US3409457A - Thermographic copying sheet - Google Patents

Thermographic copying sheet Download PDF

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Publication number
US3409457A
US3409457A US42359765A US3409457A US 3409457 A US3409457 A US 3409457A US 42359765 A US42359765 A US 42359765A US 3409457 A US3409457 A US 3409457A
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Prior art keywords
water
dye
compounds
solution
color
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English (en)
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Menzel Karl-Heinz
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Agfa Gevaert NV
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Agfa AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/009—Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/50—Acylated on said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • 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
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only

Definitions

  • ABSTRACT OF THE DISCLOSURE This invention relates to the reproduction of originals on heat sensitive copying materials by color thermography, using the heat-sensitive copying paper that contains heatsensitive compounds which form azomethine dyes when heated.
  • thermographic methods to use copying materials containing compounds which undergo color change when heated either by absorption of radiant heat such as infrared rays, or by transfer of thermal energy by contact.
  • radiant heat such as infrared rays
  • transfer of thermal energy by contact In addition to this chemical method of producing an image, other methods based on physical principles are used. For example, an image may be produced by melting an opaque surface to render it transparent. In other processes, certain parts of the layer are imagewise fixed under the influence of heat, While the parts of the layer not affected by the heat can be removed.
  • the more specific object is to provide materials which yield upon exposure to a heat pattern a colored image of excellent quality.
  • compounds having the activated methylene structure of a photographic color coupler but in which structure one hydrogen of the activated methylene is substituted with an acylamino group derived from an aliphatic carboxylic acid and the other hydrogen atom of the methylene is substituted With a pamino phenylene imino grouping which is linked to the carbon atom of the methylene by the nitrogen atom of the imino group, exhibit excellent utility for color thermoprinting.
  • the above compounds are colorless and upon the action of heat form azomethine dyes, the acylamino group is Splitting 01f.
  • Suitable compounds are derived from photographic color couplers containing activated open-chain or cyclic methylene groups. Those compounds are characterized by the following formulae:
  • a and B are negative groups such as COR COOR CO.COOR -CO.NHR CO.NR R -CN;
  • R stands for substituted or unsubstituted alkyl having up to 18 carbon atoms such as methyl, ethyl, allyl, butyl, dodecyl, octadecyl, and aryl such as phenyl, chlorophenyl, tolyl; a cycloalkyl group such as cycllopentyl, cyclohexyl, methylcyclohexyl; or an aralkyl group such as a benzyl group.
  • acyl acetic esters such as benzoylacetic esters, acyl acetoacetic esters, malonic acid ester, acyl acetonitriles, aroyl acetonitriles, cyanacetophenone, benzoylacetophenones, cyanacetic esters or acylacetic amides such as benzoy-lacet- 3,409,457 Patented Nov. 5, 1968 ice anilides which are substituted in the reactive methylene group by the radicals X and Y.
  • acyl acetic esters such as benzoylacetic esters, acyl acetoacetic esters, malonic acid ester, acyl acetonitriles, aroyl acetonitriles, cyanacetophenone, benzoylacetophenones, cyanacetic esters or acylacetic amides such as benzoy-lacet- 3,409,457 Patented Nov. 5, 1968 ice anilides which
  • D represents ring members necessary to complete a heterocyclic ring having adjacent to the carbonyl group an activated methylene group, the hydrogen atoms of which are substituted by the radicals X and Y.
  • heterocyclic rings examples are compounds which are generally referred to as photographic magenta couplers.
  • couplers particularly include pyrazolone structures particularly l-phen-ylpyrazolones such as described in the publication of O. Wahl in Zeitschrift fiir angewandte Chemie, vol. 64 (1952), pages 259/265, indazolones or benzimidazolo pyrazolones such as described in British Patent No. 918,128.
  • Y represents an acylamino group which is linked to the carbon atom by the nitrogen atom of the amino group and which is derived from aliphatic carboxylic acids preferably carboxylic acid having up to carbon atoms.
  • X stands for a p-aminophenylene imino grouping hav ing an unsubstituted imino group and which is linked to the carbon atoms by the nitrogen atom of the unsubstituted imino group.
  • the p-amino group can be substituted in particular by alkyl groups having up to 5 carbon atoms which in turn can be substituted by carboxyl groups, hydroxy groups or sulfo groups and the like.
  • the phenyl ring also can be substituted for example with alkyl in particular lower alkyl having up to 3 carbon atoms, halogen atoms in particular chlorine, alkoxy groups having up to 5 carbon atoms and the like.
  • the substituents are preferably in o-position to the unsubstituted imino group.
  • the above compounds are prepared by reacting color couplers having an activated methylene group which is substituted with an amino group, with an acid anhydrid or acid chloride, preferably in the presence of pyridine, and then reacting the resulting acyl-amino-group containing color coupler under oxidizing conditions with a pphenylene diamine or derivatives thereof which contain 1 primary amino group.
  • the preparation can :be illustrated by the following equation:
  • su'ch compounds are'p-dietlfyladiinm aniline, p-dimethylaminoahiline, 2-methyl-4-diethylamirib aniline, p-dihydroxyethylaminoaniline and p-ethylsulfobutylaminoaniline.
  • the coupling by oxidation of the indicated components with the various acylamin'osubstituted color couplers is performed preferably in an inert solvent, advantageously at temperatures below C. in effective contact with an oxidizing agent such as hydrogen peroxide.
  • an oxidizing agent such as hydrogen peroxide.
  • Water or mixtures of water and water-soluble organic compounds such as lower alcohols, can for example, be used as reaction medium.
  • the colorless reaction product which can also be called leuco compounds can be isolated and are soluble in organic solvents, e.g., methanol or dimethylforrnamide, or if substituted with acid groups, in aqueous alkalis. They are transformed into yellow or violet azomethine dyes upon being heated to temperatures of about 100'- 160 C., whether in solid form, in solution or after being applied to a suitable support material, such as paper.
