JPS62166336A - Processing of silver halide color photographic sensitive material - Google Patents
Processing of silver halide color photographic sensitive materialInfo
- Publication number
- JPS62166336A JPS62166336A JP976586A JP976586A JPS62166336A JP S62166336 A JPS62166336 A JP S62166336A JP 976586 A JP976586 A JP 976586A JP 976586 A JP976586 A JP 976586A JP S62166336 A JPS62166336 A JP S62166336A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- processing
- color
- color photographic
- 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.)
- Granted
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 163
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 92
- 239000004332 silver Substances 0.000 title claims abstract description 92
- 238000012545 processing Methods 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000000839 emulsion Substances 0.000 claims abstract description 72
- 238000011161 development Methods 0.000 claims abstract description 65
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 43
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 20
- 230000008961 swelling Effects 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 150000004989 p-phenylenediamines Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 79
- 239000003795 chemical substances by application Substances 0.000 claims description 72
- 150000001875 compounds Chemical class 0.000 claims description 49
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000004986 phenylenediamines Chemical class 0.000 claims description 2
- QTLHLXYADXCVCF-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanol Chemical group OCCN(CC)C1=CC=C(N)C(C)=C1 QTLHLXYADXCVCF-UHFFFAOYSA-N 0.000 claims 1
- 230000018109 developmental process Effects 0.000 description 63
- 239000010410 layer Substances 0.000 description 58
- 239000000975 dye Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 53
- 238000005406 washing Methods 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 230000000087 stabilizing effect Effects 0.000 description 28
- 230000000694 effects Effects 0.000 description 24
- 229940006460 bromide ion Drugs 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- 239000002738 chelating agent Substances 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 15
- 229920000159 gelatin Polymers 0.000 description 15
- 239000008273 gelatin Substances 0.000 description 15
- 235000019322 gelatine Nutrition 0.000 description 15
- 235000011852 gelatine desserts Nutrition 0.000 description 15
- 230000005291 magnetic effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000004061 bleaching Methods 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 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 9
- 239000000047 product Substances 0.000 description 9
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000005562 fading Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021612 Silver iodide Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 125000004423 acyloxy group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 229940045105 silver iodide Drugs 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 239000000298 carbocyanine Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 125000000565 sulfonamide group Chemical group 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 150000003557 thiazoles Chemical class 0.000 description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 101100496104 Mus musculus Clec2d gene Proteins 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 101100274534 Rattus norvegicus Clec2d11 gene Proteins 0.000 description 2
- 101100274532 Rattus norvegicus Ocil gene Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
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- LFHNSEYRHPYYMQ-UHFFFAOYSA-N carbamic acid;2-methyl-1h-imidazole Chemical compound NC(O)=O.CC1=NC=CN1 LFHNSEYRHPYYMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CGMKPKRNUNDACU-UHFFFAOYSA-N carbamimidoyl(dodecyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN=C(N)N CGMKPKRNUNDACU-UHFFFAOYSA-N 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019258 dehydroacetic acid Nutrition 0.000 description 1
- 229940061632 dehydroacetic acid Drugs 0.000 description 1
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 description 1
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical class C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 description 1
- PEIVHTCIMKJVJF-UHFFFAOYSA-N n-[2-amino-5-(dimethylamino)phenyl]acetamide Chemical compound CN(C)C1=CC=C(N)C(NC(C)=O)=C1 PEIVHTCIMKJVJF-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229940037201 oris Drugs 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- BRBKOPJOKNSWSG-UHFFFAOYSA-N sulfaguanidine Chemical compound NC(=N)NS(=O)(=O)C1=CC=C(N)C=C1 BRBKOPJOKNSWSG-UHFFFAOYSA-N 0.000 description 1
- 229960004257 sulfaguanidine Drugs 0.000 description 1
- QPPBRPIAZZHUNT-UHFFFAOYSA-N sulfamerazine Chemical compound CC1=CC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 QPPBRPIAZZHUNT-UHFFFAOYSA-N 0.000 description 1
- 229960002597 sulfamerazine Drugs 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- 229960005158 sulfamethizole Drugs 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
- G03C7/346—Phenolic couplers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- 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カラー写真感光材料(以下、感光
材料という、)の発色現像処理方法に関し、詳しくは補
充量の変化や蒸発の影響によって生じる臭化物イオン濃
度変動依存性及び処理時間依存性か少なくしかも迅速性
を損なわない、かつ先祖色性やスティンに優れて保存性
の高い色素画像か得られ、かつ低公害化にも優れた。新
規な処理方法に関するものてあり、特に補充量が少なく
しかも処理安定性の高い処理方法を提供する方法に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials). Dye images with low dependence on bromide ion concentration fluctuations and processing time dependence, without impairing speed, excellent ancestral color and stain, and high storage stability were obtained, and were also excellent in low pollution. The present invention relates to a new processing method, and particularly to a method that provides a processing method that requires a small amount of replenishment and has high processing stability.
[全中林]
感光材料の処理は基本的には発色現像と脱銀の2工程か
らなり、脱銀は漂白と定着工程又は漂白定着工程からな
っている。この他に付加的な処理工程としてリンス処理
、安定処理等が加えられる。[Zen Nakabayashi] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.
発色現像において、露光されたハロゲン化銀は還元され
て銀になると同時に酸化された芳香族第1級アミン現像
主薬はカプラーと反応して色素を形成する。この過程で
、ハロゲン化銀の還元によって生じたハロゲンイオンか
現像液中に溶出し蓄積する。又別にはハロゲン化銀写真
感光材料中に含まれる抑制剤等の成分も発色現像液中に
溶出して蓄積される。脱銀工程では現像により生じた銀
は酸化剤により漂白され、次いて全ての銀塩は定着剤に
より可溶性銀塩として、写真感光材料中より除去される
。なお、この漂白工程と定着工程をまとめて回持に処理
する一浴漂白定着処理方法も知られている。In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced during development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are combined and recycled.
発色現像液では前記の如く写真感光材料を現像処理する
ことによって現像抑制物質が蓄積するが、−1発色現像
主薬やベンジルアルコールは消費され、あるいは写真感
光材料中に蓄積して持ち出され、それらの成分濃度は低
下していく、従って多量のハロゲン化銀写真感光材料を
自動現像機等により連続処理する現像処理方法において
は。In color developing solutions, development inhibitory substances accumulate when photographic light-sensitive materials are developed as described above, but the -1 color developing agent and benzyl alcohol are consumed or accumulated in the photographic light-sensitive materials and taken out. In a developing method in which a large amount of silver halide photographic material is continuously processed by an automatic processor or the like, the component concentration decreases.
成分濃度の変化による現像仕上がり特性の変化を避ける
ために発色現像液の成分を一定濃度の範囲に保つための
手段か必要である。かかる手段として通常は不足成分を
補い不要な増加成分を稀釈するための補充液を補充する
方法がとられている。In order to avoid changes in development finish characteristics due to changes in component concentration, a means is required to maintain the components of the color developer within a constant concentration range. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.
この補充液の補充により必然的に多量のオーバーフロー
か生じ、廃棄されるために、この方法は経済上および公
害上大きな問題となっている。それ故に近年ては前記オ
ーバーフロー液を減少させるため、これらの補充液を濃
厚化し少量補充する所謂濃厚低補充方式か盛んに用いら
れ、又別にはオーバーフロー液に再生剤を加え再び補充
液として用いる方法も提案され実用化されている。The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, a so-called concentrated and low replenishment method has been widely used, in which the replenisher is concentrated and refilled in small amounts, and another method is to add a regenerating agent to the overflow liquid and use it again as a replenisher. has also been proposed and put into practical use.
