JPH057698B2 - - Google Patents
Info
- Publication number
- JPH057698B2 JPH057698B2 JP5185785A JP5185785A JPH057698B2 JP H057698 B2 JPH057698 B2 JP H057698B2 JP 5185785 A JP5185785 A JP 5185785A JP 5185785 A JP5185785 A JP 5185785A JP H057698 B2 JPH057698 B2 JP H057698B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver
- dye
- heat
- image
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 claims description 78
- 239000000463 material Substances 0.000 claims description 65
- 239000000126 substance Substances 0.000 claims description 45
- 229910052709 silver Inorganic materials 0.000 claims description 44
- 239000004332 silver Substances 0.000 claims description 44
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 62
- 239000000975 dye Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 30
- 108010010803 Gelatin Proteins 0.000 description 21
- 229920000159 gelatin Polymers 0.000 description 21
- 235000019322 gelatine Nutrition 0.000 description 21
- 235000011852 gelatine desserts Nutrition 0.000 description 21
- 239000008273 gelatin Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 238000011161 development Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 150000003378 silver Chemical class 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 4
- WVKWKEWFTVEVCF-UHFFFAOYSA-N 2h-benzotriazole-4-sulfonic acid Chemical class OS(=O)(=O)C1=CC=CC2=NNN=C12 WVKWKEWFTVEVCF-UHFFFAOYSA-N 0.000 description 4
- PLYFWZGSBMDRKW-UHFFFAOYSA-N 2h-benzotriazole-4-sulfonic acid;silver Chemical compound [Ag].OS(=O)(=O)C1=CC=CC2=NNN=C12 PLYFWZGSBMDRKW-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001240 enamine group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229960005219 gentisic acid Drugs 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 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 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GVTLFGJNTIRUEG-ZHACJKMWSA-N (e)-n-(3-methoxyphenyl)-3-phenylprop-2-enamide Chemical compound COC1=CC=CC(NC(=O)\C=C\C=2C=CC=CC=2)=C1 GVTLFGJNTIRUEG-ZHACJKMWSA-N 0.000 description 1
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- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- SPIDTRPQUQLJAY-UHFFFAOYSA-N silver;1h-1,2,4-triazole Chemical compound [Ag].C=1N=CNN=1 SPIDTRPQUQLJAY-UHFFFAOYSA-N 0.000 description 1
- VMPMKNVWTFEJAO-UHFFFAOYSA-N silver;2h-tetrazole Chemical compound [Ag].C=1N=NNN=1 VMPMKNVWTFEJAO-UHFFFAOYSA-N 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
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- 229950000329 thiouracil Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 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
- YFDSDPIBEUFTMI-UHFFFAOYSA-N tribromoethanol Chemical compound OCC(Br)(Br)Br YFDSDPIBEUFTMI-UHFFFAOYSA-N 0.000 description 1
- 229950004616 tribromoethanol Drugs 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- INDZTCRIYSRWOH-UHFFFAOYSA-N undec-10-enyl carbamimidothioate;hydroiodide Chemical compound I.NC(=N)SCCCCCCCCCC=C INDZTCRIYSRWOH-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
- G03C8/4033—Transferable dyes or precursors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
[産業上の利用分野]
本発明は熱源像によつて形成された拡散性の色
素を転写してカラー画像を形成せしめる熱現像カ
ラー感光材料に関し、特に熱現像によつて現像剤
の酸化体と反応して拡散性の色素を放出する新規
な色素供与物質を含有する熱現像カラー感光材料
に関する。
[従来技術]
従来から知られている感光性ハロゲン化銀を使
用する写真法は感光性、階調性および画像保存性
等において他の写真法に勝るものであり、最も広
く実用化されてきた写真法である。
しかしながら、この方法においては現像、定着
および水洗などの処理工程に湿式処理法を用いる
ために、処理に時間と手間がかかり、また処理薬
品による人体への影響が懸念されたり、或いは処
理室や作業者に対する上記薬品による汚染が心配
されたり、更には廃液による公害の発生への配慮
といつた多くの問題点が存在している。従つて感
光性ハロゲン化銀を用いかつ乾式処理の可能な感
光材料の開発が望まれていた。
上記乾式処理写真法に関しては多くの提案がな
されているが、なかでも現像工程を熱処理で行な
い得る熱現像感光材料は上記要望に適つた感光材
料として注目を集めている。
この様な熱現像感光材料については、例えば特
公昭43−4921号および同43−4924号公報にその記
載があり、有機銀塩、ハロゲン化銀および還元剤
から成る感光材料が開示されている。
かかる熱現像感光材料に改良を加え、種々の方
法によつて色画像を得る試みがなされている。
例えば、米国特許第3531286号、同第3761270号
および同第3764328号等の各明細書中に芳香族第
1級アミン現像主薬の酸化体とカプラーとの反応
によつて色画像を形成させる熱現像カラー感光材
料が開示されている。
また、リサーチ・デイスクロージヤー15108号
および同15127号には、スルホンアミドフエノー
ル或いはスルホンアミドアニリンの誘導体現像主
薬の酸化体とカプラーとの反応によつて色画像を
形成させる熱現像カラー感光材料が開示されてい
る。しかし、これらの方法においては、熱現像
後、露光部に還元銀の像と色画像とが同時に生ず
るため、色画像が濁るという問題点があつた。な
お、この問題点を解決する方法として、銀像を液
体処理により取り除くか、色素のみを他の層、例
えば受像層を有する受像シートに転写する方法が
あるが、未反応物と色素を区別して色素のみを転
写することは容易でないという問題点を有してい
る。
また、リサーチ・デイスクロージヤー16966号
に色素部を有する有機イミノ銀塩を用い、熱現像
によつて露光部でイミノ基を遊離させ、溶剤を用
いて転写紙としての受像層上に色画像を形成させ
る熱現像カラー感光材料が開示されている。しか
し、この方法では光の当つていない部分での色素
の遊離を抑制することが困難であり、鮮明な色画
像を得ることができないという問題点を有してい
る。
また、特開昭52−105821号、同52−105822号、
同56−50328号公報、米国特許第4235957号明細
書、リサーチ・デイスクロージヤー14448号、同
15227号および同18137号等に感熱銀色素漂白法に
よつてポジの色画像を形成させる熱現像カラー感
光材料が開示されている。しかし、この方法にお
いては、色素の漂白を速めるための活性化剤を含
むシートを重ねて加熱するなどの余分な工程と写
真構成材料が必要であり、かつ得られた色画像が
長期の保存中に、共存する遊離銀などによつて
徐々に還元、漂白されるという問題点を有してい
る。
また、米国特許第3180732号、同第3985565号お
よび同第4022617号の各明細書中並びにリサー
チ・デイスクロージヤー12533号にロイコ色素を
利用して色画像を形成させる熱現像カラー感光材
料が開示されている。しかし、この方法ではロイ
コ色素を安定に写真感光材料に内蔵することは困
難で、保存時に徐々に着色するという問題点を有
している。
更にまた、特開昭57−179840号公報には、色素
放出助剤および拡散性色素を放出する還元性色素
供与物質を用いて色画像を形成させる熱現像カラ
ー感光材料が開示されている。しかし、この方法
では、色素放出助剤を用いることが必須要件であ
り、この色素放出助剤とは所謂、塩基もしくは塩
基のプレカーサーである。このように塩基もしく
は塩基プレカーサーを用いる技術では、有機銀塩
酸化剤を用いる熱現像感光材料においては塩基の
存在によつてカブリが増し、最高濃度が低くなる
という問題点を有している。
上述の熱現像感光材料の有する欠点を改良する
為に、特開昭57−186744号、同57−20725号、同
59−12431号、同59−48765号、同59−116642号、
同59−116643号、同59−174834号等の公報には、
還元剤の酸化体と反応して拡散性の色素を放出す
る色素供与物質を用いて転写画像を得る熱現像カ
ラー感光材料が開示されている。しかし、これら
の公報に記載の色素供与物質は、還元剤の酸化体
との反応(カツプリング反応)性が熱現像におけ
る条件においては低い為に、十分な最高濃度
(Dmax)を有する転写画像が得られないか、あ
るいはカブリ(Dmin)が高いという欠点を有し
ておりD max及びDminとも十分な性能を有す
る画像を提供できる色素放出型の色素供与物質が
いまだ得られていない。
[発明の目的]
本発明の目的は、上述の従来の色素供与物質が
有している問題点を解決することであり、即ち、
本発明の第1の目的は新規な色素供与物質を含有
する熱現像カラー感光材料を提供することにあ
る。本発明の第2の目的は、画像の濃度が大き
く、かつカブリの少ないいカラー画像を得ること
ができる熱現像カラー感光材料を提供することに
ある。
[発明の構成]
本発明者等は上記目的を達成すべく鋭意研究の
結果、支持体上に少なくとも感光性ハロゲン化
銀、バインダー、還元剤および下記一般色(1)で表
わされる色素供与物質を有する熱現像カラー感光
材料によつて本発明の上記目的が達成されること
を見い出した。
一般式 (1)
式中、Xは酸素原子又はイオウ原子を表わし、
Yはベンゼン環又はナフタレン環を形成するのに
必要な原子の集まりを表わし、Jは2価の結合基
を表わし、Dは拡散性の色素の残基を表わし、n
は0又は1を表わす。
[発明の具体的構成]
前記一般式(1)において、Yはベンゼン環又はナ
フレタン環を形成するのに必要な原子の集まりを
表わし、
[Industrial Application Field] The present invention relates to a heat-developable color photosensitive material that forms a color image by transferring a diffusible dye formed by a heat source image, and particularly relates to a heat-developable color photosensitive material that forms a color image by transferring a diffusible dye formed by a heat source image. The present invention relates to a heat-developable color photosensitive material containing a novel dye-providing substance that releases a diffusible dye upon reaction. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may affect the human body, or the processing room and work area may be affected. There are many problems, such as concerns about contamination of people by the above-mentioned chemicals, and further consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be carried out by heat treatment are attracting attention as photosensitive materials that meet the above-mentioned demands. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, and a reducing agent. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, and U.S. Pat. No. 3,764,328 disclose thermal development in which a color image is formed by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler. A color photosensitive material is disclosed. Further, Research Disclosure No. 15108 and No. 15127 disclose a heat-developable color photosensitive material in which a color image is formed by the reaction of an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent with a coupler. has been done. However, in these methods, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in the problem that the color image becomes cloudy. To solve this problem, there is a method of removing the silver image by liquid processing or transferring only the dye to another layer, such as an image receiving sheet having an image receiving layer, but it is necessary to distinguish between unreacted materials and the dye. The problem is that it is not easy to transfer only the dye. In addition, using an organic imino silver salt having a dye part in Research Disclosure No. 16966, the imino group is liberated in the exposed area by heat development, and a color image is transferred onto the image-receiving layer as a transfer paper using a solvent. A heat-developable color photosensitive material is disclosed. However, this method has the problem that it is difficult to suppress the release of dye in areas not exposed to light, and it is not possible to obtain clear color images. Also, JP-A-52-105821, JP-A No. 52-105822,
Publication No. 56-50328, U.S. Patent No. 4235957, Research Disclosure No. 14448, U.S. Pat.
