US2712507A - Pressure sensitive record material - Google Patents
Pressure sensitive record material Download PDFInfo
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- US2712507A US2712507A US36518453A US2712507A US 2712507 A US2712507 A US 2712507A US 36518453 A US36518453 A US 36518453A US 2712507 A US2712507 A US 2712507A
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- capsules
- oil
- coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S101/00—Printing
- Y10S101/29—Printing involving a color-forming phenomenon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
- Y10T428/249995—Constituent is in liquid form
- Y10T428/249997—Encapsulated liquid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31844—Of natural gum, rosin, natural oil or lac
- Y10T428/31848—Next to cellulosic
- Y10T428/31851—Natural oil
Definitions
- This invention relates to manifold record material, and more particularly pertains to such record material which has a transfer coating thereon of microscopic gelled hydrophilic colloid capsules, each of said capsules consisting of a dense oil-impervious shell-like wall of filmforming colloid material deposited around a nucleus of an oily water-immiscible printing fluid by coacervate forces, said capsules being rupturable by printing or writing pressure applied to the record material so as to release said printing fluid for transfer to an underlying sheet.
- the encapsulating material which encloses the oil droplets is a single gelled hydrophilic colloid material as contrasted with capsules made of a complex gelled gellable hydrophilic colloid material, which characterizes the encapsulating material of the microscopic oil-containing capsules with which the record material is coated, as disclosed in application for United States Letters Patent, Serial No. 365,198, which was filed on the same day as this application, by this applicant and Lowell Schleicher.
- the record material of this invention also is .distinguished from that disclosed in applicant Greens United States Patent No. 2,374,862, and applicant Greens and Robert W. Sandbergs United States Patents 2,548,366; 2,550,466; 2,550,467; 2,550,468; and 2,550,469, in that in the patents, instead of using microscopic oil-containing capsules in the transfer coating, the oily printing fluid was contained in droplet form in a continuous gelled hydrophilic colloid film.
- the microscopic capsules although adherent to one another and to the paper, maintain their individuality so that if cracks are made by folding of the paper or otherwise, the cracks in the coating will run between the capsules and not through them. Also, in the present invention the microscopic capsules are made impermeable to the oil by a method disclosed and claimed in applicants co-pending application for United States Letters Patent, Serial No. 365,106, filed the same day as this application. That method will be described in this application, insofar as applicable, but will not be claimed herein.
- the manifold sheet of this invention is superior to those shown in the patents to which reference has been made, insofar as shelf-life and durability are concerned.
- a manifold sheet having a transfer film coating, on a surface thereof, which is composed of microscopic capsules of gelled hydrophilic colloid material, each of said capsules consisting of a dense oil-impervious shell-like wall of the colloid material deposited around a nucleus of an oily printing fluid by coacervate forces, and the capsules being present in such number as to be in substantial contiguity.
- the invention contemplates the use of color-reactant materials, which constitute the oil, or which form a part of the oil, it is another object of the invention to make such a manifold sheet in which the transfer coating is substantially colorless, but which will render colored marks upon sensitized receiving sheets.
- the invention includes certain novel features of structure and combinations of elements, a preferred form or embodiment of which is hereinafter described with reference to the drawing which accompanies and forms a part of this specification.
- the drawing shows the manifold sheet of this invention in an enlarged and exaggerated form, so that the features may be discernible.
- a manifold sheet containing as the printing mark substance the compound 3,3 bis(p-dimethylaminophenyl) 6-dimethylamino phthalide, which is colorless and forms blue marks when coming into adsorption contact with a record material sensitized with acid claylike material such as attapulgite, or zeolite material, such as sodium aluminum silicate material, or such in which the sodium has been exchanged for hydrogen or some other metal ion, as disclosed in applicants United States Letters Patents No. 2,5 81,186 and No. 2,641,557.
- a type of color reactant which oxidizm from a normally colorless form to a colored form when in contact with the clay materials just described, after the passage of some hours or days.
- This preferred compound is benzoyl leuco methylene blue.
- the phthalide compound like all triphenyl methane dyes, tends to fade in time, but the secondary color reactant of the oxidizing type forms a color which is lasting. The phthalide compound reacts instantly to form a colored mark, to be supported later by the color of the oxidized secondary color reactant.
- a gelatin although other gellable film-forming hydrophilic colloids, such as agar-agar, will do.
- the preferred method of forming the capsules includes the step of treating an aqueous sol of the colloid material having the oil emulsified therein, with a salt solution to cause the colloid material to deposit around the oil droplets, and then causing the colloid to gel.
- a salt solution to cause the colloid material to deposit around the oil droplets, and then causing the colloid to gel.
- one gallon of an oil-in-water emulsion of 20 parts, by weight, of trichlorodiphenyl containing the color reactants, and parts, by weight, of a sol of 10%, by weight, of pigskin gelatin in water is prepared, the emulsifying continuing until the drop size of the oil is from 2 to 5 microns. This material is kept at 50 centigrade to prevent the gelatin from gelling.