[発明か解決しようとする問題点]
これらはいずれも実質的に補充量か減少する方法である
。極端に補充量を減少させると現像液中に溶出する有機
抑制剤やハロゲンイオン濃度はわずかの補充量の誤差に
よっても、大きく濃度変化をこうむることになり、又、
蒸発による濃縮の影響をも受は易くなり1通常は前記の
疲労蓄積物の濃度か上昇してしまう0例えばハロゲンイ
オン濃度か上昇すると現像反応か抑制されたり、特性曲
線の脚部かより抑制されることに起因するハイコントラ
スト化という問題を生じる。これを避けるためにオーバ
ーフロー液からイオン交換樹脂や電気透析によりハロゲ
ンイオンを除去し、現像て生じた不足成分や再生処理て
ロスした不足成分を補うための再生剤を加えて再び補充
液として再生し使用する方法か提案されている。[Problems to be Solved by the Invention] All of these methods substantially reduce the amount of replenishment. If the amount of replenishment is extremely reduced, the concentration of organic inhibitors and halogen ions eluted into the developer will be subject to large changes due to even a slight error in the amount of replenishment.
It is also more susceptible to the effects of concentration due to evaporation (1) Normally, the concentration of the fatigue accumulation mentioned above will increase (0) For example, if the halogen ion concentration increases, the development reaction will be suppressed, or the legs of the characteristic curve will be more suppressed. This causes the problem of high contrast. To avoid this, halogen ions are removed from the overflow solution using an ion exchange resin or electrodialysis, and a regenerating agent is added to compensate for the missing components generated during development and missing components lost during regeneration processing, and the solution is regenerated as a replenisher. Is there a suggested way to use it?
これらイオン交換樹脂や電気透析による再生や濃厚低補
充方式ては蒸発や再生操作の影響を受は臭化物イオン濃
度の変動を受は易かったり、別には処理量の差、特に受
注量の多い遇の始めと受注量力匂表少する週末、及びハ
イシーズンと才フシーズンの差は最大l:5位の差とな
って表れ、かつ蒸発や補充液量の差の影響も受けるため
処理液の組成は大巾に異なってしまう欠点がある。These regeneration and concentrated low replenishment methods using ion exchange resins and electrodialysis are affected by evaporation and regeneration operations, and are susceptible to fluctuations in bromide ion concentration. The difference between the beginning and the weekend when the order quantity is low, and the high season and the high season is expressed as a difference of up to 1:5, and the composition of the processing liquid is affected by evaporation and the difference in the amount of replenisher. There is a drawback that the width is different.
そのため低補充処理や再生方法では再生毎に成分を定量
分析し組成を一定ならしめる努力をしており、そのため
特別なスキルがない現像所やミニラボてはこれらの再生
処理や低補充処理の実施は困難なことが多い。Therefore, in low replenishment processing and regeneration methods, efforts are made to quantitatively analyze the components and make the composition constant each time the product is regenerated. Therefore, it is difficult for photo labs and minilabs without special skills to carry out these regeneration processing and low replenishment processing. It is often difficult.
このような問題は主に現像抑制剤であるブロマイドイオ
ンの変化に起因したものであり、例えば写真材料中の臭
化銀量を減少させることにより蓄積する臭化物イオンの
量を減少させたり蒸発や補充量の誤差に伴なう臭化物イ
オンの濃度変動を減少させることも提案されている(特
願昭59−173189号、同59−205540号等
参照、)。These problems are mainly caused by changes in bromide ions, which are development inhibitors. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to errors in the amount (see Japanese Patent Application Nos. 59-173189 and 59-205540, etc.).
またこうした問題は1例えば写真材料中のハロゲン化銀
の平均粒径な小さくしたり、塗布銀量を低下させること
により現像性を向上させることにより解決できることが
推定されるか、従来の現像主薬である3−メチル−4−
アミノ−N−エチル−N−β−メタンスルホンアミドエ
チルアニリンを用いた発色現像液ては、現像性を向上さ
せると、現像液中の臭化物イオン濃度の変動の影響をか
えって受は易くなり、処理安定性が損なわれるという期
待とは逆の結果となってしまう。It is also presumed that these problems can be solved by improving developability by, for example, reducing the average grain size of silver halide in photographic materials or reducing the amount of coated silver, or by using conventional developing agents. certain 3-methyl-4-
Improving the developability of a color developer using amino-N-ethyl-N-β-methanesulfonamide ethylaniline makes it easier to absorb the effects of fluctuations in the bromide ion concentration in the developer, making processing easier. The result is the opposite of the expected stability loss.
しかしながら処理時間を短縮した上で処理安定性を高め
ることは重要な課題である。However, it is an important issue to improve processing stability while shortening processing time.
従来は実質的に塩臭化銀乳剤からなるカラーペーパー処
理では1発色現像が33℃、3分30秒−漂白定若33
°C11分30秒−水洗3分(又は安定処理3分)−乾
燥となっている。全処理時間は約8分か一般的処理時間
となっているが、時代の強い要請は経済的な意味ては前
記した低補充化であるが、短時間処理も納期の短縮とい
う点から強く要請されている。Conventionally, in color paper processing consisting essentially of a silver chlorobromide emulsion, one color development was performed at 33°C for 3 minutes and 30 seconds - bleaching and fixation.
°C for 11 minutes and 30 seconds - washing with water for 3 minutes (or stabilizing for 3 minutes) - drying. The total processing time is about 8 minutes, which is the standard processing time, but the current strong demand is for the above-mentioned low replenishment from an economical point of view, but there is also a strong demand for short processing times from the perspective of shortening delivery times. has been done.
ところが、前記したように迅速化と処理の安定化あるい
は低補充化は相反する問題であり、トレードオフの関係
といえる。However, as described above, speeding up the process and stabilizing the process or reducing replenishment are contradictory issues and can be said to be a trade-off relationship.
即ち、低補充化すれば、抑制物質である臭化物イオンの
濃度や乳剤安定剤であるイオウ化合物やメルカプト化合
物の濃度が上昇し迅速性か損なわれ、処理安定性か損な
われる。That is, if the replenishment level is low, the concentration of bromide ion, which is an inhibitor, and the concentration of sulfur compounds and mercapto compounds, which are emulsion stabilizers, increase, impairing rapidity and processing stability.
とはいえ従来から迅速化のために発色現像を速くする種
々の対策がとられてきた。特に塩臭化銀乳剤の現像に最
も適した生薬として長い間用いられてきた前記の現像主
薬は、親水性が低いため。However, various measures have been taken to speed up color development. In particular, the above-mentioned developing agent, which has been used for a long time as the most suitable crude drug for developing silver chlorobromide emulsions, has low hydrophilicity.
