US3767414A - Thermosensitive copy sheets comprising heavy metal azolates and methods for their use - Google Patents
Thermosensitive copy sheets comprising heavy metal azolates and methods for their use Download PDFInfo
- Publication number
- US3767414A US3767414A US00255617A US3767414DA US3767414A US 3767414 A US3767414 A US 3767414A US 00255617 A US00255617 A US 00255617A US 3767414D A US3767414D A US 3767414DA US 3767414 A US3767414 A US 3767414A
- Authority
- US
- United States
- Prior art keywords
- sheet
- reducing agent
- sheet material
- silver
- stratum
- 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
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 19
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical class OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 34
- SUGXYMLKALUNIU-UHFFFAOYSA-N silver;imidazol-3-ide Chemical class [Ag+].C1=C[N-]C=N1 SUGXYMLKALUNIU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 31
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002696 acid base indicator Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- UDEKGHIIDDBJRO-UHFFFAOYSA-L N1C(=CC=C1)C(=O)[O-].[Cu+2].N1C(=CC=C1)C(=O)[O-] Chemical compound N1C(=CC=C1)C(=O)[O-].[Cu+2].N1C(=CC=C1)C(=O)[O-] UDEKGHIIDDBJRO-UHFFFAOYSA-L 0.000 claims description 2
- 150000004782 1-naphthols Chemical class 0.000 claims 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims 1
- -1 silver imidazolates Chemical class 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 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 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- WZYIZZKPEXSTCK-UHFFFAOYSA-M N1C(=CC=C1)C(=O)[O-].[Ag+] Chemical compound N1C(=CC=C1)C(=O)[O-].[Ag+] WZYIZZKPEXSTCK-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- IWQFMSXYOSAMAZ-UHFFFAOYSA-N silver;benzimidazol-1-ide Chemical compound [Ag+].C1=CC=C2[N-]C=NC2=C1 IWQFMSXYOSAMAZ-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QVIKUAVXSRNDPS-UHFFFAOYSA-N 2-methoxynaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(OC)=CC=C21 QVIKUAVXSRNDPS-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241001147416 Ursus maritimus Species 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OGUAZADKHHQLTG-UHFFFAOYSA-N copper(1+);imidazol-3-ide Chemical compound [Cu+].C1=C[N-]C=N1 OGUAZADKHHQLTG-UHFFFAOYSA-N 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor
Definitions
- Heat-sensitive copy-sheets containing heavy metal salts, especially silver salts, of organic acids have been described, for example in U.S. Pat. No. 2,910,377.
- the present invention in one aspect likewise relates to heatsensitive sheet materials containing organic silver or other heavy metal salts but employing specifically different materials and providing unexpected advantages.
- Heat-sensitive copy-sheets containing organic silver salts have also been employed in conjunction with light-sensitive components, for example as described'in U.S. Pat. No. 3,094,417.
- the present invention similarly relates to the recording of lightimages, again using novel materials and with advantageous results.
- a particularly important aspect of the present invention relatesto the formation of images incolor, using the heavy metal salt copy-sheet in an intermediate process step.
- the azoles include the dinitrogen, five membered, unsaturated heterocyclic compounds having the skeletal structure
- the copy-sheet of the present invention comprises a film or coating containing a silver imidazolate or pyrazolate dispersed in 'a polymeric binder. Amounts of the. silver compound equivalent to from one-half to 14 grams of silver per square meter are useful. lmaging is accomplished by heating the coating in the presence of a suitable reducing agent, preferably together with other auxiliary components as will be further described.
- the reducing agent may be locally applied to the sheet, e.g., by inscribing with an ink containing the material or by transfer from a source sheet, and the entire sheet then heated.
- the reducing agent is supplied over the entire surface of the copy-sheet either as a separate coating or contained in a second sheet, and imaging is accomplished by localized heating, accomplished thermographically or with heated stylus or type, or by localized removal of the reducing agent followed by over-all heating.
- Hindered phenolic reducing agents e.g., butylated hydroxytoluenes
- more active reducing agents e.g., nonhindered phenols such as methyl gallate or methoxyhydroxynaphthalene.
- reduction of the silver salt occurs, accompanied by a visible change in the copy-sheet film or coating.
- the copy-sheet showing a visible image obtained as just described is useful as a permanent record, showing substantially no loss of density at image areas or darkening of non-image areas during prolonged storage.
- the sheet is additionally useful in making further copies of the image areas in color.
- the imaged sheet is promptly heated while in contact with a further sheet or stratum containing a base-sensitive color-producing system.
- the volatilizable azole compound released during formation of the silver image is transferred to the base-sensitive layer and there causes the formation of a colored image.
- the secondary colored image is formed in a separate sheet or film which is then removed, leaving the primary silver image in the first sheet.
- the base-sensitive sheet may itself carry a layer of reducing agent for reaction with the silver salt, in which event both images may be formed simultaneously.
- the silver salt of imidazole is a preferred constituent of these novel copy-sheet materials.
- Various substituted imidazoles may also be used, benzimidazole being particularly useful.
- Mixtures of azolates may be used, a mixture of a major proportion of silver imidazolate and a minor proportion of silver benzimidazolate being particularly advantageous.
- Pyrazole forms a silver salt with which visible but weak primary images may be prepared.
- Azolates of heavy metals other than silver are somewhat less desirable for producing dense primary images. but are frequently more useful in other ways.
- the copper salts for example, produce low visual density primary images butwhich are electrically conductive, and whose conductivity may be enhanced by electroless plating in the preparation of printed circuit boards or for other purposes.
