US3852093A - Heat-sensitive copy-sheet - Google Patents
Heat-sensitive copy-sheet Download PDFInfo
- Publication number
- US3852093A US3852093A US00314687A US31468772A US3852093A US 3852093 A US3852093 A US 3852093A US 00314687 A US00314687 A US 00314687A US 31468772 A US31468772 A US 31468772A US 3852093 A US3852093 A US 3852093A
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- United States
- Prior art keywords
- reducing agent
- sheet material
- sheet
- color
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- -1 nitrogenous organic base Chemical class 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 7
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 7
- 229920006267 polyester film Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 4
- 229920001220 nitrocellulos Polymers 0.000 description 4
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 4
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- CVSUAFOWIXUYQA-UHFFFAOYSA-M 2,6-Dichlorophenolindophenol sodium salt Chemical compound [Na+].C1=CC([O-])=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 CVSUAFOWIXUYQA-UHFFFAOYSA-M 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- FBWSRAOCSJQZJA-UHFFFAOYSA-N 4-iminonaphthalen-1-one Chemical compound C1=CC=C2C(=N)C=CC(=O)C2=C1 FBWSRAOCSJQZJA-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 229920006385 Geon Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LZBCVRCTAYKYHR-UHFFFAOYSA-N acetic acid;chloroethene Chemical compound ClC=C.CC(O)=O LZBCVRCTAYKYHR-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QLUXVUVEVXYICG-UHFFFAOYSA-N 1,1-dichloroethene;prop-2-enenitrile Chemical compound C=CC#N.ClC(Cl)=C QLUXVUVEVXYICG-UHFFFAOYSA-N 0.000 description 1
- SRUQARLMFOLRDN-UHFFFAOYSA-N 1-(2,4,5-Trihydroxyphenyl)-1-butanone Chemical compound CCCC(=O)C1=CC(O)=C(O)C=C1O SRUQARLMFOLRDN-UHFFFAOYSA-N 0.000 description 1
- XLEYFDVVXLMULC-UHFFFAOYSA-N 2',4',6'-trihydroxyacetophenone Chemical compound CC(=O)C1=C(O)C=C(O)C=C1O XLEYFDVVXLMULC-UHFFFAOYSA-N 0.000 description 1
- AQUUGCFXMYRQNN-UHFFFAOYSA-N 2,3,4-trihydroxy-1-phenyldecan-1-one Chemical compound CCCCCCC(O)C(O)C(O)C(=O)C1=CC=CC=C1 AQUUGCFXMYRQNN-UHFFFAOYSA-N 0.000 description 1
- GIMQRBAXJNNBQU-UHFFFAOYSA-N 2-tert-butylbenzene-1,4-diol;2-methylbenzene-1,4-diol Chemical compound CC1=CC(O)=CC=C1O.CC(C)(C)C1=CC(O)=CC=C1O GIMQRBAXJNNBQU-UHFFFAOYSA-N 0.000 description 1
- OAUWOBSDSJNJQP-UHFFFAOYSA-N 3,4,5,6-tetrabromobenzene-1,2-diol Chemical compound OC1=C(O)C(Br)=C(Br)C(Br)=C1Br OAUWOBSDSJNJQP-UHFFFAOYSA-N 0.000 description 1
- ZORMWTDEFZLFJA-UHFFFAOYSA-N 3-aminophenol;4-aminophenol Chemical compound NC1=CC=C(O)C=C1.NC1=CC=CC(O)=C1 ZORMWTDEFZLFJA-UHFFFAOYSA-N 0.000 description 1
- NDACNGSDAFKTGE-UHFFFAOYSA-N 3-hydroxydiphenylamine Chemical compound OC1=CC=CC(NC=2C=CC=CC=2)=C1 NDACNGSDAFKTGE-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 1
- XOPOEBVTQYAOSV-UHFFFAOYSA-N butyl 3,4,5-trihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 XOPOEBVTQYAOSV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- MIJRFWVFNKQQDK-UHFFFAOYSA-N furoin Chemical compound C=1C=COC=1C(O)C(=O)C1=CC=CO1 MIJRFWVFNKQQDK-UHFFFAOYSA-N 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- PRBZWMUOQVJJMD-UHFFFAOYSA-M sodium;2-chloro-4-[(3,5-dichloro-4-oxocyclohexa-2,5-dien-1-ylidene)amino]phenolate Chemical compound [Na+].C1=C(Cl)C([O-])=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 PRBZWMUOQVJJMD-UHFFFAOYSA-M 0.000 description 1
- XFFDCGLVVOTKOS-UHFFFAOYSA-M sodium;4-[(3,5-dibromo-4-oxocyclohexa-2,5-dien-1-ylidene)amino]phenolate Chemical compound [Na+].C1=CC([O-])=CC=C1N=C1C=C(Br)C(=O)C(Br)=C1 XFFDCGLVVOTKOS-UHFFFAOYSA-M 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
- B41M5/286—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using compounds undergoing unimolecular fragmentation to obtain colour shift, e.g. bleachable 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
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/165—Thermal imaging composition
Definitions
- thermographic copying wherein a copy of a differentially radiation-absorptive original is made on a heat-sensitive copy-sheet product held in'heat-conductive contact therewith by briefly exposing the original to intense infra-red radiation.