感光材料中への発色現像主薬の浸透が遅く、それを速め
るための各種の浸透剤が検討され1例えばベンジルアル
コールを発色現像液に加えて、発色現像を速める方法が
広く用いられている。しかし、この方法ては、3:l”
Cて3分以上の処理をしないと、十分に発色しなかった
し、そればかりでなく、微妙な臭化物イオン濃度の影響
も受は易い欠点かあった。発色現像液のpHをあげる方
法も知られているか、piが1000以上になると、発
色現像主薬の酸化か著しく速くなることや、適当なる緩
衝液かないためにpl+の変化を受は易くなり安定した
写真特性か得られなくなったり、処理時間の依存性か大
きくなったりするという問題点かあった。Penetration of a color developing agent into a light-sensitive material is slow, and various penetrants have been studied to speed up the penetration.1 For example, a method of speeding up color development by adding benzyl alcohol to a color developer is widely used. However, this method
Unless treated with C for 3 minutes or more, the color did not develop sufficiently, and it also had the disadvantage that it was easily affected by the subtle bromide ion concentration. Is there also a known method of increasing the pH of the color developing solution?When the pi is over 1000, the oxidation of the color developing agent becomes extremely rapid, and since there is no suitable buffer solution, it becomes more susceptible to changes in pl+ and becomes stable. There were problems in that photographic characteristics could no longer be obtained and processing time became highly dependent.
発色現像液中の発色現像主薬を増して活性な上げる方法
も知られているが、発色現像主薬か非常に高価のため割
高の処理液になると同時に前記主薬は水に溶解し難く析
出しやすいという不安定性も生じ、実用上使用できるも
のてはない。A method of increasing the activity by increasing the color developing agent in the color developing solution is known, but the color developing agent is very expensive, resulting in a relatively expensive processing solution, and at the same time, the main agent is difficult to dissolve in water and tends to precipitate. It also causes instability and cannot be used practically.
一方、発色現像の迅速化を達成するために、予め発色現
像主薬を感光材料中に内蔵させるという方法が知られて
いる。例えば発色現像主薬を金属塩にして内蔵するとい
う方法か知られている(米国特許3,719,492号
)か、この方法ては感光材料の生保存性が悪く、使用す
る前にかぶったり、さらに発色現像時にかぶり易いとい
う欠点かあった。On the other hand, in order to speed up color development, a method is known in which a color developing agent is incorporated into a light-sensitive material in advance. For example, there is a known method of incorporating a color developing agent in the form of a metal salt (U.S. Pat. No. 3,719,492); however, this method has poor storage stability for photosensitive materials, and is difficult to store before use. Another drawback was that it was prone to fogging during color development.
さらに発色現像主薬のアミン部分を不活性にするため、
例えばシッフ塩にして発色現像主薬を内蔵するという方
法(米国特許:l、:142,559号。Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of incorporating a color developing agent into a Schiff salt (US Pat. No. 142,559).
Re5earch Disclosure 、 197
6年No、15159)も知られているが、これらの方
法では発色現像主薬かアルカリ加水分解した後てないと
発色現像が開始てきず、むしろ発色現像か遅くなるとい
う欠点かあった。Research Disclosure, 197
No. 6, No. 15159) is also known, but these methods have the disadvantage that color development cannot begin until after the color developing agent has been alkaline hydrolyzed, and rather the color development is delayed.
さらに発色現像主薬を直接内蔵する場合、発色現像主薬
が不安定なため、保存中の乳剤かかぶるという欠点の他
に、乳剤膜質が弱くなるため、処理上の種々のトラブル
か発生するという欠点かあった。Furthermore, when the color developing agent is directly contained, the color developing agent is unstable, which causes the emulsion to overlap during storage, and the quality of the emulsion film becomes weak, which can lead to various processing problems. there were.
更にまた、パイトロキノンのような現像剤を含有した黒
白現像液中に3−ピラゾリドン類を加えて現像促進する
ことは知られている(例えばり、F、A。Furthermore, it is known that 3-pyrazolidones are added to a black and white developer solution containing a developer such as pytroquinone to accelerate development (for example, F, A).
Mason著、Photographic Proce
ssing Chesistrylo:l 〜107頁
、Focal Press刊、1966年)、この化合
物を感光材料中に内蔵する事実は、英国特許767.7
04号に記載されているか、しかし前記特許明細書に記
載の技術では黒白感光材料又は1反転カラー感光材料中
に内蔵しており、その目的は黒白現像のみを促進するこ
とにあり、また、特開昭53−52422号には、活性
点にオキシ型有機スプリットオフ基を有する2当量マゼ
ンタカプラーを含むカラー感光材料の未露光状態での感
度低下を防止する目的で、3−ピラゾリドン類を感光材
料中に含有させているか、これらの技術は、発色現像処
理を低補充処理て安定化するという迅速化方法としては
適していない。Author: Photographic Process
The fact that this compound is incorporated into photosensitive materials is disclosed in British Patent No. 767.7.
However, in the technology described in the above patent specification, the technology is incorporated into a black-and-white photosensitive material or a one-inversion color photosensitive material, and its purpose is to promote only black-and-white development. Japanese Patent Publication No. 53-52422 discloses that 3-pyrazolidones are added to a photosensitive material for the purpose of preventing a decrease in sensitivity in an unexposed state of a color photosensitive material containing a 2-equivalent magenta coupler having an oxy-type organic split-off group at its active site. However, these techniques are not suitable as a rapid method of stabilizing color development processing with low replenishment processing.
又、従来から知られている促進剤によって発色現像を早
くする方法としては、米国特許2,950,970号、
同 2,515,147号、同 2,496,903号
、同4,038.075号、同4,119,462号、
英国特許1.4:10.998号、同1,455,41
3号、特開昭53−15831号、同55−62450
号、同55−62451号、同55−62452号、同
55−62453号、特公昭51−12322号、同5
5−49728号等に記載された化合物等が検討された
か、促進効果が不充分な化合物が大半であり、又、高度
の促進効果を示す化合物はかぶりが生成するという欠点
を有するばかりでなく処理安定性を向上させる方法とし
ては適さなかった。Further, as a conventionally known method of accelerating color development using an accelerator, US Pat. No. 2,950,970;
No. 2,515,147, No. 2,496,903, No. 4,038.075, No. 4,119,462,
British Patent No. 1.4:10.998, No. 1,455,41
No. 3, JP-A-53-15831, JP-A No. 55-62450
No. 55-62451, No. 55-62452, No. 55-62453, Special Publication No. 51-12322, No. 5
The compounds described in No. 5-49728, etc. have been studied, but most of the compounds have insufficient accelerating effects, and the compounds that show a high accelerating effect not only have the drawback of forming fog, but also require treatment. This was not suitable as a method for improving stability.
また実質的には非感光性であるハロゲン化銀乳剤層を感
光材料中に設け、現像を促進することは、特開昭50−
23225号、同56−14236号、英国特許1.:
178,577号、 OLS 2,622,922号等
て知られているか、その機能は、現像中に放出される不
要ハロゲン及びDIRカプラーやDARカプラーの不要
離脱基等の現像抑制物質を吸着することてあり、積極的
に現像を促進するものてはなく、その現像促進効果は小
さいばかりか、ヨウ化物イオン濃度の変動には効果があ
るとはいえ臭化物イオン濃度の変動に対しては全く処理
安定化効果は得られなかった。Further, it is known that a silver halide emulsion layer which is substantially non-photosensitive is provided in a light-sensitive material to accelerate development.
No. 23225, No. 56-14236, British Patent 1. :
No. 178,577, OLS No. 2,622,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers and DAR couplers. There is nothing that actively promotes development, and its development promotion effect is not only small, but even though it is effective against fluctuations in iodide ion concentration, the process is completely stable against fluctuations in bromide ion concentration. No effect was obtained.