- the particle size of the white powdery product obtained after washing and drying the precipitate is from about 3 microns to substantially less than 1 micron as determined with a Quantimet 720 particle size analyzer using a scanning light beam. Weight loss on heating in hydrogen is 38.3 39.3 percent; theoretical for silver imidazolate is 38.3 percent.
- the metal salt is well dispersed in a liquid vehicle, together with other components as desired, the degree of dispersion being sufficient to provide a uniform coating with good optical properties.
- milling in a ball mill and in presence of an inert polymeric binder is effective.
- Vinyl resins, cellulosic derivatives and various other polymers are all useful; polyvinyl butyral resin is presently preferred.
- Phthalazinone is a known toner for silver images and is found useful in the present compositions for such purposes. Pigments are sometimes used, e.g., to provide opacity or to lighten the background color and provide improved contrast; zinc oxide is one example. Plasticizers are sometimes helpful particularly where less flexible polymeric binders are to be used. It has been discovered also that catalytically small amounts of silver nitrate are particularly useful when added to the silver azolate coatings, which are thereby rendered more sensitive, and require less reducing agent and toner to provide a given image density.
- diazo paper or film is one example of a secondary image sheet on which images in color may be formed by heating in contact with the imaged silver azolate sheet.
- Such papers contain an acid-stabilized diazonium salt in conjunction with an azo coupler. Transfer of imidazole, liberated at image areas from silver imidazolate, to the diazo sheet results in a coupling reaction between the diazonium compound and the coupler, with formation of an azo dye image.
- diazo and coupler components makes possible a variety of image colors.
- color image sheet may be identified as containing in acid form an acid-base indicator which undergoes a visible change when exposed to the basic azole liberated at the primary image areas.
- EXAMPLE 1 Silver imidazolate of minimal particle size is prepared as described hereinabove.
- the dry powder (4.5 parts) is mixed into a 12 percent solution of polyvinyl butyral in methylethyl ketone (30 parts) by prolonged milling in a ball mill.
- the resulting suspension is coated on both paper and film backing sheets using a coating bar held at an orifice of four mils (0.1 mm.) and the coatings are air dried, to provide primary copy-sheets.
- a desensitizable intermediate transfer sheet prepared as described in U.S. Pat. No. 3,094,417 and containing dye-sensitized substituted a-naphthol, is exposed to a light-image to an extent just sufficient to cause complete desensitization of the sheet at nonimage areas, leaving the a-naphthol reducing agent only at the image areas. It is then placed in face-to-face contact with the primary copy-sheet and the couplet is heated by passing around a metal roller maintained at 260 F. Upon separation of the sheets, a visible record of the light-image is observed on the copy-sheet in the form of brown images on a white background.
- the light-sensitive intermediate transfer sheet may be replaced by a transfer sheet coated with methyl gallate as used in U.S. Pat. No. 2,910,377.
- the transfer sheet is held in face-to-face contact with the copy-sheet and the couplet is held in heat-conductive contact against a printed original which is then briefly exposed to intense infra-red radiation. A copy of the printed image is formed on the copy-sheet.
- the copy formed in the latter instance is placed in face-to-face contact with a commercial Ozalid" diazo sheet and the couplet is held for one-half minute between metal platens maintained at l20l25 C. A copy of the image areas appears in color on the surface of the diazo sheet.
- Example 2 The procedures of Example 1 are duplicated except that silver benzimidazolate is substituted for the silver imidazolate. Substantially identical results in terms of image formation and appearance are obtained, along with improved stability of background against darkening during prolonged storage in an office file cabinet.
- the reducing agent a hindered phenol consisting of butylated hydroxytoluene available under the trademark designation CAO-3, is added to the ball milled mixture of the several other components under brief mixing and the composition is promptly coated on paper and film backings, and dried.
- the resulting primary copy sheets are imaged as described under Example 1 except that in the second procedure the coating of methyl gallate is applied directly to the unprinted surface of the printed original instead of on a separate source sheet. Dense black images are obtained on the primary copy-sheet in all cases. The sheet both before and after imaging has high thermal stability.
- a secondary sheet is prepared by coating a transparent film backing with a solution of 4% solution of nitrocellulose in 1:3 alcoholzether 30.0 l-diazo-2,5-dibutoxy-4-morpholinobenzene sulfate 0.75 3-hydroxy-2-naphthol-phenetide 0.25 3-hydroxy-2-naphthol-toluidide 0.25
- the film backing is a polyester film which has first been subbed with duPont 49,000," a soluble polyester of glycols, phthalic acids and sebacic acid, applied from solution in trichloroethane, or alternatively has been subjected to a surface treatment by corona discharge.
- duPont 49,000 a soluble polyester of glycols, phthalic acids and sebacic acid, applied from solution in trichloroethane, or alternatively has been subjected to a surface treatment by corona discharge.
- a freshly imaged primary copysheet is placed in face-to-face contact with the secondary sheet and the couplet is heated at 260 F.
- a faintly yellowish projection transparency is produced which when used with an overhead projector rapidly bleaches to a water-white appearance in the non-image areas and projects a blue image on a white background.
- EXAMPLE 4 pronounces a white-appearing film on which the red image appears with good contrast.
- EXAMPLE 5 Component A B silver imidazolate 0.5 2.0 reducing agent of Example 3 0.5 0.5 phthalazinone 0.5 0.5 0.5 binder (polyvinyl butyral) 2.0 0.5 solvent (MEK) 18.0 10.0
- the printed surface is briefly exposed to intense infra-red radiation, causing heating of the imaged areas and the formation of a corresponding copper image on the coated film.
- the copper image is intensified by dipping the film in an electroless copper plating solution.
- the image areas are found to be electrically conductive.
