CA1106173A

CA1106173A - Process for the production of pressure sensitive carbonless record sheets using novel hot melt systems and products therefor

Info

Publication number: CA1106173A
Application number: CA277,565A
Authority: CA
Inventors: Dale R. Shackle; Ainslie T. Young, Jr.
Original assignee: Mead Corp
Current assignee: Mead Corp
Priority date: 1976-05-07
Filing date: 1977-04-28
Publication date: 1981-08-04
Also published as: NO151081B; GB1591361A; NO151081C; FR2350205B1; DE2719935A1; FI771372A; FI69427B; BR7702906A; ZA772155B; JPS577917B2; BE854132A; US4063754A; JPS52136018A; MX146118A; SE434824B; FI69427C; AU508668B2; SE7705292L; NO770983L; IT1079639B

Abstract

PROCESS FOR THE PRODUCTION OF PRESSURE SENSITIVE
CARBONLESS RECORD SHEETS USING NOVEL HOT MELT
SYSTEMS AND PRODUCTS THEREOF

Dale R. Shackle and Ainslie T. Young, Jr.

Abstract of the Disclosure A process is provided for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot melt coating compostion, the hot melt coating composition being water insoluble and having a melting point of from about 60° C to about 140° C. The hot melt coating composition includes a chromo-genic material. The chromogenic material is a meltable color developer of the acidic electron accepting type. The melt point and the heated coating composition is applied to a substrate, the coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate. The coating composition is set by cooling the coated substrate. A novel liquid chromogenic coating composition is produced, the coating composition having a melting point of from about 60° C to about 140° C comprising from about 15% to about 100% of a chromogenic material and from about 0% to about 80% of a rheology modifying material, the chromogenic material being a meltable color developer of the acid electron accepting type. A
pressure-sensitive record sheet is produced, the record sheet comprising a substrate having a plurality of surfaces, at least one of the surfaces being coated with a set hot melt coating composition, the set hot melt suspending medium including a chromogenic material dispersed therein.

Description

~6~73 sackground of the Invention This invention relates to the production of pressure-sensitive carbonless record sheets for use in combination with a pressure-sensitive transfer sheet of the type whereby on application of pressure a color precursor is transferred to the record sheet which then develops a visible image. More particularly it relates to the production of a pressure-sensitive carbonless record sheet utilizing a hot me't system to form a coating composition containing a chromogenic material, which coating is set by cooling. For purposes of this application the term "chromogenic" shall be understood to refer to chromogenic material such as color developers, color formers and may additionally contain color inhibitors and the like. The term shall be under-stood to refer to such materials whether in microencapsulated, capsulated, dispersed or other form. For purposes of this application the term CF, shall be understood to refer to a coating normally used on a record sheet. In additiion the term CB shall be understood to refer to a coating normally used on a transfer sheet.
Carbonless paper, briefly stated, is a standard type of paper wherein during manufacture the backside of a paper substrate is coated with what is referred to as a CB coating, the CB coating conta~~ning one or more color precursors generally in capsular form. At the same time the front side of the paper substrate is coated during manufacture with what is referred to as a CF coating, which contains one or more color developers.
Both the color precursor and the color developer remain in the coating compositions on the respective back and front surfaces of the paper in colorless form. This is true until the CB and CF coatings of adjacent sheets are brought into abutting relation-ship and sufficient pressure, as by a typewriter, is applied to - rupture the ~ 3 1~6173 C-t~ cOatill~J to reLease the color precursor. At -this ti~e the col3r precursor contacts the CF' coating and reacts with the color developer therein to form an image. Carbonless paper has pxoved to be an exceptionally valuable image transfer medium for a variet~ of reasons only one of which is the fact that until a CB coating is placed ne~-t -to a CF coating both the CB and the CF are in an inac-tive sta-te as the co-reactive elerr,ents are not in contact with one another. Patents reiating to carbonless paper products are:
iO U.S. Patent 2,712,507 (1955) to Green U.S. Patent 2,730,456 (1956) to Green et al U.S. Patent 3,455,721 (1969) to Phillips et al U.S. Patent 3,466,184 tl969) to Bowler et al U.S. Patent 3,672,935 (1972) to Miller e-t al A third generation product which is in an advanced stage o~ development and commercialization at this time and which is -~ av~ilable in so.ne business sectors is reEerred to as sel~-contained paper. Very generally stated self-contained paper refers to an imaging system wherein only one side of the paper 23 needs to be coated and the one coating contains both the color precursor, generally in encapsulated form, and the colo developer. Thus when pressure is applied, again as by a type-riter or other writing instrument, the color precursor caps~le is ruptured and reacts with the surrounding color developer to

2~ Eorm an image. Both the carbonless paper imaye transfer system and the self-contained system have been the sub]ect of a great deal of patent activity. A typical autogeneous record material system, earlier sometimes referred to as "self-contained" ~ecause all elem_nts for making a mark are in a single sheet, is dis-

3~ clcsed in U~S. PateDt 2,730,457 (1956) to Green.

