than or about 3 to 1;

and (3) one or more of the aforesaid Group III body of compounds with one or more of the Group I or Group II bodies of compounds.

64. The device according to claim 63 wherein the regions are cavities in the heat-conducting carrier.

65, The device according to claim 63 wherein the solid solutions are in an essentially linear melting point-to-composition relationship over the temperature range represented by said plurality of compositions of matter.

66. The device according to claim 63 wherein the solvent is selected from one or more of the group consisting of ortho-chloronitrobenzene, ortho-bromonitrobenzene, l-thymol, 2-naphthol, 2-ethoxybenzamide, naphthalene, ortho-iodonitro-benzene, meta-iodonitrobenzene, para-iodonitrobenzene, para-dichloronitrobenzene, meta-bromonitrobenzene, para-dibromonitrobenzene, and paratoluic acid.

67. The device according to claim 63 wherein the solvent is a binary mixture of ortho-chloronitrobenzene and ortho-bromonitrobenzene.

68. The device according to claim 63 wherein the binary mixture of ortho-chloronitrobenzene and ortho-bromonitrobenzene have weight percentage ratios of from about 43.8:56.2 to about 4.0:96Ø

69. The device according to claim 64 wherein each cavity is substantially filled with a suitable absorbent bibulous material.

70. The device according to claim 63 wherein the compositions of matter have impurities of less than 0.3% rendering the com-positions of matter capable of excellent undercooling after the composition falls below the melting point.

71. The device according to claim 63 wherein the solid solutions are mixtures of the same compounds and the solvent is a binary mixture.

72. The device according to claim 70 wherein the compositions of matter have insoluble nucleating agents present in an amount of from about 0.1 to about 1.5 percent of the entire composition.

73. The device according to claim 71 wherein the solvent mixtures consist of varied amounts of paradichlorobenzene and para-bromochlorobenzene.

74. The device according to claim 67 with the novel compositions of matter, each containing an effective amount of a suitable nucleating agent.

75. The temperature indicator device recited in claim 71 wherein the indicator means is a layer of paint and the thermally-responsive compositions of matter each contain from about 0.01% to about 1.0% by weight talc.

