JPH03130764A - Silver halide color photographic sensitive material - Google Patents
Silver halide color photographic sensitive materialInfo
- Publication number
- JPH03130764A JPH03130764A JP26857589A JP26857589A JPH03130764A JP H03130764 A JPH03130764 A JP H03130764A JP 26857589 A JP26857589 A JP 26857589A JP 26857589 A JP26857589 A JP 26857589A JP H03130764 A JPH03130764 A JP H03130764A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- silver
- layer
- emulsion
- 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 78
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 73
- 239000004332 silver Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000000839 emulsion Substances 0.000 claims abstract description 109
- 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 abstract description 33
- 229910021612 Silver iodide Inorganic materials 0.000 claims abstract description 33
- 229940045105 silver iodide Drugs 0.000 claims abstract description 33
- 238000011161 development Methods 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000000565 sulfonamide group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 3
- 125000005541 phosphonamide group Chemical group 0.000 claims description 3
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 14
- 239000000837 restrainer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 114
- 239000000975 dye Substances 0.000 description 58
- 238000000034 method Methods 0.000 description 58
- 239000000243 solution Substances 0.000 description 32
- 230000001235 sensitizing effect Effects 0.000 description 29
- 238000012545 processing Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 230000018109 developmental process Effects 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 108010010803 Gelatin Proteins 0.000 description 20
- 229920000159 gelatin Polymers 0.000 description 20
- 239000008273 gelatin Substances 0.000 description 20
- 235000019322 gelatine Nutrition 0.000 description 20
- 235000011852 gelatine desserts Nutrition 0.000 description 20
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 239000007844 bleaching agent Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 238000004061 bleaching Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 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 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 4
- 150000003585 thioureas Chemical class 0.000 description 4
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002228 disulfide group Chemical group 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- YWQPZFIMVXXLCG-UHFFFAOYSA-J iron(4+) propane-1,3-diamine tetraacetate Chemical compound [Fe+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCCN YWQPZFIMVXXLCG-UHFFFAOYSA-J 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical class OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LOOCNDFTHKSTFY-UHFFFAOYSA-N 1,1,2-trichloropropyl dihydrogen phosphate Chemical compound CC(Cl)C(Cl)(Cl)OP(O)(O)=O LOOCNDFTHKSTFY-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- VQNVPKIIYQJWCF-UHFFFAOYSA-N 1-tetradecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCCCN1CCCC1=O VQNVPKIIYQJWCF-UHFFFAOYSA-N 0.000 description 1
- RWKSBJVOQGKDFZ-UHFFFAOYSA-N 16-methylheptadecyl 2-hydroxypropanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C(C)O RWKSBJVOQGKDFZ-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical group C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- BGRKGHSKCFAPCL-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC=C1O BGRKGHSKCFAPCL-UHFFFAOYSA-N 0.000 description 1
- QTLHLXYADXCVCF-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C(C)=C1 QTLHLXYADXCVCF-UHFFFAOYSA-N 0.000 description 1
- LOIUBRXCXMKWFZ-UHFFFAOYSA-J 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;iron(4+) Chemical compound [Fe+4].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O LOIUBRXCXMKWFZ-UHFFFAOYSA-J 0.000 description 1
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 1
- QQQMJWSOHKTWDZ-UHFFFAOYSA-N 2-[amino(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(N)CC(O)=O QQQMJWSOHKTWDZ-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- ZILFKJVLTVLGBF-UHFFFAOYSA-N 2-butoxy-5-(2,4,4-trimethylpentan-2-yl)aniline Chemical compound CCCCOC1=CC=C(C(C)(C)CC(C)(C)C)C=C1N ZILFKJVLTVLGBF-UHFFFAOYSA-N 0.000 description 1
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- 150000003248 quinolines Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- MSFPLIAKTHOCQP-UHFFFAOYSA-M silver iodide Chemical class I[Ag] MSFPLIAKTHOCQP-UHFFFAOYSA-M 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical compound [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 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
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical class S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 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
- 150000003548 thiazolidines Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- QGVNJRROSLYGKF-UHFFFAOYSA-N thiobarbital Chemical compound CCC1(CC)C(=O)NC(=S)NC1=O QGVNJRROSLYGKF-UHFFFAOYSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- OHRVKCZTBPSUIK-UHFFFAOYSA-N tridodecyl phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OCCCCCCCCCCCC OHRVKCZTBPSUIK-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はハロゲン化銀写真感光材料に関するものであり
、特に沃化銀含有率の高いハロゲン化銀乳剤とタイミノ
グ型DIRカプラーを含有し、粒状性、鮮鋭性、色再現
性および感材保存性の著しく優れたハロゲン化銀感光材
料に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and in particular contains a silver halide emulsion with a high silver iodide content and a Taiminog type DIR coupler, and has a granular shape. The present invention relates to a silver halide photosensitive material that has extremely excellent properties such as sharpness, sharpness, color reproducibility, and photosensitive material storage stability.
(従来の技術)
近年、ハロゲン化銀感光材料、特に撮影用感材において
は、ISO感度100並の高画質を有するI Souθ
θ感材に代表されるような高感度で粒状性、鮮鋭性1色
再現性などに優れかつ感材保存性に優れた感材が要求さ
れている。(Prior Art) In recent years, silver halide photosensitive materials, especially photographic photosensitive materials, have been developed using I Souθ, which has high image quality with an ISO sensitivity of 100.
There is a demand for photosensitive materials, such as θ photosensitive materials, which are highly sensitive, have excellent graininess, sharpness, single-color reproducibility, and have excellent storage stability.
このうち鮮鋭性、色再現性、感材保存性などを改良する
目的で、特開昭11−/Aコタダ2号。Among these, JP-A-11-A Kotada No. 2 was used for the purpose of improving sharpness, color reproducibility, and storage stability of photosensitive materials.
同< 3−373to号等rc オイ−r 、新規なり
IR化合物が提案された。確かに、これら化合物により
、鮮鋭性1色再現性などは改良されたものの、感材の経
時保存性は1だ1だ不充分であること、日本写真学会M
P!2巻/60−111頁(ivyP)に指摘されてい
るようにこれら化合物は従来のDIRIR化合物べ粒状
性に劣ることなどが明らかになってきた。No. 3-373, etc., new IR compounds were proposed. It is true that these compounds have improved sharpness and single-color reproducibility, but the long-term storage stability of photosensitive materials is unsatisfactory, and the Photographic Society of Japan
P! As pointed out in Vol. 2/pages 60-111 (ivyP), it has become clear that these compounds are inferior in graininess to conventional DIRIR compounds.
方、高沃化銀含有ハロゲン化銀乳剤について#i、特開
昭60−/473337号、同5r−tt1037号、
同AO−/コlφ亭3号、同ぶ1−24’j/j/号、
同62−41932号、特開平1−1IA’FJI号な
どに記載があるが、これら提案された感材の鮮鋭度、色
再現性は不満足なものであった。Regarding silver halide emulsions containing high silver iodide, #i, JP-A-60-/473337, JP-A No. 5r-tt1037,
Same AO-/Col φ-tei 3, Same 1-24'j/j/,
Although it is described in JP-A-62-41932 and JP-A-1-1IA'FJI, the sharpness and color reproducibility of these proposed photosensitive materials were unsatisfactory.
(発明が解決しようとする課題)
本発明の目的は粒状性、鮮鋭性1色再現性釦よび感材の
経時保存性を同時に満足させる感材を提供することにあ
る。(Problems to be Solved by the Invention) An object of the present invention is to provide a photosensitive material that satisfies graininess, sharpness, one-color reproducibility, and storage stability over time.
(課題を解決するための手段)
本発明の目的は、下記のカラー感光材料によって達成さ
れた。(Means for Solving the Problems) The objects of the present invention have been achieved by the following color photosensitive materials.
支持体上に少なくとも7つのハロゲン化銀乳剤層を設け
たハロゲン化銀カラー写真感光材料において、該乳剤層
中のハロゲン化銀粒子の←O重量多以上が、沃化銀含有
率タモル優以上の粒子で占められており、該乳剤層中に
下記一般式(I)で表わされる化合物を含有することを
特徴とするハロゲン化銀カラー写真感光材料。In a silver halide color photographic light-sensitive material having at least seven silver halide emulsion layers provided on a support, the silver halide grains in the emulsion layer have a silver iodide content of ←O or more by weight or more. 1. A silver halide color photographic light-sensitive material comprising grains and containing a compound represented by the following general formula (I) in the emulsion layer.
般式(1)
式中、R1、R2、R3およびR4は各々水素原子、低
級アルキル基を表わし、R5は水素原子、アシルアミノ
基、スルホンアミド基、ホスホンアミド基、アルコキシ
カルボニルアミノ基、アリールオキシ力ルポニルアミノ
基、アルコキシスルホ/アミド基、アリールオキシスル
ホンアミド基、カルバモイルアミノ基、又はスル7アモ
イルアミノ基を表わし、n #−i/からダの整数、T
IMEは一般式(1)で表わされる化合物が発色現像主
薬と反応することによりDIとともに離脱し、その後D
Iを放出しうるタイミング基を表わし、DIは現像抑制
剤を表わす。General formula (1) In the formula, R1, R2, R3 and R4 each represent a hydrogen atom or a lower alkyl group, and R5 represents a hydrogen atom, an acylamino group, a sulfonamide group, a phosphonamide group, an alkoxycarbonylamino group, or an aryloxy group. Represents a luponylamino group, an alkoxysulfo/amide group, an aryloxysulfonamide group, a carbamoylamino group, or a sul7amoylamino group, an integer from n #-i/ to da, T
In IME, the compound represented by the general formula (1) reacts with a color developing agent and is released together with DI, and then D
I represents a timing group capable of releasing, and DI represents a development inhibitor.
以下に本発明について詳細に説明する。The present invention will be explained in detail below.
本発明に使用して有効なハロゲン化銀乳剤は。Silver halide emulsions useful in the present invention are:
沃化銀を2モル係以上含t!・・ロダン化銀粒子が。Contains more than 2 molar percentage of silver iodide! ...Silver rodanide particles.
核層の全ハロゲン化銀粒子に対して重量比でダθ優以上
、好1しくば60%以上特に好ましく#′irθ%以上
含憬れるような乳剤である。The emulsion is such that the weight ratio of all the silver halide grains in the core layer is greater than Daθ, preferably greater than 60%, and particularly preferably greater than #'irθ%.
沃化銀の粒子内の分布は均一であっても、不均一であっ
てもよいが、後述するような二重構造粒子のようなハロ
ゲン化銀のばあいには、粒子内の沃化銀の平均値がタモ
ル肇以上であることを意味するものとする。The distribution of silver iodide within the grains may be uniform or non-uniform, but in the case of silver halide such as double structure grains as described below, the distribution of silver iodide within the grains is This means that the average value of is greater than or equal to Tamoru Hajime.
個々のハロゲン化銀粒子の沃化銀含率は、たとえばX線
マイクロアナライザーを用いて測定することが可能であ
り、この方法により、沃化銀を2モル多以上含むハロゲ
ン化銀粒子の重量比を決定することができる。The silver iodide content of individual silver halide grains can be measured using, for example, an X-ray microanalyzer, and by this method, the weight ratio of silver halide grains containing 2 or more moles of silver iodide can be measured. can be determined.
本発明に使用して有効女高ヨードハロゲン化銀乳剤のヨ
ード含量の上限は固溶限界値で決り、約グ0モル多であ
る。従って、本発明には沃化銀含量が2モル多以上約4
tOモル多以下の範囲にあるハロゲン化銀乳剤、好1し
くは沃化銀含量が10モルφ以上30モル多以下の範囲
にあるハロゲン化銀乳剤、さらに好筐しくは沃化銀含量
が12モルφ以上2!モル肇以下の範囲にあるハロゲン
化銀乳剤を1本発明の一般式(1)ので表わされる化合
物と組合せて使用する。沃化銀含量が上記の範囲の下限
以下であると、一般に本発明の目的である粒状性改良の
効果が顕著でない。筐た逆に上限以上であると、現像進
行が遅れたり、軟調化したり、筐たは脱銀不良などの弊
害が出現する傾向がある。The upper limit of the iodine content of the effective female high iodo silver halide emulsion used in the present invention is determined by the solid solubility limit value, and is approximately 0 mole. Therefore, in the present invention, the silver iodide content is more than 2 moles or more than about 4 moles.
A silver halide emulsion having a molar content of tO or less, preferably a silver halide emulsion having a silver iodide content of 10 molar or more and 30 molar or less, more preferably a silver iodide content of 12 molar or less. More than 2 moles φ! A silver halide emulsion having a molar range of less than 1 molar range is used in combination with a compound represented by the general formula (1) of the present invention. When the silver iodide content is below the lower limit of the above range, the effect of improving graininess, which is the object of the present invention, is generally not significant. On the other hand, if it exceeds the upper limit, problems such as delayed development, soft contrast, and poor desilvering tend to occur.
また本発明の高ヨードハロゲン化銀乳剤は任意の粒子サ
イズのものを使用できる。好1しくば0゜2−4.0p
m、 より好1しくは0.j〜2.0μmの高ヨート
ノ・ロダン化銀乳剤を本発明の一般式(1)と併用する
と鮮鋭性1粒状性、色再現性ふ−よび感材保存性の優れ
たカラー写真感光材料が得られる。Further, the high iodo silver halide emulsion of the present invention may have any grain size. Good 1st place 0゜2-4.0p
m, more preferably 0. When a high iotono-rhodanide silver emulsion with a particle size of J to 2.0 μm is used in combination with the general formula (1) of the present invention, a color photographic light-sensitive material with excellent sharpness, graininess, color reproducibility, and storage stability of the photosensitive material can be obtained. It will be done.
本発明に用いる高ヨード乳剤は種々の方法を用いて!!
ll製することができる。すなわち酸性法、中性法、ア
ンモニア法などのいずれでもよく、また可溶性塩と可溶
性ノ・ロダン塩を反応させる形式として片側混合法、同
時混合法、それらの組合せなどのいずれを用いてもよい
。同時混合法の一つの形式としてノ・ロゲ/化銀の生成
される液相中のpAgを一定に保つ方法、すなわちコン
トロール・ダブルジェット法を用いることができる。同
時混合法の別の形式として異なる組成の可溶性/%ロゲ
7塩を各々独立に添加するトリプルジェット法(例えば
可溶性銀塩と可溶性臭素塩と可溶性沃素塩)も用いるこ
とができる。比較的サイズの大きい乳剤を調製するとき
にアンモニア、ロダン塩、チオ尿素類、アミン類などの
ハロゲン化銀溶剤(前述のJames著書?頁)を用い
ることが好筐しい。粒子形成中のpH,pAgを調節し
て好ましい写真性を得ることは当業界では良く知られて
おり、粒子の作り方によりp Hij 、!〜10の範
囲で変わるのが好ましい。The high iodine emulsion used in the present invention can be prepared using various methods! !
ll can be made. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble salt with the soluble rhodan salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which No. Rogge/silver oxide is produced is kept constant, that is, a controlled double jet method can be used. As another type of simultaneous mixing method, a triple jet method can also be used in which soluble/% Rogge 7 salts of different compositions are each added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodine salt). When preparing relatively large emulsions, it is preferable to use silver halide solvents such as ammonia, rhodan salts, thioureas, and amines (see the above-mentioned book by James, page 2). It is well known in the art to obtain favorable photographic properties by adjusting pH and pAg during particle formation, and depending on the method of particle preparation, pH, pAg,! Preferably, it varies between 10 and 10.