No. 15227 and No. 18137, etc., disclose heat-developable color photosensitive materials in which a positive color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Further, in the specifications of U.S. Patent No. 3180732, U.S. Patent No. 3985565, and U.S. Patent No. 4022617, as well as Research Disclosure No. 12533, heat-developable color photosensitive materials are disclosed that utilize leuco dyes to form color images. ing. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, JP-A-57-179840 discloses a heat-developable color photosensitive material in which a color image is formed using a dye-releasing aid and a reducing dye-providing substance that releases a diffusible dye. However, in this method, it is essential to use a dye release aid, and this dye release aid is a so-called base or a precursor of a base. As described above, the technique using a base or a base precursor has the problem that in a heat-developable photosensitive material using an organic silver salt oxidizing agent, the presence of the base increases fog and lowers the maximum density. In order to improve the drawbacks of the above-mentioned heat-developable photosensitive materials, Japanese Patent Application Laid-Open Nos. 57-186744, 57-20725, and
No. 59-12431, No. 59-48765, No. 59-116642,
Publications such as No. 59-116643 and No. 59-174834 include
A heat-developable color photosensitive material is disclosed in which a transferred image is obtained using a dye-providing substance that reacts with an oxidized form of a reducing agent to release a diffusible dye. However, the dye-providing substances described in these publications have low reaction (coupling reaction) with the oxidized form of the reducing agent under the conditions of thermal development, so it is difficult to obtain transferred images with sufficient maximum density (Dmax). However, a dye-releasing dye-donating material that can provide an image with sufficient performance in both D max and Dmin has not yet been obtained. [Object of the invention] The object of the present invention is to solve the problems of the above-mentioned conventional dye-providing substances, namely:
A first object of the present invention is to provide a heat-developable color photosensitive material containing a novel dye-providing substance. A second object of the present invention is to provide a heat-developable color photosensitive material capable of obtaining color images with high image density and low fog. [Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have prepared at least a photosensitive silver halide, a binder, a reducing agent, and a dye-providing substance represented by the general color (1) below on a support. It has been found that the above objects of the present invention can be achieved by a heat-developable color photosensitive material having the following properties. General formula (1) In the formula, X represents an oxygen atom or a sulfur atom,
Y represents a collection of atoms necessary to form a benzene ring or a naphthalene ring, J represents a divalent bonding group, D represents a residue of a diffusible dye, and n
represents 0 or 1. [Specific structure of the invention] In the general formula (1), Y represents a collection of atoms necessary to form a benzene ring or a naprethane ring,
【式】で表わされるフエノール又は
ナフトールは環上に置換基を有していても良い。
好ましい置換基としては、ハロゲン原子(例えば
塩素原子、臭素原子)、アルキル基(例えばメチ
ル基、エチル基、イソプロピル基)、シクロアル
キル基(例えばシクロヘキシル基)、アリール基
(例えばフエニル基)、アシル基(例えばアセチル
基)、アルキルオキシカルボニル基(例えばメチ
ルオキシカルボニル基)、アリールオキシカルボ
ニル基(例えばフエニルオキシカルボニル基)、
アルキルスルホニル基(例えばメチルスルホニル
基)、アリールスルホニル基(例えばフエニルス
ルホニル基)、カルバモイル基、スルフアモイル
基、アシルオキシ基(例えばアセチルオキシ基)、
アミノ基、アルコキシ基(例えばメトキシ基、エ
トキシ基)、アリールオキシ基(例えばメチルカ
ルボニルオキシ基)、シアノ基、ウレイド基、ア
ルキルチオ基(例えばメチルチオ基)、アリール
チオ基(例えばフエニルチオ基)、カルボキシ基、
スルホ基又は複素環残基(例えばピリジル基)等
が挙あげられ、これらの置換基はさらに水酸基、
カルボキシ基、スルホ基、アルコキシ基(例えば
メトキシ基)、シアノ基、ニトロ基、アルキル基
(例えばメチル基、エチル基)、アリール基(例え
ばフエニル基)、アリールオキシ基(例えばフエ
ニルオキシ基)、アシルオキシ基(例えばアセチ
ルオキシ基)、アシル基(例えばアセチル基、イ
ソプロピルカルボニル基)、スルフアモイル基、
カルバモイル基、イミド基、ハロゲン原子(例え
ば塩素原子、臭素原子)等で置換されていてもよ
い。尚、置換基は同一又は異なるものを2つ以上
有していてもよい。
さらに上記の置換基の少なくとも1つは、前記
一般式(1)で表わされる色素供与物質を非拡散性に
するためにバラスト基又はバラスト基で置換され
た基であることが好ましい。
本発明のバラスト基としては、炭素原子数8個
以上(より好ましくは12個以上)の有機基、又は
スルホ基、カルボキシ基等の親水性基、あるいは
8個以上(より好ましくは12個以上)の炭素原子
とスルホ基、カルボキシ基等の親水性基を共に有
する基等が挙げられる。別の特に好ましいバラス
ト基としては、ポリマー鎖を挙げることができ
る。
前記一般式(1)において、Jで表わされる2価の
結合基としては好ましくは下記一般式で表わされ
る基である。
一般式(2) −O−(R1)n−−
一般式(3)The phenol or naphthol represented by the formula may have a substituent on the ring.
Preferred substituents include halogen atoms (e.g. chlorine atom, bromine atom), alkyl groups (e.g. methyl group, ethyl group, isopropyl group), cycloalkyl groups (e.g. cyclohexyl group), aryl groups (e.g. phenyl group), acyl groups. (e.g. acetyl group), alkyloxycarbonyl group (e.g. methyloxycarbonyl group), aryloxycarbonyl group (e.g. phenyloxycarbonyl group),
Alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), carbamoyl group, sulfamoyl group, acyloxy group (e.g. acetyloxy group),
Amino group, alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group (e.g. methylcarbonyloxy group), cyano group, ureido group, alkylthio group (e.g. methylthio group), arylthio group (e.g. phenylthio group), carboxy group,
Examples include a sulfo group or a heterocyclic residue (e.g. pyridyl group), and these substituents further include a hydroxyl group,
Carboxy group, sulfo group, alkoxy group (e.g. methoxy group), cyano group, nitro group, alkyl group (e.g. methyl group, ethyl group), aryl group (e.g. phenyl group), aryloxy group (e.g. phenyloxy group), acyloxy group (e.g. acetyloxy group), acyl group (e.g. acetyl group, isopropylcarbonyl group), sulfamoyl group,
It may be substituted with a carbamoyl group, an imide group, a halogen atom (for example, a chlorine atom, a bromine atom), or the like. In addition, two or more substituents may be the same or different. Furthermore, at least one of the above substituents is preferably a ballast group or a group substituted with a ballast group in order to render the dye-donating substance represented by the general formula (1) non-diffusible. The ballast group of the present invention is an organic group having 8 or more carbon atoms (more preferably 12 or more), or a hydrophilic group such as a sulfo group or a carboxy group, or a hydrophilic group having 8 or more carbon atoms (more preferably 12 or more). Examples include groups having both a carbon atom and a hydrophilic group such as a sulfo group or a carboxy group. Another particularly preferred ballast group can include polymer chains. In the general formula (1), the divalent bonding group represented by J is preferably a group represented by the following general formula. General formula (2) -O-(R 1 ) n -- General formula (3)