- the invention relates to novel heat-sensitive copy-sheet products.
- the invention relates to copy-sheet products useful in making negative color projection transparencies.
- the present invention employs a different class of color bodies and a different reaction system, and provides a heat-sensitive copy-sheet product which when locally heated, as in the thermographic copying process, is converted from a highly colored to a substantially colorless, and preferably a clear and transparent, form at the heated image areas without release of volatile decomposition products.
- the heat-sensitive copy-sheet products of the present invention contain p-quinoneimine color bodies which undergo decolorization when heated at thermographically induced temperatures in reactive association with a mild reducing agent.
- the color body is supplied in a matrix of film-forming binder as a coating on a paper, transparent film or other carrier or as a self-supporting film.
- the reducing agent may be incorporated in the same matrix, or in an adjacent stratum supported on the carrier or on a separate carrier.
- a particularly useful structure comprises a transparent flexible film carrier coated with a first stratum of p-quinoneimine color body in a transparent binder and overcoated with a mild reducing agent in a separate binder. Brief heating of the film product causes migration of at least one of the reactants and results in a decolorization of the color body at the heated area.
- Reducible p-quinoneimine color bodies which are useful in the preparation of heat-sensitive copy-sheets of the invention include those having thestructural formula.
- Ar is an aromatic radical and the R, R, R"
- R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein substituent radicals on adjacent carbon atoms may complete a fused polycyclic or heterocyclic ring, all as exemplified by 2 2-chloro-2'-methyl-N,N-diethylindoaniline 2-chloro-N(p-diethylamino-2-methylphenyl)-pbenzoquinoneimine 2-acetamido-N,N,-diethylindoaniline 3-methoxy-2'-methyl-N,N-diethylindoaniline N-( l-naphthyl )-p-benzoquinoneimine N-(2-naphthyl)-p-benzoquinoneimine N-(p-acetylphenyl)-p-benzoquinoneimine 2,6-dichloroindophenol sodium salt 2,3',6-trichloroindophenol sodium salt 2,6
- quinolinoquinoneimine N-(2,4-diamino-5-methylphenyl)-pbenzoquinoneimine trihydrate indoferron N-(p-diethylamino-2-methylphenyl)-2-carboxylic-l 4-naphthoquinoneimine N-(p-dimethylaminophenyl l ,4-
- Binder systems may include such polymeric materials as polystyrene, styrene-acrylonitrile or sytrene-acrylate copolymers, styrene-butadiene-acrylonitrile terpolymers, polyvinylchloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-acrylonitrile or vinylidene chloride-vinyl acetate copolymers, polyacrylates, polyvinyltoluene. These polymers are moistureresistant, being incapable of absorbing more than about one percent of water, and are preferred as contributing to the stability of the sheet materials during prolonged storage both before and after imaging.
- the concentration of color body in the color stratum must be sufficient to impart a distinctive color but excessive amounts require undesirably large quantities of reducing agent, or excessive heating, or may reduce the transparency of the stratum and accordingly are to be avoided.
- the amount of reducing agent available per unit area should be sufficient to react with all of the color body but need not be greatly in excess of that amount and, at least for single sheet projection transparencies, should be well within the range of full compatibility with the binder so that the stratum remains clear and non-light-diffusing.
- EXAMPLE 1 A carrier film of 2 mil (0.05 mm.) ethylene glycol terephthalate polyester film primed with a trace coating of terpolymer primer is supplied with first and second reactant strata, with intermediate and final drying, as follows:
- EXAMPLE 2 A solution containing 2-chloro-2'-mcthyl-N,N-dimethylindoaniline 0.6 polyvinyl chloride-acetate (VYNS" resin) l2.() methylethyl ketone 96 toluene 12 is applied to thin polyester film and dried in an oven at F. The dried coating is a deep blue in color and weighs 4.7 g./sq. m.
- a solution containing tertiary butyl hydroquinone l h sec. nitrocellulose l polyamidc (Elvamidc 8061" resin) l methanol 97 is applied over the first coating at approximately the same wet coating thickness and is promptly dried in the 150F. oven.
- the resulting film is imaged in a thermographic copying machine to provide a negative color projection transparency as in Example 1.
- EXAMPLE 10 EXAMPLE 7 Coated over first coat at 2 mils (0.05 mm.) and dried.
