US3063863A - Heat-sensitive compositions and elements, and processes for using same - Google Patents
Heat-sensitive compositions and elements, and processes for using same Download PDFInfo
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- US3063863A US3063863A US807761A US80776159A US3063863A US 3063863 A US3063863 A US 3063863A US 807761 A US807761 A US 807761A US 80776159 A US80776159 A US 80776159A US 3063863 A US3063863 A US 3063863A
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- 239000000203 mixture Substances 0.000 title description 24
- 238000000034 method Methods 0.000 title description 17
- 239000000123 paper Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 35
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002184 metal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- IRUHVWFVQLJFRG-UHFFFAOYSA-N 1-hydroxy-2h-pyrrol-3-one Chemical class ON1CC(=O)C=C1 IRUHVWFVQLJFRG-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 e.g. Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- SLXPAVKRBGVJJA-UHFFFAOYSA-N 5-hydroxy-4,5-dimethyl-2-oxo-1h-pyrrole-3-carbonitrile Chemical compound CC1=C(C#N)C(=O)NC1(C)O SLXPAVKRBGVJJA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229940076286 cupric acetate Drugs 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- HMXQIFUGFZEJEO-UHFFFAOYSA-N 1,2-dihydropyrrol-3-one Chemical class O=C1CNC=C1 HMXQIFUGFZEJEO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000004304 visual acuity Effects 0.000 description 3
- CIGXGWDUXOBPIO-UHFFFAOYSA-N (R)-Dihydromaleimide Chemical compound OC1NC(=O)C=C1 CIGXGWDUXOBPIO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- FSQAIQPPCOCRAX-UHFFFAOYSA-L copper;2-oxopropanoate Chemical compound [Cu+2].CC(=O)C([O-])=O.CC(=O)C([O-])=O FSQAIQPPCOCRAX-UHFFFAOYSA-L 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000033458 reproduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000222239 Colletotrichum truncatum Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 241001233242 Lontra Species 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- VVYPIVJZLVJPGU-UHFFFAOYSA-L copper;2-aminoacetate Chemical compound [Cu+2].NCC([O-])=O.NCC([O-])=O VVYPIVJZLVJPGU-UHFFFAOYSA-L 0.000 description 1
- SMBIRMBGEIZAAD-UHFFFAOYSA-L copper;2-chloroacetate Chemical compound [Cu+2].[O-]C(=O)CCl.[O-]C(=O)CCl SMBIRMBGEIZAAD-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 150000004717 pyruvic acids Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/165—Thermal imaging composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
- Y10T428/277—Cellulosic substrate
Definitions
- This invention relates to heat-sensitive compositions and elements embodying them that are useful in thermographic recording and copying systems. More particularly, it relates to such compositions and elements which upon exposure to heat darken in color and undergo the further transformation whereby the water-soluble components become water-insoluble. Still more particularly, this invention relates to heat-sensitive flexible sheets bearing coatings containing such compositions.
- Heat-sensitive paper for use in a thermographic apparatus giving copies of certain graphic originals quickly and easily by a completely dry process is commercially available.
- the primary shortcomings of this paper (which has enjoyed considerable commercial use) are (1) its limited resolving power due to the granular structure of the heat-sensitive components, and (2) the narrow exposure latitude. Other disadvantages are the unattractive appearance of the finished copy caused by the uppleasant combinations of image and background color, the thermal instability of the paper after it is used for making copies and the undesirably high flexibility of the material.
- An object of this invention is to provide a heat-sensitive element which is capable of forming rapidly, by a dry thermographic process, an image having high resolving power.
- a further object is to provide such a product which provides wide exposure latitude.
- compositions of this invention comprise an intimate mixture of (1) A S-hydroxy-3-pyrrolin-2-one, having a negative substituent in the 3-position, of the general formula:
- R is a member selected
- a small amount of a metal salt taken from the group consisting of cupric, ferrous, mercuric and silver salts of a monoor dibasic organic carboxylic acid, and if desired,
- the metal salt is a cupric salt of an organic carboxylic acid of not more than4 carbon atoms which is either unsubstituted or may be substituted by halogen, e.g., fluorine, chlorine and bromine, hydroxyl, amino or alkylamino of 1-4 carbon atoms.
- halogen e.g., fluorine, chlorine and bromine
- hydroxyl, amino or alkylamino of 1-4 carbon atoms can be made by merely admixing the compounds and, if desired, a solvent or diluent and a polymeric binding agent, e.g., a natural or synthetic water-permeable colloid having protective colloid properties, e.g., gelatin and polyvinyl alcohol.
- the novel heat-sensitive copy of recording elements of the invention comprise a suitable support having an outer surface coated or impregnated with the aforesaid compositions.
- the supports can be rigid, e.g., glass, plastic plates, or cardboard, or they can be flexible, e.g., paper or a polymeric film. Flexible supports are preferred.
- the support for the thermally sensitive, permanent imagerecording elements of the invention can vary widely in constitution but should not be a good conductor of heat because the image is produced thermally and a heat-conductive support, e.g., a metal foil or a self-supporting film or layer containing an appreciable quantity of powdered metal, would precent the formation of a sharp image.
- the flexible support can be composed of an organic polymeric material having a softening point above the temperature at which the thermographic image is formed, e.g., above l20200 C.
- Suitable such polymen'c materials include paper, thin cardboard, self-supporting films composed of cellulose and regenerated cellulose; cellulose others, eg., methyl cellulose, ethyl cellulose of low substitution; cellulose esters, e.g., cellulose triacetate; synthetic macro-molecular polymers, including polyvinyl acetals, e.g., polyvinyl formal; polyvinyl esters, e.g., polyvinyl acetate of low acetate content, and proteins, e.g., gelatin.
- the foregoing synthetic polymers can be layers on paper or another support.
- the supports can be used in the form of films and in the form of felted sheets made from fibers of the cellulosic or other polymeric materials referred to above.
- heat-sensitive layer containing 5-hydroxy-3-pyrro1in-2-one and Cu, Fe, Hg or Ag salt of monoor dibasic organic carboxylic acid Support, e.g., paper or polymeric film
- the flexible sheet support should be infrared-transparent to permit the formation of the color image in depth and in, for instance, reflex copying to permit the satisfactory development of the image on the reverse surface or within the sheet.
- the flexible sheet support can be infrared opaque.