【式】 一般式(4) −NHCO−(R1)n−− 一般式(5) −CONH−(R1)n−− 一般式(6) −NHCONH−(R1)n−− 一般式(7) −NHSO2−(R1)n−− 一般式(8) −NHSO2NH−(R1)n−− 一般式(9) −S−(R1)n−− 一般式(10)[Formula] General formula (4) −NHCO− (R 1 ) n −− General formula (5) −CONH− (R 1 ) n −− General formula (6) −NHCONH− (R 1 ) n −− General formula (7) −NHSO 2 −(R 1 ) n −− General formula (8) −NHSO 2 NH−(R 1 ) n −− General formula (9) −S−(R 1 ) n −− General formula (10) )
【式】 一般式(11) −SO2NH−(R1)n−− 一般式(12)[Formula] General formula (11) −SO 2 NH− (R 1 ) n −− General formula (12)
【式】
一般式(13) −(R1)n−−
式中、R1はアルキレン基、アリーレン基又は
アルキレン基とアリーレン基とを組み合せてなる
2価の基(例えばアラルキレン基等)を表わし、
このR1は置換基を有していてもよい。R2は水素
原子又はアルキル基を表わし、m=0、1又は2
の整数を表わす。
前記一般式(1)において、Dで表わされる拡散性
の色素の残基としては、色素の拡散性のために分
子量が800以下、より好ましくは600以下であるこ
とが好ましく、アゾ色素、アゾメチン色素、アン
トラキノン色素、ナフトキノン色素、スチリル色
素、ニトロ色素、キノリン色素、カルボニル色
素、フタロシアニン色素等の残基が挙げられる。
これらの色素残基は、熱現像時或いは転写時に複
色可能な一時短波化された形でもよい。また、こ
れらの色素残基は画像の耐光性を上げる目的で、
例えば特開昭59−48765号、同59−124337号に記
載されているキレート可能な色素残基も好ましい
一形態である。
本発明の前記一般式(1)で表わされる色素供与物
質の代表的具体例を以下に示すが、本発明はこれ
らに限定されるものではない。
本発明の色素供与物質は、例えば次のようにし
て合成される。
合成例 例示色素供与物質(10)の合成
中間体(A)の合成
2−アミノ−4,6−ジクロル−5−メチルフ
エノールの塩酸塩140gを800mlのアセトニトリル
と200mlのピリジンの混合溶液に溶解し、n−ニ
トロ安息香酸クロライド(167g)のアセトニト
リル(200ml)溶液を滴下し、2時間還流した。
この反応液を300mlに濃縮し、75gの水酸化ナト
リウムを含む水(800ml)とエタノール(400ml)
を加え、室温で1時間攪拌し、塩酸で中和して、
析出する固体をろ別して、2−(m−ニトロベン
ゾイルアミノ)−4,6−ジクロル−5−メチル
フエノール157gを得た。
このフエノール誘導体136.4gを用いて特願昭
59−35238号明細書の18〜19頁に記載の合成法と
同様に亜硝酸による酸化、接触水素添加による還
元及びベンジル化を経由して、2−メチル−3−
クロル−4−ベンジルオキシ−5−(m−ニトロ
ベンゾイル)アミノフエノール73gを得た。
このフエノール誘導体39.7gとα−ブロモ−γ
−(p−スルホ)フエニル酪酸エチル35.1gを用
いて特願昭59−35238号明細書の23頁に記載の方
法と同様に反応させて中間体(A)43gを得た。
中間体 (A)
モノマーの合成
中間体(A)(26.7g)を常法によりメタクリル酸
クロライドと反応させた後、チオニルクロライド
によりカルボキシ基及びスルホ基を共に酸クロラ
イドに変え、氷水中に加えてカルボニルクロライ
ドのみ加水分解しアセトニトリルにより再結晶し
て、p−[γ−カルボキシ−γ−{2−メチル−3
−クロル−4−ヒドロキシ−5−(m−メタクリ
ロイルアミノ)ベンゾイルアミノ}フエニルオキ
シ]プロピルベンゼンスルホニルクロライド24.8
gを得た。続いて、この酸クロライド24.8gと2
−(m−アミノ)フエニルアゾ−4−メトキシ−
1−ナフトール11.7gとを反応させモノマー25g
を得た。
例示色素供与物質(10)の合成
12gの上記モノマーとn−ブチルアクリレート
8gを150mlのジオキサンに溶解し、窒素ガスを
導入しながら80〜82℃に加熱し、この温度を維持
しながら、2,2′−アゾビスイソブチロニトリル
600mlを加え、4時間反応させた。反応液を1
の水に注加し、沈殿をろ別し、この沈殿を200ml
の酢酸エチルに溶解し、硫酸マグネシウムで乾燥
させた後、ろ過した。ろ液を濃縮、乾固させて目
的物18gを得た。
本発明の色素供与物質は単独で用いてもよい
し、2つ以上用いてもよい。その使用量は限定的
でなく、色素供与物質の種類、単用かまたは2種
以上の併用使用か、或いは本発明の感光材料の写
真構成層が単層かまたは2層以上の重層か等に応
じて決定すればよいが、例えばその使用量は1m2
当たり0.005g〜50g、好ましくは0.1g〜10g用
いることができる。
本発明に用いる色素供与物質を熱現像カラー感
光材料の写真構成層に含有せしめる方法は任意で
あり、例えば低沸点溶媒(メタノール、エタノー
ル、酢酸エチル等)または高沸点溶媒(ジブチル
フタレート、ジオクチルフタレート、トリクレジ
ルホスフエート等)に溶解した後、超音波分散す
るか、あるいはアルカリ水溶液(例えば、水酸化
ナトリウム10%水溶液等)に溶解した後、鉱酸
(例えば、塩酸または硝酸等)にて中和して用い
るか、あるいは適当なポリマーの水溶液(例え
ば、ゼラチン、ポリビニルブチラール、ポリビニ
ルピロリドン等)と共にボールミルを用いて分散
させた後、使用することができる。
本発明の熱現像カラー感光材料は、前記色素供
与物質と共に感光性ハロゲン化銀を含有する。
本発明に用いられる感光性ハロゲン化銀として
は、塩化銀、臭化銀、沃化銀、塩臭化銀、塩沃化
銀、沃臭化銀、塩沃臭化銀等があげられる。該感
光性ハロゲン化銀は、写真技術分野のシングルジ
エツト法やダブルジエツト法等の任意の方法で調
製することができるが、本発明に於いては、通常
のハロゲン化銀ゼラチン乳剤の調製方法に従つて
調製した感光性ハロゲン化銀を含む感光性ハロゲ
ン化銀乳剤が好ましい結果を与える。
該感光性ハロゲン化銀乳剤は、写真技術分野の
任意の方法で化学的に増感しても良い。かかる増
感法としては、金増感、イオウ増感、金−イオウ
増感、還元増感等各種の方法があげられる。
上記感光性乳剤中のハロゲン化銀は、粗粒子で
あつても微粒子であつても良いが、好ましい粒子
サイズは、その径が約0.001μm〜約1.5μmであり、
さらに好ましくは約0.01μm〜約0.5μmである。
上記のように調製された感光性ハロゲン化銀乳
剤を本発明の感光材料の構成層である熱現像性感
光層に最も好ましく適用することができる。
本発明において、他の感光性ハロゲン化銀の調
製法として、感光性銀塩形成成分を後述する有機
銀塩と共存させ、有機銀塩の一部に感光性ハロゲ
ン化銀を形成させることもできる。この調製法に
用いられる感光性銀塩形成成分としては、無機ハ
ロゲン化物、例えば、MXnで表わされるハロゲ
ン化物(ここで、MはH原子、NH4基または金
属原子を表わし、XはC、BrまたはIを表わ
し、nはMがH原子、NH4基の時は1、Mが金
属原子の時はその原子価を示す。金属原子として
は、リチウム、ナトリウム、カリウム、ルビジウ
ム、セシウム、銅、金、ベリリウム、マグネシウ
ム、カルシウム、ストロンチウム、バリウム、亜
鉛、カドミウム、水銀、アルミニウム、インジウ
ム、ランタン、ルテニウム、タリウム、ゲルマニ
ウム、錫、鉛、アンチモン、ビスマス、クロム、
モリブデン、タングステン、マンガン、レニウ
ム、鉄、コバルト、ニツケル、ロジウム、パラジ
ウム、オスミウム、イリジウム、白金、セリウム
等があげられる。)、含ハロゲン金属錯体(例え
ば、K2PtC6,K2PtBr6,HAuC4,(NH4)2
IrC6,(NH4)3IrC6,(NH4)2RuC6,
(NH4)3RuC6,(NH4)3RhC6,(NH4)3
RhBr6等)、オニウムハライド(例えば、テトラ
メチルアンモニウムブロマイド、トリメチルフエ
ニルアンモニウムブロマイド、セチルエチルジメ
チルアンモニウムブロマイド、3−メチルチアゾ
リウムブロマイド、トリメチルベンジルアンモニ
ウムブロマイドのような4級アンモニウムハライ
ド、テトラエチルフオスフオニウムブロマイドの
ような4級フオスフオニウムハライド、ベンジル
エチルメチルスルホニウムブロマイド、1−エチ
ルチアゾリウムブロマイドのような3級スルホニ
ウムハライド等)、ハロゲン化炭化水素(例えば、
ヨードホルム、ブロモホルム、四臭化炭素、2−
ブロモ−2−メチルプロパン等)、N−ハロゲン
化合物(N−クロロコハク酸イミド、N−ブロモ
コハク酸イミド、N−ブロモフタル酸イミド、N
−ブロモアセトアミド、N−ヨードコハク酸イミ
ド、N−ブロモフタラジノン、N−クロロフタラ
ジノン、N−ブロモアセトアニリド、N,N−ジ
ブロモベンゼンスルホンアミド、N−ブロモ−N
−メチルベンゼンスルホンアミド、1,3−ジブ
ロモ−4,4−ジメチルヒダントイン等)、その
他の含ハロゲン化合物(例えば塩化トリフエニル
メチル、臭化トリフエニルメチル、2−ブロモ酪
酸、2−ブロモエタノール等)などをあげること
ができる。
これら感光性ハロゲン化銀および感光性銀塩形
成成分は、種々の方法において組合せて使用で
き、使用量は、一層当り1m2に対して、0.001g
〜50gであることが好ましく、より好ましくは、
0.1g〜10gである。
本発明の熱現像カラー感光材料は、青色光、緑
色光、赤色光に感光性を有する各層、即ち熱現像
青感光性層、熱現像緑感光性層、熱現像赤感光性
層として多層構成とすることもできる。また、同
色感光性層に2層以上(例えば、高感度層と低感
度層)に分割して設けることもできる。
上記の場合、各々用いられる青感光性ハロゲン
化銀乳剤、緑感光性ハロゲン化銀乳剤、赤感光性
ハロゲン化銀乳剤は、前記ハロゲン化銀乳剤に各
種の分光増感色素を加えることによつて得ること
ができる。
本発明に用いられる代表的な分光増感色素とし
ては、例えばシアニン、メロシアニン、コンプレ
ツクス(3核又は4核の)シアニン、ホロポーラ
−シアニン、スチリル、ヘミシアニン、オキソノ
ール等があげられる。シアニン類の色素のうちで
チアゾリン、オキサゾリン、ピロリン、ピリジ
ン、オキサゾール、チアゾール、セレナゾール、
イミダゾールの様な塩基性核を有するものが、よ
り好ましい。この様な核にはアルキル基、アルキ
レン基、ヒドロキシアルキル基、スルホアルキル
基、カルボキシアルキル基、アミノアルキル基ま
たは縮合炭素環式または複素環色環を作る事の出
来るエナミン基を有していてもよい。また対称形
でも非対称形でもよく、またメチン鎖、ポリメチ
ン鎖にアルキル基、フエニル基、エナミン基、ヘ
テロ環置換基を有していてもよい。
メロシアニン色素は上記塩基性核の他に、例え
ばチオヒダントイン核、ローダニン核、オキサゾ
ツール酸核、チアゾリンチオン核、マロノニトリ
ル核、ピラゾロン核の様な酸性核を有していても
よい。これらの酸性核は更にアルキル基、アルキ
レン基、フエニル基、カルボキシアルキル基、ス
ルホアルキル基、ヒドロキシアルキル基、アルコ
キシアルキル基、アルキルアミン基又はヘテロ環
式核で置換されていてもよい。又必要ならばこれ
らの色素を組合わせて使用してもよい。更にアス
コルビン酸誘導体、アザインデンカドミウム塩、
有機スルホン酸等、例えば米国特許第2933390号、
同第2937089号の明細書等に記載されている様な
可視光を吸収しない超増感性添加剤を併用するこ
とができる。
これら色素の添加量はハロゲン化銀またはハロ
ゲン化銀形成成分1モル当り1×10-4モル〜1モ
ルである。更に好ましくは、1×10-4モル〜1×
10-1モルである。
本発明の熱現像カラー感光材料においては、必
要に応じて感度の上昇や現像性の向上を目的とし
て各種の有機銀塩を用いることができる。
本発明の熱現像カラー感光材料に用いられる有
機銀塩としては、特公昭43−4921号、同44−
26582号、同45−18416号、同45−12700号、同45
−22185号、特開昭49−52626号、同52−31728号、
同52−137321号、同52−141222号、同53−36224
号および同53−37610号等の各公報ならびに米国
特許第3330633号、同第3794496号、同第4105451
号、同第4123274号、同第4168980号等の各明細書
中に記載されているような脂肪族カルボン酸の銀
塩、例えばラウリン酸銀、ミリスチン酸銀、パル
ミチン酸銀、ステアリン酸銀、アラキドン酸銀、
ベヘン酸銀、α−(1−フエニルテトラゾールチ
オ)酢酸銀など、芳香族カルボン酸銀、例えば安
息香酸銀、フタル酸銀など、特公昭44−26582号、
同45−12700号、同45−18416号、同45−22185号、
特開昭52−31728号、同52−137321号、特開昭58
−118638号、同58−118639号等の各公報に記載さ
れているようなイミノ基の銀塩、例えばベンゾト
リアゾール銀、5−ニトロベンゾトリアゾール
銀、5−クロロベンゾトリアゾール銀、5−メト
キシベンゾトリアゾール銀、4−スルホベンゾト
リアゾール銀、4−ヒドロキシベンゾトリアゾー
ル銀、5−アミノベンゾトリアゾール銀、5−カ
ルボキシベンゾトリアゾール銀、イミダゾール
銀、ベンズイミダゾール銀、6−ニトロベンズイ
ミダゾール銀、ピラゾール銀、ウラゾール銀、
1,2,4−トリアゾール銀、1H−テトラゾー
ル銀、3−アミノ−5−ベンジルチオ−1,2,
4−トリアゾール銀、サツカリン銀、フタラジノ
ン銀、フタルイミドなど、その他2−メルカプト
ベンゾオキサゾール銀、メルカプトオキサジアゾ
ール銀、2−メルカプトベンゾチアゾール銀、2
−メルカプトベンズイミダゾール銀、3−メルカ
プト−4−フエニル−1,2,4−トリアゾール
銀、4−ヒドロキシ−6−メチル−1,3,3a,
7−テトラザインデン銀および5−メチル−7−
ヒドロキシ−1,2,3,4,6−ペンタザイン
デン銀などが挙げられる。以上の有機銀塩のうち
でもイミノ基の銀塩が好ましく、特にベンゾトリ
アゾール誘導体の銀塩、より好ましくはスルホベ
ンゾトリアゾール誘導体の銀塩が好ましい。
本発明に用いられる有機銀塩は、単独でも或い
は2種以上併用して用いてもよく、単離したもの
を適当な手段によりバインダー中に分散して使用
に供してもよいし、また適当なバインダー中で銀
塩を調製し、単離せずにそのまま使用に供しても
よい。
該有機銀塩の使用量は、感光性ハロゲン化銀1
モル当り0.01〜500モルであることが好ましく、
より好ましくは0.1モル〜100モルである。
本発明の熱現像カラー感光材料に用いられる還
元剤は、熱現像カラー感光材料の分野で通常用い
られるものを用いることができ、例えば米国特許
第3531286号、同第3761270号、同第3764328号各
明細書、またRD No.12146、同No.15108、同No.