- the heated coacervate mixture this point the encapsulation of the oil with the gelled hydrophilic colloid material has taken place and the further steps are to put it in condition for use as intended.
- the material is filtered and washed with water, the temperature being kept below the melting point of the gelatin, to remove the salt.
- the filtered material is hardened by combining it with 2 gallons of a 37% solu- This hardened mass is then filtered and washed to remove the residual formaldehyde.
- the resulting filter cake is adjusted to the proper water content by the addition of water or the removal thereof, by ordinary means such as centrifuging or spray drying, and the material is ready for use.
- this material is intended for a paper coating composition, it is kept in aqueous suspension and applied directly to the paper, which is then dried, leaving the capsules adherent to the paper and to each other in a film.
- this fluid is sparsely dispersed in water and placed under a microscope, it will be seen to consist of microscopic capsules of the hydrophilic colloid material, the individual capsules being several microns in diameter and each containing a nucleus of oil. As the water content is decreased, the capsules tend to form aggregations, like bunches of grapes.
- the material is of the right consistency, it is coated on paper by rollers, spray, brushes, or any other of the commonly used methods of coating paper, and allowed to dry. The material is of such a nature that the capsules are adherent to each other in the coating, and will adhere to the paper, without the addition of any other binder material.
- the material in the oil which produces the mark on the receiving sheet need not be a reactive material but may have an intrinsic color of itself, such as dissolved v dyes, like Sudan III.
- oils which may be substituted for trichloro-diphenyl are any of the water immiscible oils, which are inert as to the other materials used in forming the capsules, such as petroleum fractions like paratfin oil, vegetable oil such as castor oil, and cottonseed oil, animal oils, such as sperm oil and lard oil, and any other various synthetic oils, such as methyl salicylate.
- the coating material should be used in such quantity on the paper that when dried the coated area will be profusely supplied with the microscopic capsules, but such thickness need be no more than a fraction of a thousandth of an inch, because the size of the capsules is in terms of several microns.
- a four pound coating on a ream of paper 25 inches by 38 inches is satisfactory.
- a sheet of ordinary writing paper, coated on one surface With the described coating composition laid with that coated surface on the attapulgite-sensitized surface of a receiving sheet, forms a manifold system which is responsive to very light printing or writing pressures, such as are ordinarily used in every-day printing and writing, so asto make clear and distinct marks on the receiving sheet, yet the coating is so durable that it will undergo,
- the capsules may be rendered porous if the gelled material is allowed to dry without washing out the salt.
- a record material base sheet having on a surface thereof a coating consisting of a profusion of microscopic pressurerupturable capsules having walls of gelled film-forming hydrophilic colloid material in substantial contiguity, each of the capsules consisting of an oily water-immiscible printing fluid as a central nucleus around which has been evenly deposited by coacervation forces a dense oil-impermeable shell-like coating of the colloid material, said capsules being rupturable by printing or marking pressures applied to the coated sheet.
- a sheet of paper having on a surface thereof a coating that is substantially colorless, said coating consisting of a profusion of pressure-rupturable microscopic capsules having walls of gelled film-forming hydrophilic colloid material in substantial contiguity, each of the capsules consisting of a dense shell-like oil-impermeable Wall of the colloid material deposited about a central nucleus of a colorless oily water-immiscible printing fluid by coacervation forces.
- the record material of claim 3 in WhlCll'thfi oily printing fluid consists of a water-immiscible oil vehicle in which is carried a colorless color reactant which turns to a colored form on contact with paper sensitized by having thereon acid clay-like material.
Description
July 5, 1955 GREEN 2,712,507
PRESSURE SENSITIVE RECORD MATERIAL Filed June 30, 1953 PAPER COATING OF MICROSCOPIC HYDROPHILIC COLLOID RUPTURABLE CAPSULES CONTAINING PRINTING FLUID INVENTOR BARRETT K. GREEN gwa HIS ATTORNEYS United States Patent 6 PRESSURE SENSITIVE RECGRD MATERIAL Barrett K. Green, Dayton, Ohio, assignor to The National Cash Register Company, Dayton, Ohio, a corporation of Maryland Application June 30, 1953, Serial No. 365,184
4 Claims. (Cl. 117-36) This invention relates to manifold record material, and more particularly pertains to such record material which has a transfer coating thereon of microscopic gelled hydrophilic colloid capsules, each of said capsules consisting of a dense oil-impervious shell-like wall of filmforming colloid material deposited around a nucleus of an oily water-immiscible printing fluid by coacervate forces, said capsules being rupturable by printing or writing pressure applied to the record material so as to release said printing fluid for transfer to an underlying sheet.
The encapsulating material which encloses the oil droplets is a single gelled hydrophilic colloid material as contrasted with capsules made of a complex gelled gellable hydrophilic colloid material, which characterizes the encapsulating material of the microscopic oil-containing capsules with which the record material is coated, as disclosed in application for United States Letters Patent, Serial No. 365,198, which was filed on the same day as this application, by this applicant and Lowell Schleicher.
