JPH03287253A - Silver halide photographic sensitive material and image forming method using same - Google Patents
Silver halide photographic sensitive material and image forming method using sameInfo
- Publication number
- JPH03287253A JPH03287253A JP8813690A JP8813690A JPH03287253A JP H03287253 A JPH03287253 A JP H03287253A JP 8813690 A JP8813690 A JP 8813690A JP 8813690 A JP8813690 A JP 8813690A JP H03287253 A JPH03287253 A JP H03287253A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- group
- halide photographic
- sensitive material
- hydrophilic colloid
- 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.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 132
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 95
- 239000004332 silver Substances 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 108010010803 Gelatin Proteins 0.000 claims abstract description 32
- 229920000159 gelatin Polymers 0.000 claims abstract description 32
- 239000008273 gelatin Substances 0.000 claims abstract description 32
- 235000019322 gelatine Nutrition 0.000 claims abstract description 32
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 32
- 238000012545 processing Methods 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims description 73
- 238000001035 drying Methods 0.000 claims description 22
- 239000000084 colloidal system Substances 0.000 claims description 18
- 238000011161 development Methods 0.000 claims description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 125000005157 alkyl carboxy group Chemical group 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 51
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 66
- 239000000243 solution Substances 0.000 description 37
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000002245 particle Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 230000018109 developmental process Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 230000001235 sensitizing effect Effects 0.000 description 12
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 12
- 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 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 9
- 239000007888 film coating Substances 0.000 description 9
- 238000009501 film coating Methods 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 239000007864 aqueous solution 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
- 239000013078 crystal Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000006224 matting agent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
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- 150000007949 saponins Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
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- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
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- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
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- 235000011941 Tilia x europaea Nutrition 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 244000309464 bull Species 0.000 description 1
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- 239000003093 cationic surfactant Substances 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
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- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- KPCHOCIEAXFUHZ-UHFFFAOYSA-N oxadiazole-4-thiol Chemical class SC1=CON=N1 KPCHOCIEAXFUHZ-UHFFFAOYSA-N 0.000 description 1
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- CELWCAITJAEQNL-UHFFFAOYSA-N oxan-2-ol Chemical compound OC1CCCCO1 CELWCAITJAEQNL-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 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
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000003831 tetrazolyl group Chemical class 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- WEQHQGJDZLDFID-UHFFFAOYSA-J thorium(iv) chloride Chemical compound Cl[Th](Cl)(Cl)Cl WEQHQGJDZLDFID-UHFFFAOYSA-J 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上のス１４用分野］
本発明はハロゲン化銀写真感光材料及びその画像形成方
法に関し、特に濃度、硬調性、残色、定着性及び乾燥性
が改良された迅速現像処理用のハロゲン化銀写真感光材
料及びその画像形成方法に関する。[Detailed Description of the Invention] [Industrial Field] The present invention relates to a silver halide photographic material and an image forming method thereof, and particularly to a silver halide photographic material having improved density, contrast, residual color, fixing property, and drying property. The present invention relates to a silver halide photographic material for rapid development processing and an image forming method thereof.
［発明の背景］
近年、１１書好の５様化や情報量の増加に伴ない、印刷
製版分野においては、印刷物の多種多量短納期化が、ま
た、医療分野においては、高齢化に伴い、詮療１１．７
間の短縮化か望まれている。即ち、このような分野に使
用されるハロゲン化銀写真感光材料を迅速に現像処理（
一般に現像、定着、水洗又は安定化、乾燥の各工程より
なる）出来るようにする事、つまり同一時間内での現像
処理量を高める事か強く望まれている。現像処理時間を
短縮するには、自動現像機の搬送速度を高めるのが一方
法である。しかし現像処理時間を短縮しようとして、そ
の自動現像機］敗退速度を早くすると、（ａ）濃度が充
分でない（最高濃度、硬調性、感度の低下）、（ｂ）定
着不良が生じる、（ｃ）水洗か充分に行われない（処理
後の画像保存性低下、残色の増加）、（ｄ）フィルムの
乾燥不良が生しる、等の問題を生じる。[Background of the Invention] In recent years, with the increasing number of 11 types of books and the increase in the amount of information, in the printing and plate making field, there has been an increase in the number of different types of printed matter and shorter delivery times, and in the medical field, with the aging of the population, Snooping 11.7
It is hoped that the time will be shortened. That is, silver halide photographic materials used in such fields are rapidly developed (
In general, it is strongly desired to increase the amount of development processing performed within the same amount of time (generally consisting of each step of development, fixation, water washing, stabilization, and drying). One way to shorten the development processing time is to increase the conveyance speed of an automatic processor. However, in an attempt to shorten the processing time, if the automatic processor speed is increased, (a) the density will not be sufficient (decreased maximum density, contrast, and sensitivity), (b) poor fixing will occur, and (c) Problems such as insufficient washing with water (deterioration of image storage stability and increase in residual color after processing) and (d) insufficient drying of the film occur.
上記（ａ）〜（Ｃ）の問題に対する有効手段の一方法に
、ハロゲン化銀写真感光材料の親水性バインダー膜物性
を軟らかくすること（以降、硬膜度低下と表現する）が
あげられるが、水洗工程て親水性バインダーが更に膨潤
し、より一層フィルム乾燥が劣化してしまう問題をもっ
ている。硬［模度低下手段によるこの乾燥性劣化を補う
手段としては、定着液にアルくニウム化合物を添加し、
定着工程で親水性バインター膜の硬膜度を上昇させる方
法が当業界て知られている。しかしなから、この方法は
、定着液内で硬膜が急激に進んでしまって結局定着性の
劣化を引き起こすこと、及びアルミニウム化合物は定着
波に多量添加すると経時で白色沈殿を生しることから、
真の解決策とは言いかたいものであった。One effective method for solving the above problems (a) to (C) is to soften the physical properties of the hydrophilic binder film of the silver halide photographic light-sensitive material (hereinafter referred to as reducing hardness). There is a problem in that the hydrophilic binder further swells during the water washing process, further deteriorating film drying. As a means to compensate for this deterioration in drying property due to hardness reduction means, an aluminium compound is added to the fixing solution.
Methods are known in the art to increase the hardness of hydrophilic Binter films during the fixing step. However, this method is difficult because the hardening film rapidly progresses in the fixing solution, eventually causing deterioration of fixing properties, and the addition of aluminum compounds in large quantities to the fixing wave causes white precipitate over time. ,
It was hard to call it a true solution.
［発明の目的］
本発明の第１の目的は迅速現像処理て生しる上述（ａ）
〜（ｄ）の問題点を全て解消てきる、即ち最高濃度、硬
調性、残色、定着性、及び乾燥性に（量れたハロゲン化
銀写真感光材料を提供することにある。また、第２の目
的は該ハロゲン化銀写真感光材料に適し、かつ処理液の
経時保存性に優れた画像形成方法を提供することにある
。[Object of the Invention] The first object of the present invention is to improve the above-mentioned (a) resulting from rapid development processing.
The object of the present invention is to provide a silver halide photographic light-sensitive material that can solve all of the problems in (d), that is, in terms of maximum density, high contrast, residual color, fixing property, and drying property. The second object is to provide an image forming method that is suitable for the silver halide photographic light-sensitive material and has excellent storage stability over time of a processing solution.
［発明の構成］
上記した本発明のこれらの目的は、支持体の方の側に少
なくとも一層のゼラチンを含む感光性ハロゲン化銀乳剤
層を有し、かつ支持体の他方の側に少ｔＸ くとも−層
のゼラチンを含む親水性コロイド層を有してなるハロゲ
ン化銀写真感光側斜において、該ハロゲン化銀写真感光
材料を構成する親水性コロイド層のうち、セラチンを含
む少なくとも一層の親木性コロイド層に少なくとも一種
の下記一般式［Ｉ］及び／または一般式［Ｉ＋ ］て表
される化合物を含有させてなる事を特徴とするハロゲン
化銀写真感光材料によって達成される。[Structure of the Invention] These objects of the present invention described above have a light-sensitive silver halide emulsion layer containing at least one gelatin on one side of the support, and a light-sensitive silver halide emulsion layer containing at least one gelatin on the other side of the support. In a silver halide photographic light-sensitive side film having hydrophilic colloid layers containing gelatin in both layers, at least one parent layer containing seratin among the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material. This is achieved by a silver halide photographic light-sensitive material characterized in that the sexual colloid layer contains at least one compound represented by the following general formula [I] and/or general formula [I+].
又、これらの目的は、該ハロゲン化銀写真感光材料を構
成する親水性コロイド層のうち、少なくとも一層の親木
・［生コロイド層にヨウ素イオンを乖離する化合物を少
なくとも一種含有させることおよび／またはヨウ素イオ
ンを含有する定着液及び／または安定液でｆｉ埋するこ
とによってより効果的に達成される。These objects also include at least one parent colloid layer of the hydrophilic colloid layer constituting the silver halide photographic light-sensitive material containing at least one compound that dissociates iodine ions, and/or This can be achieved more effectively by filling the fi with a fixer and/or stabilizer containing iodine ions.
一般式［ＩＩ 一般式［ＩＩ ］１
［式中、ＲＩ Ｒ２及びＲ３は各々、アルキル基、ア
ルケニル基、アルキニル基、アリル基、アラルキル基、
または複素環基を表し、Ｒ、Ｒ４及びＲ５は水素原子、
アルキル基、アルケニル基、アルキニル基、アリル基、
アラルキル基、カルボニル基、アルコキシ基、ハロゲン
原子、又は複素環基を表し、ｘｌは水素原子、ハロゲン
原子、アルキル基、トシロキシ基、アルコキシ基、又は
−ＣＨ（Ｘ２）Ｒ６を示す。Ｒ６は水素原子、アルキル
基、アルケニル基、アルキニル基、アリル基、アラルキ
ル基、カルボニル基、または複素環基を表し、Ｘ２はハ
ロゲン原子、トシロキシ基、アルコキシ基、又はアルキ
ルカルボキシ基を示す。また、Ｒ４、Ｒ６、ｘ ｌは−
Ｃ＝Ｃ−と共同して複素環を形成してもよい。］
以下、本発明の構成について詳細に具体的に説明する。General formula [II] General formula [II] 1 [wherein RI R2 and R3 are each an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aralkyl group,
or represents a heterocyclic group, R, R4 and R5 are hydrogen atoms,
Alkyl group, alkenyl group, alkynyl group, allyl group,
It represents an aralkyl group, a carbonyl group, an alkoxy group, a halogen atom, or a heterocyclic group, and xl represents a hydrogen atom, a halogen atom, an alkyl group, a tosyloxy group, an alkoxy group, or -CH(X2)R6. R6 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aralkyl group, a carbonyl group, or a heterocyclic group, and X2 represents a halogen atom, a tosyloxy group, an alkoxy group, or an alkylcarboxy group. Moreover, R4, R6, x l are -
A heterocycle may be formed in conjunction with C=C-. ] Hereinafter, the structure of the present invention will be specifically explained in detail.
上記一般式［１］および／または一般式［ＩＩ ］にお
いて、各々のアルキル基、アルケニル基、アルキニル基
、アリル基、アラルキル基、カルボニル基、複素環基は
置換でも無置換でもよいが置換する場合の置換基として
は、例えばハロゲン原子ヒドロキシ基、アルコキシ基、
カルボニル基、アルコキシカルボニル基、ヒドロキシカ
ルボニル基、カルボキシ基、アくノカルボニル基、アシ
ルアミノ基、アルキルスルホニル基、スルホンアくド基
、シアノ基、スルホニル基、カルバモイル基、スルファ
モイル基、アミノ基、メルカプトキシ基、アルキルメル
カプトキシ基、ヒドラジド基、アルキル基、アリール基
、アラルキル基、アルケニル基、カルボニル基、複素環
基、シリル基、シロキシ基、アルケニル基、アリ−レニ
ル基、アラルケニル基等の多基を挙げることができる。In the above general formula [1] and/or general formula [II], each alkyl group, alkenyl group, alkynyl group, allyl group, aralkyl group, carbonyl group, and heterocyclic group may be substituted or unsubstituted, but when substituted Examples of substituents include halogen atom hydroxy group, alkoxy group,
Carbonyl group, alkoxycarbonyl group, hydroxycarbonyl group, carboxy group, acinocarbonyl group, acylamino group, alkylsulfonyl group, sulfonate group, cyano group, sulfonyl group, carbamoyl group, sulfamoyl group, amino group, mercaptoxy group , alkylmercaptoxy group, hydrazide group, alkyl group, aryl group, aralkyl group, alkenyl group, carbonyl group, heterocyclic group, silyl group, siloxy group, alkenyl group, arylenyl group, aralkenyl group, etc. be able to.
これらの置換基は現像処理に用いられる各処理液に対す
る溶解度や経時安定性や加水分解性の度合を適度にせし
める為には有用である。These substituents are useful for adjusting the solubility in each processing solution used in development processing, stability over time, and degree of hydrolyzability to an appropriate level.
以下に本発明に用いられる一般式［ＩＩおよび／または
一般式［ＩＩ ］で表される化合物（以降、まとめて本
発明の化合物と呼ぶ）の具体例を挙げるが、本発明の化
合物は、これに限定されるものではない。Specific examples of compounds represented by general formula [II and/or general formula [II] (hereinafter collectively referred to as compounds of the present invention) used in the present invention are listed below. It is not limited to.