又一方て、発色現像の速度は使用するパラフェニレンジ
アミン誘導体の種類によって異なり酸化二元電位に依存
するといわれている。これらの発色現像主薬の中てもN
、N−ジエチル−p−フェニレンシアミン硫酸塩や3−
メチル−4−アミノ−N、N−ジエチルアニリン塩酸塩
等のN−アルキル置換の水溶性の低い発色現像↑薬は現
像活性か高く迅速化か可能であるか、処理後の発色色素
の暗褪色性か低く好ましくないことか知られている。一
方、現像活性か高く好ましいといわれている(米国特許
3,656.950号、同:I、658,525号等参
照)3−メチル−4−アミノ−N−エチル−N−β−メ
トキシエチルアニリン−シーp−トルエンスルホン酸塩
は確かに迅速性は得られるものの臭化物イオン濃度安定
性は得られずかつ処理後の写真感光材料の未露光部にイ
エロースティンか著しく発生し、特に短時間処理したと
き、発色現像主薬が残留して荒いスティン発生の原因と
なる欠点かあり、迅速処理では使用できない。On the other hand, the speed of color development varies depending on the type of paraphenylenediamine derivative used and is said to depend on the oxidation binary potential. Among these color developing agents, N
, N-diethyl-p-phenylenecyamine sulfate and 3-
Color development with low water solubility of N-alkyl substituted drugs such as methyl-4-amino-N,N-diethylaniline hydrochloride ↑ Is the development activity high and is it possible to speed up the development? Dark fading of the coloring dye after processing It is known that it has low sex and is undesirable. On the other hand, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl is said to be preferable because of its high development activity (see U.S. Pat. No. 3,656.950, U.S. Pat. No. 658,525, etc.) Aniline-C-p-toluenesulfonate does indeed provide rapid processing speed, but it does not provide stable bromide ion concentration, and yellow stain occurs significantly in the unexposed areas of photographic materials after processing, especially during short processing times. When this is done, the color developing agent remains and causes rough staining, so it cannot be used in rapid processing.
一方、N−アルキル基に水溶性基であるアルキルスルホ
ンアミド基やヒドロキシアルキル基を導入した3−メチ
ル−4−アミノ−N−エチル−β−メタンスルホンアミ
トエチルアニリンセスキサルフェートモノヒトラートや
3−メチル−4−アミノ−N−β−ヒトロキシエチルア
ニリン硫酸k12等はフォトクラフィック・サイエンス
アント エンシニアソンクVo1.8.No、:1.
5〜6月、1964年、P、125〜137にみられ
る如く、酸化還元電位を示す半波電位にはあまり差かな
くかつ両者とも現像活性は弱いといわれていた。On the other hand, 3-methyl-4-amino-N-ethyl-β-methanesulfonamitoethylaniline sesquisulfate monohydrate and 3- Methyl-4-amino-N-β-hydroxyethylaniline sulfate k12, etc., are available from Photocratic Science Ant Encinia Song Vol. 1.8. No: 1.
As seen in May-June, 1964, P, 125-137, it was said that there was not much difference in half-wave potential indicating the oxidation-reduction potential, and that both had weak developing activity.
従って実質的塩臭化銀乳剤の現像活性か得られかつ色素
画像の保存安定性か優れた発色現像主薬はほとんどなく
、一般には3−メチル−・1−アミノ−N−エチル−N
−β−メタンスルホンアミトエチルアニリン硫酸塩か、
ベンジルアルコールとともに使用することにより前記目
的を達していた。Therefore, there are few color developing agents that can provide substantial development activity of silver chlorobromide emulsions and have excellent storage stability of dye images; generally, 3-methyl-1-amino-N-ethyl-N
-β-methanesulfonamitoethylaniline sulfate,
The above objective was achieved by using it with benzyl alcohol.
しかしながら、この場合には前記したように臭化物イオ
ン濃度の変化の影響を受は易い。また補充液を減少させ
た濃厚低補充処理では、別の問題として他の処理液成分
の混入蓄積の増大がある。However, in this case, as mentioned above, it is easily affected by changes in bromide ion concentration. Further, in the concentrated low replenishment process in which the amount of replenisher is reduced, another problem is an increase in the contamination and accumulation of other processing liquid components.
これは補充量が減少したためにタンク液が補充液て更新
される率か低くなるためてあり、液の使用期間が長くな
ることも加わるためである。他の処理液の混入は処理機
内での隣りの処理液のスプラッシュや搬送リーダー、ベ
ルト又はフィルムを吊り下げるハンガー等により発色現
像液中に現像直後の処理液成分が持ち込まれる所謂バッ
クコンタミネーションにより引き起こされる。これらの
蓄積する混入成分のうち、定着剤であるチオ硫酸イオン
は現像促進する。即ち1発色現像後に直接漂白定着処理
される場合に特にこの問題は強く起こる。特に写真特性
曲線の肩部な促進することによって著しいハイコントラ
スト化を生じる。また漂白剤である金属塩、特に第2鉄
塩の混入増大は保恒剤であるヒドロキシルアミンの分解
を促進しアンモニアイオンを生成する。この分解反応は
30℃以上で大きく促進される。このアンモニアイオン
の発生はチオ硫酸イオンと同様に物理現像を促進し、ハ
イコントラスト化する欠点があった。This is because the rate at which the tank liquid is replaced with replenisher becomes lower due to the decrease in the amount of replenishment, and also because the period of use of the liquid becomes longer. Contamination with other processing solutions is caused by so-called back contamination, in which processing solution components immediately after development are brought into the color developer by splashes from adjacent processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. It will be done. Among these contaminant components that accumulate, thiosulfate ion, which is a fixing agent, accelerates development. That is, this problem occurs particularly when bleach-fixing is performed directly after one-color development. In particular, by promoting the shoulder portion of the photographic characteristic curve, remarkable high contrast is produced. Further, increased contamination of metal salts as bleaching agents, especially ferric salts, accelerates the decomposition of hydroxylamine as a preservative, producing ammonia ions. This decomposition reaction is greatly accelerated at temperatures above 30°C. The generation of ammonia ions, like thiosulfate ions, has the disadvantage of accelerating physical development and increasing contrast.
従って、経済的及び環境汚染改善のために低補充量化し
ても、iJ!、速処理が可能てあり、かつ写真性能が一
定に維持され、かつ処理液が長い間使用されても有効成
分が分解したり、写真処理性能が変化したりしない安定
処理可能な発色現像液の出現が強く望まれているのが現
状である。Therefore, even if the amount of replenishment is reduced in order to improve economical and environmental pollution, iJ! , a color developing solution that can be processed quickly, maintains constant photographic performance, and does not degrade the active ingredients or change the photographic processing performance even if the processing solution is used for a long period of time. The current situation is that its appearance is strongly desired.
本発明の目的は、発色現像液を用いて低補充量て処理し
ても臭化物イオン濃度の変化を受けず常に一定の適正な
写真性能が長期に亘って維持でき、かつ得られた発色色
素や未発色部が長期に保存しても褪色したり変色したり
しない迅速で安定な感光材料の処理方法を提供すること
にある。It is an object of the present invention to maintain constant appropriate photographic performance over a long period of time without any change in bromide ion concentration even when processed with a color developing solution at a low replenishment amount, and to produce a color developing agent and To provide a rapid and stable method for processing a photosensitive material in which uncolored areas do not fade or change color even when stored for a long period of time.
本発明のその他の目的は本明細書の以下の記載から明ら
かになろう。Other objects of the invention will become apparent from the description below.