The record material of this invention also is .distinguished from that disclosed in applicant Greens United States Patent No. 2,374,862, and applicant Greens and Robert W. Sandbergs United States Patents 2,548,366; 2,550,466; 2,550,467; 2,550,468; and 2,550,469, in that in the patents, instead of using microscopic oil-containing capsules in the transfer coating, the oily printing fluid was contained in droplet form in a continuous gelled hydrophilic colloid film.
In forming a continuous hydrophilic colloid film, there is a permeable condition set up whereby, even though the surface of the film is hardened by treatment that closes the surface pores, cracks may form through handling, or due to environmental conditions, which rupture the film. In such cracks the voids holding the oil are opened up because the cracks run straight through the voids. As the walls separating the voids in the film are somewhat permeable to the oil, oil may leak out, not only from the region of the'cracks, but from uncracked portions of the film, leaving the film inadequate to perform its function.
In the present invention the microscopic capsules, although adherent to one another and to the paper, maintain their individuality so that if cracks are made by folding of the paper or otherwise, the cracks in the coating will run between the capsules and not through them. Also, in the present invention the microscopic capsules are made impermeable to the oil by a method disclosed and claimed in applicants co-pending application for United States Letters Patent, Serial No. 365,106, filed the same day as this application. That method will be described in this application, insofar as applicable, but will not be claimed herein.
The manifold sheet of this invention, therefore, is superior to those shown in the patents to which reference has been made, insofar as shelf-life and durability are concerned.
Therefore, it is an object of this invention to provide 2,712,507 Patented July 5, 1955 a manifold sheet having a transfer film coating, on a surface thereof, which is composed of microscopic capsules of gelled hydrophilic colloid material, each of said capsules consisting of a dense oil-impervious shell-like wall of the colloid material deposited around a nucleus of an oily printing fluid by coacervate forces, and the capsules being present in such number as to be in substantial contiguity.
Inasmuch as the invention contemplates the use of color-reactant materials, which constitute the oil, or which form a part of the oil, it is another object of the invention to make such a manifold sheet in which the transfer coating is substantially colorless, but which will render colored marks upon sensitized receiving sheets.
With these and incidental objects in view, the invention includes certain novel features of structure and combinations of elements, a preferred form or embodiment of which is hereinafter described with reference to the drawing which accompanies and forms a part of this specification.
The drawing shows the manifold sheet of this invention in an enlarged and exaggerated form, so that the features may be discernible.
In the preferred embodiment of the invention there will be described a manifold sheet containing as the printing mark substance the compound 3,3 bis(p-dimethylaminophenyl) 6-dimethylamino phthalide, which is colorless and forms blue marks when coming into adsorption contact with a record material sensitized with acid claylike material such as attapulgite, or zeolite material, such as sodium aluminum silicate material, or such in which the sodium has been exchanged for hydrogen or some other metal ion, as disclosed in applicants United States Letters Patents No. 2,5 81,186 and No. 2,641,557. As a secondary color-reactant in the oily printing fluid of the preferred embodiment there is provided a type of color reactant which oxidizm from a normally colorless form to a colored form when in contact with the clay materials just described, after the passage of some hours or days. This preferred compound is benzoyl leuco methylene blue. The phthalide compound, like all triphenyl methane dyes, tends to fade in time, but the secondary color reactant of the oxidizing type forms a color which is lasting. The phthalide compound reacts instantly to form a colored mark, to be supported later by the color of the oxidized secondary color reactant.
As the oily vehicle in which the color-reactants named above are carried, applicant has chosen for the preferred embodiment trichlorodiphenyl, the color reactants being used therein in amounts equal to several percent, by weight, of the total amount of the printing fluid.
As the encapsulating colloid material for the preferred embodiment, applicant has selected a gelatin, although other gellable film-forming hydrophilic colloids, such as agar-agar, will do.
The preferred method of forming the capsules includes the step of treating an aqueous sol of the colloid material having the oil emulsified therein, with a salt solution to cause the colloid material to deposit around the oil droplets, and then causing the colloid to gel. In making up the capsular material, one gallon of an oil-in-water emulsion of 20 parts, by weight, of trichlorodiphenyl containing the color reactants, and parts, by weight, of a sol of 10%, by weight, of pigskin gelatin in water, is prepared, the emulsifying continuing until the drop size of the oil is from 2 to 5 microns. This material is kept at 50 centigrade to prevent the gelatin from gelling. With the temperature of the ingredients still kept at 50 C., coacervation then is induced by adding, slowly and uniformly, four-tenths of a gallon of 20%, by weight, of sodium sulphate in water. The uniform addition of this material is accomplished by continuous agitation.
, tion of formaldehyde in water.