例示化合物
（１） （Ｃ１ｈ） ３ｓｉｏ−ＣＨ２−Ｏ５ｉ （Ｃ
１１３） ３（２） （Ｃ１ｈ） ５ｓｉＯ−ＣｌｌＣ
（ＣＨ３） ３−０５ｉ （Ｃ１１３） ３（３）
以下余白
（５）
（６）
（７） ０１１２−ＣＩ−Ｏ５ｉ（ＣＩ（ｓ）＋（８
） Ｃ１ｈＣＩＩ−Ｃ１１−Ｏ５ｉ（ＣＩ（３）３（
９） （Ｃ１１３） ２Ｃ−Ｃｌｌ−Ｏ５ｉ （Ｃ１
ｈ） ３（１０） （［；１１３） ３ｓｉＯ−Ｃ
Ｈ２Ｃ８−Ｃｔｌ−Ｏ５ｘ （ＣＨｓ）ｓ（１１）
Ｃ１１３０Ｃｔ１２ＣＩ＋２０（：１（２Ｇ）１１：
）Ｉ−Ｏ５ｉ、（ＣＩ＋＋）３（１２）
（１３）
（１４）
（に１１３） ３ｓｉｏ（：Ｉｆ−ＣＩＣＩ−Ｃ１１−
Ｃ５１（Ｃｌｈ） ３（ＣＨ３） ３Ｓ １ｏ−Ｃ１１
−Ｃ（ＣＨ３） −Ｃ（Ｃｌｈ） ”Ｃ：１ｌ−０５ｉ
（Ｃ１（３） ３（２２） Ｃ１１３０Ｇ１１２Ｃ
Ｉｌ−Ｃ１ｆ−０５１（ＣＨ１３） ３（２３）
（１５） ｆｉｒ−Ｃ１１−Ｃ１１−Ｃ５１（Ｃ１１３
） ３（１６）
［１ｒ
、 Ｃ−Ｃｌｌ−０５ｉ （Ｃ１ｆ３） ｓｒ
（１７）
（２４）
（２５）
（２６） Ｂｒ−Ｃ１１（Ｃ１１３）Ｃ１１−Ｃ１（
−ＱＳｉ（Ｃ１ｈ）３（１８）
（１９） ｃｐ−ｃｌｌ−ｃｏ−ｏｓｔ （ＣＨ３）
３（２０）
１ｒ
＞Ｃ−Ｃ（Ｃｌｆ３）−０５１（Ｃ１ｆ３）３ｒ
（２１） Ｂｒ−Ｃ１ｈＣ１１−Ｃｌｆ−Ｃ５１（Ｃ
ｌｈ）３木発明の感光月別に用いられる未発明に係る化
合物を含有させるハロゲン化銀写真感光月別を構成する
親水↑１コロイド層としては、ゼラチンを含有している
層てあれはどの層であってもよい。Exemplified compound (1) (C1h) 3sio-CH2-O5i (C
113) 3(2) (C1h) 5siO-CllC
(CH3) 3-05i (C113) 3 (3) Below margin (5) (6) (7) 0112-CI-O5i (CI(s) + (8
) C1hCII-C11-O5i(CI(3)3(
9) (C113) 2C-Cll-O5i (C1
h) 3(10) ([;113) 3siO-C
H2C8-Ctl-O5x (CHs)s(11)
C1130Ct12CI+20(:1(2G)11:
)I-O5i, (CI++)3(12) (13) (14) (to113) 3sio(:If-CICI-C11-
C51(Clh) 3(CH3) 3S 1o-C11
-C(CH3) -C(Clh) ”C:1l-05i
(C1(3) 3(22) C1130G112C
Il-C1f-051 (CH13) 3 (23) (15) fir-C11-C11-C51 (C113
) 3 (16) [1r, C-Cll-05i (C1f3) sr (17) (24) (25) (26) Br-C11 (C113) C11-C1 (
-QSi(C1h)3(18) (19) cp-cll-co-ost (CH3)
3(20) 1r >C-C(Clf3)-051(C1f3)3r (21) Br-C1hC11-Clf-C51(C
lh) Hydrophilic ↑ 1 Which colloid layer is the layer containing gelatin, which constitutes the silver halide photographic sensitizer containing the uninvented compound used in the sensitizer of the 3-wood invention? It's okay.
支持体に対してハロゲン化銀乳剤層塗設面側のゼラチン
含有層の少なくともいずれかの層（例えはハロゲン化銀
乳剤層、乳剤層保護層、中間層等）に未発明に係る化合
物を含有せしめることて、最高濃度、硬調性、感度、定
着性、画像保存性、残色の著しい改善効果が得られる。Contains an uninvented compound in at least one of the gelatin-containing layers (for example, silver halide emulsion layer, emulsion layer protective layer, intermediate layer, etc.) on the side on which the silver halide emulsion layer is coated with respect to the support. In particular, significant improvements in maximum density, contrast, sensitivity, fixing properties, image storage stability, and residual color can be obtained.
また、支持体に対してハロゲン化銀乳剤層塗設面と反対
側のゼラチン含有層の少なくともいずれかの層（例えば
バッキング層、バッキング保護層等）に未発明の化合物
を含有せしめたとしても、画像保存性と残色の改善効果
を得ることがてきる。特に好ましい未発明の態様として
は、支持体に対してハロゲン化銀乳剤層塗設面側の少な
くとも１層と該ハロケン化銀乳剤層塗設面と反対側の少
なくとも１層にともに含有せしめることか挙げられる。Further, even if an uninvented compound is contained in at least one of the gelatin-containing layers (for example, a backing layer, a backing protective layer, etc.) on the opposite side of the support from the side on which the silver halide emulsion layer is coated, The effect of improving image storage stability and residual color can be obtained. A particularly preferred uninvented embodiment is to contain both in at least one layer on the side on which the silver halide emulsion layer is coated and at least one layer on the side opposite to the side on which the silver halide emulsion layer is coated. Can be mentioned.
未発明の感光材料に用いられる未発明に係る化金物の好
ましい含有量は、化合物の種類、ゼラチン量、バインダ
ーの種類や硬膜度によって異なり一概には表現できない
が、該感光材料１ｍ２当り１０−” ｍｍｏｕ 〜１０
−’ｍｏＪ２か挙げられる。The preferred content of the uninvented metal compound used in the uninvented photosensitive material varies depending on the type of compound, the amount of gelatin, the type of binder, and the degree of hardness, but it cannot be expressed unconditionally, but it is 10 -/m2 of the photosensitive material. ” mmou ~10
-'moJ2 can be mentioned.
特に好ましくは、該感光材料１ｍ２当り１０−１〜１０
２ｍｍｏｊ２の範囲で用いられる。Particularly preferably, 10 -1 to 10 per m2 of the photosensitive material
It is used in the range of 2 mmoj2.
未発明の感光材料に用いられる未発明に係る化合物の含
イ〒量をコントロールする好ましい方法としては、１つ
の態様どして、対応する塗設層塗布用調製液へ未発明に
係る化合物を添加するその量自身を適宜コントロールす
る方法が挙げられる。One preferred method for controlling the content of the uninvented compound used in the uninvented photosensitive material is to add the uninvented compound to the corresponding coating layer coating solution. An example of this method is to appropriately control the amount itself.
また別の態様としては、未発明に係る化合物を塗設層塗
布用調製液に添加する際に、該塗設層塗布用調製液やそ
の隣接層塗布用調製液のｐＨまたはヨウ素イオン濃度を
各々適宜コントロールする方法、即ち、該化合物の添加
あるいは拡散層のｐｌ＋を低下せしめたり、またヨウ素
イオン濃度を上げて、その層での未発明に係る化合物の
分解を促進させ、あらかしめゼラチンと反応せしめる方
法が挙げられる。In another embodiment, when adding the uninvented compound to the coating layer coating solution, the pH or iodine ion concentration of the coating layer coating solution or the adjacent layer coating solution may be adjusted. Appropriate control methods, i.e., adding the compound or lowering the pl+ of the diffusion layer, or increasing the iodine ion concentration, promote the decomposition of the uninvented compound in that layer, and preliminarily react with gelatin. There are several methods.
本発明に係る化合物を本発明の感光材料に含有せしめる
更に他の態様としては、該化合物を適当な有機溶媒、例
えばメタノール、エタノール等のアルコール類やテトラ
ヒドロフラン、ジオキサン、ジグライム等のエーテル類
やジメチルスルホキサイド、ジメチルホルムアミド、エ
チルアセテート等に溶解し、オーバーコート法等により
ハロゲン化銀写真感光材料の最外層になる部分に直接塗
布してハロゲン化銀写真感光材料に含有せしめても良い
。Still another embodiment of incorporating the compound of the present invention into the light-sensitive material of the present invention is to incorporate the compound into a suitable organic solvent, such as alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, dioxane, and diglyme, and dimethyl sulfonate. It may also be incorporated into the silver halide photographic material by dissolving it in dimethylformamide, ethyl acetate, etc., and applying it directly to the outermost layer of the silver halide photographic material using an overcoating method or the like.
本発明の感光材料に用いられる本発明に係る化合物は、
ｐＨが７〜１２のアルカリ性水溶液に、実質上難溶であ
ることが好ましい。これは現像液中での感光材料からの
該化合物の流出を抑え、続く定着液や安定化液といった
低ｐＨ液中での該化合物の分解量を相対的に増大させる
ためと考えられる。The compound according to the present invention used in the photosensitive material of the present invention is:
It is preferable that it is substantially hardly soluble in an alkaline aqueous solution having a pH of 7 to 12. This is thought to be because the compound is prevented from flowing out from the photosensitive material in the developing solution, and the amount of the compound decomposed in the subsequent low pH solution such as a fixing solution or a stabilizing solution is relatively increased.
本発明の感光材料に用いられる本発明に係る化合物は、
単独で用いても良いが、複数種をいかなる比率で組合せ
て用いてもよく、好ましい特性を劣化させることはない
。The compound according to the present invention used in the photosensitive material of the present invention is:
Although they may be used alone, they may be used in combination in any ratio without deteriorating the desirable characteristics.
親水性コロイド層に含有させるヨウ素イオンを乖離する
化合物の具体例としては、ヨウ化カリウム、ヨウ化ナト
リウム、ヨウ化リチウム、２−ヨウ素−酢酸等が挙げら
れるが、これらに限定されるものではない。Specific examples of compounds that dissociate iodine ions contained in the hydrophilic colloid layer include, but are not limited to, potassium iodide, sodium iodide, lithium iodide, and 2-iodine-acetic acid. .
本発明の感光材料には、疎水性の支持体上に親水性層を
塗設する為にあらかじめ支持体上に単層あるいは複数層
を支持体に塗設したいわゆる下引き層を設けることがで
き、いかなる種類の下引き層てあってもよい。その例と
しては特開昭４９−３９７２号公報等記載のポリヒドロ
キシベンゼン類を含む有機溶剤系での下引き加工層、特
開昭４９−ｐＨ１８号、同５２−１０４９１３号、同５
９−１９９４１号、同５９−１９９４０号、同５９−１
８９４５号、同５１−１１２３２６号、同５１−１１７
６１７号、同５１−５８４６９号、同５１−１１４１２
０号、同５１−ｐＨ３２３号、同５１−１２３１３９号
、同５１−１１４１２１号、同５２−１３９３２０号、
同５２−６５４２２号、同５２−１０９９２３号、同５
２−１１９９１９号、同５５−６５９４９号、同５７−
１２８３３２号、同５９−１９９４号各公報等に記載の
水系ラテックス下引き加工層が挙げられる。In order to coat a hydrophilic layer on a hydrophobic support, the photosensitive material of the present invention may be provided with a so-called subbing layer, which is a single layer or multiple layers coated on the support in advance. , any type of subbing layer may be present. Examples include the undercoating layer using an organic solvent containing polyhydroxybenzenes as described in JP-A-49-3972, etc., JP-A-49-pH18, JP-A-52-104913, and JP-A-5.
No. 9-19941, No. 59-19940, No. 59-1
No. 8945, No. 51-112326, No. 51-117
No. 617, No. 51-58469, No. 51-11412
No. 0, No. 51-pH323, No. 51-123139, No. 51-114121, No. 52-139320,
No. 52-65422, No. 52-109923, No. 5
No. 2-119919, No. 55-65949, No. 57-
Examples include water-based latex subbing layers described in Japanese Patent Publications No. 128332 and No. 59-1994.
また特開昭６１−１７４５４２号等に記載されるような
導電性ポリマーや酸化スズ、酸化インジウムを混合した
導電性改質下引層も挙げられる。Also included is a conductive modified undercoat layer containing a conductive polymer, tin oxide, or indium oxide as described in JP-A-61-174542.
また、該下引き層は通常、表面を化学的ないし物理的に
処理することができる。該処理としては薬品処理、機械
的処理、コロナ放電処理、火焔処理、紫外線処理、高周
波処理、グロー放電処理、活性プラズマ処理、レーザー
処理、混酸処理、オゾン酸化処理などの表面活性化処理
が挙げられる。Further, the surface of the undercoat layer can usually be chemically or physically treated. Such treatments include surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. .
前記本発明に係る化合物をゼラチンを含む塗設層に添加
する方法としては、水溶液の形で添加させる方法の他に
例えば米国特許第３，８７６．１３７号に記載のある高
沸点有機溶媒に溶かしてから上記親水性コロイド層中に
分散させる方法、さらには水溶性有機溶媒、例えばメタ
ノール、フッ化アルコール、アセトン、テトラヒドロフ
ラン、ジメチルホルムアルデヒド、エチレングリコール
、エチルアセテート、ジメチルスルホキサイド、ジオキ
サン等に溶かして親木性コロイド層塗布液に添加する方
法等を適用することができる。The compound according to the present invention can be added to the coating layer containing gelatin by adding it in the form of an aqueous solution, or by dissolving it in a high-boiling organic solvent as described in US Pat. No. 3,876.137. and then dispersing it in the hydrophilic colloid layer, or further dissolving it in a water-soluble organic solvent such as methanol, fluorinated alcohol, acetone, tetrahydrofuran, dimethyl formaldehyde, ethylene glycol, ethyl acetate, dimethyl sulfoxide, dioxane, etc. A method of adding it to a coating solution for a wood-philic colloid layer, etc. can be applied.
本発明の感光材料の支持体、両面各々のゼラチンを含む
塗設層は１層でも、２層以上であってもよく、本発明に
係る化合物はこれらのゼラチンを含む塗設層の内の少な
くとも１層に含有されなければならない。The number of gelatin-containing coating layers on each side of the support of the photosensitive material of the present invention may be one or two or more layers, and the compound according to the present invention may be applied to at least one of these gelatin-containing coating layers. Must be contained in one layer.
本発明の感光材料に用いられる支持体には、α−オレフ
ィンポリマー（例えばポリエチレン、ポリプロピレン、
エチレン／ブテン共重合体）等をうくネートした紙、合
成紙等の可撓性反射支持体、酢酸セルロース、硝酸セル
ロース、ポリスチレン、ポリ塩化ビニル、ポリエチレン
テレフタレート、ポリカーボネイト、ボリアくド等の半
合成または合成高分子からなるフィルムや、これらのフ
ィルムに反射層を設けた可撓性支持体、金属等が含まれ
る。The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
flexible reflective supports such as synthetic paper, semi-synthetic materials such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and boria Examples include films made of synthetic polymers, flexible supports provided with reflective layers on these films, metals, and the like.