- the initial magenta color gradually fading during stor- The solutions are coated on separate sheets of thin age. Some improvement in performance may be polyester film, and the two sheets are combined and achieved by increasing the proportion of binder but processed, as in Example 6, with similar results. these sheets are generally less permanent and hence As an alternate structure a second sheet is prepared less desirable than those in which the 'tWO reactants are from a solution of ten parts of t-butyl hydroquinone in separate strata.
- Second coat stannous chloride 1 vinyl acrylate latex (Ucar 360) (55% NVM) O Simple contact heating with heated type or stylus is also effective and permits more accurate determination of temperature if desired for comparison or test purposes.
- Colored sheet material capable of undergoing localized loss of color when thermographically heated in presence of a reducing agent and containing a pquinoneimine color body in a film-forming binder, wherein said color body has the structure wherein Ar is an aromatic radical and the R, R, R and R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein adjacent substituent radicals may constitute a fused polycyclic or heterocyclic ring.
- Sheet material of claim 1 disposed in face-to-face relationship with a second sheet containing said reducing agent.
- Sheet material of claim 3 wherein said reducing agent is a hydroquinone, catechol, resorcinol or trihydroxy-aromatic mild reducing agent.
- Sheet material of claim 6 wherein said strata are supported on a thin flexible transparent film carrier.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
A transparent colored film product, which becomes clear and colorless at image areas when heated thermographically, contains a p-quinoneimine color body and a mild reducing agent.
Description
United States Patent OLeary Dec. 3, 1974 [541 HEAT-SENSITIVE COPY-SHEET 3,682,684 s/1972 Newman et a1 117/369 3,684,552 8/1972 Wiese et a1. 117/368 [75] inventor W" OLeary, Mmneapohs 3,715,213 2/1973 Nihyakumen 6131 117/369 x Minn. 3,730,677 5/1973 Kalopissis et al. 8/l0.2 3,751,249 8/1973 Hiller.....; 117/368 X [73] Asslgnee' Mmnesota Mmmg Manufacturmg 3,764,333 10 1973 Leclair 61231 117 369 x Company, St. Paul, Minn. [22] Filed: D 13, 1972 Primary ExaminerThomas .1. Herbert, Jr. 21] A L 314 7 Attorney, Agent, or Firm-Alexander, Sell, Steldt &
- DeLaHunt [52] US. Cl. ll7/36.8, 117/369, 260/65 T 51 Int. Cl 841m 5/00 ABSTRA T [58] Field of Search ..l17/36.9, 36.2, 36.8; A transparent Colored film product, which becomes 8/10-2; 250/65 T clear and colorless at image areas when heated thermographically, contains a p-quinoneimine color body [56] References C'ted and a mild reducing agent.
UNITED STATES PATENTS 9/1971 Wiese..... 250/65 T 7 Claims, No Drawings HEAT- SENSITIVE COPY-SHEET This invention relates to thermographic copying, wherein a copy of a differentially radiation-absorptive original is made on a heat-sensitive copy-sheet product held in'heat-conductive contact therewith by briefly exposing the original to intense infra-red radiation. In one aspect the invention relates to novel heat-sensitive copy-sheet products. In a particularly important aspect the invention relates to copy-sheet products useful in making negative color projection transparencies.
Negative-acting copy-sheets adapted for making color projection transparencies have previously been described. In US. Pat. No. 3,609,360 the decolorization involves the heat-induced decomposition of a colored reaction product of components including a volatilizable acid which is then released to the atmosphere. U.S. Pat. No. 3,684,552 somewhat analogously uses an amine-reactive color body and a heat-decomposable salt of a nitrogenous organic base.
The present invention employs a different class of color bodies and a different reaction system, and provides a heat-sensitive copy-sheet product which when locally heated, as in the thermographic copying process, is converted from a highly colored to a substantially colorless, and preferably a clear and transparent, form at the heated image areas without release of volatile decomposition products.
The heat-sensitive copy-sheet products of the present inventioncontain p-quinoneimine color bodies which undergo decolorization when heated at thermographically induced temperatures in reactive association with a mild reducing agent. The color body is supplied in a matrix of film-forming binder as a coating on a paper, transparent film or other carrier or as a self-supporting film. The reducing agent may be incorporated in the same matrix, or in an adjacent stratum supported on the carrier or on a separate carrier. A particularly useful structure comprises a transparent flexible film carrier coated with a first stratum of p-quinoneimine color body in a transparent binder and overcoated with a mild reducing agent in a separate binder. Brief heating of the film product causes migration of at least one of the reactants and results in a decolorization of the color body at the heated area.