15127および特開昭56−27132号公報等に記載のp
−フエニレンジアミン系およびp−アミノフエノ
ール系現像主薬、フオスフオロアミドフエノール
系およびフルホンアミドフエノール系現像主薬、
またヒドラゾン系発色現像主薬が挙げられる。ま
た、米国特許第3342599号、同第3719492号、特開
昭53−135628号、同54−79035号等に記載されて
いる発色現像主薬プレカーサー等も有利に用いる
ことができる。
特に好ましい還元剤として、特開昭56−146133
号に記載されている下記一般式(14)で表わされ
る還元剤が挙げられる。
一般式 (14)
式中、R3およびR4は水素原子、または置換基
を有してもよい炭素原子数1〜30(好ましくは1
〜4)のアルキル基を表わし、R3とR4とは閉環
して複素環を形成してもよい。R5,R6,R7およ
びR8は水素原子、ハロゲン原子、ヒドロキシ基、
アミノ基、アルコキシ基、アシルアミド基、スル
ホンアミド基、アルキルスルホンアミド基または
置換基を有してもよい炭素原子数1〜30(好まし
くは1〜4)のアルキル基を表わし、R5とR3お
よびR7とR4はそれぞれ閉環して複素環を形成し
てもよい。Mはアルカリ金属原子、アンモニウム
基、含窒素有機塩基または第4級窒素原子を含む
化合物を表わす。
上記一般式(14)における含窒素有機塩基とは
無機酸と塩を生成し得る塩基性を示す窒素原子を
含む有機化合物であり、特に重要な有機塩基とし
てはアミン化合物が挙げられる。そして鎖状のア
ミン化合物としては第1級アミン、第2級アミ
ン、第3級アミンなどが、また環状のアミン化合
物としては典型的なヘテロ環式有機塩基の例とし
て著名なピリジン、キノリン、ピペリジン、イミ
ダゾール等が挙げられる。この他ヒドロキシルア
ミン、ヒドラジン、アミジンなどの化合物も鎖状
のアミンとして有用である。また含窒素有機塩基
の塩としては上記のような有機塩基の無機酸塩
(例えば塩酸塩、硫酸塩、硝酸塩等)が好ましく
用いられる。
一方、上記一般式における第4級窒素を含む化
合物としては、4価の共有結合を有する窒素化合
物の塩または水酸化物等が挙げられる。
次に、前記一般式(14)で示される還元剤の好
ましい具体例を以下に示す。
上記一般式(14)で表わされる還元剤は、公知
の方法、例えばHouben−Weyl,Methodender
Organischen Chemie,BandXI/2645−703頁に
記載されている方法に従つて合成できる。
その他以下に述べるような還元剤を用いること
もできる。
例えば、フエノール類(例えばp−フエニルフ
エノール、p−メトキシフエノール、2,6−ジ
−tert−ブチル−p−クレゾール、N−メチル−
p−アミノフエノール等)、スルホンアミドフエ
ノール類[例えば4−ベンゼンスルホンアミドフ
エノール、2−ベンゼンスルホンアミドフエノー
ル、2,6−ジクロロ−4−ベンゼンスルホンア
ミドフエノール、2,6−ジブロモ−4−(p−
トルエンスルホンアミド)フエノール等]、また
はポリヒドロキシベンゼン類(例えばハイドロキ
ノン、tert−ブチルハイドロキノン、2,6−ジ
メチルハイドロキノン、クロロハイドロキノン、
カルボキシハイドロキノン、カテコール、3−カ
ルボキシカテコール等)、ナフトール類(例えば
α−ナフトール、β−ナフトール、4−アミノナ
フトール、4−メトキシナフトール等)、ヒドロ
キシビナフチル類およびメチレンビスナフトール
類[例えば1,1′−ジヒドロキシ−2,2′−ビナ
フチル、6,6′−ジブロモ−2,2′−ジヒドロキ
シ−1,1′−ビナフチル、6,6−ジニトロ−
2,2′−ジヒドロキシ−1,1′−ビナフチル、
4,4′−ジメトキシ−1,1′−ジヒドロキシ−
2,2′−ビナフチル、ビス(2−ヒドロキシ−1
−ナフチル)メタン等]、メチレンビスフエノー
ル類[例えば1,1−ビス(2−ヒドロキシ−
3,5−ジメチルフエニル)−3,5,5−トリ
メチルヘキサン、1,1−ビス(2−ヒドロキシ
−3−tert−ブチル−5−メチルフエニル)メタ
ン、1,1−ビス(2−ヒドロキシ−3,5−ジ
−tert−ブチルフエニル)メタン、2,6−メチ
レンビス(2−ヒドロキシ−3−tert−ブチル−
5−メチルフエニル)−4−メチルフエノール、
α−フエニル−α,α−ビス(2−ヒドロキシ−
3,5−ジ−tert−ブチルフエニル)メタン、α
−フエニル、α,α−ビス(2−ヒドロキシ−3
−tert−ブチル−5−メチルフエニル)メタン、
1,1−ビス(2−ヒドロキシ−3,5−ジメチ
ルフエニル)−2−メチルプロパン、1,1,5,
5−テトラキス(2−ヒドロキシ−3,5−ジメ
チルフエニル)−2,4−エチルペンタン、2,
2−ビス(4−ヒドロキシ−3,5−ジメチルフ
エニル)プロパン、2,2−ビス(4−ヒドロキ
シ−3−メチル−5−tert−ブチルフエニル)プ
ロパン、2,2−ビス(4−ヒドロキシ−3,5
−ジ−tert−ブチルフエニル)プロパン等]、ア
スコルビン酸類、3−ピラゾリドン類、ピラゾロ
ン類、ヒドラゾン類およびパラフエニレンジアミ
ン類が挙げられる。
これら還元剤は単独、或いは2種以上組合せて
用いることもできる。還元剤の使用量は、使用さ
れる感光性ハロゲン化銀の種類、有機酸銀塩の種
類およびその他の添加剤の種類などに依存する
が、通常は感光性ハロゲン化銀1モルに対して
0.01〜1500モルの範囲であり、好ましくは0.1〜
200モルである。
本発明の熱現像カラー感光材料に用いられるバ
インダーとしては、ポリビニルブチラール、ポリ
酢酸ビニル、エチルセルロース、ポリメチルメタ
クリレート、セルロースアセテートブチレート、
ポリビニルアルコール、ポリビニルピロリドン、
ゼラチンおよびフタル化ゼラチン等の合成或いは
天然の高分子物質を1又は2以上組合せて用いる
ことができる。特に、ゼラチンまたはその誘導体
とポリビニルピロリドン、ポリビニルアルコール
等の親水性ポリマーとを併用することは好まし
く、より好ましくは特開昭58−104249号に記載の
以下の如きバインダーである。
このバインダーは、ゼラチン及びビニルピロリ
ドン重合体を含むものである。ビニルピロリドン
重合体はビニルピロリドンの単一重合体であるポ
ロビニルピロリドンであつてもよいし、ビニルピ
ロリドンと共重合可能な他のモノマーの1又は2
以上との共重合体(クラフト共重合体を含む。)
であつてもよい。これらのポリマーはその重合度
に関係なく用いることができる。ポリビニルピロ
リドンは置換ポリビニルピロリドンであつてもよ
く、好ましいポリビニルピロリドンは分子量1000
〜400000のものである。ビニルピロリドンと共重
合可能な他のモノマーとしては、アクリル酸、メ
タクリル酸及びそのアルキルエステルの如き(メ
タ)アクリル酸エステル類、ビニルアルコール
類、ビニルイミダゾール類、(メタ)アクリルア
ミド類、ビニルカルビノール類、ビニルアルキル
エーテル類等のビニル系モノマー等が挙げられる
が、組成比の少なくとも20%(重量%、以下同
じ)はポリビニルピロリドンであることが好まし
い。かかる共重合体の好ましい例はその分子量が
5000〜400000のものである。
ゼラチンは石灰処理によるものでも酸処理によ
るものでもよく、オセインゼラチン、ピツグスキ
ンゼラチン、ハイドゼラチン又はこれらをエステ
ル化、フエニルカルバモイル化等とした変性ゼラ
チンであつてもよい。
上記バインダーにおいて、全バインダー量に対
しゼラチンが10〜90%であることが好ましく、よ
り好ましくは20〜60%であり、ビニルピロリドン
が5〜90%であることが好ましく、より好ましく
は10〜80%である。
上記バインダーは、他の高分子物質を含有して
もよく、ゼラチン及び分子量1000〜400000のポリ
ビニルピロリドンと他の1又は2以上の高分子物
質との混合物、ゼラチン及び分子量5000〜400000
のビニルピロリドン共重合体と他の1又は2以上
の高分子物質との混合物が好ましい。用いられる
他の高分子物質としては、ポリビニルアルコー
ル、ポリアクリルアミド、ポリメタクリルアミ
ド、ポリビニルブチラール、ポリエチレングリコ
ール、ポリエチレングルコールエステルや、或い
はセルロース誘導体等のタンパク質や、デンプ
ン、アラビアゴム等の多糖類のような天然物質が
挙げられる。これらは0〜85%、好ましくは0〜
70%含有されてもよい。
なお、上記ビニルピロリドン重合体は架橋ポリ
マーであつてもよいが、この場合、支持体状に塗
布した後に架橋させること(自然放置による架橋
反応の進行の場合を含む)が好ましい。
バインダーの使用量は、通常一層当り1m2に対
して0.05g〜50gであり、好ましくは0.1g〜10
gである。また、バインダーは、色素供与性物質
モノマー単位1gに対して0.1〜10g用いること
が好ましく、より好ましくは0.25〜4gである。
本発明の熱現像カラー感光材料に用いられる支
持体としては、例えばポリエチレンフイルム、セ
ルロースアセテートフイルムおよびポリエチレン
テレフタレートフイルム、ポリ塩化ビニル等の合
成プラスチツクフイルム、並びに写真用原紙、印
刷用紙、バライタ紙およびレジンコート紙等の紙
支持体、並びに上記の合成プラスチツクフイルム
に反射層を設けた支持体等が挙げられる。
特に本発明の熱現像カラー感光材料には各種の
熱溶剤が添加されることが好ましい。本発明の熱
溶剤とは熱現像および/または熱転写を促進する
物質であればよく、好ましくは常温下では固体、
半固体又は液体(好ましくは、常圧において沸点
100℃以上、より好ましくは150℃以上)であつて
加熱することによつてバインダー中で溶解又は溶
融する物質であつて、好ましくは尿素誘導体(例
えば、ジメチルウレア、ジエチルウレア、フエニ
ルウレア等)、アミド誘導体(例えば、アセトア
ミド、ベンズアミド等)、多価アルコール類(例
えば、1,5−ペンタンジオール、1,6−ペン
タンジオール、1,2−シクロヘキサンジオー
ル、ペンタエリスリトール、トリメチロールエタ
ン等)、又はポリエチレングリコール類が挙げら
れる。詳しい具体例としては、特願昭58−104249
に記載されている。これらの熱溶剤は単独でも二
種以上併用して用いても良い。
本発明の熱現像カラー感光材料には、上記各成
分以外に必要に応じ各種添加剤を添加することが
できる。例えば現像促進剤としては、米国特許第
3220840号、同第3531285号、同第4012260号、同
第4060420号、同第4088496号、同第4207392号各
明細書、RDNo.15733、同No.15734、同No.15776、
特開昭56−130745号、同56−132332号等に記載さ
れた尿素、グアニジウムトリクロロアセテート等
のアルカリ放出剤、特公昭45−12700号記載の有
機酸、米国特許第3667959号記載の−CO−,−
SO2−,−SO−基を有する非水性極性溶媒化合
物、米国特許第3438776号記載のメルトフオーマ
ー、米国特許第3666477号、特開昭51−19525号に
記載のポリアルキレングリコール類等がある。ま
た色調剤としては、例えば特開昭46−4928号、同
46−6077号、同49−5019号、同49−5020号、同49
−91215号、同49−107727号、同50−2524号、同
50−67132号、同50−67641号、同50−114217号、
同52−33722号、同52−99813号、同53−1020号、
同53−55115号、同53−76020号、同53−125014
号、同54−156523号、同54−156524号、同54−
156525号、同54−156526号、同55−4060号、同55
−4061号、同55−32015号等の公報ならびに西独