本発明に用いる感光材料のバインダーとしてはゼラチン
を用いるのが有利であるが、セラチン誘導体、セルロー
ス誘導体、ゼラチンと他の高分子のグラフトポリマー、
それ以外の蛋白質、糖誘導体、セルロース誘導体、単一
あるいは共重合体の如き合成親水性高分子物質等の親水
性コロイドも用いることができる。It is advantageous to use gelatin as the binder for the photosensitive material used in the present invention; however, seratin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.
ゼラチンとしては石灰処理セラチンのばか酸処理セラチ
ン、ビュレヂン オブ ソサエティ オブ ジャパン（
Ｂｕｌｌ、Ｓｏｃ、Ｓｃｉ、Ｐｈｏｔ、Ｊａｐａｎ）
Ｎｏ、 １６．３０頁（１９６６）に記載されたような
酵素ＩＡ理ゼラヂンを用いてもよく、またゼラチンの加
水分解物や酵素分解物も用いることができる。セラチン
誘導体としては、セラチンに例えば酸ハライド、酸無水
物、インシアナート類、ブロモ酢酸、アルカンサルトン
類、ビニルスルホンアよド類、マレインイくト化合物類
、ポリアルキレオンキシド類、エポキシ化合物類等種々
の化合物を反応させて得られるものか用いられる。その
具体例は米国特許第２，６１４．９２８号、同３．１３
２９４５号、同３，１８６，８４６号、同３３１２．５
５３号、英国特許第８６１．４１４号、同１，０３３，
１８９号、同１，００５，７８４号各明細書、特公昭４
２−２６８４５号公報等に記載されている。As for gelatin, lime-treated ceratin, acid-treated ceratin, Bureau of Society of Japan (
Bull, Soc, Sci, Photo, Japan)
Enzyme IA geladin as described in No., p. 16.30 (1966) may be used, and gelatin hydrolysates and enzymatic decomposition products may also be used. Seratin derivatives include various types of seratin, such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonate compounds, maleic acid compounds, polyalkyleonoxides, and epoxy compounds. The compound obtained by reacting the following compounds is used. Specific examples thereof include U.S. Patent No. 2,614.928 and U.S. Pat.
No. 2945, No. 3,186,846, No. 3312.5
53, British Patent No. 861.414, British Patent No. 1,033,
No. 189, Specifications of No. 1,005,784, Special Publication No. 4
It is described in Publication No. 2-26845 and the like.
蛋白質としては、アルブミン、カセイン、セルロース誘
導体としてはヒドロキシエチルセルロース、カルボキシ
メチルセルロース、セルロースの硫酸エステル、または
糖誘導体としてはアルギン酸ソーダ、澱粉誘導体が好ま
しい。Preferred proteins include albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, and sugar derivatives such as sodium alginate and starch derivatives.
前記ゼラチンと他の高分子のグラフトポリマーとしては
セラチンにアクリル酸、メタアクリル酸それらのエステ
ル、アミドなどの誘導体、アクリロニ］・リル、スチレ
ンなどの如きビニル系モノマーの単一（ホモ）または共
重合体をグラフトさせたものを用いることかてきる。こ
とに、ゼラチンとある程度相溶性のあるボッマー例えは
アクリル酸、アクリルアくト、メタアクリルアくト、ヒ
ドロキシアルキルメタアクリレート等の重合体とのグラ
フトポリマーが好ましい。これらの例は、米国特許第２
，７６３，６２５号、同２．８３１７６７号、同２，９
５６，８８４号等に記載されている。Examples of graft polymers of gelatin and other polymers include single (homo) or copolymer of vinyl monomers such as seratin, acrylic acid, methacrylic acid, their esters, amides, etc., acrylonitrile, styrene, etc. It is possible to use a grafted graft. In particular, graft polymers with polymers having some degree of compatibility with gelatin, such as acrylic acid, acrylate, methacrylate, hydroxyalkyl methacrylate, etc., are preferred. Examples of these are U.S. Pat.
, 763,625, 2.831767, 2.9
No. 56,884, etc.
代表的な合成親水性高分子物質は、ポリビニルアルコー
ル、ポリビニルアルコール部分のアセタール、ポリ−Ｎ
−ビニルピロリドン、ポリアクリル酸、ポリメタクリル
酸、ポリアクリルアミド、ポリビニルイミダゾール、ポ
リビニルピラゾール等の単一あるいは共重合体等であり
、例えば***特許出願（ＯＬＳ）２．３１２．７０８号
、米国特許第３．６２０．７５１Ｊｉｆ、同３，８７９
，２０５号各明細書、特公昭４３−７５６１号公報に記
載のものである。Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, acetal of polyvinyl alcohol, and poly-N
- Single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., such as West German patent application (OLS) No. 2.312.708, U.S. Pat. .620.751 Jif, 3,879 Jif
, No. 205, and Japanese Patent Publication No. 7561/1983.
次に、本発明に係る感光材料に用いられるハロゲン化銀
（以下単にハロゲン化銀乳剤という）について述べる。Next, silver halide (hereinafter simply referred to as silver halide emulsion) used in the light-sensitive material according to the present invention will be described.
ハロゲン化銀乳剤には、ハロゲン化銀として臭化銀、沃
臭化銀、沃塩化銀、塩臭化銀および塩化銀等の通常のハ
ロゲン化銀乳剤に使用される任意のものを用いることが
てきる。For the silver halide emulsion, any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used. I'll come.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、酸
性法、中性法およびアンモニア法のいずれで得られたも
のでもよい。該粒子は一時に成長させてもよいし、種粒
子をつくった後成長させてもよい。種粒子をつくる方法
と成長させる方法は同しであっても、異なってもよい。The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.
ハロゲン化銀乳剤はハロゲン化物イオンと銀イオンを同
時に混合しても、いずれか一方が存在する７夜中に、他
方を混合してもよい。また、ハロゲン化銀結晶の臨界成
長速度を考慮しつつ、ハロゲン化物イオンと銀イオンを
混合液内ｐｌ（、ｌ’Ａｇをコントロールしつつ逐次同
時に添加する事により、生成させてもよい。この方法に
より、結晶形が規則的で粒子サイズが均一に近いハロゲ
ン化銀ａ 子が得られる。成長後にコンバージョン法を
用いて、粒子のハロゲン組成を変化させてもよい。In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one may be mixed during the presence of the other. Alternatively, while considering the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them to the mixed solution while controlling pl(, l'Ag).This method By this method, silver halide particles having a regular crystal shape and a nearly uniform grain size can be obtained.After growth, a conversion method may be used to change the halogen composition of the grains.
ハロゲン化銀乳剤は、その製造時に、必要に応してハロ
ゲン化銀溶剤を用いて、ハロゲン化銀粒子の粒子サイズ
、粒子の形状、粒子サイズ分布および粒子の成長速度を
コントロールすることができる。When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.
ハロゲン化銀溶剤としては、アンモニア、ヂオエーテル
、チオ尿素、４置換チオ尿素等のチオ尿素誘導体、イミ
ダゾール誘導体を挙げることができる。ヂオエーテルに
関しては、米国特許第３゜２７１．１５７号、同３，７
９０，３８７号、同３．５７４，６２８号等を参考にす
ることができる。Examples of the silver halide solvent include ammonia, dioether, thiourea, thiourea derivatives such as 4-substituted thiourea, and imidazole derivatives. Regarding the dioether, U.S. Pat.
No. 90,387, No. 3.574,628, etc. may be referred to.
溶剤の使用量は、溶剤がアンモニア以外の場合は反応溶
剤１０−３〜１．０重量％、特に１０−２〜１ｏ−１重
量％が好ましい。アンモニアの場合は任意に選ぶ事がで
きる。When the solvent is other than ammonia, the amount of the reaction solvent used is preferably 10-3 to 1.0% by weight, particularly 10-2 to 1o-1% by weight. In the case of ammonia, it can be selected arbitrarily.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、粒
子を形成する過程および／または成長させる過程で、ル
テニウム塩、カドミウム塩、亜鉛塩、鉛塩、タリウム塩
、イリジウム塩又はこれを含む錯塩）、ロジウム塩又は
これを含む錯塩および鉄塩又はこれを含む錯塩から選ば
れる少なくとも１種を用いて金属イオンを添加し、粒子
内部におよび／または粒子表面にこれらの金属元素を含
有させることかでき、また適当な還元的雰囲気におくこ
とにより、粒子内部および／または粒子表面に還元増感
様を付与てきる。The silver halide grains used in the silver halide emulsion are prepared in the process of forming and/or growing the grains by using ruthenium salts, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts containing these. Metal ions can be added using at least one selected from rhodium salts or complex salts containing the same, and iron salts or complex salts containing the same, and these metal elements can be contained inside the particles and/or on the particle surfaces, Furthermore, by placing the particles in an appropriate reducing atmosphere, reduction sensitization can be imparted to the interior of the particles and/or the surface of the particles.
ハロゲン化銀乳剤は、ハロゲン化銀粒子の成長の終了後
に不要な可溶性塩類を除去してもよいし、あるいは含有
させたままでもよい。該塩類を除去する場合には、リサ
ーチ ディスクロジャー（Ｒｅ５ｅｒｃｈ Ｄｉｓｃ
ｌｏｓｕｒｒｅ） １７８４３号記載の方法に基づいて
行うことができる。Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Disc
It can be carried out based on the method described in Japanese Patent No. 17843.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、粒
子内において均一なハロゲン化銀組成分布を有するもの
でも、粒子の内部と表面層とでハロゲン化銀組成が異な
るコア／シェル粒子であってもよい。The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、潜
像が主として表面に形成されるような粒子てあってもよ
く、また主として粒子内部に形成されるような粒子でも
よい。The silver halide grains used in the silver halide emulsion may be such that a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、立
方体、八面体、十四面体のような規則的な結晶形を持つ
ものでもよいし、球状や板状のような変則的な結晶形を
持つものでもよい。これらの粒子において、（１００）
面と（ｐＨ）面の比率は任意のものが使用できる。また
、これら結晶形の複合形を持つものでもよく、様々な結
晶形の粒子が混合されてもよい。Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It can be something you have. In these particles, (100)
Any ratio between the surface and the (pH) surface can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.
ハロゲン化銀粒子の平均粒子サイズ（粒子サイズは投影
面積と等しい面積の円の直径を表す）は、０．５μｍ以
下が好ましいが、特に好ましいのは０．３ μｍ以下で
ある。The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 0.5 μm or less, and particularly preferably 0.3 μm or less.
ハロゲン化銀乳剤は、いかなる粒子サイズ分布を持つも
のを用いても構わない。粒子サイズ分布の広い乳剤（多
分散乳剤と称する）を用いてもよいし、粒子サイズ分布
の狭い乳剤（単分散乳剤と称する。ここでいう単分散乳
剤とは、粒径の分布の標準偏差を平均粒径で割ったとき
に、その値が０．２０以下のものをいう。ここで粒径は
球状のハロゲン化銀の場合はその直径を、球状以外の形
状の粒子の場合は、その投影像を同面積の円像に換算し
たときの直径を示す。）を単独又は数種類混合してもよ
い。また、多分散乳剤と単分散乳剤を混合して用いても
よい。但し、定着性と最大濃度を有利にする観点からは
単分散度３０％よりも単分散な乳剤を用いるのか好まし
い。Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. However, from the viewpoint of improving fixability and maximum density, it is preferable to use an emulsion with a monodispersity of more than 30%.
ハロゲン化銀乳剤は、別々に形成した２種以上のハロゲ
ン化銀乳剤を混合して用いてもよい。The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.
ハロゲン化銀乳剤は、常法により化学増感することがて
きる。即ち、硫黄増感法、セレン増感法、還元増感法、
金その他の貴金属化合物を用いる貴金属ｉ１感法などを
単独て又は組合せて用いることができる。Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal i1 sensitization method using gold or other noble metal compounds can be used alone or in combination.
ハロゲン化銀乳剤は、例えば英国特許第６１８．０６１
号、同１，３１５，７５５号、同１３９６．６９６号、
特公昭４４−１５７４８号、米国特許第１，５７４，９
４４号、同１．６２３．４９９号、同１，６７３，５２
２号、同２２７８．９４７号、同２，３９９，０８３号
、同２．４１０，６８９号、同２，４１９．９７４号、
同２，４４８，０６０号、同２，４８７．８５０号、同
２，５１８，６９８号、同２，５２１，９２６号、同２
，６４２，３６１号、同２６９４．６３７号、同２，７
２８，６６８号、同２．７３９，０６０号、同２，７４
３，１８２号、同２，７４３，１８３号、同２，９８３
，６０９号、同２，９８３，６１０号、同３，０２１．
２１５号、同３，０２６，２０３号、同３２９７．４４
６号、同３，２９７，４４７号、同３．３６１，５６４
号、同３，４１１，９１４号、同３，５５４，７５７号
、同３，５６５，６３１号、同３，５６５，６３３号、
同３，５９１．３８５号、同３，６５６，９５５号、同
３７６１．２６７号、同３，７７２，０３１号、同３．
８５７，７１１号、同３，８９１，４４６号、同３，９
０１，７１４号、同３，９０４，４１５号、同３，９３
０，８６７号、同３，９８４．２４９号、同４，０５４
，４５７号、同４０６７．７４０号、リサーチディスク
ロージャー（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ
） １２００８号、同１３４５２号、同１３６５４号、
ザ セオリー オブザ フォトグラフィック プロセス
（Ｔ、１１．Ｊａｍｅｓ著Ｔｈｅ Ｔｈｃｏｒｙ
ｏｆ 目１ｅ Ｐｌ＋ｏｌｏｇｒｕｐｈｉｃ Ｐ
ｒｏｃｅｓｓ４ｔｈ、Ｅｄ、 Ｍａｃｍｉｌｌａｎ、１
９７７ ） ｐｐ６７〜７６等に記載の化学増感剤や増
感方法を用いて増感することが好ましい。Silver halide emulsions can be used, for example, in British Patent No. 618.061.