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1 1~ 6 1 7 3 ~ dis~dvantacje of coated paper produc~s such as carbonless and self-contairled stems from the necessity of applying a liquid coating composition containing the color forminy ingredients during the manufacturing process. In the application of such coatings volatile solvents are somstimes used which then in turn requires evapor~tion of excess solvent to dry the coating thus producing volatile solvent vapors. An alternate method of coating involves the application of the color forming ingredients in an aqueous slurry, again requiring removal of excess water by dryiny. Both methods suffer from serious disadvantages. In particular the solvent coating method necessarily involves the production of generally volatile solven~ vapors creating both a health and a fire hazard in the surrounding environment. In addition, when using an aqueous solvent system the water must be evaporated which involves the e~pencllture of significant amounts oE energy. Further, the necessity of a drylng skep requires the use of complex and expensive apparatus to continuously dry a substrate which has been coated with an aqueous coating compound. A separate but related problem involves the disposal of polluted water xesulting from the preparation and cleanup of the aqueous coa-ting com-positions. The application of heat not only is expensi~e, making t~e total product manufacturing operation less cost effective, but also is potentially damaging to the color forming-ingredients wnich are generally coated onto the paper substrate during ~anufacture. The problems encountered in the actual coating step are generally attributable to the necessity for a hea ed clri-ing step following the coa=ing operation.

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~larly oE the particular advantages of the process and product of this invention are derived from the fact that a hot r~elt coating composition is used to coat the paper substrate.
~hi~ is in contrast to the coa-tings used by the prior art which have generall~ required an aqueous or solvent coating. For pur~oses of this application the term "100~ solicls coating"
will someti}nes be usecl to describe the coating operation and should be understood to refer to the fact that a hot melt coating composition is used and therefore the drying . .
ln ~tep normally present in the manufacture of paper and in coating - has been eliminated.
In this regard, it should be noted that spot coating of aaueous and solvent systems has been known. See, for example, Vassil~ade~, U. S. Patent No. 3,914,511, Macauley (3,01~308) r S~aneslow et al (3,079,351), Miller et al (3f672/935)~ and Shank (3,684,549). But to the best o~ our knowledge none of the hot melt coatings of the past are particularly effective.
ThereEore, the need exists for an improved hot melt s~s~em for coating CF carbonless paper sheets so that spot coated sheet~ can be prepared. Additionally, the most preferred embodi-ment of ~his invention relates to a process for the continuous production of manifold carbonless forms and more particularly ~o a process for utiliziny a hot melt system containing dispersed , 1 c'o7 or developing ma~erial.
As can be appreciated from the above the continuous production of a manifold paper product would require simultaneous coating, simultaneous drying, simultaneous printing, and simul-taneous collating and finislling of a pluralit~ of paper sub~trates.
Thus, Bussh in Canadian Patent No. 945,443 indicates that in order 5(i to do so ~here shoulcl be a minimum ~etting oE che pa~er ~Yeb by water duri-ng application of an erllulsion coat. For that purpose _ ~ .

a hiyll solid~ content emulsion is used and special driers are desc:ribc-~d in Busch Elowever, because of the complexities of the drying step this process has not been commercially possible to-date. More particularly, the drying step involvin~ solvent evaporation and/or water evaporation and the input of heat does not permit the simultaneous or continuous manufacture of mani-fold forms. In addition to the drying step which prevents con-tinuous manifold form production the necessity for the appli-cation of heat for sclvent evaporation is a serious disadvantage since aqueous and other liquid coatings require that special grades of generally more expensive paper be employed and even these often result in buckling, distortion or warplng O:e the paper since water and other liquids tend to strike through or penetrate the paper substrate. Additionally, aqueous coatings and some solvent coatings are generally not suitable for spot application or application to limited areas oE one side of a sheet of paper. They are generally suitable only for appli-cation to the entire surface area of a sheet to produce a con-tinuous coating.
Another problem which has been commonly encountered in attempts to continuously manufacture manifold forms has been the fact that a paper manufacturer must design paper from a strength and durability standpoint to be ade~uate for use in a - - variety of printing and Einishing machines. This requires a 2S paper manuEacturer to evaluate the coating apparatus of the forms manufacturers he supplies in order that the paper can be designed to accommodate the apparatus and process exhibiting the most demanding conditions. Because of this, a higher long ~ood fiber to short ~ood fiber ratio mus-t be used b~ the paper manufacturer than is necessary for most coating, 1 ~C 6173 ~ .

