EP0119615B1 - Procédé de formation d'images à sec - Google Patents
Procédé de formation d'images à sec Download PDFInfo
- Publication number
- EP0119615B1 EP0119615B1 EP19840102945 EP84102945A EP0119615B1 EP 0119615 B1 EP0119615 B1 EP 0119615B1 EP 19840102945 EP19840102945 EP 19840102945 EP 84102945 A EP84102945 A EP 84102945A EP 0119615 B1 EP0119615 B1 EP 0119615B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- group
- light
- silver
- fixing
- 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
Links
- 238000000034 method Methods 0.000 title claims description 95
- 230000008569 process Effects 0.000 title claims description 62
- 239000000463 material Substances 0.000 claims description 209
- -1 silver halide Chemical class 0.000 claims description 122
- 150000001875 compounds Chemical class 0.000 claims description 99
- 229910052709 silver Inorganic materials 0.000 claims description 82
- 239000004332 silver Substances 0.000 claims description 82
- 239000002904 solvent Substances 0.000 claims description 65
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 58
- 238000010438 heat treatment Methods 0.000 claims description 56
- 238000011161 development Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 31
- 238000012546 transfer Methods 0.000 claims description 31
- 239000011230 binding agent Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 claims description 3
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical group [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 220
- 239000010410 layer Substances 0.000 description 133
- 239000002585 base Substances 0.000 description 49
- 230000018109 developmental process Effects 0.000 description 39
- 239000000243 solution Substances 0.000 description 39
- 239000000839 emulsion Substances 0.000 description 35
- 108010010803 Gelatin Proteins 0.000 description 33
- 229920000159 gelatin Polymers 0.000 description 33
- 235000019322 gelatine Nutrition 0.000 description 33
- 235000011852 gelatine desserts Nutrition 0.000 description 33
- 239000008273 gelatin Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 18
- 239000004094 surface-active agent Substances 0.000 description 17
- 239000008199 coating composition Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 235000013877 carbamide Nutrition 0.000 description 11
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000011241 protective layer Substances 0.000 description 10
- 125000004442 acylamino group Chemical group 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 150000003378 silver Chemical class 0.000 description 9
- 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 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 229910021612 Silver iodide Inorganic materials 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- CZLCEPVHPYKDPJ-UHFFFAOYSA-N guanidine;2,2,2-trichloroacetic acid Chemical compound NC(N)=N.OC(=O)C(Cl)(Cl)Cl CZLCEPVHPYKDPJ-UHFFFAOYSA-N 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 229940045105 silver iodide Drugs 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000004414 alkyl thio group Chemical group 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 125000005110 aryl thio group Chemical group 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910003844 NSO2 Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UMBBGOALZMAJSF-UHFFFAOYSA-N n-benzylethenamine;hydrochloride Chemical compound [Cl-].C=C[NH2+]CC1=CC=CC=C1 UMBBGOALZMAJSF-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KPVMVJXYXFUVLR-UHFFFAOYSA-N 12-ethyltetradecan-1-amine Chemical compound CCC(CC)CCCCCCCCCCCN KPVMVJXYXFUVLR-UHFFFAOYSA-N 0.000 description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 2
- MOXDGMSQFFMNHA-UHFFFAOYSA-N 2-hydroxybenzenesulfonamide Chemical class NS(=O)(=O)C1=CC=CC=C1O MOXDGMSQFFMNHA-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- YLNKRLLYLJYWEN-UHFFFAOYSA-N 4-(2,2-dibutoxyethoxy)-4-oxobutanoic acid Chemical compound CCCCOC(OCCCC)COC(=O)CCC(O)=O YLNKRLLYLJYWEN-UHFFFAOYSA-N 0.000 description 2
- CJEKMBRTGTXPDG-UHFFFAOYSA-N 4-(2-ethylhexoxy)-4-oxobutanoic acid;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(O)=O CJEKMBRTGTXPDG-UHFFFAOYSA-N 0.000 description 2
- CLENKVQTZCLNQS-UHFFFAOYSA-N 9-propylheptadecan-9-yl dihydrogen phosphate Chemical compound CCCCCCCCC(CCC)(OP(O)(O)=O)CCCCCCCC CLENKVQTZCLNQS-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- 229920002472 Starch Polymers 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
- 241001061127 Thione Species 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 2
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- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- RUVFQTANUKYORF-UHFFFAOYSA-M silver;2,4-dichlorobenzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=C(Cl)C=C1Cl RUVFQTANUKYORF-UHFFFAOYSA-M 0.000 description 1
- OEVSPXPUUSCCIH-UHFFFAOYSA-M silver;2-acetamidobenzoate Chemical compound [Ag+].CC(=O)NC1=CC=CC=C1C([O-])=O OEVSPXPUUSCCIH-UHFFFAOYSA-M 0.000 description 1
- JRTHUBNDKBQVKY-UHFFFAOYSA-M silver;2-methylbenzoate Chemical compound [Ag+].CC1=CC=CC=C1C([O-])=O JRTHUBNDKBQVKY-UHFFFAOYSA-M 0.000 description 1
- OXOZKDHFGLELEO-UHFFFAOYSA-M silver;3-carboxy-5-hydroxyphenolate Chemical compound [Ag+].OC1=CC(O)=CC(C([O-])=O)=C1 OXOZKDHFGLELEO-UHFFFAOYSA-M 0.000 description 1
- UCLXRBMHJWLGSO-UHFFFAOYSA-M silver;4-methylbenzoate Chemical compound [Ag+].CC1=CC=C(C([O-])=O)C=C1 UCLXRBMHJWLGSO-UHFFFAOYSA-M 0.000 description 1
- RDZTZLBPUKUEIM-UHFFFAOYSA-M silver;4-phenylbenzoate Chemical compound [Ag+].C1=CC(C(=O)[O-])=CC=C1C1=CC=CC=C1 RDZTZLBPUKUEIM-UHFFFAOYSA-M 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- OIZSSBDNMBMYFL-UHFFFAOYSA-M silver;decanoate Chemical compound [Ag+].CCCCCCCCCC([O-])=O OIZSSBDNMBMYFL-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- GXBIBRDOPVAJRX-UHFFFAOYSA-M silver;furan-2-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CO1 GXBIBRDOPVAJRX-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- PLTCLMZAIZEHGD-UHFFFAOYSA-M sodium;quinoline-2-carboxylate Chemical compound [Na+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 PLTCLMZAIZEHGD-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
Definitions
- the present invention relates to a completely dry image-forming process using a silver halide light-sensitive material
- a dry image-forming process which comprises heat developing a light-sensitive material comprising a support having thereon at least a photosensitive silver halide, a binder, and a dye-releasing redox compound, said dye-releasing redox compound being reductive to the photosensitive silver halide and being capable of releasing a hydrophilic dye upon reaction with the photosensitive silver halide under heating, after or simultaneously with imagewise exposure, to form imagewise a mobile hydrophilic dye and heating, after or simultaneously with the heat development, the light-sensitive material together with a dye-fixing layer in the presence of a hydrophilic thermal solvent to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer to form a dye image and fix the dye image thereon.
- a photographic process using silver halide is excellent in photographic properties such as sensitivity and gradation control as compared to other photographic processes such as electrophotography and diazo photographic process, the silver halide photographic process has hitherto been most widely used.
- a technique capable of more easily and rapidly obtaining images has been developed by changing an image-forming process of a silver halide photographic material from a conventional wet process such as a process which uses a liquid developer to a dry process such as a developing process which uses heating.
- Heat-developable photographic materials are known in this art and the heat-developable materials and image-forming processes using these heat-developable materials are described in, for example, Shahin Kogaku no Kiso (The Basis of Photographic Engineering), pages 553-555, published by Corona K.K. in 1979; Eizo Jooho (Image Information), page 40, published in April, 1978; Nebletts Handbook of Photography and Reprography, 7th ed., pages 32-33, (Van Nostrand Reinhold Company); U.S. Patents 3,152,904, 3,301,678, 3,392,020, 3,457,075; U.K. Patents 1,131,108 and 1,167,777; and Research Disclosure (RD-17029), pages 9-15, June 1978.
- This process is an image-forming process wherein a photosensitive material capable of releasing a mobile hydrophilic dye is heated in a state containing substantially no water to release the mobile hydrophilic dye and the hydrophilic dye is transferred onto a dye-fixing layer mainly in the presence of a solvent.
