US3348945A - Heat developable light-sensitive photographic material - Google Patents
Heat developable light-sensitive photographic material Download PDFInfo
- Publication number
- US3348945A US3348945A US342528A US34252864A US3348945A US 3348945 A US3348945 A US 3348945A US 342528 A US342528 A US 342528A US 34252864 A US34252864 A US 34252864A US 3348945 A US3348945 A US 3348945A
- Authority
- US
- United States
- Prior art keywords
- transfer
- heat
- photographic material
- photographic
- silver halide
- 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
- 239000000463 material Substances 0.000 title claims description 55
- -1 SILVER HALIDE Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 3
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- GWDSGOHVPDCTMD-UHFFFAOYSA-N 1-(4-bromophenyl)pyrazolidin-3-one Chemical compound C1=CC(Br)=CC=C1N1NC(=O)CC1 GWDSGOHVPDCTMD-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 1
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 1
- FIARATPVIIDWJT-UHFFFAOYSA-N 5-methyl-1-phenylpyrazolidin-3-one Chemical compound CC1CC(=O)NN1C1=CC=CC=C1 FIARATPVIIDWJT-UHFFFAOYSA-N 0.000 description 1
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- 241000857945 Anita Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 101000637835 Homo sapiens Serum amyloid A-4 protein Proteins 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000605112 Scapanulus oweni Species 0.000 description 1
- 102100032016 Serum amyloid A-4 protein Human genes 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- SAQSTQBVENFSKT-UHFFFAOYSA-M TCA-sodium Chemical compound [Na+].[O-]C(=O)C(Cl)(Cl)Cl SAQSTQBVENFSKT-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 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
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- WPBIBPXOGNQYIN-UHFFFAOYSA-N chembl2140596 Chemical compound N1=C(C)C=C(O)N2C=NN=C21 WPBIBPXOGNQYIN-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical compound CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/32—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to acyclic carbon atoms and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- 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
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
Description
United States Patent Ofilice 3,348,945 Patented Oct. 24, 1957 3,348,945 IEAT DEVELOPABLE LIGHT-SENSITIVE PHOTOGRAPI-HC MATERIAL Helmut Miider and Hans Ulrich, Leverkusen, Walter Piischel, Koeln-Stammheim, and Anita von Kiinig, Leverknsen, Germany, assignors to Agfa Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Feb. 4, 1964, Ser. No. 342,528 Claims priority, application Germany, Feb. 18, 1963,
A 42,356, Patent 1,174,159 7 Claims. (Cl. 96-29) ABSTRACT OF THE DISCLOSURE Heat development of exposed silver halide emulsions is accomplished with the usual moisture-or alkali-providing additives reduced in concentration or entirely eliminated by incorporating a compound of the formula in which R represents a hydrogen atom, or an alkyl or aryl group, such as a phenyl or naphthyl group, which groups may be substituted, R an optionally substituted aryl radical or a heterocyclic radical, R and R together are moreover able to represent the ring members necessary for forming a ring system, preferably a carbocylic ring system, R represents a hydrogen atom or an optionally substituted alkyl or aryl radical, and R represents an electron-attracting group, e.g. NO o-r CEN. Heat development of the foregoing emulsions can be used either in a conventional or in a diffusion transfer operation in which excess developer is transferred.
The invention relates to a photographic material comprising a light sensitive silver halide emulsion layer, which material contains a silver halide developer substance and is developable by the application of heat without the use of a liquid developing solution.
The heat development of imagewise exposed silver halide emulsion layers is known in principle from German patent specification No. 888,045. In order to increase the sensitivity of heat-developable photographic materials, substances which contain water in loosely combined form, e.g. inorganic salts forming definite hydrates in solid phase, are added to the emulsion layers. The Water liberated by the action of heat probably leads to an increase in the developer activity in the layer. Substances can also be added to the layers, which substances are decomposed on being heated in the presence of moisture to form substances having an alkali reaction; e.g. sodium trichloracetate can be used and this dissociates into sodium bicarbonate and chloroform.
A developer-containing, heat developable photographic material is known from British specification No. 930,572, which contains a 3-pyrazolidone silver halide developing agent and an alkaline substance for accelerating development of a latent image.
However, the use of relatively large quantities of alkaline substances with heat-developable photographic materials leads to a relatively strong fogging. The liability to fogging is certainly reduced with smaller quantities of alkali, but the photographic material has a lower sensitivity and the developed images do not have sufficient density. Furthermore, with addition of substances which form defined hydrates in solid form, e.g. sodium acetate, photographic silver halide emulsions have a tendency to tackiness after casting, and this renders the making-up and packing difficult. Developer-containing materials which are for example produced with sodium acetate are also not suitable for storage.