printi~ or ~inishin(J machines in order to achieve a proper high l.evel o~ strength in his inished paper product. I'his makes the final sheet product more expensive as the long fiber is generally more expensive than a shor-t fiber. In essence, the separation ol paper manufacturer from :Eo.rms manu~acturer, which is now co~,~on, requires that the paper manufacturer over~esign his final product for a va.riety o:E machines, instead of specifically desiyning the paper product for ~nown machine conditions~
By combining the manufacturing, printing and finishing iO operations into a single on-line system a number of advantages are achieved. First, the paper can be made using groundwood and a lower long fiber to short fiber ratio as was developed supra This is a co~t and potentially a quality improvement in the ~inal pap2r product. A second advantage which can be derived : 15 rrom a combination of manufacturing, printing and finishing is that waste or re-cycled paper,hereinafter sometimes referred to as "broke",can he used in the manufacture of the paper since the quality OI the paper is not of an overdesigned high standard~
Third,and mos-t important, several steps in the normal process of the manufacture of forms can be completely eliminated.
Specifically,drying steps can be eliminated by using a non- -a~ueous, solvent-free coating system and in addition the ware-: housing and shipping steps can be avoided thus resulting in a more cost ef~icient product.
Addi~i.onally, by using appropriate coating methods, namely hot melt coating compositions and methods r and by com-bining the necessary manufacturing and printing s-teps, spot printing and spo-t coatiny car-l be realized~ Both oE these reprQsent a significant cost savin~s, but nevertheless one wrlich is not c,enerally availablQ when aqueous or solvent coatings ( ar~ used cr wllere tile manuEacture, printing and finishin~ of paper are perEormed as separate functions. An addi-tional-~cl~arltage of the use of ho-t melt coating compositions and the co~~ination of paper manufacturer, printer and finisher is -that ~.hen the option o, printing followed by coating is avail-ab:Le significant cost advantages occur.

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_ 9 _ ~;6~73 t Statemen-t of the Invention A process is provided -for producing a pressure-sensitive carbonless record sheet comprising the steps of preparing a hot nelt coating composition, the hot melt coating composition being water insoluble and having a melting point of from about 60 C to about 140 C. The hot mslt coating composition includes a chromo-genic material. The chromogenic material LS a meltable color develo~er of the acidic electron accepting type. The hot melt coating composition is heated to a temperature above its melting point and the heated coating composition is applied to a substrate, the coating composition ~eing applied at a coat weight of from ahout 0.2 pounds to about 8.0 pounds per 3300 s~uare feet of substrate. The coating composition is set b~ cooling ~he coated s-~bstrate. A novel liquid chromogenic coating composition is produced, the coating composition having a melting point of ~rom about 60 C. to about 140~ C. and comprising from about 15% to about 1~0~ of a chromogenic material and from about 0~ to about 80~ of a rheology modifying material, the chromogenic material being a meltable color developer of the acid electron accepting type. A pressure-sensitive record sheet is produced, the record ; 20 s'rleet comprising a substrate having a plurality of surfaces, at least one cE the surfaces being coa-ted with a set hot melt coa,ing composition, the set hot melt suspending medium including a chromo~enic materiai dispersed therein.

11~61~3 Detailed Description of the Invention .
The chromogenic coating composition of this invention is essentially a water insoluble, meltable color developer. In a preferred form, rheology modifying materials, such as resins, waxes and liquid plasticizers, can be added to improve the coatability of the coating composition ln a hot melt system. The ' color developer and rheology modifying materials are preferably miscible or partially miscible in melted form so that separation of the components of the composition does not occur during the application of the hot melt coating composition.
Filler materials can also be added to the coating composition, if desired. The use of solvents, which require heat to remove them during the drying or setting of the coating composition, is avoided. I~owever, minor amounts of solvents can be tolerated without requiring a separate step for drying during any subsequent setting step. Although the product and process of this invention are useful in the manufacture of a variety of products the preferred use of the process and product of this invention is in the continuous production of a manifold carbonless substrate.
The chromogenic color developers most useful in the practice of this invention are the acidic electron-acceptors and include phenolic materials such as 2-ethylhexyl gallate, 3,5-di-tert-butyl salicylic acid, phenolic resins of the novolak type and metal modified phenolic materials, such as the zinc salt of 3,5-di-tert-butyl salicylic acid and the zinc modified novolak type resins. The most preferred chromogenic color developers are the novolaks of p-phenylphenol, p-octylphenol and p-tert-butylphenol and their zinc modifications. Mixtures of these color developers may be used, if desired. The resinous color devel-opers can be used as the sole components of the hot melt coating composition providing the viscosity of the composition at coating ` temperatures is low enough to permit the composition to be coated or printed by the desired method as is hereinafter developed, ~.