'To gel the coacervate, the heated coacervate mixture this point the encapsulation of the oil with the gelled hydrophilic colloid material has taken place and the further steps are to put it in condition for use as intended. The material is filtered and washed with water, the temperature being kept below the melting point of the gelatin, to remove the salt. If desired, the filtered material is hardened by combining it with 2 gallons of a 37% solu- This hardened mass is then filtered and washed to remove the residual formaldehyde. The resulting filter cake is adjusted to the proper water content by the addition of water or the removal thereof, by ordinary means such as centrifuging or spray drying, and the material is ready for use. As this material is intended for a paper coating composition, it is kept in aqueous suspension and applied directly to the paper, which is then dried, leaving the capsules adherent to the paper and to each other in a film.
If a portion of this fluid is sparsely dispersed in water and placed under a microscope, it will be seen to consist of microscopic capsules of the hydrophilic colloid material, the individual capsules being several microns in diameter and each containing a nucleus of oil. As the water content is decreased, the capsules tend to form aggregations, like bunches of grapes. When the material is of the right consistency, it is coated on paper by rollers, spray, brushes, or any other of the commonly used methods of coating paper, and allowed to dry. The material is of such a nature that the capsules are adherent to each other in the coating, and will adhere to the paper, without the addition of any other binder material.
For more details concerning the process of making the microscopic capsular material, reference is made to my co-pending application, Serial No. 365,106, regarding the process, to which attention has been drawn.
Other colorless adsorption color reactants which form color immediately on contact with acid clay-like material, such as the mentioned attapulgite, are malachite green lactone, which is 3,3 bis(p-dimethylaminophenyl) phthalide, and the ethyl and propyl homologues thereof, which form bluish green marks on the acid-like clay sensitized receiving sheet. Other comparable and equivalent materials are found in United States Patent No. 2,548,366, to which attention has been directed.
The material in the oil which produces the mark on the receiving sheet need not be a reactive material but may have an intrinsic color of itself, such as dissolved v dyes, like Sudan III.
The oils which may be substituted for trichloro-diphenyl are any of the water immiscible oils, which are inert as to the other materials used in forming the capsules, such as petroleum fractions like paratfin oil, vegetable oil such as castor oil, and cottonseed oil, animal oils, such as sperm oil and lard oil, and any other various synthetic oils, such as methyl salicylate.
The coating material should be used in such quantity on the paper that when dried the coated area will be profusely supplied with the microscopic capsules, but such thickness need be no more than a fraction of a thousandth of an inch, because the size of the capsules is in terms of several microns. A four pound coating on a ream of paper 25 inches by 38 inches is satisfactory.
A sheet of ordinary writing paper, coated on one surface With the described coating composition laid with that coated surface on the attapulgite-sensitized surface of a receiving sheet, forms a manifold system which is responsive to very light printing or writing pressures, such as are ordinarily used in every-day printing and writing, so asto make clear and distinct marks on the receiving sheet, yet the coating is so durable that it will undergo,
rough handling without premature rupture of the capsules and is proof against the deleterious influences of the environment, either atmospheric 'or artificial.
The capsules may be rendered porous if the gelled material is allowed to dry without washing out the salt.
While the form of the invention herein shown and described is admirably adapted to fulfill the objects primarily stated, it is to be understood that it is not intended to confine the invention to the one form or embodiment herein disclosed, for it is susceptible of embodiment in vvarious other forms.
What is claimed is:
l. A record material base sheet having on a surface thereof a coating consisting of a profusion of microscopic pressurerupturable capsules having walls of gelled film-forming hydrophilic colloid material in substantial contiguity, each of the capsules consisting of an oily water-immiscible printing fluid as a central nucleus around which has been evenly deposited by coacervation forces a dense oil-impermeable shell-like coating of the colloid material, said capsules being rupturable by printing or marking pressures applied to the coated sheet.
2. Paper having coated on a surface thereof microscopic capsules having walls of gelledfilm-forming hydrophilic colloid material, the capsules being present in such number that they are in substantial contiguity, and each of said capsules consisting of an oily waterimrniscible printing fluid as a central nucleus around which has been evenly deposited by coacervation forces a dense oil-impermeable coating of the colloid mate'- rial, said cupsules being rupturable by printing or marking pressures applied to the coated sheet of paper.
3. A sheet of paper having on a surface thereof a coating that is substantially colorless, said coating consisting of a profusion of pressure-rupturable microscopic capsules having walls of gelled film-forming hydrophilic colloid material in substantial contiguity, each of the capsules consisting of a dense shell-like oil-impermeable Wall of the colloid material deposited about a central nucleus of a colorless oily water-immiscible printing fluid by coacervation forces.
4. The record material of claim 3 in WhlCll'thfi oily printing fluid consists of a water-immiscible oil vehicle in which is carried a colorless color reactant which turns to a colored form on contact with paper sensitized by having thereon acid clay-like material.