- DE-A-3 215 485 and EP-A-66 282 describe a dry image forming process which comprises heat developing a light sensitive material comprising a support having thereon at least a photo-sensitive silver halide, a binder and a dye-releasing redox compound which is reductive to the photosensitive halide and capable of releasing a hydrophilic dye upon heating the material after imagewise exposure. It is possible to heat the light-sensitive material together with a dye-fixing layer to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer in the presence of a thermal solvent and of a base on the support of the light-sensitive material. However, the image quality and preservative property of dye images obtained according to this process are not sufficient.
- An object of the present invention is, therefore, to provide a process of fixing a hydrophilic dye image formed by heat development, which is performed after or simultaneously with imagewise exposure, on a dye-fixing material suited for the image-forming process, which comprises a support having provided thereon one or more layers containing at least a dye-fixing agent, a thermal solvent and a base and/or a base precursor.
- a dry image-forming process which comprises heat developing a light-sensitive material comprising a support having thereon at least a photosensitive silver halide, a binder, and a dye-releasing redox compound being reductive to the photo- sensitive silver halide and being capable of releasing a hydrophilic dye upon reaction with the photosensitive silver halide under heating, after or simultaneously with imagewise exposure, to form imagewise a mobile hydrophilic dye and heating, after or simultaneously with the heat development, the light-sensitive material together with a dye-fixing layer in the presence of a hydrophilic thermal solvent to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer to form a dye image and fix the dye image thereon, which is characterized in that said dye-fixing layer is provided in a dye-fixing material which comprises a support having thereon at least a dye-fixing agent, a hydrophilic thermal solvent and a base and/or a base precursor.
- an oxidation reduction reaction occurs between the photosensitive silver halide and the reductive dye releasing redox compound with the exposed photosensitive silver halide as a catalyst upon heating in a state containing substantially no water after or simultaneously with image exposure, whereby an image of a mobile hydrophilic dye released from the dye releasing redox compound, which has become an oxidized product by being oxidized with the silver halide, is obtained together with a silver image at the exposed area.
- the development step is called “heat development” but it is difficult to distinguish the released mobile hydrophilic dye image by the heat development only since the unreacted dye releasing redox compound is co-present.
- the dye of the dye image obtained is a mobile hydrophilic dye
- the dye can be transferred onto a dye-fixing layer in an atmosphere wherein the hydrophilic dye has an affinity, whereby a dye image having excellent image quality and preservative property can be obtained.
- This step is “dye fixing” step in the invention. It was already disclosed in European Patent Application 0076492 that in this case the atmosphere having an affinity with the hydrophilic dye can be realized by mainly supplying a solvent.
- the atmosphere having an affinity with the hydrophilic dye is realized by the existence of a hydrophilic thermal solvent and hence, it is not necessary to particularly supply a solvent. Accordingly, a dye image having a color reproducibility can be formed by a completely dry process without need of supplying a solvent in the whole of steps from light exposure to heat development and dye fixing.
- the oxidation-reduction reaction of a photo-sensitive silver halide and a dye releasing redox compound and the subsequently occurred dye-releasing reaction can take place upon heating in a state containing substantially no solvent.
- heating means heating to 80°C to 250°C
- a state containing substantially no water means that the reaction system is in an equilibrium state with moisture in air and hence, water is not supplied for causing the reaction or for accelerating the reaction.
- Such a state is described in The Theory of the Photographic Process, 4th Edition, page 374, Edited by T. H. James, published by Macmillan.
- dyes which are released can be selected by selecting dye releasing redox compounds and therefore, various colors can be reproduced. Accordingly, by selecting a combination of dye-releasing redox compounds, multicolour images can be obtained, dye images in the invention include not only monochromatic images but also multicolor images, and the monochromatic images include a monochromatic image composed of a mixture of two or more colors.
- the dye releasing reaction is caused by the attack of a so-called nucleophilic reagent and the reaction is usually performed in an aqueous solution having a high pH as higher than 10. Therefore, it is quite exceptional that a light-sensitive material shows a high reactivity upon mere heating in a state containing substantially no water as the case of the light-sensitive material used in the invention.
- the dye releasing redox compound used in the invention can cause an oxidation-reduction reaction with a silver halide without need of the aid of a so-called auxiliary developing agent (see European Patent Application 0076492).
- reaction proceeds particularly well when an organic silver salt oxidizing agent is co-present in the reaction system, and a high image density can be obtained. Therefore, it is a particularly preferred embodiment that an organic silver salt oxidizing agent is co-present in the reaction system.
- the dye releasing redox compound which releases a hydrophilic diffusible dye used in the present invention is preferably represented by the following general formula (I): wherein Ra represents a reducing group capable of being oxidized by the silver halide; and D represents an image forming dye portion containing a hydrophilic group.
- the reducing group Ra in the dye releasing redox compound Ra-S0 2- D has an oxidation-reduction potential to a saturated calomel electrode of 1.2 V or less measuring the polarographic half wave potential using acetonitrile as a solvent and sodium perchlorate as a base electrolyte.
- Preferred examples of the reducing group Ra include those represented by the following general formulae (II) to (IX).
- Ra, R a 2 , R3 and Ra each represents a hydrogen atom or a substituent selected from an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryloxyalkyl group, an alkoxyalkyl group, an N-substituted carbamoyl group, an N-substituted sulfamoyl group, a halogen atom, an alkylthio group or an arylthio group.
- the alkyl moiety and the aryl moiety in the above described substituents may be further substituted with an alkoxy group, a halogen atom, a hydroxy group, a cyano group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group or a carboalkoxy group.
- the hydroxy group and the amino group included in the reducing group represented by Ra may be protected by a protective group capable of reproducing the hydroxy group and the amino group by the action of a nucleophilic agent.
- the reducing group Ra is represented by the following general formula (X).
- X represents an electron donating substituent when n is 1 or substituents, which may be the same or different, one of the substituents being an electron donating group and the second or second and third substituents being selected from an electron donating group or a halogen atom when n is 2 or 3, respectively;
- X 10 groups may form a condensed ring with each other or with OR a 10 ; and the total number of the carbon atoms included in R 10 a and X 10 is not less than 8.
- reducing groups represented by the general formula (X) more preferred reducing groups Ra are represented by the following general formulae (Xa) and (Xb): wherein Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis; R a 11 and R a 12 , which may be the same or different, each represents an alkyl group or R a 11 and R a 12 may be bonded to each other to form a ring; R a 13 represents a hydrogen atom or an alkyl group; R a 10 represents an alkyl group or an aromatic group; X" and X 12 , which may be the same or different, each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an acylamino group or an alkylthio group; and R a 10 and X 12 or R a 10 and R a 13 may be bonded to each other to form a ring, wherein Ga represents a hydroxy group or a group giving a hydroxy group upon
- the reducing group Ra is represented by the following general formula (XI). wherein Ga, X 10 , R a 10 and n each has the same meaning as Ga, X 10 , R a 10 and n defined in the general formula (X).
- reducing groups represented by the general formula (XI) more preferred reducing groups Ra are represented by the following general formulae (Xla), (Xlb) and (Xlc) wherein Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis; R a 21 and R a 22 , which may be the same or different, each represents an alkyl group or an aromatic group, and R a 21 and R a 22 may be bonded to each other to form a ring; R a 23 represents a hydrogen atom, an alkyl group or an aromatic group; R a 24 represents an alkyl group or an aromatic group; R a 25 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group; p is 0, 1 or 2; R a 24 and R a 25 may be bonded to each other to form a condensed ring; R a 21 and R a 24 may be bonded to each
- Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis
- R a 31 represents an alkyl group or an aromatic group
- R; 2 represents an alkyl group or an aromatic group
- R a 33 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group
- q is 0, 1 or 2
- R; 2 and R a 33 may be bonded to each other to form a condensed ring
- R a 31 and R a 22 may be bonded to each other to form a condensed ring
- R a 31 and R a 31 may be bonded to each other to form a condensed ring
- the total number of the carbon atoms included in R a 31 , R a 32 and (R a 33 ) q is more than 7.
- Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis
- R a 41 represents an alkyl group or an aromatic group
- R a 42 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group
- r is 0, 1 or 2
- the group of represents a group in which 2 to 4 saturated hydrocarbon rings are.condensed, the carbon atom in the condensed ring which is connected to the phenol nucleus (or a precursor thereof), represents a tertiary carbon atom which composes one of the pivot of the condensed ring, a part of the carbon atoms (excluding the above described tertiary carbon atom) in the hydrocarbon ring may be substituted for oxygen atom(s), the hydrocarbon ring may have a substituent, and an aromatic ring may be further condensed to the hydrocarbon ring; R a 41 or Ra 2 and the group of
- the essential part in the groups represented by the general formulae (Ill) and (IV) is a para(sulfonyl)aminophenol part.