rheology modifylng materials selected to lower the viscosity of these resins can be added. Phenolic compounds, such as 2-ethylhexyl gallate and 3,5-di-tert-butyl salicylic acid generally have a sharper melting point and lower melt viscosity.
In this case, rheology modifying materials selected to raise the viscosity of these compounds are generally added.
The color developers can be present in the hot melt coating composition in the range of from about 15% to about 100% by weight of the coating composition. At 100% the color developers function as the hot melt in addition to their chromogenic function. The preferred range of color developer in the coating composition is from about 50% to about 100% and the most preferred range is from about 65~ to about ~5%.
The rheology modifying materials generally useful in the practice of this invention include a wide variety of resins, waxes and liquid plasticizers. In general, these rheology modifying materials can be non-polar or polar. By polar it is meant that a certain amount of polarity is characteristic of these materials, the polar materials being characterized by the presence of functional groups selected from ~he group consisting of carboxyl, carbonyl, hydroxy], ester, amide, amine, heterocyclic groups and combinations thereof. The rheology modifying materials may vary in viscosity from liquids such as monoisopropylbiphenyl to the low molecular weight polypropylenes. Examples of rheology modifying materials which may be used are polyethylenes and polypropylenes, polyethylene glycols, polystyrenes, polyesters, polyacrylates, rosin, modified rosins, polyphenyls, fatty acid derivatives, ; oxazoline, waxes, Montan waxes, paraffin waxes and micro-crystalline waxes. The rheology modifying materials may be present in an amount of from about 0% to about ~5~ by weight of the hot melt coating composition. The preferred range is from about 0% to about 50~ and the most preferred range is from about 15% to about 35% of the coating composition.

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~ 1~'6173 A desirable characteristic of the hot melt coating composition of this invention is a melting point of from about ~0C to about 140C., although a more preferred melting point for the coating compositions is from about 70C
to about 100C. Also relative to the melting point, it is desirable for the coating composition of this invention to set rapidly after application to the particular substrate. More specifically, a practical melting range limitation or in other words range of temperature in which the liquid hot melt coating composition sets into a solid composition, is from about 0.1C to about 15C. The preferred setting time is from about 0.5 seconds to about 5 seconds while the most preferred setting time is from about 0.5 seconds to about 2 seconds. While hot melt compositions having a melting range of more than 15C can be used, the time necessary for such a coating composition to set requires special apparatus and handling and makes use of these hot melt compositions commercially unattractive.
The preferred hot melt coating compositions of this invention have a low viscosity when in a molten state in order to facilitate ease of spreading on the substrate. In general, it is desirable that the hot melt coating composition have a viscosity of less than about 500 centipoises at a temperature of approximately 5 above the melting point of a - particular hot melt coating composition.

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y - 13 -:~1¢6~3 In addition, it is preferred that the hot melt coating composition of this invention have a light color in order to be compatible with the final paper or plastic product being produced. This means that it is preferred for the hot melt to he white or colorless after application to the particular substrate being coated.
Filler materials can be added to the coating composition as flat~tening agents to reduce the glossy appearance of the cured hot melt coatings and preserve the appearance of the substrate. Thus a bond paper which has been coated with the coating composition of this invention and which is then cured to a solid gives the impression of being an uncoated bond paper.
The preferred filler materials are of the colloidally precipitated or fumed silicas. Typical of the silicas which can be used are the ones trade marked LoVel 27 (a precipitated silica manufactured and sold by PPG Industries, Inc., Pittsburgh, ;`
; Pennsylvania), Syloid 72 (ahydrogel silica manufactured and sold by W. R. Grace & Co., Davison Chemical Division, Baltimore, ; Maryland) and Cab-o-sil (a fumed silica manufactured and sold by Cabot Corporation, Boston, ~lassachusetts). All of these silicas are known to give an initial bluish color with color precursors such as crystal violet lactone. However, this color fades quickly on aging. Using the record sheet produced by the process of this invention, the developed color does not fade easily. The filler material through its large surface area provides for increased porosity of the cured resin film, thereby promoting more rapid and more complete transfer of an oil solution of color precursors from a transfer sheet to the record sheet surface. The amount of filler materials can be up to about 15% by weight of the coating composition and the preferred range is from about 1~ to about 10~ by weight.