- EXAMPLE 8 A primary copy-sheet prepared as described under Example 3 is first overcoated with a minimal continuous barrier coating of vinyl chloride-vinyl acetate copolymer and then with a photo-sensitive overcoat of dye-sensitized 4-methoxy-l-naphthol. The resulting integral sheet is first exposed to a light-image to densensitize the photosensitive layer at the light-struck areas and is then heated to cause an image-forming reaction at the unexposed areas, the substituted naphthol difius- Mixtures A and B are separately prepared and coated on paper substrates, and the dried primary copy-sheets are imaged by heating in contact with a reflexexposed light-sensitive intermediate transfer sheet as described under Example 1 and under identical conditions. Sheet A produces a dense visible image on a substantially unchanged background; sheet B produces an image of still greater density but with some background darkening.
- a receptor sheet is prepared by coating polyester film at a coater bar setting of four mils, with a solution containing r vinyl chloride-acetate copolymer 40 N-(bis(4-dimethylaminophenyl)methyl)pyr- I rolidi ne l salicylic acid 1 0.2 methylethyl ketone 160
- Copper (I) imidazolate is prepared by mixing cupric chloride in 0.05 molar solution with an excess of imidazole, adding ascorbic acid and sodium sulfite to reduce the'copper (II) to copper (I) as shown by conversion from blue to straw color, adding molar sodium hydroxide solution to cause precipitation, filtering, and washing and drying the resultant white powder.
- a mixture of 10 parts of the powder with 100 parts of 10 percent solution of polyvinyl butyral in a mixture of methylethyl ketone and toluene is applied at 6 mils to a polyester film and dried.
- a printed sheet having on the reverse surface a coating of methyl gallate is placed against the coated film in face-to-face contact and the ing through the very thin separating layer for reaction with the silver imidazolate.
- EXAMPLE 9 A commercial Ozalid diazo sheet as used in Example 1 is first overcoated with a photosensitive layer of dye-sensitized substituted a-naphthol as also employed in Example 1. The sheet is exposed to a light-image sufficient to desensitize the coating at the light-exposed areas. It is then placed in face-to-face contact with a primary copy-sheet prepared as described in Example 3 and the composite is heated. A dense black image forms on the primary copy-sheet; a colored reverse image appears on the diazo print sheet.
- Method of imaging comprising subjecting a first sheet material having a stratum containing a polymeric heavy metal azolate to heat at least at image areas and in the presence of a reducing agent to provide on said sheet material a visible image.
- Method of claim 1 including the further step of heating the imaged first sheet in face-to-face contact with a base sensitive print sheet.
- said first sheet material includes at least in the image areas thereof a layer containing a said reducing agent which is Photosensitive.
- Sheet material including a paper-thin backing carrying an image-forming stratum comprising a heavy metal azolate.
- Sheet material of claim 12 wherein said heavy metal azolate is silver imidazolate.
- Sheet material of claim 13 wherein said stratum includes a hindered phenolic reducing agent for silver ion, and phthalazinone.
- Sheet material of claim 15 having over said stratum a coterminous vapor-transmissive polymeric barrier layer and an outer layer comprising a volatilizable reducing agent for silver ion.
- Sheet material of claim 11 wherein said heavy metal azolate is a copper azolate.
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Abstract
Copy-sheets containing heavy metal azolates, such as silver imidazolates, are imaged by heating with a reducing agent applied in image-forming pattern. Colored images are then produced in base-sensitive copy-sheets by heating the imaged azolate sheet thereagainst.
Description
United States Patent 91 Huffman et al.
[ 1 Oct. 23, 1973 THERMOSENSITIVE COPY SHEETS COMPRISING HEAVY METAL AZOLATES AND METHODS FOR THEIR USE inventors: William A. Huffman, White Bear Lake; Dean R. Lowrey, North Oaks; Brian K. Hill, Village of Cottage Grove, Jacquelyn D. Bush, St. Paul, all of Minn.
Assignee: Minnesota Mining and Manufacturing Company, St. Paul,
Minn.
Filed: May 22, 1972 Appl. No.: 255,617
US. Cl..... 96/114.6, 9 6/114.1, 117/369, 250/65 T Int. Cl G03c 1/02, G03c 1/72, B4ln 5/00 [58] Field of Search 96/114.6, 114.1; 1l7/36.8, 36.9; 1250/65 T References Cited OTHER PUBLICATIONS Chemical Abstracts, 1964, 733 b,c.
Primary ExaminerNorman G. Torchin Assistant ExaminerA1fonso T. Suro Pico Att0meyl(inney, Alexander, Sell, Steldt & Delahunt [57] ABSTRACT 20 Claims, No Drawings THERMOSENSITIVE COPY SHEETS COMPRISING HEAVY METAL AZOLATES AND METHODS FOR THEIR USE This invention'relates to the image recording art particularly as exemplified by the copying or reproduction of documents, designs, and similar graphic originals in making projection transparencies as well as hard cop'- ies. In one important aspect there are involved novel compositions and coated sheet materials.
Heat-sensitive copy-sheets containing heavy metal salts, especially silver salts, of organic acids have been described, for example in U.S. Pat. No. 2,910,377. The present invention in one aspect likewise relates to heatsensitive sheet materials containing organic silver or other heavy metal salts but employing specifically different materials and providing unexpected advantages.
Heat-sensitive copy-sheets containing organic silver salts have also been employed in conjunction with light-sensitive components, for example as described'in U.S. Pat. No. 3,094,417. In another aspect the present invention similarly relates to the recording of lightimages, again using novel materials and with advantageous results.
A particularly important aspect of the present invention relatesto the formation of images incolor, using the heavy metal salt copy-sheet in an intermediate process step.