- Specific examples of these reducing groups are described in U.S. Patents, 3,928,312 and 4,076,529, U.S. Published Patent Application B 351,673, U.S. Patents 4,135,929 and 4,258,120. These groups are also effective for the reducing group Ra according to the present invention.
- the reducing group Ra is represented by the following general formula (XII). wherein Ballast represents a diffusion-resistant group; Ga represents a hydroxy group or a precursor of a hydroxy group; Ge represents an aromatic ring directly condensed to the benzene nucleus to form a naphthalene nucleus; and n and m are dissimilar positive integers of 1 to 2.
- the reducing groups represented by the above described general formulae (V), (VII), (VIII) and (IX) are characterized by containing a heterocyclic ring. Specific examples of the groups are described in U.S. Patent 4,198,235, JP ⁇ A ⁇ 46730/78 and U.S. Patent 4,273,855.
- dyes which can be used for image forming dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes and phthalocyanine dyes. Representative examples of them are set forth below and are calssified by hue. Further, these dyes can be used in a form temporarily shifted to shorter wavelength region which is capable of regeneration during the development processing.
- R" to R; 6 each represents a hydrogen atom or a substituent selected from an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylsulfonyl group, a hydroxyalkyl group, a cyanoalkyl group, an alkoxycarbonylalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, a nitro group, a halogen atom, a sulfamoyl group, an N-substituted sulfamoyl group, a carbamoyl group, an N-substituted carbamoyl group, an N-substi
- alkyl moiety and the aryl moiety in the above described substituents may be further substituted with a halogen atom, a hydroxy group, a cyano group, an acyl group, an acylamino group, an alkoxy group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxy group, an alkylsulfonylamino group, an arylsulfonylamino group or a ureido group.
- hydrophilic groups include a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, an imido group, a hydroxamic acid group, a quaternary ammonium group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a sulfamoylamino group, a substituted sulfamoylamino group, a ureido group, a substituted ureido group, an alkoxy group, a hydroxyalkoxy group, an alkoxyalkoxy group.
- those in which the hydrophilic property thereof is increased by dissociation of a proton under a basic condition are particularly preferred.
- these groups include a phenolic hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, an imido group, a hydroxamic acid group, a (substituted) sulfamoyl group, a (substituted) sulfamoylamino group.
- Characteristics required for the image forming dye are as follows.
- H 2 NS0 2 - represents a group necessary to bond to the reducing group.
- the dye releasing redox compound used in the present invention can be introduced into a layer of the light-sensitive material by known methods such as a method as described in U.S. Patent 2,322,027.
- a method as described in U.S. Patent 2,322,027 In this case, an organic solvent having a high boiling point or an organic solvent having a low boiling point as described below can be used.
- the dye releasing redox compound is dispersed in a hydrophilic colloid after dissolved in an organic solvent having a high boiling point, for example, a phthalic acid alkyl ester (for example, dibutyl phthalate and dioctyl phthalate), a phosphoric acid ester (for example diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), a citric acid ester (for example, and tributyl acetylcitrate), a benzoic acid ester-(for example, octyl benzoate), an alkylamide (for example, diethyl laurylamide), an aliphatic acid ester (for example, dibutoxyethyl succinate, and dioctyl azelate), a trimesic acid ester (for example, tributyl trimesate), or an organic solvent having a high boiling
- An amount of the organic solvent having a high boiling point used in the present invention is 10 g per g of the dye releasing redox compound used or less and preferably 5 g per g or less.
- the silver halide used in the present invention includes silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide and silver iodide.
- silver halide in the embodiment of the present invention in which the organic silver salt oxidizing agent is not used together with but with silver halide is used alone, particularly preferred silver halide is silver halide partially containing a silver iodide crystal in its particle. That is, the silver halide the X-ray diffraction pattern of which shows that of pure silver iodide is particularly preferred.
- a silver halide containing two or more kinds of halogen atoms can be used.
- Such a silver halide yields a completely mixed crystal in a conventional silver halide emulsion.
- the particle of silver iodobromide shows X-ray diffraction pattern at a position corresponding to the mixed ratio of silver iodide crystal and silver bromide crystal but not at a position corresponding to pure silver iodide crystal and pure silver bromide crystal separately.
- silver halide used in the present invention include silver chloroiodide, silver iodobromide, and silver chloroiodo-bromide each containing silver iodide crystal in its particle and showing X-ray diffraction pattern of silver iodide crystal.
- the process for preparing those silver halides is explained taking the case of silver iodobromide. That is, the silver iodobromide is prepared by first adding silver nitrate solution to potassium bromide solution to form silver bromide particles and then adding potassium iodide to the mixture.
- Two or more kinds of silver halides in which a particle size and/or a halogen composition are different to each other may be used in mixture.
- An average particle size of the silver halide used in the present invention is preferably from 0.001 Il m to 10 pm and more preferably from 0.001 um to 5pm.
- the silver halide used in the present invention may be used as is. However, it may be chemically sensitized with a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
- a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
- a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
- a particularly preferred embodiment is to use an organic silver salt oxidizing agent in the light-sensitive material.
- the silver halide used is not always required to have a feature that the silver halide contains a pure silver iodide crystal in the case of using silver halide solely, but all silver halides used in the field of the art can be used.
- the organic silver salt oxidizing agent used in the invention is one which reacts with, when heated at above 80°C, preferably at above 100°C in the presence of an exposed silver halide, the foregoing image-forming material or, if necessary, a reducing agent which exists together with the image-forming material to form a silver image.
- the light-sensitive material coloring in higher density can be obtained by using an organic silver salt oxidizing agent together with the silver halide in the light-sensitive material.
- organic silver salt oxidizing agent examples include silver salts of organic compounds having a carboxy group and typically silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.
- silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linolate, silver oleate, silver adipate, silver sebacate, silver succinate, silver acetate, silver butyrate and silver camphorate.
- These silver salts which are substituted with a halogen atom or a hydroxy group are also effectively used.
- Examples of the silver salts of aromatic carboxylic acid and other carboxyl group containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenylbenzoate, silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, as described in U.S. Patent 3,785,830, and a silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Patent 3,330,663.
- a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate
- a silver salt of a compound containing a mercapto group or a thione group and a derivative thereof can be used.
- Examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-mercaptobenzothiazole, a silver salt of 2-(S-ethylglycolamido)benzothiazole, a silver salt of thioglycolic acid such as a silver salt of of an S-alkyl thioglycol acetic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in JP-A-28221n3, a silver salt of dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thiomamide, a silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercap
- Patent 4,123,274 for example, a silver salt of 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole, a silver salt of thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as described in U.S. Patent 3,301, 678.
- 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole
- thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as described in U.S. Patent 3,301, 678.
- a silver salt of a compound containing an imino group can be used.
- these compounds include a silver salt of benzotriazole and a derivative thereof as described in JP-B-30270/69 and 18416/70, for example, a silver salt of benzotriazole, a silver salt of alkyl substituted benzotriazole such as a silver salt of methylbenzotriazole, a silver salt of a halogen substituted benzotriazole such as a silver salt of 5-chlorobenzotriazole, a silver salt of carboimidobenzotriazole such as a silver salt of butylcarbo- imidobenzotriazole, a silver salt of 1,2,4-triazole or 1-H-tetrazole as described in U.S. Patent 4,220,709, a silver salt of carbazole, a silver salt of saccharin, a silver salt of imidazole and an imidazole derivative.
- the silver salts as described in Research Disclosures, Vol. 170, No. 17029 of June, 1978 and organic metal salts such as copper stearate, can be also used as the foregoing various silver salts.
- the organic silver salt oxididing agents may be used solely or as a mixture of two or more thereof.
- the so-called auxiliary developing agent can be used even when the dye releasing redox compound is used.
- the auxiliary developing agent in this case is a compound which is oxidized upon the silver halide to form its oxidized product having an ability to oxidize the reducing group Ra in the dye releasing redox compound.