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il~tj1 73 rne chromocJellic color developing coating composition can be applied hot to a su~strateJ such as paper or a plasti.c film by any of the co~mon paper coati.ng processes, such as roll, blade coating or.by any of the common printing processes, such as plano- -yraphic, gravure, or fle~ographic printing. The rheolo~ical properties, par-ticularly the viscosi-ty of the coating composition, can be adjusted for each type oE application by proper selection of the typ2 and relative amounts of rheology modifying materials.
While the actual amount of the hot melt coating composition applied to the substrate can vary depending on the particular final product desired, for purposes of coating paper substrates, the practical range of coat weight.s for the CF chromogenic coating compositions of this invention are from about 0.2 pounds. to about 8 pounds per 3300 square feet of substrate, the preferred range being from abaut 0.2 pounds to about 5 pounds per 3300 square feet of substrate and the most preferred range being rom about 0.2 pounds to about 2.5 pounds per 3300 square feet of substrate.
Coat weights above the most preferred range do not show any substantia.1 improvement over those within the most preferred range.
~0 These hot melt coating compositions can be set by any cooling means. Preferably a chill roll is used on the coating apparatus : which cools the hot melt coating immediately after coating, butis also quite co~on to simply allo-~ the coating composition to cool naturally b~ at~ospheric exposure. As the temperature of the coating composition is substantially higher than room tempera-ture and in light of the fact that the coating thickness is generally less than 50 microns it can be seen that when spread out over a coated s~l.strat:e the hot melt material cools very rapidly. The actual eY~posure or chill time necessary ~or .setting of ~he chron~ogenic coating composition is dep~ndent on a 61'73 i number of variables, such as coat weight, the particular color developers and rheology modifying materials used, type of cooling means, temperature of the cooling means and others.
In the preferred application of the process and products of this invention a manifold carbonless form is produced. In this process a continuous web is marked with a pattern on at least one surface. A non-aqueous, solvent free hot melt coating of chromogenic material is applied to at least a portion of at least one surface of the continuous web. The coated surface is then set by cooling. The continuous web having the set coating is then combined with at least one additional continuous web which has been previously or simultaneously coated with a hot melt material and set by cooling. A manifold carbonless form - is then made by a variety of collating and finishing steps.
In the most preferred application of the process and products of this invention a manifold form is continously produced. In this most preferred embodiment a plurality of continuous webs are advanced at substantially the same speed, the plurality of continous webs being spaced apart and being ~ 20 advanced in cooperating relationship with one another. At ; best one web of the plurality of continuous webs is marked with a pattern and at least one non-aqueous, solvent-free hot melt coating containing the chromogenic material is applied to at least a portion of at least one of the plurality of continuous webs. The hot melt material is then set by cooling. The continuous webs are then collated and placed in contiguous relationship to one another to create a manifold form.

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After the continuous webs are placed in collated, contiguous relationship they can be finished by any combination of the steps of combining, partitioning, stacking, packaging and the like.
~ 5 Examples I-III illustrate the preparation of such a -~ hot melt CF coating. In that regard it is noted that in actual practice the color developers are mainly novolak resins of the substituted phenol-formaldehyde variety, either zincated, unzincated or a mixture of zincated and unzincated resins. The hot melt liquid can be composed of about 15 to about 100% of these resins and up to about 85% by weight of a rheology modifying material. Generally, these rheology modifying materials can be taken from a variety of inert high boiling liquid plasticizers or non-crystalline or microcrystalline solids such as resins and waxes with melting points less than 110 C.
The set, coated paper was tested by placing the coated surfaces thereof in contact with the coated side of a paper coated with gelatin microcapsules containing a marking oil made up of 180 parts of monoisopropylbiphenyl, 5.3 parts of crystal violet lactone, 0.62 parts of 3,3-bis-(1-ethyl-2-methylindol-3-yl)-phthalide, 1.25 parts of 3-N-N-diethylamino-7-(N,N-dibenzylamino)-fluoran, and 0.95 parts of 2,3-(-1'-phenyl-3'-methylpyrazolo)-7-diethylamino-4-spirophthalido~chromene and 122 parts of odorless kerosene. These sheet couples were imaged with an electric typewriter using the character "m" in a repeating block pattern, and the intensity of the images was measured as the ratio of the reflectance of the imaged area to the reflectance of the unimaged ' il~61~73 background, after an elapsed time of 10 minutes. Thus, the more intense or darker images show as lower values, and higher values indicate weak or ~aint images. This test is called Typewriter Intensity and may be expressed mathematically as T.I. = (100) Ro where Ri is reflectance of the image area and Ro is reflectance of the background (unimaged) area as measured with a Bausch and Lomb Opacimeter.
The following examples illustrate but do not limit the invention as defined in the claims.

EXAMPLE I
A mixture of 15 parts by weight of zincated p-octylphenol novolak resin (4.3%Zn) and 5 parts by weight of ; p-phenylphenol novolak resin were mixed in a metal beaker and heated with continuous stirring to 120C. This hot liquid was drawn down on a paper substrate weighing 13.5 pounds per 3300 square foot with a hot blade to give a 1.2 pound coating of the resin mixture on the substrate. The resulting tackless coating had a slight gloss and a faint yellow color and gave a typewriter intensity - value of 68.