76. A method of determining a temperature to be measured comprising the steps of:
(a) providing a temperature-indicating device comprising a heat-conducting carrier having one or more spaced regions defined therein to determine a like number of predetermined temperatures in a predetermined temperature range, said spaced regions containing like number of different compositions of matter therein, each a solid solution, said carrier having a transparent cover sheet means in sealing engagement therewith, each of the compositions of matter changing color visible to the naked eye upon transition of the compositions of matter from a liquid state to a solid state, which transition occurs at a known temperature different from the compositions of matter in the remaining regions, each composition of matter exhibiting a sharp color change upon transition from a solid state to a liquid state capable of being supercooled for at least several minutes, and substantially free of impurities, consisting essentially of:
(1) a solvent adapted to change from a solid to a liquid state at substantially the predetermined temperature; and (2) an effective amount of one or more suitable moieties dissolved in and inert toward said solvent to form a solid solution when the composition is in the solid state, and adapted to change the color of the composition visible to the naked eye upon the change in state at substantially the predetermined temperature when so dissolved, and selected from one of the groups consisting of:
(A) one or more of a Group III body of compounds consisting of pina-cyanol iodide, quinaldine red, l,l'-diethyl-2,2'-cyanine iodide, pinacyanol chloride, thionin, methylene blue, cresol red, chlorophenol red, crystal violet, acridin orangc, Orasol Orangc RLNTM, Orasol Navy BlueTM, Irgalith Red PRTM, Fat Red BSTM, Xylene Cyanol FFTM, Rhodamine BTM, Rhodamine 6GTM
Irgalith Magenta TCBTM, Irgalith pink TYNCTM, Toluidine Blue O, SavinylGreen 8TM, Savinyl Blue RSTM, purpurin, 3,3 -diethylthiadicarbocyanine iodide, cryptocyanine, Dicyanine ATM , Merocyanine 540TM, 4-(p-ethoxyphenyl-azo)-m-phenylene diamine monohydrochloridc, Yellow Orange STM, Chrysoidin GTM, fuchsin, aurintricarboxylic acid (ammonium salt), Victoria Blue RTM, Pyronin GTM, gallein, Erythrosin Yellow BlendTM, chlorophenol blue, bromo-phenol blue, bromocresol purple, Coriphosphine OTM, acriflavine, acridine orange, rhoduline violet, Alizarin Cyanin 2RTM, Alizarin Red STM, alcannin, Aurantia, Direct Green GTM, Fast Red Salt 3GLTM, Fast Blue Salt BBTM, Fast Garnet Salt GBCTM, Carta Yellow G 180 o/o, Savinyl Blue GLS , Irgalith Blue GLSMTM, phthalocyanine, Di Amingreen BTM, Alizarin blue S, Celliton Blue ExtraTM, neocyanine, Janus Green, dimethyl yellow, Fast Yellow, methyl red sodium salt, Alizarin yellow RTM, Eriochrome Black TTM, Chromotrope 2RTM
Ponceau 6RTM, Brilliant Ponceau G/R/2RTM, chromolan yellow, Sudan Red BTM, Bismarck brown GTM, Fat BlackTM , Resorcin BrownTM, Benzofast pink 2BLTM, Oil Red EGNTM, Euroglaucine, Fuchsin NBTM, parafuchsin, Patent BlueTM, Irgalith Blue TNCTM, Phloxin BTM, fluorescein sodium salt, Rhodamine B
base TM, Eosin Scarlet, Eosin YellowishTM, Erythrosin extra bluish, 4,5-di-bromofluorescein, ethyleosin, PhloxineTM, Cyanovin BTM, chlorocresol green, pinacyanol bromide, 2-(p-dimethylaminostyryl)-l-l-ethyl pyridinium iodide, ethyl red, neutral red iodide, nigrosine, Savinyl Blue BTM, Orasol Blue BLNTM, Safranin OTM, Azocarnun GTM, Phenosafranine, Azocarmine BXTM, Solophenyl Brilliant Blue BLTM, Nile Blue ATM, gallocyanine, gallamine blue, celestine blue, methylene green, Azure A/B/CTM, Blue VIF OrganolTM, Alizarin, Nitrofast Green GSBTM, quinalizarine, Oil Blue NTM, Solvay purple, Ciba BlueTM, Indigo syntheticTM, Chromophtal Bordeaux RSTM, Acid Alizarin RedBTM, 5-aminofluorescein, Rose BengalTM, Martius YellowTM, Chicago Blue 6BTM, Alcian Blue 8GXTM, cresyl violet, 4,4'Bis(dimethylamino)benzylhydrol, Zinc Phthalocyanine, Sudan IIITM, Pyronin YTM, Tolylene BlueTM, cresyl violet perchlorate, Mendola's BlueTM, 3,3'-diethylthiadicarbocyanine iodide, Phosphine DyerTM, NitronTM, cresyl violet acetate, Ceres Orange RTM, 4-phenylazo-1-naphthyl-amine, 4-(4-Dimethylamino-1-naphthylazo-3-methoxy-benzene)sulfonic acid, Bindschedler's GreenTM, and p-(p-dimethylamino-phenylazo)benzoic acid;
(B) a binary mixture of:
(1) one or more of a Group I body of compounds soluble in said solvent consisting of the halogenated sulfonphthaleins and the organic acids having a pK1 of less than or about four; and (2) one or more of a Group II body of compounds consisting of the aminotriphenylmethanes and their soluble salts, 8-hydroxyquinoline, and the cyanines;
with the proviso that if the Group II compounds consist solely of one or more aminotriphenylmethanes or their soluble salts, then the Group I compound must be selected from one or more of the group consisting of oxalic acid, suitable soluble sulfonic acids, the tetrahalogenated sulfonphthaleins, and the other soluble organic acids, having a pK1 of less than or about 2, and wherein the weight ratio of the Group I body of compounds to the Group II
body of compounds is more than or about 3 to 1; and (C) one of more of the aforesaid Group III body of compounds with one or more of the Group I or Group II bodies of compounds;
(b) subjecting each of the compositions of matter to the temperature to be determined, which is in the predetermined temperature range to cause one or more of the chemical means to change color corresponding to a change in phase; and (c) determining the highest of the predetermined temperatures at which one of the chemical means has changed color.