No. 1,315,755, No. 1396.696,
Special Publication No. 44-15748, U.S. Patent No. 1,574,9
No. 44, No. 1.623.499, No. 1,673,52
No. 2, No. 2278.947, No. 2,399,083, No. 2.410,689, No. 2,419.974,
No. 2,448,060, No. 2,487.850, No. 2,518,698, No. 2,521,926, No. 2
, No. 642,361, No. 2694.637, No. 2,7
No. 28,668, No. 2.739,060, No. 2,74
No. 3,182, No. 2,743,183, No. 2,983
, No. 609, No. 2,983,610, No. 3,021.
No. 215, No. 3,026,203, No. 3297.44
No. 6, No. 3,297,447, No. 3,361,564
No. 3,411,914, No. 3,554,757, No. 3,565,631, No. 3,565,633,
No. 3,591.385, No. 3,656,955, No. 3761.267, No. 3,772,031, No. 3.
No. 857,711, No. 3,891,446, No. 3,9
No. 01,714, No. 3,904,415, No. 3,93
No. 0,867, No. 3,984.249, No. 4,054
, No. 457, No. 4067.740, Research Disclosure
) No. 12008, No. 13452, No. 13654,
The Theory of the Photographic Process (T, 11. The Theory of the Photographic Process) by James
of eye 1e Pl+olographic P
rocess4th, Ed, Macmillan, 1
977) It is preferable to sensitize using the chemical sensitizers and sensitization methods described in pp. 67 to 76.
本発明に係る感光材料に用いられるハロゲン化銀乳剤は
、写真業界において増感色素として知られている色素を
用いて、所要の波長域に光学的に増感できる。増感色素
は単独で用いてもよいが、２種以上を組合せて用いても
よい。増感色素とともにそれ自身分光増感作用を持たな
い色素、あるいは可視光を実質的に吸収しない化合物で
あって、増感色素の：ｌＩ！感作用を強める強色増感剤
を乳剤中に含有させてもよい。The silver halide emulsion used in the light-sensitive material of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb visible light; A supersensitizer that enhances the sensitization effect may be included in the emulsion.
増感色素としては、シアニン色素、メロシアニン色素、
複合シアニン色素、複合メロシアニン色素、ホロポーラ
−シアニン色素、ヘミシアニン色素、ステリル色素およ
びヘミオキサノール色素が用いられる。Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.
特に有用な色素は、シアニン色素、メロシアニン色素、
および複合メロシアニン色素である。これらの色素類に
は、塩基性異部環核としてシアニン色素類に通常利用さ
れる核のいずれをも適用できる。すなわち、ピロリン核
、オキサゾリン核、チアゾリン核、ピロール核、オキサ
ゾール核、チアゾール核、セレナゾール核、イミダゾー
ル核、テトラゾール核、ピリジン核およびこれらの核に
脂環式炭化水素環が融合した核：およびこれらの核に芳
香族炭化水素環が融合した核、即ち、インドレニン核、
ベンズインドレニン核、インドール核、ベンズオキサゾ
ール核、ナフトオキサゾール核、ベンゾデアゾール核、
ナフトチアゾール核、ベンゾセレナゾール核、ベンズイ
ミダゾール核、キノリン核などである。これらの核は炭
素原子上で置換されたもよい。Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzodeazole nucleus,
These include naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei may also be substituted on carbon atoms.
メロシアニン色素または複合メロシアニン色素にはケト
メチレン構造を有する核として、ピラゾリン−５−オン
核、チオヒダントイン核、２−チオオキサゾリジン−２
，４−ジオン核、デアシリジン−２，４−ジオン核、ロ
ーダニン核、ヂオバルビツール酸核などの５〜６員異節
環核な適用することができる。Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, deacylidine-2,4-dione nucleus, rhodanine nucleus, diobarbituric acid nucleus, and other 5- to 6-membered heterocyclic nuclei can be applied.
青感光性ハロゲン化銀乳剤層に用いられる有用な増感色
素としては、例えは***特許９２９，０８０号、米国特
許２，２３１，６５８号、同２４９３．７４８号、同２
，５０３，７７６号、同２．５１９，００１号、同２，
９１２，３２９号、同３，６５６，９５９号、同３，６
７２，８９７号、同３，６９４，２１７号、同４，０２
５．３４９号、同４，０４６．５７２号、英国特許１，
２４２，５８８号、特公昭４４−１４０３０号、同５２
−２４８４４号等に記載されたものを挙げることができ
る。また緑感光性ハロゲン化銀乳剤に用いられる有用な
増感色素としては、例えば米国特許１，９３９，２０１
号、同２，０７２．９０８号、同２，７３９．１４９号
、同２９４５．７６３号、英国特許５０５，９７９号等
に記載されている如きシアニン色素、メロシアニン色素
または複合シアニン色素をその代表的なものとして挙げ
ることがてきる。さらに、赤感光性ハロゲン化銀乳剤に
用いられる有用な増感色素としては、例えば米国特許２
，２６９，２３４号、同２，２７０，３７８号、同２，
４４２，７１０号、同２，４５４，６２９号、同２，７
７６．２８０号等に記載されている如きシアニン色素、
メロシアニン色素または複合シアニン色素をその代表的
なものとして挙げることができる。Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat.
, No. 503,776, No. 2.519,001, No. 2,
No. 912,329, No. 3,656,959, No. 3,6
No. 72,897, No. 3,694,217, No. 4,02
No. 5.349, No. 4,046.572, British Patent No. 1,
No. 242,588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,072.908, No. 2,739.149, No. 2945.763, British Patent No. 505,979, etc. It can be mentioned as something. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
, No. 269,234, No. 2,270,378, No. 2,
No. 442,710, No. 2,454,629, No. 2,7
Cyanine dyes such as those described in No. 76.280, etc.
Typical examples include merocyanine dyes and complex cyanine dyes.
更にまた米国特許２，２１３，９９５号、同２．４９３
，７４８号、同２，５１９，００１号、***特許９２９
，０８０号等に記載されている如きシアニン色素または
複合シアニン色素を緑感光性ハロゲン化銀乳剤または赤
感光性ハロゲン化銀乳剤に有利に用いることができる。Furthermore, U.S. Pat. No. 2,213,995, 2.493
, No. 748, No. 2,519,001, West German Patent No. 929
Cyanine dyes or composite cyanine dyes such as those described in , No. 080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.
これらの増感色素は単独に用いてもよいが、それらの組
合せを用いてもよい。増感色素の組合せは特は、強色増
感の目的でしばしば用いられる。These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.
その代表例は、特公昭４３−４９３２号、同４３−４９
３３号、同４３−４９３６号、同４４−３２７５３号、
同４５−２５８３１号、同４５−２６４７４号、同４６
−１１６２７号、同４６−１８１０７号、同４７−８７
４１号、同４７−ｐＨ１４号、同４７−２５３７９号、
同４７−３７４４３号、同４８−２８２９３号、同４８
−３８４０６号、同４８−３８４０７号、同４８−３８
４０８号、同４８−４１２０３号、同４８−４１２０４
号、同４９−６２０７号、同５０−４０６６２号、同５
３−１２３７５号、同５４−３４５３５号、同５５−１
５６９号、特開昭５０−３３２２０号、同５０−３３８
２８号、同５０−３８５２６号、同５１−１０７１２７
号、同５１−１１５８２０号、同５１−１３５５２８号
、同５１−１５１５２７号、同５２−２３９３１号、同
５２−５１９３２号、同５２−１０４９１６号、同５２
−１０４９１７号、同５２−１０９９２５号、同５２−
１１０６１８号、同５４−８０１１８号、同５６−２５
７２８号、同５７−１４８３号、同５Ｂ−１０７５３号
、同５Ｂ−９１４４５号、同５Ｂ−１５３９２６号、同
５９−１１４５３３号、同５９−１１６６４５号、同５
９−１１６６４７号、米国特許２，６６８，５４５号、
同２．９７７．２２９号、同３，３９７，０６０号、同
３，５０６，４４３号、同３，５７８，４４７号、同３
，６７２，８９８号、同３，６７９．４２８号、同３，
７６９，３０１号、同３゜８１４．６０９号、同３，８
３７，８６２号の各公報に記載されている。Typical examples are Special Publication No. 43-4932 and No. 43-49.
No. 33, No. 43-4936, No. 44-32753,
No. 45-25831, No. 45-26474, No. 46
-11627, 46-18107, 47-87
No. 41, No. 47-pH14, No. 47-25379,
No. 47-37443, No. 48-28293, No. 48
-38406, 48-38407, 48-38
No. 408, No. 48-41203, No. 48-41204
No. 49-6207, No. 50-40662, No. 5
No. 3-12375, No. 54-34535, No. 55-1
No. 569, JP-A No. 50-33220, JP-A No. 50-338
No. 28, No. 50-38526, No. 51-107127
No. 51-115820, No. 51-135528, No. 51-151527, No. 52-23931, No. 52-51932, No. 52-104916, No. 52
-104917, 52-109925, 52-
No. 110618, No. 54-80118, No. 56-25
No. 728, No. 57-1483, No. 5B-10753, No. 5B-91445, No. 5B-153926, No. 59-114533, No. 59-116645, No. 5
No. 9-116647, U.S. Patent No. 2,668,545,
2.977.229, 3,397,060, 3,506,443, 3,578,447, 3
, No. 672,898, No. 3,679.428, No. 3,
No. 769,301, No. 3゜814.609, No. 3,8
It is described in each publication of No. 37,862.
増感色素とともに用いられる、それ自身分光増感作用を
持たない色素、あるいは可視光を実質的に吸収しない物
質であって強色増感を示す物質としては、例えば芳香族
有機酸ホルムアルデヒド縮合物（例えば、米国特許３，
４７３，５１０号に記載のもの）、カドミウム塩、アザ
インデン化合物、含窒素異部環基で置換されたアミノス
チルベン化合物（例えば、米国特許２，９３３，３９０
号、同３，６３５，７２１号に記載のもの）等がある。Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( For example, U.S. Patent 3,
473,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. No. 2,933,390
No. 3,635,721).
これらの化合物と米国特許３，６１５，６１３号、同３
，６１５，６４１号、同３，６１７．２９５号、同３，
６３５，７２１号に記載の組合せは特に有用である。These compounds and U.S. Pat. Nos. 3,615,613 and 3
, No. 615,641, No. 3,617.295, No. 3,
The combinations described in No. 635,721 are particularly useful.
本発明に係るハロゲン化銀乳剤には、感光材料の製造工
程、保存中、あるいは写真処理中のカブリの防止、又は
写真性能を安定に保つことを目的として化学熟成中、化
学熟成の終了時、および／または化学熟成の終了後、ハ
ロゲン化銀乳剤を塗布するまでに、写真業界においてカ
ブリ防止剤または安定剤として知られている化合物を加
えることができる。The silver halide emulsion according to the present invention may be used during chemical ripening or at the end of chemical ripening for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to maintain stable photographic performance. and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers may be added.
カブリ防止剤、安定剤としては、米国特許２゜７１３．
５４１号、同２，７４３，１８０号、同２．７４３，１
８１号に記載されたペンタザインデン類、米国特許２，
７１６，０６２号、同２４４４．６０７号、同２，４４
４，６０５号、同２．７５６，１４７号、同２，８３５
，５８１号、同２，８５２，３７５号、リサーチ ディ
スクロージャー （Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓ
ｕｒｅ） １４８５１号に記載されたテトラザインデン
類、米国特許２゜７７２．１６４号に記載されたトリア
ザインデン類および特開昭５７−２ｐＨ４２号に記載さ
れたポリマー化アザインデン類等のアザインデン類、米
国特許２，１３１，０３８号、同３．３４２．５９６号
、同３，９５４，４７８号に記載されたデアゾリウム塩
、米国特許３，１４８，０６７号に記載されたピリリウ
ム塩、および特公昭５０−４０６６５号に記載されたホ
スホニウム塩等の４級オニウム塩、米国特許２，４０３
，９２７号、同３，２６６．８９７号、同３，７０８，
３０３号、特開昭５５−１３５８３５４、同５９７１０
４７号に記載されたメルカプ（・テトラシル類、メルカ
プトトリアゾール類、メルカプ１−ジアゾール類、米国
特許２，８２４，００１号に記載されたメルカプトチア
ソール類、米国特許３９３７．９８７号に記載されたメ
ルカプトオキサジアゾール類、メルカプトベンズイミダ
ゾール類、米国特許２，８４３．４９１号に記載された
メルカプトオキサジアゾール類、米国特許３，３６４．
０２８号に記載されたメルカプトチアジアゾール類等の
メルカプト置換へテロ環化合物類、米国特許３，２３６
，６５２号、特公昭４３−１０２５６号に記載されたカ
テコール類、特公昭５６−
よび特公昭４３−４１３３号に記載された没食子酸エス
テル等のポリヒドロキシベンゼン類、***特許１．１８
９，３８０号に記載されたテトラゾール類、米国特許３
，１５７，５０９号に記載されたトリアゾール類、米国
特許２，７０４，７２１号に記載されたヘンズトリアゾ
ール類、米国特Ｈｑ３，２８７．１３５号に記載された
ウラゾール類、米国特許３，１０６，４６７号に記載さ
れたピラゾール類、米国特許２，２７１．、２２９号に
記載されたインタゾール類、および特開昭５９−９０８
４４号に記載されたポリマー化ベンゾトリアゾール類等
のアゾール類や米国特許３，１６１、５１５号に記載さ
れたピリミジン類、米国特許２，７５１，２９７号に記
載された３−ビラソリトン類、および米国特許３，０２
１，２１３号に記載されたポリマー化ピロリドン即ちポ
リビニルピロリドン類等のへテロ環化合物類、特開昭５
４−１３０９２９号、同５９−１３７９４５号、同５９
−１４０４４５号、英国特許１．３５６１４２号、米国
特許３，５７５．６９９号、同３、６４９，２６７号等
に記載された各種の抑制剤プレカーサー、米国特許３，
０４７，３９３号に記載されたスルフィン酸、スルフィ
ン酸銹導体、米国特許２，５６６、２６３号、同２，８
３９、４０５号、同２，４８８，７０９号、同２７２８
、６６３号に記載された無機塩類等がある。As antifoggants and stabilizers, US Pat. No. 2,713.