- auxiliary developing agents examples include hyroquinone, alkyl substituted hydroquinones such as tertiary butylhydroquinone, 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen substituted hydroquinones such as chlorohydroquinone, dichlorohydroquinone, alkoxy substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methyl hydroxynaphthalene.
- alkyl substituted hydroquinones such as tertiary butylhydroquinone, 2,5-dimethylhydroquinone, catechols, pyrogallols
- halogen substituted hydroquinones such as chlorohydroquinone, dichlorohydroquinone
- alkoxy substituted hydroquinones such as methoxyhydroquinone
- polyhydroxybenzene derivatives such as methyl hydroxynaphthalene.
- methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N-di(2- ethoxyethyl)hydroxylamine, pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones and hydroxy tetronic acids are useful.
- the auxiliary developing agent can be used in an amount of a fixed range.
- a suitable range is 0.0005 times by mol to 20 times by mol based on silver.
- a particularly suitable range is 0.001 time by mol to 4 times by mol.
- the heat development mechanism in the present invention upon heating has not yet been sufficiently clarified but is considered as follows.
- the dye releasing redox compound of the invention acts as a reducing agent to reduce the silver halide and/or the organic silver halide oxidizing agent with the latent image nuclei as a catalyst to form silver, and the dye releasing redox compound itself is oxidized.
- the thus oxidized dye releasing redox compound is cleaved to release a dye.
- the organic silver salt oxidizing agent is further used together, it is necessary for quickly initiating the reaction that the silver halide and the organic silver salt oxidizing agent exist within a substantially effective distance from each other. Accordingly, it is preferred that the silver halide and the organic silver halide oxidizing agent exist in the same layer.
- thermal solvent in the invention a thermal solvent can be used as a means for improving the forgoing inconvenience.
- the term 'thermal solvent means a non-hydrolyzable organic material which is solid at an ambient temperature but melts together with other components at a temperature of heat treatment or below.
- thermal solvents incude compounds which can act as a solvent for the developing agent and compounds having a high dielectric constant which accelerate physical development of silver salts.
- preferred thermal solvents include polyglycols as described in U.S.
- Patent 3,347,675 for example, polyethylene glycol having an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as polyethylene oxide oleic acid ester, beeswax, monostearin, compounds having a high dielectric constant which have an -S0 2 - or -CO- group such as acetamide, succinimide, ethylcarbamate, urea, methylsulfonamide or ethylene carbonate, polar substances as described in U.S.
- Patent 3,667,959 lactone of 4-hydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-1,1-dioxide and 1,10-decanediol, methyl anisate and biphenyl suberate as described in Research Disclosure, pages 26 to 28 (Dec., 1976).
- the role of the thermal solvent in the invention is not always clear but it is considered that the main role is to accelerate the diffusion of the reaction molecules at development.
- the light-sensitive silver halide and the organic silver salt oxididing agent used in the present invention are prepared in the binder as described below. Further, the dye releasing redox compound is dispersed in the binder described below.
- the binder which can be used in the present invention can be employed individually or in a combination thereof.
- a hydrophilic binder can be used as the binder according to the present invention.
- the typical hydrophilic binder is a transparent or translucent hydrophilic colloid, examples of which include a natural substance, for example, protein such as gelatin, a gelatin derivative, a cellulose derivative, a polysaccharide such as starch, gum arabic, and a synthetic polymer, for example, a water-soluble polyvinyl compound such as polyvinyl pyrrolidone, acrylamide polymer.
- Another example of the synthetic polymer compound is a dispersed vinyl compound in a latex form which is used for the purpose of increasing dimensional stability of a photographic material.
- the silver halide used in the present invention can be spectrally sensitized with methine dyes or other dyes.
- Suitable dyes which can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonal dyes. Of these dyes, cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventionally utilized nucleus for cyanine dyedsuch as basic heterocyclic nuclei, is applicable to these dyes.
- nuclei having a ketomethylene structure 5-or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus, may also be applicable.
- 5-or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus
- Useful sensitizing dyes include those described in German Patent 929,080, U.S. Patents 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Patent 1,242,588, JP-B-14030/69 and 24844/77.
- sensitizing dyes can be employed individually, and can also be employed in combination thereof.
- a combination of sensitizing dyes is often used, particularly for the purpose of supersensitization.
- the sensitizing dyes may be present in the emulsion together with dyes which themselves do not give rise to spectrally sensitizing effects but exhibit a supersensitizing effect or materials which do not substantially absorb visible light but exhibit a supersensitizing effect.
- aminostilbene compounds substituted with a nitrogen-containing heterocyclic group e.g., those described in U.S. Patents 2,933, 390 and 3,635,721
- aromatic organic acid-formaldehyde condensates e.g., those described in U.S. Patent 3,743,510
- cadmium salts e.g., those described in U.S. Patent 3,743,510
- cadmium salts e.g., those described in U.S. Patent 3,743,510
- cadmium salts e.g., those described in U.S. Patent 3,743,510
- cadmium salts e.g., those described in U.S. Patent 3,743,510
- various dye releasing activators can be used by various manners, for example, by incorporating them in any one of the layers of the light-sensitive material or the dye-fixing material.
- the dye releasing activator is a compound capable of accelerating the oxidation-reduction of the photosensitive silver halide and/or the organic silver salt oxidizing agent with the dye releasing redox compound or capable of nucleophilically reacting with the oxidized dye releasing redox compound in the subseqeuent dye releasing reaction to accelerate the release of dye.
- Bases or base precursors are useful as the dye releasing activators.
- amines which include trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes.
- amines which include trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes.
- betaine tetramethylammonium iodide and diaminobutane dihydrochloride as described in U.S.
- the base precursor is a substance which releases a basic component by heating. Examples of typical base precursors are described in British Patent 998,949.
- a preferred base precursor is a salt of a carboxylic acid and an organic base, and examples of the suitable carboxylic acids include trichloroacetic acid and trifluoroacetic acid and examples of the suitable bases include guanidine, piperidine, morpholine, p-toluidine and 2-picoline. Guanidine trichloroacetate as described in U.S. Patent 3,220,846 is particularly preferred.
- aldonic amides as described in JP ⁇ A ⁇ 22625/75 are preferably used because they decompose at a high temperature to form bases.
- dye releasing activators can be used in an amount of a broad range.
- a useful range is up to 50% by weight based on the amount of dry layer coated of the light-sensitive material.
- a range of 0.01 % by weight to 40% by weight is more preferred.
- a 1 , A 2 , A3 and A4 which may be the same or different, each represents a hydrogen atom or a substituent selected from an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group and a heterocyclic group; and A 1 and A 2 or A3 and A4 may combine with each other to form a ring.
- the compounds include H 2 NS0 2 NH 2 , H 2 NS0 2 N(CH 3 ) 2 , H 2 NSO 2 N(C 2 H 5 ) 2 , H 2 NSO 2 NHCH 3 , H 2 NSO 2 N(C 2 H 4 OH) 2 , CH 3 NHS0 2 NHCH 3 ,
- the above described compound can be used in an amount of broad range.
- a useful range is up to 20% by weight based on the amount of a dry layer coated of the light-sensitive material.
- a range of 0.1 % by weight to 15% by weight is more preferred.
- the water releasing compound means a compund which releases water by decomposition during heat development.
- These compounds are particularly known in the field of printing of fabrics, and NH Fe(S0 4 ) 2' 12H 2 0, as described in JP ⁇ A ⁇ 88386/75 are useful.
- a support used in the present invention is that which can endure at the processing temperature.
- an ordinary support not only glass, paper, metal or analogues thereof may be used, but also an acetyl cellulose film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polycarbonate film, a polyethylene terephthalate film, and a film related thereto or a plastic material may be used.
- the polyesters described in U.S. Patents 3,634,089 and 3,725,070 are preferably used.
- a coating composition used in the invention can be prepared by blending, before use, a silver halide and an organic metal salt oxidizing agent formed separately, and it is also effective for the preparation of the coating composition to blend both the components in a ball mill for a long period of time. It is also effective to add a halogen-containing compound to the organic silver salt oxidizing agent to form a silver halide with silver in the organic silver salt oxidizing agent.
- a suitable coating amount of the light-sensitive silver halide and the organic silver salt oxidizing agent employed in the present invention is in a total of from 50 mg/m 2 to 10 g/m 2 calculated as an amount of silver.