本発明の高ヨード乳剤は六面体、八面体、十二面体、十
四面体のような規則的な結晶形を有するものでもよく、
また球状、平板状などの結晶形のものでもよh0乳剤粒
子の内部と表面が異Zるハロゲン組成から成り立ってい
ても、均一なハロゲン組成でもよい。粒子内部(Cor
e部)が高濃度の沃化銀を含む沃塩臭化銀あるいは沃臭
化銀で粒子の外側(5he11部)が沃化銀含量の低い
塩沃臭化銀あるいは沃臭化銀から成る特開昭40−/4
t333/号、同ぶ/−2ψ!/!lなどの二重構造粒
子筐たは多重構造粒子は本発明の乳剤として好筐しい。The high iodine emulsion of the present invention may have a regular crystal shape such as hexahedron, octahedron, dodecahedron, or dodecahedron.
Furthermore, the h0 emulsion grains may have a crystalline shape such as a spherical or tabular shape, and may have a uniform halogen composition, even if the interior and surface of the h0 emulsion grains have different halogen compositions. Inside the particle (Cor
Part e) is silver iodochlorobromide or silver iodobromide containing a high concentration of silver iodide, and the outer side of the grain (5he11 parts) is silver iodobromide or silver iodobromide with a low content of silver iodide. Kaisho 40-/4
t333/issue, same/-2ψ! /! Double-structure grains or multi-structure grains such as 1 are suitable as the emulsion of the present invention.
Core部と5hel1部の銀量比は広い範囲で選べる
が!/l〜//jが好筐しい。You can choose the silver ratio between Core part and 5hel part in a wide range! /l~//j is good.
このような二重構造粒子オたは多重構造粒子においては
1粒子内の沃化銀含量の平均値が2モルφ以上となるよ
うなハロゲン化銀乳剤のばあいに、本発明の目的が達成
される。さらに詳述すれば、Core部分の好筐しい沃
化銀金tは/jモル多以上であるが、さらに好ましくは
2!モル蝿以上、より好筐しくは3!モル多から沃臭化
銀固溶限界値(前記James著書のダ頁参照)の間の
値を選ぶことである。She 11部分の沃化銀含量は
3モル多以下にするのが好筐しいかさらに3モルφ以下
に押えるのが望ましい。The object of the present invention can be achieved in the case of a silver halide emulsion in which the average value of the silver iodide content in one grain is 2 mol φ or more in such double-structure grains or multi-structure grains. be done. More specifically, it is preferable that the silver iodide t in the core portion is at least /j molar, more preferably 2! More than a mole fly, preferably 3! The value is selected between the molar ratio and the silver iodobromide solid solubility limit value (see page 2 of the book by James). It is preferable that the silver iodide content in the She 11 portion be 3 mol or less, or more preferably 3 mol φ or less.
ハロゲン化銀粒子形成又は物理熟成の過程に釦いて、カ
ドミウム塩、亜鉛塩、鉛塩、タリウム塩、イリジウム塩
又はその錯塩、ロジウム塩又はその錯塩、鉄塩又は鉄錯
塩などを、共存させてもよい。During the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may be allowed to coexist. good.
乳剤は沈澱形成後あるいは物理熟成後に、通常可溶性塩
類を除去されるが、そのための手段としては古くから知
られたゼラチンをゲル化させて行うヌーデル水洗法を用
いてもよく、また多価アニオンより成る無機塩類5例え
ば硫酸ナトリウム。After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Nudel water washing method, which involves gelatinization, may be used. Inorganic salts consisting of 5, such as sodium sulfate.
アニオン性界面活性剤、アニオン性ポリマー(例えはポ
リスチレンスルホン酸)、あるいはセラチン誘導体(例
えば脂肪族アシル化セラチン、芳香族アシル化ゼラチン
、芳香族カルバモイル化ゼラチンなど)を利用した沈降
法(フロキュレーション)を用いてもよい。Precipitation methods (flocculation) using anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or seratin derivatives (e.g. aliphatic acylated seratin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may be used.
ハロゲン化銀乳剤は、通常は化学増感される。Silver halide emulsions are usually chemically sensitized.
化学増感のためには、例えばl(、Frleser編″
Die Grundlagen der Photog
raphischenProzesse mit Si
lberhalogeniden”(Akademis
che Verlagsgesellschaft/り
tl”)t7j〜7317頁に記載の方法を用いること
ができる。For chemical sensitization, e.g.
Die Grundlagen der Photog
raphischenprozesse mit Si
lberhalogeniden” (Akademis
The method described in Verlagsgesellschaft/Retl'')t7j-7317 can be used.
すなわち、活性ゼラチンや銀と反応しうる硫黄を含む化
合物(例えば、チオ硫酸塩、チオ尿素類、メルカプト化
合物類、ローダニア類)を用いる硫黄増感法:還元性物
質(例えば、第一すず塩、アミン類、ヒドラジ/誘導体
、ホルムアミジンスルフィン酸、シラン化合物)を還元
増感法:貴金属化合物(例えば、全錯塩のほかPt、I
r%Pdなとの周期律表■族の金属の錯塩)を用いる資
金属増感法などを単独筐たは組み合わせて用いることが
できる。That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodania); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazines/derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g., total complex salts as well as Pt, I
A metal sensitization method using a complex salt of a metal of group (I) of the periodic table, such as r%Pd, can be used alone or in combination.
本発明に用いられる写真乳剤には、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を防止し、あるい
は写真性能を安定化させる目的で。The photographic emulsion used in the present invention is used for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance.
種々の化合物を含有させることができる。すなわちアゾ
ール類1例えばベンゾチアゾリウム塩、ニトロイミダゾ
ール類、ニトロベンズイミダゾール類、クロロベンズイ
ミダゾール類、プロモヘンスイミダゾール類、メルカプ
トチアゾール類、メルカプトベンゾチアゾール類、メル
カプトベンズイミダゾール類、メルカプトチアジアゾー
ル類、アミノトリアゾール類、ベンゾトリアゾール類、
ニトロベンゾトリアゾール類、メルカプトテトラゾール
類(4!に7−フェニル−!−メルカプトテトラゾール
)など:メルカプトビリミジン類;メルカプトトリアジ
ン類;たとえばオキサドリンチオノのようなチオケト化
合物:アザインデン類、たとえばトリアザインデン類、
テトラアザインデン類(%にu−ヒドロキシ置換(/
、J 、3a 、7)テトラアザインデン類)、尺ンタ
アザインデ7類ナト:ヘンゼンチオスルフオン酸、ベン
ゼンスルフィン酸、にンゼンスルフオン酸アミド等のよ
うなカブリ防止剤iたは安定剤として知られた。多くの
化合物を加えることができる。Various compounds can be included. That is, azoles 1 such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (4! to 7-phenyl-!-mercaptotetrazole), etc.; Mercaptovirimidines; Mercaptotriazines; Thioketo compounds, such as oxadolinthiono; Azaindenes, such as triazaindene; kind,
Tetraazaindenes (% u-hydroxy substituted (/
, J, 3a, 7) tetraazaindene), tetraazaindene 7): known as antifoggants or stabilizers such as henzene thiosulfonic acid, benzene sulfinic acid, nitrogen sulfonic acid amide, etc. . Many compounds can be added.
本発明に用いられる写真乳剤は、メチン色素類その他に
よって分光増感されてもよい。用いられる色素には、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−シアニア色素、ヘミ
シアニン色素、スチリル色素シよびヘミオキソノール色
素が包含される。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ア色素に属する
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、
ピリジン核など:これらの核に脂環式炭化水素環が融合
した核;及びこれらの核に芳香族炭化水素環が融合した
核、即チ、イ/ドレニン核、ベンズインドレニン核。The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyania dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyania dyes. 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, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., 1, 2/drenine nucleus, benzindolenine nucleus.
インドール核、ベンズオキサドール核、ナフトオキサゾ
ール核、ベンゾチアゾール核、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
核などが適用できる。これらの核は炭素原子上に置換さ
れていてもよい。Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.
メロシアニン色素筐たは複合メロシアニン色素にはケト
メチレノ構造を有する核として、ピラゾリン−!−オン
核、チオヒダントイン核、2−チオオキサゾリジン−j
、4t−ジオン核、チアゾリジン−2,φ−ジオン核、
ローダニン核、チオバルビッール酸根なとの夕〜ぶ員異
節環核を適用することができる。The merocyanine dye case or composite merocyanine dye has a pyrazoline-! -on nucleus, thiohydantoin nucleus, 2-thioxazolidine-j
, 4t-dione nucleus, thiazolidine-2,φ-dione nucleus,
It is possible to apply heterocyclic ring nuclei such as rhodanine nuclei and thiobarbital acid radicals.
有用な増感色素としては例えば、ドイツ特許りat、o
ro4!r、米国特許2,23/、tj1号、同コ、q
り3,7ψを号、同コ、 j03.77A号、同コ、j
/り、00/号、同J、p/j、jコ2号、同3.ti
t、9jり号、同3,672゜tデフ号、同3.6タダ
、217号、同名、Oコ!、3171号、同ψ、0グt
、!72号、英国特許/、2172,110号、特公昭
4444−117030号、同!2−2vtea号に記
載されたものを挙げることが出来る。Useful sensitizing dyes include, for example, German patents at, o
ro4! r, U.S. Patent 2,23/, tj1, same, q
No. 3,7ψ, same, j03.77A, same, j
/ri, 00/issue, same J, p/j, jko 2, same 3. Ti
t, 9j issue, same 3,672゜t def issue, same 3.6 free, 217, same name, Oko! , No. 3171, same ψ, 0gt
,! No. 72, British Patent/, No. 2172,110, Japanese Patent Publication No. 4444-117030, same! Examples include those described in No. 2-2vtea.
これらの増感色素は単独に用いてもよいが、それらの組
合せを用いてもよく、増感色素の組合せは特に、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, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
その代表例は米国特許コ、try、tar号、同2、り
77.コ2り号、同3,327.060号、同3 、!
22.012号、同J、jJ7.Aψ1号、同J、4/
7.2PJ号、同3.t2r、Y6グ号、同j、A4A
、!lO号、同J、A7J。A typical example is US Pat. Ko2ri issue, 3,327.060, 3,!
No. 22.012, same J, jJ7. Aψ1, same J, 4/
7.2 PJ No. 3. t2r, Y6gu, same j, A4A
,! No. 1O, No. 1J, A7J.
ryr号、同j、A75’、4(Jf号、同3,703
.377号、同3.7tり、30/号、同3゜fill
、A09号、同3,137,162号、同φ、Oコt
、707号、英国特許7.3グダ、2r/号、同/、6
07,103号、特公昭ダ3−ψ236号、同13−/
2,371号、特開昭!J−/10.t/♂号、同fj
−10り、22/号に記載されている。ryr No. J, A75', 4 (Jf No. 3,703
.. No. 377, 3.7t, No. 30, 3゜fill
, A09 No. 3,137,162, same φ, Okot
, No. 707, British Patent 7.3 Guda, 2r/No., Same/, 6
No. 07,103, Tokuko Shoda 3-ψ236, No. 13-/
No. 2,371, Tokukai Sho! J-/10. T/♂ issue, same fj
-10, No. 22/.
増感色素とともに、それ自身分光増感作用をもたない色
素あるいは可視光を実質的に吸収しない物質であって1
強色増感を示す物質を乳剤中に含んでもよい。例えば、
含窒素異部環基で置換されたアミノスチル化合物(たと
えば米国特許J、P33.3り0号、同3.63!、7
コ/号に記載のもの)、芳香族有機酸ホルムアルデヒド
縮合物(たとえば米国特許3,7≠J、jloぢに記載
のもの)、カドミウム塩、アザインデン化合物などを含
んでもよい。米国特許3.t/!、613号、同3.t
it、tv1号、同3.ぶ/7.コ?!号、同J 、4
37.7J/号に記載の組合せFi特に有用である。Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light, 1
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Patent J, P33.30, P3.63!, 7
2), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,7≠J, JLO), cadmium salts, azaindene compounds, and the like. US Patent 3. T/! , No. 613, 3. t
it, tv issue 1, same 3. Bu/7. Ko? ! No. J, 4
Particularly useful is the combination Fi described in No. 37.7J/No.
次に一般式(I)について説明する。Next, general formula (I) will be explained.
R,は水累原子筐たは炭素数/〜ψの低級アルキル基(
たとえば、メチル基、エチlし基、n−プロピル基、n
−グチル基など)を表わすが、一般式N)のTIME−
DIt−放出する速度という観点から、水素であること
が好!しい。R2およびR3は各々水素原子筐たは炭素
数/〜ψの低級アルキル基(例えばメチル基、エチル基
、プロピル基、1so−プロピル基、ブチル基、1so
−ブチル基、5ec−ブチル基など)を表わす。このア
ルキル基は、ヒドロキシル基、アルキルチオ基(例えば
メチルチオ基)、アルコキシカルボニル基(例えばメト
キシカルボニル基、エトキシカルボニル基耽ど)の置換
基を有していてもよい。R is a water atom box or a lower alkyl group with carbon number/~ψ (
For example, methyl group, ethyl group, n-propyl group, n
-butyl group, etc.), but TIME- of the general formula N)
DIt- Hydrogen is preferred from the viewpoint of release rate! Yes. R2 and R3 each represent a hydrogen atom or a lower alkyl group having carbon number/~ψ (e.g., methyl group, ethyl group, propyl group, 1so-propyl group, butyl group, 1so
-butyl group, 5ec-butyl group, etc.). This alkyl group may have a substituent such as a hydroxyl group, an alkylthio group (eg, methylthio group), or an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.).
好筐しくばR2、R3はそれぞれ水素原子である。In each case, R2 and R3 are hydrogen atoms.
R4は水素原子または炭素数l−グの低級アルキル基(
たとえばメチルt、エチル基、プロピル基、1so−プ
ロピル基、ブチル基、1so−ブチルL、s e c−
ブチル基など)を表わす。このアルキル基はヒドロキシ
ル基、アルコキン基(例えばメトキシ基、エトキシ基な
ど)で置換されていてもよい。R4は、現像生薬欧化体
と一般式(1)で表わされる化合物のカップリング反応
した結果生成するシアン色素の感光材料からの流出性が
良好ということから、水素原子またはメチル基であるこ
とが特に好ましい。R5は水素原子、アシルアミノ基、
スルホンアミド基、ホスホンアミド基、アルコキシカル
ボニルアミノ基、アリールオキシカルボニルアミノ基、
アルコキシスルボンアミド基、アリールオキシスルボン
アミド基、カルバモイルアミ7基、又はスルファモイル
アミ7基を表わすが、水素原子、炭素数/〜グのアルキ
ル基で置換されたアシルアミノ基、スルボンアミド基、
アルコキシアシルアミノ基が好ましい。TIMEは一般
式(1)で表わされる化合物が発色現像主薬の酸化体と
反応すること□より、DIとともに離脱し、その後DI
i放出しうるタイミング基を表わす。T I M Eで
示されるタイミング基の一例として米国特許第Q、24
tJ’、742号、特開昭57−!tl’37号明細書
に開示されている分子内求核置換反応によってPUGi
放出するものや、特開昭5t−ii名5Pφ6号、特開
昭j7−/!φ2341号明細Vなどに開示されている
共役鎖にそった電子移動反応によってPUGを放出する
ものなどが挙げられる。その他、特開昭57−/1ro
Js号、向j1−917211−91フ21/173!
l’号、同to−xxsraa号、同6。R4 is a hydrogen atom or a lower alkyl group having l-g carbon atoms (
For example, methyl t, ethyl group, propyl group, 1so-propyl group, butyl group, 1so-butyl L, sec-
butyl group, etc.). This alkyl group may be substituted with a hydroxyl group or an alkoxy group (eg, methoxy group, ethoxy group, etc.). R4 is particularly preferably a hydrogen atom or a methyl group, since the cyan dye produced as a result of the coupling reaction between the developing herbal drug and the compound represented by the general formula (1) has good flowability from the light-sensitive material. preferable. R5 is a hydrogen atom, an acylamino group,
Sulfonamide group, phosphonamide group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents an alkoxysulfonamide group, an aryloxysulfonamide group, a carbamoylamide 7 group, or a sulfamoylamide 7 group, but is substituted with a hydrogen atom, an alkyl group having a carbon number of ~5, an acylamino group, a sulfonamide group,
An alkoxyacylamino group is preferred. TIME is released together with DI because the compound represented by the general formula (1) reacts with the oxidized form of the color developing agent, and then DI
i represents a releasable timing group. An example of a timing group represented by T I M E is U.S. Patent No. Q, 24.
tJ', No. 742, JP-A-57-! PUGi by intramolecular nucleophilic substitution reaction disclosed in tl'37
Things that emit, JP-A-5T-II name 5Pφ6, JP-A-Show J7-/! Examples include those that release PUG through an electron transfer reaction along a conjugated chain, as disclosed in φ2341 Specification V and the like. Others, JP-A-57-/1RO
Js issue, direction j1-917211-91fu 21/173!