  • a conversion of the leuco compounds into the azomethine dyes can be accelerated by using alkalis, such as alkali alcoholates.
  • the leuco compounds are suitable for the production of heat-sensitive printing materials which permit reproduction of an image 'with the aid of infrared radiation or by contact transfer of heat energy.
  • the heat-sensitive compounds of the present invention are conveniently applied to a sheet-like support in the form of a dispersion or solution in a suitable volatile solvent either alone or in combination with a film-forming binding agent such as cellulose ester of inorganic or organic acids, for example nitro cellulose or cellulose acetate, polyvinyl butyral, polyvinyl alcohol, cyclized rubber and the like.
  • a film-forming binding agent such as cellulose ester of inorganic or organic acids, for example nitro cellulose or cellulose acetate, polyvinyl butyral, polyvinyl alcohol, cyclized rubber and the like.
  • thermographic printing artix The:heat-sensitivercopying material- "of the present invention may fibe utilized: 1 :for contact printing, refiex pr inting or the' inscribingof m'arke ings by means"of'beatedstylus'or heate'd stamps,all-well e thermographic printing artix:
  • a solution of 6.5 g. of -p-diethylaminoaniline sulfate in 100 cc. of water is added to a solution of g. of 2-phenyl 3-propionyl-amino-pyrazolo-(1,5a)-benzimidazole sulfonic acid-6 and g. of anhydrous sodium carbonate in 75 cc. of Water.
  • a solution of 2.8 cc. of hydrogen peroxide (30%) in cc. of water is added dropWise thereto. The mixture is then left to stand for 1 /2 hours and then the product is precipitated by adding 3% hydrochloric acid, whereupon it is suction-filtered and washed with water until the discharging filtrate is colorless. About 8 g. of product in accordance with the above formula are obtained. Upon heating it changes color at 120 C. with decomposition above 220 C.
  • the mixture is left standing for 1 hour at room temperature and the ,addition compound is then precipitated with 3% hydro- 1 g. of the above leuco compound is heated to boiling point in 15 cc. of dimethylformamide until a dyestuif solution has been formed.
  • the solvent is distilled off in water jet vacuum while heating gently. The residue is taken up in.10 cc. of methanol. After evaporating the solvent, about 0.8 g. of the azomethine dye are obtained.
  • EXAMPLE 4 (a) Preparation of the colorless leuco compound. A solution of 10.2 g. of p-diethylaminoaniline sulfate in 160 cc. of Water is added at room temperature to a solution of 9.24 g. of 1 phenyl 3 methyl 4 acetylaminopyrazolone 5 in cc. of 4% sodium hydroxide solution and 200 cc. of water. While stirring, a solution of 4.5 g. of hydrogen peroxide (30%) in 40 cc. of water is then added dropwise at 30 C. After standing overnight in a refrigerator, the substance is suction-filtered and washed neutral with water. About 6 g. of product are isolated. Upon heating it changes color at C., melting at -147" C. Empiral formula molecular weight 377.
  • 1,-amino 1 (4'-meth0xy)benzoylacetic acid-(2"-methoxy-5-carboxy) anilide-12 g. of the above nitroso product are stirred with 100 cc. of methanol and dissolved by adding 20 cc. of 25% ammonia. Hydrogenation takes place in the presence of Raney nickel for one hour at 50 C. and 50 atm. of H the substance is filtered off from the catalyst and the filtrate is made neutral with 20% sulphuric acid. After cooling, this is suction-filtered. The crude product is extracted by boiling with 200 cc. of water. About 9 g. of amine are obtained. M.P. 203 C.
  • Example 6 Absorbent writing paper (so-called absorbent post paper) is impregnated with a colution of 2 g. of the leuco compound according to Example 1 in 200 cc. of methanol and 2.5 cc. of 4% sodium hydroxide solution and dried. A heat-sensitive copying paper is obtained, which changes in colour to violet on heating to C.
  • the paper is either treated with a writing or marking instrument at a temperature of about C. or processed in a manner known per se in the so-called thermal copying apparatus. A brief strong infrared irradiation then takes place, which leads to a brief heating at the image areas of the original.
  • the heat-sensitive copying paper which is in contact takes up this heat with formation of an image of the original.
  • Example 7 2 g.-of the leuco compound according to Example 2 are dissolved in 200 cc. of methanol and 3 cc. of 4% sodium hydroxide solution. The procedure is as in Example 6. The copying paper which is obtained changes to violet in colour on heating to 120 C.
  • Example 8 2 g. of the leuco compound according to Example 3 are dissolved in 200 cc. of methanol and 2 cc. of 4% sodium hydroxide solution. By following the procedure of Example 6, a copying paper is obtained which changes to violet in colour on heating to 160 C.
  • Example 9 2 g. of the'leuco compound according to Example 4 are dissolved in 200 cc. of methanol. The procedure followed is that set out in Example 6. The copying paper which is obtained changes to violet in colour on heating to C.
  • thermographic copying material having a sheetlike support carrying a heat sensitive compound that changes in color upon heating
  • said compound is a leuco form of an azomethane dye having a p-amino-phenylene-imino group substituted for a hydrogen of an active methylene in a photographic color coupler, the other hydrogen of the methylene being substituted by an acylamino group in which acyl is that of an aliphatic carboxylic acid having up to 5 carbons, and the imino portion of the p-aminophenylene-imino group is unsubstituted.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US42359765 1964-01-11 1965-01-05 Thermographic copying sheet Expired - Lifetime US3409457A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531286A (en) * 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images
US3813677A (en) * 1972-02-23 1974-05-28 Matsushita Electric Ind Co Ltd Heat-sensitive record
US4022617A (en) * 1974-07-25 1977-05-10 Eastman Kodak Company Photothermographic element, composition and process for producing a color image from leuco dye
US5192645A (en) * 1988-07-18 1993-03-09 Polaroid Corporation Thermal imaging method
US5236884A (en) * 1991-05-06 1993-08-17 Polaroid Corporation Thermal imaging methods and materials
US5372917A (en) * 1992-06-30 1994-12-13 Kanzaki Paper Manufacturing Co., Ltd. Recording material
US5424475A (en) * 1988-07-18 1995-06-13 Polaroid Corporation Thermal imaging dye precursors