It has now been'found possible to employ heavy metal, particularly silver, azolates as components of primary copy-sheets having improved stability against backgrounding and which are further useful, e.g., in the preparation of secondary copies in color.
The azoles include the dinitrogen, five membered, unsaturated heterocyclic compounds having the skeletal structure In its simplest form the copy-sheet of the present invention comprises a film or coating containing a silver imidazolate or pyrazolate dispersed in 'a polymeric binder. Amounts of the. silver compound equivalent to from one-half to 14 grams of silver per square meter are useful. lmaging is accomplished by heating the coating in the presence of a suitable reducing agent, preferably together with other auxiliary components as will be further described. The reducing agent may be locally applied to the sheet, e.g., by inscribing with an ink containing the material or by transfer from a source sheet, and the entire sheet then heated. Alternatively, the reducing agent is supplied over the entire surface of the copy-sheet either as a separate coating or contained in a second sheet, and imaging is accomplished by localized heating, accomplished thermographically or with heated stylus or type, or by localized removal of the reducing agent followed by over-all heating.
Hindered phenolic reducing agents, e.g., butylated hydroxytoluenes, are useful but by themselves require undesirably high temperature for reaction with the silver salt in reasonable time and are therefore more effectively used in conjunction with at least minor proportions of more active reducing agents, e.g., nonhindered phenols such as methyl gallate or methoxyhydroxynaphthalene. In all cases, reduction of the silver salt occurs, accompanied by a visible change in the copy-sheet film or coating.
The copy-sheet showing a visible image obtained as just described is useful as a permanent record, showing substantially no loss of density at image areas or darkening of non-image areas during prolonged storage. The sheet is additionally useful in making further copies of the image areas in color. For the latter use the imaged sheet is promptly heated while in contact with a further sheet or stratum containing a base-sensitive color-producing system. The volatilizable azole compound released during formation of the silver image is transferred to the base-sensitive layer and there causes the formation of a colored image. Preferably the secondary colored image is formed in a separate sheet or film which is then removed, leaving the primary silver image in the first sheet. The base-sensitive sheet may itself carry a layer of reducing agent for reaction with the silver salt, in which event both images may be formed simultaneously.
The silver salt of imidazole is a preferred constituent of these novel copy-sheet materials. Various substituted imidazoles may also be used, benzimidazole being particularly useful. Mixtures of azolates may be used, a mixture of a major proportion of silver imidazolate and a minor proportion of silver benzimidazolate being particularly advantageous. Pyrazole forms a silver salt with which visible but weak primary images may be prepared. Azolates of heavy metals other than silver are somewhat less desirable for producing dense primary images. but are frequently more useful in other ways. The copper salts, for example, produce low visual density primary images butwhich are electrically conductive, and whose conductivity may be enhanced by electroless plating in the preparation of printed circuit boards or for other purposes.
Heavy metal salts of various azoles have been reported in chemical literature. For example, Bauman and Wang, at page 370 of Inorganic Chemistry, Volume 3, (1964), describe the preparationof silver, zinc, copper, nickel and cadmium salts, (by them referred to as complexes) of imidazole and N-methylimidazole, and the titration of silver imidazolate with sodium hydroxide The silver salt of imidazole is represented by these authors as corresponding on ultimate analysis to the formula Ag(C l-l N However the compound has now been further found to have a molecular weight of the order of 20,000 and to have very low solubility, and is therefore to be considered as polymeric in nature, a conclusion which is further supported by the results of infra-red analysis.
The methods of preparation of the metal azolates described in the publication by Bauman and Wang result in products which in many cases produce only marginally operable copy-sheets. Modifications of these processes which result in materials of much smaller particle size are believed to be well within the skill of the art and involve changes in temperature of reaction mixture, rate of addition of reactants, concentration of reactants, extent of agitation, and the like; and reduction in particle size of the azolates is found to give greatly increased efficiency in copy sheet applications. In a typical laboratory scale example, following the general procedure described by Bauman and Wang, silver nitrate solution is diluted to 1/4 molar and the mixture is maintained at 2-5 C. with vigorous agitation during addition of imidazole. 0.75 Molar sodium hydroxide solution is added dropwise to a final pH of 10.50, and vigorous agitation is continued for an additional half hour prior to filtration. The particle size of the white powdery product obtained after washing and drying the precipitate is from about 3 microns to substantially less than 1 micron as determined with a Quantimet 720 particle size analyzer using a scanning light beam. Weight loss on heating in hydrogen is 38.3 39.3 percent; theoretical for silver imidazolate is 38.3 percent.
For coating purposes the metal salt is well dispersed in a liquid vehicle, together with other components as desired, the degree of dispersion being sufficient to provide a uniform coating with good optical properties. For such purposes milling in a ball mill and in presence of an inert polymeric binder is effective. Vinyl resins, cellulosic derivatives and various other polymers are all useful; polyvinyl butyral resin is presently preferred.
Incorporation of hindered phenolic reducing agents in the coating containing the azolate lessens the amount of reducing agent which must be supplied at image areas and is usually desirable. Phthalazinone is a known toner for silver images and is found useful in the present compositions for such purposes. Pigments are sometimes used, e.g., to provide opacity or to lighten the background color and provide improved contrast; zinc oxide is one example. Plasticizers are sometimes helpful particularly where less flexible polymeric binders are to be used. It has been discovered also that catalytically small amounts of silver nitrate are particularly useful when added to the silver azolate coatings, which are thereby rendered more sensitive, and require less reducing agent and toner to provide a given image density.