特許第2140406号、同第2147063号、同2220618号、
米国特許第3080254号、同第3847612号、同第
3782941号、同第3994732号、同第4123282号、同
第4201582号等の各明細書に記載されている化合
物であるフタラジノン、フタルイミド、ピラゾロ
ン、キナゾリノン、N−ヒドロキシナフタルイミ
ド、ベンツオキサジン、ナフトオキサジンジオ
ン、2,3−ジヒドロ−フタラジンジオン、2,
3−ジヒドロ−1,3−オキサジン−2,4−ジ
オン、オキシピリジン、アミノピリジン、ヒドロ
キシキノリン、アミノキノリン、イソカルボスチ
リル、スルホンアミド、2H−1,3−ベンゾチ
アジン−2,4−(3H)ジオン、ベンゾトリアジ
ン、メルカプトトリアゾール、ジメルカプトテト
ラザペンタレン、フタル酸、ナフタル酸、フタル
アミン酸等があり、これらの1つまたは、それ以
上とイミダゾール化合物との混合物、またフタル
酸、ナフタル酸等の酸または酸無水物の少なくと
も1つおよびフタラジン化合物の混合物、さらに
は、フタラジンとマレイン酸、イタコン酸、キノ
リン酸、ゲンチジン酸等の組合せ等を挙げること
ができる。また、特開昭58−189628合、同58−
193460号公報に記載された、3−アミノ−5−メ
ルカプト−1,2,4ートリアゾール類、3−ア
シルアミノ−5−メルカプト−1,2,4−トリ
アゾール類も有効である。
またさらに、カブリ防止剤としては、例えば、
特公昭47−11113号、特開昭49−90118号、同49−
10724号、同49−97613号、同50−101019号、同49
−130720号、同50−123331号、同51−47419号、
同51−57435号、同51−78227号、同51−104338
号、同53−19825号、同53−20923号、同51−
50725号、同51−3223号、同51−42529号、同51−
81124号、同54−51821号、同55−93149号等の公
報、ならびに英国特許第1455271号、米国特許第
3885968号、同第3700457号、同第4137079号、同
第4138265号、西独特許第2617907号等の各明細書
に記載されている化合物である第2水銀塩、或い
は酸化剤(例えば、N−ハロゲノアセトアミド、
N−ハロゲノコハク酸イミド、過塩素酸およびそ
の塩類、無機過酸化物、過硫酸塩等)、或いは、
酸およびその塩(例えば、スルフイン酸、ラウリ
ン酸リチウム、ロジン、ジテルペン酸、チオスル
ホン酸等)、或いはイオウ含有化合物(例えば、
メルカプト化合物放出性化合物、チオウラシル、
ジスルフイド、イオウ単体、メルカプト−1,
2,4−トリアゾール、チアゾリンチオン、ポリ
スルフイド化合物等)、その他、オキサゾリン、
1,2,4−トリアゾール、フタルイミド等の化
合物が挙げられる。さらに別のカブリ防止剤とし
て特開昭59−111636号に記載されているチオール
(好ましくはチオフエノール化合物)化合物も有
効である。
また、他のカブリ防止剤としては、特願昭59−
56506号に記載のハイドロキノン誘導体(例えば、
ジ−t−オクチルハイドロキノン、ドデカニルハ
イドロキノン等)や特願昭59−66380号に記載の
ハイドロキノン誘導体とベンゾトリアゾール誘導
体(例えば、4−スルホベンゾトリアゾール、5
−カルボキシベンゾトリアゾール等)との併用が
好ましく用いることができる。
また安定剤として特に処理後のプリントアウト
防止剤を同時に用いてもよく、例えば特開昭48−
45228号、同50−119624号、同50−120328号、同
53−46020号公報等に記載のハロゲン化炭化水素
類、具体的にはテトラブロモブタン、トリブロモ
エタノール、2−ブロモ−2−トリルアセトアミ
ド、2−ブロモ−2−トリルスルホニルアセトア
ミド、2−トリブロモメチルスルホニルベンゾチ
アゾール、2,4−ビス(トリブロモメチル)−
6−メチルトリアジンなどがあげられる。
また特公昭46−5393号、特開昭50−54329号、
同50−77034号各公報記載のように含イオウ化合
物を用いて後処理を行なつてもよい。
さらには、米国特許第3301678号、同第3506444
号、同第3824103号、同第3844788号各明細書に記
載のイソチウロニウム系スタビライザープレカー
サー、また米国特許第3669670号、同第4012260
号、同第4060420号明細書等に記載されたアクチ
ベータースタビライザープレカーサー等を含有し
てもよい。
また、シヨ糖、NH4Fe(SO4)2・12H2O等の水
放出剤を用いてもよく、さらにまた、特開昭56−
132332号のように水を供給し熱現像を行なつても
よい。
本発明の熱現像カラー感光材料には、さらに上
記成分以外に必要に応じて、分光増感染料、ハレ
ーシヨン防止染料、蛍光増白剤、硬膜剤、帯電防
止剤、可塑剤、延展剤等各種の添加剤、塗布助剤
等が添加される。
本発明の熱現像カラー感光材料は、基本的には
同一層中に(1)感光性ハロゲン化銀、(2)還元剤、(3)
色素供与物質及び(4)バインダーを含有し、さらに
必要に応じて(5)有機銀塩を含有することが好まし
い。
しかし、これらは必ずしも単一の写真構成層中
に含有させる必要はなく、例えば、感光性層を2
層に分け、前記(1)、(2)、(4)、(5)の成分を一方側の
感光性層に含有させ、この感光性層に隣接する他
方側の層に色素供与物質(3)を含有せしめる等、相
互に反応可能な状態であれば2以上の写真構成層
に分けて含有せしめてもよい。
また、感光性層を例えば、高感度層と低感度層
等の2層以上に分割して設けてもよく、さらに他
の感色性を異にする1又は2以上の感光性層を有
してもよいし、上塗り層、下塗り層、バツキング
層、中間層等各種の写真構成層を有していてもよ
い。
本発明の熱現像感光層と同様、保護層、中間
層、下塗層、バツク層、その他の写真構成層につ
いてもそれぞれの塗布液を調製し、浸漬法、エア
ーナイフ法、カーテン塗布法または米国特許第
3681294号に記載のホツパー塗布法等の各種の塗
布法により感光材料を作成することができる。
更に必要ならば、米国特許第2761791号および
英国特許第837095号に記載されている方法によつ
て2層またはそれ以上を同時に塗布することもで
きる。
本発明の熱現像カラー感光材料の写真構成層に
用いられる前記の成分は、支持体上に塗布され、
塗布の厚みは、乾燥後1〜1000μmが好ましく、
より好ましくは3〜20μmである。
本発明の熱現像カラー感光材料は、そのまま像
様露光した後、通常80℃〜200℃、好ましくは120
℃〜170℃の温度範囲で、1秒間〜180秒間、好ま
しくは1.5秒間〜120秒間加熱されるだけで発色現
像される。また、必要に応じて水不透過性材料を
密着せしめて現像してもよく、或いは露光前に70
℃〜180℃の温度範囲で予備加熱を施してもよい。
本発明による熱現像カラー感光材料には、種々
の露光手段を用いることができる。潜像は可視光
を含む輻射線の画像状露光によつて得られる。一
般には通常のカラープリントに使用される光源、
例えばタングステンランプ、水銀灯、キセノンラ
ンプ、レーザー光線、CRT光線等を光源として
用うることができる。
加熱手段は、通常の熱現像感光材料に適用し得
る方法がすべて利用でき、例えば加熱されたブロ
ツクないしプレートに接触させたり、熱ローラー
や熱ドラムに接触させたり、高温の雰囲気中を通
過させたり、あるいは高周波加熱を用いたり、さ
らには、本発明の感光材料中もしくは熱転写用受
像層(要素)中に導電性層を設け、通電や強磁界
によつて生ずるジユール熱を利用することもでき
る。加熱パターンは特に制限されることはなく、
あらかじめ予熱(プレヒート)した後、再度加熱
する方法をはじめ、高温で短時間、あるいは低温
で長時間、連続的に上昇、下降あるいは繰りかえ
し、さらには不連続加熱も可能ではあるが、簡便
なパターンが好ましい。また露光と加熱が同時に
進行する方式であつてもよい。
本発明に用いられる受像部材は、熱現像により
放出乃至形成された色素を受容する機能を有すれ
ばよく、色素拡散転写型感光材料に用いられる媒
染剤や特開昭57−207250号等に記載されたガラス
転移温度が40℃以上、250℃以下の耐熱性有機高
分子物質で形成されることが好ましい。
前記媒染剤の具体的な例としては、含窒素二
級、三級アミン類、含窒素複素環化合物、これら
の四級カチオン性化合物、米国特許第2548564号、
同2484430号、同3148061号、同3756814号に開示
されているビニルピリジンポリマーおよびビニル
ピリジニウムカチオンポリマー、米国特許第
2675316号に開示されているジアルキルアミノ基
を含むポリマー、米国特許第2882156号に開示さ
れているアミノグアニジン誘導体、特開昭54−
137333号に記載の共有結合性の反応性ポリマー、
米国特許第3625694号、同3859096号、英国特許第
1277453号、同2011012号に開示されているゼラチ
ンなどと架橋可能な媒染剤、米国特許第3958995
号、同2721852号、同2798063号に開示されている
水性ゾル型媒染剤、特開昭50−61228号に開示さ
れている水不溶性媒染剤、米国特許第3788855号、
西独特許出願(OLS)第2843320号、特開昭53−
30328号、同52−155528号、同53−125号、同53−
1024号、同54−74430号、同54−124726号、同55
−22766号、米国特許第3642482号、同3488706号、
同3557066号、同3271147号、同3271148号、特公
昭55−29418号、同56−36414号、同57−12139号、
RD12045(1974年)に開示されている各種媒染剤
をあげることができる。
特に有用な媒染剤はアンモニウム塩を含むポリ
マーで、米国特許第3709690号に記載の四級アミ
ノ基を含むポリマーである。アンモニウム塩を含
むポリマーとしては、例えばポリスチレン−コ−
N,N,N−トリ−n−ヘキシル−N−ビニルベ
ンジルアンモニウムクロライドで、スチレンとビ
ニルベンジルアンモニウムクロライドの比率は、
1:4〜4:1、好ましくは1:1である。
典型的な色素拡散転写用の受像層はアンモニウ
ム塩を含むポリマーをゼラチンと混合して支持体
上に塗布することにより得られる。
前記耐熱性有機高分子物質の例としては、分子
量2000〜85000のポリスチレン、炭素数4以下の
置換基をもつポリスチレン誘導体、ポリビニルシ
クロヘキサン、ポリビニルベンゼン、ポリビニル
ピロリドン、ポリビニルカルバゾル、ポリアリル
ベンゼン、ポリビニルアルコール、ポリビニルホ
ルマールおよびポリビニルブチラールなどのポリ
アセタール類、ポリ塩化ビニル、塩素化ポリエチ
レン、ポリ三塩化ふつ化エチレン、ポリアクリロ
ニトリル、ポリ−N,N−ジメチルアクリルアミ
ド、p−シアノフエニル基、ペンタクロロフエニ
ル基および2,4−ジクロロフエニル基をもつポ
リアクリレート、ポリアクリルクロロアクリレー
ト、ポリメチルメタクリレート、ポリエチルメタ
クリレート、ポリプロピルメタクリレート、ポリ
イソプロピルメタルクリレート、ポリイソブチル
メタクリレート、ポリ−tert−ブチルメタクリレ
ート、ポリシクロヘキシルメタクリレート、ポリ
エチレングリコールジメタクリレート、ポリ−2
−シアノ−エチルメタクリレート、ポリエチレン
テレフタレートなどのポリエステル類、ポリスル
ホン、ビスフエノールAポリカーボネート等のポ
リカーボネート類、ポリアンヒドライド、ポリア
ミド類並びにセルロースアセテート類等があげら
れる。また、Polymer Handbook 2nd ed.(J.