- the photographic emulsion layer and other hydrophilic colloid layers in the light-sensitive material of the present invention may contain various surface active agents for various purposes, for example, as coating aids or for prevention of electrically charging, improvement of lubricating property, emulsification, prevention of adhesion, improvement of photographic properties (for example, acceleration of development, rendering hard tone or sensitization).
- nonionic surface active agents such as saponin (steroid), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamine or amides, polyethylene oxide adducts of silicone), glycidol derivatives (for example, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), polyhydric alcohol aliphatic acid esters or saccharide alkyl esters; anionic surface active agents containing acid groups such as a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as alkylcarboxylic acid salts, alkylsulfonic acid salts, alkyl
- polyethylene glycol type nonionic surface active agents having a recurring unit of ethylene oxide in their molecules may be preferably incorporated into the light-sensitive material. It is particularly preferred that the molecule contains 5 or more of the recurring units of ethylene oxide.
- nonionic surface active agents capable of satisfying the above described conditions are well known as to their structures, properties and methods of synthesis. These nonionic surface active agents are widely used even outside this field. Representative references relating to these agents include: Surfactant Science Series, Vol. 1, Nonionic Surfactants (edited by Martin J. Schick, Marcel Dekker Inc., 1967), and Surface Active Ethylene Oxide Adducts, (edited by Schoufeldt N. Pergamon Press, 1969). Among the nonionic surface active agents described in the above mentioned references, those capable of satisfying the above described conditions are preferably employed in connection with the present invention.
- the nonionic surface active agents can be used individually or as a mixture of two or more of them.
- the polyethylene glycol type nonionic surface active agents can be used in an amount of less than 100% by weight, preferably less than 50% by weight, based on a hydrophilic binder.
- the light-sensitive material of the present invention may contain a cationic compound containing a pyridinium salt.
- a cationic compound containing a pyridinium group used are described in PSA Journal Section B 36 (1953), U.S. Patents 2,648,604 and 3,671,247, JP-B-30074/69 and 9503/69.
- a compound which activates development simultaneously while stabilizing the image it is preferred to use isothiuroniums including 2-hydroxyethylisothiuronium trichloroacetate as described in U.S. Patent 3,301,678, bisisothiuroniums including 1,8-(3,6-dioxaoctane)-bis(isothiuronium trifluoroacetate), etc., as described in U.S. Patent, 3,669,670, thiol compounds as described in German Patent Application (OLS) No.
- isothiuroniums including 2-hydroxyethylisothiuronium trichloroacetate as described in U.S. Patent 3,301,678, bisisothiuroniums including 1,8-(3,6-dioxaoctane)-bis(isothiuronium trifluoroacetate), etc., as described in U.S. Patent, 3,669,670, thiol compounds as described in German Patent Application (OL
- thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiazolium trichloroacetate, as described in U.S. Patent 4,012,260, compounds having a-sulfonylacetate as an acid part such as bis(2-amino-2-thiazolium)methylene-bis(sulfonylacetate), 2-amino-2-thiazolium phenylsulfonyl-acetate, as described in U.S. Patent 4,060,420, and compounds having 2-carboxycarboxamide as an acid part as described in U.S. Patent 4,088,496.
- the light-sensitive material used in the present invention may contain, if necessary, various additives known for the heat-developable light-sensitive materials and may have a layer other than the light-sensitive layer, for example, an antistatic layer, an electrically conductive layer, a protective layer, an intermediate layer, an antihalation layer, a strippable layer.
- a layer other than the light-sensitive layer for example, an antistatic layer, an electrically conductive layer, a protective layer, an intermediate layer, an antihalation layer, a strippable layer.
- additives examples include those described in Research Disclosure, Vol. 170, No. 17029 (June, 1978), for example, plasticizers, dyes for improving sharpness, antihalation dyes, sensitizing dyes, matting agents, fluorescent whitening agents and fading preventing agent.
- the protective layer, the intermediate layer, the subbing layer, the back layer and other layers can be produced by preparing each coating solution and applying to a support by various coating methods such as a dip coating method, an air-knife coating method, a curtain coating method or a hopper coating method as described in U.S. Patent 2,681,294 and drying in the same manner as used in preparing the heat-developable light-sensitive layer of the present invention, by which the light-sensitive material is obtained.
- various coating methods such as a dip coating method, an air-knife coating method, a curtain coating method or a hopper coating method as described in U.S. Patent 2,681,294 and drying in the same manner as used in preparing the heat-developable light-sensitive layer of the present invention, by which the light-sensitive material is obtained.
- two or more layers may be applied at the same time by the method as described in U.S. Patent 2,761,791 and British Patent 837,095.
- the resulting latent image can be developed by heating the whole material to a suitably elevated temperature, for example, about 80°C to about 250°C for about 0.5 second to about 300 seconds.
- a higher temperature or lower temperature can be utilized to prolong or shorten the heating time, if it is within the above described temperature range.
- a temperature range of about 110°C to about 160°C is useful.
- the light-sensitive material can be heated for development by an ordinary means such as a simple heating plate, a heating iron, a heat roller, a heating element utilizing carbon or titanium white, or a similar means.
- the transfer of the mobile dye may be initiated simultaneously with the release of the dye or after completing the release of the dye. Accordingly, heating for the transfer of the mobile dye may be after heat development or similtaneously with heat development.
- heating simultaneously with heat development means that heating for development also acts as heating for transferring the dye released.
- the optimum heating temperature for development and the heating time necessary for the development do not always coincide with those for transferring the dye and hence, the heating temperatures may be selected independently.
- the heating temperature for transferring the dye is 60°C to 250°C from the viewpoints of preservative property and workability of the light-sensitive material
- a material which exhibits the action as a hydrophilic thermal solvent in this temperature range may be properly used. It is, as a matter of course, necessary that the hydrophilic thermal solvent assists the quick transfer of dye, but considering also the heat resistance of the light-sensitive material, the hydrophilic thermal solvent is required to have a melting point of 40°C to 250°C, preferably 40°C to 200°C, more preferably 40°C to 150°C.
- the "hydrophilic thermal solvent” referred to in the invention is defined to be a compound which is in a solid state at room temperature but becomes in a liquid state upon heating, has an (inorganic property/ organic property) value of larger than 1, and has a solubility in water at room temperature of higher than 1.
- the term "inorganic property/organic property” is a conception for estimating the properties of a compound and is described in detail in, for example, Kagaku no Ryoiki (The Domain of Chemistry), 11, page 719 (1957).
- the hydrophilic thermal solvent has a role for assisting the transfer of the hydrophilic dye, it is preferred that the hydrophilic thermal solvent is a compound capable of acting as a solvent for the hydrophilic dye.
- the (inorganic property/organic property) value of the solvent is close to the (inorganic property/organic property) value of the organic compound.
- the (inorganic property/organic property) value of the dye releasing redox compound used in the present invention is about 1, and the (inorganic property/organic property) value of the hydrophilic dye released from the dye releasing redox compound is larger than the (inorganic property/organic property) value of the dye releasing redox compound and is preferably larger than 1.5, more preferably larger than 2.
- the hydrophilic thermal solvent used in the invention transfers only the hydrophilic dye and does not transfer the dye releasing redox compound, it is necessary that the (inorganic property/organic property) value of the hydrophilic thermal solvent is larger than the (inorganic property/organic property) value of the dye releasing redox compound. That is, it is necessaryy that the (inorganic property/organic property) value of the hydrophilic thermal solvent used in the invention be larger than 1, preferably larger than 2:
- the molecular weight of the hydrophilic thermal solvent used in the invention be low, i.e., less than about 200, preferably less than about 100.
- the hydrophilic thermal solvent used in the invention can substantially assist the transfer of the hydrophilic dye formed from the dye releasing redox compound by heat development onto a dye-fixing layer. Therefore, the hydrophilic thermal solvent may be incorporated in not only a dye-fixing layer but also a photosensitive layer or in both the dye-fixing layer and the photosensitive layer. Furthermore, an independent layer containing a hydrophilic thermal solvent may be provided in the light-sensitive material and/or independent dye-fixing material having the dye-fixing layer. However, from the viewpoint of increasing the transfer efficiency of the dye onto the dye-fixing layer, it is preferred that the hydrophilic thermal solvent be incorporated in the dye-fixing layer and/or a layer adjacent to the dye-fixing layer.
- the hydrophilic thermal solvent is usually dissolved in water and dispersed in a binder, but it may be used by dissolving in an alcohol such as methanol, ethanol, etc.