No. l', No. to-xxsraa, No. 6.
−222030号、同4θ−233tψり号、同tO−
2371111を号、同60−237’Al17号明細
書に開示されたタイミング基も挙げられる。-222030, 4θ-233tψri, tO-
Also mentioned are the timing groups disclosed in No. 2371111 and No. 60-237'Al17.
本発明に有用なTIMEとしては次の一般式(It)、
(m)、(IV)で示されるものを包含するが、これら
に限定されるものではない。TIME useful in the present invention includes the following general formula (It),
It includes, but is not limited to, those shown in (m) and (IV).
一般式(■)
7
式中、Xは、置換基があってもよいベンゼン環またはナ
フタレン環を完成するのに必要耽原子群8
を表わす。Yは一〇ー1ーSー1ーN−金表わし。General formula (■) 7 In the formula, X represents a group 8 of atoms necessary to complete a benzene ring or naphthalene ring which may have a substituent. Y represents 10-1-S-1-N-gold.
一般式(I)で表わされる化合物(以下、l−ナフトー
ルカプラー基と称す。ンのカップリング位に結合してお
り、R6.R7,およびR8は水素原子、アルキル基寸
たはアリール基を表わ丁。また、
一C−基はYに対し、
7
オルト位またはパラ位
に置換されており、
結合している。In the compound represented by the general formula (I) (hereinafter referred to as l-naphthol coupler group), R6, R7, and R8 represent a hydrogen atom, an alkyl group, or an aryl group. Also, one C-group is substituted at the 7 ortho or para position to Y, and is bonded to it.
一般式(fil)
DIに含箇れるヘテロ原子に
式中、Y,R6,R7は各々一般式(It)と同義であ
る。R9は水素原子、アルキル基、アリール基、アシル
基、スルホニル基、アルコキシカルボニル基、複素環残
基であり、RIOは水素原子、アルキル基、アリール基
、複素環残基、アルコキシ基、アミノ基、酸アミド基、
スルホンアミド基、カルボキシ、アルコキシカルボニル
基、カルバモイル基、77/f示す。また、このタイミ
ング基は、一般式(口)と同様にYでもって一般式CI
)で表わされる/−ナフトールカプラー基のカップR7
に結合する。General formula (fil) In the hetero atom contained in DI, Y, R6, and R7 each have the same meaning as in general formula (It). R9 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic residue, and RIO is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, acid amide group,
Sulfonamide group, carboxy, alkoxycarbonyl group, carbamoyl group, 77/f. In addition, this timing group is represented by Y as in the general formula (2), and the general formula CI
) is bonded to the cup R7 of the /-naphthol coupler group.
次に分子内求核置換反応によりDIt−放出するタイミ
ング基の例を一般式(IV)で示す。Next, an example of a timing group that releases DIt-by an intramolecular nucleophilic substitution reaction is shown by general formula (IV).
一般式(IV)
Nu
−E−
式中、Nuは電子の豊富R酸累、@黄又は窒素原子tV
している求核基であり、一般式CI)で表わされる/−
ナフトールカプラー基のカンプリング位に結合している
。Efl、電子の不十分耽カルボニル基、チオカルボニ
ル基、ホスフィニル基又はチオホスフィニル基ヲ有して
いる不電子基であり、DIのへテロ原子と結合している
。XはNu及びE=i立体的に関係づけていて、一般式
(1)で表わされる/−ナフトールカプラー基からNu
が放出せしめられた後、3員環耽いし7員環の形成を伴
う分子内求核置換反応を被り、かつそれによってI)I
z−放出することのできる結合基である。General formula (IV) Nu -E- In the formula, Nu is an electron-rich R acid, @yellow or nitrogen atom tV
is a nucleophilic group represented by the general formula CI) /-
It is attached to the campling position of the naphthol coupler group. Efl is an electronless group having an electron-poor carbonyl, thiocarbonyl, phosphinyl or thiophosphinyl group and is bonded to the heteroatom of DI. X has a steric relationship with Nu and E=i, and from the /-naphthol coupler group represented by the general formula (1), Nu
is released, undergoes an intramolecular nucleophilic substitution reaction with the formation of a 3- to 7-membered ring, and thereby I)I
z - is a linking group capable of being released.
DIH現像抑?ii′II剤を表わし、その代表的な例
として、米国特許第3.227.611号、同第3゜3
tψ、6!7号、同第3,6/よ、!06号、同第3.
t/7,22/号、同第3.733,207号および英
国特許第/、グ!0,417F号明細書等に記載されて
いるメルカプトテトラゾール基、セレノテトラゾール基
、メルカプトベンゾチアゾール基、セレノベンゾチアゾ
ール基、メルカプトベンゾオキサゾール基、セレノベン
ゾオキサノ゛−ル基、メルカプトベンゾチアゾール基、
セレノベンズイミダゾール基、ベンゾトリアゾール基、
ベンゾジアゾール基および沃素原子などがある。DIH development suppression? ii' II agents, and representative examples thereof include U.S. Pat.
tψ, 6! No. 7, same No. 3, 6/Yo! No. 06, No. 3.
No. t/7,22/, No. 3.733,207 and British Patent No./, Gu! Mercaptotetrazole group, selenotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, selenobenzoxanol group, mercaptobenzothiazole group, which are described in No. 0,417F specification etc.
Selenobenzimidazole group, benzotriazole group,
These include benzodiazole groups and iodine atoms.
以下に本発明の化合物の具体的代表例を示すが本発明の
化合物はこれらに限定されるものではない。Specific representative examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.
例示化合物
O2
〔Rについて〕
CH2CH2C00CH3
−CH2CH2COOC2H5
−CH2CH2COOC3H7(iso)−CH2CH
2COOC4H9
−CH2CH2COOCH2CH20H−CH2CH2
C00CH2CH20CH3−CH2C00CH3
−CH2COOH
−CH2CH2COOH
−CHCOOCH3
CH3
−CHCOOCR3
C3H7(iso)
−CHCOOCH3
CH2H2CH3
CH3
−CHCOOC2H5
H20H
−CHCOOCR3
CH2CH28CH3
−CHCOOCH3
CH2COOCH3
−CHCOOCH3
CH2CH2COOCH3
−CH2CH2CH2COOCH3
−CH2CH2CH2CH2COOCH3H
2
〔Zについて〕
(19ン
02
(20)
02
(21)
(22)
NO3
(23ン
(24)
(25)
NHCOC口H23
(26)
C5H1t(t)
(27)
(28)
(29)
COOC4H9
(30)
(31)
(32)
○
(33)
(36)
H
(37)
H
これら一般式(1)で表わされる化合物は、米国特許箒
グ、!≠r 、 5’Z、T号、特開昭S乙−7/ψタ
グ6号、同3!−/6.2りψり号および同A 3−J
73り0号などに記載の方法により合成することがで
きる。Exemplary compound O2 [About R] CH2CH2C00CH3 -CH2CH2COOC2H5 -CH2CH2COOC3H7(iso)-CH2CH
2COOC4H9 -CH2CH2COOCH2CH20H-CH2CH2
C00CH2CH20CH3-CH2C00CH3 -CH2COOH -CH2CH2COOH -CHCOOCH3 CH3 -CHCOOCR3 C3H7(iso) -CHCOOCH3 CH2H2CH3 CH3 -CHCOOC2H5 H20H -CHCOOCR3 CH2CH28CH3 -CHCOOCH3 CH2COOCH3 -CHCOOCH3 CH2CH2COOCH3 -CH2CH2CH2COOCH3 -CH2CH2CH2CH2COOCH3H 2 [About Z] (19n02 (20) 02 ( 21) (22) NO3 (23n (24) (25) NHCOC port H23 (26) C5H1t(t) (27) (28) (29) COOC4H9 (30) (31) (32) ○ (33) (36 ) H (37) H These compounds represented by the general formula (1) are described in U.S. Patent Broomstick, !≠r, 5'Z, T No., JP-A-Sho S Otsu-7/ψ Tag No. 6, 3! -/6.2 ψ and A 3-J
It can be synthesized by the method described in No. 73-0.
本発明の一般式(I)で表わされる化合物は、感光材料
中の感光性ノ・ロダン化銀乳剤層もしくはその隣性層に
添加することが好1しく、その添加量44/X1O−6
−jXlo ”mol/m2であり、好筐しくは3X
10 −JXlo mol/m 2 より好まし
くtri/×IO−1×10 ’mol/m であ
る。The compound represented by the general formula (I) of the present invention is preferably added to a photosensitive silver rhodanide emulsion layer or a layer adjacent thereto in a light-sensitive material, and the amount added is 44/X1O-6.
−jXlo ”mol/m2, preferably 3X
10-JXlo mol/m2, more preferably tri/xIO-1x10'mol/m.
本発明の一般式CI)で表わされる化合物の添加方法は
後述のように通常のカプラーと同様にして添加すること
が可能である。The compound represented by the general formula CI) of the present invention can be added in the same manner as for ordinary couplers, as described below.
不発明の一般式(I)で表わされる化合vlJは、層間
効果向上による色再現性向上と、隣接現像効・果肉上に
よる鮮鋭性の向上のために現像抑制剤であるDIが異耽
る二種類以上を用いることが特に好ましい。The compound vlJ represented by the uninvented general formula (I) has two types of DI, which are development inhibitors, in order to improve color reproducibility by improving interlayer effect and improve sharpness by adjacent development effect and on pulp. It is particularly preferable to use the above.
寸た一般式(I)で表わされる化合物は下記に示す/i
t博成において、特に赤感光性乳剤層以外の感光性乳剤
鳩、すなわち青感性乳剤f−1緑感光性乳剤層で用いら
れることが好ましい。The compound represented by the general formula (I) is shown below /i
It is particularly preferable to use it in a light-sensitive emulsion layer other than the red-sensitive emulsion layer, that is, the blue-sensitive emulsion f-1 and the green-sensitive emulsion layer.
本発明では、感光材料の保存性を改良する目的で下記一
般式[11)および/またば〔■〕で表わされる化合物
寸たはそれらの塩を含有することが特に好ましい。In the present invention, it is particularly preferable to contain a compound represented by the following general formula [11] and/or [■] or a salt thereof for the purpose of improving the storage stability of the photosensitive material.
一般式〔■〕
2
〔式中、XlおよびXzld酸累原子または−NH基、
R,およびR2は水素原子、アシル基または置換基t−
Vしてもよい炭化水素残基、R3およびR4は水素原子
、水酸基、置換基余有してもよいアミノ基、置換基余有
してもよい炭化水素残基または一〇R基(Rは置換基余
有してもよい炭化水素残基)金表わし、R3とR4は連
結して夕〜2員飽和炭素環核を形成してもよい。ただし
R1およびR2は水成化メチル基であることはなく、ま
たXlおよびX2がともに酸素原子であってしかもR3
およびR4がともに置換基を有してもよいアミノ基以外
の基であるときlたはR3とR4が連結して!〜を員飽
和炭素環核を形成するときにはR,およびR2の少なく
とも1つは水素原子である。〕
一般式(1)
〔式中、X3およびX4は酸素原子または=NH基、R
5およびR6は水素原子、アシル基lたは#換基を有し
てもよい炭化水素残基、R7は置換基余有してもよいイ
ミノ基または置換基を有してもよい炭化水素残Mk表わ
す。ただしR5およびR6は水数化メチル基であること
はすく、またX3およびX4がともに嫉累原子であって
しかもR7が置換基を有してもよい炭化水素残基である
ときV?−ばR5およびR6の少なくとも1つは水素原
子である。General formula [■] 2 [In the formula, Xl and Xzld acid cumulative atoms or -NH group,
R and R2 are hydrogen atoms, acyl groups, or substituents t-
R3 and R4 are hydrogen atoms, hydroxyl groups, amino groups that may have a substituent, hydrocarbon residues that may have a substituent, or 10R groups (R is (Hydrocarbon residue which may have a substituent) R3 and R4 may be connected to form a two-membered saturated carbocyclic nucleus. However, R1 and R2 are not aqueous methyl groups, and both Xl and X2 are oxygen atoms, and R3
And when R4 is a group other than an amino group which may have a substituent, or R3 and R4 are connected! When ~ forms a saturated carbocyclic nucleus, at least one of R and R2 is a hydrogen atom. ] General formula (1) [wherein, X3 and X4 are oxygen atoms or =NH group, R
5 and R6 are a hydrogen atom, an acyl group or a hydrocarbon residue which may have an # substituent, and R7 is an imino group which may have an additional substituent or a hydrocarbon residue which may have a substituent. Mk represents. However, R5 and R6 are rarely hydroxyl methyl groups, and when X3 and X4 are both trivalent atoms and R7 is a hydrocarbon residue which may have a substituent, V? - At least one of R5 and R6 is a hydrogen atom.
〕 以下にこれら化合物の具体的例を挙げる。] Specific examples of these compounds are listed below.
(S−/) (s−r) (S−2) (S−6 ) (S−J) (S−7) (S−ψ) ( s−r) (S−タ ) (S−10 ) (s−ii ) (S−/、2 ) (S−/3 ) ( S−/F) (S−/ り ( S−/ 乙 ) (S−/ ) (S−/f ) (S−/ り ) 4H9 (S コ O) (S 、2 l ) (S−,2,2 ) (S−,23 ) (S−2≠ ) H3 (S−2り) H3 (S−、?J) H3 (S−27) (S xr> (S−22) H (S−30) (S−J/) C)(3 (S−3,2 ) 0CH3 (S−33) (S−3グ) (S−3t) (S−36) (S−37) (S−31) (S−37 ) (S−tt。(S-/) (s-r) (S-2) (S-6 ) (S-J) (S-7) (S-ψ) ( s-r) (S-ta ) (S-10 ) (s-ii ) (S-/, 2 ) (S-/3 ) ( S-/F) (S-/ the law of nature ( S-/ Otsu ) (S-/ ) (S-/f ) (S-/ the law of nature ) 4H9 (S Ko O) (S , 2 l) (S-,2,2 ) (S-, 23 ) (S-2≠) H3 (S-2ri) H3 (S-,?J) H3 (S-27) (S xr> (S-22) H (S-30) (S-J/) C) (3 (S-3,2 ) 0CH3 (S-33) (S-3g) (S-3t) (S-36) (S-37) (S-31) (S-37 ) (S-tt.