77. A composition of matter substantially free o impurities consist-ing essentially of a solid solution of:

(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of chlorophenol blue and ethyl red soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

78. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion or ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromochlorophenol blue and ethyl violet soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

79. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromophenol blue and basic fuchsin soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

80. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:

(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromophenol red and brilliant green soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

81. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromochlorophenol blue and pinacyanol chloride soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

82. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chlornitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of 3,3'-diethylthiadicarbocyanine iodide and bromocresol purple soluble in and inert towards binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a pre-determined temperature.

83. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of 3,3'-diethylthiodicarbocyanine iodide and bromophenol blue soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

84. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of pinacyanol chloride and 3,4,5,6-tetrabromophenolsulfonphthalein soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

85. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of pinacyanol chloride and bromo-cresol purple soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

86. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of ethyl red and bromochloro-phenol blue soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

87. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of pinacyanol chloride and chlorocresol green soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a pre-determined temperature.

88. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of pinacyanol iodide soluble in and inert towards said binary mixture (a) and adapted to change the color of the com-position visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

89. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene to about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of quinaldine red soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

90. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of 1,1'-diethyl-2,2'-cyanine iodide soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

91. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromo-nitrobenzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitrobenzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromophenol blue and ethyl red soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

92. A composition of matter substantially free of impurities consist-ing essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of chlorophenol red soluble in and inert towards said binary mixture (a) and adapted to change the color of the 2??

composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

93. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of ethyl red and 3,4,5,6-tetra-bromosulfonphthalein soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a pre-determined temperature.

94. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of ethyl red and bromophenol red soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

95. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4 0:96.0 and (b) an effective amount of a mixture of ethyl red and bromocresol purple soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

24?

96. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of crystal violet and bromophenol blue soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

97. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of bromochlorophenol blue and brilliant green soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

98. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of naphthalene sulfonic acid and ethyl violet soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

99. A composition of matter substantially free of impurities consisting 2??

essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of naphthalene sulfonic acid and crystal violet soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

100. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of naphthalene sulfonic acid and ethyl red soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

101. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of trichloroacetic acid and cryptocyanine soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predeter-mined temperature.

102. A composition of matter substantially free of impunities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzcnc and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of trichloroacetic acid and ethyl violet soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

103. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of 3-ethyl-2-[5-(3-ethyl-2-benzothiazolinylidene)-1,3-pentadienyl]-benzothiazolium iodide and trichloro-acetic acid soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

104. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of chloroanilic acid and basic fuchsin soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

105. A composition of matter substantially free of impurities consisting essentially of a solid solution of:

(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of chlorophenol red and dicyanine A soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

106. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of chlorophenol red and crypto-cyanine soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

107. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96,0 and (b) an effective amount of a mixture of bromochlorophenol blue and dicyanine A soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

108. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of orth0-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-2??

benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of 5-p-dimethylaminobenzylidine rhodanine and dicyanine A soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a predetermined temperature.

109. A composition of matter substantially free of impurities consisting essentially of a solid solution of:
(a) a binary mixture of ortho-chloronitrobenzene and ortho-bromonitro-benzene having a proportion of ortho-chloronitrobenzene to ortho-bromonitro-benzene of about 43.8:56.2 to about 4.0:96.0 and (b) an effective amount of a mixture of 5-p-dimethylaminobenzylidine rhodanine and cryptocyanine soluble in and inert towards said binary mixture (a) and adapted to change the color of the composition visible to the naked eye upon a change in state from a solid state to a liquid state at a determined temperature.