References Cited in the file of this patent UNITED STATES PATENTS 2,183,053 Taylor Dec. 12, 1939 2,410,110 Taylor Oct. 29, 1946 2,548,366 Green Apr. 10, 1951 2,550,573 Green Apr. 24, 1951
Claims (1)
1. A RECORD MATERIAL BASE SHEET HAVING ON A SURFACE THEREOF A COATING CONSISTING OF A PROFUSION OR MICROSCOPIC, PRESSURE-RUPTURABLE CAPSULES HAVING WALLS OF GELLED FILM-FORMING HYDROPHILIC COLLOID MATERIAL IN SUBSTANTIAL CONTIGUITY, EACH OF THE CAPSULES CONSISTING OF AN OILY WATER-IMMISCIBLE PRINTING FLUID AS A CENTRAL NUCLEUS AROUND WHICH HAS BEEN EVENLY DEPOSITED BY COACERVATION FORCES A DENSE OIL-IMPERMEABLE SHELL-LIKE COATING OF THE COLLOID MATERIAL, SAID CAPSULES BEING RUPTURABLE BY PRINTING OR MAKING PRESSURES APPLIED TO THE CAOTED SHEET.
Priority Applications (1)
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US36518453 US2712507A (en) | 1953-06-30 | 1953-06-30 | Pressure sensitive record material |
Applications Claiming Priority (1)
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US36518453 US2712507A (en) | 1953-06-30 | 1953-06-30 | Pressure sensitive record material |
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US2712507A true US2712507A (en) | 1955-07-05 |
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US36518453 Expired - Lifetime US2712507A (en) | 1953-06-30 | 1953-06-30 | Pressure sensitive record material |
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Cited By (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2915415A (en) * | 1957-06-19 | 1959-12-01 | Caribonum Ltd | Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith |
US2929736A (en) * | 1957-07-25 | 1960-03-22 | Ncr Co | Heat and pressure responsive record material |
US2953470A (en) * | 1957-06-27 | 1960-09-20 | Ncr Co | Method for electrostatic printing |
US3016308A (en) * | 1957-08-06 | 1962-01-09 | Moore Business Forms Inc | Recording paper coated with microscopic capsules of coloring material, capsules and method of making |
US3058586A (en) * | 1959-12-03 | 1962-10-16 | Gen Foods Corp | Technique of bundling |
US3080250A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Self-tackifying xerographic toner |
US3080251A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Method of xerographic development |
US3080318A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Three-component xerographic toner |
US3138515A (en) * | 1959-02-10 | 1964-06-23 | Dritz Arthur | Transfer sheets and means and combinations thereof |
US3199444A (en) * | 1963-01-11 | 1965-08-10 | Ncr Co | Coded tag printer using punched tags |
US3244550A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3244548A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3244549A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3364052A (en) * | 1965-02-17 | 1968-01-16 | Frank D. Martino | Method for desensitizing sensitized record sheets and resultant article |
US3373682A (en) * | 1966-01-17 | 1968-03-19 | Arthur M. Angel | Transaction recorder for printing on pressure-sensitive journal tape |
US3395018A (en) * | 1964-04-29 | 1968-07-30 | Du Pont | Light-sensitive color-forming composition |
US3447945A (en) * | 1966-04-09 | 1969-06-03 | Fuji Photo Film Co Ltd | Process for the preparation of pressure-sensitive copying papers |
US3769066A (en) * | 1971-06-22 | 1973-10-30 | Ncr Co | Replacement of capsule contents |
DE2612036A1 (en) * | 1975-03-24 | 1976-10-14 | Moore Business Forms Inc | CARBON-FREE MULTIPLE COPY SHEET SYSTEM |
US3988492A (en) * | 1974-04-18 | 1976-10-26 | The Mead Corporation | Pressure sensitive copy paper employing pyrazoloxanthene compounds |
US4003245A (en) * | 1974-03-26 | 1977-01-18 | Fuji Photo Film Co., Ltd. | Method for pressure measurement |
US4140336A (en) * | 1974-07-29 | 1979-02-20 | Moore Business Forms, Inc. | Product and process for reducing discoloration in carbonless copying systems |
US4182714A (en) * | 1976-12-29 | 1980-01-08 | Sterling Drug Inc. | Carbazole containing phthalides |
US4188456A (en) * | 1977-12-23 | 1980-02-12 | Ncr Corporation | Pressure-sensitive recording sheet |
US4199174A (en) * | 1976-05-13 | 1980-04-22 | Moore Business Forms, Inc. | Carbonless manifold business forms |
US4263047A (en) * | 1978-09-11 | 1981-04-21 | Fuji Photo Film Co., Ltd. | Color developing ink |
US4307018A (en) * | 1979-04-04 | 1981-12-22 | Sterling Drug Inc. | Heteroarylphthalides |
US4322352A (en) * | 1979-04-04 | 1982-03-30 | Sterling Drug Inc. | Indolyl phthalide compounds |