- the flexible sheet support can be transparent or opaque to visible light.
- the optimum ratio of the hydroxypyrrolinone and metal salt will dependupon the type of product desired but, in general, the preferred range is considered to be 0.1 to 0.5 mols of the metal salt per mol of the substituted hydroxypyrrolinone compound with a useful range extending from 0.01 to 1.0 mols of metal salt per mol of the substituted hydroxypyrrolinone.
- Increasing the relative concentration of metal salt increases the speed of the thermochemical reaction but this may be at the expense of higher background density or stain depending on the particular metal ion employed. This background is, of course, no problem when the print can be washed.
- Thermographic speed also is increased by increasing total coating weight of the heat-sensitive materials.
- Useful hydroxypyrrolinone coating weights are in the range 20-5 mg./dm. depending on intended application, while the preferred coating weight range is 50-200 mg./dm.
- an aqueous solution of 3-cyano-4,5dimethyl- 5-hydroxy-3-pyrrolin-2-one and cupric acetate are coated on paper or other suitable base material and exposed as described in C. S. Miller U.S. Patent 2,740,896 of April 3, 1956, in a commercial Thermo-Fax (made by Minnesota Mining and Manufacturing Co.) thermographic copying machine, whereby there is produced a copy of a graphic original, said copy having an intense dark-colored, grainless, high resolution image against a light-colored badground.
- EXAMPLE 1 3-cyano-4,5-dirnethyl-5-hydroxy-3-pyrrolin-2-one 104 mg.) and 34.2 mg. of Cu(CH COO) -H O were dissolved in 4 ml. of water at room temperature and, after standing for 1 hour, the solution was brush-coated onto a 4" x 4" piece of onionskin paper (Eagle-A Trojan). The coating, after being air-dried at room temperature, was exposed at the No. 1 setting of a Premier Model 19 Thermo-Fax (Minnesota Mining and Manufacturing Co.) thermographic copying machine to produce a copy of a paper sheet on which letter characters were printed in carbon black ink, said copy having a coal black image against a light colored background.
- a Premier Model 19 Thermo-Fax Minnesota Mining and Manufacturing Co.
- Example III in Example II were mixed, the resulting solution allowed to stand for 1 hour at room temperature, spread out over the surface of a 2" x 2" area of the treated film base. and then air dried at room temperature to yield a smooth, transparent coating. The coating was exposed as described in Example I to yield a copy having a coal black image against a light colored background.
- Another portion of the coating was dipped for 30 seconds in water, drained, and then dipped for 10 seconds in 0.1 M HCl solution, followed by a 30-second water wash. It was then air dried. The background was a pure white, while the image remained a coal black. Heating at 180 C. up to 1 minute had no efiect on the copy so treated.
- EXAMELE VI A solution of 0.25 g. of 3-cyano-4,S-dimethyl-S-hydroxy-3-pyrrolin-2-one in 3 ml. of water was mixed with 0.15 ml. of 0.3 M Cu(CH COO) solution to give a Cu +/hydroxypyrrolinone mol ratio of 0.027.
- the miX- ture was coated fresh on a 5 x 8 /2 inch piece of onionskin paper and air dried. Its sensitivity was tested by heating a small disk of the coating on a Fisher melting point apparatus, the temperature of the metal block being read by a thermometer whose bulb was inserted inside the block. The coating darkened somewhat after holding 20 seconds at 150 C. and was a dark gray-black after 20 seconds at 180 C.
- thermographic sensitivity is shown in tabular form below.
- Example II After drying in air at room temperature, the four coated papers were exposed as in Example I to yield copies having coal black images against light-colored backgrounds. The four coatings were roughly equivalent in thermographic sensitivity.
- EXAMPLE V-IH One gram of a solution of polyvinyl alcohol as described in Example 11 was coated on a 2" x 3" piece of tracing paper (Albanene) and air-dried at room temperature. A mixture of 0.25 ml. of an aqueous l M solution of 3-cyano-4,S-dimethyl-S-hydroxy-3-pyrrolin-2- one and 0.60 ml. of an aqueous 0.1 M solution of mercuric acetate was allowed to stand overnight and then flowed over the surface of the polyvinyl alcohol treated tracing paper. After air drying at room temperature, the coating was exposed as in Example I to yield a copy having a dark purple image against :a light pink background.
- Example VIII A mixture of 0.80 ml. of the 0.0725 M AgOCOCH solution and 0.25 ml. of an aqueous l M Solution of 3-cyano-4,5-dimethyl-5-hydroxy-3-pyrrolin-2-one was coated on a polyvinyl alcohol treated tracing paper support described in Example VIII. With drying and exposure as described in Example I, there was formed a copy having a dark brown image against a lighter brown background.
- thermographic exposure A similar coating upon appreciable exposure to room light showed indications of photolysis so that with such a coating it is desirable to provide for protection against excessive exposure to light prior to the thermographic exposure.
- the fixing step following thermographic exposure is particularly recommended for a coating containing silver.
- EXAMPLE XI which was added an amount of the solution or suspension containing 0.1 millimol of the respective copper salt. These mixtures were coated on 3" x 4" pieces of onionskin paper and air dried at room temperature. Each of the respective coated papers showed some color changev when heated for 15-30 sec. at C. and turned black upon heating for the same length of time at 180 C.
- EXAMPLE m1 Approximately 41.5 mg. (0.25 millimol) of 3-cyano-(4,5-methyl, ethyl)-5-hydroxy-3-pyrrolin-2-one was dissolved in 2 ml. ethanol. To this solution was added 0.15 ml. of 0.3 M Cu(CH COO) solution and the mixture coated fresh on a 2 X 3" piece of onionskin paper. After air-drying the coating was exposed to a printed paper sheet in the Thermo-Fax machine described in Example I. Three exposure passes at setting No. 1 produced a faint black image on a light blue-green background.
- Procedure B To make copper propionate, one-half of the Cu(OH) precipitate from Procedure A was mixed with 1.80 ml. of propionic acid and the mixture diluted to 50 ml. with water to make a 0.5 M suspension. Additional propionic acid was required to dissolve all the Cu(QH) forming a clear green solution.