- the hydrophilic thermal solvent used in the invention can be used in a coating amount of 5 to 500% by weight, preferably 20 to 200% by weight, more preferably 30 to 150% by weight, based on the total coating amount of the coating compositions for the light-sensitive material and/or the dye-fixing material.
- hydrophilic thermal solvent there are, for example, ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocyclic compounds.
- the compounds (1), (2), (3), and (10) in ureas, the compounds (17) and (19) in pyridines, the compounds (26), (30), and (33) in amides, the compounds (34) and (36) in sulfonamides, the compounds (40), (41), (43), and (44) in imides, and the compounds (46) and (54) in alcohols are particularly preferred.
- the foregoing compounds used as the hydrophilic thermal solvent may be used solely or as a mixture of two or more thereof.
- the light-sensitive material of this invention is composed of a support having thereon at least a photosensitive layer (I) containing a silver halide, an organic silver salt oxidizing agent which may be used if necessary, a dye releasing redox compound which is also a reducing agent for the organic silver salt oxidizing agent, and a binder and dye-fixing layer (II) capable of receiving a mobile hydrophilic dye formed in the layer (I).
- a photosensitive layer (I) and a dye-fixing layer (II) may be formed on the same support or separate supports respectively.
- the dye-fixing layer (II) and the photosensitive layer (I) may be peeled off from each other.
- the dye-fixing layer (II) or the photosensitive layer (I) may be peeled off from the other.
- a light-sensitive material having the photosensitive layer (I) on a support and a dye- fixing material having the dye-fixing layer (II) on another support are prepared separately, after imagewise exposing the light-sensitive material and uniformly heating, the dye-fixing material is superposed on the resulting light-sensitive material to thereby transfer the mobile dye onto the dye-fixing layer (II).
- the light-sensitive material can be closely brought into contact with the dye-fixing material by usual manners such as those by press roller, etc., and in this case, for sufficiently performing the close contact of both the materials, the heating is employable during the contacting.
- the latter heating can contribute to only the dye transfer and hence, the heating temperature and the heating time for the latter heating may be selected independent on the heating for development.
- the heating for development it is preferred to perform the heating for development such that the heating contributes to the dye transfer as less as possible, and that the reaction for the development is finished in a short period of time.
- the heating for transferring the dye released imagewise is performed at a temperature of as low as possible such that the heat reaction of the unexposed area does not occur, in a proper range of a transferring period of time.
- the dye-fixing layer (II) may have a white reflection layer.
- a layer of titanium dioxide dispersed in gelatin may be formed on a mordanting layer provided on a transparent support.
- the titanium dioxide layer forms a white opaque layer and hence, when the transferred dye image is viewed from the side of the transparent support, a reflection-type color image can be viewed.
- the dye transfer from the light-sensitive layer to the dye-fixing layer can be carried out using a dye transfer assistant.
- useful dye transfer assistant include water and an alkaline aqueous solution containing sodium hydroxide, potassium hydroxide or an inorganic alkali metal salt.
- a solvent having a low boiling point such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, and a mixture of such a solvent having a low boiling point with water or an alkaline aqueous solution can be used.
- the dye transfer assistant can be employed by wetting the image receiving layer with the transfer assistant or by incorporating it in the form of water of crystalliszation or microcapsules into the material.
- the dye-fixing layer may contain a dye mordant for fixing the dye, a hydrophilic thermal solvent for assisting the transfer of the dye, a base and/or a base precursor for accelerating the dye releasing reaction, and further a binder for these materials.
- a dye mordant for fixing the dye for fixing the dye
- a hydrophilic thermal solvent for assisting the transfer of the dye
- a base and/or a base precursor for accelerating the dye releasing reaction
- a binder for these materials may be particularly preferred.
- the dye in the light-sensitive material may transferred into the individually provided dye-fixing material, in order to obtain a high-quality ultimate image fixed in the dye- fixing material, a specific means is required. That is, in order to increase the quality of the dye image transferred onto the dye-fixing layer, it is useful to incorporate a base and/or a base precursor into any one of the layers constituting the dye-fixing material.
- a base and/or a base precursor into the dye-fixing layer or a layer provided on the dye-fixing layer because the image density is sufficiently high as well as a sharp dye image can be obtained.
- a base and/or base precursor the above-described bases and/or base precursors as the dye releasing activators useful in the light-sensitive material can, for example, be exemplified.
- the ultimate image is formed in the dye-fixing material which is not light-sensitive.
- the function for imparting "light sensitivity" and that for fixing the ultimate image be imparted to the light-sensitive material and the dye-fixing material independently, materials which sufficiently exhibit the respective functions can be widely selected.
- base and/or base precursor used in the dye-fixing material of the invention usual inorganic or organic bases and/or base precursor are useful.
- base precursors mean ones releasing a basic component upon thermal decomposition.
- Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals, disphosphates, triphosphates, borates, carbonates, quinolinates, pyrophosphates, metaphosphates, ammonium hydroxide, quaternary alkylammonium hydroxides, and other hydroxides.
- these inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium quinolinate, potassium quinolinate, sodium diphosphate, potassium diphosphate, sodium triphosphate, potassium triphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium metaphosphate, potassium metaphosphate, borax, ammonium hydroxide, tetramethylammonium, tetrabutylammonium, ammonia.
- Examples of the organic base used for the dye releasing activator of the present invention include aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, quanidines, and cyclic quanidines, with those having a pKa of higher than 8 being particularly useful.
- precursors of these organic bases can be used as preferred base precursors.
- Examples of such base precursors include salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, and acetoacetic acid, and salts of 2-carboxy carboxide as disclosed in U.S. Patent 4,088,496.
- base precursors as disclosed in British Patent 998,945, U.S. Patent 3,220,846 and JP- ⁇ -22625n5 can also be used.
- bases which are used as alkaline agents and buffers in the conventional photographic materials and their treating solutions may also be used.
- the base precursor used in the invention can be used in a wide range in terms of its amount. But it is suitably used in an amount of less than 50% by weight, preferably 0.01 to 40% by weight, as calculated on the basis of the weight of the coated surface of the dye-fixing layer.
- the base and/ or base precursor may be used either alone or in admixture of two or more thereof.
- the base and/or base precursor is usually dissolved in water or an alcohol and then dispersed in the dye-fixing layer.
- the dispersion may be performed in accordance with a method as disclosed in U.S. Patent 2,322,027 in which an organic solvent having a high boiling point is used.
- the base and/or base precursor is dissolved in an organic solvent having a boiling point of about 30 to 160°C, such as lower alkyl acetates (e.g., ethyl acetate or butyl acetate), ethyl proprionate, sec- butyl alcohol, methyl isobutyl ketone, (3-ethoxyethyt acetate, methyl cellosolve acetate, cyclohexane, and then dispersed in the dye-fixing layer.
- an organic solvent having a boiling point of about 30 to 160°C such as lower alkyl acetates (e.g., ethyl acetate or butyl acetate), ethyl proprionate, sec- butyl alcohol, methyl isobutyl ketone, (3-ethoxyethyt acetate, methyl cellosolve acetate, cyclohexane, and then dispersed in the dye-fixing layer.
- organic solvent having a high boiling point examples include, for example, a phthalic acid alkyl ester (for example, dibutyl phthalate, and dioctyl phthalate), a phosphoric acid ester (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), a citric acid ester (for example, tributyl acetylcitrate), a benzoic acid ester (for example, octyl benzoate), an alkylamide (for example, diethyl laurylamide), an aliphatic acid ester (for example, dibutoxyethyl succinate, dioctyl azelate), a trimesic acid ester (for example, tributyl trimesate).
- a phthalic acid alkyl ester for example, dibutyl phthalate, and dioctyl phthal
- organic solvents having a high boiling point and organic solvents having a low boiling point may be used as a mixture thereof. Further, it is possible to use a dispersion method using a polymer as described in JP-B-29853n6 and JP-A-59943/76.
- the dye-fixing material of the invention may be constructed by plural layers of the dye-fixing layer and a layer or layers other than the dye-fixing layers, e.g., a protective layer, an interlayer.
- the dye-fixing layer of the invention is constructed by a single layer or plural layers and contains a dye mordant for fixing the dye.
- the base and/or base precursor is used by dispersing in a layer or layers containing the dye mordant.
- the base and/or base precursor may be used by dispersing in a binder in a layer adjacent to the layer containing the dye mordant.
- various mordants can be used. Among them are particularly preferred polymer mordants.