No. 541, No. 2,743,180, No. 2.743,1
Pentazaindenes described in No. 81, U.S. Patent No. 2,
No. 716,062, No. 2444.607, No. 2,44
No. 4,605, No. 2.756,147, No. 2,835
, No. 581, No. 2,852,375, Research Disclosure
azaindenes such as tetrazaindenes described in U.S. Pat. No. 14851, triazaindenes described in U.S. Pat. Deazolium salts described in U.S. Pat. No. 2,131,038, U.S. Pat. Quaternary onium salts such as phosphonium salts described in US Pat. No. 40,665, US Pat.
, No. 927, No. 3,266.897, No. 3,708,
No. 303, JP-A-55-1358354, JP-A No. 59710
Mercapto (tetrasils, mercaptotriazoles, mercap-1-diazoles) described in US Pat. No. 47, mercaptothiazoles described in US Pat. No. 2,824,001, mercapto described in US Pat. Oxadiazoles, mercaptobenzimidazoles, mercaptooxadiazoles described in U.S. Pat. No. 2,843.491, U.S. Pat. No. 3,364.
Mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in No. 028, U.S. Pat. No. 3,236
, No. 652, catechols described in Japanese Patent Publication No. 43-10256, polyhydroxybenzenes such as gallic acid esters described in Japanese Patent Publication No. 56-1983 and Japanese Patent Publication No. 43-4133, West German Patent No. 1.18
Tetrazoles described in No. 9,380, U.S. Patent No. 3
, 157,509, Henz triazoles described in U.S. Pat. No. 2,704,721, urazoles described in U.S. Pat. No. 3,287.135, U.S. Pat. No. 3,106,467. pyrazoles described in US Pat. No. 2,271. , No. 229, and JP-A-59-908.
Azoles such as polymerized benzotriazoles described in U.S. Pat. No. 44, pyrimidines described in U.S. Pat. Patent 3,02
Heterocyclic compounds such as polymerized pyrrolidones, that is, polyvinylpyrrolidones, described in JP-A No. 1,213, JP-A-Sho 5
No. 4-130929, No. 59-137945, No. 59
-140445, British Patent No. 1.356142, U.S. Patent No. 3,575.699, U.S. Patent No. 3,649,267, etc.;
047,393, sulfinic acid salt conductor, U.S. Pat. No. 2,566,263, U.S. Pat. No. 2,8
39, 405, 2,488,709, 2728
, No. 663, and the like.
さらに本発明に用いられる感光利判の全ての親水性コロ
イド層には必要に応じて各種写真用添加剤、例えはゼラ
チン可塑剤、硬膜剤、界面活性剤、画像安定剤、紫外線
吸収剤、アンプスティン剤、ｐｌ＋調整剤、酸化防止剤
、弗：電防止剤、増粘剤、粒状性向上剤、染料、モルタ
ント、増白剤、現像速度調整剤、マット剤等を本発明の
効果が損？Ｚねれない範囲内で使用することができる。Furthermore, all the hydrophilic colloid layers of the photosensitive printing plate used in the present invention contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, The effects of the present invention may be impaired by the use of amplifier staining agents, PL+ regulators, antioxidants, anti-static agents, thickeners, graininess improvers, dyes, moltants, brighteners, development speed regulators, matting agents, etc. ? It can be used within the range that does not cause Z twist.
上記各種添加剤のうち、本発明に特に好ましく使用でき
るのとしては、可塑剤としては、例えば特開昭４８−６
３７１５号、英国特許第１，２３９，３３７号、米国特
許第３０６，４７０号、同２．３２７ ８０８号、同２
，７５９．８２１号、同２ ７７２．１６６号、同２，
８３５．５８２号、同２，８６０，９８０号、同２，８
６５，７９２号、同２．９０４，４３４号、同２．９６
０、４０４号、同３，００３，８７８号、同３０３３、
６８０号、同３，１７３，７９０号、同３ ２８７．２
８９号、同３，３６１，５６５号、同３，３９７，９８
８号、同３，４１２，１５９号、同３，５２０．６９４
号、同３．５２０７５８号、同３，６１５，６２４号、
同３。Among the various additives mentioned above, plasticizers that can be particularly preferably used in the present invention include, for example, JP-A No. 48-6
No. 3715, British Patent No. 1,239,337, U.S. Patent No. 306,470, U.S. Patent No. 2.327 808, U.S. Pat.
, No. 759.821, No. 2 772.166, No. 2,
No. 835.582, No. 2,860,980, No. 2,8
No. 65,792, No. 2.904,434, No. 2.96
0,404, 3,003,878, 3033,
No. 680, No. 3,173,790, No. 3 287.2
No. 89, No. 3,361,565, No. 3,397,98
No. 8, No. 3,412,159, No. 3,520.694
No. 3.520758, No. 3,615,624,
Same 3.
６３５、８５３号、同３，６４０，７２１号、同３ ６
５６．９５６号、同３，６９２，７５３号、同３，７９
１，８５７号等の各明細書に記載のものを９了ましく用
し）ることかできる。No. 635, 853, No. 3,640,721, No. 3 6
No. 56.956, No. 3,692,753, No. 3,79
No. 1,857, etc., can be freely used.
硬膜剤としては、アルデヒド系、アジリジン系（例えは
、ＰＢレポート、１９，９２１、米国特許第２，９５０
．１９７号、同２，９６４，４０４号、同２，９８３，
６１１号、同３，２７１，１７５号の各明細書、特公昭
４６−４０８９８号、特開昭５０−９１３１５号の各公
報に記載のもの）、イソオキサゾール系（例えば、米国
特許第３３１．６０９号明細書に記載のもの）エポキシ
系（例えば、米国特許第３．０４７，３９４号、***特
許第１，０８５，６６３号、英国特許第１．０３３，５
１８号の各明細書、特公昭４８３５４９５号公報に記載
のもの）、ビニールスルホン系（例えばＰ［］レポート
１９，９２０、***特許第１，１００，９４２号、同２
，３３７，４１２号、同２，５４５，７２２号、同２，
６３５゜５１８号、同２，７４２，３０８号、同２，７
４９．２６０号、英国特許第１．２５１，０９１号、特
願昭４５−５４２３６号、同４８−１１０９９６号、米
国特許第３，５３９，６４４号、同第３，４９０．９１
１号の各明細書に記載のもの）、アクリロイル系（例え
ば、特願昭４８−２７９４９号、米国特許第３，６４０
，７２０号の各明細書に記載のもの）、カルボジイミド
系（例えば、米国特許第２，９３８，８９２号、同４゜
０４３．８１８号、同４，０６１，４９９号の各明細書
、特公昭４６−３８７１５号公報、特願昭４９−１５０
９５号、明細書に記載のもの）、トリアジン系（例えば
、***特許第２，４１０，９７３号、同２，５５３，９
１５号、米国特許第３．３２５，２８７号の各明細書、
特開昭５２１２７２２号公報に記載のもの）、高分子型
（例えは、英国特許第８２２，０６１号、米国特許第３
６２３．８７８号、同３，３９６，０２９号、同３，２
２６，２３４号の各明細書、特公昭４７−１８５７８号
、同４７−１８５７９号、同４７−４８８９６号の各公
報に記載のもの）、その他マレイミＦ系、アセチレン系
、メタンスルホン酸エステル系、（Ｎ−メチロール系：
）の硬膜剤か単独または組み合せて使用できる。有用な
組合せ技術として、例えば***特許＠２，４４７゜５８
７号、同２，５０５，７４６号、同２．５１４．２４５
号、米国特許第３，０４７，９５７号、同３，８３２，
１８１号、同３，８４０，３７０号の各明細書、特開昭
４８−４３３１９号、同５０−６３０６２号、同５２−
１２７３２９号、特公昭４Ｂ−３２３６４号の各公報に
記載の組み合せが挙げられる。Hardening agents include aldehyde-based and aziridine-based (for example, PB Report, 19,921, U.S. Patent No. 2,950)
．． No. 197, No. 2,964,404, No. 2,983,
611, 3,271,175, Japanese Patent Publication No. 46-40898, and Japanese Patent Application Laid-Open No. 50-91315), isoxazole type (for example, U.S. Pat. No. 331.609) No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,5
18, those described in Japanese Patent Publication No. 4,835,495), vinyl sulfone systems (for example, P[] Report 19,920, West German Patent No. 1,100,942, and 2)
, No. 337,412, No. 2,545,722, No. 2,
635゜518, 2,742,308, 2,7
49.260, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, Japanese Patent Application No. 48-110996, U.S. Patent No. 3,539,644, British Patent No. 3,490.91
1), acryloyl type (e.g. Japanese Patent Application No. 48-27949, U.S. Patent No. 3,640)
, 720), carbodiimides (for example, those described in the specifications of U.S. Pat. No. 2,938,892, U.S. Pat. Publication No. 46-38715, patent application 1984-150
No. 95, described in the specification), triazine-based (for example, West German Patent No. 2,410,973, West German Patent No. 2,553,9
No. 15, U.S. Patent No. 3,325,287,
(described in Japanese Patent Application Laid-Open No. 5212722), polymer type (for example, British Patent No. 822,061, U.S. Patent No. 3)
No. 623.878, No. 3,396,029, No. 3,2
26,234, those described in Japanese Patent Publication Nos. 47-18578, 47-18579, and 47-48896), maleimi F-based, acetylene-based, methanesulfonic acid ester-based, (N-methylol type:
) can be used alone or in combination. As a useful combination technique, for example, the West German patent @2,447°58
No. 7, No. 2,505,746, No. 2.514.245
No. 3,047,957, U.S. Patent No. 3,832,
Specifications of No. 181, No. 3,840,370, JP-A No. 48-43319, No. 50-63062, No. 52-
Examples include combinations described in Japanese Patent Publications No. 127329 and Japanese Patent Publication No. 4B-32364.
紫外線吸収剤としては、ベンゾフェノン化合物（例えば
、特開昭４６−２７８４号、米国特許第３２１５．５３
０号、同３，６９８，９０７号に記載のもの）、ブタジ
ェン化合物（例えば、米国特許第４．０４５，２２９号
に記載のもの）、ケイヒ酸エステル化合物（例えば、米
国特許第３７０５．８０５号、同３，７０７，３７５号
、特開昭５２−４９０２９号に記載のもの）を用いるこ
とができる。さらに、米国特許第３．４９９．７６２号
、特開昭５４−４８５３５号に記載のものも用いること
ができる。紫外線吸収性のカプラー（例えば、α−ナフ
トール系のシアン色素形成カプラー）や、紫外線吸収性
のポリマー（例えば、特開昭５８−ｐＨ９４２号、同５
８−１７８３５１号、同５Ｂ−１８１０４１号、同５９
−１９９４５号、同５９−２３３４４号公報に記載のも
の）などを用いることができる。これらの紫外線吸収剤
は特定の層に媒染されていてもよい。As ultraviolet absorbers, benzophenone compounds (for example, JP-A-46-2784, U.S. Pat. No. 3,215.53)
No. 0, No. 3,698,907), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805). , No. 3,707,375, and JP-A No. 52-49029) can be used. Furthermore, those described in U.S. Pat. No. 3,499,762 and Japanese Patent Application Laid-open No. 54-48535 can also be used. UV-absorbing couplers (e.g., α-naphthol-based cyan dye-forming couplers) and UV-absorbing polymers (e.g., JP-A-58-pH942;
No. 8-178351, No. 5B-181041, No. 59
19945 and 59-23344), etc. can be used. These ultraviolet absorbers may be mordanted in specific layers.
フィルター染料、あるいはイラジェーション防止その他
種々の目的で用いられる染料には、オキサノール染料、
ヘミオキサノール染料、メロシアニン染料、シアニン染
料、スチリル染料、アゾ染料が含有される。なかでもオ
キサノーヘル染料；ヘミオキサノール染料およびメロシ
アニン染料が有用である。用い得る染料の具体例は***
特許第６１６．００７号、英国特許第５８４，６０９号
、同１，１７７．４２９号、特公昭２６−７７７７号、
同３９−２２０６９号、同５４−３８１２９号、特開昭
４８−８５１３０号、同４９−９９６２０号、同４９−
１１４４２０号、同４９−１２９５３７号、同５０−２
８８２７号、同５２−１０８１１５号、同５７−１８５
０３８号、米国特許第１，８７８，９６１号、同１，８
８４゜０３５号、同１，９１２，７９７号、同２，０９
８．８９１号、同２，１５０，６９５号、同２゜２７４
．７８２号、同２，２９８，７３１号、同２．４０９，
６１２号、同２，４６１，４８４号、同２，５２７，５
８３号、同２，５３３，４７２号、同２，８６５，７５
２号、同２．９５６．８７９号、同３，０９４，４１８
号、同３１２５．４４８号、同３．１４８，１８７号、
同３．１７７．０７８号、同３，２４７，４２７号、同
３，２６０．６ｆ）１号、同３．２８２６９９号、同３
，４０９，４３３号、同３．５４０．８８７号、同３．
５７５．７０４＋、同３６５３．９０５号、同３，７１
８，４７２号、同３．８６５，８１７号、同４．０７０
３５２号、同４，０７１，３１２号、ＰＢリレボーア４
１７５号各明細書、フォトグラフィック アブストラク
ト（Ｐｈｏｔｏ、Ａｂｓｔｒ、） １２ Ｂ （’
２１ ）等に記載されているものである。Filter dyes or dyes used for irradiation prevention and other purposes include oxanol dyes,
Contains hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanohel dyes; hemioxanol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include West German Patent No. 616.007, British Patent No. 584,609, British Patent No. 1,177.429, Japanese Patent Publication No. 1977-7777,
No. 39-22069, No. 54-38129, JP-A-48-85130, No. 49-99620, No. 49-
No. 114420, No. 49-129537, No. 50-2
No. 8827, No. 52-108115, No. 57-185
No. 038, U.S. Patent No. 1,878,961, U.S. Patent No. 1,8
No. 84゜035, No. 1,912,797, No. 2,09
No. 8.891, No. 2,150,695, No. 2゜274
．． No. 782, No. 2,298,731, No. 2.409,
No. 612, No. 2,461,484, No. 2,527,5
No. 83, No. 2,533,472, No. 2,865,75
No. 2, No. 2.956.879, No. 3,094,418
No. 3125.448, No. 3.148,187,
3.177.078, 3,247,427, 3,260.6f) 1, 3.282699, 3
, No. 409,433, No. 3.540.887, No. 3.