The invention has for its object to produce a heat developable photographic material which does not have the aforementioned disadvantages.
According to the present invention, there is provided a heat-developable photographic material comprising a support bearing a light sensitive silver halide emulsion layer, which material contains a silver halide developer substance and a compound of the following general formula R1 R3 l l\ R, OH H R in which R represents a hydrogen atom, or an alkyl or aryl group, such as a phenyl or naphthyl group, which groups may be substituted,
R an optionally substituted aryl radical or a heterocyclic radical,
R and R together are moreover able to represent the ring members necessary for forming a ring system, preferably a carbocyclic ring system,
R represents a hydrogen atom or an optionally substituted alkyl or aryl radical,
R represents an electron-attracting group, e.g. -NO or --CEN.
The preferred compounds are B-nitroethanols which are substituted in u-position by a phenyl radical or by a phenyl radical which is substituted by an alkyl group having preferably 1-5 carbon atoms, an alkoXy group having 1-5 C-atoms in the alkyl radical and/ or a halogen atom, such as chlorine and bromine.
By introducing such compounds into photographic silver halide emulsion layers or adjacent layers which have an incorporated developer substance, images with good speed and density gradation are obtained after exposure to light and heat development. Simultaneously, the stability in storage of such materials is improved.
By adding the compounds according to the invention, alkalis or compounds which split off alkalis or water under the action of heat become substantially superfluous. In individual cases, such compounds can of course be added, but the quantity necessary is so small that the photographic properties of the material and its stability in storage are notimpairecl. Suitable compounds are for example:
a-Phenyl-B-nitroethanol a-4-methoxyphenyl-fi-nitroethan ol a-Z-furyl-fi-nitroethanol l-nitromethybcyclohexanol-i The compounds to 1 to 5 are prepared by the process which is described in Zeitschrift fiir Naturforshung, Year 1952, vol. 712, pages 344*352, by reacting aromatic or heterocyclic aldehydes with nitromethane in the presence of sodium.methylate in alcoholic solution.
Compound 6 is prepared in analogous manner by reacting cyclohexanone with nitromethane. A distillation of the crude product obtained after the working up is not possible because of decomposition.
Compound 7 is prepared by the following method: 60 g. of 4-methylbenzaldehyde and 58.5 g. of benzyl cyanide are dissolved in 300 ml. of absolute alcohol. At a temperature of 5 to 8 C., a sodium methylate solution prepared from 11.5 g. of sodium and 300 ml. of absolute methanol is introduced dropwise while stirring. Heating then takes place for 2 /2 hours to 50 C. On cooling, an orange-red precipitate is formed, and after this has been suction-filtered and washed with methanol, it is introduced into a mixture of 140 g. of ice, 280 ml. of Water.
and 80 g. of glacial acetic acid. The White crystal mass is suction-filtered, washed with cold water and dried. M.P. 51-52 C.
Compounds 8 to 11 are obtainable in corresponding manners.
For the preparation of a heat-developable, photographic material, a silver halide emulsion containing 0.050.5 g. mole of silver halide per liter has added thereto a developer substance, e.g. a 3-pyrazolidone, in quantities of 5-20 g. per liter and one of the condensation products according to the invention in quantities of about 10-50 g., advantageously 20-40 g. per liter, and the mixture is cast on to a suitable support, e.g. a paper or film support.
These materials may usually contain 1-10 g. of said con-.
densation products per square meter. In order further to activate the developer, it is also. possible to introduce into the emulsion an inorganic salt which contains water of crystallisation or which has an alkaline reaction. e.g. sodium acetate, sodium carbonate or sodium sulphate.
These additions may also be incorporated wholly or partially into auxiliary colloid layers underlying or overlying the emulsion layer, such as gelatin layers.
The compounds used according to the invention may be dissolved in highest possible concentration in a suitable solvent such as methanol, ethanol, dimethylformamide and the like and added in this form to the casting solution. The compounds can be present in the emulsion layers or auxiliary layers in a dissolved or finely divided form.
After imagewise exposure, the material is heated for 1 to 3 seconds to temperatures of approximately 70-160 C., advantageously -150 C., the material being thus developed. The fixing is then eifected in the usual manner with organic or inorganic fixing agents, e.g. sodium thiosulphate or mercapto compounds.
Such quickly developable photographic materials are of importance in all cases where a photographically recorded operation is tobe quickly evaluated, e.g. with recording papers.