Commercial diazo paper or film is one example of a secondary image sheet on which images in color may be formed by heating in contact with the imaged silver azolate sheet. Such papers contain an acid-stabilized diazonium salt in conjunction with an azo coupler. Transfer of imidazole, liberated at image areas from silver imidazolate, to the diazo sheet results in a coupling reaction between the diazonium compound and the coupler, with formation of an azo dye image. Proper selection of diazo and coupler components makes possible a variety of image colors.
Another form of color image sheet may be identified as containing in acid form an acid-base indicator which undergoes a visible change when exposed to the basic azole liberated at the primary image areas.
The following Examples, in which all proportions are in parts by weight unless otherwise indicated, will serve further to illustrate but not to limit the invention.
EXAMPLE 1 Silver imidazolate of minimal particle size is prepared as described hereinabove. The dry powder (4.5 parts) is mixed into a 12 percent solution of polyvinyl butyral in methylethyl ketone (30 parts) by prolonged milling in a ball mill. The resulting suspension is coated on both paper and film backing sheets using a coating bar held at an orifice of four mils (0.1 mm.) and the coatings are air dried, to provide primary copy-sheets.
A desensitizable intermediate transfer sheet, prepared as described in U.S. Pat. No. 3,094,417 and containing dye-sensitized substituted a-naphthol, is exposed to a light-image to an extent just sufficient to cause complete desensitization of the sheet at nonimage areas, leaving the a-naphthol reducing agent only at the image areas. It is then placed in face-to-face contact with the primary copy-sheet and the couplet is heated by passing around a metal roller maintained at 260 F. Upon separation of the sheets, a visible record of the light-image is observed on the copy-sheet in the form of brown images on a white background.
The light-sensitive intermediate transfer sheet may be replaced by a transfer sheet coated with methyl gallate as used in U.S. Pat. No. 2,910,377. The transfer sheet is held in face-to-face contact with the copy-sheet and the couplet is held in heat-conductive contact against a printed original which is then briefly exposed to intense infra-red radiation. A copy of the printed image is formed on the copy-sheet.
The copy formed in the latter instance is placed in face-to-face contact with a commercial Ozalid" diazo sheet and the couplet is held for one-half minute between metal platens maintained at l20l25 C. A copy of the image areas appears in color on the surface of the diazo sheet.
EXAMPLE 2 The procedures of Example 1 are duplicated except that silver benzimidazolate is substituted for the silver imidazolate. Substantially identical results in terms of image formation and appearance are obtained, along with improved stability of background against darkening during prolonged storage in an office file cabinet.
EXAMPLE 3 Silver imidazolate 4.5 12% Polyvinyl butyral in MEK 30 Phthalazinone l .25 Reducing agent 0.3 Silver nitrate 0.045
The reducing agent, a hindered phenol consisting of butylated hydroxytoluene available under the trademark designation CAO-3, is added to the ball milled mixture of the several other components under brief mixing and the composition is promptly coated on paper and film backings, and dried. The resulting primary copy sheets are imaged as described under Example 1 except that in the second procedure the coating of methyl gallate is applied directly to the unprinted surface of the printed original instead of on a separate source sheet. Dense black images are obtained on the primary copy-sheet in all cases. The sheet both before and after imaging has high thermal stability.
A secondary sheet is prepared by coating a transparent film backing with a solution of 4% solution of nitrocellulose in 1:3 alcoholzether 30.0 l-diazo-2,5-dibutoxy-4-morpholinobenzene sulfate 0.75 3-hydroxy-2-naphthol-phenetide 0.25 3-hydroxy-2-naphthol-toluidide 0.25
applied at a wet thickness of about 3 mils, and dried, in absence of light. The film backing is a polyester film which has first been subbed with duPont 49,000," a soluble polyester of glycols, phthalic acids and sebacic acid, applied from solution in trichloroethane, or alternatively has been subjected to a surface treatment by corona discharge. A freshly imaged primary copysheet is placed in face-to-face contact with the secondary sheet and the couplet is heated at 260 F. A faintly yellowish projection transparency is produced which when used with an overhead projector rapidly bleaches to a water-white appearance in the non-image areas and projects a blue image on a white background. 7
EXAMPLE 4 duces a white-appearing film on which the red image appears with good contrast.
EXAMPLE 5 Component A B silver imidazolate 0.5 2.0 reducing agent of Example 3 0.5 0.5 phthalazinone 0.5 0.5 binder (polyvinyl butyral) 2.0 0.5 solvent (MEK) 18.0 10.0
printed surface is briefly exposed to intense infra-red radiation, causing heating of the imaged areas and the formation of a corresponding copper image on the coated film. The copper image is intensified by dipping the film in an electroless copper plating solution. The image areas are found to be electrically conductive.
EXAMPLE 8 A primary copy-sheet prepared as described under Example 3 is first overcoated with a minimal continuous barrier coating of vinyl chloride-vinyl acetate copolymer and then with a photo-sensitive overcoat of dye-sensitized 4-methoxy-l-naphthol. The resulting integral sheet is first exposed to a light-image to densensitize the photosensitive layer at the light-struck areas and is then heated to cause an image-forming reaction at the unexposed areas, the substituted naphthol difius- Mixtures A and B are separately prepared and coated on paper substrates, and the dried primary copy-sheets are imaged by heating in contact with a reflexexposed light-sensitive intermediate transfer sheet as described under Example 1 and under identical conditions. Sheet A produces a dense visible image on a substantially unchanged background; sheet B produces an image of still greater density but with some background darkening.