575.704+, 3653.905, 3,71
No. 8,472, No. 3.865,817, No. 4.070
No. 352, No. 4,071,312, PB Lilleboer 4
No. 175, each specification, Photographic Abstract (Photo, Abstract,) 12 B ('
21) etc.
蛍光増白剤としては、スチルベン系、トリアジン系、ピ
ラゾリン系、クマリン系、アセヂレン系の蛍光増白剤を
好ましく用いることができる。As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.
これらの化合物は水溶性のものてもよく、また不溶性の
ものを分散物の形て用いてもよい。These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion.
アニオン性界面活性剤としては、例えはアルキルカルホ
ン酸塩、アルキルスルホン酸塩、アルキルヘンセンスル
ホン酸塩、アルキルナフタレンスルボン酸塩、アルキル
硫酸エステル類、アルキルリン酸エステル類、Ｎ−アシ
ル−アルキルタウリン類、スルホフキハク酸エステル類
、スルホアルキルポリオキシエチレンアルキルフェニル
エーテル類、ポリオキシエチレンアルキルリン酸エステ
ル類等のような、カルホキシ基、スルホ基、ホスホ基、
硫酸エステル基、燐酸エステル基等の酸性基を含むもの
が好ましい。Examples of anionic surfactants include alkylcarphonates, alkylsulfonates, alkylhensene sulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl- Carboxyl groups, sulfo groups, phosphor groups such as alkyl taurines, sulfofuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a sulfate ester group or a phosphate ester group are preferred.
両性界面活性剤としては、例えばアミノ酸類、アミノア
ルキルスルホン酸類、アミノアルキル硫酸または燐酸エ
ステル類、アルキルベタイン類、アミンオキシド類等か
好ましい。Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides.
カチオン性界面活性剤としては、例えばアルキルアミン
塩類、脂肪族あるいは芳香族第４級アンモニウム塩類、
ピリジニウム、イミタゾリウムなとの複素環第４級アン
モニウム塩類、および脂肪族または複素環を含むホスホ
ニウムまたはスルホニウム塩類等か好ましい。Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Preferred are heterocyclic quaternary ammonium salts such as pyridinium and imitazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.
ノニオン性界面活性剤としては、例えはサポニン（ステ
ロイド系）、アルキレンオキザイト話専体（例えはポリ
エチレングリコール、ポリエヂレンルリコール／ポリプ
ロピレングリコール縮合物、ポリエチレングリコールア
ルキルエーテル類またはポリエチレングリコールアルキ
ルアリールエーテル類、ポリエチレングリコールエステ
ル類、ポリエチレングリコールソルビタンエステル類、
ポリアルキレンゲリコールアルキルア主ンまたばアくド
類、シリコーンのポリエチレンオキサイドｆ」加物類）
、グリシドール誘導体（例えはアルケニルコハク酸ポリ
グリセリド、アルキルフェノールポリグリセリド）、う
価アルコールの脂肪酸エステル類、糖のアルキルエステ
ル類等が好ましい。Examples of nonionic surfactants include saponin (steroids), alkylene oxite-based products (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers, or polyethylene glycol alkyl aryl ethers). , polyethylene glycol esters, polyethylene glycol sorbitan esters,
Polyalkylene gelicol alkyl alcohols, silicone polyethylene oxide additives)
, glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of hydric alcohols, alkyl esters of sugars, and the like are preferred.
マット剤としては、英国特許第１，０５５，７１３号、
米国特許第１，９３９，２１３号、同第２．２２１，８
７３号、同２，２６８，６６２号、同：）、、３３２．
０３７号、同２，３７６．０ＯＳ−；、同２，３９１，
１８１号、同２，７０１．２４５号、同２，９９２，１
０１号、同３０７９．２５７号、同３，２６２．７８２
号、同３．５１６，８３２号、同３．５３９．３４４号
、同３，５９１．３７９号、同３，７５４，９２４号、
同３．７６７．４４８号等に記載されている有機マツ］
−剤、***特許２，５９２，３２１号、英国持前第７６
０，７７５号、同１．２６０．７７２号、米国特許第１
，２０１．９０５号、同２，１９２．２４１号、同３，
０５３，６６２号、同３，０６２，６４９号、同３，２
５７．２０６号、同３，３２２，５５５号、同３３５３
．９５８号、同３，３７０．９５１号、同３．４１１，
９０７号、同３，４３７，４８４号、同３，５２３．０
２２号、同３．６１５５５４号、同３，６３５，７１４
号、同３，７６９．０２０号、同４，０２１，２４５号
、同４゜０２９．５０４号等に記載されている無機マッ
ト剤等を好ましく用いることかできる。As a matting agent, British Patent No. 1,055,713,
U.S. Patent No. 1,939,213, U.S. Patent No. 2.221,8
No. 73, No. 2,268,662, No. 73: ), 332.
No. 037, 2,376.0OS-;, 2,391,
No. 181, No. 2,701.245, No. 2,992.1
No. 01, No. 3079.257, No. 3,262.782
No. 3,516,832, No. 3,539.344, No. 3,591.379, No. 3,754,924,
Organic pine described in No. 3.767.448, etc.]
- Agent, West German Patent No. 2,592,321, British Patent No. 76
No. 0,775, No. 1.260.772, U.S. Patent No. 1
, 201.905, 2,192.241, 3,
No. 053,662, No. 3,062,649, No. 3,2
57.206, 3,322,555, 3353
．． No. 958, No. 3,370.951, No. 3.411,
No. 907, No. 3,437,484, No. 3,523.0
No. 22, No. 3.615554, No. 3,635,714
Inorganic matting agents described in Japanese Patent Application No. 3,769.020, Japanese Patent No. 4,021,245, Japanese Patent No. 4゜029.504, etc. can be preferably used.
甜電防止剤としては、英国特許第１．４６６６００号、
リザーチ ディスクロージャー （Ｒｅｓｅａｒｃｌ＋
Ｄｉｓｃｌｏｓｕｒｅ） １５８４０号、同１６２５
８号、同１６６３０号、米国特許第２，３２７．８２８
号、同２，８６１．０５６号、同３，２０６，３１２号
、同３，２４５，８３３号、同３゜４２８．４５１号、
同３，７７５，１２６号、同３．９６３，４９８号、同
４，０２５，３４２号、同４，０２５，４６３号、同４
，０２５．６９１号、同４．０２５．７０４号等に記載
の化合物や導電性ポリマーや酸化スズ、酸化インジウム
等を好ましく用いることができる。As an antistatic agent, British Patent No. 1.466600,
Research Disclosure (Research Disclosure
Disclosure) No. 15840, No. 1625
No. 8, No. 16630, U.S. Patent No. 2,327.828
No. 2,861.056, No. 3,206,312, No. 3,245,833, No. 3゜428.451,
No. 3,775,126, No. 3,963,498, No. 4,025,342, No. 4,025,463, No. 4
, No. 025.691, No. 4.025.704, conductive polymers, tin oxide, indium oxide, etc. can be preferably used.
さらに硬調化を助長する調子コントロール剤として、特
開昭６２−１１２５３号公報に記載のテトラゾリウム化
合物、ポリエチレンオキサイド誘導体、リン４級塩化合
物、あるいはヒドラジン化合物等を用いることもできる
。Furthermore, as a tone control agent that promotes high contrast, it is also possible to use tetrazolium compounds, polyethylene oxide derivatives, phosphorus quaternary salt compounds, hydrazine compounds, etc. described in JP-A-62-11253.
また、ポリマーラテックスをハロゲン化銀乳剤層、バッ
キング層に含有させ、寸法安定性を向上サセる技術も本
発明の態様とともに用いることができる。これらの技術
は、例えば特公昭９３−４２７２号、同３９−１７７０
２号、同４３−１３４８２号、米国特許第２，３７６．
００５号、同２．７６３．’６２５号、同２，７７２，
１６６号、同２，８５２，３８６号、同２，８５３，４
５７号、同３，３９７，９８８号等に記載されている。Further, a technique for improving dimensional stability by incorporating a polymer latex into a silver halide emulsion layer and a backing layer can also be used in conjunction with the embodiments of the present invention. These techniques are disclosed in, for example, Japanese Patent Publication Nos. 93-4272 and 39-1770.
No. 2, No. 43-13482, U.S. Patent No. 2,376.
No. 005, 2.763. '625, 2,772,
No. 166, No. 2,852,386, No. 2,853,4
No. 57, No. 3,397,988, etc.
本発明の感光材料は、該感光材料を構成する乳剤層が感
度を有しているスペクトル領域の電磁波を用いて露光で
きる。光源としては自然光（日光）、タングステン電灯
、蛍光灯、水銀灯、キセノナーク灯、炭素アーク灯、キ
セノンフラッシュ灯、陰極線管フライングスポット、ヨ
ー素クォーツ光源各種レーザー光、発光ダイオード光、
電子線、Ｘ線、γ線、α線などによって励起されに蛍光
体から放出される光等、公知の光源のいずれをも用いる
ことができる。The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, iodine quartz light sources, various laser lights, light emitting diode lights,
Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.
露光時間は通常カメラで用いられる１ミリ秒から１秒の
露光時間はもちろん、１マイクロ秒より短い露光、例え
は陰極線管やキセノン閃光管を用いた１００ナノ秒〜１
マイクロ秒の露光を用いることもてき、また１秒より長
い露光を与えることも可能である。これらの露光は連続
して行われても、間欠的に行われてもよい。Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposures shorter than 1 microsecond, such as 100 nanoseconds to 100 nanoseconds using a cathode ray tube or xenon flash tube.
Microsecond exposures may be used, and it is also possible to provide exposures longer than 1 second. These exposures may be performed continuously or intermittently.
本発明は、印刷用、Ｘ−レイ用、一般ネガ用、−酸リバ
ーサル用、一般ボジ用、直接ポジ用等の各種感光材料に
適用することができるが、極めて高いコントラストを要
求される印刷用感光材料に適用した場合特に著しい効果
が得られる。The present invention can be applied to various photosensitive materials such as those for printing, X-ray, general negative, -acid reversal, general positive, and direct positive, but for printing which requires extremely high contrast. Particularly remarkable effects can be obtained when applied to photosensitive materials.
本発明の方法による感光材料の現像処理には、公知の方
法による黒白、カラー、反転等の各種現像処理を用いる
ことができるが、高コントラストを与える印刷用感光材
料のための処理を行う場合特に有効である。Various types of development processing such as black and white, color, and reversal processing using known methods can be used to develop the photosensitive material according to the method of the present invention. It is valid.
以下実施例を挙げて本発明を更に説明するが、本発明は
これによって限定されるものではない。The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
まず臭化銀含有率の比較的小さい明室返し感材用ハロゲ
ン化銀感光材料を下記の様にして作製した。First, a silver halide light-sensitive material for a bright room return light-sensitive material having a relatively low silver bromide content was prepared as follows.
（乳剤Ｅ−１およびＥ−２の調製）
下記のようにして臭化銀含有率２モル％の塩臭化銀乳剤
Ｅ−１を調製した。(Preparation of Emulsions E-1 and E-2) Silver chlorobromide emulsion E-1 having a silver bromide content of 2 mol % was prepared as follows.
硝酸銀１モル当り１．０Ｘ１０’モルのペンタクロロジ
ウムナトリウム塩、塩化ナトリウムおよび臭化カリウム
を含有する水溶液と硝酸銀水溶液とをゼラチン水溶液中
に攪拌しつつ、４０°Ｃ１２５分間で同時混合して平均
粒径約０．１８μｍの塩臭化銀乳剤を作製した。この時
の単分散度は２０％であった。An aqueous solution containing 1.0 x 10' mol of pentachlorodium sodium salt, sodium chloride, and potassium bromide per 1 mol of silver nitrate and an aqueous silver nitrate solution were simultaneously mixed in an aqueous gelatin solution at 40°C for 125 minutes to form average grains. A silver chlorobromide emulsion with a diameter of about 0.18 μm was prepared. The degree of monodispersity at this time was 20%.
この乳剤に安定剤として６−メチル−４−ヒドロキシ−
１，３，３ａ、７−チトラザインデンをハロゲン化銀１
モル当り５７０ｍｇ加えた後、水洗、脱塩した。This emulsion was added with 6-methyl-4-hydroxy- as a stabilizer.
1,3,3a,7-chitrazaindene as silver halide 1
After adding 570 mg per mole, the mixture was washed with water and desalted.
これにハロゲン化銀１モル当り６０ｍｇの６メチルー４
−ヒドロキシ−１，３，３ａ、７−テトラザインデンを
加えた後、イオウ増感をした。イオウ増感後、安定剤と
して６−メチル−４−ヒドロキシ１．３．３ａ、７−チ
トラザインデンを加え、次いで水にてハロゲン化銀１モ
ル当り１１に仕上げて乳剤Ｅ−１を調製した。ヨウ化銀
０．５モル％の塩ヨウ臭化銀を用いた以外乳剤Ｅ−４と
同様の方法で乳剤Ｅ−２を調製した。To this was added 60 mg of 6-methyl-4 per mole of silver halide.
After adding -hydroxy-1,3,3a,7-tetrazaindene, sulfur sensitization was performed. After sulfur sensitization, 6-methyl-4-hydroxy 1.3.3a, 7-chitrazaindene was added as a stabilizer, and the emulsion was then worked up to 11 per mole of silver halide with water to prepare emulsion E-1. Emulsion E-2 was prepared in the same manner as Emulsion E-4 except that 0.5 mol % of silver iodide was used as silver chloride iodobromide.