Reducible p-quinoneimine color bodies which are useful in the preparation of heat-sensitive copy-sheets of the invention include those having thestructural formula.
wherein Ar is an aromatic radical and the R, R, R"
and R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein substituent radicals on adjacent carbon atoms may complete a fused polycyclic or heterocyclic ring, all as exemplified by 2 2-chloro-2'-methyl-N,N-diethylindoaniline 2-chloro-N(p-diethylamino-2-methylphenyl)-pbenzoquinoneimine 2-acetamido-N,N,-diethylindoaniline 3-methoxy-2'-methyl-N,N-diethylindoaniline N-( l-naphthyl )-p-benzoquinoneimine N-(2-naphthyl)-p-benzoquinoneimine N-(p-acetylphenyl)-p-benzoquinoneimine 2,6-dichloroindophenol sodium salt 2,3',6-trichloroindophenol sodium salt 2,6-dibromoindophenol sodium salt 2,5-dibromo-N(2,4-dibromophenyl)-pbenzoquinoneimine N-(p-diethylamino-Z-methylphenyl )-l ,4-
naphthoquinoneimine N-(p-diethylamino-2-methylphenyl )-5 ,8-
quinolinoquinoneimine N-(2,4-diamino-5-methylphenyl)-pbenzoquinoneimine trihydrate indoferron N-(p-diethylamino-2-methylphenyl)-2-carboxylic-l 4-naphthoquinoneimine N-(p-dimethylaminophenyl l ,4-
naphthoquinoneimine The following mild reducing agents have been found a useful:
2,5-dihydroxybenzoic acid chlorohydroquinone 2,5-dichlorohydroquinone tetrachlorohydroquinone bromohydroquinone diiodohydroquinone phenylhydroquinone 2,6-di-t-butylhydroquinone 2,S-di-t-butylhydroquinone 2,5 bis( 1,1-dimethylpropyl) hydroquinone 2,5-di-pentylhydroquinone trimethylhydroquinone t-butylhydroquinone methylhydroquinone catechol 3-methylcatechol 4-methylcatechol 4-t-butylcatechol 3-isopropylcatechol v4-isopropylcatechol 4-t-octylcatechol 3,5-diisopropylcatechol 3,6-diisopropylcatechol 3,5-di-t-butylcatechol 3-t-butyl-5-methylcatechol 3-methyl-5-t-butylcatechol 3-methyl- 5-octylcatechol 3-methoxycatechol tetrabromocatechol resorcinol 4-ethylresorcinol 4-n-propylresorcinol 4'-phenylazoresorcinol 4,6-dichlororesorcinol o-hydroxyethylresorcinol 2,6-dihydroxybenzoic acid 2,4-dihydroxybenzaldehyde 2, 6'-dihydroxyacetophenone 2,4,6-trihydroxyacetophenone methyl gallate butyl gallate l ,2,3-trihydroxybenzene 2 ,3 ,4 -trihydroxydecanophenone l ,2,4-trihydroxybenzene 2,4,5-trihydroxybutyrophenone o-aminophenol m-aminophenol p-aminophenol 4-amino-2,-dibromophenol 4-amino-2,6-dichlorophenol 2-amino-4-chlorophenol 3-diethylaminophenol 2,4-diaminophenol p-benzylaminophenol 4-amino-2,S-dimethylphenol -amino-m-cresol 4-amino-m-cresol S-amino-l -naphthol m-hydroxydiphenylamine 4-aminoacetanilide 2,6-diaminotoluene 3,4-diaminotoluene 1,4-diaminobenzene 1,8-diaminonaphthalene tetramethyl-l ,4-diaminobenzene furoin 1,3-dihydroxyacetone L-ascorbic acid arabo-ascorbic acid 4-methoxyl -naphthol Z-methoxy-l-naphthol l-amino-2-methoxynaphthalene 2,3-naphthalene diol 1,4-naphthalene diol 5 ,S-dihydroxyl ,4-dihydro-2-methylnaphthalene l-naphthol Strong reducing agents may also be used in some cases, in particular with the lower molecular weight color bodies and in constructions involving separate sheets, but are presently of only minor interest.
Binder systems may include such polymeric materials as polystyrene, styrene-acrylonitrile or sytrene-acrylate copolymers, styrene-butadiene-acrylonitrile terpolymers, polyvinylchloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-acrylonitrile or vinylidene chloride-vinyl acetate copolymers, polyacrylates, polyvinyltoluene. These polymers are moistureresistant, being incapable of absorbing more than about one percent of water, and are preferred as contributing to the stability of the sheet materials during prolonged storage both before and after imaging.
The concentration of color body in the color stratum must be sufficient to impart a distinctive color but excessive amounts require undesirably large quantities of reducing agent, or excessive heating, or may reduce the transparency of the stratum and accordingly are to be avoided. Similarly, the amount of reducing agent available per unit area should be sufficient to react with all of the color body but need not be greatly in excess of that amount and, at least for single sheet projection transparencies, should be well within the range of full compatibility with the binder so that the stratum remains clear and non-light-diffusing.
The following Examples, in which all proportions are in parts by weight unless otherwise indicated, will further illustrate the practice of the invention which however is not to be construed as limited thereto.