EXAMPLE II
The fo]lowing mixture in parts by weight of novolak resins and binder materials was mixed in a metal container and melted in an oven at 120C. The following are given in parts by weight.
761 parts p-phenylphenol novolak resin 2284 parts zincated p-octylphenol novolak resin (4.3% Zn) 471 parts mono-isopropylbiphenyl 109 parts Epolene M-85 (Eastman, a low M.W.
polypropylene) The resulting hot liquid was coated on a paper substrate weighing 13 pounds on a gravure hot melt coater. The coater ~1 .

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c~n-tained a heated 200 lines per inch quadrangular machine etched gravur~ roll at 150 C and a heated smoothing roll. The hot liquid resin mixture was applied to the paper su~strate at a sp2ed of 130 Eeet per minute to give a coat weight of 0.48 pounds per 3300 sq~are Eeet. Typing intensity o~ the sheet was 83.

Example III
A series of hot melt coating compositions containing color developers were prepared and coated on a paper substrate as in Example I. In each instance, the coating composi-tion was applied at a coat weight of at least 3 pounds per 3300 square feet of :~ 10 paper. The composition of the hot melts and Typewriter Intensities ~ for each coated paper are yiven in Table I as follows: -', ,~-.~,, :` :

, .

: , ~ - 19 -., ' .

h O
h Q
~ ~ P~
.,~ ., ~ H
~ O O
E~ H o Z
h ~:
Q) u~ oooo oooooo o o o Q
O ~

a ~ O O O O O O O O O O O O O
d~ O
h Cl o ~1oooo oooooo o o o O dP ~ C~ ~ CO ~ I` <'~ ~0 00 ~ ~ ~0 a~
U P~
oooo Lr~In ~oooo o o o rd O O

S ,~
~ C O ~
'~ ~ O
rl ~rl O ~1 ~1 ~ h O ~
~1 O O ~ ~1 U ~ tn ~ O U ~ ~~ ~ O ~ S ~ri ~ ~rl ~1 ~
h h~-I h ~1 O tl~
s :1 o m o ~ o~ 0 .¢ ~1 ~ ~ ~~ ~ ~a)E; h h E~ ~ ~ ~ h ~1 ~d .~: S~ ~~ SO ~ U ~ C) 111 0 0 1~ U ~ ~ ~ ~ O l~
rl ~1 O O ~~ ~ ~ ~ O u~ O t~
h ~ ~ ~ u~ ~ ~S ~ h O h O
a~ 0 --I --I ~.4R--I~1 _Ir-l ~1 ~-1 ~ m ~ h ~ h ,1: 0 0 ~ ~ :1 0 0 0 0 0 ~ u ~ p~
:
: ~ ~ ~
u u ~ u u ~ u o ~ ~
O U H H
a) .Y ~ u o u ~
~1 O rl ~rl O O O ~ ~1 ~'0 Hr~l ~I H H H
~ ~1 A A U UC.) O O O ~rl ~rl O ~ h h K K rl ` O C) _I ~ Id ~d O O O E3Ul Ul U~ Ul o o u s ~ ~ e E3 U ::~ 0 n~
~: ~ o o ~: ~ U~ S .C ~-1 h h 1~ ~ ~ O OO n~ 1~ 0 a) u, u~ IU aJ a~

~
C~
p, ~ U~ I o O O ~ NCO C~
O O -I IC7 lel I
O O ~ t~ a~1 .~ ~ a a Z ~ ~~X U~ "~ " * ~q -I X X X X X *
3 3: 3 33 1 ~1 ~ o o o oo a~ o ~; ~ O OO O O :~
~r1 Q) R R ~ I ~1 U~ I U U
'a ~ ~ h ~ O 0 3~rl 0 0~ h O 11~ 1~ d Q ~ O
c~ u u~ 3 ~ a K ~ U
. . . . . . . . .

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Q) ~ ~
~c o E~
h .' OQ d~ m o O O O O o O OO O O O

I O O O O O O . . . . . U~
~ O
: ~ ~ ~ ~ ~ ~ U-o U~ U~ Ln .~ ~ P~ O O O O O O. . . . . U~
O d~ ~ OD ~ 03 CO ~ ~ ~ N~ ~ 1` ~1 U P

i' ~ S ' ~r '~
~, a~ o . O
~~I S-l a~
e e ~ u e ~
,~ o ., ~ ~ ~) h O O
,, ._ o ~ ~ o ~1 ~a R ~ X r~
-' ~ ~ a) a) ~ ~ rd 3 .' ~ O h 5-1 ~ 3 ~n ~ ~
a~ u ~ ~ a)x :~ o o ~:
m ~ x s~
. . E`~ ~ a) ~ ~ ~ S~ 3 0 R.
~1 ~ a~ a) ~ o . . 11l O ~ 1 S ~
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~ ~ ~ m E~ o ~ æ ~1 æ æ E~
.. ~ U~ .
,. ~ H Q~ U 3 H
.. ~ ~ ~ u .c o ,, tJ ~ H ~ ~ O O 00~,1 o :~ ~ a~ ~ $ u u u o ~ m In U~ ~ U ~ ~ OO ~
.: S ~ ~ U
r ~ O S~ UO ~ O
~: O U r~ h l~ 0 u~
r~ 5 ~ U ~ ~ U oo ~
H