- Procedure C To make copper chloroacetate, one-half of the Cu(OH) precipitate from Procedure A was mixed with a solution of 2.30 grams chloroacetic acid in 25 ml. H O. The mixture, also a suspension, was diluted to 50 ml. with water. Additional chloroacetic acid was required to dissolve all the Cu(OH) Procedure D.To make copper glycinate, 0.02 mole of Cu(OH) was prepared as described in Procedure A to which was added a solution of 1.50 g. glycine dissolved in 25 ml. H O. The slurry was diluted to 100ml. with P1 0. A few drops of cone. HCl was added to help dissolve the suspension.
- Procedure F -Copper trifiuoroacetate was prepared by mixing 0.02 mole of Cu(OH) with 1.49 ml. triiluoroacetic acid followed by dilution to 100' ml. with H O. No attempt was made to dissolve the small portion of Cu(OH) that did not dissolve.
- thermographic image in the new elements of the present invention can be achieved in any way whereby the element comprising the flexible sheet support and in operative association therewith the hydroxypyrrolinone and metal salt is selectively exposed to the required color-developing temperatures to form the desired pattern.
- the thermographic element can be pressed with a heated stylus operated manually or mechanically as the recording or copy arm of a sensing system driven by a photoelectric scanning beam.
- thermographic element In a similar fashion, heated type characters, slugs, or cornplete composed plates may be pressed directly in contact with the thermographic element.
- the therinog'raph'ic images can be prepared by suitable selective infrared absorption.
- a master to be reproduced will generally have a dark text on a white background. Accordingly, on exposure to infrared radiation or to normal light, the black areas are selectively warmer than the white areas by virtue of the selective absorption of the infrared radiation in the dark areas.
- the original With light of suflicient intensity directed on such an original held in contact with one of the thermographic elements of the present invention, the original is heated in the dark areas to temperature ranges wherein the thermographic reaction occurs in the therrnographic element, thereby producing a colored direct positive duplicate of the original.
- thermographic elements The temperatures to which these thermographic elements must be brought in order to develop the thermographic image will vary with the specific substituted hydroxypyrroiinone, the nature of the support, the relative concentration of the hydroxypyrrolinone, the specific metal ion and the amount of such ion. Generally satisfactory colored images are obtained when the thermographic element is brought to temperatures between about 120 C. and about 200 C. A generally satisfactory average temperature would thus be in the neighborhood of about 140170 C.
- the times at which these thermographic elements must be selectively held at such temperatures in order to develop satisfactory image quality likewise vary with the nature of the substituents on the hydroxypyrrolinone, themetal salt and in part with the nature of the support in the sense of the optical contrast qualities thereof.
- An approximate shortest color development time at these temperatures is in the neighborhood of about 0.1-2.0 seconds; whereas, with some of the less reactive mixtures of lower heat sensitivity, reaction times of up to 1015 seconds or even a minute are needed.
- an average color development time at the average development temperature of about 175 C. will be about 1.0 to 2.0 seconds.
- thermographic copying paper for example as a general copying paper.
- the elements are also useful as a thermogr'aphic microfilm, for making copies via enlargement or reduction projection and for use in recording information in recording instruments, e.g., spectrograms.
- This invention has the advantage that it provides thermally-sensitive recording elements of high potential resolving power since it is a grainless system as contrasted with the non-grainless commercially available systems described in US. 2,663,654 through 2,663,657. Exposure latitude of the element is unusually broad. This invention makes possible the production of a copy which is pleasing to the eye, giving an intense black image against a white of light-colored background.
- Another advantage of the present invention is that it provides the art with a new class of thermally sensitive image recording elements which are economical to make and easy to use in making positive images directly.
- the novel elements do not require skilled operators or technicians when used to make positive images. A large number of reproductions can be made rapidly from any printed or other material'to be copied.
- Another advantage is that the novel elements can be readily fixed to remove discoloration and obtain a white background bywashing in wateror dilute mineral. acid (e.g., hydro"- chloric solutions). Still other advantages will be apparent to those skilled in the art of image formation or reproduction.
- the novel thermally-sensitive recording elements of this invention have advantages over prior art elements when used in charts to be marked with a stylus.
- the latter generally employ a dark-colored paper with a white, opaque coating that becomes clear on application of heat, thereby producing a dark area on a white background.
- Typical coatings of this type are based on opaque, waxy, or crystalline materials, blushed resin coatings (see U.S. Patent 2,519,660) or plastic films coritaining microscopic voids (see US. Patent 2,739,909). Waxy coatings stick to adjacent layers and because of their softness are easily damaged. The blushed resin coatings must be applied under carefully controlled conditions to avoid variations in opacity of the coatings.
- the third type of film-that containing the microscopic Voids is widely used, but careful balancing of ingredients is required to produce a film which can be marked at available temperatures but at the same time is not unduly sensitive to pressure. All of these prior types ofcoatings must be applied to a colored base, which is generally paper carrying a dark pigmented coating. In addition, volatile organic solvents are necessarily employed in the production of all three types.
- thermo-sensitive, image-recording copy element comprising a support of low heat conductivity having an outerrstratum containing as the essential heat-sensitive components (1) a 5-hydroxy-3-pyrrolin-2-one having a negative substituent in the 3-position and the general formula:
- R is a member selected from the group consisting of hydrogen, monovalent hydrocarbon radicals of not more than 10 carbon atoms, amino and dialkylamino of 1-2 carbon atoms, the radicals R when separate are each selected from the group consisting of hydrogen, alkyl of 1-10 carbons, cycloalkyl of 4-6 carbons, aryl of 6-10 carbons and aralkyl of 7-10 carbons and when linked together constitute a single divalent hydrocarbon radical which forms with the 4- and 5-carbon atoms of the pyrrolinone ring a carbocyclic radical of 5-7 ring atoms, said substituted pyrrolinones being further characterized in that when substituted with the members recited, not more than one of the 4- and S-carbons have an aromatic substituent and (2) from 0.01 to 1.0 mole per mole of
- metal salt is a cupric salt of an organic carboxylic acid of not more than 4- carbon atoms.