- the polymer mordant and the base and/or base precursor can be dispersed in the binder described below.
- the binder which can be used in the present invention can be employed individually or in a combination thereof.
- a hydrophilic binder can be preferably used as the binder according to the present invention.
- the typical hydrophilic binder is a transparent or translucent hydrophilic colloid, examples of which include a natural substance, for example, protein such as gelatin, a gelatin derivative, and a cellulose derivative, a polysaccharide such a starch, and gum arabic, and a synthetic polymer, for example, a water-soluble polyvinyl compound such as polyvinyl pyrrolidone, and acrylamide polymer.
- Another example of the synthetic polymer compound is a dispersed vinyl compound in a latex form which is used for the purpose of increasing dimensional stability of a photographic material.
- the dye mordant is a polymer mordant
- the mordant also acts as a binder and hence, the amount of the binder may be reduced or the binder may not particularly be used. Contrarily, when the binder has a function as a mordant, the dye mordant may not be used. Any materials which are usually used as a binder for photographic light-sensitive materials can be used as the binder in the invention.
- the mordant used for the dye-fixing layer of the invention can be properly selected from conventional mordants and among them, polymer mordants are particularly preferred.
- Polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, polymers having quaternary cation groups thereof, having a molecular weight of from 5,000 to 200,000, and particularly from 10,000 to 50,000.
- mordants disclosed in U.S. Patents 2,675,316 and 2,882,156 can be used.
- mordants capable of cross-linking with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants are preferably used.
- gelatin for the mordant layer Various kinds of known gelatins can be employed as gelatin for the mordant layer.
- gelatin which is produced in a different manner such as lime-processed gelatin, acid-processed gelatin, or a gelatin derivative which is prepared by chemically modifying gelatin such as phthalated gelatin, sulfonylated gelatin, can be used.
- gelatin subjected to a desalting treatment can be used, if desired.
- the ratio of polymer mordant to gelatin and the amount of the polymer mordant coated can be easily determined by one skilled in the art depending on the amount of the dye to be mordanted, the type and composition of the polymer mordant and further on the image-forming process used.
- the ratio of mordant to gelatin is from 20/80 to 80/20 (by weight) and the amount of the mordant coated is from 0.5 to 8 g/ m2.
- a typical dye-fixing material used in the invention can be obtained by coating a mixture of a polymer containing an ammonium salt and gelatin on a transparent support.
- a protective layer may be formed thereon, if desired.
- a protective layer materials usually used for protective layers for photographic light-sensitive materials can be used, but when the dye-fixing layer is formed on a support different from the support of the light-sensitive material, it is preferred that the protective layer is rendered hydrophilic in order to prevent hindering the transfer of the hydrophilic dye.
- the above described support used in the light-sensitive material can be optionally chosen.
- organic polymers which are resistant to the heating for the development or the dye transfer are preferred.
- organic polymers used in the dye-fixing material of the invention include polystyrene having a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent of up to 4 carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallyl- benzene, polyvinyl alcohol, polyacetals (e.g., polyvinylformal or polyvinylbutyral), polyvinyl chloride, chlorinated polyethylene, polyethylene trichlorofluoride, polyacrylonitrile, poly-N,N-dimethylallylamide, a polyacrylate having a p-cyanophenyl group, a pentachlorophenyl group, or a 2,4-dichlorophenyl group, a pentachlorophenyl group, or a 2,4-dichlorophenyl group, polyacryl
- Examples of the support advantageously used in this invention are films of cellulose acetates such as triacetate, diacetate; films of polyamides such as combinations of heptamethylenediamine and terephthalic acid, fluorenedipropylamine and adipic acid, hexamethylenediamine and diphenic acid, hexamethylenediamine and isophthalic acid; films of polyesters such as the combinations of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, etc., polyethylene terephthalate films, polycarbonate films. These films may be denatured.
- a polyethylene terephthalate film denatured by using cyclohexane dimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, as a denaturant is advantageously used.
- the photographic emulsion layer and other binder layers may contain inorganic or organic hardeners. It is possible to use chromium salts (chromium alum, and chromium acetate), aldehydes (formaldehyde, glyoxal, and glutaraldehyde), N-methylol compounds (dimethylolurea, methylol and dimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloylhexahydro-s-triazine, and 1,2-vinylsulfonyl-2-propanol), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (mucochloric acid, and mucophenoxychloric acid), which are used individually or as a combination thereof.
- chromium salts chromium alum, and chromium
- heating means for transferring the dye various heating means as described above in regard to the heating means for the heat development can be used.
- the light-sensitive material having the photosensitive layer and the dye-fixing layer on the same support or the dye-fixing material having the dye-fixing layer on a different support from that of the light-sensitive material can be prepared by coating respective coating compositions for the dye- fixing layer, protective layer, interlayer, subbing layer, backing layer, in the same manner as described in the case of forming the photosensitive layer or other layer using a dipping method, an air knife method, a curtain coating method, or a hopper coating method as described in U.S. Patent No. 3,681,294, followed by drying.
- Latent images are obtained by imagewise exposure by radiant rays including visible rays.
- light sources used for conventional color prints can be used, examples of which include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes and light-emitting diodes.
- the original may be line drawings or photographs having gradation. Further, it is possible to take a photograph of a portrait or landscape by means of a camera. Printing from the original may be carried out by contact printing by superposing the original on the material or may be carried out by reflection printing or enlargement printing.
- CTR cathode ray tube
- FOT fiber optical tube
- LED light-emitting diode
- the light-sensitive material is produced using a construction such that the green-sensitive part (layer) contains a yellow dye releasing redox compound, the red-sensitive part (layer) contains a magenta dye releasing redox compound and the infrared-sensitive part (layer) contains a cyan dye releasing redox compound.
- Other combinations can be utilized, if necessary.
- the image-forming process of the invention is a very convenient image-forming process wherein the whole of steps from light exposure to heat development and dye-fixing can be performed in a completely dry system without particularly supplying a solvent from the outside. Furthermore, since in the image-forming process of the invention, not only sensitivity of a conventional so-called silver halide photographic material can be maintained but also dye image formed is fixed in the dye-fixing material, the quality and the preservative property of the dye image thus formed are very good, the color reproducibility is good, and in spite of the completely dry system, the reproduction of color images can be sufficiently performed.
- the image-forming process of the invention having such excellent features can be applied for the field of photography as well as can meet the recent requirement for the transfer of so-called soft images to hard images.
- the dye image formed is fixed in the dye- fixing layer, whereby the dye image has a good preservative property and hence, the process of the invention can be conveniently utilized even in the case of requiring the preservation of dye images for a long period of time.
- the image-forming process of the invention exceeds conventional photographic techniques in the foregoing points.
- a silver iodobromide emulsion was prepared by the following manner.
- the pH of the silver iodobromide emulsion thus obtained was adjusted to cause sedimentation, and after removing excessive salts, the pH of the emulsion was adjusted to 6.0 to provide 400 g of the silver iodobromide emulsion.
- magenta dye releasing redox compound (42) In 20 ml of ethyl acetate were dissolved 5 g of the magenta dye releasing redox compound (42), 0.5 g of a surface active agent, succinic acid 2-ethylhexyl ester sodium sulfonate, and 5 g of tricresyl phosphate (TCP) under heating to about 60°C to form a homogeneous solution.
- the solution was mixed with 100 g of an aqueous solution of 10% limed gelatin with stirring and mixture was treated by means of a homogenizer for 10 minutes at 10,000 r.p.m. to provide a dispersion of the magenta dye releasing redox compound.
- a photosensitive layer was formed as follows.
- a protective layer was formed on the photosensitive layer thus formed by the following manner.
- a mixture of the foregoing components was coated on the photosensitive layer at a wet thickness of 25 um and then dried to provide light-sensitive material D-1.
- the mixture was uniformly coated on the layer thus formed at a wet thickness of 60 11 m and dried.
- the 2nd layer was called as a hydrophilic thermal solvent layer.
- dye-fixing material R-2 was prepared.
- dye-fixing materials R-3 and R-4 were prepared, respectively.
- dye- fixing material R-5 was prepared.
- dye-fixing material R-6 was prepared.
- dye-fixing material R-7 was prepared.
- Light-sensitive material D-1 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds on a heat block heated to 140°C.
- each of dye-fixing materials R-1 to R-9 was closely brought into contact with the light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 120°C.