EXAMPLE 1 A carrier film of 2 mil (0.05 mm.) ethylene glycol terephthalate polyester film primed with a trace coating of terpolymer primer is supplied with first and second reactant strata, with intermediate and final drying, as follows:
First stratum 2-chloro-2'-methyl-N,N-diethylindoaniline polyvinyl chloride-acetate (Geon 42 l resin) methylethyl ketone toluene dry at IF. coating weight, dry, 2.5 g./sq. m.
Second stratum tertiarybutylhydroquinone polyvinyl butyral (Butvar B-76 resin) nitrocellulose (A see.) I methanol 8 dry at F. coating weight, dry, 4.0 g./sq. m.
EXAMPLE 2 A solution containing 2-chloro-2'-mcthyl-N,N-dimethylindoaniline 0.6 polyvinyl chloride-acetate (VYNS" resin) l2.() methylethyl ketone 96 toluene 12 is applied to thin polyester film and dried in an oven at F. The dried coating is a deep blue in color and weighs 4.7 g./sq. m.
A solution containing tertiary butyl hydroquinone l h sec. nitrocellulose l polyamidc (Elvamidc 8061" resin) l methanol 97 is applied over the first coating at approximately the same wet coating thickness and is promptly dried in the 150F. oven.
The resulting film is imaged in a thermographic copying machine to provide a negative color projection transparency as in Example 1.
EXAMPLE 3 First trip solution 2-chloro-2'-methyl-N,N-diethylindoaniline polystyrene (Styron 690" resin) methylethyl ketone Second trip solution tertiarybutyl hydroquinone 13.5% solution of nitrocellulose in methanol 13.5% solution of polyvinylbutyral in ethanol Coating weights and procedures are as described in previous Examples. By thermographic copying a good negative color projection transparency is obtained.
and 9 parts of polyvinyl butyral resin in 91 parts of ace- EXAMPLE 4 tone, coated on thin (21 V2 lb/ream) glassine. Substantially the same results are obtained.
First trip solution 2-chlore-2-methyl-N,N diethylindoaniline 0.50 5 EXAMPLE 8 vinyl chloride-acetate polymer (Geon 421 resin) 75 acetone 67.5 Flrst coat Second trip solution t-butyl hydroquinone 1.3 21 clellulose "o-200 resin) 5 2-chloro-2'-methyl-N,N-diethylindoaniline 0.25 at 95 polyvinyl chloride-acetate l l0 methylethyl ketone 90 Procedures and results are generally as described in preceding Examples. The solution is applied at an orifice of 3 mils (0.075 mm.) to map overlay tracing paper and is thoroughly EXAMPLE dried 15 Second coat First trip solution 2-chloro-2'-methyl-N,N-diethylindoaniline 0.25 vinyl chloride-acetate polymer 5 4-meth xy-ln ph hol l5 methylethyl ketone 36 polyvinyl butyral 30 toluene 9 titanium dioxide pigment 10 Second trip solution ethanol 222 t-butyl hydroquinone 5 methanol 35 acrylate latex (unhoplex A061"), 45% MM 36 The mlxture 1s homogemzed by prolonged m1ll1ng 1n polloidal silica o A 24 a ball mill, applied over the first coat at the same orifice, and dried. Introduction of silica improves the resistance of the 25 Th coated Sheet id a hi image against an coating to surface picking and roughening during theropaque bl b k d when used as a then-n0 mographic copying without appreciably reducing the hi h clarity. Procedures and results are substantially as described in the preceding Examples. 1 EXAMPLE 9 EXAMPLE 6 F st coat methyl gallate 3 sohmon A ethyl cellulose 5 N-(p acetylphenyl)-p-benzoqu1none1mme 0.4 ethanol 95 polyvinyl chloride-acetate (VYNS" resin) 5 methylethyl ketone 40.5 l
toluene Coated on 2-m1l (0.05 mm.) polyester film at 2 ml Solution B methyl hydroquinone m (0.05 mm.) orifice, and dried.
polyvinyl chloride-acetate (VYHH" resin) 2 Second coat polyvinyl butyral (Butvar 8-76 resin) 10 methylethyl ketone 76 40 Solution A is applied to thin 2 mil (0.05 mm.) polyese 2,6-dichloroindophenol sodium salt 0.3 ter f1lm from a coater bar at a 2 ml (0.05 mm.) orifice polystyrene acrylonimle (Tym resin) l5 and the coatmg 1s dried. S milarly, solut1on B is coated acetone 85 at the same thickness on a separate portion of 1 mil (0.025 mm.) film and the coating is dried. The two sheets are placed in face-to-face contact. The composite is placed against a printed original which is then subjected to brief exposure to intense infra-red radiation. Th p duct provides a negative color projection The second sheet is peeled from the first, leaving a pro transparency b thermographic copying jection transparency withclear image areas and yellow 1 background areas. EXAMPLE 10 EXAMPLE 7 Coated over first coat at 2 mils (0.05 mm.) and dried.