' EXAMPLE 6 A receptor sheet is prepared by coating polyester film at a coater bar setting of four mils, with a solution containing r vinyl chloride-acetate copolymer 40 N-(bis(4-dimethylaminophenyl)methyl)pyr- I rolidi ne l salicylic acid 1 0.2 methylethyl ketone 160 EXAMPLE 7 Copper (I) imidazolate is prepared by mixing cupric chloride in 0.05 molar solution with an excess of imidazole, adding ascorbic acid and sodium sulfite to reduce the'copper (II) to copper (I) as shown by conversion from blue to straw color, adding molar sodium hydroxide solution to cause precipitation, filtering, and washing and drying the resultant white powder.
A mixture of 10 parts of the powder with 100 parts of 10 percent solution of polyvinyl butyral in a mixture of methylethyl ketone and toluene is applied at 6 mils to a polyester film and dried. A printed sheet having on the reverse surface a coating of methyl gallate is placed against the coated film in face-to-face contact and the ing through the very thin separating layer for reaction with the silver imidazolate.
EXAMPLE 9 A commercial Ozalid diazo sheet as used in Example 1 is first overcoated with a photosensitive layer of dye-sensitized substituted a-naphthol as also employed in Example 1. The sheet is exposed to a light-image sufficient to desensitize the coating at the light-exposed areas. It is then placed in face-to-face contact with a primary copy-sheet prepared as described in Example 3 and the composite is heated. A dense black image forms on the primary copy-sheet; a colored reverse image appears on the diazo print sheet. There is involved first a transfer of the residual a-naphthol from the diazo sheet to the copy-sheet where it reacts with the silver salt to form a silver image, followed by transfer of the liberated imidazole from the copy-sheet to the diazo sheet where it neutralizes the acid stabilizer component and permits the diazo and coupler components to unite with formation of an azo dye image.
What is claimed is as follows:
1. Method of imaging comprising subjecting a first sheet material having a stratum containing a polymeric heavy metal azolate to heat at least at image areas and in the presence of a reducing agent to provide on said sheet material a visible image.
2. Method of claim 1 wherein said metal is silver.
3. Method of claim 1 wherein said reducing agent is photosensitive.
4. Method of claim 3 wherein said reducing agent is supplied from a second sheet held in face-to-face contact with said first sheet material.
5. Method of claim 4 wherein said-second sheet is first exposed to a light-image to an extent just sufficient to desensitize all of said reducing agent in the lighted areas.
6. Method of claim 1 including the further step of heating the imaged first sheet in face-to-face contact with a base sensitive print sheet.
7. Method of claim 6 wherein said print sheet contains an acid stabilized diazo.
8. Method of claim 6 wherein said print sheet contains a base-reactive acid-base indicator.
9. Method of claim 7 wherein said first sheet material includes at least in the image areas thereof a layer containing a said reducing agent which is Photosensitive.
10. Method of claim 1 wherein said stratum contains a catalytically small proportion of silver nitrate.
11. Sheet material including a paper-thin backing carrying an image-forming stratum comprising a heavy metal azolate.
12. Sheet material of claim 11 wherein said heavy metal iS silver.
13. Sheet material of claim 12 wherein said heavy metal azolate is silver imidazolate.
14. Sheet material of claim 13 wherein said stratum includes a hindered phenolic reducing agent for silver ion, and phthalazinone.
15. Sheet material of claim 12 wherein is included a catalytically smallamount of silver nitrate.
16. Sheet material of claim 15 having over said stratum a coterminous vapor-transmissive polymeric barrier layer and an outer layer comprising a volatilizable reducing agent for silver ion. a
17. Sheet material of claim 11 wherein said heavy metal azolate is a copper azolate.
18. A print sheet useful in a couplet with the sheet material of claim 15 in forming an image in color and comprising a base-reactive color-producing stratum and an outer stratum containing a photosensitive reducing agent for silver ion.
19. Print sheet of claim 18 wherein the colorproducing Stratum comprises an acid-stabilized diazo and an azo coupler component and said reducing agent is a substituted a-naphthol.
20. A couplet of the sheet material of claim 16 and in face-to-face contact therewith a print sheet having a base-reactive color-producing stratum and an outer stratum containing a photosensitive reducing agent for silver ion.
Claims (19)
- 2. Method of claim 1 wherein said metal is silver.
- 3. Method of claim 1 wherein said reducing agent is photosensitive.
- 4. Method of claim 3 wherein said reducing agent is supplied from a second sheet held in face-tO-face contact with said first sheet material.
- 5. Method of claim 4 wherein said second sheet is first exposed to a light-image to an extent just sufficient to desensitize all of said reducing agent in the lighted areas.
- 6. Method of claim 1 including the further step of heating the imaged first sheet in face-to-face contact with a base sensitive print sheet.
- 7. Method of claim 6 wherein said print sheet contains an acid stabilized diazo.
- 8. Method of claim 6 wherein said print sheet contains a base-reactive acid-base indicator.
- 9. Method of claim 7 wherein said first sheet material includes at least in the image areas thereof a layer containing a said reducing agent which is photosensitive.
- 10. Method of claim 1 wherein said stratum contains a catalytically small proportion of silver nitrate.
- 11. Sheet material including a paper-thin backing carrying an image-forming stratum comprising a heavy metal azolate.
- 12. Sheet material of claim 11 wherein said heavy metal is silver.
- 13. Sheet material of claim 12 wherein said heavy metal azolate is silver imidazolate.
- 14. Sheet material of claim 13 wherein said stratum includes a hindered phenolic reducing agent for silver ion, and phthalazinone.
- 15. Sheet material of claim 12 wherein is included a catalytically small amount of silver nitrate.
- 16. Sheet material of claim 15 having over said stratum a coterminous vapor-transmissive polymeric barrier layer and an outer layer comprising a volatilizable reducing agent for silver ion.
- 17. Sheet material of claim 11 wherein said heavy metal azolate is a copper azolate.