)
(S−←/ )
(S−4tJ
)
(S−ψ3
)
これら化合物は、たとえばブレタン・オブ・ザ・ケミカ
ル・ンサイアテイ・オブ・ジャパン(Bulletin
of the Chemical 5oci
etyof Japan)3 !7巻/!17−/j
/、7頁、/73←〜/73g頁(/PJ4>、ケミツ
シエ・ベリヒテ(Chemische Berich
te)jlcB巻/r0.2−1133頁、j4Z!/
−24’7P頁1/92/)f(どに記載されている方
法に準じて合成することができる。) (S-←/) (S-4tJ) (S-ψ3) These compounds are available from, for example, Bulletin of the Chemical Research Institute of Japan.
of the Chemical 5oci
etyofJapan)3! Volume 7/! 17-/j
/, 7 pages, /73←~/73g pages (/PJ4>, Chemische Berichte
te) jlcB volume/r0.2-1133 pages, j4Z! /
-24'7P page 1/92/) f (can be synthesized according to the method described in .
これら化合物は7種!た02種以上をmみ合わせて感光
材料中のいか次層に添加されてもよいが、中間層、フィ
ルター層、保護層、アンチノ・レーンヨノ層など感光性
乳剤層以外の補助層に添加することが好せしい。There are 7 types of these compounds! A combination of two or more of these compounds may be added to any subsequent layer in the light-sensitive material, but they may be added to auxiliary layers other than the light-sensitive emulsion layer, such as intermediate layers, filter layers, protective layers, antino-lane/layer layers, etc. is good.
本発明の感光材料は、支持体上に青感色性層、緑感色性
層、赤感色性層のハロゲン化銀乳剤層の少なくとも1層
が設けられていればよく、ハロゲン化銀乳剤層および非
感光性層の層数および層順に特に制限はない。典型的な
例としては、支持体上に、実質的に感色性は同じである
が感光度の異なる複数のハロゲン化銀乳剤層から成る感
光性層を少なくとも1つ有するハロゲン化銀写真感光材
料であり、該感光性層は青色光、緑色光、および赤色光
の何れかに感色性を有する単位感光性層であり、多層ハ
ロゲン化銀カラー写真感光材料においては、一般に単位
感光性層の配列が、支持体側から順に赤感色性層、緑感
色性層、青感色性の順に設置される。しかし、目的に応
して上記設置順が逆であっても、また同一感色性層中に
異なる感光性層が挟まれたような設置順をもとりえる。The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.
上記、ハロゲン化恨感光性層の間および最上層、最下層
には各種の中間層等の非感光性層を設けてもよい。Non-photosensitive layers such as various intermediate layers may be provided between the halogenated photosensitive layers and between the uppermost layer and the lowermost layer.
該中間層には、特開昭61−43748号、同59−1
13438号、同59−113440号、同61−20
037号、同61−20038号明細書に記載されるよ
うなカプラー、DIR化合物等が含まれていてもよく、
通常用いられるように混色防止剤を含んでいてもよい。The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.
各単位感光性層を構成する?ji数のハロゲン化銀乳剤
層は、***特許第1..121,470号あるいは英国
特許第923,045号に記載されるように高感度乳剤
層、低感度乳剤層の2層構成を好ましく用いることがで
きる0通常は、支持体に向かって順次感光度が低くなる
様に配列するのが好ましく、また各ハロゲン乳剤層の間
には非感光性層が設けられていてもよい、また、特開昭
57−112751号、同62200350号、同62
−206541号、62−206543号等に記載され
ているように支持体より離れた側に低感度乳剤層、支持
体に近い側に高感度乳剤層を設置してもよい。What constitutes each unit photosensitive layer? ji number of silver halide emulsion layers is disclosed in West German Patent No. 1. .. As described in British Patent No. 121,470 or British Patent No. 923,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, the sensitivity increases sequentially toward the support. It is preferable that the halogen emulsion layers be arranged in such a manner that the height of the halogen emulsion layer is lower than that of the halogen emulsion layer, and a non-photosensitive layer may be provided between each halogen emulsion layer.
As described in No. 206541 and No. 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.
具体例として支持体から最も遠い側から、低感度青感光
性層(BL) /高感度青感光性層(BH) /高感度
緑感光性層(GH) /低感度緑感光性層(GL)/高
感度赤感光性N(RH) /低感度赤感光性層(RL)
の順、またはBH/BL/GL/GW/RH/RLの順
、または811/BL/GH/GL/RL/R1+の順
等に設置することができる。As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (RL)
They can be installed in the order of BH/BL/GL/GW/RH/RL, or the order of 811/BL/GH/GL/RL/R1+.
また特公昭55−34932号公報に記載されているよ
うに、支持体から最も遠い側から青感光性層/Gll/
R11/GL/RCの順に配列することもできる。また
特開昭56−25738号、同62−63936号明細
書に記載されているように、支持体から最も遠い側から
青感光性層/GL/RL/GH/R)Iの順に配列する
こともできる。Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R11/GL/RC. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/R)I may be arranged in this order from the farthest side from the support. You can also do it.
また特公昭49−15495号公報に記載されているよ
うに上層を最も感光度の高いハロゲン化銀乳剤層、中層
をそれよりも低い感光度のハロゲン化銀乳剤層、下層を
中層よりも更に感光度の低いハロゲン化銀乳剤層を配置
し、支持体に向かって感光度が順次低められた感光度の
異なる3層からi或される配列が挙げられる。このよう
な感光度の異なる3Nから構成される場合でも、特開昭
59−202464号明細書に記載されているように、
同一感色性層中において支持体より離れた側から中感度
乳剤層/高感度乳剤層/低感度乳剤層の順に配置されて
もよい。In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is arranged, and three layers having different photosensitivity are sequentially lowered toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.
その他、高感度乳剤層/低感度乳剤層/中感度乳剤層、
あるいは低感度乳剤層/中感度乳剤N/高感度乳剤層な
どの順に配置されていてもよい。In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the following order: low-speed emulsion layer/medium-speed emulsion N/high-speed emulsion layer.
また、4層以上の場合にも、上記の如く配列を変えてよ
い。Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.
色再現性を改良するために、米国特許第4,663゜2
71号、同第4.705,744号7同第4,707,
436号、特開昭62−160448号、同63−89
580号の明細書に記載の、BL、GL、RLなどの主
感光層と分光感度分布が異なる重層効果のドナー層(C
L)を主感光層に隣接もしくは近接して配置することが
好ましい。To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.
上記のように、それぞれの感光材料の目的に応して種々
の層構成・配列を選択することができる。As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.
本発明に用いられる写真感光材料の写真乳剤層に含有さ
れる本発明以外の好ましいハロゲン化銀は約30モル%
以下のヨウ化銀を含む、ヨウ臭化銀、ヨウ塩化銀、もし
くはヨウ塩臭化銀である。特に好ましいのは約2モル%
から約25モル%までのヨウ化銀を含むヨウ臭化銀もし
くはヨウ塩臭化銀である。The preferred silver halide other than the present invention contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides: Particularly preferred is about 2 mol%.
silver iodobromide or silver iodochlorobromide containing up to about 25 mole percent silver iodide.
写真乳剤中の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を有するもの、球状、板状
のような変則的な結晶形を有するもの、双晶面などの結
晶欠陥を有するもの、あるいはそれらの複合形でもよい
。Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.
ハロゲン化銀の粒径は、約0.2ミクロン以下の微粒子
でも投影面積直径が約10ミクロンに至るまでの大サイ
ズ粒子でもよく、多分散乳剤でも単分散乳剤でもよい。The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.
本発明に使用できるハロゲン化銀写真乳剤は、例えばリ
サーチ・ディスクロージャー(RD)No。Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) No.
17643 (1978年12月)、22〜23頁、“
″1.乳剤製造(Emulsion preparat
ion and types) ” 、および同No、
18716 (1979年11月) 、 648頁、
グラフキデ著F写真の物理と化学」、ボールモンテル社
用(P、GIafkides、 Chemie et
Ph1sique Photographique、
Paul Montel、 1967)、ダフィン著「
写真乳剤化学」、フォーカルプレス社用(G、F、 D
uffinPhotographic Emulsio
n Chen+1stry (Foca! Pres
s1966))、ゼリクマンら著「写真乳剤の製造と塗
布」、フォーカルプレス社用(ν、 L、 Zelik
manet al。Making and Coati
ng Photographic Emulsion
Focal Press+ 1964)などに記載さ
れた方法を用いて調製することができる。17643 (December 1978), pp. 22-23, “
``1. Emulsion preparation
ion and types)”, and the same No.
18716 (November 1979), 648 pages,
"Physics and Chemistry of Photography" by F. Grafkides, for Beaumontel (P, GIafkides, Chemie et
Ph1sique Photographique,
Paul Montel, 1967), Duffin,
"Photographic Emulsion Chemistry", for Focal Press (G, F, D
uffinPhotographic Emulsio
n Chen+1try (Foca! Pres
s1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., for Focal Press (ν, L, Zelik
Manet al. Making and Coati
ng Photographic Emulsion
Focal Press+ 1964).
米国特許第3,574,628号、同3,655,39
4号および英国特許第1,413,748号などに記載
された単分散乳剤も好ましい。U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.
また、アスペクト比が約5以上であるような平板状粒子
も本発明に使用できる。平板状粒子は、ガトフ著、フォ
トグラフィック・サイエンス・アンド・エンジニアリン
グ(Gutoff、 PhotographicSci
ence and Engineering ) 、第
14巻248〜257頁(1970年);米国特許第4
.434,226号、同4,414.310号、同4,
433,048号、同4,439,520号および英国
特許第2.112.157号などに記載の方法により簡
単にjIl製することができる。Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
.. No. 434,226, No. 4,414.310, No. 4,
433,048, 4,439,520, and British Patent No. 2.112.157.
結晶構造は−様なものでも、内部と外部とが異質なハロ
ゲン組成からなるものでもよく、層状構造をなしていて
もよい、また、エピタキシャル接合によって!戒の異な
るハロゲン化銀が接合されていてもよく、また例えばロ
ダン銀、酸化鉛などのハロゲン化銀以外の化合物と接合
されていてもよい。The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or it may be formed by epitaxial bonding! Silver halides having different properties may be bonded, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.
また種々の結晶形の粒子の混合物を用いてもよい。Also, mixtures of particles of various crystal forms may be used.
ハロゲン化銀乳剤は、通常、物理熟成、化学熟成および
分光増感を行ったものを使用する。このような工程で使
用される添加剤はリサーチ・ディスクロージャーNα1
7643および同Nα18716に記載されており、そ
の該当箇所を後掲の表にまとめた。The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα18716, and the relevant parts are summarized in the table below.
本発明に使用できる公知の写真用添加剤も上記の2つの
リサーチ・ディスクロージャーに記載されており、下記
の表に関連する記載箇所を示した。Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.
蚕貝■盪且 1?D17643 RD18716
1 化学増感剤 23頁 648頁右欄2 感
度上昇剤 同 上3 分光増感剤、
23〜24頁 648頁右欄〜強色増感剤
649頁右横4 増白剤 24頁
5 かぶり防止剤 24〜25頁 649頁右欄〜お
よび安定剤
6 光吸収剤、 25〜26頁 649頁右欄〜フ
ィルター染料、 650頁左欄紫外線吸収剤
7 スティン防止剤 25頁右欄 650頁左〜右欄8
色素画像安定剤 25頁
9 硬膜剤 26頁 651頁左欄lOバ
インダー 26頁 同 上11 可塑剤、潤
滑剤 27頁 650頁右欄12 塗布助剤、
26〜27頁 650頁右欄表面活性剤
13 スタチック 27頁 同 上防止剤
本発明には種々のカラーカプラーを使用することができ
、その具体例は前出のリサーチ・ディスクロージャー(
RD)Nα17643、■−C−Gに記載された特許に
記載されている。Silkworm ■●且 1? D17643 RD18716
1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, Page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static Page 27 Same as above Inhibitor Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-G.
イエローカプラーとしては、例えば米国特許第3.93
3,501号、同第4,022,620号、同第4.3
26.024号、同第4,401,752号、同第4,
248,961号、特公昭58−10739号、英国特
許第1,425,020号、同第L 476、760号
、米国特許第3,973.968号、同第4.314,
023号、同第4.511.649号、欧州特許第24
9.473A号、等に記載のものが好ましい。As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26.024, No. 4,401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. L 476,760, U.S. Patent No. 3,973.968, British Patent No. 4.314,
No. 023, No. 4.511.649, European Patent No. 24
9.473A, etc. are preferred.
マゼンクカプラーとしては5−ピラゾロン系及びピラゾ
ロアゾール系の化合物が好ましく、米国特許第4,31
0.619号、同第4,351,897号、欧州特許第
73,636号、米国特許第3.061,432号、同
第3゜725.067号、リサーチ・ディスクロージャ
ーNα24220 (1984年6月)、特開昭60−
33552号、リサーチ・ディスクロージャー隘242
30 (1984年6月)、特開昭60−43659号
、同61−72238号、同60−35730号、同5
5−118034号、同60−185951号、米国特
許第4゜500.630号、同第4,540,654号
、同第4,556,630号、国際公開WO38104
795号等に記載のものが特に好ましい。As the Mazenk coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,31
0.619, European Patent No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3.061,432, European Patent No. 3.725.067, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure No. 242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
No. 5-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Pat. No. 4,540,654, U.S. Pat.
Particularly preferred are those described in No. 795 and the like.
シアンカプラーとしては、フェノール系及びナフトール
系カプラーが挙げられ、米国特許第4.052.212
号、同第4.146,396号、同第4 、228 、
233号、同第4,296.200号、同第2.369
.929号、同第2,801.171号、同第2,77
2. I62号、同第2.895.826号、同第3.
772□002号、同第3.758,308号、同第4
,334.011号、同第4,327.173号、***
特許公開第3゜329.729号、欧州特許第121.
365A号、同第249゜453A号、米国特許第3,
446,622号、同第4,333,999号、同第4
,775,616号、同第4,451,559号、同第
4,427,767号、同第4.690.889号、同
第4 、254 。Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4.146,396, No. 4, 228,
No. 233, No. 4,296.200, No. 2.369
.. No. 929, No. 2,801.171, No. 2,77
2. I62, No. 2.895.826, No. 3.
772□002, same No. 3.758,308, same No. 4
, No. 334.011, No. 4,327.173, West German Patent Publication No. 3.329.729, European Patent No. 121.
No. 365A, No. 249°453A, U.S. Patent No. 3,
No. 446,622, No. 4,333,999, No. 4
, 775,616, 4,451,559, 4,427,767, 4,690.889, 4,254.
212号、同第4,296.199号、特開昭61−4
2658号等に記載のものが好ましい。No. 212, No. 4,296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.
発色色素の不要吸収を補正するためのカラード・カプラ
ーは、リサーチ・ディスクロージャー隘17643の■
−G項、米国特許第4,163,670号、特公昭57
−39413号、米国特許第4,004,929号、同
第4.138.258号、英国特許第1,146.36
8号に記載のものが好ましい。また、米国特許第4,7
74,181号に記載のカップリング時に放出された蛍
光色素により発色色素の不要吸収を補正するカプラーや
、米国特許第4.777.1.20号に記載の現像主薬
と反応して色素を形成しうる色素プレカーサー基を離脱
基として有するカプラーを用いることも好ましい。Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1,146.36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
No. 74,181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and a coupler that reacts with a developing agent to form a dye, as described in U.S. Pat. No. 4.777.1.20. It is also preferred to use couplers which have a dye precursor group as a leaving group.