- Each of light-sensitive materials D-1 to D-3 in Examples 1 to 3 was exposed and heat developed as in Example 15.
- Each of the light-sensitive materials was closely brought into contact with dye-fixing material R-1 shown in Example 6 with the coated layers in a face-to-face relationship and each assembly was heated for 30 seconds on a heat block at 120°C.
- the dye-fixing material was peeled off from each of the light-sensitive sheets, each of negative magenta, yellow, and cyan images was obtained on the dye- fixing material.
- the densities of each negative image thus obtained were measured using a Macbeth densitometer (RD-504) and the results are shown in Table 2.
- Each of light-sensitive materials D-4 to D-6 in Example 6 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux. Each of the light-sensitive materials was closely brought into contact with dye-fixing material R-8 in Example 13 with the coated layers in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block of 130°C.
- dye-fixing material R-10 was prepared.
- Light-sensitive material D-8 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds to 130°C. Then, the light-sensitive material was closely brought into contact with dye-fixing material R-10 with the coated layer in a face-to-face relationship with each other and the assembly was heated for 20 seconds to 120°C. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta image having a high density was obtained on the dye-fixing material. When the density of the negative color image was measured using a Macbeth densitometer (RD-504), the maximum density was 1.22 and the minimum density was 0.19. Thus, it has been confirmed that a dye image having a high density can be obtained by heating in a short period of time without supplying water by incorporating the hydrophilic thermal solvent in the light-sensitive material.
- RD-504 Macbeth densitometer
- Dye-fixing material R-11 used in the invention was prepared as follows.
- Light-sensitive material D-1 was imagewise exposed for 10 minutes using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds on a heat block heated to 140°C.
- the light-sensitive material was closely brought into contact with dye-fixing material R-11 with the coated layers in a face-to-face relationship with each other and the assembly was heated for 30 seconds on a heat block at 120°C.
- the pH of the silver iodobromide emulsion thus obtained was adjusted to cause sedimentation and after removing excessive salts, the pH of the emulsion was adjusted to 6.0 to provide 400 g of the silver iodobromide emulsion.
- a photosensitive coating composition was prepared by the following manner.
- a protective layer was formed on the photosensitive layer thus formed by the following manner.
- a mixture of the foregoing components was coated on the photosensitive layer at a wet thickness of 25 um.
- a dye-fixing material containing a dye-fixing agent was by the following manner.
- solution A was uniformly coated on the layer thus formed at a wet thickness of 60 ⁇ m.
- This coating sample was dried and used as a dye-fixing material (hereinafter "sheet A”).
- sheet A a dye-fixing material
- solution B a coating solution
- a dye-fixing material was obtained in the same manner as above (this dye-fixing material being hereinafter referred to "sheet B").
- the light-sensitive material as obtained above was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
- each of the dye-fixing materials as prepared above was closely brought into contact with the light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.
- Example 21 A sample was prepared in the same manner as in Example 21 except that 0.8 g of guanidine trichloroacetate was used as a base precursor in the solution A, and then treated in the same manner as in Example 21. The results obtained are shown below.
- Example 21 The same procedure as in Example 21 was repeated except that each of the dye releasing redox compounds as shown below was used in place of the dye releasing redox compound (42). Thus, a dispersion of dye releasing redox compound was prepared.
- Example 24 is an example in which an organic silver salt oxidizing agent was used.
- a benzotriazole silver emulsion was prepared by the following manner.
- a photosensitive coating composition was prepared by the following manner.
- the sheet A and sheet B as used in Example 21 were respectively used.
- the light-sensitive material as obtained above was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
- each of the dye-fixing materials (sheet A and sheet B) was closely brought into contact with the exposed light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.
- each of the solution (hereinafter “solutions D, E, F, G and H”, respectively) was uniformly coated on a layer containing the dye-fixing agent as in Example 21 at a wet thickness of 60 pm. Then, each coated sample was dried to prepare dye-fixing materials (hereinafter “sheets D, E, F, G and H", respectively).
- hydrophilic thermal solvents used are as follows.
- the light-sensitive material as obtained in Example 24 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
- each of the dye-fixing materials was closely brought into contact with the exposed light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Claims (17)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP42092/83 | 1983-03-16 | ||
JP4209283A JPS59168439A (ja) | 1983-03-16 | 1983-03-16 | 乾式画像形成方法 |
JP55172/83 | 1983-04-01 | ||
JP5517283A JPS59182447A (ja) | 1983-04-01 | 1983-04-01 | 乾式画像形成のための色素固定材料 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0119615A2 EP0119615A2 (fr) | 1984-09-26 |
EP0119615A3 EP0119615A3 (en) | 1984-12-12 |
EP0119615B1 true EP0119615B1 (fr) | 1988-01-13 |
Family
ID=26381736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19840102945 Expired EP0119615B1 (fr) | 1983-03-16 | 1984-03-16 | Procédé de formation d'images à sec |
Country Status (3)
Country | Link |
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EP (1) | EP0119615B1 (fr) |
CA (1) | CA1243536A (fr) |
DE (1) | DE3468751D1 (fr) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6291942A (ja) * | 1985-10-18 | 1987-04-27 | Fuji Photo Film Co Ltd | 画像形成方法 |
DE3539996A1 (de) * | 1985-11-12 | 1987-05-21 | Agfa Gevaert Ag | Waermeentwicklungsverfahren und hierfuer geeignetes farbfotografisches aufzeichnungsmaterial |
US6277537B1 (en) * | 1991-12-06 | 2001-08-21 | Eastman Kodak Company | Dye diffusion image separation systems with thermal solvents |
US5240809A (en) * | 1992-04-20 | 1993-08-31 | Minnesota Mining And Manufacturing Company | Imageable articles having dye selective interlayers |
US5238792A (en) * | 1992-04-20 | 1993-08-24 | Minnesota Mining And Manufacturing Company | Imageable articles having dye selective interlayers |
US5264321A (en) * | 1992-07-16 | 1993-11-23 | Minnesota Mining And Manufacturing Company | Photothermographic elements with novel layer structures |
US5275927A (en) * | 1992-07-16 | 1994-01-04 | Minnesota Mining And Manufacturing Company | Photothermographic articles containing novel barrier layers |
US5262272A (en) * | 1992-10-08 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Dye permeable polymer interlayers |
EP0687572B1 (fr) | 1994-06-15 | 1997-08-20 | Agfa-Gevaert N.V. | Méthode pour l'enregistrement par la chaleur |
DE69505605T2 (de) | 1994-07-13 | 1999-05-27 | Agfa-Gevaert N.V., Mortsel | Wärmeempfindliches Aufzeichnungsmaterial |
EP0775595B1 (fr) | 1995-11-27 | 1999-09-15 | Agfa-Gevaert N.V. | Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant |
EP0775592B1 (fr) | 1995-11-27 | 2002-09-11 | Agfa-Gevaert | Procédé thermique pour former des images |
EP0782043B1 (fr) | 1995-12-27 | 2003-01-15 | Agfa-Gevaert | Matériel thermographique pour l'enregistrement avec reproduction améliorée du ton |
EP0845709B1 (fr) | 1996-11-29 | 2006-01-18 | Agfa-Gevaert | Elément d'enregistrement thermosensible et méthode pour la fabrication d'un cliché pour l'imprimerie utilisant cet élément |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL274438A (fr) * | 1961-02-17 | |||
US3438776A (en) * | 1964-12-28 | 1969-04-15 | Eastman Kodak Co | Non-aqueous silver halide photographic process |
DE1572048C3 (de) * | 1965-09-10 | 1978-10-26 | Hoechst Ag, 6000 Frankfurt | Wärmeentwickelbares Diazotypiematerial |
JPS57179840A (en) * | 1981-04-30 | 1982-11-05 | Fuji Photo Film Co Ltd | Heat developing color photosensitive material |
JPS57198458A (en) * | 1981-06-01 | 1982-12-06 | Fuji Photo Film Co Ltd | Heat developing color photosensitive material |
-
1984
- 1984-03-16 DE DE8484102945T patent/DE3468751D1/de not_active Expired
- 1984-03-16 CA CA000449791A patent/CA1243536A/fr not_active Expired
- 1984-03-16 EP EP19840102945 patent/EP0119615B1/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1243536A (fr) | 1988-10-25 |
EP0119615A3 (en) | 1984-12-12 |
EP0119615A2 (fr) | 1984-09-26 |
DE3468751D1 (en) | 1988-02-18 |
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