Silver chloride or silver bromide or mixtures thereof, possibly with a small addition of silver iodide, are suitable as light-sensitive silver salts. If necessary, the layers can also be optically sensitised, for example, when processes registered on a cathode ray oscillograph are to be photographically recorded.
The degree of hardening of the layers is of subordinate importance as regards the efiicacy of the layers according to the invention, but it must be adapted to the actual purpose for which the layers are used.
To be considered as binding agents for the photographic layers are all known layer-forming colloids, more especially gelatin, which can be wholly or partially replaced.
by other layer-forming substances, e.g. cellulose derivatives such as carboxymethyl cellulose, methyl hydroxyethyl cellulose, polyvinylalcohol, polyvinyl acetal, polyvinyl acetate, partially hydrolysed polyvinyl acetates, alginic acid derivatives such as alginates, alginic acid propylene glycol ester, polyvinyl pyrrolidone, zein and other natural or synthetic substances. The additives usual in the emulsion art can be used in the silver halide emulsion, for example, antifogging agents, such as benztriazolc, 1-phenyl-S-mercaptotetrazole, 4-hydroxy-6-methyl- 1,2,3a,7-tetrazaindene and others.
Developer substances of the pyrazolidone series are excellently suitable for the light-sensitive material according to the present invention. Examples of these are the following compounds:
1-phenyl-3-pyrazolidone 1-m-tolyl-3-pyrazolidone 1-p-tolyl-3-pyrazolidone l-phenyl-4-methyl-3-pyrazolidone 1-phenyl-5-methyl-3-pyrazolidone l,4-dimethyl-3-pyrazolidone 4-methyl-3-pyrazolidone 4,4-dimethyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1- (4-bromophenyl -3 -pyrazolidone The emulsion layer can be cast on to any suitable layer support which is durable at the temperatures of the heat development, e.g. paper, baryta-coated paper, filmforming synthetic polymers such as polycarbonate, more especially based on bis-hydroxyarylalkanes or polyesters based on terephthalic acid and ethylene glycol, as well as cellulose esters, fabrics or metal foils.
Negative materials with a content of the substances according to the invention can also be used for transfer processes, more especially with developer transfer processes. With processes of this type, the developer not used in the unexposed areas of the negative layer is transferred by heat into a transfer layer in contact therewith and are utilised therein for the production of coloured images.
In this connection, reference is to be made for example to the process of copending application S.N. 303,685, filed Aug. 21, 1963. The negative material used in the process described therein contains considerable quantities of sodium acetate, which can be wholly or partially replaced by the compounds according to the invention. Thereby, the storability is considerably improved.
EXAMPLE 1 To 1 liter of a gelatine silver chloride emulsion containing 0.3 mole of silver chloride per liter there are added:
20 mg. of 1-phenyl-5-mercaptotetrazole (1% in alcohol) 20 ml. of saponin solution (5% in water) 3 ml. of formalin (30% in water) g. of 1-phenyl-3-pyrazolidone and g. of compound 1 (dissolved in a little alcohol).
The casting solution thus prepared is applied in the usual way to baryta-coated paper and dried.
After exposure to form an image, the material is heated to about 120 C. for 2 seconds in close contact with a heated metal plate or a pair of heated rollers. A blackishbrown image is obtained, which can be stabilised in the usual way with an acid fixing bath.
EXAMPLE 2 A photographic material as described in Example 1 is prepared by using 20 g. of compound 2 instead of compound 1. After the exposure to form a latent image, it is heated for, 2 /2 seconds to 100 C., a brownish-black image being formed. It is fixed in the usual way with an acid fixing bath.
EXAMPLE 3 To 1 liter of a silver chloride emulsion there are added:
30 mg. of 1-phenyl-5-mercaptotetrazole (1% in alcohol) 20 ml. of saponin solution (5% in water) 10 g. of l-phenyl-3-pyrazolidone 30 g. of compound 7 (in a little alcohol) and 3 ml of formalin (30% in water).
The emulsion is cast on to baryta-coated paper. After exposure, it is heated for 2 seconds to 120 C. A violet black image is obtained.
EXAMPLE 4 An emulsion is prepared as described in Example 3, but 40 g. of the compound 6 are used instead of compound 7. After development, a brownish-black image is obtained.
EXAMPLE 5 To 1 liter of a silver chloride emulsion there are added:
20 mg. of 1-phenyl-S-mercaptotetrazole (1% in alcohol) 20 ml. of saponin solution (5% in water) 3 ml. of formalin (30% in water) 12 g. of 1-phenyl-3-pyrazolidone 20 g. of compound 2 (in a little alcohol) and 5 g. of sodium acetate.