発色色素が適度な拡散性を有するカプラーとしては、米
国特許第4,366.237号、英国特許第2.125
、570号、欧州特許第96.570号、***特許(公
開)第3,234,533号に記載のものが好ましい。Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
, No. 570, European Patent No. 96.570, and German Patent Publication No. 3,234,533 are preferred.
ポリマー化された色素形成カプラーの典型例は、米国特
許第3,451,820号、同第4,080,211号
、同第4,367.282号、同第4,409,320
号、同第4,576゜910号、英国特許2.102.
173号等に記載されている。Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.
カップリングに伴って写真的に有用な残基を放出するカ
プラーもまた本発明で好ましく使用できる。現像抑制剤
を放出するDIRカプラーは、本発明のもの以外に、前
述のRD 17643、■〜F項に記載された特許、特
開昭57−151944号、同57−154234号、
同60−184248号、同63−37346号、同6
3−37350号、米国特許4,248.962号、同
4.782.012号に記載されたものが好ましい。Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include, in addition to those of the present invention, the patents described in the above-mentioned RD 17643, Items ① to F, JP-A-57-151944, JP-A-57-154234,
No. 60-184248, No. 63-37346, No. 6
Preferred are those described in US Pat. No. 3-37350, US Pat. No. 4,248.962, and US Pat. No. 4.782.012.
現像時に画像状に造核剤もしくは現像促進剤を放出する
カプラーとしては、英国特許筒2,097,140号、
同第2.131.188号、特開昭59−157638
号、同59−170840号に記載のものが好ましい。Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.
その他、本発明の感光材料に用いることのできるカプラ
ーとしては、米国特許筒4,130,427号等に記載
の競争カプラー、米国特許筒4.283,472号、同
第4,338,393号、同第4□310.618号等
に記載の多売量カプラー、特開昭60−185950号
、特開昭6224252号等に記載のDIRレドックス
化合物放出カプラー、DIRカプラー放出カプラー、D
IRカプラー放出レドしクス化合物もしくはDIRレド
ックス放出レドしクス化合物、欧州特許第173゜30
2A号、同第313,308A号に記載の離脱後復色す
る色素を放出するカプラー、R,D、No、 1144
9、同24241、特開昭61−201247号等に記
載の漂白促進剤放出カプラー、米国特許筒4.553.
477号等に記載のリガンド放出カプラー、特開昭63
−75747号に記載のロイコ色素を放出するカプラー
、米国特許筒4゜774.181号に記載の蛍光色素を
放出するカプラー等が挙げられる。Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-6224252, etc., DIR coupler-releasing couplers, D
IR coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.30
R, D, No. 1144, a coupler that releases a dye that recolors after separation, as described in No. 2A and No. 313,308A.
9, No. 24241, bleaching accelerator releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553.
Ligand releasing coupler described in No. 477 etc., JP-A-63
Couplers that emit leuco dyes as described in US Pat. No. 4,774,181 and couplers that emit fluorescent dyes are mentioned.
本発明に使用するカプラーは、種々の公知分散方性によ
り感光材料に導入できる。The coupler used in the present invention can be introduced into the light-sensitive material using various known dispersion properties.
水中油滴分散法に用いられる高沸点溶媒の例は米国特許
筒2,322.027号などに記載されている。Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Patent No. 2,322.027 and the like.
水中油滴分散法に用いられる常圧での沸点が175°C
以上の高沸点有機溶剤の具体例としては、フタル酸エス
テル類(ジブチルフタレート、ジシクロへキシルフタレ
ート、ジー2−エチルへキシルフタレート、デシルフタ
レート、ビス(2,4−ジーを一アミルフェニル)フタ
レート、ビス(2,4−ジー上アミルフェニル)イソフ
タレート、ビス(1,1−ジエチルプロピル)フタレー
トなど)、リン酸またはホスホン酸のエステル類(トリ
フェニルホスフェート、トリクレジルホスフェート、2
−エチルヘキシルジフェニルホスフェート、トリシクロ
へキシルホスフェート、トリー2−エチルへキシルホス
フェート、トリドデシルホスフェート、トリブトキシエ
チルホスフェート、トリクロロプロピルホスフェート、
ジー2−エチルヘキシルフェニルホスホネートなど)、
安息香酸エステル!!(2−エチルヘキンルヘンゾエー
ト、ドデシルベンゾエート、2−エチルへキシル−p−
ヒドロキシベンゾエートなど)、アミド類(N、N−ジ
エチルドデカンアミド、N、Nジエチルラウリルアミド
、N−テトラデシルピロリドンなど)、アルコール類ま
たはフェノール類(イソステアリルアルコール、2,4
−ジーter t−アミルフ エノールなど)、脂肪族
カルボン酸エステル類 (ビス(2−エチルヘキシル)
セバケート、ジオクチルアゼレート、グリセロールトリ
ブチレート、イソステアリルラクテート、トリオクチル
シミーレートなど)、アニリン誘導体(N、N−ジプチ
ル2−ブトキシ−5−ter t−オクチルアニリンな
ど)、炭化水素類(パラフィン、ドデンルベンゼン、ジ
イソプロピルナフタレンなど)などが挙げられる。The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-monoamylphenyl) phthalate, bis(2,4-di-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid ester! ! (2-ethylhexylhexyl p-
hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4
-diter t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl)
sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl cimylate, etc.), aniline derivatives (N,N-diptyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodenlebenzene, diisopropylnaphthalene, etc.).
また補助溶剤としては、沸点が約30°C以上、好まし
くは50°C以上約160°C以下の有機溶剤などが使
用でき、典型例としては酢酸エチル、酢酸ブチル、プロ
ピオン酸エチル、メチルエチルケトン、シクロヘキサノ
ン、2−エトキシエチルアセテート、ジメチルホルムア
ミドなどが挙げられる。Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.
ラテンラス分散法の工程、効果および含浸用のラテック
スの具体例は、米国特許筒4,199,363号、***
特許出願(OLS)第2,541,274号および同第
2゜541 、230号などに記載されている。Specific examples of the process, effects, and latex for impregnation of the Latin lath dispersion method include U.S. Pat. It is described in.
本発明のカラー感光材料中には、特開昭63−2577
47号、同62−272248号、および特開平1−8
0941号に記載の1,2−ベンズイソチアゾリン−3
−オン、n−ブチル p−ヒドロキシベンゾエート、フ
ェノール、4−クロル−3,5−ジメチルフェノール、
2−フヱノキシエタノール、2−(4−チアゾリル)ヘ
ンズイミダゾール等の各種の防腐剤もしくは防黴剤を添
加することが好ましい。The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)henzimidazole.
本発明は種々のカラー感光材料に適用することができる
。一般用もしくは映画用のカラーネガフィルム、スライ
ド用もしくはテレビ用のカラー反転フィルム、カラーペ
ーパー、カラーポジフィルムおよびカラー反転ペーパー
などを代表例として挙げることができる。The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.
本発明に使用できる適当な支持体は、例えば、前述のR
D、Nα17643の28頁、および同Nα18716
の647頁右欄から648真左横に記載されている。Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643 and Nα18716
It is written from the right column of page 647 to the immediate left side of page 648.
本発明の感光材料は、乳剤層を有する側の全親水性コロ
イド層の膜厚の総和が28μm以下であることが好まし
く、23μ履以下がより好ましく、20μm以下が更に
好ましい。また膜膨潤速度T1/2は30秒以下が好ま
しく、20秒以下がより好ましい。In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
膜厚は、25°C相対湿度55%調湿下(2日)で測定
した膜厚を意味し、膜膨潤速度TI/□は、当該技術分
野において公知の手法に従って測定することができる。The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art.
例えば、ニー・グリーン(A、Green)らによりフ
ォトグラフインク・サイエンス・アンド・エンジニアリ
ング(Photogr、Sci、Eng、)、 19巻
、2号、124〜129頁に記載の型のスエロメーター
(膨潤膜)を使用することにより、測定でき、TI/!
は発色現像液で30゛C13分15秒処理した時に到達
する最大膨潤膜厚の90%を飽和膜厚とし、飽和膜厚の
1/2に到達するまでの時間と定義する。For example, a swellometer (swelling) of the type described by Green, A. et al. membrane), it can be measured and TI/!
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds, and is defined as the time required to reach 1/2 of the saturated film thickness.
膜膨潤速度TI/□は、バインダーとしてのゼラチンに
硬膜剤を加えること、あるいは塗布後の経時条件を変え
ることによって調整することができる。また、膨潤率は
150〜400%が好ましい、膨潤率とは、さきに述べ
た条件下での最大膨潤膜厚から、弐: (最大膨潤膜厚
−膜厚)/膜厚 に従って計算できる。The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to: (maximum swollen film thickness - film thickness)/film thickness.
本発明に従ったカラー写真感光材料は、前述のRD、N
α17643の28〜2つ頁、および同NCL1871
6の615左欄〜右欄に記載された通常の方法によって
現像処理することができる。The color photographic material according to the present invention includes the above-mentioned RD, N
Pages 28 to 2 of α17643, and NCL1871 of the same
6, 615, left column to right column.
本発明の感光材料の現像処理に用いる発色現像液は、好
ましくは芳香族第一級アミン系発色現像主薬を主成分と
するアルカリ性水溶液である。この発色現像主薬として
は、アミノフェノール系化合物も有用であるが、p〜フ
ェニレンジアミン系化合物が好ましく使用され、その代
表例としては3メチル−4−アミノ−N、Nジエチルア
ニリン、3−メチル−4−アミノ−N−エチル−N−β
−ヒドロキシエチルアニリン、3−メチル−4−アミノ
−N−エチル−Nβ−メタンスルホンアミドエチルアニ
リン、3−メチル−4−アミノ−N−エチル−β−メト
キシエチルアニリン及びこれらの硫酸塩、塩酸塩もしく
はpトルエンスルホン酸塩などが挙げられる。これらの
中で、特に、3−メチル−4−ア稟ノーN−エチルーN
β−ヒドロキシエチルアニリン硫酸塩が好ましい。これ
らの化合物は目的に応し2種以上併用することもできる
。The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates and hydrochlorides Alternatively, examples include p-toluenesulfonate. Among these, in particular, 3-methyl-4-amine-N-ethyl-N
β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.
発色現像液は、アルカリ金属の炭酸塩、ホウ酸塩もしく
はリン酸塩のようなpHJl衝剤、塩化物塩、臭化物塩
、沃化物塩、ベンゾチアゾール類、ベンゾチアゾール類
もしくはメルカプト化合物のような現像抑制剤またはカ
ブリ防止剤などを含むのが一般的である。また必要に応
じて、ヒドロキシルアミン、ジエチルヒドロキシルア5
ン、亜硫酸塩、N、N−ビスカルボキシメチルヒドラジ
ンの如きヒドラジン類、フェニルセミカルバジド類、ト
リエタノールアミン、カテコールスルホン酸類の如き各
種保恒剤、エチレングリコール、ジエチレングリコール
のような有機溶剤、ベンジルアルコール、ポリエチレン
グリコール、四級アンモニウム塩、アミン類のような現
像促進剤、色素形成カプラー、競争カプラー、1、フェ
ニル−3−ピラゾリドンのような補助現像主薬、粘性付
与剤、アミノポリカルボン酸、アミノポリホスホン酸、
アルキルホスホン酸、ホスホノカルボン酸に代表される
ような各種牛レート剤、例えば、エチレンシアミン四節
酸、ニトリロ三酢酸、ジエチレントリアミン五節酸、シ
クロヘキサンジアミン四酢酸、ヒドロキシエチルイミノ
ジ酢酸、■−ヒドロキシエチリデンーI11〜ジホスホ
ン酸、ニトリロ−N、N、N−) IJ メチレンホス
ホン酸、エチレンシア稟ンーN、N N、Nテトラメチ
レンホスホン酸、エチレンジアミンジ(0−ヒドロキシ
フェニル酢酸)及びそれらの塩を代表例として挙げるこ
とができる。Color developers include pHJl buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzothiazoles, developing compounds such as benzothiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxyl 5
sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, various preservatives such as phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, and polyethylene. Development accelerators such as glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1, phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids. ,
Various caloric acid agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenecyamine tetranodic acid, nitrilotriacetic acid, diethylenetriamine pentacholic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■- Hydroxyethylidene-I11~diphosphonic acid, nitrilo-N,N,N-) IJ Methylenephosphonic acid, ethylenecyarine-N,N N,N tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid) and salts thereof can be cited as a representative example.
また反転処理を実施する場合は通常黒白現像を行ってか
ら発色現像する。この黒白現像液には、ハイドロキノン
などのジヒドロキシベンゼン類、l−フェニル−3−ピ
ラゾリドンなどの3−ピラゾリドン類またはN−メチル
−p−アミノフェノールなどのアミノフェノール類など
公知の黒白現像主薬を単独であるいは組み合わせて用い
ることができる。Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.
これらの発色現像液及び黒白現像液のplは9〜l2で
あることが一般的である。またこれらの現像液の補充量
は、処理するカラー写真感光材料にもよるが、−iに感
光材料l平方メートル当たり32以下であり、補充液中
の臭化物イオン濃度を低減させておくことにより500
−以下にすることもできる。補充量を低減する場合には
処理槽の空気との接触面積を小さくすることによって液
の蒸発、空気酸化を防止することが好ましい。Generally, the pl of these color developing solutions and black and white developing solutions is 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -i is 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
−Can also be less than or equal to: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.
処理槽での写真処理液と空気との接触面積は、以下に定
義する開口率で表わすことができる。The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.
即ち、
処理液の容量(C−)
上記の開口率は、0.1以下であることが好ましく、よ
り好ましくは0.001〜0.05である。このように
開口率を低減させる方法としては、処理槽の写真処理液
面に浮き蓋等の遮蔽物を設けるほかに、特開平1−82
033号に記載された可動蓋を用いる方法、特開昭63
−216050号に記載されたスリント現像処理方法を
挙げることができる。開口率を低減させることは、発色
現像及び黒白現像の両工程のみならず、後続の諸工程、
例えば、漂白、漂白定着、定着、水洗、安定化などの全
ての工程において適用することが好ましい、また、現像
液中の臭化物イオンの蓄積を印える手段を用いることに
より補充量を低減することもできる。That is, Capacity of treatment liquid (C-) The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slint development method described in Japanese Patent No.-216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it in all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.It is also possible to reduce the amount of replenishment by using a means that indicates the accumulation of bromide ions in the developer. can.
発色現像処理の時間は、通常2〜5分の間で設定される
が、高温高pHとし、かつ発色現像主薬を高濃度に使用
することにより、更に処理時間の短縮を図ることもでき
る。The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.
発色現像後の写真乳剤層は通常漂白処理される。After color development, the photographic emulsion layer is usually bleached.