:: ~ ~ I ~ U
, tJ
1:: ~1 U~ X ~ *
1~ * O ~) E4 X )~
>~ ~ 3 X
O O
~o ~ ~ 3 ~ O
~: X ~ m ~ o ~ U
.. .... ... . .. .. E~
. ~r u~ ~D 1` CO O~ O ~ ~ ~ ~ In I N ~ ~ ~I N ~`I

,.~r ~ -21-~- .

o ~
~ ~ p~
~ ~ r~
a) a QI~J ~a ~ O
E~ H U

O U~ o o ` OQ dP a p~
dP I r- '~
O d~

d~l U~

X
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O O
C~ ~ ~, 3 .,1 S~
U7 U ~ d~
~1 O Orl o`P W
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-21a-617'3 From Examples I-III it can be seen that various CF coatings of the hot melt type can effectively be prepared, coated in fluid hot melt form, set by cooling, and joined with a CB sheet to produce a carbonless copy sheet which upon application of pressure gives good transfer and a sharp developed image. It is thus possible to utilize the hot melt CF coatings of Examples I-III in the continuous production of manifold carbonless forms, especially ones in which the CF coatings are spot coated as a savings.
The only requirement is that a hot melt coating or printing operation (i.e., one in which the coating is maintained at above melting point of the coating) is followed by a cooling step to set the resulting coating. As mentioned such a system is much less expensive and cumbersome, requires less floor space and requires less energy than systems which require expensive driers and/or solvent recovery systerns.
While the method herein described constitutes a preferred embodiment of the invention, it is to be understood that the invention is not limited to this precise method, and that changes may be made therein withoùt departing from the scope of the invention which is defined in the appended claims.
X