110. The composition of claim 88, wherein the amount of pinacyanol iodide employed is about 0.035 weight percent of the entire solid solution.

111. The composition of claim 2 or 3 wherein said indicator material is Savinyl Green BTM.

112. The composition of claim 2 or 3 wherein said indicator material is Savinyl Blue RSTM.

113. The composition of claim 2 or 3 wherein said indicator material is purpurin.

114. The composition of claim 2 or 3 wherein said indicator material is 3,3'-diethylthiadicarbocyanine iodide.

115. The composition of claim 2 or 3 wherein said indicator material is cryptocyanine.

116. The composition of claim 2 or 3 wherein said indicator material is Dicyanine ATM.

117. The composition of claim 2 or claim 3 wherein said indicator material is Merocyanine 540TM.

118. The composition of claim 2 or claim 3 wherein said indicator material is 4-(p-ethoxyphenylazo)-m-phenylene diamine hydrochloride.

119. The composition of claim 2 or claim 3 wherein said indicator material is Yellow Orange STM.

120. The composition of claim 2 or claim 3 wherein said indicator material is Chrysoidan GTM.

121. The composition of claim 2 or claim 3 wherein said indicator material is fuchsin.

122. The composition of claim 2 or claim 3 wherein said indicator material is aurintricarboxylic acid (ammonium salt).

123. The composition of claim 2 or claim 3 wherein said indicator material is Victoria Blue RTM.

124. The composition of claim Z or claim 3 wherein said indicator material is Pyronin GTM.

125. The composition of claim 2 or claim 3 wherein said indicator material is gallein.

126. The composition of claim 2 or claim 3 wherein said indicator material is Erythrosin Yellow BlendTM.

127. The composition of claim 2 or claim 3 wherein said indicator material is chlorophenol blue.

128. The composition of claim 2 or claim 3 wherein said indicator material is bromophenol blue.

129. The composition of claim 2 or claim 3 wherein said indicator material is bromocresol purple.

130. The composition of claim 2 or claim 3 wherein said indicator material is Coriphosphine OTM.

131. The composition of claim 2 or claim 3 wherein said indicator material is acriflavine.

132. The composition of claim 2 or claim 3 wherein said indicator material is acridine orange.

133. The composition of claim 2 or claim 3 wherein said indicator material is rhoduline violet.

134. The composition of claim 2 or claim 3 wherein said indicator material is Alizarin Cyanine 2RTM.

135. The composition of claim 2 or claim 3 wherein said indicator material is Alizarin Red STM.

136. The composition of claim 2 or claim 3 wherein said indicator material is alcannin.

137. The composition of claim 2 or claim 3 wherein said indicator material is Aurantia.

138. The composition of claim 2 or claim 3 wherein said indicator material is Direct Green GTM.

139. The composition of claim 2 or claim 3 wherein said indicator material is Fast Salt Red 3 GLTM.

140. The composition of claim 2 or claim 3 wherein said indicator material is Fast Salt Blue BBTM.

141. The composition of claim 2 or claim 3 wherein said indicator material is Fast Garnet Salt GBCTM.

142. The composition of claim 2 or claim 3 wherein said indicator material is Carta Yellow G 180 0/0TM.

143. The composition of claim 2 or claim 3 wherein said indicator material is murexide.

144. The composition of claim 2 or claim 3 wherein said indicator material is Savinyl Blue GLSTM.

145. The composition of claim 2 or claim 3 wherein said indicator material is Irgalith Blue GLSMTM.

25?