漂白処理は定着処理と同時に行なわれてもよいしく漂白
定着処理)、個別に行なわれてもよい。更に処理の迅速
化を図るため、漂白処理後漂白定着処理する処理方法で
もよい。さらに二種の連続した漂白定着浴で処理するこ
と、漂白定着処理の前に定着処理すること、又は漂白定
着処理後漂白処理することも目的に応し任意に実施でき
る。漂白剤としては、例えば鉄(I[[)などの多価金
属の化合物、過酸類、キノン類、ニトロ化合物等が用い
られる。代表的漂白剤としては鉄(III)の有機錯塩
、例えばエチレンジアミン四酢酸、ジエチレントリアミ
ン五酢酸、シクロヘキサンジアミン四酢酸、メチルイミ
ノニ酢酸、1.3−ジアミノプロパン四酢酸、グリコー
ルエーテルジアミン四酢酸、などのアミノポリカルボン
酸類もしくはクエン酸、酒石酸、リンゴ酸などの錯塩な
どを用いることができる。これらのうちエチレンジアミ
ン四酢酸鉄([1)18塩、及び1.3−ジアミノプロ
パン四酢酸鉄(m)錯塩を始めとするアミノポリカルボ
ン酸鉄〔II〕錯塩は迅速処理と環境汚染防止の観点か
ら好マしい。さらにアミノポリカルボン酸鉄([[I)
錯塩は漂白l夜においても、漂白定着液においても特に
有用である。これらのアミノポリカルボン酸鉄(III
)錯塩を用いた漂白液又は漂白定着液のpi+は通常4
.0〜8であるが、処理の迅速化のためにさらに低いp
Hで処理することもできる。The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron [II] complex salts, including ethylenediaminetetraacetate iron ([1) 18 salt and 1,3-diaminopropane tetraacetate iron (m) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. I like it. In addition, iron aminopolycarboxylate ([[I)
Complex salts are particularly useful in both bleaching and bleach fixing solutions. These aminopolycarboxylic acid iron (III
) The pi+ of bleach or bleach-fix solutions using complex salts is usually 4.
.. 0-8, but lower p for faster processing
It can also be treated with H.
漂白液、漂白定着液及びそれらの前浴には、必要に応し
て漂白促進剤を使用することができる。A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.
有用な漂白促進剤の具体例は、次の明細書に記載されて
いる:米国特許第3,893,858号、***特許第1
,290.812号、同2,059,988号、特開昭
53−32736号、同53−57831号、同53−
37418号、同53−72623号、同53−956
30号、同53−95631号、同53−104232
号、同53−124424号、同53−141623号
、同53−28426号、リサーチ・ディスクロージャ
ーNa17129号(1978年7月)などに記載のメ
ルカプト基またはジスルフィド基を有する化合物:特開
昭50−140129号に記載のチアゾリジン誘導体;
特公昭45−8506号、特開昭52−20832号、
同53−32735号、米国特許第3.706.561
号に記載のチオ尿素誘導体;***特許第1,127,7
15号、特開昭58−16,235号に記載の沃化物塩
;***特許第966.410号、同2,748,430
号に記載のポリオキシエチレン化合物類;特公昭45−
8836号記載のボリアごン化合物;その他特開昭49
−42.434号、同49−59.644号、同53−
94,927号、同54−35,727号、同55−2
6.506号、同58−163.940号記載の化合物
;臭化物イオン等が使用できる。なかでもメルカプト基
またはジスルフィド基を有する化合物が促進効果が大き
い観点で好ましく、特に米国特許第3,893,858
号、***特許第1.290,812号、特開昭53−9
5,630号に記載の化合物が好ましい9更に、米国特
許第4,552,834号に記載の化合物も好ましい。Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Na17129 (July 1978), etc.: JP-A-50-140129 Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3.706.561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Boriagon compounds described in No. 8836; other JP-A-1988
-42.434, 49-59.644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5,630.9 Also preferred are the compounds described in US Pat. No. 4,552,834.
これらの漂白促進剤は感材中に添加してもよい。撮影用
のカラー感光材料を漂白定着するときにこれらの漂白促
進剤は特に有効である。These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.
漂白液や漂白定着液には上記の化合物の他に、漂白ステ
ィンを防止する目的で有機酸を含有させることが好まし
い。特に好ましい有機酸は、酸解離定数(pea)が2
〜5である化合物で、具体的には酢酸、プロピオン酸な
どが好ましい。In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pea) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.
定着液や漂白定着液に用いられる定着剤としてはチオ硫
酸塩、チオシアン酸塩、チオエーテル系化合物、チオ尿
素類、多量の沃化物塩等をあげることができるが、チオ
硫酸塩の使用が一般的であり、特にチオ硫酸アンモニウ
ムが最も広範に使用できる。また、チオ硫酸塩とチオシ
アン酸塩、チオエーテル系化合物、チオ尿素などの併用
も好ましい、定着液や漂白定着液の保恒剤としては、亜
硫酸塩、重亜硫酸塩、カルボニル重亜硫酸付加物あるい
は欧州特許第294769A号に記載のスルフィン酸化
合物が好ましい。更に、定着液や漂白定着液には液の安
定化の目的で、各種アミノポリカルボン酸類や有機ホス
ホンMlの添加が好ましい。Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphones Ml to the fixing solution or bleach-fixing solution for the purpose of stabilizing the solution.
脱銀工程の時間の合計は、脱銀不良が生じない範囲で短
い方が好ましい。好ましい時間は1分〜3分、更に好ま
しくは1分〜2分である。また、処理温度は25°C〜
50°C1好ましくは35°C−45°Cである。好ま
しい温度範囲においては、脱銀速度が向上し、かつ処理
後のスティン発生が有効に防止される。The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C-45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.
脱銀工程においては、攪拌ができるだけ強化されている
ことが好ましい。攪拌強化の具体的な方法としては、特
開昭62−183460号、同62−183461号に
記載の感光材料の乳剤面に処理液の噴流を衝突させる方
法や、特開昭62−183461号の回転手段を用いて
撹拌効果を上げる方法、更には液中に設けられたワイパ
ーブレードと乳剤面を接触させながら感光材料を移動さ
せ、乳剤表面を乱流化することによってより撹拌効果を
向上させる方法、処理液全体の循環流量を増加させる方
法が挙げられる。このような撹拌向上手段は、漂白液、
漂白定着液、定着液のいずれにおいても有効である。撹
拌の向上は乳剤膜中への漂白剤、定着剤の供給を速め、
結果として脱銀速度を高めるものと考えられる。また、
前記のPil、押開上手段は、漂白促進剤を使用した場
合により有効であり、促進効果を著しく増加させたり漂
白促進剤による定着阻害作用を解消させることができる
。In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, and the method of JP-A-62-183461. A method of increasing the stirring effect using a rotating means, and a method of further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. , a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved stirring speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The above-mentioned pil and push-open means are more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.
本発明の感光材料に用いられる自動現像機は、特開昭6
0−191257号、同60−191258号、同60
−191259号に記載の感光材料搬送手段を有してい
ることが好ましい、前記の特開昭60−191257号
に記載のとおり、このような搬送手段は前浴から後浴へ
の処理液の持込みを著しく削減でき、処理順の性能劣化
を防止する効果が高い、このような効果は各工程におけ
る処理時間の短縮や、処理液補充量の低減に特に有効で
ある。The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.
本発明のハロゲン化銀カラー写真感光材料は、脱銀処理
後、水洗及び/又は安定工程を経るのが−C的である。It is preferable that the silver halide color photographic material of the present invention undergoes a water washing and/or stabilization process after desilvering treatment.
水洗工程での水洗水量は、感光材料の特性(例えばカプ
ラー等使用素材ムこよる)、用途、更には水洗水温、水
洗タンクの数(段数)、向流、順流等の補充方式、その
他種々の条件によって広範囲に設定し得る。このうち、
多段向流方式における水洗タンク数と水量の関係は、J
ournal of the 5ociety of
Motion Picture and Te1evi
sion Engineers第64巻、P、 248
〜253 (1955年5月号)に記載の方法で、求め
ることができる。The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other factors. It can be set over a wide range depending on the conditions. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety of
Motion Picture and Te1evi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).
前記文献に記載の多段向流方式によれば、水洗水量を大
幅に減少し得るが、タンク内における水の滞留時間の増
加により、バクテリアが繁殖し、生成した浮遊物が感光
材料に付着する等の問題が生しる0本発明のカラー感光
材料の処理において、このような問題が解決策として、
特開昭62−288,838号に記載のカルシウムイオ
ン、マグネシウムイオンを低減させる方法を極めて有効
に用いることができる。また、特開昭57−8,542
号に記載のイソチアゾロン化合物やサイアベンダゾール
類、塩素化イソンアヌール酸ナトリウム等の塩素系殺菌
剤、その他ヘンシトリアゾール等、堀口博著「防菌防黴
剤の化学J (1986年)三共出版、衛生技術全編
「微生物の滅菌、殺菌、防黴技術J (1982年)
工業技術会、日本防菌防黴学会線「防菌防黴剤事典」(
1986年)に記載の殺菌剤を用いることもできる。According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to this problem,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Isothiazolone compounds and thiabendazole compounds, chlorinated disinfectants such as chlorinated sodium isonurate, and other chlorinated disinfectants such as hensitriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology" Full volume “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Society, Japan Antibacterial and Mildew Society Line “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).
本発明の感光材料の処理における水洗水のpifは、4
〜9であり、好ましくは5〜8である。水洗水温、水洗
時間も、感光材料の特性、用途等で種々設定し得るが、
一般には、15〜45°Cで20秒〜10分、好ましく
は25〜40’Cで30秒〜5分の範囲が選択される。The pif of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40'C is selected.
更に、本発明の感光材料は、上記水洗に代り、直接安定
液によって処理することもできる。Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.
このような安定化処理においては、特開昭57−854
3号、同58−14834号、同60−220345号
に記載の公知の古注はすべて用いることができる。In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known old notes described in No. 3, No. 58-14834, and No. 60-220345 can be used.
また、前記水洗゛処理に続いて、更に安定化処理する場
合もあり、その例として、撮影用カラー感光材料の最纒
浴として使用される、色素安定化剤と界面活性剤を含有
する安定浴を挙げることができる。色素安定化剤として
は、ホルマリンやグルタルアルデヒドなどのアルデヒド
類、N−メチロール化合物、ヘキサメチレンテトラミン
あるいはアルデヒド亜硫酸付加物などを挙げることがで
きる。Further, following the water washing treatment, a further stabilization treatment may be performed, such as a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final coating bath for color photosensitive materials for photography. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
この安定浴にも各種キレート剤や防黴剤を加えることも
できる。Various chelating agents and antifungal agents can also be added to this stabilizing bath.
上記水洗及び/又は安定液の補充に伴うオーバーフロー
液は脱銀工程等地の工程において再利用することもでき
る。The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.
自動現像機などを用いた処理において、上記の各処理液
が蒸発によりfimtM化する場合には、水を加えて濃
縮補正することが好ましい。In a process using an automatic processor or the like, when each of the above-mentioned processing liquids becomes fimtM due to evaporation, it is preferable to add water to correct the concentration.
本発明のハロゲン化銀カラー感光材料には処理の簡略化
及び迅速化の目的で発色現像主薬を内蔵しても良い。内
蔵するためには、発色現像主薬の各種プレカーサーを用
いるのが好ましい0例えば米国特許第3.342,59
7号記載のインドアニリン系化合物、同第3.342.
599号、リサーチ・ディスクロージャー14,850
号及び同15.159号記載のシッフ塩基型化合物、同
13,924号記載のアルドール化合物、米国特許第3
,719.492号記載の金属塩錯体、特開昭5343
5628号記載のウレタン系化合物を挙げることができ
る。The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719.492, JP-A-5343
Examples include urethane compounds described in No. 5628.
本発明のハロゲン化銀カラー感光材料は、必要に応して
、発色現像を促進する目的で、各種のlフェニル−3−
ピラゾリドン類を内蔵しても良い。The silver halide color light-sensitive material of the present invention may contain various l-phenyl-3-
Pyrazolidones may also be incorporated.
典型的な化合物は特開昭56−64339号、同57−
144547号、および同58−115438号等に記
載されている。Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.
本発明における各種処理液は10’C〜50°Cにおい
て使用される。通常は33”0〜38°Cの温度が標準
的であるが、より高恩にして処理を促進し処理時間を短
縮したり、逆により低温にして画質の向上や処理液の安
定性の改良を達成することができる。The various treatment liquids in the present invention are used at 10'C to 50C. Normally, the standard temperature is 33"0 to 38°C, but it is possible to increase the temperature to accelerate processing and shorten processing time, or conversely to lower the temperature to improve image quality and improve the stability of the processing solution. can be achieved.
また、感光材料の両眼のため***特許第2,226,7
70号または米国特許第3,674.499号に記載の
コバルト補力もしくは過酸化水素補力を用いた処理を行
ってもよい。In addition, West German Patent No. 2,226,7 for the use of photosensitive materials for both eyes
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.
また、本発明のハロゲン化銀感光材料は米国特許第4,
500.626号、特開昭60−133449号、同5
9−218443号、同61−238056号、欧州特
許210,66042号などに記載されている熱現像感
光材料にも適用できる。Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210,66042, and the like.
(実施例) 以下に、 本発明を実施例により、 更に詳細に説 明するが、 本発明はこれらに限定されるものでは ない。(Example) less than, The present invention is illustrated by examples. Explain in more detail To clarify, The present invention is not limited to these do not have.
実施例/ 下記の方法でハロゲン化銀乳剤AおよびBを訪製した。Example/ Silver halide emulsions A and B were produced in the following manner.
0、It1モルの臭化カリウムと0.01.モルC沃化
カリウムを含す!2多ゼラチン水溶液100θccをt
oocm(攪拌しながら、コノ中1/CO,33モルの
硝酸銀を含む水溶液♂00 ccを20分ドア添加し、
20分間物理熟成したのち0.67モルの硝酸銀を含む
水溶液/ 000 ccと0.67モル/Eの臭化カリ
ウム水溶液を同時に!O分阻添加し、その間のpAgが
f、4になるように貨った。脱塩後コ×1o−5モルの
チオ硫酸ナトリウムとu×1o−sモルの塩化金酸を添
加し60″Cで60分間化学増感した。こうして平均サ
イズ/、7μmの2モル優の沃化銀を含む沃臭化鋤乳剤
を得た。これを乳剤Aとする。0.37モルの臭化カリ
ウムと0.10モルの沃化カリウムを含む2%ゼラチン
水溶液を用意し乳剤Aとほぼ戸様の行程でi、oμmの
10モル優の沃化銀を自t!沃臭化銀乳剤Bを得た。0, It1 mole of potassium bromide and 0.01. Contains mole C potassium iodide! 2 Polygelatin aqueous solution 100θcc
oocm (while stirring, add 00 cc of an aqueous solution containing 1/CO, 33 moles of silver nitrate in a container for 20 minutes,
After 20 minutes of physical ripening, an aqueous solution containing 0.67 mol of silver nitrate/000 cc and an aqueous potassium bromide solution of 0.67 mol/E are added at the same time! O was added for 1 minute, and the pAg was adjusted to f4 during that time. After desalting, 10-5 mol of sodium thiosulfate and 10-s mol of chloroauric acid were added and chemically sensitized at 60''C for 60 minutes. An iodobromide emulsion containing silver oxide was obtained.This will be referred to as Emulsion A.A 2% aqueous gelatin solution containing 0.37 mol of potassium bromide and 0.10 mol of potassium iodide was prepared. In the same process, more than 10 moles of silver iodide of i.o.mu.m was obtained as silver iodobromide emulsion B.
次いで下塗りを施した三酢酸セルロースフィルム支持体
上に、下記に示すような組成の各層を重層塗布して多層
カラー感光材料である試料10/を作製した。Next, each layer having the composition shown below was coated on an undercoated cellulose triacetate film support to prepare sample 10/, which is a multilayer color light-sensitive material.
(感光増組成)
各取分に対応する数字は、g/m2単位で表わした塗布
量を示し、ハロゲン化銀については、銀換算の塗布量を
示す。ただし増感色素については、同一層のハロゲン化
銀1モルに対する塗布量をモル単位で示す。(Sensitivity Enhancement Composition) The number corresponding to each portion indicates the coating amount in units of g/m2, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.