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Description
llnited States atent 3,063,863 Patented Nov. 13, 1962 iee 3,063,863 EAT-SENSITIVE COMPOSITIONS AND ELE- MENTS, AND PROCESSES FOR USHWG SAME Russell Sedgwick Holland, Milltown, and Robert Ellis Wayrynen, Little Silver, NJL, assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Apr. 21, 1959, Ser. No. 807,761
6 Claims. (Cl. 11736.8)
This invention relates to heat-sensitive compositions and elements embodying them that are useful in thermographic recording and copying systems. More particularly, it relates to such compositions and elements which upon exposure to heat darken in color and undergo the further transformation whereby the water-soluble components become water-insoluble. Still more particularly, this invention relates to heat-sensitive flexible sheets bearing coatings containing such compositions. v. Heat-sensitive paper for use in a thermographic apparatus giving copies of certain graphic originals quickly and easily by a completely dry process is commercially available. The primary shortcomings of this paper (which has enjoyed considerable commercial use) are (1) its limited resolving power due to the granular structure of the heat-sensitive components, and (2) the narrow exposure latitude. Other disadvantages are the unattractive appearance of the finished copy caused by the uppleasant combinations of image and background color, the thermal instability of the paper after it is used for making copies and the undesirably high flexibility of the material.
An object of this invention is to provide a heat-sensitive element which is capable of forming rapidly, by a dry thermographic process, an image having high resolving power. A further object is to provide such a product which provides wide exposure latitude. A still further object is to provide an element capable of forming a dark-colored image on a white or light-colored background having improved appearance and good legibility. Additional objects are to provide an element which is thermally stable after the initial image has been formed and has good handling characteristics. Still other objects will be apparent from the following description of the invention.
The heat-sensitive compositions of this invention comprise an intimate mixture of (1) A S-hydroxy-3-pyrrolin-2-one, having a negative substituent in the 3-position, of the general formula:
HO/ \N/ Bi l wherein X is a negative substituent selected from the group consisting of quaternary onium and inium salts and carboxyl groups and groups hydrolyzable thereto, R is a member selected from the group consisting of hydrogen, monovalent hydrocarbon radicals of not more than carbon atoms, amino and dialkyl amino of l-2 carbons, the radicals R when separate can be the same or different and are each selected from the group consisting of hydrogen, alkyl of 1 through 10 carbon atoms, cycloalkyl of 4 through 6 carbon atoms, aryl of 6 through 10 carbon atoms and alkaryl of 7 through 10 carbon atoms and the R's when together constitute a single divalent hydrocarbon radical that forms with the 4- and S-carbon atoms of the pyrrolincne ring a carbocyclic radical of 5 to 7 ring atoms, said substituted pyrrolinones being further characterized in that only one of the 4- and S-carbon atoms have an aromatic substituent;
(2) A small amount of a metal salt taken from the group consisting of cupric, ferrous, mercuric and silver salts of a monoor dibasic organic carboxylic acid, and if desired,
(3) A polymeric binding agent, and
(4) A solvent or diluent.
In the preferred aspect of the invention, the metal salt is a cupric salt of an organic carboxylic acid of not more than4 carbon atoms which is either unsubstituted or may be substituted by halogen, e.g., fluorine, chlorine and bromine, hydroxyl, amino or alkylamino of 1-4 carbon atoms. These compositions can be made by merely admixing the compounds and, if desired, a solvent or diluent and a polymeric binding agent, e.g., a natural or synthetic water-permeable colloid having protective colloid properties, e.g., gelatin and polyvinyl alcohol.
The novel heat-sensitive copy of recording elements of the invention comprise a suitable support having an outer surface coated or impregnated with the aforesaid compositions. The supports can be rigid, e.g., glass, plastic plates, or cardboard, or they can be flexible, e.g., paper or a polymeric film. Flexible supports are preferred. The support for the thermally sensitive, permanent imagerecording elements of the invention can vary widely in constitution but should not be a good conductor of heat because the image is produced thermally and a heat-conductive support, e.g., a metal foil or a self-supporting film or layer containing an appreciable quantity of powdered metal, would precent the formation of a sharp image. In general, the flexible support can be composed of an organic polymeric material having a softening point above the temperature at which the thermographic image is formed, e.g., above l20200 C. Suitable such polymen'c materials include paper, thin cardboard, self-supporting films composed of cellulose and regenerated cellulose; cellulose others, eg., methyl cellulose, ethyl cellulose of low substitution; cellulose esters, e.g., cellulose triacetate; synthetic macro-molecular polymers, including polyvinyl acetals, e.g., polyvinyl formal; polyvinyl esters, e.g., polyvinyl acetate of low acetate content, and proteins, e.g., gelatin. Instead of films, the foregoing synthetic polymers can be layers on paper or another support. The supports can be used in the form of films and in the form of felted sheets made from fibers of the cellulosic or other polymeric materials referred to above.
The following symbolic diagrams illustrate two embodiments of the invention:
Coated and/ or impregnated heat-sensitive layer containing 5-hydroxy-3-pyrro1in-2-one and Cu, Fe, Hg or Ag salt of monoor dibasic organic carboxylic acid Support, e.g., paper or polymeric film Heat-sensitive layer of organic colloid binder, S-hydroxy- 3-pyrrolin-2-one and Cu, Fe, Hg or Ag salt of m0noor dibasic organic carboxylic acid Support, e.g., paper or polymeric film For some uses the flexible sheet support should be infrared-transparent to permit the formation of the color image in depth and in, for instance, reflex copying to permit the satisfactory development of the image on the reverse surface or within the sheet. For other uses, for instance, recording paper for a suitably driven hot stylus, the flexible sheet support can be infrared opaque. The flexible sheet support can be transparent or opaque to visible light. For contrast purposes, it is generally desirable that the flexible sheet support be somewhat opaque to visible light and, ideally, should exhibit a color which contrasts to the colorof th thermographic image.
The optimum ratio of the hydroxypyrrolinone and metal salt will dependupon the type of product desired but, in general, the preferred range is considered to be 0.1 to 0.5 mols of the metal salt per mol of the substituted hydroxypyrrolinone compound with a useful range extending from 0.01 to 1.0 mols of metal salt per mol of the substituted hydroxypyrrolinone. Increasing the relative concentration of metal salt increases the speed of the thermochemical reaction but this may be at the expense of higher background density or stain depending on the particular metal ion employed. This background is, of course, no problem when the print can be washed. Thermographic speed also is increased by increasing total coating weight of the heat-sensitive materials. Useful hydroxypyrrolinone coating weights are in the range 20-5 mg./dm. depending on intended application, while the preferred coating weight range is 50-200 mg./dm.