（乳剤添加用ラテックス（Ｌ）の作製）水４０乏に名糖
産業製ＫＭＤＳ （デキストラン硫酸エステルナトリウ
ム塩）を０．２５ ｋｇおよび過硫酸アンモニウム０．
０５ ｋｇ加えた液に液温８１°Ｃで攪拌しつつ窒素雰
囲気下でｎ−ブチルアクリレート４．５１ ｋｇ、スチ
レン５．４９ ｋｇおよびアクリル酸０．１ ｋｇの混
合液を１時間かけて添加、その後過硫酸アンモニウムを
０．００５ｋｇ加え、更に１．５時間攪拌後、冷却、更
にアンモニア水にてｐＨを６に合せた。得られたラテッ
クス液をＷｈｏＬｍａｎ社製ＧＦ／Ｄフィルターで濾別
し、水で５０．５ ｋｇに仕上げる事で平均粒径約０．
２５μの単分散な乳剤液添加用ラテックス液（Ｌ）を作
製した。(Preparation of latex (L) for emulsion addition) Add 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Meito Sangyo to 40 kg of water and 0.2 kg of ammonium persulfate.
A mixed solution of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene, and 0.1 kg of acrylic acid was added over 1 hour under a nitrogen atmosphere while stirring at a liquid temperature of 81°C. Thereafter, 0.005 kg of ammonium persulfate was added, and after further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 with aqueous ammonia. The obtained latex liquid was filtered using a WhoLman GF/D filter and made up to 50.5 kg with water, reducing the average particle size to approximately 0.5 kg.
A monodisperse latex liquid (L) for adding a 25 μm emulsion liquid was prepared.
（乳剤塗布液Ｆ−１〜Ｆ−５の調製）（乳剤層）前記乳
剤Ｅ−１およびＥ−２を、表−ｌを作成するに必要な分
割をし、ハロゲン化銀乳剤塗布液Ｆ−１〜Ｆ−５を下記
の様にして調製した。(Preparation of emulsion coating solutions F-1 to F-5) (Emulsion layer) The emulsions E-1 and E-2 were divided as necessary to prepare Table 1, and silver halide emulsion coating solution F- 1 to F-5 were prepared as follows.
分割された乳剤Ｅ−１またばＥ−２に殺菌剤として下記
化合物（Ｋ）を２５ ｍｇ／ＡｇＸ １モルを加えた後
、０．５規定水酸化すトリウム液を用いてｐｌ＋を６．
５に調整、次いで本発明化合物である例示化合物を表〜
１に従って塗布１ｍ２当り４０ｍｇ加え、更に、ハロゲ
ン化銀１モル当りザボニン２０％水溶液ヲ１４ ｍｆ
、ドデシルヘンゼンスルフォン酸ナトリウムを１５０
ｍｇ／ＡｇＸ １モル、下記化合物（Ｒ）を２．７Ｘ
１０−３モル／Ａ８Ｘ １モル、前記乳剤液添加用ラテ
ックス液（Ｌ）を１２１ ｍｊ２／ＡｇＸ１モル、下記
化合物（Ｍ）を１４０ ｔｕｇ／ＡｇＸ １ モル、お
よび増粘剤として、スチレン−マレイン酸共重合体水性
ポリマーを］、 ｇ ／ＡｇＸ １モルを順次加えて、
ハロゲン化銀１モル当り１．３４ Ｎに仕上げて乳剤塗
布液Ｆ−１〜Ｆ−４を調製した。なお、例示化合物を加
えず乳剤Ｅ−１を用いて、同様に乳剤塗布液Ｆ−５を調
製した。After adding 25 mg/AgX 1 mol of the following compound (K) as a bactericide to the divided emulsion E-1 or E-2, pl+ was reduced to 6.5 mg using 0.5 N thorium hydroxide solution.
5, and then list the exemplary compounds that are the compounds of the present invention.
1, add 40 mg per 1 m2 of coating, and further add 14 mf of a 20% aqueous solution of Zabonin per mol of silver halide.
, sodium dodecylhenzenesulfonate 150
mg/AgX 1 mol, the following compound (R) 2.7X
10-3 mol/1 mol of A8X, 121 mj2/1 mol of the latex liquid for adding the emulsion (L), 140 tug/AgX 1 mol of the following compound (M), and styrene-maleic acid as a thickener. polymer aqueous polymer], g/AgX 1 mol were added sequentially,
Emulsion coating solutions F-1 to F-4 were prepared by finishing to 1.34 N per mole of silver halide. Incidentally, emulsion coating solution F-5 was similarly prepared using emulsion E-1 without adding the exemplified compound.
化合物（Ｋ） 化合物（Ｒ）化合物（Ｍ）
として平均粒径６μの不定型シソ力を２０ｇ、おるよう
に加え、更にクエン酸液でｐ Ｈ５，４とした後、水に
て１７℃に仕上げて乳剤保護膜塗布液Ｐ３を調製した。Compound (K) Compound (R) Compound (M) 20g of amorphous perilla with an average particle size of 6μ was added to the mixture, and after adjusting the pH to 5.4 with citric acid solution, the mixture was heated to 17°C with water. Emulsion protective film coating solution P3 was prepared.
乳剤保護膜塗布液Ｐ−１を、例示化合物を添加せずに、
乳剤層８！塗布液Ｐ−３と同様に調製した。Emulsion protective film coating solution P-1 was prepared without adding any exemplified compounds.
Emulsion layer 8! It was prepared in the same manner as coating liquid P-3.
化合物（Ｚ）
〇
一北〜
ＣＩｌ□ ＯＣＨｚ （ＣＨｚ） ｚｃＩｌ＊次いで
乳剤保護膜塗布液Ｐ−１およびＰ−３を下記の様にして
調製した。Compound (Z) 〇Ikkita~ CIl□ OCHz (CHz) zcIl* Then, emulsion protective film coating solutions P-1 and P-3 were prepared as follows.
（乳剤保護膜塗布液ｐ−１およびＰ−３の調製）（乳剤
保護層）
ゼラチン１ｋｇ中に純水１０Ｅを加え、膨潤後４゜°Ｃ
で溶解、次いで塗布助剤として、下記化合物（Ｚ）の１
％水？容客演２．９℃、ハロゲンアクセフ。(Preparation of emulsion protective film coating solutions p-1 and P-3) (emulsion protective layer) Add 10E of pure water to 1 kg of gelatin and heat at 4°C after swelling.
Then, as a coating aid, 1 of the following compound (Z) was added.
%water? Temperature: 2.9℃, halogen temperature.
クーとして下記化合物（Ｎ）を８０ｇ、マット剤化合物
（Ｎ）
化合物（Ｈ）
（バッキング塗布液Ｂ−１およびＢ−２の調製）（バッ
キング下層）
次いで、バッキング下層を塗布するに用いるバッキング
塗布液Ｂ−１およびＢ＝２を下記の様にして１周製した
。80 g of the following compound (N) as a coating, matting agent compound (N), compound (H) (Preparation of backing coating liquids B-1 and B-2) (Backing lower layer) Next, backing coating liquid used to apply the backing lower layer. B-1 and B=2 were produced once in the following manner.
ゼラチン３６ｋｇを水に膨潤し、加温して溶解後、染料
として下記化合物（Ｃ−１）を１．６ ｋｇ、（Ｃ２）
を３１０ｇ、（Ｃ−３）を１．９ ｋｇ、前記化合物（
Ｎ）を２．９ ｋｇ、水溶液にして加え、次にサポニン
の２０％水溶液を１１ｆｆｉ、物性調整剤として下記化
合物（Ｃ−４）を５ｋｇ加え更に、メタノール溶液とし
て、下記化合物（Ｃ−５）を６３ｇ、下記化合物（Ｃ−
６）を２７０ｇおよび平均分子量ｌＯ万の下記高分子（
Ｃ−７）を８ｇ加えた。Swell 36 kg of gelatin in water, heat and dissolve, then add 1.6 kg of the following compound (C-1) as a dye, (C2)
310 g, (C-3) 1.9 kg, the above compound (
Add 2.9 kg of N) as an aqueous solution, then add 11ffi of a 20% aqueous solution of saponin and 5 kg of the following compound (C-4) as a physical property modifier, and further add the following compound (C-5) as a methanol solution. 63g, the following compound (C-
6) and 270 g of the following polymer (
8g of C-7) was added.
この液に増粘剤として、スチレン−マレイン酸共重合体
水溶性ポリマーを８００ｇ加え粘度調製、例示化合物（
１）を塗布后４０ｍｇ／ｍ”になる量加え、更にクエン
酸水溶液を用いてｐ Ｈ５，４に調製し、最後にグリオ
キザールを１４４ｇ加え、水にて９６０１に仕上げてバ
ッキング塗布液Ｂ−２を調製した。バッキング塗布液Ｂ
−１をバッキング塗布液Ｂ−２と同様であるが、例示化
合物（１）を除いて調製した。To this liquid, 800 g of a water-soluble styrene-maleic acid copolymer was added as a thickener to adjust the viscosity, and the exemplified compound (
After coating, add 1) in an amount of 40 mg/m'', adjust the pH to 5.4 using an aqueous citric acid solution, and finally add 144 g of glyoxal and finish to 9601 with water to create backing coating liquid B-2. Prepared: Backing coating solution B
-1 was prepared in the same manner as backing coating liquid B-2 except that exemplified compound (1) was excluded.
化合物（Ｃ−１） に１１．５Ｏ３１１ 化合物（Ｃ−２） 化合物（（，５） 化合物（Ｃ−６） Ｃ２１１５ 化合物（Ｃ−３） 高分子（Ｃ−７） 化合物（Ｃ−４） ｃＩ！。Compound (C-1) 11.5O311 Compound (C-2) Compound ((,5) Compound (C-6) C2115 Compound (C-3) Polymer (C-7) Compound (C-4) cI! .
−＋ＣＨｚ ＣＩｌ＋−ｉ−と→Ｃ１１，−Ｃ）−ＣＯ
ＺＣ４Ｈ９ＣＩ！。-+CHz CIl+-i- and →C11,-C)-CO
ZC4H9CI! .
のコポリマーラテックス
但しｍ：ｎ＝１ｊｌ
（バッキング層保護膜塗布液ｐ−２およびＰの調製）（
バッキング上層）
ゼラチン５０ｋｇを水に膨潤し、加温溶解後、２スルボ
ネ−１ヘーコハク酸ビス（２−エチルヘキシル）エステ
ルナトリウム塩を３４０ｇ加え、マット剤としてポリメ
チルメタアクリレ−１−（平均粒径約７μ）を１．７
ｋｇ、塩化すトリウムを３．４ ｋｇ加え、例示化合物
（１）を塗布層４０ｍｇ／ｍ”になる量加え、更にグリ
オキザールを１．１ ｋｇ、ムコクロル酸を５４０ｇ加
え、水にて１０００ｆｉに仕上げてバッキング層保護膜
塗布液Ｐ−４を調製した。バンキング層保護膜塗布液Ｐ
−２をバッキング層保護膜塗布液Ｐ−４と同様ではある
が、例示化合物（１）を除いて調製した。Copolymer latex with m: n = 1jl (Preparation of backing layer protective film coating solutions p-2 and P) (
Backing upper layer) Swell 50 kg of gelatin in water, dissolve it by heating, add 340 g of 2-sulfone-1 hesuccinic acid bis(2-ethylhexyl) ester sodium salt, and add polymethyl methacrylate-1 (average particle size) as a matting agent. approximately 7μ) to 1.7
3.4 kg of thorium chloride, added exemplified compound (1) in an amount to give a coating layer of 40 mg/m'', further added 1.1 kg of glyoxal and 540 g of mucochloric acid, and finished with water to 1000 fi. Backing layer protective film coating solution P-4 was prepared.Banking layer protective film coating solution P
-2 was prepared in the same manner as backing layer protective film coating solution P-4 except that exemplified compound (1) was excluded.
（’！ｉ）電防止層を有する支持体の調製〕下引処理し
たポリエチレンテレフタレートに５０Ｗ／ｍ２ ・ｍｉ
ｎのエネルギーでコロナ放電した後下記組成の帯電防止
液を下記の付量になる様に３０ｍ／ｍｉｎの速さでロー
ルフィッＩ・コーティングパン及びエアーナイフを使用
して塗布した。('!i) Preparation of support with antistatic layer] 50 W/m2 ・mi on subbed-treated polyethylene terephthalate
After corona discharge with an energy of n, an antistatic liquid having the composition shown below was applied at a speed of 30 m/min using a roll-fit I coating pan and an air knife in the amount shown below.
水溶性導電性ポリマー（Ａ） ０．６ｇ／ｍ２疎水性
ポリマー粒子（Ｂ） ０．３ｇ／ｍ２硬膜剤（Ｈ）
０．１５ｇ／ｍ２ノニオン活性剤（
Ｃ） ０．０６ｇ／ｍ”これを９０°Ｃ，２分
間乾燥し、１４０°ｃ１９０秒間熱処理して帯電防止層
を有する支持体を調製した。Water-soluble conductive polymer (A) 0.6g/m2 Hydrophobic polymer particles (B) 0.3g/m2 Hardener (H)
0.15g/m2 nonionic activator (
C) 0.06 g/m'' This was dried at 90°C for 2 minutes and heat treated at 140°C for 190 seconds to prepare a support having an antistatic layer.
ここで、
Ｍｎ ＝７０００
Ｂ ： Ｃ１＋３
−（−ＣＩｌ ２ Ｃ１１）−ｒＴ−（Ｃｔｌ ２ Ｃ
＋−ａＴ−（Ｃ１１ｚ Ｃ１１）−−ＣＩｌ ｚ Ｃ１
１）４ＣＯ□Ｃ４Ｈ９ｃｏ□Ｃ４１１９（ＣＩＩ□ＣＩ
Ｉ□Ｏ）、ｌ−１＋但し、ｎ＝７〜９
Ｃ： １１０（ＣＩｈＣＨｚＯ）３≦１（（塗布時
乾燥条件）
３５°Ｃの塗布液を塗布後５°Ｃの冷風で６秒間処理し
て冷却凝固さセ、その後乾球温度２３°Ｃ１相対湿度２
０％の乾燥風を用い塗設面温度１０°Ｃで塗布層ゼラチ
ン含水率１６００％まで乾燥し、次いで乾燥温度２７゛
Ｃ１相対湿度２０％の乾燥風を用い含水水率８００％ま
で乾燥した。次に乾燥温度３４°Ｃで乾燥条件Ｉをみた
すように乾燥させた。塗設乾燥面の平均温度が３３°Ｃ
になったのち５秒後に乾燥条件■で乾燥さセた。Here, Mn = 7000 B: C1+3 -(-CIl2C11)-rT-(Ctl2C
+-aT-(C11z C11)--CIl z C1
1) 4CO□C4H9co□C4119 (CII□CI
I□O), l-1+, where n = 7 to 9 C: 110 (CIhCHzO) 3≦1 ((drying conditions during application) After applying the coating solution at 35°C, treat it with cold air at 5°C for 6 seconds. Cool and solidify, then dry bulb temperature 23°C 1 relative humidity 2
The coated gelatin layer was dried to a water content of 1600% using 0% drying air at a coating surface temperature of 10°C, and then dried to a water content of 800% using drying air at a drying temperature of 27°C and a relative humidity of 20%. Next, it was dried at a drying temperature of 34°C so as to satisfy drying condition I. The average temperature of the coating drying surface is 33°C
After 5 seconds, it was dried under drying condition (■).