[問題を解決するための手段]
本発明者は上述の本発明の目的を達成するために種々検
討した結果、特定のハロゲン化銀の現像に際し臭化物イ
オン濃度の影響をほとんど受けない特異な発色現像主薬
を見い出すことに成功したか、得られた発色色素の保存
安定性が低下してしまうという障害につき当り、これを
解決する方法を更に検討した。その結果、感光材料を現
像処理する方法において、少なくとも1層の感光性乳剤
層のハロゲン化銀乳剤が実質的に塩臭化銀乳剤であり、
バインダーのv11!’潤速度T I/2が30秒以下
で、かつ下記一般式(I)、(II )又は(m)て表
されるシアンカプラーを少なくとも1種含有する感光材
料を、N−ヒドロキシアルキル置換−p−フェニレンシ
アミン誘導体を発色現像液中のp−フェニレンジアミン
発色現像主薬に対し30モル%以上含有し、かつ実質的
にペンシルアルコールを含有しない発色現像液を用いて
30℃以上で現像処理することを特徴とする感光材料の
処理方法によって上記目的を達成することかてきること
を見い出した。[Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object of the present invention, the present inventor has developed a unique color development that is almost unaffected by the bromide ion concentration when developing a specific silver halide. Although we succeeded in finding the main drug, we also encountered the problem that the storage stability of the obtained coloring dye decreased, and we further investigated ways to solve this problem. As a result, in the method for developing a photosensitive material, the silver halide emulsion in at least one photosensitive emulsion layer is substantially a silver chlorobromide emulsion;
Binder v11! A photographic material having a wettability rate T I/2 of 30 seconds or less and containing at least one cyan coupler represented by the following general formula (I), (II) or (m) is Development processing is carried out at 30°C or higher using a color developing solution containing 30 mol% or more of a p-phenylenecyamine derivative based on the p-phenylenediamine color developing agent in the color developing solution and substantially free of pencil alcohol. It has been found that the above object can be achieved by a method of processing a photosensitive material characterized by the following.
一般式([)
式中、R及びR1は一方が水素原子であり、他方が少な
くとも炭素数2〜12の直鎖又は分岐のアルキル基であ
り、Xは水素原子又はN−ヒドロキシアルキル置換−p
−フェニレンジアミン誘導体発色現像主薬の酸化体との
カプリング反応により誰脱しうる基を表し、 R2は
バラスト基を表す。General formula ([) In the formula, one of R and R1 is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an N-hydroxyalkyl substituted -p
-phenylenediamine derivative represents a group that can be released by a coupling reaction with an oxidized form of a color developing agent, and R2 represents a ballast group.
一般式(II)
H
一般式(m)
OH
式中、Yは−COR4、
(但しR4はアルキル基、アルケニル基、シクロアルキ
ル基、アリール基またはへテロ環基を表し、Rgは水素
原子、アルキル基、アルケニル基、シクロアルキル基、
アリール基またはへテロ環基を表し、R4とRsとが互
いに結合して5〜6員のへテロ環を形成してもよい、)
を表し、R3はバラスト基を表し、Zは水素原子又はト
ヒドロキシアルキル置換−ρ−フェニレンシアミン誘導
体発色現像主薬の酸化体とのカプリング反応により離脱
しつる基を表す。General formula (II) H General formula (m) OH In the formula, Y is -COR4, (However, R4 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Rg is a hydrogen atom, an alkyl group, alkenyl group, cycloalkyl group,
represents an aryl group or a heterocyclic group, and R4 and Rs may be bonded to each other to form a 5- to 6-membered heterocycle)
, R3 represents a ballast group, and Z represents a hydrogen atom or a group that is separated by a coupling reaction with an oxidized product of a hydroxyalkyl-substituted -ρ-phenylenecyamine derivative color developing agent.
本発明者は、特定のハロゲン化銀、即ち塩臭化銀主体(
特に臭化銀含有率か90モル%以下)の乳剤を用いたカ
ラー写真感光材料の現像に際し発色現像主薬がN−ヒド
ロキシアルキル置換−p−フェニレンジアミン訪導体を
用いたとき、臭化物イオン濃度か変化しても得られる色
素濃度がほとんど変化しないという第〈べき事実を見出
した。この発色現像主薬の前記特徴はヨウ化銀を0.5
モル%以上含有する実質的にヨウ臭化銀乳剤を用いたカ
ラー写真感光材料では得られないことてあり、従来この
タイプの発色現像主薬かヨウ臭化銀乳剤の現像専用に用
いられてきたことから予期しえないことてあり、特に実
質的塩臭化銀乳剤を用いたカラー写真感光材料の現像に
際して臭化物イオン濃度を大巾に高めても現像速度が遅
れないという事実は予想もし得ないことてあり、一般的
な発色現像主薬の酸化還元電位や半波電位からも理解て
きることではなく、虞らく現像スピードとカプリングス
ピードの最適なバランスか保たれない限り起こり得ない
ことてあり、驚くべきことであった。The present inventor has discovered that a specific silver halide, namely silver chlorobromide-based (
In particular, when developing a color photographic light-sensitive material using an emulsion with a silver bromide content of 90 mol% or less, the bromide ion concentration changes when an N-hydroxyalkyl-substituted p-phenylenediamine conductor is used as the color developing agent. The first and most important fact has been discovered that there is almost no change in the density of the dye obtained. The above-mentioned characteristics of this color developing agent include silver iodide of 0.5
This cannot be obtained with color photographic materials that use silver iodobromide emulsions containing more than mol% of silver iodobromide, and conventionally this type of color developing agent has been used exclusively for the development of silver iodobromide emulsions. In particular, the fact that the development speed is not delayed even if the bromide ion concentration is greatly increased when developing a color photographic light-sensitive material using a substantial silver chlorobromide emulsion is unexpected. This is not something that can be understood from the oxidation-reduction potential or half-wave potential of common color developing agents, and it is surprising that this phenomenon cannot occur unless an optimal balance between development speed and coupling speed is maintained. It was the right thing to do.
しかしながら本発明者は次の障害につき当った。それは
N−ヒドロキシアルキル置換−p−フェニレンジアミン
発色現像主薬を用いた場合には迅速てかつ、臭化物イオ
ン濃度の変化を受けず、特に高い臭化物イオン濃度下で
現像できることから連続処理した場合に補充する量を大
巾に低下でき、かつ処理安定性か著しく高いという大き
な利点が得られるものの、得られた発色色素の保存安定
性、特に光褪色性の低下やスティンの発生、特にシアン
スティンか発生するという欠点かあることかわかった。However, the inventor encountered the following problem. When an N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent is used, it is rapid and unaffected by changes in bromide ion concentration, and can be developed especially under high bromide ion concentrations, so it is necessary to replenish it during continuous processing. Although it has the great advantage of being able to greatly reduce the amount of color and having extremely high processing stability, the storage stability of the resulting coloring dye is affected, especially the reduction in photofading resistance and the occurrence of staining, especially cyan staining. I found out that there is a drawback.
色素画像の保存安定性は特にプリント材料の場合には致
命的なことであり大きな障害になった。The storage stability of dye images has become a critical and major obstacle, especially in the case of print materials.