- 18. A print sheet useful in a couplet with the sheet material of claim 15 in forming an image in color and comprising a base-reactive color-producing stratum and an outer stratum containing a photosensitive reducing agent for silver ion.
- 19. Print sheet of claim 18 wherein the color-producing Stratum comprises an acid-stabilized diazo and an azo coupler component and said reducing agent is a substituted Alpha -naphthol.
- 20. A couplet of the sheet material of claim 16 and in face-to-face contact therewith a print sheet having a base-reactive color-producing stratum and an outer stratum containing a photosensitive reducing agent for silver ion.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US25561772A | 1972-05-22 | 1972-05-22 |
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US00255617A Expired - Lifetime US3767414A (en) | 1972-05-22 | 1972-05-22 | Thermosensitive copy sheets comprising heavy metal azolates and methods for their use |
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Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960908A (en) * | 1973-01-22 | 1976-06-01 | Fuji Photo Film Co., Ltd. | Process for preparing organosilver carboxylates |
US4123274A (en) * | 1977-03-16 | 1978-10-31 | Eastman Kodak Company | Heat developable imaging materials and process |
US4168980A (en) * | 1977-08-19 | 1979-09-25 | Eastman Kodak Company | Heat developable photographic material and process |
US4220709A (en) * | 1977-12-08 | 1980-09-02 | Eastman Kodak Company | Heat developable imaging materials and process |
US4237213A (en) * | 1976-01-30 | 1980-12-02 | Canon Kabushiki Kaisha | Image forming method |
US4260677A (en) * | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
EP0391314A2 (en) * | 1989-04-05 | 1990-10-10 | Matsushita Electric Industrial Co., Ltd. | Method for patterning on a substrate |
EP0671283A1 (en) * | 1994-03-10 | 1995-09-13 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
EP0671284A1 (en) * | 1994-03-10 | 1995-09-13 | Agfa-Gevaert N.V. | Thermal imaging process and an assemblage of a donor and receiving element for use therein |
EP0674216A1 (en) * | 1994-03-25 | 1995-09-27 | Agfa-Gevaert N.V. | Thermal transfer imaging process and donor element for use therein |
EP0674217A1 (en) * | 1994-03-25 | 1995-09-27 | Agfa-Gevaert N.V. | Method for the formation of heat mode image |
EP0677775A1 (en) * | 1994-03-25 | 1995-10-18 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
EP0677776A1 (en) * | 1994-03-25 | 1995-10-18 | Agfa-Gevaert N.V. | Thermal transfer printing process using a mixture of reducing agents for image-wise reducing a silver source |
EP0678775A1 (en) * | 1994-03-25 | 1995-10-25 | Agfa-Gevaert N.V. | Thermal transfer process |
EP0683428A1 (en) * | 1994-05-17 | 1995-11-22 | Agfa-Gevaert N.V. | Thermal transfer imaging system based on the heat transfer of a reducing agent for reducing a silver source to metallic silver |
EP0696515A1 (en) * | 1994-07-11 | 1996-02-14 | Agfa-Gevaert N.V. | Ink jet printing process |
EP0697282A1 (en) * | 1994-07-11 | 1996-02-21 | Agfa-Gevaert N.V. | Process for the prodcution of a printing plate by inkjet |
EP0706080A1 (en) * | 1994-06-27 | 1996-04-10 | Agfa-Gevaert N.V. | Thermal transfer printing of a reducing agent to a silver source contained in an image receiving layer |
EP0713133A1 (en) * | 1994-10-14 | 1996-05-22 | Agfa-Gevaert N.V. | Receiving element for use in thermal transfer printing |
US5587268A (en) * | 1994-03-25 | 1996-12-24 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
US5601962A (en) * | 1994-03-25 | 1997-02-11 | Agfa-Gevaert N.V. | Thermal transfer process wherein a reducing agent and toning agent are transferred to a receiving element containing a thermoreducible silver source |
US5627008A (en) * | 1994-03-25 | 1997-05-06 | Agfa-Gevaert N.V. | Thermal transfer printing process using a mixture of reducing agents for image-wise reducing a silver source |
EP0849625A1 (en) * | 1996-12-19 | 1998-06-24 | Eastman Kodak Company | Thermographic imaging composition and element comprising said composition |
US5858913A (en) * | 1994-10-14 | 1999-01-12 | Agfa-Gevaert | Receiving element for use in thermal transfer printing |
US5922528A (en) * | 1998-03-20 | 1999-07-13 | Eastman Kodak Company | Thermographic imaging element |
US5928856A (en) * | 1998-03-20 | 1999-07-27 | Eastman Kodak Company | Thermographic imaging element |
US5928855A (en) * | 1998-03-20 | 1999-07-27 | Eastman Kodak Company | Thermographic imaging element |
EP0943958A1 (en) * | 1998-03-20 | 1999-09-22 | Eastman Kodak Company | Thermographic imaging element |
-
1972
- 1972-05-22 US US00255617A patent/US3767414A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
Chemical Abstracts, 1964, 733 b,c. * |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960908A (en) * | 1973-01-22 | 1976-06-01 | Fuji Photo Film Co., Ltd. | Process for preparing organosilver carboxylates |
US4237213A (en) * | 1976-01-30 | 1980-12-02 | Canon Kabushiki Kaisha | Image forming method |
US4260677A (en) * | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