Claims

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

l. A process for producing a pressure-sensitive carbonless record sheet comprising the steps of:
(a) preparing a hot melt coating composition, said hot melt coating composition being non-aqueous and solvent free, said hot melt coating composition additionally being water insoluble and having a melting point of from about 60°C to about 140°C, said hot melt coating composition including a chromogenic material, said chromogenic material being a meltable color developer of the acidic electron accepting type;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said heated coating composition to a substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of substrate; and (d) setting said coating composition by cooling said coated substrate, said set coating composition being free from any liquid.
2. The process of claim 1 wherein said substrate is paper.
3. The process of claim l wherein said coating composition contains from about 15% to about 100% of a color developer.
4. The process of claim 1 wherein said coating composition also includes a rheology modifying material, said rheology modifying material being selected from the group consisting of:
resins, waxes and liquid plasticizers.
5. The process of claim 1 wherein said color developer is selected from the group consisting of: 2-ethylhexyl gallate, 3,5-di-tert-butyl salicylic and, the novolaks of p-phenylphenol, p-octylphenol and p-tert-butylphenol, the zinc-modified novolaks of p-phenylphenol, p-octylphenol, p-tert-butylphenol and mixtures thereof.
6. The process of claim 1 wherein said coating composition also includes: rheology modifying material, said rheology modifying material being selected from the group consisting of polyethylenes and polypropylenes, polyethylene glycols, polystyrenes, polyesters, polyacrylates, rosin, modified rosins, polyphenyls, fatty acid derivatives, oxazoline waxes, montan waxes, paraffin waxes and microcrystalline waxes.
7. A process for producing a pressure-sensitive carbonless record sheet comprising the steps of:
(a) preparing a hot melt coating composition, said hot melt coating composition being non-aqueous and solvent-free, said hot melt coating composition additionally being water insoluble and having a melting point of from about 60°C to about 140°C, said hot melt coating composition including from about 15% to about 100% of a chromogenic material and from about 0% to about 85%
of a modifying material, said chromogenic material being a color developer of the acidic electron accepting type selected from the group consisting of the novolaks of p-phenylphenol, p-octylphenol and p-tert-butylphenol, the zinc-modified novolaks of p-phenylphenol, p-octylphenol and p-tert-butylphenol and mixtures thereof, said modifying material being added to improve the coatability of said coating composition;
(b) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition;
(c) applying said coating composition to a paper substrate, said coating composition being applied at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of paper substrate; and (d) setting said coating composition by cooling said coated paper substrate, said set coating composition being free from any liquid.
8. The process of claim 7 wherein said rheology modifying material is selected from the group consisting of: resins, waxes and liquid plasticizers.
24 A hot melt chromogenic coating composition for the preparation of pressure-sensitive carbonless record sheets, said hot melt chromogenic coating composition being non-aqueous and solvent-free, said hot melt chromogenic coating composition additionally being water insoluble and having a melting point of from about 60°C to about 14°C, said coating composition comprising from about 15% to 85% by weight of a chromogenic material, said chromogenic material being a meltable color developer of the acidic electron accepting type, said chromogenic material being selected from the group consisting of 3,5 di-tert-butyl salicylic acid, phenol resins of the novolak type, zinc salts of 3,5 di-tert-butyl salicylic acid and zinc modified novolak resins and mixtures thereof, and from about 15% to about 85% by weight of a rheology modifying material.
10. The coating composition of claim 9 wherein said rheology modifying material is seleeted from the group consisting of: resins, waxes and liquid plasticizers.
11. The coating composition of claim 9 wherein said rheology modifying material is selected from the group consisting of polyethylenes, polypropylenes, polyethylene glycols, polystyrenes, polyesters, polyacrylates, rosin, modified rosins, polyphenyls, fatty acid derivatives, oxazoline waxes, montan waxes, paraffin waxes, microcrystalline waxes and eombinations thereof.
12. The coating composition of claim 9 wherein said chromogenic material includes a zinc modified phenolic novolak resin.
13. The coating composition of claim 9 wherein said chromogenic material includes a phenolic novolak resin.
14. The coating composition of claim 9 wherein said chromogenic material includes a zinc salt of 3,5 di-tert-butyl salicylic acid.
15. The coating composition of claim 9 wherein said chromogenic material includes 3,5 di-tert-butyl salicylic acid.
16. A pressure-sensitive record sheet comprising a substrate having a plurality of surfaces, at least one of said surfaces being coated with a non-aqueous, solvent-free hot melt chromogenic coating composition, said coating composition additionally being water insoluble and having a melting point of from about 60°C to about 140°C, said coating composition comprising from about 15% to 85% by weight of a chromogenic material, said chromogenic material being a meltable color developer of the acidic electron accepting type, said chromogenic material being selected from the group consisting cf 3,5 di-tert-butyl salicylic acid, phenol resins of the novolak type, zinc salts of 3,5 di-tert-butyl salicylic acid and zinc modified novolak resins and mixtures thereof, and from about 15% to about 85% by weight of a rheology modifying material, said hot melt coating composition being set to a tack-free film, said hot melt coating composition including a meltable color developer dispersed therein, said set coating composition being free from any liquid.
17. A process for the production of a manifold carbonless form having one ox more surfaces coated with chromogenic material comprising:
(a) providing a continuous paper substrate;
(b) marking at least one surface of said paper substrate with a pattern;
(c) preparing a hot melt coating composition, said hot melt coating composition being non-aqueous and solvent-free, said hot melt coating composition additionally being water insoluble and having a melting point of from about 60°C to about 140°C, said hot melt coating composition including a chromogenic material, said chromogenic material being a meltable color developer of the acidic electron accepting type;
(d) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composition to form a liquid chromogenic coating composition;
(e) coating said liquid chromogenic coating composition onto said paper substrate, said coating composition being applied to a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of said paper substrate;
(f) setting said coating composition by cooling said coated paper substrate, said set coating composition being free from any liquid;
(g) combining said marked, coated paper substrate with at least one additional paper substrate to form a plurality of paper substrates, each of said additional paper substrates being characterized by having at least a portion of at least one surface coated with at least one non-aqueous, solvent-free coating of said chromogenic material, said coating being set;
(h) collating said plurality of marked, coated paper substrates; and (i) placing said collated paper substrates in contiguous relationship to one another to create a manifold carbon-less form.
18. A process for the continuous production of a manifold carbonless form having one or more surfaces coated with capsular chromogenic material comprising:
(a) providing a plurality of continuous paper substrates;
(b) advancing each substrate of said plurality of continuous substrates at substantially the same speed, said plurality of continuous substrates being spaced apart and being advanced in a cooperating relationship with one another;
(c) marking at least one substrate of said plurality of continuous substrates with a pattern;
(d) preparing a hot melt coating composition, said hot melt coating composition being non-aqueous and solvent-free, said hot melt coating composition additionally being water soluble and having a melting point of from about 60°C
to about 140°C, said hot melt coating composition including a chromogenic material, said chromogenic material being a meltable color developer of the acidic electron accepting type;
(e) heating said hot melt coating composition to a temperature above the melting point of said hot melt coating composi-tion to form a liquid chromogenic coating composition;
(f) applying said coating composition to one or more of said paper substrates at a coat weight of from about 0.2 pounds to about 8.0 pounds per 3300 square feet of said paper substrate;
(g) setting said coating composition by cooling said coated paper substrate, said set coating composition being free from any liquid;
(h) collating said plurality of continuous webs; and (i) placing said collated continuous webs in contiguous relationship to one another to create a manifold form.