US4363664A (en) * | 1980-01-25 | 1982-12-14 | Sterling Drug Inc. | Novel compositions and processes |
US4477676A (en) * | 1976-01-22 | 1984-10-16 | The Hilton-Davis Chemical Co. | 4-(3-Indolyl)-2,3-dichloro-4-oxo-2-butenoic acids |
US4495509A (en) * | 1983-06-09 | 1985-01-22 | Moore Business Forms, Inc. | Microencapsulation by interchange of multiple emulsions |
DE3530562A1 (en) * | 1984-08-28 | 1986-03-06 | Mitsubishi Paper Mills, Ltd., Tokio/Tokyo | ORGANIC CAPSULE |
US4599271A (en) * | 1983-06-09 | 1986-07-08 | Moore Business Forms, Inc. | Microencapsulation of polyisocyanates by interchange of multiple |
US4626471A (en) * | 1985-02-25 | 1986-12-02 | Moore Business Forms, Inc. | Microencapsulation by in-situ polymerization of multifunctional epoxy resins |
US4636818A (en) * | 1985-06-05 | 1987-01-13 | Moore Business Forms, Inc. | Carbonless system including solvent-only microcapsules |
EP0233450A2 (en) | 1986-01-17 | 1987-08-26 | MITSUI TOATSU CHEMICALS, Inc. | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal-resins of the copolymers, and color-developing sheets employing the agents |
US4785048A (en) * | 1988-02-08 | 1988-11-15 | Moore Business Forms, Inc. | Polyurea and polyurea-epoxy microcapsules |
US4927802A (en) * | 1988-12-09 | 1990-05-22 | Ppg Industries, Inc. | Pressure-sensitive multi-part record unit |
US4931420A (en) * | 1986-04-30 | 1990-06-05 | Mitsui Toatsu Chemicals, Inc. | Temperature history indicator and its manufacturing method |
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US5135437A (en) * | 1989-11-13 | 1992-08-04 | Schubert Keith E | Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same |
US5137494A (en) * | 1989-11-13 | 1992-08-11 | Schubert Keith E | Two-sided forms and methods of laying out, printing and filling out same |
US5154668A (en) * | 1989-04-06 | 1992-10-13 | Schubert Keith E | Single paper sheet forming a two-sided copy of information entered on both sides thereof |
US5197922A (en) * | 1989-04-06 | 1993-03-30 | Schubert Keith E | Method and apparatus for producing two-sided carbonless copies of both sides of an original document |
US5224897A (en) * | 1989-04-06 | 1993-07-06 | Linden Gerald E | Self-replicating duplex forms |
US5248279A (en) * | 1989-04-06 | 1993-09-28 | Linden Gerald E | Two-sided, self-replicating forms |
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EP0697293A1 (en) | 1994-07-26 | 1996-02-21 | Copigraph | New organic solvent for microcapsules useful notably for pressure-sensitive copy paper and pressure-sensitive copy coated with such microcapsules |
EP0714786A1 (en) | 1994-12-02 | 1996-06-05 | Copigraph | New microcapsules comprising as solvent a terpene derivative or an abietic acid derivative, notably for chemical copy papers and messure sensitive papers coated with such microcapsules |
US5709738A (en) * | 1996-06-06 | 1998-01-20 | Moore Business Forms Inc | Coating composition for ink jet printing |
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WO2008038645A1 (en) | 2006-09-29 | 2008-04-03 | Nippon Paper Industries Co., Ltd. | Heat-sensitive recording material |
US7647809B1 (en) | 2004-03-13 | 2010-01-19 | Spectrum Aeronautical, Llc | Approach for indicating the occurrence of a mechanical impact on a material, such as a low-ductility composite material |
US20110220006A1 (en) * | 2007-08-08 | 2011-09-15 | Airbus Uk Limited | Composite laminate structure |
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WO2016185171A1 (en) | 2015-05-20 | 2016-11-24 | Lambson Limited | Capsules |
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US2915415A (en) * | 1957-06-19 | 1959-12-01 | Caribonum Ltd | Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith |
US2953470A (en) * | 1957-06-27 | 1960-09-20 | Ncr Co | Method for electrostatic printing |
US2929736A (en) * | 1957-07-25 | 1960-03-22 | Ncr Co | Heat and pressure responsive record material |
US3016308A (en) * | 1957-08-06 | 1962-01-09 | Moore Business Forms Inc | Recording paper coated with microscopic capsules of coloring material, capsules and method of making |
US3080250A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Self-tackifying xerographic toner |
US3080251A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Method of xerographic development |
US3080318A (en) * | 1958-03-13 | 1963-03-05 | Xerox Corp | Three-component xerographic toner |