To a solution of 0.08 part 2,6-dichloro-N(pmorpholinophenyl)-p-benzoquinoneimine and 5 parts A f 1 f m 1 h 1 d r11 1 2-chloro-2'-methyl-N,Ndiethylindoaniline 0.25 0 F P ymefo me y met y ate f e y ypolyvinyl chloride-acetate 5 late 1n 20 parts of methylethyl ketone 1s added 0.45
:gfgg'j 2; part of 2,5-dihydroxybenzoic acid and the mixture is Solution B quickly coated on transparent film and dried. The sheet t-butyl hydroquinone W ethyl cellulose (mom resin) l0 .prov1des a color pro3ect1on transparency when printed ethanol I 80 thermographically but is found to have short shelf life,
the initial magenta color gradually fading during stor- The solutions are coated on separate sheets of thin age. Some improvement in performance may be polyester film, and the two sheets are combined and achieved by increasing the proportion of binder but processed, as in Example 6, with similar results. these sheets are generally less permanent and hence As an alternate structure a second sheet is prepared less desirable than those in which the 'tWO reactants are from a solution of ten parts of t-butyl hydroquinone in separate strata.
EXAMPLE 11 First solution N-(p-diethylamino-Z-methylphenyl)-5,8-
quinolino quinoneimine polyvinyl chloride-acetate 6 mcthylethyl kctonc 44 nickel resinutt: q.v Second solution tertiarybutyl hydroquinone 0.67
13.5% solution of nitrocellulose in methanol 8 l3.5% solution of polyvinylbutyral in ethanol 2 EXAMPLE [2 First coat N-( l'naphthyll-p-benzoquinoneimine 0.3 polyvinyl chloride-acetate 0.5 methylcthyl ketone 25 toluene 24.5 Coated at .05 mm. on polyester film and dried.
Second coat stannous chloride 1 vinyl acrylate latex (Ucar 360) (55% NVM) O Simple contact heating with heated type or stylus is also effective and permits more accurate determination of temperature if desired for comparison or test purposes.
What is claimed is as follows:
1. Colored sheet material capable of undergoing localized loss of color when thermographically heated in presence of a reducing agent and containing a pquinoneimine color body in a film-forming binder, wherein said color body has the structure wherein Ar is an aromatic radical and the R, R, R and R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein adjacent substituent radicals may constitute a fused polycyclic or heterocyclic ring.
2. Sheet material of claim 1 disposed in face-to-face relationship with a second sheet containing said reducing agent.
3. Sheet material of claim 1 wherein is included a said reducing agent.
4. Sheet material of claim 3 wherein said reducing agent is a hydroquinone, catechol, resorcinol or trihydroxy-aromatic mild reducing agent.
5. Sheet material of claim 3 wherein said reducing agent is contained in said binder.
6. Sheet material of claim 3 wherein said reducing agent is contained in a different film-forming binder as a separate stratum adjacent the stratum containing said color body.
7. Sheet material of claim 6 wherein said strata are supported on a thin flexible transparent film carrier.
Claims (7)
1. COLORED SHEET MATERIAL CAPABLE OF UNDERGOING LOCALIZED LOSS OF COLOR WHEN THERMOGRAPHICALLY HEATED IN PRESENCE OF A REDUCING AGENT AND CONTAINING A P-QUINONEIMENE COLOR BODY IN A FILM-FORMING BINDER WHEREIN SAID COLOR BODY HAS THE STRUCTURE
2. Sheet material of claim 1 disposed in face-to-face relationship with a second sheet containing said reducing agent.
3. Sheet material of claim 1 wherein is included a said reducing agent.
4. Sheet material of claim 3 wherein said reducing agent is a hydroquinone, catechol, resorcinol or trihydroxy-aromatic mild reducing agent.
5. Sheet material of claim 3 wherein said reducing agent is contained in said binder.
6. Sheet material of claim 3 wherein said reducing agent is contained in a different film-forming binder as a separate stratum adjacent the stratum containing said color body.