After being applied in the usual way to a suitable layer support (paper or film), the film obtained is exposed to form an image and heated for 2 seconds to 120 C. A black image is obtained. The same material, but without the compound 2, merely gives -a brown image of weaker density after the dry development.
. e EXAMPLE 6 This example describes the use of the compounds according to the invention in a transfer process.
Negative material To 1 liter of a silver chloride emulsion there are added:
0.5 g. of benztriazole (5% in alcohol) 200 cc. of a 15% hydrosol of silicic acid 20 g. of crystalline sodium acetate 50 g. of compound 7 and 7.5 g. of 1-phenyl-3-pyrazolidone.
The pH value is adjusted with sulphuric acid to 4.9. The emulsion is applied in known manner to a layer support, e.g. paper, and dried.
Positive material The positive (transfer) material is prepared as follows: 1 gram of a cobalt leucophthalocyanine, such as Phthalogen'blau 1B of Far-benfabriken Bayer A.G., dissolved in 30 ml. of a polyethylene glycol having an average molecular weight of about 400, 2 ml. of lactic acid, 3 g. of tartaric acid and 5 ml. of a 30% aqueous solution of saponine are added to 1 liter of a 0.7% aqueous solution of a gallactomannan, for example Guar CSAA (trade name of Meypro A.G., Kreuzlingen, Switzerland). This solution is coated on a paper or film support and dried.
After exposure, the negative material is brought into contact with the positive material. Both are then exposed for up to 10 seconds to a temperature of 170 C. by means of a developer apparatus as described in French Patent 1,346,705 or by means of a glazing press or a drying drum. After separation of the two materials, a blue image on a yellow background is obtained.
The negative material prepared according to the above prescription has also still not changed after a relatively long storage time, whereas a material without compound 7 is unsuitable for use after relatively short storage.
What we claim is:
1. In a heat developable photographic material comprising a support bearing a light sensitive silver halide emulsion layer and containing a silver halide developing substance, the improvement according to which the material also carries a compound of the following general formula wherein R and R represent a member of the group consisting of hydrogen atoms, an alkyl and an aryl radical,
R represents agfiiiember of the group consisting of an aryl and a heterocyclic radical,
R and R together may represent the ring members forming a cyclohexyl ring, and
R represents a nitrile or nitro group.
2. A heat developable photographic material according to claim 1, wherein R is a nitro group.
3. A heat developable photographic material according to claim 1, wherein R is a. nitrile group.
4. A heat developable photographic material according to claim 1, wherein said component is a 1-aryl-2- nitroethanol.
5. A heat developable photographic material according to claim 1, wherein said compound is a l-phenyl-Z-cyanoethanol.
6. A process for producing photographic silver images which comprises exposing to a subject to be reproduced a photographic material as claimed in claim 1 and subjecting the exposed material to heat to develop a silver image therein.
7. A process of producing photographic transfer images which comprises exposing to a subject to be reproduced a photographic material as claimed in claim 1, subjecting the exposed material to heat While it is in contact with a non-light sensitive transfer material to develop a silver image in said exposed material, to transfer developer substance from the unexposed areas of said exposed materials to the transfer layer and to produce a visible image in said transfer material by the action of said transferred developer substance.
8 References Cited UNITED STATES PATENTS 11/ 1944 Baldsiefen 96-95 6/1962, Haist et a1. 9666 NORMAN G. TORCHIN, Primary Examiner.