In exemplification of a preferred embodiment of this invention, an aqueous solution of 3-cyano-4,5dimethyl- 5-hydroxy-3-pyrrolin-2-one and cupric acetate are coated on paper or other suitable base material and exposed as described in C. S. Miller U.S. Patent 2,740,896 of April 3, 1956, in a commercial Thermo-Fax (made by Minnesota Mining and Manufacturing Co.) thermographic copying machine, whereby there is produced a copy of a graphic original, said copy having an intense dark-colored, grainless, high resolution image against a light-colored badground.
The invention will be further illustrated by but is not intended to be limited by the following examples.
EXAMPLE 1 3-cyano-4,5-dirnethyl-5-hydroxy-3-pyrrolin-2-one 104 mg.) and 34.2 mg. of Cu(CH COO) -H O were dissolved in 4 ml. of water at room temperature and, after standing for 1 hour, the solution was brush-coated onto a 4" x 4" piece of onionskin paper (Eagle-A Trojan). The coating, after being air-dried at room temperature, was exposed at the No. 1 setting of a Premier Model 19 Thermo-Fax (Minnesota Mining and Manufacturing Co.) thermographic copying machine to produce a copy of a paper sheet on which letter characters were printed in carbon black ink, said copy having a coal black image against a light colored background.
EXAMPLE II To 1 g. of a solution of 100 g. of polyvinyl alcohol (99% hydrolyzed, viscosity of 4% aqueous solution centipoises at 20 C.) in 900 g. of water were added 0.25 ml. of a 1 molar solution of 3-cyano-4,5-dimethyl-S- hydroxy-3-pyrrolin-2-one and 0.60 ml. of a 0.1 molar cupric acetate solution. The mixture was allowed to stand overnight at room temperature and was coated with the aid of a doctor knife on a 2 x 3 piece of tracing paper. The dried coating was exposed as in Example I to pro duce a copy having a coal black image against a lightcolored background.
EXAMPLE III in Example II were mixed, the resulting solution allowed to stand for 1 hour at room temperature, spread out over the surface of a 2" x 2" area of the treated film base. and then air dried at room temperature to yield a smooth, transparent coating. The coating was exposed as described in Example I to yield a copy having a coal black image against a light colored background.
EXAMPLE IV Six and six-tenths ml. of the hydroxypyrrolinone solution of Example Ii, 8.8 ml. of a 0.15 molar cupric acetate solution and 6.7 ml. of a solution of 15 g. of deionized gelatin dissolved in g. of water were mixed, allowed to stand for an hour at room temperature, and a portion of this reaction mixture was spread uniformly over the surface of a 4 x 4" piece of polyethylene terephthalate film base which had been made and coated with a vinylidene chloride/methyl acrylate/itaconic acid copolymer and gelatinsubstrata as disclosed in Alles U.S. Patent 2,779,684. After air drying at room temperature, the coating was exposed as described in Example I to yield a copy having a coal black image against a light'colored background.
EXAMPLE V 3-cyano-4,S-dirnethyl-S-hydroxy-3-pyrrolin-2-one (608 mg.) was dissolved in 4 ml. H O, to which was added 2.4 ml. of 0.3 molar Cu(CI-I CO0) solution. This mixture without prior aging was coated on an 8 /2 x 11" sheet of onionskin paper and the coating was air-dried. It was then exposed for 2 passes at the No. 1 setting of the copying machine for Example I to produce a copy of a paper sheet on which letter characters were printed in carbon black ink, said copy having a black image on a light bluegreen background.
A portion of this exposed coating was dipped for 30 seconds in water, blotted to remove excess water and air dried. The black letters remained unchanged by this treatment while the background became a very faint pinkishblue which is stable to atmospheric humidity. This paper upon heating for 1 minute at 180 C. turned very slightly yellowish, the image remaining essentially unchanged.
Another portion of the coating was dipped for 30 seconds in water, drained, and then dipped for 10 seconds in 0.1 M HCl solution, followed by a 30-second water wash. It was then air dried. The background was a pure white, while the image remained a coal black. Heating at 180 C. up to 1 minute had no efiect on the copy so treated.
EXAMELE VI A solution of 0.25 g. of 3-cyano-4,S-dimethyl-S-hydroxy-3-pyrrolin-2-one in 3 ml. of water was mixed with 0.15 ml. of 0.3 M Cu(CH COO) solution to give a Cu +/hydroxypyrrolinone mol ratio of 0.027. The miX- ture was coated fresh on a 5 x 8 /2 inch piece of onionskin paper and air dried. Its sensitivity was tested by heating a small disk of the coating on a Fisher melting point apparatus, the temperature of the metal block being read by a thermometer whose bulb was inserted inside the block. The coating darkened somewhat after holding 20 seconds at 150 C. and was a dark gray-black after 20 seconds at 180 C.
The above procedure was repeated several times in all details except for the use of increasing quantities of Cu(Ci-I COO) solution which resulted in increasing the ratio Cu++ /hydroxypyrrolinone. The effect on thermographic sensitivity is shown in tabular form below.
Table I w/ Volume 0.3 M ydroxypyr- 'Ilicrrnographic Effects CutGHaCOO): rolinone mol ratio 0. 027 Some darkening after 20 sec. at 150 0.
Dark grey-black after 20 sec. at 180 C. Darkening after 20 sec. at 135 C. Darkening after 20 sec. at 120 0.
Dark grey-black at 135 C. Pronourgced darkening after 20 see.
Slight darkening after 20 see. at 0. Jet block otter 20 sec. at C.
A mixture which contained 5 millimols of 3-cyano-4,5- dimethyl-5-hydroxy-3-pyrrolin-2-one in aqueous solution and 1 millimol of Cu(CH COO) in aqueous solution was brought up to a volume of 10 ml. by addition of water. Approximately one ml. of this mixture was evenly spread, with the aid of a small brush, over the surfaces of 3" x 4" pieces of each of the following papers:
(a) Onionskin paper (Eagle-A Trojan) paper.
-(b) Tracing paper (Keuffel and Esser No. 195L Albanene) from the surface of which the wax treating material had been removed with acetone.
() A high-grade bond paper.
(d) A very thin (55 g./sq. m.), 100% rag-based, translucent, non-coated photographic paper stock.
After drying in air at room temperature, the four coated papers were exposed as in Example I to yield copies having coal black images against light-colored backgrounds. The four coatings were roughly equivalent in thermographic sensitivity.