7. Sheet material of claim 6 wherein said strata are supported on a thin flexible transparent film carrier.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00314687A US3852093A (en) | 1972-12-13 | 1972-12-13 | Heat-sensitive copy-sheet |
CA185,752A CA981453A (en) | 1972-12-13 | 1973-11-14 | Heat-sensitive copy-sheet |
JP48139269A JPS4991239A (en) | 1972-12-13 | 1973-12-12 | |
GB5759873A GB1399958A (en) | 1972-12-13 | 1973-12-12 | Heat-sensitive copy-sheet |
DE2362377A DE2362377B2 (en) | 1972-12-13 | 1973-12-12 | Colored thermographic sheet material |
IT7354272A IT1000446B (en) | 1972-12-13 | 1973-12-12 | IMPROVEMENT IN THE MATERIALS IN SHEETS FOR THERMOGRAPHIC REPRODUCTION |
FR7344295A FR2330260A5 (en) | 1972-12-13 | 1973-12-12 | THERMOCOPIANT SHEETS AND THEIR MANUFACTURING PROCESS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00314687A US3852093A (en) | 1972-12-13 | 1972-12-13 | Heat-sensitive copy-sheet |
Publications (1)
Publication Number | Publication Date |
---|---|
US3852093A true US3852093A (en) | 1974-12-03 |
Family
ID=23221008
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00314687A Expired - Lifetime US3852093A (en) | 1972-12-13 | 1972-12-13 | Heat-sensitive copy-sheet |
Country Status (7)
Country | Link |
---|---|
US (1) | US3852093A (en) |
JP (1) | JPS4991239A (en) |
CA (1) | CA981453A (en) |
DE (1) | DE2362377B2 (en) |
FR (1) | FR2330260A5 (en) |
GB (1) | GB1399958A (en) |
IT (1) | IT1000446B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2379833A1 (en) * | 1977-02-07 | 1978-09-01 | Eastman Kodak Co | THERMODEVELOPABLE PHOTOGRAPHIC PRODUCT |
US4187108A (en) * | 1977-02-07 | 1980-02-05 | Eastman Kodak Company | Heat developable material and process |
US4265978A (en) * | 1978-09-20 | 1981-05-05 | Mitsubishi Paper Mills, Ltd. | Heat-sensitive recording paper improved in keeping quality of ground color |
US4594312A (en) * | 1983-03-15 | 1986-06-10 | Minnesota Mining And Manufacturing Company | Heat bleachable dye systems |
US5156709A (en) * | 1991-07-30 | 1992-10-20 | Xerox Corporation | Fusible white stripe transparency sheets |
US5290346A (en) * | 1991-08-28 | 1994-03-01 | Brother Kogyo Kabushiki Kaisha | Ink for printer |
US5314795A (en) * | 1992-12-21 | 1994-05-24 | Minnesota Mining And Manufacturing Company | Thermal-dye-bleach construction comprising a polymethine dye and a thermal carbanion-generating agent |
US5324627A (en) * | 1992-12-21 | 1994-06-28 | Minnesota Mining And Manufacturing Company | Tetra-alkylammonium phenylsulfonylacetate thermal-dye-bleach agents |
US5395747A (en) * | 1993-12-20 | 1995-03-07 | Minnesota Mining & Manufacturing Company | Stabilized thermal-dye-bleach constructions |
US5935758A (en) * | 1995-04-20 | 1999-08-10 | Imation Corp. | Laser induced film transfer system |
US5945249A (en) * | 1995-04-20 | 1999-08-31 | Imation Corp. | Laser absorbable photobleachable compositions |
US6294308B1 (en) | 1999-10-15 | 2001-09-25 | E. I. Du Pont De Nemours And Company | Thermal imaging process and products using image rigidification |
US20160202233A1 (en) * | 2015-01-14 | 2016-07-14 | International Business Machines Corporation | Recyclate verification |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3524519A1 (en) * | 1984-07-11 | 1986-01-16 | Mitsubishi Chemical Industries Ltd., Tokio/Tokyo | Dyes for heat-sensitive sublimation transfer recording |
JPS6453893A (en) * | 1987-08-25 | 1989-03-01 | Fuji Photo Film Co Ltd | Thermal transfer material |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3609360A (en) * | 1969-09-15 | 1971-09-28 | Joseph A Wiese Jr | Negative projection transparencies and method |
US3682684A (en) * | 1971-03-10 | 1972-08-08 | Minnesota Mining & Mfg | Wide latitude heat-sensitive copy-sheet and method of making |
US3684552A (en) * | 1970-11-16 | 1972-08-15 | Minnesota Mining & Mfg | Heat-sensitive sheet material |
US3715213A (en) * | 1969-02-19 | 1973-02-06 | Mita Industrial Co Ltd | Diazo-type multicolor reproduction |
US3730677A (en) * | 1969-07-08 | 1973-05-01 | Oreal | Dyeing keratinous fibers with a quinoneimine and a coupler |
US3751249A (en) * | 1971-03-15 | 1973-08-07 | Eastman Kodak Co | Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent |
US3764333A (en) * | 1972-05-15 | 1973-10-09 | Nashua Corp | Thermographic copy sheet containing 2-phenyl 1,3-indanedione |
-
1972