Brandrup,E.H.Immergut 編)John Wiley&
Sons出版、に記載されているガラス転移温度40
℃以上の合成ポリマーも有用である。これらの高
分子物質は、単独で用いられても、また複数以上
を組み合せて共重合体として用いてもよい。
特に有用なポリマーとしては、トリアセテー
ト、ジアセテートなどのセルロースアセテート、
ヘプタメチレンジアミンとテレフタル酸、フルオ
レンジプロピルアミンとアジピン酸、ヘキサメチ
レンジアミンとジフエン酸、ヘキサメチレンジア
ミンとイソフタル酸などの組み合せによるポリア
ミド、ジエチレングリコールとジフエニルカルボ
ン酸、ビス−p−カルボキシフエノキシブタンと
エチレングリコールなどの組み合せよるポリエス
テル、ポリエチレンテレフタレート、ポリカーボ
ネート、塩化ビニル等があげられる。これらのポ
リマーは改質されたものであつてもよい。たとえ
ば、シクロヘキサンジメタノール、イソフタル
酸、メトキシポリエチレン−グリコール、1,2
−ジカルボメトキシ−4−ベンゼンスルホン酸な
どを改質剤として用いたポリエチレンテレフタレ
ートも有効である。これらのうち特に好ましく
は、特願昭58−97907号に記載のポリ塩化ビニル
よりなる層及び特願昭58−128600号に記載のポリ
カーボネートと可塑剤よりなる層が挙げられる。
上記のポリマーは適当な溶剤に溶かして支持体
上に塗布して受像層とするか、あるいは上記ポリ
マーより成るフイルム状受像層を支持体にラミネ
ートして用いられるか、または支持体上に塗布す
ることなく、上記ポリマーより成る部材(例えば
フイルム)単独で受像層を構成すること(受像層
支持体兼用型)もできる。
さらに受像層としては、透明支持体上の受像層
の上にゼラチン分散した二酸化チタン等を含む不
透明化層(反射性層)を設けて構成することもで
きる。この不透明化層は、転写色画像を受像層の
透明支持体側から見ることにより反射型の色像が
得られる。
[実施例]
以下に本発明の実施例を示すが、本発明の実施
態様はこれらに限定されるものではない。
実施例 1
例示色素供与物質(10)730mgを酢酸エチル2.1ccに
溶解した。この溶液を界面活性剤を含む2.5%ゼ
ラチン水溶液3ccと混合し、水を加えて6.5ccとし
た後、ホモジナイザーで分散し、色素供与物質の
分散液を得た。
上記分散液6.5ccを450mgのポリビニルピロリド
ン(平均分子量30000)および1,5−ペンタン
ジオール500mgを含む水3.5ccと混合し、10%のグ
アニジントリクロル酢酸のエタノール液0.1ml及
び前記例示還元剤(R−3)200mgを加えた後、
3%のクエン酸でPHを5.5とした。この分散液に
平均粒径0.1μmの沃臭化銀乳剤を銀に換算して1
×10-3モル添加(ゼラチン85mg含有)し、水を加
えて15ccに仕上げた後ポリエチレンテレフタレー
ト支持体上に乾燥膜厚が8μmとなるようにワイヤ
ーバーにて塗布し感光層を塗設した。
得られた感光材料を乾燥後、16000CMSの白色
露光をステツプウエツジを通して与えた。
次いで、別にバライタ紙上に受像層材料として
のポリ塩化ビニル(分子量20000)を塗設した受
像シートの受像層面と前記露光済み感光材料の塗
布面とを重ね合わせて、150℃で1分間熱現像を
行ない、受像シートを剥がして受像シート上にマ
ゼンタの転写画像を得た。得られた転写画像の最
高反射濃度(Dmax)およびカブリ(Dmin)を
表−1に示す。
比較例 1
実施例1の感光材料において、色素供与物質を
下記比較色素供与物質(A)に代えた以外は実施例1
と同様の感光材料を作成し、実施例1と同様の熱
現像を行なつた。結果を表−1に示す。
[Formula] General formula (13) −(R 1 ) n −− In the formula, R 1 represents an alkylene group, an arylene group, or a divalent group formed by combining an alkylene group and an arylene group (for example, an aralkylene group, etc.) ,
This R 1 may have a substituent. R 2 represents a hydrogen atom or an alkyl group, m = 0, 1 or 2
represents an integer. In the general formula (1), the residue of the diffusible dye represented by D preferably has a molecular weight of 800 or less, more preferably 600 or less, for the sake of dye diffusivity, and includes azo dyes, azomethine dyes, etc. , anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like.
These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used to increase the light resistance of images.
For example, chelatable dye residues described in JP-A-59-48765 and JP-A-59-124337 are also preferred. Typical specific examples of the dye-providing substance represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. The dye-providing substance of the present invention is synthesized, for example, as follows. Synthesis Example Synthesis of Exemplary Dye Donor Substance (10) Synthesis of Intermediate (A) 140 g of hydrochloride of 2-amino-4,6-dichloro-5-methylphenol was dissolved in a mixed solution of 800 ml of acetonitrile and 200 ml of pyridine. A solution of n-nitrobenzoic acid chloride (167 g) in acetonitrile (200 ml) was added dropwise to the mixture, and the mixture was refluxed for 2 hours.
Concentrate this reaction solution to 300 ml, add water (800 ml) containing 75 g of sodium hydroxide and ethanol (400 ml).
was added, stirred at room temperature for 1 hour, neutralized with hydrochloric acid,
The precipitated solid was filtered off to obtain 157 g of 2-(m-nitrobenzoylamino)-4,6-dichloro-5-methylphenol. A patent application was made using 136.4g of this phenol derivative.
2-methyl-3-
73 g of chloro-4-benzyloxy-5-(m-nitrobenzoyl)aminophenol was obtained. 39.7g of this phenol derivative and α-bromo-γ
Using 35.1 g of ethyl -(p-sulfo)phenylbutyrate, the reaction was carried out in the same manner as described on page 23 of Japanese Patent Application No. 59-35238 to obtain 43 g of Intermediate (A). Intermediate (A) Synthesis of monomer Intermediate (A) (26.7 g) was reacted with methacrylic acid chloride in a conventional manner, then both the carboxy group and sulfo group were converted to acid chloride with thionyl chloride, and the mixture was added to ice water to hydrolyze only the carbonyl chloride. It was recrystallized from acetonitrile to give p-[γ-carboxy-γ-{2-methyl-3
-Chlor-4-hydroxy-5-(m-methacryloylamino)benzoylamino}phenyloxy]propylbenzenesulfonyl chloride 24.8
I got g. Next, 24.8g of this acid chloride and 2
-(m-amino)phenylazo-4-methoxy-
25g of monomer by reacting with 11.7g of 1-naphthol
I got it. Synthesis of Exemplary Dye-Providing Substance (10) 12 g of the above monomer and 8 g of n-butyl acrylate were dissolved in 150 ml of dioxane, heated to 80-82°C while introducing nitrogen gas, and while maintaining this temperature, 2. 2'-Azobisisobutyronitrile
600ml was added and reacted for 4 hours. 1 of the reaction solution
of water, filter out the precipitate, and add 200ml of this precipitate to
The solution was dissolved in ethyl acetate, dried over magnesium sulfate, and then filtered. The filtrate was concentrated and dried to obtain 18 g of the target product. The dye-providing substances of the present invention may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers. You can decide accordingly, but for example, the usage amount is 1 m 2
It can be used in an amount of 0.005g to 50g, preferably 0.1g to 10g. The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material using any method. tricresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.), and then dissolved in mineral acid (e.g., hydrochloric acid or nitric acid, etc.). It can be used after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.). The heat-developable color photosensitive material of the present invention contains photosensitive silver halide together with the dye-providing substance. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as a single-jet method or a double-jet method, but in the present invention, a conventional method for preparing a silver halide gelatin emulsion is used. Light-sensitive silver halide emulsions containing light-sensitive silver halides prepared accordingly give favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm,
More preferably, it is about 0.01 μm to about 0.5 μm. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an NH 4 group or a metal atom, and X represents C, Br or I, n is 1 when M is an H atom or NH 4 group, and the valence when M is a metal atom.Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, Gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium,
Examples include molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g., K 2 PtC 6 , K 2 PtBr 6 , HAuC 4 , (NH 4 ) 2
IrC 6 , (NH 4 ) 3 IrC 6 , (NH 4 ) 2 RuC 6 ,
(NH 4 ) 3 RuC 6 , (NH 4 ) 3 RhC 6 , (NH 4 ) 3
RhBr 6 , etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosph quaternary phosphonium halides such as onium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g.
Iodoform, bromoform, carbon tetrabromide, 2-
bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromo-2-methylpropane, etc.),
-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N
-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) etc. can be given. These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount used is 0.001 g per m 2 per layer.