US3138515A (en) * | 1959-02-10 | 1964-06-23 | Dritz Arthur | Transfer sheets and means and combinations thereof |
US3058586A (en) * | 1959-12-03 | 1962-10-16 | Gen Foods Corp | Technique of bundling |
US3244550A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3244548A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3244549A (en) * | 1961-08-31 | 1966-04-05 | Burroughs Corp | Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking |
US3199444A (en) * | 1963-01-11 | 1965-08-10 | Ncr Co | Coded tag printer using punched tags |
US3395018A (en) * | 1964-04-29 | 1968-07-30 | Du Pont | Light-sensitive color-forming composition |
US3364052A (en) * | 1965-02-17 | 1968-01-16 | Frank D. Martino | Method for desensitizing sensitized record sheets and resultant article |
US3373682A (en) * | 1966-01-17 | 1968-03-19 | Arthur M. Angel | Transaction recorder for printing on pressure-sensitive journal tape |
US3447945A (en) * | 1966-04-09 | 1969-06-03 | Fuji Photo Film Co Ltd | Process for the preparation of pressure-sensitive copying papers |
US3769066A (en) * | 1971-06-22 | 1973-10-30 | Ncr Co | Replacement of capsule contents |
US4003245A (en) * | 1974-03-26 | 1977-01-18 | Fuji Photo Film Co., Ltd. | Method for pressure measurement |
US3988492A (en) * | 1974-04-18 | 1976-10-26 | The Mead Corporation | Pressure sensitive copy paper employing pyrazoloxanthene compounds |
US4140336A (en) * | 1974-07-29 | 1979-02-20 | Moore Business Forms, Inc. | Product and process for reducing discoloration in carbonless copying systems |
DE2612036A1 (en) * | 1975-03-24 | 1976-10-14 | Moore Business Forms Inc | CARBON-FREE MULTIPLE COPY SHEET SYSTEM |
US4477676A (en) * | 1976-01-22 | 1984-10-16 | The Hilton-Davis Chemical Co. | 4-(3-Indolyl)-2,3-dichloro-4-oxo-2-butenoic acids |
US4199174A (en) * | 1976-05-13 | 1980-04-22 | Moore Business Forms, Inc. | Carbonless manifold business forms |
US4182714A (en) * | 1976-12-29 | 1980-01-08 | Sterling Drug Inc. | Carbazole containing phthalides |
US4188456A (en) * | 1977-12-23 | 1980-02-12 | Ncr Corporation | Pressure-sensitive recording sheet |
US4263047A (en) * | 1978-09-11 | 1981-04-21 | Fuji Photo Film Co., Ltd. | Color developing ink |
US4307018A (en) * | 1979-04-04 | 1981-12-22 | Sterling Drug Inc. | Heteroarylphthalides |
US4322352A (en) * | 1979-04-04 | 1982-03-30 | Sterling Drug Inc. | Indolyl phthalide compounds |
US4363664A (en) * | 1980-01-25 | 1982-12-14 | Sterling Drug Inc. | Novel compositions and processes |
US4599271A (en) * | 1983-06-09 | 1986-07-08 | Moore Business Forms, Inc. | Microencapsulation of polyisocyanates by interchange of multiple |
US4495509A (en) * | 1983-06-09 | 1985-01-22 | Moore Business Forms, Inc. | Microencapsulation by interchange of multiple emulsions |
DE3530562A1 (en) * | 1984-08-28 | 1986-03-06 | Mitsubishi Paper Mills, Ltd., Tokio/Tokyo | ORGANIC CAPSULE |
DE3530562C2 (en) * | 1984-08-28 | 1987-11-05 | Mitsubishi Paper Mills, Ltd., Tokio/Tokyo, Jp | |
US4626471A (en) * | 1985-02-25 | 1986-12-02 | Moore Business Forms, Inc. | Microencapsulation by in-situ polymerization of multifunctional epoxy resins |
US4636818A (en) * | 1985-06-05 | 1987-01-13 | Moore Business Forms, Inc. | Carbonless system including solvent-only microcapsules |
EP0233450A2 (en) | 1986-01-17 | 1987-08-26 | MITSUI TOATSU CHEMICALS, Inc. | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal-resins of the copolymers, and color-developing sheets employing the agents |
US4783521A (en) * | 1986-01-17 | 1988-11-08 | Mitsui Toatsu Chemicals, Incorporated | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal-resins of the copolymers |
US4931420A (en) * | 1986-04-30 | 1990-06-05 | Mitsui Toatsu Chemicals, Inc. | Temperature history indicator and its manufacturing method |
US5049606A (en) * | 1987-05-06 | 1991-09-17 | Mitsui Toatsu Chemicals, Incorporated | Thermosetting resin composition |
US4785048A (en) * | 1988-02-08 | 1988-11-15 | Moore Business Forms, Inc. | Polyurea and polyurea-epoxy microcapsules |
US5026763A (en) * | 1988-08-09 | 1991-06-25 | Basf Aktiengesellschaft | Polyamide molding materials |
US4927802A (en) * | 1988-12-09 | 1990-05-22 | Ppg Industries, Inc. | Pressure-sensitive multi-part record unit |
US5154668A (en) * | 1989-04-06 | 1992-10-13 | Schubert Keith E | Single paper sheet forming a two-sided copy of information entered on both sides thereof |