本発明者は更に鋭意この聞届の解決にとり組んだ結果、
光褪色性は色素そのものの保存安定性か低いためによる
ものではなく1発色現像主薬や発色現像主薬の酸化体か
カラー写真感光材料に残留し易いために起こり、特にカ
ラペーパー用発色現像液に一般に用いられているベンジ
ルアルコールが発色現像液に存在する場合に上記のよう
な問題か生じることかわかった。しかしながら発色現像
液中のベンジルアルコールを実質的にフリーにするとい
うことはカラー写真感光材料の現像処理性か充分改良さ
れないと達成てきることてはない。As a result of further efforts by the inventor to resolve this issue,
The photofading property is not due to the low storage stability of the dye itself, but is caused by the fact that single-color developing agents and oxidized products of color developing agents tend to remain in color photographic materials. It has been found that the above problem occurs when the benzyl alcohol used is present in the color developer. However, substantially freeing benzyl alcohol from the color developing solution cannot be achieved unless the development processability of the color photographic material is sufficiently improved.
又、シアンスティンについてはカプラーの構造によると
ころが大きく、色素画像の光褪色性やスティン特性を損
わずに低補充化と処理安定性を達成するためには本発明
のカプラーを用い、かつ本発明の発色現像液を用いて実
質的にベンジルアルコールをフリーにすることか必要で
あることか判明した。Regarding cyan stain, it largely depends on the structure of the coupler, and in order to achieve low replenishment and processing stability without impairing the photobleaching properties and stain characteristics of the dye image, the coupler of the present invention must be used, and the coupler of the present invention must be used. It has been found that it is necessary to use a color developing solution substantially free of benzyl alcohol.
この場合、従来の写真感光材料のままでは現像時間が不
足し充分な写真画像か得られないという問題か生じてし
まう。そこて更に本発明者は検討を重ね、本発明の発色
現像主薬を使用し臭化物イオン濃度の増加の影響を受け
ずに低補充化処理するだめに少なくとも1層、好ましく
は全ての感光性乳剤層のハロゲン化銀乳剤か実質的に塩
臭化銀乳剤てあり、かつバインダーの膜膨潤速度T l
/2か30秒以下であるカラー写真感光材料なN−ヒド
ロキシアルキル数換−p−フェニレンジアミン誘導体を
少なくとも発色現像液中のp−フェニレンジアミン発色
現像主薬に対して30モル%以上含む現像液で処理する
ことによって現像速度を改良し1色素画像の安定性を損
わずに前記の本発明の目的を達成することに成功したも
のである。In this case, if conventional photographic materials are used as they are, the problem arises that developing time is insufficient and sufficient photographic images cannot be obtained. Therefore, the inventors of the present invention have made further studies and found that in order to perform low replenishment processing without being affected by the increase in bromide ion concentration by using the color developing agent of the present invention, at least one layer, preferably all photosensitive emulsion layers, can be processed. The silver halide emulsion is substantially a silver chlorobromide emulsion, and the binder film swelling rate T l
/2 or less than 30 seconds in a color photographic light-sensitive material, a developer containing at least 30 mol % or more of an N-hydroxyalkyl di-substituted-p-phenylenediamine derivative based on the p-phenylenediamine color developing agent in the color developer. By processing, the development speed was improved and the object of the present invention was successfully achieved without impairing the stability of the one-dye image.
本明細書において、「実質的に塩臭化銀乳剤」とは、塩
臭化銀の他にWL量の沃化銀を含んてもよいことてあり
、例えば0.3モル%以下、より好ましくは0.1モル
以下の沃化銀を含有してもよいことを意味する。しかし
なから本発明では沃化銀を含まない塩臭化銀乳剤か最も
好ましい。In this specification, the term "substantially silver chlorobromide emulsion" may include a WL amount of silver iodide in addition to silver chlorobromide, for example, 0.3 mol% or less, more preferably means that it may contain 0.1 mol or less of silver iodide. However, in the present invention, silver chlorobromide emulsions containing no silver iodide are most preferred.
以下、本発明について更に詳述する。The present invention will be described in further detail below.
カラー写真感光材料のハロゲン化銀を塗布するために使
用する親水性のバインダーは通常はゼラチンを使用する
か、高分子ポリマーを用いる場合もあり、膜膨潤速度T
1/2か30秒より小さくなければならず、バインダ
ーの膜膨潤速度T1/2はこの技術分野において公知な
任意の手法に従い測定することかでき、例えば八、Gr
een及びG、LP。The hydrophilic binder used to coat silver halide in color photographic light-sensitive materials is usually gelatin, or sometimes a high molecular weight polymer, and the film swelling rate T
The film swelling rate T1/2 of the binder can be measured according to any technique known in the art, for example,
een and G, LP.
Lcvenson、 J、photo、sci、、、2
0.p 205〜210に記載のタイプのスエロメータ
(膨潤膜)を使用することによって測定することができ
、T1/2は発色現像で30℃、3分30秒処理したと
きに到達する最大膨潤膜厚の90%を飽和膜厚とし、こ
のl/2の112厚に到達する迄の時間と定義する(第
1図参照)。Lcvenson, J. photo, sci., 2
0. It can be measured by using a swellometer (swelling film) of the type described in p. The saturation film thickness is defined as 90%, and is defined as the time required to reach 112 thickness of 1/2 (see FIG. 1).
本発明のハロゲン化銀カラー写真感光材料に用いられる
写真構成層のバインダーはその膨潤速度T1/2が30
秒以下てあり、小さい程好ましいが、下限はあまり小さ
いと硬膜されずにスクラッチ等の故障が生じ易くなるた
め2秒以上が好ましい。The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T1/2 of 30
The lower limit is less than 2 seconds, and the smaller the better, but the lower limit is preferably 2 seconds or more because if it is too small, failures such as scratches may occur without hardening.
特に好ましくは、20秒以下、最も好ましくは15秒以
下である。30秒より大の場合は色素画像の保存安定性
が低いばかりか短時間に充分な色素形成か得られない、
膜膨潤速度T l/Zは硬膜剤の使用量によってJ[す
ることがてきる。Particularly preferably, the time is 20 seconds or less, most preferably 15 seconds or less. If it is longer than 30 seconds, not only will the storage stability of the dye image be low, but also sufficient dye formation will not be obtained in a short period of time.
The membrane swelling rate Tl/Z can be determined by the amount of hardener used.
本発明によって処理される感光材料の感光性乳剤層は、
少なくともその1層が実質的に塩臭化銀乳剤から成れば
よいが、感光性乳剤層の全てが塩臭化銀乳剤から成るこ
とが好ましい、該塩臭化銀は臭化銀のモル%が小さい程
1発色現像が短時間でも充分な色素形成が得られるため
、臭化銀含有率80モル%以下が好ましく、70モル%
以下40モル%以上が最も好ましい結果となる。The light-sensitive emulsion layer of the light-sensitive material processed according to the present invention is
It is sufficient that at least one layer consists essentially of a silver chlorobromide emulsion, but it is preferable that all of the light-sensitive emulsion layers consist of a silver chlorobromide emulsion, and the silver chlorobromide is contained in a mol% of silver bromide. The smaller the silver bromide content is, the more sufficient dye formation can be obtained even with short one-color development, so the silver bromide content is preferably 80 mol% or less, and 70 mol%.
The most preferable results are below 40 mol% or more.
本発明に係るシアンカプラーは前記一般式CI)〜(I
II)で表すことができるが、該一般式CI)について
更に説明する。The cyan coupler according to the present invention has the general formulas CI) to (I
The general formula CI) can be represented by II), and the general formula CI) will be further explained.
本発明において、前記一般式CI)のR+ 、Rで表さ
れる炭素数2〜12の直鎖又は分岐のアルキル基は、例
えばエチル基、プロピル基、ブチル基である。In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R+ and R in the general formula CI) is, for example, an ethyl group, a propyl group, or a butyl group.