J. T. BROWN, Assistant Examiner.
Claims (2)
1. IN A HEAT DEVELOPABLE PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT BEARING A LIGHT SENSITIVE SILVER HALIDE EMULSION LAYER AND CONTAINING A SILVER HALIDE DEVELOPING SUBSTANCE, THE IMPROVEMENT ACCORDING TO WHICH THE MATERIAL ALSO CARRIES A COMPOUND OF THE FOLLOWING GENERAL FORMULA
7. A PROCESS OF PRODUCING PHOTOGRAPHIC TRANSFER IMAGES WHICH COMPRISES EXPOSING TO A SUBJECT TO BE REPRODUCED A PHOTOGRAPHIC MATERIAL AS CLAIMED IN CLAIM 1, SUBJECTING THE EXPOSED MATERIAL TO HEAT WHILE IT IS IN CONTACT WITH A NON-LIGHT SENSITIVE TRANSFER MATERIAL TO DEVELOP A SILVER IMAGE IN SAID EXPOSED MATERIAL, TO TRANSFER DEVELOPER SUBSTANCE FROM THE UNEXPOSED AREAS OF SAID EXPOSED MATERIALS TO THE TRANSFER LAYER AND TO PRODUCE A VISIBLE IMAGE IN SAID TRANSFER MATERIAL BY THE ACTION OF SAID TRANSFERRED DEVELOPER SUBSTANCE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEA42356A DE1174159B (en) | 1963-02-18 | 1963-02-18 | Thermal copying process using photosensitive materials with developer-containing emulsion layers and photographic material for this |
Publications (1)
Publication Number | Publication Date |
---|---|
US3348945A true US3348945A (en) | 1967-10-24 |
Family
ID=6933041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US342528A Expired - Lifetime US3348945A (en) | 1963-02-18 | 1964-02-04 | Heat developable light-sensitive photographic material |
Country Status (5)
Country | Link |
---|---|
US (1) | US3348945A (en) |
BE (1) | BE643960A (en) |
CH (1) | CH456341A (en) |
DE (1) | DE1174159B (en) |
GB (1) | GB1053537A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6037115A (en) * | 1996-05-22 | 2000-03-14 | Eastman Kodak Company | Photothermographic and thermographic films containing low levels of formate to prevent fog |
US6040130A (en) * | 1997-02-10 | 2000-03-21 | Eastman Kodak Company | Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2364017A (en) * | 1941-06-13 | 1944-11-28 | Du Pont | Production of blue-black toned silver images |
US3041170A (en) * | 1959-10-29 | 1962-06-26 | Eastman Kodak Co | New class of development promoter precursors for dry processing self-developing silver halide coatings |
-
0
- GB GB1053537D patent/GB1053537A/en active Active
-
1963
- 1963-02-18 DE DEA42356A patent/DE1174159B/en active Pending
-
1964
- 1964-02-04 US US342528A patent/US3348945A/en not_active Expired - Lifetime
- 1964-02-14 CH CH176764A patent/CH456341A/en unknown
- 1964-02-18 BE BE643960D patent/BE643960A/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2364017A (en) * | 1941-06-13 | 1944-11-28 | Du Pont | Production of blue-black toned silver images |
US3041170A (en) * | 1959-10-29 | 1962-06-26 | Eastman Kodak Co | New class of development promoter precursors for dry processing self-developing silver halide coatings |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6037115A (en) * | 1996-05-22 | 2000-03-14 | Eastman Kodak Company | Photothermographic and thermographic films containing low levels of formate to prevent fog |
US6040130A (en) * | 1997-02-10 | 2000-03-21 | Eastman Kodak Company | Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog |
Also Published As
Publication number | Publication date |
---|---|
GB1053537A (en) | |
BE643960A (en) | 1964-08-18 |
CH456341A (en) | 1968-07-15 |
DE1174159B (en) | 1964-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3764329A (en) | Heat activated dry silver | |
US4126461A (en) | Black-and-white photographic elements and processes | |
US4088496A (en) | Heat developable photographic materials and process | |
US4168980A (en) | Heat developable photographic material and process | |
US3844785A (en) | Color photographic diffusion transfer process and photographic material for use in this process | |
US3751255A (en) | Photosensitive and thermosensitive element, composition and process | |
US4187108A (en) | Heat developable material and process | |
JPS6242261B2 (en) | ||
US3938995A (en) | Silver halide color photographic element and process containing leuco dyes | |
US4499181A (en) | Photographic recording material with indole redox releaser | |
US3893863A (en) | Photographic elements, compositions and processes | |
US3711546A (en) | N-(ortho-substituted benzene or naphthalene carboxamidoethyle)para-phenylene diamines as coupler-developers | |
US4246333A (en) | Development inhibitor precursor and a photographic element containing the same | |
CA1140789A (en) | Heat developable silver halide photographic material including an acylhydrazine activator-stabilizer precursor compound | |
US3348945A (en) | Heat developable light-sensitive photographic material | |
US3887376A (en) | Photographic elements, compositions and processes | |
CA1047820A (en) | Photographic elements containing iodoso compounds or iodoxy compounds | |
US3419395A (en) | Light-sensitive material with incorporated developer | |
US4443537A (en) | Hydroquinone derivatives and their use in photographic materials | |
US3676124A (en) | Photographic negative material for color diffusion transfer process | |
US4407941A (en) | Photographic element with pyrazole electron donors | |
US2719088A (en) | Photographic element containing silver salt-forming bleachable filter dyes | |
US3761278A (en) | Bonic acid ester stabilizing agent silver halide element containing a benzimidazoline 2 thione n n dicar | |
US4168169A (en) | Dry heat-activated bleaching of silver images | |
US4569899A (en) | Photographic element for silver salt diffusion transfer process |