US5197922A (en) * | 1989-04-06 | 1993-03-30 | Schubert Keith E | Method and apparatus for producing two-sided carbonless copies of both sides of an original document |
US5224897A (en) * | 1989-04-06 | 1993-07-06 | Linden Gerald E | Self-replicating duplex forms |
US5248279A (en) * | 1989-04-06 | 1993-09-28 | Linden Gerald E | Two-sided, self-replicating forms |
US5395288A (en) * | 1989-04-06 | 1995-03-07 | Linden; Gerald E. | Two-way-write type, single sheet, self-replicating forms |
US5135437A (en) * | 1989-11-13 | 1992-08-04 | Schubert Keith E | Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same |
US5137494A (en) * | 1989-11-13 | 1992-08-11 | Schubert Keith E | Two-sided forms and methods of laying out, printing and filling out same |
US6280322B1 (en) | 1989-11-13 | 2001-08-28 | Gerald E. Linden | Single sheet of paper for duplicating information entered on both surfaces thereof |
US5472489A (en) * | 1991-06-18 | 1995-12-05 | The Wiggins Teape Group Limited | Solvent compositions for use in pressure-sensitive copying paper |
US5281266A (en) * | 1991-06-18 | 1994-01-25 | The Wiggins Teape Group Limited | Solvent compositions for use in pressure-sensitive copying paper |
US5376615A (en) * | 1991-07-18 | 1994-12-27 | Mitsui Toatsu Chemicals, Incorporated | Color-developing compositions and their use |
US5447901A (en) * | 1991-07-18 | 1995-09-05 | Mitsui Toatsu Chemical, Inc. | Color-developing compositions and their use |
US5464803A (en) * | 1992-06-04 | 1995-11-07 | The Wiggins Teape Group Limited | Pressure-sensitive record material |
US5350729A (en) * | 1993-03-02 | 1994-09-27 | The Mead Corporation | Developer sheet with structured clays and process thereof |
US5476829A (en) * | 1993-07-03 | 1995-12-19 | The Wiggins Teape Group Limited | Pressure-sensitive copying material |
US5474968A (en) * | 1993-09-20 | 1995-12-12 | Brother Kogyo Kabushiki Kaisha | Printing tape and printing-tape cartridge |
EP0697292A1 (en) | 1994-07-20 | 1996-02-21 | The Wiggings Teape Group Limited | Pressure-sensitive copying material |
US5605874A (en) * | 1994-07-20 | 1997-02-25 | The Wiggins Teape Group Limited | Pressure-sensitive copying material |
EP0697293A1 (en) | 1994-07-26 | 1996-02-21 | Copigraph | New organic solvent for microcapsules useful notably for pressure-sensitive copy paper and pressure-sensitive copy coated with such microcapsules |
EP0714786A1 (en) | 1994-12-02 | 1996-06-05 | Copigraph | New microcapsules comprising as solvent a terpene derivative or an abietic acid derivative, notably for chemical copy papers and messure sensitive papers coated with such microcapsules |
US5709738A (en) * | 1996-06-06 | 1998-01-20 | Moore Business Forms Inc | Coating composition for ink jet printing |
US6242167B1 (en) | 1999-04-12 | 2001-06-05 | Rentech, Inc. | Developer for use with carbonless copy paper and photo imaging systems |
US6403528B1 (en) | 1999-04-12 | 2002-06-11 | Rentech, Inc. | Developer for use with carbonless copy paper and photo imaging system |
US6310002B1 (en) | 2000-03-07 | 2001-10-30 | Appleton Papers Inc. | Record material |
US7647809B1 (en) | 2004-03-13 | 2010-01-19 | Spectrum Aeronautical, Llc | Approach for indicating the occurrence of a mechanical impact on a material, such as a low-ductility composite material |
WO2008038645A1 (en) | 2006-09-29 | 2008-04-03 | Nippon Paper Industries Co., Ltd. | Heat-sensitive recording material |
US9334039B2 (en) * | 2007-08-08 | 2016-05-10 | Airbus Operations Limited | Composite laminate structure |
US20110220006A1 (en) * | 2007-08-08 | 2011-09-15 | Airbus Uk Limited | Composite laminate structure |
WO2013041415A1 (en) | 2011-09-20 | 2013-03-28 | U-Nica Technology Ag | Method and device for producing color images on substrates containing color bodies and products produced thereby |
US8953008B2 (en) | 2011-09-20 | 2015-02-10 | U-Nica Technology Ag | Method and device for producing color images on substrates containing color bodies and products produced thereby |
US9372177B2 (en) | 2013-03-15 | 2016-06-21 | The Boeing Company | Method and system for detecting exposure of composites to high-temperature |
US20150308907A1 (en) * | 2014-04-23 | 2015-10-29 | The Boeing Company | Witness Material and Method for Monitoring the Environmental History of an Object |
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WO2016185171A1 (en) | 2015-05-20 | 2016-11-24 | Lambson Limited | Capsules |
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