EXAMPLE V-IH One gram of a solution of polyvinyl alcohol as described in Example 11 was coated on a 2" x 3" piece of tracing paper (Albanene) and air-dried at room temperature. A mixture of 0.25 ml. of an aqueous l M solution of 3-cyano-4,S-dimethyl-S-hydroxy-3-pyrrolin-2- one and 0.60 ml. of an aqueous 0.1 M solution of mercuric acetate was allowed to stand overnight and then flowed over the surface of the polyvinyl alcohol treated tracing paper. After air drying at room temperature, the coating was exposed as in Example I to yield a copy having a dark purple image against :a light pink background.
EXAMPLE IX To 0.6 ml. of a 0.1 M Fe(CH COO) solution, there was mixed with 0.25 ml. of an aqueous 1 M solution of 3-cyano-4,5-dimethyl-5-hydroxy-3-pyrrolin-2-one and 1 g. of the polyvinyl alcohol solution described in Example II. After standing overnight, the mixture was coated on a 2" x 3" piece of tracing paper (Albanene). Exposure as in Example I yielded a copy having a brownishblack image against a yellowish tan background.
EXAMPLE X To 0.85 g. AgNO dissolved in 5 ml. pure, distilled water there were added 5 ml. of an aqueous 1 M NaOH solution. The resultant Ag O precipitate was separated from the supernatant liquid by centrifugation and to the precipitate was added slowly a acetic acid solution in which the brown Ag O precipitate dissolved. The silver acetate solution thus formed was diluted with water to a total volume of 50 ml. to give an 0.0725 M solution.
A mixture of 0.80 ml. of the 0.0725 M AgOCOCH solution and 0.25 ml. of an aqueous l M Solution of 3-cyano-4,5-dimethyl-5-hydroxy-3-pyrrolin-2-one was coated on a polyvinyl alcohol treated tracing paper support described in Example VIII. With drying and exposure as described in Example I, there was formed a copy having a dark brown image against a lighter brown background.
A similar coating upon appreciable exposure to room light showed indications of photolysis so that with such a coating it is desirable to provide for protection against excessive exposure to light prior to the thermographic exposure. The fixing step following thermographic exposure (as described in Example V) is particularly recommended for a coating containing silver.
EXAMPLE XI which was added an amount of the solution or suspension containing 0.1 millimol of the respective copper salt. These mixtures were coated on 3" x 4" pieces of onionskin paper and air dried at room temperature. Each of the respective coated papers showed some color changev when heated for 15-30 sec. at C. and turned black upon heating for the same length of time at 180 C.
EXAMPLE m1 '(a) Approximately 41.5 mg. (0.25 millimol) of 3-cyano-(4,5-methyl, ethyl)-5-hydroxy-3-pyrrolin-2-one was dissolved in 2 ml. ethanol. To this solution was added 0.15 ml. of 0.3 M Cu(CH COO) solution and the mixture coated fresh on a 2 X 3" piece of onionskin paper. After air-drying the coating was exposed to a printed paper sheet in the Thermo-Fax machine described in Example I. Three exposure passes at setting No. 1 produced a faint black image on a light blue-green background.
(b) The procedure described in the preceding paragraph (a) was repeated but using 48 mg. of 1-allyl-3- cyano-4,5-dimethyl-5-hydroxy-3-pyrrolin-2-one in 1 ml. ethanol instead of the pyrrolin-Z-one described therein. The reaction product of this hydroxypyrrolinone with copper acetate yielded a faint brown image on a light greenish-tan background.
(0) The procedure of paragraph (a) was repeated but using 48.5 mg. of 1-dimethylamino-3-cyano-4,5-dimethyl- 5-hydroxy-3-pyrrolin-2-one in 1 ml. ethanol instead of the pyrrolin-Z-one of that paragraph. The reaction product of this hydroxypyrrolinone with copper acetate yielded a faint brown image on a light green background.
(d) 93 mg. (0.5 millimol) of 3-thiocarbamyl-4,5-dimethyl-5-hydroxy-3-pyrrolin-2-one was dissolved in a small quantity of a water-methanol mixture. To this was added 0.3 ml. of 0.3 M Cu(CH COO) solution and the mixture coated fresh on a 3" x 4" piece of onionskin paper. After air-drying the coating was heated on a melting point block as described under Example VI, yielding a brown-black color after 15 sec. at C. The color before heating was a medium brown.
Addition of many copper salts of organic acids with exclusion of foreign ions requires preparation of the organic copper salt compound from Cu(OH) and the appropriate organic acid. The following procedures are useful for this purpose.
Procedure A.To make Cu(OH) 8.53 gm. (0.05 mole) CuCl -H O was dissolved in 50 ml. H O. To this was added with stirring 50 ml. of 1 M NaOH solution. A slight excess of NaOH was added to raise the pH to 8 to 9. After filtering, the Cu(OH precipitate was washed with water.
Procedure B.-To make copper propionate, one-half of the Cu(OH) precipitate from Procedure A was mixed with 1.80 ml. of propionic acid and the mixture diluted to 50 ml. with water to make a 0.5 M suspension. Additional propionic acid was required to dissolve all the Cu(QH) forming a clear green solution.
Procedure C.To make copper chloroacetate, one-half of the Cu(OH) precipitate from Procedure A was mixed with a solution of 2.30 grams chloroacetic acid in 25 ml. H O. The mixture, also a suspension, was diluted to 50 ml. with water. Additional chloroacetic acid was required to dissolve all the Cu(OH) Procedure D.To make copper glycinate, 0.02 mole of Cu(OH) was prepared as described in Procedure A to which was added a solution of 1.50 g. glycine dissolved in 25 ml. H O. The slurry was diluted to 100ml. with P1 0. A few drops of cone. HCl was added to help dissolve the suspension.
Procedure E.Copper glycolate and copper pyruvate were made in a manner similar to that described for copper giycinate, except that 2.17 grams of 70% glycolic acid solution and 1.76 grams of pyruvic acid Were used in place of the glycine. Also, excess glycolic and pyruvic acids, respectively, were used instead of concentrated a scess HCl to complete dissolution of the CuKOI-Dg. The copper pyruvate, however, was observed to decompose on standing. A solid material separated, but remained sus pended, while an unidentified gas was evolved.