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1561272A (en) * 1976-04-27 1980-02-20 Ciba Geigy Ag Azomethine compounds their manufacture and use
JPH0794180B2 (ja) * 1987-09-03 1995-10-11 富士写真フイルム株式会社 感熱転写材料
EP0665462B1 (en) * 1994-01-28 2001-04-18 New Oji Paper Co., Ltd. Thermofixable photosensitive recording material and process for preparing thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976294A (en) * 1959-01-26 1961-03-21 Du Pont Dye intermediates
US3219470A (en) * 1962-02-13 1965-11-23 Agfa Ag Heat sensitive copying layers
US3293061A (en) * 1963-11-21 1966-12-20 Man Res Lab Inc Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet
US3312551A (en) * 1962-07-25 1967-04-04 Keuffel & Esser Co Heat and light sensitive diazo sulfonate and azo coupler coated sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976294A (en) * 1959-01-26 1961-03-21 Du Pont Dye intermediates
US3219470A (en) * 1962-02-13 1965-11-23 Agfa Ag Heat sensitive copying layers
US3312551A (en) * 1962-07-25 1967-04-04 Keuffel & Esser Co Heat and light sensitive diazo sulfonate and azo coupler coated sheet
US3293061A (en) * 1963-11-21 1966-12-20 Man Res Lab Inc Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531286A (en) * 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images
US3813677A (en) * 1972-02-23 1974-05-28 Matsushita Electric Ind Co Ltd Heat-sensitive record
US4022617A (en) * 1974-07-25 1977-05-10 Eastman Kodak Company Photothermographic element, composition and process for producing a color image from leuco dye
US5192645A (en) * 1988-07-18 1993-03-09 Polaroid Corporation Thermal imaging method
US5424475A (en) * 1988-07-18 1995-06-13 Polaroid Corporation Thermal imaging dye precursors
US5236884A (en) * 1991-05-06 1993-08-17 Polaroid Corporation Thermal imaging methods and materials
US5350870A (en) * 1991-05-06 1994-09-27 Polaroid Corporation Thermal imaging methods and materials
US5372917A (en) * 1992-06-30 1994-12-13 Kanzaki Paper Manufacturing Co., Ltd. Recording material

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BE658107A (en)) 1965-07-12

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