US4123274A (en) * | 1977-03-16 | 1978-10-31 | Eastman Kodak Company | Heat developable imaging materials and process |
US4128557A (en) * | 1977-03-16 | 1978-12-05 | Eastman Kodak Company | Silver salts of 1,2,4-mercaptotriazole derivatives |
US4168980A (en) * | 1977-08-19 | 1979-09-25 | Eastman Kodak Company | Heat developable photographic material and process |
US4220709A (en) * | 1977-12-08 | 1980-09-02 | Eastman Kodak Company | Heat developable imaging materials and process |
EP0391314A2 (en) * | 1989-04-05 | 1990-10-10 | Matsushita Electric Industrial Co., Ltd. | Method for patterning on a substrate |
EP0391314A3 (en) * | 1989-04-05 | 1991-08-14 | Matsushita Electric Industrial Co., Ltd. | Method for patterning on a substrate |
US5173330A (en) * | 1989-04-05 | 1992-12-22 | Matsushita Electric Industrial Co., Ltd. | Patterning composition and method for patterning on a substrate |
EP0671283A1 (en) * | 1994-03-10 | 1995-09-13 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
EP0671284A1 (en) * | 1994-03-10 | 1995-09-13 | Agfa-Gevaert N.V. | Thermal imaging process and an assemblage of a donor and receiving element for use therein |
US5587270A (en) * | 1994-03-10 | 1996-12-24 | Agfa-Gevaert N.V. | Thermal imaging process and an assemblage of a donor and receiving element for use therein |
US5589317A (en) * | 1994-03-10 | 1996-12-31 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
US5627008A (en) * | 1994-03-25 | 1997-05-06 | Agfa-Gevaert N.V. | Thermal transfer printing process using a mixture of reducing agents for image-wise reducing a silver source |
EP0677775A1 (en) * | 1994-03-25 | 1995-10-18 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
EP0678775A1 (en) * | 1994-03-25 | 1995-10-25 | Agfa-Gevaert N.V. | Thermal transfer process |
US5601962A (en) * | 1994-03-25 | 1997-02-11 | Agfa-Gevaert N.V. | Thermal transfer process wherein a reducing agent and toning agent are transferred to a receiving element containing a thermoreducible silver source |
US5595854A (en) * | 1994-03-25 | 1997-01-21 | Agfa-Gevaert N.V. | Method for the formation of heat mode image |
EP0674217A1 (en) * | 1994-03-25 | 1995-09-27 | Agfa-Gevaert N.V. | Method for the formation of heat mode image |
US5587269A (en) * | 1994-03-25 | 1996-12-24 | Afga-Gevaert N.V. | Thermal transfer imaging process and donor element for use therein |
EP0677776A1 (en) * | 1994-03-25 | 1995-10-18 | Agfa-Gevaert N.V. | Thermal transfer printing process using a mixture of reducing agents for image-wise reducing a silver source |
US5587268A (en) * | 1994-03-25 | 1996-12-24 | Agfa-Gevaert N.V. | Thermal transfer imaging process |
EP0674216A1 (en) * | 1994-03-25 | 1995-09-27 | Agfa-Gevaert N.V. | Thermal transfer imaging process and donor element for use therein |
US5547809A (en) * | 1994-05-17 | 1996-08-20 | Agfa-Gevaert, N.V. | Thermal transfer imaging system based on the heat transfer of a reducing agent for reducing a silver source to metallic silver |
EP0683428A1 (en) * | 1994-05-17 | 1995-11-22 | Agfa-Gevaert N.V. | Thermal transfer imaging system based on the heat transfer of a reducing agent for reducing a silver source to metallic silver |
US5558972A (en) * | 1994-06-27 | 1996-09-24 | Agfa-Gevaert | Thermal transfer printing of a reducing agent to a silver source contained in an image receiving layer |
EP0706080A1 (en) * | 1994-06-27 | 1996-04-10 | Agfa-Gevaert N.V. | Thermal transfer printing of a reducing agent to a silver source contained in an image receiving layer |
EP0697282A1 (en) * | 1994-07-11 | 1996-02-21 | Agfa-Gevaert N.V. | Process for the prodcution of a printing plate by inkjet |
EP0696515A1 (en) * | 1994-07-11 | 1996-02-14 | Agfa-Gevaert N.V. | Ink jet printing process |
EP0713133A1 (en) * | 1994-10-14 | 1996-05-22 | Agfa-Gevaert N.V. | Receiving element for use in thermal transfer printing |
US5858913A (en) * | 1994-10-14 | 1999-01-12 | Agfa-Gevaert | Receiving element for use in thermal transfer printing |
EP0849625A1 (en) * | 1996-12-19 | 1998-06-24 | Eastman Kodak Company | Thermographic imaging composition and element comprising said composition |
US6066445A (en) * | 1996-12-19 | 2000-05-23 | Eastman Kodak Company | Thermographic imaging composition and element comprising said composition |
US5922528A (en) * | 1998-03-20 | 1999-07-13 | Eastman Kodak Company | Thermographic imaging element |
US5928856A (en) * | 1998-03-20 | 1999-07-27 | Eastman Kodak Company | Thermographic imaging element |
US5928855A (en) * | 1998-03-20 | 1999-07-27 | Eastman Kodak Company | Thermographic imaging element |
EP0943958A1 (en) * | 1998-03-20 | 1999-09-22 | Eastman Kodak Company | Thermographic imaging element |
EP0943960A1 (en) * | 1998-03-20 | 1999-09-22 | Eastman Kodak Company | Thermographic imaging element |
EP0943959A1 (en) * | 1998-03-20 | 1999-09-22 | Eastman Kodak Company | Thermographic imaging element |
EP0943957A1 (en) * | 1998-03-20 | 1999-09-22 | Eastman Kodak Company | Thermographic imaging element |
US5994052A (en) * | 1998-03-20 | 1999-11-30 | Eastman Kodak Company | Thermographic imaging element |
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