表−３乾燥条件Ｉ（＋１２０／ゼラヂンの重量比８００
％〜２００％での表面
温度の最高値および乾燥時間）
表−４乾燥条件■
（評価試料の作成）
前記の各塗布液を表−１に示す組み合わせで乳剤層塗布
面に特開昭５１−１９９４１の実施例−１の下引き層を
施しバッキング層塗布面には前記バンキング用下引き層
を施したポリエチレンテレフタレートフィルム（厚さ１
００μ）上の両面に塗布し、表１に示す評価試料を作成
した。その際、下引き層を塗設した支持体の一方の面上
にバツキフグ下層をバンキング塗布液Ｂ−１を用いてゼ
ラチン乾燥重量が２ｇ／ｍ２になる様に塗布し、同時に
その上部にバッキング層保護膜塗布液Ｐ−２を用いて保
護膜層をゼラチン乾燥重量が１ｇ７ｍ２となる様に塗布
した。次いで支持体の他の１面上に乳剤層をゼラチン乾
燥重量が２ｇ／ｍ２、塗布銀量が３．５ｇ／ｍ２となる
様に塗布し、その上部に乳剤保護膜層をゼラチン乾燥重
量が１ ｇ／ｍ”となる様に硬膜剤としてホルマリンを
加えながら乳剤層と同時に塗布し表１の評価試料Ａ−１
〜Ａ８および比較試料Ｂを作製した。Table-3 Drying conditions I (+120/geladine weight ratio 800
% to 200% and drying time) Table 4 Drying conditions ■ (Preparation of evaluation samples) The above-mentioned coating solutions were applied to the coating surface of the emulsion layer using the combinations shown in Table 1. A polyethylene terephthalate film (thickness 1
00μ) to prepare evaluation samples shown in Table 1. At that time, on one side of the support coated with the undercoat layer, a Bakukifugu lower layer was coated using banking coating liquid B-1 so that the gelatin dry weight was 2 g/m2, and at the same time, a backing layer was applied on top of the lower layer. A protective film layer was coated using protective film coating liquid P-2 so that the gelatin dry weight was 1g7m2. Next, an emulsion layer was coated on the other side of the support so that the dry weight of gelatin was 2 g/m2 and the amount of coated silver was 3.5 g/m2, and on top of that, an emulsion protective layer was coated with a dry weight of gelatin of 1 g/m2. Evaluation sample A-1 in Table 1 was coated simultaneously with the emulsion layer while adding formalin as a hardening agent so that the
~A8 and comparative sample B were produced.
得られた評価試料Ａ−１〜Ａ−８、および比較試料Ｂを
用いて以下の方法で諸々の評価を行った。Using the obtained evaluation samples A-1 to A-8 and comparative sample B, various evaluations were performed by the following methods.
（実用濃度の評価）
Ａ−１−Ａ−８及びＢの評価試料を網点％５０％のチン
トを原稿として大日本スクリーン社製明室プリンターＰ
−６２７ＦＡで密着返し露光した。(Evaluation of Practical Density) Evaluation samples of A-1-A-8 and B were printed on Dainippon Screen Co., Ltd.'s Bright Room Printer P using tint with halftone dots of 50% as manuscripts.
Close contact back exposure was carried out with -627FA.
各評価試料の露光に用いた露光時間は露光済みフィルム
を現像処理後した時にできる網点％が５０％になるよう
に設定した。露光済みフィルムの現像処理は自動現像機
をもちいて下記現像処理条件で行った。この時得られた
処理後フィルム上の網点最大濃度を実用濃度として測定
し、下記表−２に結果を記載した。The exposure time used for exposing each evaluation sample was set so that the percentage of halftone dots formed when the exposed film was developed was 50%. The exposed film was developed using an automatic processor under the following development conditions. The maximum halftone dot density on the processed film obtained at this time was measured as the practical density, and the results are shown in Table 2 below.
（定着ハロゲン化銀ヌケ性の評価）
上記現像処理後のフィルムを目視観察しハロゲン化銀の
残存度合を３ランク評価し、下記表−２に結果を記載し
た。(Evaluation of fixed silver halide removal property) The film after the above development process was visually observed and the degree of silver halide remaining was evaluated in three ranks, and the results are listed in Table 2 below.
ランク〇二透明であり、ハロゲン化銀による濁りが認め
られない。Rank 02: Transparent, with no turbidity due to silver halide.
ランクΔ：試料の中央部に薄い濁りが認められる。Rank Δ: Light turbidity is observed in the center of the sample.
ランクズ：試料の中央部に強い濁りが認められる。Ranks: Strong turbidity is observed in the center of the sample.
（処理後フィルムの経時着色の評価）
上記現像処理後のフィルムを６０°Ｃ×８０％の環境条
件に５日間放置した後に発生した黄色残色をブルー濃度
として測定し、下記表−２に結果を記載した。(Evaluation of coloration over time of processed film) The yellow residual color that occurred after the film was left in an environmental condition of 60°C x 80% for 5 days was measured as blue density, and the results are shown in Table 2 below. is listed.
（乾燥性の評価）
上記現像処理条件で各評価試料（サイズ＝５０８ｍｍＸ
６１０ｍｍ）をそれぞれ３０枚連続処理し、最後に処
理した試料の乾燥度合を手の触感によって判定した。評
価は乾燥している場合○とし、濡れている場合×とし、
下記表−２に記載した。(Evaluation of drying property) Each evaluation sample (size = 508 mm
610 mm) were continuously processed, and the degree of dryness of the last processed sample was judged by the touch of the hand. The evaluation is ○ if it is dry, × if it is wet,
It is described in Table 2 below.
尚、現像処理条件、現像液処方、定着液組成は次の通り
であった。The development processing conditions, developer formulation, and fixer composition were as follows.
（現像処理条件）
（工 程）
現像
定着
水洗
乾燥
（現像液処方）
（組成Ａ）
（温 度）
３４°Ｃ
３４°Ｃ
常温
４０°Ｃ
（時 間）
１５秒
１５秒
１０秒
１０秒
（組成り）
現像液の使用時に水５００＋ｎｊ！中に上記（組成Ａ）
、（組成り）の順に溶かし、１１に仕上げて用いた。(Development processing conditions) (Process) Developing, fixing, washing and drying (Developer formulation) (Composition A) (Temperature) 34°C 34°C Room temperature 40°C (Time) 15 seconds 15 seconds 10 seconds 10 seconds (Composition ri) Water 500+nj when using developer! Above (composition A)
, (composition) and finished to 11 for use.
（定着液組成）
（組成Ａ）
０■或Ｂ）
定着液の使用時に水５００ｍｊ２中に上記Ｍｉ威Ａ、組
成りの順に溶かし、１Ｎに仕上げて用いた。(Fixer Composition) (Composition A) 0 or B) When using a fixer, the above MiA was dissolved in 500 mj2 of water in the following order, and the solution was finished to 1N.
この定着液のｐ ）（ば約４．５であった。The p of this fixer was approximately 4.5.
以下余白
表−２の結果から明らかなように、本発明の試料は、実
用濃度、銀ヌケ性、経時着色、乾燥性のいずれの点にお
いても大巾な向上が達成されており、特に、ヨウ素季離
化合物を併用した場合（Ａ７、Ａ−８）には顕著な向上
が得られている。As is clear from the results in Margin Table 2 below, the samples of the present invention have achieved significant improvements in practical density, silver removal properties, coloring over time, and drying properties, and in particular, iodine When the seasoning compound was used in combination (A7, A-8), a remarkable improvement was obtained.
本発明は、一般式（１）及び一般式（ＩＩ）で表される
化合物を含有させることにより、迅速現像処理を行った
場合に最高濃度、硬調性、残色、定着性及び乾燥性を同
時に満足することができる優れたハロゲン化銀写真感光
材料を得ることができる。By containing the compounds represented by the general formula (1) and the general formula (II), the present invention achieves maximum density, high contrast, residual color, fixing property, and drying property at the same time when rapid development processing is performed. A satisfactory and excellent silver halide photographic material can be obtained.
また前記ハロゲン化銀写真感光材料を適用した場合、処
理液の経時保存性に優れた画像形成方法が提供される。Furthermore, when the silver halide photographic light-sensitive material is applied, an image forming method is provided in which the processing solution has excellent storage stability over time.
Claims (1)
む感光性ハロゲン化銀乳剤層を有し、かつ支持体の他方
の側に少なくとも一層のゼラチンを含む親水性コロイド
層を有してなるハロゲン化銀写真感光材料において、該
ハロゲン化銀写真感光材料を構成する親水性コロイド層
のうち、ゼラチンを含む少なくとも一層の親水性コロイ
ド層に少なくとも一種の下記一般式［ I ］及び／また
は下記一般式［II］で表される化合物を含有させてなる
事を特徴とするハロゲン化銀写真感光材料。 一般式［ I ］ 一般式［II］ ［式中、Ｒ＾１、Ｒ＾２及びＲ＾３は各々、アルキル基
、アルケニル基、アルキニル基、アリル基、アラルキル
基、または複素環基を表し、Ｒ、Ｒ＾４及びＲ＾５は水
素原子、アルキル基、アルケニル基、アルキニル基、ア
リル基、アラルキル基、カルボニル基、アルコキシ基、
ハロゲン原子、又は複素環基を表し、Ｘ＾１は水素原子
、ハロゲン原子、アルキル基、トシロキシ基、アルコキ
シ基、又は−ＣＨ（Ｘ＾２）Ｒ＾６を示す。Ｒ＾６は水
素原子、アルキル基、アルケニル基、アルキニル基、ア
リル基、アラルキル基、カルボニル基、または複素環基
を表し、Ｘ＾２はハロゲン原子、トシロキシ基、アルコ
キシ基、又はアルキルカルボキシ基を示す。また、Ｒ＾
４、Ｒ＾５、Ｘ＾１は−Ｃ＝Ｃ−と共同して複素環を形
成してもよい。］ ２）請求項１記載のハロゲン化銀写真感光材料において
、該ハロゲン化銀写真感光材料を構成する親水性コロイ
ド層のうち、少なくとも一層の親水性コロイド層にヨウ
素イオンを乖離する化合物を少なくとも一種含有させて
なる事を特徴とするハロゲン化銀写真感光材料。 ３）請求項１記載のハロゲン化銀写真感光材料において
、該ハロゲン化銀写真感光材料を構成する親水性コロイ
ド層のうち、少なくとも一層の親水性コロイド層にヨウ
化銀を含有するハロゲン化銀乳剤を含有させてなる事を
特徴とするハロゲン化銀写真感光材料。 ４）請求項１記載のハロゲン化銀写真感光材料をｐＨ７
以上の銀画像形成用現像液で処理した後、ヨウ素イオン
を含有する定着液及び／又は安定液で処理し、続いて洗
浄、乾燥する事を特徴とする画像形成方法。 ５）請求項４記載の画像形成方法において、全現像処理
時間が６０秒以下である事を特徴とする画像形成方法。[Scope of Claims] 1) A photosensitive silver halide emulsion layer containing at least one gelatin on one side of the support, and a hydrophilic colloid layer containing at least one gelatin on the other side of the support. In a silver halide photographic light-sensitive material comprising: of the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material, at least one hydrophilic colloid layer containing gelatin contains at least one of the following general formulas [I] and/or a silver halide photographic material containing a compound represented by the following general formula [II]. General formula [I] General formula [II] [wherein R^1, R^2 and R^3 each represent an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aralkyl group, or a heterocyclic group, R, R^4 and R^5 are hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, allyl groups, aralkyl groups, carbonyl groups, alkoxy groups,
It represents a halogen atom or a heterocyclic group, and X^1 represents a hydrogen atom, a halogen atom, an alkyl group, a tosyloxy group, an alkoxy group, or -CH(X^2)R^6. R^6 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, an aralkyl group, a carbonyl group, or a heterocyclic group, and X^2 represents a halogen atom, a tosyloxy group, an alkoxy group, or an alkylcarboxy group. show. Also, R^
4, R^5, and X^1 may form a heterocycle in collaboration with -C=C-. 2) In the silver halide photographic light-sensitive material according to claim 1, at least one hydrophilic colloid layer of the hydrophilic colloid layers constituting the silver halide photographic light-sensitive material contains at least one compound that releases iodine ions. A silver halide photographic light-sensitive material characterized by containing silver halide. 3) In the silver halide photographic material according to claim 1, a silver halide emulsion containing silver iodide in at least one hydrophilic colloid layer of the hydrophilic colloid layers constituting the silver halide photographic material. A silver halide photographic material characterized by containing. 4) The silver halide photographic material according to claim 1 is adjusted to pH 7.
An image forming method characterized by processing with the above silver image forming developer, followed by processing with a fixer and/or stabilizer containing iodine ions, followed by washing and drying. 5) The image forming method according to claim 4, wherein the total development processing time is 60 seconds or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8813690A JPH03287253A (en) | 1990-04-04 | 1990-04-04 | Silver halide photographic sensitive material and image forming method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8813690A JPH03287253A (en) | 1990-04-04 | 1990-04-04 | Silver halide photographic sensitive material and image forming method using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03287253A true JPH03287253A (en) | 1991-12-17 |
Family
ID=13934517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8813690A Pending JPH03287253A (en) | 1990-04-04 | 1990-04-04 | Silver halide photographic sensitive material and image forming method using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03287253A (en) |
-
1990
- 1990-04-04 JP JP8813690A patent/JPH03287253A/en active Pending
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