Procedure F .-Copper trifiuoroacetate was prepared by mixing 0.02 mole of Cu(OH) with 1.49 ml. triiluoroacetic acid followed by dilution to 100' ml. with H O. No attempt was made to dissolve the small portion of Cu(OH) that did not dissolve.
Procedure G.Cupric salts of the following acids were made by dissolving the amounts of acid specified below in about 1 ml. H O, adding 118 mg. of commercial basic copper carbonate and heating very gently to drive off CO These mixtures did not dissolve completely and were evaluated as suspensions.
(a) 104 mg. malonic acid 7 Y (b) 136 mg. alpha,alpha'-oxydiacetic acid 360 mg. acetylsalicylic acid (d) .068 ml. formic acid Production of the thermographic image in the new elements of the present invention can be achieved in any way whereby the element comprising the flexible sheet support and in operative association therewith the hydroxypyrrolinone and metal salt is selectively exposed to the required color-developing temperatures to form the desired pattern. For instance, the thermographic element can be pressed with a heated stylus operated manually or mechanically as the recording or copy arm of a sensing system driven by a photoelectric scanning beam. In a similar fashion, heated type characters, slugs, or cornplete composed plates may be pressed directly in contact with the thermographic element. Alternatively, the therinog'raph'ic images can be prepared by suitable selective infrared absorption. Thus, a master to be reproduced will generally have a dark text on a white background. Accordingly, on exposure to infrared radiation or to normal light, the black areas are selectively warmer than the white areas by virtue of the selective absorption of the infrared radiation in the dark areas. With light of suflicient intensity directed on such an original held in contact with one of the thermographic elements of the present invention, the original is heated in the dark areas to temperature ranges wherein the thermographic reaction occurs in the therrnographic element, thereby producing a colored direct positive duplicate of the original.
The temperatures to which these thermographic elements must be brought in order to develop the thermographic image will vary with the specific substituted hydroxypyrroiinone, the nature of the support, the relative concentration of the hydroxypyrrolinone, the specific metal ion and the amount of such ion. Generally satisfactory colored images are obtained when the thermographic element is brought to temperatures between about 120 C. and about 200 C. A generally satisfactory average temperature would thus be in the neighborhood of about 140170 C. The times at which these thermographic elements must be selectively held at such temperatures in order to develop satisfactory image quality likewise vary with the nature of the substituents on the hydroxypyrrolinone, themetal salt and in part with the nature of the support in the sense of the optical contrast qualities thereof. An approximate shortest color development time at these temperatures is in the neighborhood of about 0.1-2.0 seconds; whereas, with some of the less reactive mixtures of lower heat sensitivity, reaction times of up to 1015 seconds or even a minute are needed. Generally speaking, an average color development time at the average development temperature of about 175 C. will be about 1.0 to 2.0 seconds.
The primary use for the thermally-sensitive elements is as a thermographic copying paper, for example as a general copying paper. The elements are also useful as a thermogr'aphic microfilm, for making copies via enlargement or reduction projection and for use in recording information in recording instruments, e.g., spectrograms. I
This invention has the advantage that it provides thermally-sensitive recording elements of high potential resolving power since it is a grainless system as contrasted with the non-grainless commercially available systems described in US. 2,663,654 through 2,663,657. Exposure latitude of the element is unusually broad. This invention makes possible the production of a copy which is pleasing to the eye, giving an intense black image against a white of light-colored background.
Further advantages are the excellent thermal stability which can be achieved in a copy which has been subjected to a simple fixing operation, the good handling characteristics derived from satisfactory performance of the element in existing exposure devices to produce the desired direct positve copy without having to go through a negative intermediate. 7
These advantages are in addition to those resulting from the simplicity of use of the elements in a completely dry processing image formation and the rapidity with which a finished copy may be produced.
Another advantage of the present invention is that it provides the art with a new class of thermally sensitive image recording elements which are economical to make and easy to use in making positive images directly. The novel elements do not require skilled operators or technicians when used to make positive images. A large number of reproductions can be made rapidly from any printed or other material'to be copied. Another advantage is that the novel elements can be readily fixed to remove discoloration and obtain a white background bywashing in wateror dilute mineral. acid (e.g., hydro"- chloric solutions). Still other advantages will be apparent to those skilled in the art of image formation or reproduction.
The novel thermally-sensitive recording elements of this invention have advantages over prior art elements when used in charts to be marked with a stylus. The latter generally employ a dark-colored paper with a white, opaque coating that becomes clear on application of heat, thereby producing a dark area on a white background. Typical coatings of this type are based on opaque, waxy, or crystalline materials, blushed resin coatings (see U.S. Patent 2,519,660) or plastic films coritaining microscopic voids (see US. Patent 2,739,909). Waxy coatings stick to adjacent layers and because of their softness are easily damaged. The blushed resin coatings must be applied under carefully controlled conditions to avoid variations in opacity of the coatings. The third type of film-that containing the microscopic Voidsis widely used, but careful balancing of ingredients is required to produce a film which can be marked at available temperatures but at the same time is not unduly sensitive to pressure. All of these prior types ofcoatings must be applied to a colored base, which is generally paper carrying a dark pigmented coating. In addition, volatile organic solvents are necessarily employed in the production of all three types.
What is claimed is:
'1. A thermo-sensitive, image-recording copy element comprising a support of low heat conductivity having an outerrstratum containing as the essential heat-sensitive components (1) a 5-hydroxy-3-pyrrolin-2-one having a negative substituent in the 3-position and the general formula:
HO if R! wherein X is a negative substituent selected from the group consisting of quaternary onium and inium salts and carboxyl groups and groups hydrolyzable thereto, R is a member selected from the group consisting of hydrogen, monovalent hydrocarbon radicals of not more than 10 carbon atoms, amino and dialkylamino of 1-2 carbon atoms, the radicals R when separate are each selected from the group consisting of hydrogen, alkyl of 1-10 carbons, cycloalkyl of 4-6 carbons, aryl of 6-10 carbons and aralkyl of 7-10 carbons and when linked together constitute a single divalent hydrocarbon radical which forms with the 4- and 5-carbon atoms of the pyrrolinone ring a carbocyclic radical of 5-7 ring atoms, said substituted pyrrolinones being further characterized in that when substituted with the members recited, not more than one of the 4- and S-carbons have an aromatic substituent and (2) from 0.01 to 1.0 mole per mole of said 5-hydroXy-3-pyrrolin-2-one of a metal salt selected from the group consisting of cupric, ferrous, mercuric, and silver salts of monoand dibasic organic carboxylic acids of not more than 4 carbon atoms, said stratum having a coating weight of 20-500 milligrams per square decimeter.