(試料10))
第1層;ハレーション防止層
黒色コロイド銀 ・・・銀0./ざゼラチン
・・・ O,UO第2層;中間層
コ、!−ジーt−ペンタデシル
ハイドロキノン ・・・ 0./ざEX−/
・・・ 0.07EX−3・・
・ 0.02
EX−/コ ・・・ o、ooxU−7
・ ・ ・ 0.04
U−コ ・ ・ ・ o
、orU−J ・ ・
・ O,10HB S −/
・ ・ ・ 0.10HBS−2・ ・ ・
0.02
ゼラチ/ ・・・ i、oゲ第3層(
第1赤感乳剤N)
単分散ヨウ臭化銀乳剤(ヨウ化銀ψモル嘩、平均粒径0
.!μ、粒径に関する変動係数0゜/j
・・・銀θ、3!増感色素I ・・・6
.りxio−s増感色素■ ・・・/、r×1
0 5増感色素■ ・・・1./X10−4増
感色素■ ・・・u、0x10−5EX−λ
・・・ θ、3!θEX−io
・・−o、or。(Sample 10)) 1st layer; antihalation layer black colloidal silver...silver 0. /Za gelatin... O, UO second layer; middle layer,! -d-t-pentadecylhydroquinone...0. /ZEX-/
... 0.07EX-3...
・ 0.02 EX-/ko... o, ooxU-7
・ ・ ・ 0.04 U-co ・ ・ ・ o
, orU-J ・ ・
・O,10HB S −/
・ ・ ・ 0.10HBS-2・ ・ ・
0.02 Gelatin/...i, oge 3rd layer (
1st red-sensitive emulsion N) Monodispersed silver iodobromide emulsion (silver iodide molar ratio, average grain size 0)
.. ! μ, coefficient of variation regarding particle size 0°/j
...Silver θ, 3! Sensitizing dye I...6
.. ri xio-s sensitizing dye■.../, r×1
0 5 Sensitizing dye■ ...1. /X10-4 sensitizing dye ■...u, 0x10-5EX-λ
... θ, 3! θEX-io
...-o, or.
ゼラチン ・・・ /、00第q層
(第1赤感乳剤N)
平板状ヨウ臭化銀乳剤(ヨウ化銀3モルφ、平均粒径0
.7μ、平均アスペクト比!、!。Gelatin ... /, 00 qth layer (first red-sensitive emulsion N) Tabular silver iodobromide emulsion (silver iodide 3 mol φ, average grain size 0
.. 7μ, average aspect ratio! ,! .
平均厚みO,コμ) 増感色素■ 増感色素■ 増感色素■ 増感色素■ EX−、z EX−3 EX−7゜ ゼラチン 第1層(第3赤感乳剤層) 乳剤A 増感色素■ 増感色素■ 増感色素■ 増感色素■ EX−7゜ EX−J EX−μ HB S −/ B5−2 ・・・銀0.70 ・ !、/X10−5 ・ /、41X10−5 ・ 2.3 × 10−4 ・ j、OX/ O−5 ・ ・ ・ O,4t Oθ ・ ・ ・ o 、ot。Average thickness O, μ) Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-,z EX-3 EX-7゜ gelatin 1st layer (3rd red-sensitive emulsion layer) Emulsion A Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-7゜ EX-J EX-μ HB S -/ B5-2 ...Silver 0.70 ・! , /X10-5 ・/, 41X10-5 ・ 2.3 × 10-4 ・j, OX/O-5 ・ ・ ・ O, 4t Oθ ・ ・ ・ o ,ot.
・ ・ ・ 0.0/! ・ ・ ・ / 、θ θ ・・・銀i、s。・ ・ ・ 0.0/! ・ ・ ・ / ,θ θ ...Silver i, s.
・ J−、ItXlo−5 ・ / 、グ X10−5 ・ +2 護×l θ−4 ・ 3./X10−5 ・ ・ ・ 0 .007 ・ ・ ・ 0#4tO ・ ・ ・ o 、 i +2 。・J-, ItXlo-5 ・/ 、gu X10-5 ・+2 protection×l θ−4 ・3. /X10-5 ・ ・ ・ 0. 007 ・ ・ ・ 0#4tO ・ ・ ・ o , i +2 .
・ ・ ・ 0.2 +2
・ ・ ・ 0./ θ
セ゛ラチン ・・・ 1.コO第6
層(中間層)
EX−s ・・・0.0≠Of−■
BS−/ −−−o 、o2゜ゼラチ
ン ・・・ 0.fO第7ノ曽(第
1青感乳剤層)
平板状ヨウ臭化銀乳剤(ヨウ化銀ψモル多、平均粒径0
.1μ、平均アスペクト比t、o。・ ・ ・ 0.2 +2 ・ ・ ・ 0. / θ Seratin... 1. Koo No. 6
Layer (middle layer) EX-s...0.0≠Of-■
BS-/---o, o2゜gelatin...0. fO No. 7 (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide ψ molar ratio, average grain size 0)
.. 1μ, average aspect ratio t,o.
平均厚みo、is) ・・・銀o、4L。Average thickness o, is)...Silver o, 4L.
#1感色素■ ・・・J、O×10−5#7感
色素■ ・・・/、0X10−4増感色素■
・・・3.ざX1O−4EX−4・・・o、、
xt。#1 Sensitizing Dye■ ...J, O×10-5 #7 Sensitizing Dye■ .../, 0X10-4 Sensitizing Dye■
...3. zaX1O-4EX-4...o,,
xt.
EX−i ・・・0.0λ1EX−
7・・・0.030
EX−、r −−−o、oxsl−
I B S−/ ・・・0.100H
f3S−// ・・・0,010ゼラチ
ン ・・・ 0.10第g/齋(第
2緑感乳剤層)
単分散ヨウ臭化銀乳剤(ヨウ化銀qモル多、平均粒径0
.7μ、粒径に関する変動係数03llr)
・・・銀0.A0増感色素■ ・・・2
./×10−5増感色素Vl −−−7,o
xto−s増感色素■ ・・・コ、t×1O−
4EX−7・・・0./ざ0
EX−ざ ・・・θ、010EX−y
−−・o、oorEX−7・・・
0.0/2
HB S −/ ・・・θ、/60H
BS−// ・・・o、oogゼラチン
・・・ OlりO第り層(第3緑感
乳剤層)
ヨウ臭化銀乳剤(ヨウ化@ぶモル嘩、平均粒径1.0μ
) ・・・ 銀/、2増感色素■
・・・3.jT×10−5増感色素■ ・・・
1.0×/θ−5増感色素■ ・・・3,0X
10 4EX−1・・・o、otr
EX−r −−−o、
o 2゜EX−/ / ・
・ ・ 0.030EX−7・ ・ ・ 0.02!
HBS−/ −−−0、J
jHB S −x ・
・ ・ 0.10ゼラチ/ ・・・
/ 、20第107曽(イエローフィルター層)
黄色コロイド釦 ・・・銀0.0!EX−s
−−−o、orHB S−/
・・・ 0.03ゼラチン
・・・ 0.12第1/層(第1青感乳剤層
)
平板状ヨウ臭化銀乳剤(ヨウ化銀グモル多、平均粒径0
.1μ、平均アスペクト比7.3、平均厚み0./グ)
・・・銀O,コψ増感色素■ ・・・j
、jXlo−4E X−タ ・・・
0.1!EX−ざ ・・・o、or
yHBS =/ ・−・ 0.21’
セラチ/ ・・・ 、1.00第1
2rfiIC第2青感乳剤層)
単分散ヨウ臭化銀乳剤(ヨウ化銀6モル多、平均粒径0
.、rμ、粒径に関する変動係数θ。EX-i...0.0λ1EX-
7...0.030 EX-, r---o, oxsl-
IBS-/...0.100H
f3S-// ... 0,010 gelatin ... 0.10 g/sai (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide q mole, average grain size 0
.. 7μ, coefficient of variation regarding particle size 03llr)
...Silver 0. A0 sensitizing dye■ ...2
.. /×10-5 sensitizing dye Vl ---7,o
xto-s sensitizing dye ■...ko, t×1O-
4EX-7...0. /za0 EX-za...θ, 010EX-y
--・o, oorEX-7...
0.0/2 HB S −/ ... θ, /60H
BS-// ... o, oog gelatin ... OloriO second layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (iodide @ bmol, average grain size 1.0μ
)... Silver/, 2 sensitizing dye■
...3. jT×10-5 sensitizing dye■...
1.0×/θ-5 sensitizing dye■...3,0X
10 4EX-1...o, otr EX-r ---o,
o 2゜EX-/ / ・
・ ・ 0.030EX-7・ ・ ・ 0.02! HBS-/---0, J
jHB S -x ・
・ ・ 0.10 gelati/ ・ ・
/ , 20th 107th (yellow filter layer) Yellow colloid button...Silver 0.0! EX-s
---o, orHB S-/
... 0.03 gelatin
... 0.12 1st/layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide gmol content, average grain size 0)
.. 1μ, average aspect ratio 7.3, average thickness 0. /g)
...Silver O, Coψsensitizing dye■ ...j
, jXlo-4E X-ta...
0.1! EX-za...o, or
yHBS =/ ・−・ 0.21'
Serachi/..., 1.00 1st
2rfiIC second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 moles of silver iodide, average grain size 0)
.. , rμ, coefficient of variation θ with respect to particle size.
lj) ・・・銀0.41!増感色素■
・・・λ、/X10 4EX−タ
・ ・ ・ 0.20EX−10・・・0
,0/!
HBS−t ・・・ 0.03ゼラチ
ン ・傘・ O1事!第73層(第
3肯感乳剤層)
ヨウ臭化銀乳剤(ヨウ化銀ψモル優、平均粒径i、3μ
) ・・・銀0.77増感色累■
・・・2..2X10 4EX−2・ ・・ O,コ
O
f(B S −i ・・・0.07ゼ
ラチン ・・・ 0.70第1q層
(第7保護層)
ヨウ臭化銀乳剤(ヨウ化銀3モル%、平均粒径0107
μ) ・・・ 銀0.jU−ψ
・ ・ ・ 0 、/ /U−
r ・ ・ ・
O1/711138−/ ・・・
OoりOゼラチン ・・・ /、θO
第1s)’tj<第λ保護層)
ポリメチルアクリレート粒子
(直径約/、jtμm) ・・・ o、r名例示化
合物5−29 ・・・ Q、/!例示の化合物S
−/7 ・・・ 0.0!ゼラチン
・・・ 0,72各層には上記の取分の他に、ゼ
ラチン硬化剤)1/、l−1−Jや界面活性剤を添加し
た。lj) ...Silver 0.41! Sensitizing dye■
...λ, /X10 4EX-ta
・ ・ ・ 0.20EX-10...0
,0/! HBS-t...0.03 Gelatin・Umbrella・O1 thing! 73rd layer (third positive emulsion layer) Silver iodobromide emulsion (silver iodide ψ molar predominance, average grain size i, 3μ
)...Silver 0.77 sensitized color cumulative■
...2. .. 2X10 4EX-2... O, KoO f (B S -i...0.07 Gelatin...0.70 1st q layer (7th protective layer) Silver iodobromide emulsion (3 moles of silver iodide %, average particle size 0107
μ) ... Silver 0. jU−ψ
・ ・ ・ 0, / /U-
r・・・・
O1/711138-/...
Oori O gelatin... /, θO
1st)'tj<λth protective layer) Polymethyl acrylate particles (diameter approx. /, jt μm) ... o, r name Exemplary compound 5-29 ... Q, /! Exemplary compound S
-/7... 0.0! gelatin
... 0,72 In addition to the above-mentioned portions, gelatin hardener) 1/1/1-1-J and a surfactant were added to each layer.
(試料10.2.1o3)
試料10/の第3層、第q層、および第1層のEX−y
oを各々2.1倍モルの本発明のカブ2(lり)、釦よ
び(20)に置き換えて試料102および103とした
。(Sample 10.2.1o3) EX-y of the third layer, q-th layer, and first layer of sample 10/
Samples 102 and 103 were prepared by replacing o with 2.1 times the molar amount of Turnip 2 (1), Button (20) of the present invention, respectively.
(試料1041〜1ot)
試料ioi〜103の第1層の乳剤Aを乳剤Bにそれぞ
れ置き換えて試料1041〜/θ2とした。(Samples 1041-1ot) Emulsion A in the first layer of Samples ioi-103 was replaced with Emulsion B to prepare Samples 1041-/θ2.
(試料/に17)
試料IOAの第1j層に添加されている(S−22)と
(S−/7)を除去して試料107とした。(Sample/17) Sample 107 was obtained by removing (S-22) and (S-/7) added to the 1j layer of sample IOA.
これら試料に赤色像様露光を与えて下記カラー現像を行
な−、(カブリ+0.2)のシアン濃度を与える臓光量
の逆数の対数を相対感度として表1に示した。These samples were exposed to red imagewise light and subjected to the following color development, and the relative sensitivity is shown in Table 1 as the logarithm of the reciprocal of the amount of internal light that gives a cyan density of (fog + 0.2).
′またグtμm直径のアパーチャーで測定した(カブI
J+0.2)の!1度に釦けるRMS値を表1に示した
。'It was also measured using an aperture with a diameter of 1 μm (Cub I
J+0.2)! Table 1 shows the RMS value of each button.
さらに、20サイクル/mmの777画像のM’l’F
値を求めた。MTF値の測定は、TheTheory
of the Photographic Proc
ess。Furthermore, M'l'F of 777 images at 20 cycles/mm
I found the value. Measurement of MTF value is performed using TheTheory.
of the Photographic Proc
ess.
3 rd ed、 (マクミラン社用、ミース著)の記
載の方法にならった。The method was followed as described in 3rd ed. (for Macmillan, by Mies).
これら試料をuo 0c相相対変&0%の条件(強制劣
化条件)下で7日間保存した後、カラ現像し、そのシア
ンカブリ濃度の変動も表1に示した。またシアン濃度/
、jを与える露光におけるマゼンタ濃度からマゼンタの
カブリ濃度を減じた値を色濁り度として示した。These samples were stored for 7 days under conditions of uo 0c phase relative change & 0% (forced deterioration conditions) and then color developed, and the fluctuations in cyan fog density are also shown in Table 1. Also, cyan density/
The value obtained by subtracting the magenta fog density from the magenta density at exposure giving , j is shown as the degree of color turbidity.
カラー現像処理は、自動現像機により3♂ 0Cにて地
下の処理を行なった。Color development processing was carried out underground at 3♂ 0C using an automatic developing machine.
発色現像 3分/!秒
漂 白 7分漂白定着
3分l!秒
水洗■ グθ秒
水洗■ 7分
安 定 ≠θ秒
乾 燥(jOoC)/分l!秒
上記処理工程において、水洗■と■は、■から■への向
流水洗方式とした。次に、各処理液の組成を記す。Color development 3 minutes/! Second bleach 7 minute bleach fixing
3 minutes! Washing for seconds ■ Washing for θ seconds ■ Stable for 7 minutes ≠ θ seconds Drying (jOoC)/min l! Sec. In the above treatment steps, water washing (1) and (2) were performed using a countercurrent water washing method from (1) to (2). Next, the composition of each treatment liquid will be described.
尚各処理液の補充量はカラー感光材料/m2当り発色現
像は1200m1. 他は水洗を含め全てgooml
とした。又水洗工程への前浴持込量はカラー感光材料1
m2当り10m1lであった。The replenishment amount of each processing solution is 1200 m1 for color development per m2 of color photosensitive material. Everything else is done on *** including washing with water.