It is preferable that it is ~50g, more preferably,
It is 0.1g to 10g. The heat-developable color photosensitive material of the present invention has a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. You can also. Further, the photosensitive layer of the same color can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, the merocyanine dye may have an acidic nucleus such as a thiohydantoin nucleus, rhodanine nucleus, oxazoturic acid nucleus, thiazolinthione nucleus, malononitrile nucleus, or pyrazolone nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts,
Organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,390;
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these dyes added is 1.times.10.sup. -4 mol to 1 mol per mol of silver halide or silver halide-forming component. More preferably, 1×10 −4 mol to 1×
10 -1 mole. In the heat-developable color photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts used in the heat-developable color photosensitive material of the present invention include Japanese Patent Publication No. 43-4921 and Japanese Patent Publication No. 44-4921;
No. 26582, No. 45-18416, No. 45-12700, No. 45
-22185, JP-A-49-52626, JP-A-52-31728,
No. 52-137321, No. 52-141222, No. 53-36224
No. 53-37610, and U.S. Patent No. 3330633, U.S. Patent No. 3794496, U.S. Patent No. 4105451
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, arachidone as described in the specifications of No. 4123274, No. 4168980, etc. acid silver,
Silver aromatic carboxylates such as silver behenate, silver α-(1-phenyltetrazolethio)acetate, etc., such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582,
45-12700, 45-18416, 45-22185,
JP-A-52-31728, JP-A-52-137321, JP-A-58
Silver salts of imino groups such as those described in publications such as No. 118638 and No. 58-118639, such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, and silver 5-methoxybenzotriazole. Silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver,
1,2,4-triazole silver, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,
4-triazole silver, saccharin silver, phthalazinone silver, phthalimide, etc. 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2
-Silver mercaptobenzimidazole, 3-mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene silver and 5-methyl-7-
Examples include silver hydroxy-1,2,3,4,6-pentazaindene. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred. The organic silver salts used in the present invention may be used alone or in combination of two or more, and isolated ones may be used by dispersing them in a binder by appropriate means, or they may be used in a suitable form. The silver salt may be prepared in a binder and used as is without isolation. The amount of the organic silver salt used is 1 photosensitive silver halide.
Preferably, it is 0.01 to 500 mol per mol,
More preferably, it is 0.1 mol to 100 mol. As the reducing agent used in the heat-developable color photosensitive material of the present invention, those commonly used in the field of heat-developable color photosensitive materials can be used, such as those disclosed in U.S. Pat. Specification, RD No. 12146, RD No. 15108, RD No.
15127 and p described in Japanese Patent Application Laid-Open No. 56-27132, etc.
- phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenol type and fluoramide phenol type developing agents,
Further examples include hydrazone color developing agents. Further, color developing agent precursors and the like described in U.S. Pat. No. 3,342,599, U.S. Pat. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (14) described in No. General formula (14) In the formula, R 3 and R 4 are hydrogen atoms, or have 1 to 30 carbon atoms (preferably 1 carbon atom), which may have a substituent.
-4) represents an alkyl group, and R 3 and R 4 may be ring-closed to form a heterocycle. R 5 , R 6 , R 7 and R 8 are hydrogen atoms, halogen atoms, hydroxy groups,
Represents an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R 5 and R 3 And R 7 and R 4 may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula (14) is an organic compound containing a basic nitrogen atom capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. Next, preferred specific examples of the reducing agent represented by the general formula (14) are shown below. The reducing agent represented by the above general formula (14) can be prepared by a known method such as Houben-Weyl, Methodender
It can be synthesized according to the method described in Organischen Chemie, Band XI/pages 2645-703. Other reducing agents as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1′ -dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol,
α-phenyl-α,α-bis(2-hydroxy-
3,5-di-tert-butylphenyl)methane, α
-phenyl, α,α-bis(2-hydroxy-3
-tert-butyl-5-methylphenyl)methane,
1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,
5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy- 3,5
-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide used, the type of organic acid silver salt, and the types of other additives, but it is usually per mol of photosensitive silver halide.
It ranges from 0.01 to 1500 mol, preferably from 0.1 to 1500 mol.
It is 200 moles. Examples of the binder used in the heat-developable color photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate,
polyvinyl alcohol, polyvinylpyrrolidone,
One or a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin can be used. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-58-104249. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including kraft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1000
~400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl imidazoles, (meth)acrylamides, and vinyl carbinols. and vinyl monomers such as vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. Preferred examples of such copolymers have a molecular weight of
5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pitgskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on a support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05g to 50g per square meter per layer, preferably 0.1g to 10g.
It is g. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of the monomer unit of the dye-donating substance. Examples of the support used in the heat-developable color photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coating. Examples include a paper support such as paper, a support made of the above-mentioned synthetic plastic film provided with a reflective layer, and the like. In particular, it is preferable that various heat solvents be added to the heat-developable color photosensitive material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably a substance that is solid at room temperature.
Semi-solid or liquid (preferably boiling point at normal pressure)
100°C or higher, more preferably 150°C or higher) and dissolves or melts in the binder by heating, preferably urea derivatives (e.g. dimethylurea, diethylurea, phenylurea, etc.), amides. derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycol Examples include: For a detailed concrete example, see patent application No. 58-104249.
It is described in. These thermal solvents may be used alone or in combination of two or more. In addition to the above-mentioned components, various additives may be added to the heat-developable color photosensitive material of the present invention, if necessary. For example, as a development accelerator, US Pat.
No. 3220840, No. 3531285, No. 4012260, No. 4060420, No. 4088496, No. 4207392, RD No. 15733, No. 15734, No. 15776,
Alkali release agents such as urea and guanidium trichloroacetate described in JP-A-56-130745 and JP-A-56-132332, organic acids as described in JP-A-45-12700, - as described in U.S. Pat. No. 3,667,959 CO−,−
Non-aqueous polar solvent compounds having SO 2 -, -SO- groups, melt formers described in U.S. Pat. No. 3,438,776, polyalkylene glycols described in U.S. Pat. . In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5020, No. 49
−91215, No. 49-107727, No. 50-2524, No.
No. 50-67132, No. 50-67641, No. 50-114217,
No. 52-33722, No. 52-99813, No. 53-1020,
No. 53-55115, No. 53-76020, No. 53-125014
No. 54-156523, No. 54-156524, No. 54-
No. 156525, No. 54-156526, No. 55-4060, No. 55
Publications such as -4061 and 55-32015, as well as West German Patent Nos. 2140406, 2147063, 2220618,
U.S. Patent No. 3080254, U.S. Patent No. 3847612, U.S. Patent No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in the specifications of No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. , 2,3-dihydro-phthalazinedione, 2,
3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and phthalic acid, naphthalic acid, etc. Examples include mixtures of at least one acid or acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, JP-A No. 58-189628, No. 58-
3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles described in Japanese Patent No. 193460 are also effective. Furthermore, as antifoggants, for example,
Special Publication No. 11113, No. 49-90118, No. 49-
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen acetamide,
N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or
Acids and their salts (e.g., sulfuric acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g.,
mercapto compound releasing compound, thiouracil,
Disulfide, simple sulfur, mercapto-1,
2,4-triazole, thiazolinthione, polysulfide compound, etc.), others, oxazoline,
Examples include compounds such as 1,2,4-triazole and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. In addition, as other anti-fogging agents,
Hydroquinone derivatives described in No. 56506 (e.g.
di-t-octylhydroquinone, dodecanylhydroquinone, etc.), hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole,
-carboxybenzotriazole, etc.) can be preferably used in combination. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45228, No. 50-119624, No. 50-120328, No. 45228, No. 50-119624, No. 50-120328, No.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-
Examples include 6-methyltriazine. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be carried out using a sulfur-containing compound as described in each publication of No. 50-77034. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain activator stabilizer precursors and the like as described in No. 4,060,420 and the like. Furthermore, a water release agent such as sucrose, NH 4 Fe (SO 4 ) 2.12H 2 O, etc. may be used.
Heat development may be carried out by supplying water as in No. 132332. In addition to the above-mentioned components, the heat-developable color photosensitive material of the present invention may optionally contain various components such as a spectral sensitizer, an antihalation dye, a fluorescent brightener, a hardening agent, an antistatic agent, a plasticizer, and a spreading agent. Additives, coating aids, etc. are added. The heat-developable color photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) reducing agent, (3) in the same layer.
It is preferable that the composition contains a dye-providing substance and (4) a binder, and further contains (5) an organic silver salt if necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, two photosensitive layers may be included.
The components (1), (2), (4), and (5) are contained in one photosensitive layer, and the dye-providing substance (3) is contained in the other layer adjacent to this photosensitive layer. ) may be contained separately in two or more photographic constituent layers as long as they are in a state where they can react with each other. Further, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and may further include one or more other photosensitive layers having different color sensitivities. It may also have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and an intermediate layer. Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or Patent No.
Photosensitive materials can be prepared by various coating methods such as the hopper coating method described in No. 3681294. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. The above-mentioned components used in the photographic constituent layers of the heat-developable color light-sensitive material of the present invention are coated on a support,
The thickness of the coating is preferably 1 to 1000 μm after drying.
More preferably, it is 3 to 20 μm. After the heat-developable color photosensitive material of the present invention is subjected to imagewise exposure as it is, the temperature is usually 80°C to 200°C, preferably 120°C.
Color development can be achieved by simply heating at a temperature range of 170° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be developed at 70% before exposure.
Preheating may be performed at a temperature range of 180°C to 180°C. Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. A light source commonly used for normal color printing,
For example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam, etc. can be used as the light source. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, to provide a conductive layer in the photosensitive material of the present invention or in the image receiving layer (element) for thermal transfer, and to utilize the Joule heat generated by electricity or a strong magnetic field. The heating pattern is not particularly limited;
Although it is possible to preheat in advance and then reheat it, to heat it at a high temperature for a short time, or at a low temperature for a long time, continuously raising, lowering, or repeating it, and even discontinuously heating, there is a simple pattern. preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image-receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and can be used as a mordant used in dye diffusion transfer type light-sensitive materials or as described in JP-A No. 57-207250. It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower. Specific examples of the mordant include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, US Pat. No. 2,548,564,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
Polymers containing dialkylamino groups disclosed in U.S. Pat. No. 2,675,316; aminoguanidine derivatives disclosed in U.S. Pat. No. 2,882,156;
covalently reactive polymers as described in No. 137333;
US Patent No. 3625694, US Patent No. 3859096, British Patent No.
Mordant capable of crosslinking with gelatin etc. disclosed in No. 1277453 and No. 2011012, US Patent No. 3958995
No. 2721852 and No. 2798063; water-insoluble mordants disclosed in JP-A-50-61228; U.S. Patent No. 3788855;
West German Patent Application (OLS) No. 2843320, JP-A-53-
No. 30328, No. 52-155528, No. 53-125, No. 53-
No. 1024, No. 54-74430, No. 54-124726, No. 55
−22766, U.S. Patent No. 3642482, U.S. Patent No. 3488706,
No. 3557066, No. 3271147, No. 3271148, Special Publication No. 55-29418, No. 56-36414, No. 57-12139,
Examples include various mordants disclosed in RD12045 (1974). Particularly useful mordants are polymers containing ammonium salts, such as those containing quaternary amino groups as described in US Pat. No. 3,709,690. Polymers containing ammonium salts include, for example, polystyrene copolymer.
In N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, the ratio of styrene and vinylbenzylammonium chloride is:
The ratio is 1:4 to 4:1, preferably 1:1. A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. Examples of the heat-resistant organic polymer substances include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, and polyvinyl alcohol. , polyacetals such as polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorofluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylacrylamide, p-cyanophenyl group, pentachlorophenyl group, and 2, Polyacrylate with 4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl metal acrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene Glycol dimethacrylate, poly-2
Examples include polyesters such as -cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also, Polymer Handbook 2nd ed. (J.