一般式(I)において、 R2で表されるバラストノ
、(は、カプラーが適用される層からカプラーを実質的
に他居に分散できないようにするのに十分ながさばりを
カプラーに与えるところの大きさと形状を有する有機基
である0代表的なパラスト基としては、全炭素a8〜3
2のアルキル基又はアリール基が挙げられるが、好まし
くは全炭素数13〜28である。これらのアルキル基と
7リール基はこ換基を有してもよく、このアリール基の
置換基としては、例えばアルキル基、アリール基、アル
コキシ基、アリルオキシ基、カルボキシ基、アシル基、
エステル基、ヒドロキシ基、シアン基、ニトロ基、カル
バモイル基、カルボンアミド基、アルキルチオ基、アリ
ールチオ基、スルホニル基、スルホンアミド基、スルフ
ァモイル基、ハロゲンが挙げられ、またアルキル基の置
換基としては、アルキル基を除く前記アリール基に挙げ
た置換基が挙げられる。In general formula (I), the ballast, represented by R2, is of a size that provides the coupler with sufficient bulk to prevent the coupler from being substantially dispersed elsewhere from the layer to which it is applied. A typical palust group, which is an organic group with a shape, has a total carbon a8 to 3
2 alkyl groups or aryl groups, preferably having a total carbon number of 13 to 28. These alkyl groups and 7-aryl groups may have a substituent, and examples of the substituent for this aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxy group, an acyl group,
Examples of substituents for alkyl groups include ester groups, hydroxy groups, cyanide groups, nitro groups, carbamoyl groups, carbonamide groups, alkylthio groups, arylthio groups, sulfonyl groups, sulfonamide groups, sulfamoyl groups, and halogens. The substituents listed above for the aryl group excluding the group may be mentioned.
該パラスト基として好ましいものは下記一般式%式%
R12は炭素数1〜12のアルキル基を表し、Arはフ
ェニル基等の7リール基を表し、このアリール基は置換
基を有していてもよい、置換基としては、アルキル基、
ヒドロキシ基、ハロゲン原子。A preferable example of the palast group is the following general formula: % R12 represents an alkyl group having 1 to 12 carbon atoms, Ar represents a 7-aryl group such as a phenyl group, and even if this aryl group has a substituent, Good substituents include alkyl groups,
Hydroxy group, halogen atom.
アルキルスルホンアミド基等が挙げられるが、最も好ま
しものはt−ブチル基等の分岐のアルキル基が挙げられ
る。Examples include alkylsulfonamide groups, and the most preferred are branched alkyl groups such as t-butyl.
前記一般式CI)でXにより定義される発色現像主薬の
酸化体とのカプリングで離脱しうる基は、当業者によく
知られているように、カプラーの当量数を決定すると共
に、カプリングの反応性を左右する0代表例としては、
塩素、フッ素に代表されるハロゲン、アリールオキシ基
、置換又は未置換のフルコキシ基、アシルオキシ基、ス
ルホンアミド基、アリールチオ基、ヘテロイルチオ基、
ヘテロイルオキシ基、スルホニルオキシ基。The group defined by X in the above general formula CI) that can be split off upon coupling with the oxidized form of the color developing agent determines the number of equivalents of the coupler and also controls the coupling reaction, as is well known to those skilled in the art. Typical examples of 0 that affect gender are:
Halogens represented by chlorine and fluorine, aryloxy groups, substituted or unsubstituted flukoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups,
Heteroyloxy group, sulfonyloxy group.
カルバモイルオキシ基等が挙げられる。さらに具体的な
例としては、特開昭50−10135号、同50−12
0334号、同50−130414号、同54−482
37号、同51−146828号、同54−14736
号、同47−37425号、同50−123341号、
同58−95345号、特公昭48−36894号、米
国特許3.478,583号、同3,737,318号
、同3,227,551号等に記載されている基が挙げ
られる7
次に一般式CI)表されるシアンカプラーの例示化合物
を挙げるが、これらに限定されない、該例示化合物とし
ては、一般式CI)において、下記のようにR1,X、
R2,Rを特定したものが挙げられる。Examples include carbamoyloxy group. More specific examples include JP-A-50-10135 and JP-A-50-12.
No. 0334, No. 50-130414, No. 54-482
No. 37, No. 51-146828, No. 54-14736
No. 47-37425, No. 50-123341,
Examples include groups described in US Pat. No. 58-95345, Japanese Patent Publication No. 48-36894, US Pat. Exemplary compounds of the cyan coupler represented by the general formula CI) are listed below, but are not limited to these. In the general formula CI), R1, X,
Examples include those in which R2 and R are specified.
以下余白
以下に本発明例示化合物の合成法を示すが、他の例示化
合物も同様の方法により合成することができる。The synthesis method of the exemplified compounds of the present invention is shown below in the margins, but other exemplified compounds can also be synthesized by the same method.
例示化合物C−5の合成例
[(1)−t ] ]2−二トロー4.8−ジクロロ
ー5エチルフェノールの合成
2−ニトロ−5−エチルフェノール33g、沃素0.6
8及び塩化第2鉄1.5gを氷酢酸150■見に溶解す
る。Synthesis Example of Exemplified Compound C-5 [(1)-t ] Synthesis of 2-nitro-4.8-dichloro-5-ethylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 iodine
8 and 1.5 g of ferric chloride were dissolved in 150 g of glacial acetic acid.
これに40℃でスルフリルクロライド75+jLを3時
間で滴下する0滴下途中で生成した沈澱はスルフリルク
ロライド滴下終了後、加熱還流することにより、反応溶
解する。加熱還流は約2時間を要する0反応液を水中に
注ぎ生成した結晶はメタノールにより再結晶精製する。To this, 75+jL of sulfuryl chloride was added dropwise over 3 hours at 40° C. The precipitate formed during the 0 dropwise addition was reacted and dissolved by heating and refluxing after the completion of the dropwise addition of sulfuryl chloride. Heating and refluxing takes about 2 hours.The reaction solution is poured into water, and the resulting crystals are purified by recrystallization with methanol.
(1)−aの確認は核磁気共鳴スペクトル及び元素分
析により行った。(1)-a was confirmed by nuclear magnetic resonance spectroscopy and elemental analysis.
[(1)−b 1 2−ニトロ−4,6−ジクロロ−5
−エチルフェノールの合成
[(1)−a 1の化合物21.2gを300+sjL
のアルコールに溶解し、これに触媒量のラネーニッケル
を加え、常圧にて水素吸収がなくなるまで水素を通じた
0反応後ラネーニッケルを除去し、アルコール減圧にて
留去した。残渣の[(1)−b ]は精製することなく
次のアシル化を行った。[(1)-b 1 2-nitro-4,6-dichloro-5
-Synthesis of ethylphenol [(1)-a 21.2g of compound 1 was added to 300+sjL
A catalytic amount of Raney nickel was added thereto, and after hydrogen was passed through the reaction at normal pressure until hydrogen absorption disappeared, the Raney nickel was removed and the alcohol was distilled off under reduced pressure. The residue [(1)-b] was subjected to the next acylation without being purified.