And so. Also, the amount of pre-bath carried into the water washing process is 1 for color photosensitive materials.
The amount was 10ml/m2.
(発色現像液〉
母 液 補充液
ジエチレントリアミン
五酢酸 /、Og
ヒドロキシルチ
リブ/−/、/−
ジホスホン酸
亜硫酸ナトリウム
炭酸カリウム
臭化カリウム
沃化カリウム
ヒドロキシルアミン
硫酸塩
ψ−(N−エチル−
N−β−ヒドロキ
シエチルアミノ)
2−メチルアニ
リン硫酸塩 ψ、tg
水を加えて /、01
pH10,θ
(漂白液〉母液・補充液共通
エチレンジアミン四酢酸第二
鉄アンモニウム塩
、q g
0g
1t、Og
3θ 、Og
73g
/、Jmg
、/ g
、2g
、ψ g
、Og
。7g
、Ag
6.0g
/、011
/ O、θ !
/20.Og
エチレンジアミ7四酢酸二ナ
トリウム塩
硝酸アンモニウム
臭化アンモニウム
漂白促進剤
10、Og
10、Og
100、Og
!;×10−3モル
アンモニア水を加えて
水を加えて
〈漂白定着液)母液・補充液共通
エチレンジアミ7四酢酸二
ナ
エチレンジアミ7四酢酸二ナ
トリウム塩
亜硫酸ナトリウム
チオ硫酸アンモニア水溶液
(70%)
アンモニア水を加えて
水を加えて
pH6,3
/、01
!0.0 g
1、Og
/ コ 、Og
2グOml
pH
7、3
(水洗水〉・
カルシウムイオン3xmg/l、 マグネシウムイオ
:y7.3mg/lを含む水道水をII形強酸性カチオ
ン交換樹脂とOH形強塩基性アニオン交換樹脂を充てん
したカラムに通水し、カルシウムイオ7/ 、2mg/
1. マクネシウムイオンO,グmg/lに処理した
水に、二塩化イソシアヌル酸ナトリウムを/l当り20
mg添加して用いた。(Color developer) Mother solution Replenisher Diethylenetriaminepentaacetic acid /, Og Hydroxyltilib /-/, /- Diphosphonic acid Sodium sulfite Potassium carbonate Potassium iodide Hydroxylamine sulfate ψ-(N-ethyl-N-β -Hydroxyethylamino) 2-methylaniline sulfate ψ, tg Add water /, 01 pH 10, θ (Bleach solution>Mother solution/replenisher common ethylenediaminetetraacetic acid ferric ammonium salt, q g 0g 1t, Og 3θ, Og 73g /, Jmg, / g, 2g, ψ g, Og.7g, Ag 6.0g /, 011 / O, θ! /20.Og Ethylenediami7tetraacetic acid disodium salt Ammonium nitrate Ammonium bromide bleach accelerator 10, Og10, Og100, Og!; Ammonia sulfate aqueous solution (70%) Add ammonia water and add water to pH 6.3 /, 01! 0.0 g 1, Og / Co, Og 2 g Oml pH 7.3 (Washing water > Calcium ion 3xmg / Tap water containing 7.3 mg/l of magnesium ion was passed through a column filled with a type II strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin, and calcium ion 7/, 2 mg/l
1. Add sodium isocyanurate dichloride to water treated with magnesium ion O,g mg/l at 20% per liter.
mg was added and used.
(安定液〉母液・補充液共通
ホルマリン(37%w/v ) 2 、0ml
ポリオキシエチレン−p−モ
ノノニルフェニルエーテル
(平均重合度10) 0.3gエチレン
ジアミン四酢酸二
ナトリウム塩 0.03g水を加え
て /lpH!、、r
く乾燥〉
乾燥温度はto 0cとした。(Stabilizing solution) Mother solution/replenisher common formalin (37% w/v) 2, 0ml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Ethylenediaminetetraacetic acid disodium salt 0.03g Add water /lpH! ,,r Drying> The drying temperature was set to 0c.
表1より、本発明の試料は強制劣化条件でのカブリが少
なく、RMS値で表わさせる粒状性およびM、TF値で
表わされる鮮鋭性に優れかっ色濁り度で表わされる色再
現性に優れることが明らかである。From Table 1, the samples of the present invention have less fog under forced aging conditions, excellent graininess expressed by RMS value, sharpness expressed by M and TF values, and excellent color reproducibility expressed by color turbidity. That is clear.
実施例2
下記の方法に従って、比較用乳剤C>よび本願発明の高
ヨードハロゲン化銀乳剤りとEをv4製した。0.11
1モルの臭化カリウムと0.0tモルの沃化カリウムを
含むJ%ゼラチン水溶液10θOccをjz’cで攪拌
しながら、この中に0.33モルの硝酸銀を含む水溶液
100 cCを30分間で添加し20分間物理熟成した
のち、0.lr7モルの硝酸銀を含む水溶液1oooc
cHo、t7モル/lの臭化カリウム水溶液を同時にi
o。Example 2 Comparative emulsion C> and high iodosilver halide emulsion R and E of the present invention were prepared in accordance with the following method. 0.11
While stirring 10θOcc of a J% gelatin aqueous solution containing 1 mol of potassium bromide and 0.0 t mol of potassium iodide with a jz'c, 100 cC of an aqueous solution containing 0.33 mol of silver nitrate was added over 30 minutes. After physical aging for 20 minutes, 0. 1oooc of an aqueous solution containing lr7 mol of silver nitrate
cHo, t7 mol/l potassium bromide aqueous solution was simultaneously i
o.
分間添加しその間のpAgがr、Oになるように保った
。脱塩後/X10−5モルのチオ硫黄ナトリウムと2×
10−5の塩化金酸を添加し600Cでto分間化学増
感した。こうして平均サイズO8りμmの6モル多の沃
化銀を含む沃臭化銀乳剤Cを得た。0.37モルの臭化
カリウムとo、i。The solution was added for a minute, and the pAg was maintained at r,O during that time. After desalination/X10−5 moles of sodium thiosulfur and 2×
Chemical sensitization was carried out at 600 C for up to minutes by adding 10-5 chloroauric acid. In this way, a silver iodobromide emulsion C containing 6 moles of silver iodide with an average size of O8 μm was obtained. 0.37 mol of potassium bromide and o,i.
モルの沃化カリウムを含む1悌ゼラチン水溶液を用意し
乳剤Cとほぼ同様の行程で0.9μmの10モル条の沃
化銀を含む沃臭化銀乳剤りを得た。An aqueous gelatin solution containing 1 mole of potassium iodide was prepared, and a silver iodobromide emulsion containing 10 moles of silver iodide having a diameter of 0.9 μm was obtained in substantially the same manner as in Emulsion C.
0.3sモルの臭化カリウムと0172モルの沃化カリ
ウムを含む2%ゼラチン水溶液を用意し乳剤Cとほぼ同
様の行程で0.9μmの72モル%の沃化銀を含t!沃
臭化銀乳剤Eを得た。A 2% gelatin aqueous solution containing 0.3 smol of potassium bromide and 0.172 mol of potassium iodide was prepared, and in almost the same process as Emulsion C, 72 mol% of silver iodide of 0.9 μm was prepared. Silver iodobromide emulsion E was obtained.
(試料コO/)
試料10/の第7wI、第g層ふ・よび第り鳩のEX−
,1’をEX−/3に2倍モルで置き換えかつ、第り層
の乳剤をCK置き換えて試料20/を作製した。(Sample Ko O/) Sample 10/7th wI, G layer F-Y, and EX-
.
(試料コOコ、103)
試料20/の第7層、第rN$−よび第り層のEX−/
3を本発明のカプラー(lり)および(22)にそれぞ
れ0.7倍モルで置き換えて試料20λ、203とした
。(Sample KoOko, 103) Sample 20/7th layer, rN$- and 2nd layer EX-/
Samples 20λ and 203 were obtained by replacing 3 with the couplers (1) and (22) of the present invention at 0.7 times the mole.
(試料20グ〜コOF)
試料roi〜203の第り層の乳剤Cを本発明の乳剤り
ふ・よびEに代えて試料2011〜206および試料、
207〜.2θヂとした。(Samples 20 to 20F) Samples 2011 to 206 and samples,
207~. 2θ angle.
これら試料を実施例1で評価した方法に準じて評価した
。ただし赤色露光を緑色露光に、シア/濃度はマゼンタ
濃度に置き換えた。These samples were evaluated according to the method evaluated in Example 1. However, red exposure was replaced with green exposure, and shea/density was replaced with magenta density.
表コは1本発明の試料は粒状性、鮮鋭性1色再現性およ
び感材保存性のすべてに優れていることを示している。Table 1 shows that the samples of the present invention are excellent in graininess, sharpness, one-color reproducibility, and photosensitive material storage stability.
実施例/、コで用いた化合物 U−/ −2 −3 し4月9(す Iノ リ ! EX / EX−コ EX−J H EX EX り EX 0 IN(J2 EX−i / EX / 2 α じX 3 1−(B S−/ トリクレジルフォスフェート 11 B S−1 ジ n−ブチルフタレート )IBS−// I / コ 増感色素 ■ C2H5 C2I■5 特許出軌人 富士写真フィルム株式会社 手続補正書Examples/Compounds used in U-/ -2 -3 April 9th I no Li ! EX / EX-ko EX-J H EX EX the law of nature EX 0 IN(J2 EX-i / EX /2 α JX 3 1-(B S-/ tricresyl phosphate 11 B S-1 Ji n-butyl phthalate )IBS-// I / Ko sensitizing dye ■ C2H5 C2I■5 Patent issuer Fuji Photo Film Co., Ltd. Procedural amendment
Claims (2)
を設けたハロゲン化銀カラー写真感光材料において、該
乳剤層中のハロゲン化銀粒子の40重量%以上が、沃化
銀含有率9モル%以上の粒子で占められており、該乳剤
層中に下記一般式( I )で表わされる化合物を含有す
ることを特徴とするハロゲン化銀カラー写真感光材料。 一般式( I ) ▲数式、化学式、表等があります▼ 式中、R_1、R_2、R_3およびR_4は各々水素
原子、低級アルキル基を表わし、R_5は水素原子、ア
シルアミノ基、スルホンアミド基、ホスホンアミド基、
アルコキシカルボニルアミノ基、アリールオキシカルボ
ニルアミノ基、アルコキシスルホンアミド基、アリール
オキシスルホンアミド基、カルバモイルアミノ基、又は
スルファモイルアミノ基を表わし、nは1から4の整数
、TIMEは一般式( I )で表わされる化合物が発色
現像主薬と反応することによりDIとともに離脱し、そ
の後DIを放出しうるタイミング基を表し、DIは現像
抑制剤を表わす。(1) In a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, 40% by weight or more of the silver halide grains in the emulsion layer have a silver iodide content of 9 mol. % or more of grains, and the emulsion layer contains a compound represented by the following general formula (I). General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3 and R_4 each represent a hydrogen atom or a lower alkyl group, and R_5 represents a hydrogen atom, an acylamino group, a sulfonamide group, or a phosphonamide group. basis,
represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxysulfonamide group, an aryloxysulfonamide group, a carbamoylamino group, or a sulfamoylamino group, n is an integer from 1 to 4, and TIME is the general formula (I) DI represents a timing group capable of releasing DI after a compound represented by reacts with a color developing agent and then releases DI, and DI represents a development inhibitor.
される化合物もしくはその塩を含有することを特徴とす
る請求項(1)に記載のハロゲン化銀カラー写真感光材
料。 一般式〔II〕 ▲数式、化学式、表等があります▼ 〔式中、X_1およびX_2は酸素原子または=NH基
、R_1およびR_2は水素原子、アシル基または炭化
水素残基、R_3およびR_4は水素原子、水酸基、ア
ミノ基、炭化水素残基または−OR基(Rは置換基を有
してもよい炭化水素残基)を表わし、R_3とR_4は
連結して5〜6員飽和炭素環核を形成してもよい。ただ
しR_1およびR_2は水酸化メチル基であることはな
く、またX_1およびX_2がともに酸素原子であつて
しかもR_3およびR_4がともにアミノ基以外の基で
あるときまたはR_3とR_4が連結して5〜6員飽和
炭素環核を形成するときにはR_1およびR_2の少な
くとも1つは水素原子である。〕 一般式〔III〕 ▲数式、化学式、表等があります▼ 〔式中、X_3およびX_4は酸素原子または=NH基
、R_5およびR_6は水素原子、アシル基または炭化
水素残基、R_7はイミノ基または炭化水素残基を表わ
す。ただしR_5およびR_6は水酸化メチル基である
ことはなく、またX_3およびX_4がともに酸素原子
であつてしかもR_7が炭化水素残基であるときにはR
_5およびR_6の少なくとも1つは水素原子である。 〕(2) The silver halide color photographic material according to claim (1), further comprising a compound represented by the general formula [II] and/or [III] or a salt thereof. General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1 and Represents an atom, hydroxyl group, amino group, hydrocarbon residue, or -OR group (R is a hydrocarbon residue that may have a substituent), and R_3 and R_4 are connected to form a 5- to 6-membered saturated carbon ring nucleus. may be formed. However, R_1 and R_2 are not methyl hydroxide groups, and when X_1 and X_2 are both oxygen atoms and R_3 and R_4 are both groups other than amino groups, or R_3 and R_4 are connected and When forming a 6-membered saturated carbocyclic nucleus, at least one of R_1 and R_2 is a hydrogen atom. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X_3 and X_4 are oxygen atoms or =NH group, R_5 and R_6 are hydrogen atoms, acyl groups or hydrocarbon residues, and R_7 is imino group or represents a hydrocarbon residue. However, R_5 and R_6 are never methyl hydroxide groups, and when X_3 and X_4 are both oxygen atoms and R_7 is a hydrocarbon residue, R
At least one of _5 and R_6 is a hydrogen atom. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26857589A JPH03130764A (en) | 1989-10-16 | 1989-10-16 | Silver halide color photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26857589A JPH03130764A (en) | 1989-10-16 | 1989-10-16 | Silver halide color photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03130764A true JPH03130764A (en) | 1991-06-04 |
Family
ID=17460428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP26857589A Pending JPH03130764A (en) | 1989-10-16 | 1989-10-16 | Silver halide color photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03130764A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0519428A (en) * | 1991-07-16 | 1993-01-29 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57133450A (en) * | 1981-02-11 | 1982-08-18 | Konishiroku Photo Ind Co Ltd | Color photographic material |
JPS6254259A (en) * | 1985-05-13 | 1987-03-09 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material and processing method thereof |
JPS62121457A (en) * | 1985-11-21 | 1987-06-02 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPS62192740A (en) * | 1986-02-19 | 1987-08-24 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
JPH0199046A (en) * | 1987-10-12 | 1989-04-17 | Konica Corp | Silver halide photographic sensitive material having toxic gas resistance |
-
1989
- 1989-10-16 JP JP26857589A patent/JPH03130764A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57133450A (en) * | 1981-02-11 | 1982-08-18 | Konishiroku Photo Ind Co Ltd | Color photographic material |
JPS6254259A (en) * | 1985-05-13 | 1987-03-09 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material and processing method thereof |
JPS62121457A (en) * | 1985-11-21 | 1987-06-02 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
JPS62192740A (en) * | 1986-02-19 | 1987-08-24 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
JPH0199046A (en) * | 1987-10-12 | 1989-04-17 | Konica Corp | Silver halide photographic sensitive material having toxic gas resistance |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0519428A (en) * | 1991-07-16 | 1993-01-29 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
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