146. The composition of claim 2 or claim 3 wherein said indicator material is phthalocyanine.

147. The composition of claim 2 or claim 3 wherein said indicator material is Di Amingreen BTM.

148. The composition of claim 2 or claim 3 wherein said indicator material is Alizarin Blue STM.

149. The composition of claim 2 or claim 3 wherein said indicator material is Celliton Blue ExtraTM.

150. The composition of claim 2 or claim 3 wherein said indicator material is neocyanine.

151. The composition of claim 2 or claim 3 wherein said indicator material is Janus GreenTM.

152. The composition of claim 2 or claim 3 wherein said indicator is dimethyl yellow.

153. The composition of claim 2 or claim 3 wherein said indicator material is Fast YellowTM.

154. The composition of claim 2 or claim 3 wherein said indicator material is methyl red sodium salt.

155. The composition of claim 2 or claim 3 wherein said indicator material is Alizarin Yellow RTM.

156. The composition of claim 2 or claim 3 wherein said indicator material is Eriochrome Black TTM.

157. The composition of claim 2 or claim 3 wherein said indicator material is Chromotrope 2RTM.

158. The composition of claim 2 or claim 3 wherein said indicator material is Ponceau 6RTM.

159. The composition of claim 2 or claim 3 wherein said indicator material is Brilliant Ponceau G/R/2RTM.

160. The composition of claim 2 or claim 3 wherein said indicator material is chromolan yellow.

2?

161. The composition of claim 2 or claim 3 wherein said indicator material is Sudan Red BTM.

162. The composition of claim 2 or claim 3 wherein said indicator material is Bismark brown GTM.

163. The composition of claim 2 or claim 3 wherein said indicator material is Fat BlackTM.

164. The composition of claim 2 or claim 3 wherein said indicator material is Resorcin BrownTM.

165. The composition of claim 2 or claim 3 wherein said indicator material is Benzofast Pink 2BLTM.

166. The composition of claim 2 or claim 3 wherein said indicator material is Oil Red EGNTM.

167. The composition of claim 2 or claim 3 wherein said indicator material is Euroglaucine.

168. The composition of claim 2 or claim 3 wherein said indicator material is Fuchsin NBTM.

169. The composition of claim 2 or claim 3 wherein said indicator material is parafuchsin.

170. The composition of claim 2 or claim 3 wherein said indicator material is Patent BlueTM.

171. The composition of claim 2 or claim 3 wherein said indicator material is Irgalith Blue TNCTM.

172. The composition of claim 2 or claim 3 wherein said indicator material is Phloxin BTM.

173. The composition of claim 2 or claim 3 wherein said indicator material is fluorescein sodium salt.

174. The composition of claim 2 or claim 3 wherein said indicator material is Rhodamine B baseTM.

175. The composition of claim 2 or claim 3 wherein said indicator material is Eosin Scarlet.

2?

176. The composition of claim 2 or claim 3 wherein said indicator material is Eosin Yellowish.

177. The composition of claim 2 or claim 3 wherein said indicator material is Erythrosin extra bluish.

178. The composition of claim 2 or claim 3 wherein said indicator material is 4,5-dibromofluorescein.

179. The composition of claim 2 or claim 3 wherein said indicator material is ethyleosin.

180. The composition of claim 2 or claim 3 wherein said indicator material is PhloxinTM.

181. The composition of claim 2 or claim 3 wherein said indicator material is Cyanovin BTM.

182. The composition of claim 2 or claim 3 wherein said indicator material is chlorocresol green.

183. The composition of claim 2 or claim 3 wherein said indicator material is pinacyanol bromide.

184. The composition of claim 2 or claim 3 wherein said indicator material is 2-(p-dimethylaminostyryl)-1-ethyl pyridinium iodide.

185. The composition of claim 2 or claim 3 wherein said indicator material is ethyl red.

186. The composition of claim 2 or claim 3 wherein said indicator material is nigrosine.

187. The composition of claim 2 or claim 3 wherein said indicator material is Savinyl Blue BTM.

188. The composition of claim 2 or claim 3 wherein said indicator material is Orasol Blue BLNTM.

189. The composition of claim 2 or claim 3 wherein said indicator material is SAfranin OTM.

2?