2. An element according to claim 1 wherein said 10 stratum also contains a water-permeable organic colloid binding agent having protective colloid properties.
3. An element according to claim 1 wherein said metal salt is a cupric salt of an organic carboxylic acid of not more than 4- carbon atoms.
4. An element according to claim 1 wherein said metal salt is cupric acetate.
5. An element according to claim 1 wherein said support of low heat conductivity is a thin, flexible sheet.
6. An element according to claim 1 wherein said support is paper.
References Cited in the file of this patent UNITED STATES PATENTS 1,944,293 Martinez Jan. 23, 1934 1,976,302 Shepphard et a1. Oct. 9, 1934 2,910,377 Owen Oct. 27, 1959 2,950,987 Howard Aug. 30, 1960 2,995,468 Steiger Aug. 8, 1961
Claims (1)
1. A THERMO-SENSITIVE, IMAGE-RECORDING COPY ELEMENT COMPRISING A SUPPORT OF LOW THAT CONDUCTIVITY HAVING AN OUTER STRATUM CONTAINING AS THE ESSENTIAL HEAT-SENSITIVE COMPONENTS (1) A 5-HYDROXY-3-PYRROLIN-I-ONE HAVING A NEGATIVE SUBSTITUENT IN THE 3-POSITION AND THE GENERAL FORMULA:
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE588328D BE588328A (en) | 1959-04-21 | ||
NL249149D NL249149A (en) | 1959-04-21 | ||
US807761A US3063863A (en) | 1959-04-21 | 1959-04-21 | Heat-sensitive compositions and elements, and processes for using same |
GB5318/60A GB905699A (en) | 1959-04-21 | 1960-02-15 | Improvements relating to heat-sensitive compositions |
FR822105A FR1258460A (en) | 1959-04-21 | 1960-03-22 | Improvements to heat-sensitive compositions containing a polysubstituted 5-hydroxy-2-pyrrolinone |
DEP24511A DE1194878B (en) | 1959-04-21 | 1962-02-26 | Thermographic copying material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US807761A US3063863A (en) | 1959-04-21 | 1959-04-21 | Heat-sensitive compositions and elements, and processes for using same |
Publications (1)
Publication Number | Publication Date |
---|---|
US3063863A true US3063863A (en) | 1962-11-13 |
Family
ID=25197120
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US807761A Expired - Lifetime US3063863A (en) | 1959-04-21 | 1959-04-21 | Heat-sensitive compositions and elements, and processes for using same |
Country Status (5)
Country | Link |
---|---|
US (1) | US3063863A (en) |
BE (1) | BE588328A (en) |
DE (1) | DE1194878B (en) |
GB (1) | GB905699A (en) |
NL (1) | NL249149A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3315598A (en) * | 1960-07-28 | 1967-04-25 | Minnesota Mining & Mfg | Copying of graphic originals |
US3492145A (en) * | 1966-06-13 | 1970-01-27 | Mallinckrodt Chemical Works | Heat or pressure-sensitive copying sheets |
US3650805A (en) * | 1967-06-30 | 1972-03-21 | Saburo Imoto | Method of manufacturing coated paper |
US3673211A (en) * | 1968-03-23 | 1972-06-27 | Basf Ag | Manufacture of {60 ,{62 -dihalo-{65 -hydroxycrotonic lactams |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4332795A1 (en) * | 1993-09-27 | 1995-03-30 | Bayer Ag | Recording material for pictures or data |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1944293A (en) * | 1930-11-17 | 1934-01-23 | Martinez Michele | Photographically sensitive element |
US1976302A (en) * | 1930-12-11 | 1934-10-09 | Eastman Kodak Co | Photothermographic composition |
US2910377A (en) * | 1956-06-28 | 1959-10-27 | Minnesota Mining & Mfg | Heat-sensitive copying-paper |
US2950987A (en) * | 1958-10-28 | 1960-08-30 | Du Pont | Thermally-sensitive recording elements |
US2995468A (en) * | 1960-03-22 | 1961-08-08 | Stepan Chemical Co | Glaze and enamel compositions including lithium fluosilicate and method of making them |
-
0
- BE BE588328D patent/BE588328A/xx unknown
- NL NL249149D patent/NL249149A/xx unknown
-
1959
- 1959-04-21 US US807761A patent/US3063863A/en not_active Expired - Lifetime
-
1960
- 1960-02-15 GB GB5318/60A patent/GB905699A/en not_active Expired
-
1962
- 1962-02-26 DE DEP24511A patent/DE1194878B/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1944293A (en) * | 1930-11-17 | 1934-01-23 | Martinez Michele | Photographically sensitive element |
US1976302A (en) * | 1930-12-11 | 1934-10-09 | Eastman Kodak Co | Photothermographic composition |
US2910377A (en) * | 1956-06-28 | 1959-10-27 | Minnesota Mining & Mfg | Heat-sensitive copying-paper |
US2950987A (en) * | 1958-10-28 | 1960-08-30 | Du Pont | Thermally-sensitive recording elements |
US2995468A (en) * | 1960-03-22 | 1961-08-08 | Stepan Chemical Co | Glaze and enamel compositions including lithium fluosilicate and method of making them |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3315598A (en) * | 1960-07-28 | 1967-04-25 | Minnesota Mining & Mfg | Copying of graphic originals |
US3492145A (en) * | 1966-06-13 | 1970-01-27 | Mallinckrodt Chemical Works | Heat or pressure-sensitive copying sheets |
US3650805A (en) * | 1967-06-30 | 1972-03-21 | Saburo Imoto | Method of manufacturing coated paper |
US3673211A (en) * | 1968-03-23 | 1972-06-27 | Basf Ag | Manufacture of {60 ,{62 -dihalo-{65 -hydroxycrotonic lactams |
Also Published As
Publication number | Publication date |
---|---|
GB905699A (en) | 1962-09-12 |
DE1194878B (en) | 1965-06-16 |
NL249149A (en) | |
BE588328A (en) |
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