- 1972-12-13 US US00314687A patent/US3852093A/en not_active Expired - Lifetime
-
1973
- 1973-11-14 CA CA185,752A patent/CA981453A/en not_active Expired
- 1973-12-12 JP JP48139269A patent/JPS4991239A/ja active Pending
- 1973-12-12 DE DE2362377A patent/DE2362377B2/en active Granted
- 1973-12-12 IT IT7354272A patent/IT1000446B/en active
- 1973-12-12 GB GB5759873A patent/GB1399958A/en not_active Expired
- 1973-12-12 FR FR7344295A patent/FR2330260A5/en not_active Expired
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3715213A (en) * | 1969-02-19 | 1973-02-06 | Mita Industrial Co Ltd | Diazo-type multicolor reproduction |
US3730677A (en) * | 1969-07-08 | 1973-05-01 | Oreal | Dyeing keratinous fibers with a quinoneimine and a coupler |
US3609360A (en) * | 1969-09-15 | 1971-09-28 | Joseph A Wiese Jr | Negative projection transparencies and method |
US3684552A (en) * | 1970-11-16 | 1972-08-15 | Minnesota Mining & Mfg | Heat-sensitive sheet material |
US3682684A (en) * | 1971-03-10 | 1972-08-08 | Minnesota Mining & Mfg | Wide latitude heat-sensitive copy-sheet and method of making |
US3751249A (en) * | 1971-03-15 | 1973-08-07 | Eastman Kodak Co | Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent |
US3764333A (en) * | 1972-05-15 | 1973-10-09 | Nashua Corp | Thermographic copy sheet containing 2-phenyl 1,3-indanedione |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2379833A1 (en) * | 1977-02-07 | 1978-09-01 | Eastman Kodak Co | THERMODEVELOPABLE PHOTOGRAPHIC PRODUCT |
US4187108A (en) * | 1977-02-07 | 1980-02-05 | Eastman Kodak Company | Heat developable material and process |
US4265978A (en) * | 1978-09-20 | 1981-05-05 | Mitsubishi Paper Mills, Ltd. | Heat-sensitive recording paper improved in keeping quality of ground color |
US4594312A (en) * | 1983-03-15 | 1986-06-10 | Minnesota Mining And Manufacturing Company | Heat bleachable dye systems |
US5156709A (en) * | 1991-07-30 | 1992-10-20 | Xerox Corporation | Fusible white stripe transparency sheets |
US5290346A (en) * | 1991-08-28 | 1994-03-01 | Brother Kogyo Kabushiki Kaisha | Ink for printer |
US5314795A (en) * | 1992-12-21 | 1994-05-24 | Minnesota Mining And Manufacturing Company | Thermal-dye-bleach construction comprising a polymethine dye and a thermal carbanion-generating agent |
US5324627A (en) * | 1992-12-21 | 1994-06-28 | Minnesota Mining And Manufacturing Company | Tetra-alkylammonium phenylsulfonylacetate thermal-dye-bleach agents |
US5384237A (en) * | 1992-12-21 | 1995-01-24 | Minnesota Mining And Manufacturing Company | Quaternary-ammonium phenylsulfonylacetate thermal-dye-bleach agents |
US5395747A (en) * | 1993-12-20 | 1995-03-07 | Minnesota Mining & Manufacturing Company | Stabilized thermal-dye-bleach constructions |
US5935758A (en) * | 1995-04-20 | 1999-08-10 | Imation Corp. | Laser induced film transfer system |
US5945249A (en) * | 1995-04-20 | 1999-08-31 | Imation Corp. | Laser absorbable photobleachable compositions |
US6171766B1 (en) | 1995-04-20 | 2001-01-09 | Imation Corp. | Laser absorbable photobleachable compositions |
US6291143B1 (en) | 1995-04-20 | 2001-09-18 | Imation Corp. | Laser absorbable photobleachable compositions |
US6294308B1 (en) | 1999-10-15 | 2001-09-25 | E. I. Du Pont De Nemours And Company | Thermal imaging process and products using image rigidification |
US6569585B2 (en) | 1999-10-15 | 2003-05-27 | E.I. Du Pont De Nemours And Company | Thermal imaging process and products using image rigidification |
US20160202233A1 (en) * | 2015-01-14 | 2016-07-14 | International Business Machines Corporation | Recyclate verification |
US9708463B2 (en) | 2015-01-14 | 2017-07-18 | International Business Machines Corporation | Recyclate verification |
US9778244B2 (en) | 2015-01-14 | 2017-10-03 | International Business Machines Corporation | Recyclate verification |
US9783645B2 (en) | 2015-01-14 | 2017-10-10 | International Business Machines Corporation | Recyclate verification |
US9908989B2 (en) * | 2015-01-14 | 2018-03-06 | International Business Machines Corporation | Recyclate verification |
Also Published As
Publication number | Publication date |
---|---|
DE2362377A1 (en) | 1974-07-04 |
JPS4991239A (en) | 1974-08-31 |
IT1000446B (en) | 1976-03-30 |
CA981453A (en) | 1976-01-13 |
FR2330260A5 (en) | 1977-05-27 |
GB1399958A (en) | 1975-07-02 |
DE2362377B2 (en) | 1975-12-11 |
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