190. The composition of claim 2 or claim 3 wherein said indicator material is Azocarmin GTM.

191. The composition of claim 2 or claim 3 wherein said indicator material is PhenosafranineTM.

192. The composition of claim 2 or claim 3 wherein said indicator material is Azocarmine BXTM.

193. The composition of claim 2 or claim 3 wherein said indicator material is Solophenyl Brilliant Blue BLTM.

194. The composition of claim 2 or claim 3 wherein said indicator material is Nile Blue ATM.

195. The composition of claim 2 or claim 3 wherein said indicator material is gallocyanine.

196. The composition of claim 2 or claim 3 wherein said indicator material is gallamine blue.

197. The composition of claim 2 or claim 3 wherein said indicator material is celestin blue.

198. The composition of claim 2 or claim 3 wherein said indicator material is methylene green.

199. The composition of claim 2 or claim 3 wherein said indicator material is Azure A/B/CTM.

200. The composition of claim 2 or claim 3 wherein said indicator material is Blue VIF OrganolTM.

201. The composition of claim 2 or claim 3 wherein said indicator material is Alizarin.

202. The composition of claim 2 or claim 3 wherein said indicator material is Nitrofast Green GSBTM.

203. The composition of claim 2 or claim 3 wherein said indicator material is quinalizarine.

204. The composition of claim 2 or claim 3 wherein said indicator material is Oil Blue NTM.

2?

205. The composition of claim 2 or claim 3 wherein said indicator material is Solvay purple.

206. The composition of claim 2 or claim 3 wherein said indicator material is Ciba BlueTM.

207. The composition of claim 2 or claim 3 wherein said indicator material is Indigo SyntheticTM.

208. The composition of claim 2 or claim 3 wherein said indicator material is Chromophthal Bordeau RSTM.

209. The composition of claim 2 or claim 3 wherein said indicator material is Acid Alizarin Red BTM.

210. The composition of claim 2 or claim 3 wherein said indicator material is 5-aminofluorescein.

211. The composition of claim 2 or claim 3 wherein said indicator material is Rose BengalTM.

212. The composition of claim 2 or claim 3 wherein said indicator material is Martius YellowTM.

213. The composition of claim 2 or claim 3 wherein said indicator material is Chicago Blue 6BTM.

214. The composition of claim 2 or claim 3 wherein said indicator material is Alcian Blue 8GXTM.

215. The composition of claim 2 or claim 3 wherein said indicator material is cresyl violet.

216. The composition of claim Z or claim 3 wherein said indicator material is 4,4-bis(dimethylamino)-benzhydrol.

217. The composition of claim 2 or claim 3 wherein said indicator material is Zinc phthalocyanine.

218. The composition of claim 2 or claim 3 wherein said indicator material is Sudan IIITM.

219. The composition of claim 2 or claim 3 wherein said indicator material is Pyronin yTM.

220. The composition of claim 2 or claim 3 wherein said indicator material is Toluylene BlueTM.

221. The composition of claim 2 or claim 3 wherein said indicator material is cresyl violet perchlorate.

222. The composition of claim 2 or claim 3 wherein said indicator material is Mendola's Blue TM.

223. The composition of claim 2 or claim 3 wherein said indicator material is NitronTM.

224. The composition of claim 2 or claim 3 wherein said indicator material is cresyl violet acetate.

225. The composition of claim 2 or claim 3 wherein said indicator material is Ceres Orange RTM.

226. The composition of claim 2 or claim 3 wherein said indicator material is 4-phenylazo-1-naphthyl-amine.

227. The composition of claim 2 or claim 3 wherein said indicator material is 4-(4-dimethylamino-1-naphthylazo)-3-methoxybenzene sulfonic acid.

228. The composition of claim 2 or claim 3 wherein said indicator material is Bindschedler's GreenTM.

229. The composition of claim 2 or claim 3 wherein said indicator material is p-(p-dimethylaminophenylazo)-benzoic acid.