Brandrup, EHImmergut (eds.) John Wiley &
Glass transition temperature listed in Sons Publishing, 40
Synthetic polymers at temperatures above 0.degree. C. are also useful. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetate, such as triacetate and diacetate;
Polyamides made from combinations of heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane Examples include polyester, polyethylene terephthalate, polycarbonate, vinyl chloride, etc., which can be combined with ethylene glycol, etc. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2
Polyethylene terephthalate using -dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective. Particularly preferred among these are the layer made of polyvinyl chloride described in Japanese Patent Application No. 58-97907, and the layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 128600-1982. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer by a member (for example, a film) made of the above-mentioned polymer alone (a type that also serves as an image-receiving layer support). Furthermore, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer provides a reflective color image when the transferred color image is viewed from the transparent support side of the image-receiving layer. [Example] Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Example 1 730 mg of exemplified dye-providing substance (10) was dissolved in 2.1 cc of ethyl acetate. This solution was mixed with 3 cc of a 2.5% gelatin aqueous solution containing a surfactant, water was added to make 6.5 cc, and the mixture was dispersed with a homogenizer to obtain a dispersion of the dye-providing substance. 6.5 cc of the above dispersion was mixed with 3.5 cc of water containing 450 mg of polyvinylpyrrolidone (average molecular weight 30,000) and 500 mg of 1,5-pentanediol, and 0.1 ml of 10% guanidine trichloroacetic acid in ethanol and the above-mentioned reducing agent (R -3) After adding 200mg,
The pH was adjusted to 5.5 with 3% citric acid. A silver iodobromide emulsion with an average grain size of 0.1 μm was added to this dispersion in terms of silver.
x10 -3 mol (containing 85 mg of gelatin) was added, water was added to make the total volume to 15 cc, and the photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar to a dry film thickness of 8 μm. After drying the resulting light-sensitive material, it was exposed to white light at 16,000 CMS through a step wedge. Next, the image-receiving layer surface of an image-receiving sheet on which polyvinyl chloride (molecular weight 20,000) as an image-receiving layer material was separately coated on baryta paper and the coated surface of the exposed photosensitive material were overlapped and heat developed at 150° C. for 1 minute. The image-receiving sheet was peeled off to obtain a magenta transferred image on the image-receiving sheet. Table 1 shows the maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image. Comparative Example 1 Example 1 except that the dye-providing substance in the light-sensitive material of Example 1 was replaced with the comparative dye-providing substance (A) below.
A photosensitive material similar to that in Example 1 was prepared and thermally developed in the same manner as in Example 1. The results are shown in Table-1.
【表】
表−1の結果から明らかなように、有機銀塩を
用いない熱現像カラー感光材料において、本発明
の色素供与物質を用いた試料では、比較試料に比
べてDmaxが大きく、かつDminが小さいことが
わかる。
実施例 2
[4−スルホベンゾトリアゾール銀の調製]
24gの4−スルホベンゾトリアゾール及び4g
の水酸化ナトリウムをエタノール−水(1:1)
混合液300mlに加え溶解した。この溶液に5規定
の硝酸銀溶液20mlを滴下した。この際5規定の水
酸化ナトリウム溶液も同時に滴下し、PHを7〜8
に維持した。この溶液を1時間室温で攪拌した
後、水で400mlに仕上げて4−スルホベンゾトリ
アゾールを20%過剰に含む4−スルホベンゾトリ
アゾール銀溶液を調製した。
[感光材料の作製]
実施例1と同じ例示色素供与物質(10)730mgおよ
び1,4−ジオクチルハイドロキノン30mgを酢酸
エチル2.1ccに溶解した。この溶液を界面活性剤
を含む2.5%ゼラチン水溶液3ccと混合し、水を加
えて6.5ccとした後、ホモジナイザーで分散し、
色素供与物質の分散液を得た。上記の4−スルホ
ベンゾトリアゾール銀溶液4mlと上記色素供与物
質の分散液6ccを混合し、さらにポリビニルピロ
リドン(平均分子量30000)450mg、ペンタエリス
リトール120mg、1,5−ペンタンジオール420mg
および実施例1で用いたと同様の還元剤(R−
3)200mgを加えた後、3%のクエン酸でPHを5.5
とした。この分散液に平均粒径0.05μmの沃臭化
銀乳剤を銀に換算して3×10-4モル添加(ゼラチ
ン75mg含有)し、水を加えて14mlに仕上げた後、
ポリエチレンテレフタレート支持体上に乾燥膜厚
が8μmとなるようにワイヤーバーにて塗布して感
光層を塗設した。
得られた感光材料を乾燥後、32000CMSの白色
露光をステツプウエツジを通して与えた後、実施
例1と同様の受像シートに同様の条件で熱現像を
行ない、受像シート上にマゼンタの転写画像を得
た。得られた転写画像の最高反射濃度(Dmax)
およびカブリ(Dmin)を表−2に示す。
実施例 3
実施例2の感光材料において、色素供与物質を
表−2に示す色素供与物質に代えた以外は、実施
例2と同様の感光材料を作製し、実施例2と同様
の熱現像を行ない受像シート上に転写画像を得
た。得られた転写画像濃度の結果を併せて表−2
に示す。
実施例 4
実施例2の感光材料において、還元剤を表−2
に示す還元剤に代えた以外は、実施例2と同様の
感光材料を作製し、実施例2と同様の露光、熱現
像を行ないマゼンタの転写画像を得た。得られた
転写画像濃度の結果を併せて表−2に示す。
比較例 2
実施例−2の感光材料において、色素供与物質
(10)を前記比較色素供与物質(A)及び下記比較色素供
与物質(B)に代えた以外は、実施例2と同様の感光
材料を作製し、実施例2と同様の熱現像を行ない
受像シート上に転写画像を得た。結果を表−2に
示す。
[Table] As is clear from the results in Table 1, in the heat-developable color photosensitive materials that do not use organic silver salts, the samples using the dye-providing substance of the present invention have larger Dmax and Dmin than the comparative samples. It can be seen that is small. Example 2 [Preparation of silver 4-sulfobenzotriazole] 24 g of 4-sulfobenzotriazole and 4 g
of sodium hydroxide in ethanol-water (1:1)
It was added to 300 ml of the mixed solution and dissolved. 20 ml of 5N silver nitrate solution was added dropwise to this solution. At this time, 5N sodium hydroxide solution was also added dropwise at the same time to bring the pH to 7-8.
maintained. This solution was stirred at room temperature for 1 hour and then made up to 400 ml with water to prepare a 4-sulfobenzotriazole silver solution containing 20% excess of 4-sulfobenzotriazole. [Preparation of photosensitive material] 730 mg of the same exemplary dye-providing substance (10) as in Example 1 and 30 mg of 1,4-dioctylhydroquinone were dissolved in 2.1 cc of ethyl acetate. This solution was mixed with 3 cc of a 2.5% gelatin aqueous solution containing a surfactant, water was added to make 6.5 cc, and then dispersed with a homogenizer.
A dispersion of a dye-providing substance was obtained. Mix 4 ml of the above 4-sulfobenzotriazole silver solution and 6 cc of the above dispersion of the dye-providing substance, and then add 450 mg of polyvinylpyrrolidone (average molecular weight 30,000), 120 mg of pentaerythritol, and 420 mg of 1,5-pentanediol.
and a reducing agent similar to that used in Example 1 (R-
3) After adding 200mg, adjust the pH to 5.5 with 3% citric acid.
And so. A silver iodobromide emulsion with an average particle size of 0.05 μm was added to this dispersion at 3 × 10 −4 mol in terms of silver (containing 75 mg of gelatin), and water was added to make a total volume of 14 ml.
A photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar so that the dry film thickness was 8 μm. After drying the obtained photosensitive material, it was exposed to white light at 32,000 CMS through a step wedge, and then thermally developed on the same image-receiving sheet as in Example 1 under the same conditions to obtain a magenta transferred image on the image-receiving sheet. Maximum reflection density (Dmax) of the obtained transferred image
and fog (Dmin) are shown in Table 2. Example 3 A photosensitive material similar to Example 2 was prepared except that the dye-providing substance in the photosensitive material of Example 2 was replaced with the dye-providing substance shown in Table 2, and the same photosensitive material as in Example 2 was subjected to heat development. A transferred image was obtained on the image-receiving sheet. The results of the obtained transferred image density are also shown in Table 2.
Shown below. Example 4 In the photosensitive material of Example 2, reducing agents were added as shown in Table-2.
A photosensitive material similar to that in Example 2 was prepared, except that the reducing agent shown in 2 was used, and the same exposure and heat development as in Example 2 were carried out to obtain a magenta transferred image. The results of the obtained transferred image density are also shown in Table 2. Comparative Example 2 In the light-sensitive material of Example-2, the dye-providing substance
The same photosensitive material as in Example 2 was prepared except that (10) was replaced with the comparative dye-providing substance (A) and the comparative dye-providing substance (B) below, and the same heat development as in Example 2 was carried out to obtain an image. A transferred image was obtained on the sheet. The results are shown in Table-2.
【表】
表−2の結果から明らかなように、有機銀塩を
用いた熱現像カラー感光材料において、本発明の
色素供与物質を用いた試料は、比較試料に比べて
Dmaxが大きく、かつDminが小さいことがわか
る。[Table] As is clear from the results in Table 2, in the heat-developable color photosensitive materials using organic silver salts, the samples using the dye-providing substance of the present invention were more effective than the comparative samples.
It can be seen that Dmax is large and Dmin is small.
Claims (1)
銀、バインダー、還元剤及び下記一般式(1)で表わ
される色素供与物質を有することを特徴とする熱
現像カラー感光材料。 一般式 (1) 式中、Xは酸素原子又はイオウ原子を表わし、
Yはベンゼン環又はナフタレン環を形成するのに
必要な原子の集まりを表わし、Jは2価の結合基
を表わし、Dは拡散性の色素の残基を表わし、n
は0又は1を表わす。[Scope of Claims] 1. A heat-developable color photosensitive material, comprising at least a photosensitive silver halide, a binder, a reducing agent, and a dye-providing substance represented by the following general formula (1) on a support. General formula (1) In the formula, X represents an oxygen atom or a sulfur atom,
Y represents a collection of atoms necessary to form a benzene ring or a naphthalene ring, J represents a divalent bonding group, D represents a residue of a diffusible dye, and n
represents 0 or 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5185785A JPS61210350A (en) | 1985-03-15 | 1985-03-15 | Heat developable color photosensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5185785A JPS61210350A (en) | 1985-03-15 | 1985-03-15 | Heat developable color photosensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61210350A JPS61210350A (en) | 1986-09-18 |
JPH057698B2 true JPH057698B2 (en) | 1993-01-29 |
Family
ID=12898531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5185785A Granted JPS61210350A (en) | 1985-03-15 | 1985-03-15 | Heat developable color photosensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61210350A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61261737A (en) * | 1985-05-16 | 1986-11-19 | Fuji Photo Film Co Ltd | Heat developing color photosensitive material |
-
1985
- 1985-03-15 JP JP5185785A patent/JPS61210350A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61210350A (en) | 1986-09-18 |
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