[(1)−c ] 2[(2,a−ジーtert−ア
シルフェノキシ)アセトアミド]−4,6−ジクロロ−
5−エチルフェノールの合成
[(1)−b ]で得たクルードなアミド体1B−5g
を500a+1の氷酢酸と18.7gの酢酸ソーダより
なる混液に溶解し、これに2,4−ジーtert−アシ
ルフェノキシ酢酸クロリド28.0gを酢酸50mJl
に溶解した酢酸溶液を室温にて滴下する。30分間で滴
下し、更に30分間攪拌後1反応液を氷水中に注入する
。生成した沈澱を濾取し、乾燥後、アセトニトリルにて
2回再結晶すると目的物が得られる。目的物の確認は元
素分析及び核磁気共鳴スペクトルにて行った。[(1)-c] 2[(2,a-di-tert-acylphenoxy)acetamide]-4,6-dichloro-
Crude amide compound 1B-5g obtained by synthesis of 5-ethylphenol [(1)-b]
was dissolved in a mixture of 500a+1 glacial acetic acid and 18.7g of sodium acetate, and 28.0g of 2,4-di-tert-acylphenoxyacetic acid chloride was added to 50mJl of acetic acid.
A solution of acetic acid dissolved in is added dropwise at room temperature. The mixture was added dropwise over 30 minutes, and after stirring for an additional 30 minutes, one reaction solution was poured into ice water. The generated precipitate is collected by filtration, dried, and then recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectroscopy.
以下余白
CnHsN(hCQ
次に、本発明に用いられる一般式(n)または(III
)で示されるシアンカプラーについて説明する。前記一
般式(n)及び(m)において、Yは、 −(:OR4
。The following margin is CnHsN (hCQ) Next, the general formula (n) or (III
) will be explained. In the general formulas (n) and (m), Y is -(:OR4
.
で表される基である。但しR4はアルキル基、好ましく
は炭素数1〜20のフルキル基(例えばメチル、エチル
、t−ブチル、ドデシルの各基等)、アルケニル基好ま
しくは炭素数2〜20のアルケニル基(アリル基、ヘプ
タデセニル基等)、シクロアルキル基、好ましくは5〜
7員環のもの(例えばシクロへ午シル等)、アリール基
(例えばフェニル基、トリル基、ナフチル基等)、ヘテ
ロ環基。It is a group represented by However, R4 is an alkyl group, preferably a furkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (allyl group, heptadecenyl group, etc.). group, etc.), cycloalkyl group, preferably 5-
Seven-membered rings (for example, cyclohexyl, etc.), aryl groups (for example, phenyl, tolyl, naphthyl, etc.), and heterocyclic groups.
好ましくは窒素原子、酸素原子もしくはイオウ原子を1
〜4個含む5員〜6員環のへテロ環基(例えばフリル基
、チェニル基、ベンゾチアゾリル基等)を表す、 R
sは水素原子もしくはR4で表される基を表す、 R
4とR5と互いに結合して5〜6員のへテロ環を形成し
てもよい、なお、 R2及びR3には任意の置換基を導
入することができ、例えば炭素数1−10のアルキル基
(例えばメチル、i−プロピル、i−ブチル、t−ブチ
ル、t−オクチル等)、アリール基(例えばフェニル、
ナフチル等)、ハロゲン原子(フッ素、塩素、臭素等)
。Preferably 1 nitrogen atom, oxygen atom or sulfur atom
R represents a 5- to 6-membered heterocyclic group containing ~4 members (e.g., furyl group, chenyl group, benzothiazolyl group, etc.)
s represents a hydrogen atom or a group represented by R4, R
4 and R5 may be combined with each other to form a 5- to 6-membered heterocycle. Furthermore, any substituent can be introduced into R2 and R3, such as an alkyl group having 1 to 10 carbon atoms. (e.g. methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), aryl groups (e.g. phenyl,
naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.)
.
シアノ、ニトロ、スルホンアミド基(例えばメタンスル
ホンアミド、ブタンスルホンアミド、p−トルエンスル
ホンアミド等)、スルファモイル基(例えばメチルスル
ファモイル、フェニルスルファモイル等)、スルホニル
基(例えばメタンスルホニル、p−)ルエンスルホニル
等)、フルオロスルホニル基、カルバモイル基(例えば
ジメチルカルバモイル、フェニルカルバモイル等)、オ
キシカルボニル基(例えばエトキシカルボニル、フェノ
キシカルボニル等)、アシル基(例えばアセチル、ベン
ゾイル等)、ヘテロ環基(例えばピリジル基、ピラゾリ
ル基等)、アルコキシ基、アリールオキシ基、アシルオ
キシ基等を挙げることができる。Cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-toluenesulfonamide, etc.) ) luenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl groups (e.g. acetyl, benzoyl, etc.), heterocyclic groups (e.g. pyridyl group, pyrazolyl group, etc.), alkoxy group, aryloxy group, acyloxy group, etc.
一般式(Il)及び一般式(m)において、 R3は一
般式(n)及び一般式(III)で表されるシアンカプ
ラー及び該シアンカプラーから形成されるシアン色素に
耐拡散性を付与するのに必要なバラスト基を表す、好ま
しくは炭素数4〜30のアルキル基、アリール基または
へテロ環基である6例えば直鎖又は分岐のアルキル基(
例えばt−ブチル、n−オクチル、t−オクチル、n−
ドデシル等)、アルケニル基、シクロアルキル基、5員
もしくは6員環へテロ環基等が挙げられる。In the general formula (Il) and the general formula (m), R3 imparts diffusion resistance to the cyan coupler represented by the general formula (n) and the general formula (III) and the cyan dye formed from the cyan coupler. represents a ballast group necessary for 6, preferably an alkyl group, aryl group or heterocyclic group having 4 to 30 carbon atoms, such as a straight-chain or branched alkyl group (
For example, t-butyl, n-octyl, t-octyl, n-
dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and the like.
一般式(n)及び一般式〔■〕において、Zは水素原子
又はN−ヒドロキシアルキル置換−p−フェニレンジア
ミン誘導体現像主薬の酸化体とのカプリング反応時に離
脱可能な基を表す0例えば、ハロゲン原子(例えば塩素
、臭素、フッ素等)、置換又は未置換のアルコキシ基、
アリールオキシ基、ヘテロ環オキシ基、アシルオキシ基
、カルバモイルオキシ基、スルホニルオキシ基、アルキ
ルチオ基、アリールチオ基、ヘテロ環チオ基、スルホン
7ミド基等が挙げられ、更に具体的な例としては米国特
許3,741.5+1t3号、特開昭47−37425
号、特公昭4B−36894号、特開昭50−1013
5号、同50−117422号、同50−130441
号、同51−108841号、同50−120343号
、同52−18315号、同53−105226号、同
54−14736号、同54−48237号、同55−
32071号、同55−65957号、同56−193
8号、同56−12643号、同56−27147号、
同59−146050号、同59−166956号、同
60−24547号、同60−35731号、同60−
37557号等に記載されているものを挙げることがで
きる。In the general formula (n) and the general formula [■], Z represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent 0 For example, a halogen atom (e.g. chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups,
Examples include aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfone 7-mido groups, and more specific examples include U.S. Pat. , No. 741.5+1t3, JP-A-47-37425
No., JP 4B-36894, JP 50-1013
No. 5, No. 50-117422, No. 50-130441
No. 51-108841, No. 50-120343, No. 52-18315, No. 53-105226, No. 54-14736, No. 54-48237, No. 55-
No. 32071, No. 55-65957, No. 56-193
No. 8, No. 56-12643, No. 56-27147,
No. 59-146050, No. 59-166956, No. 60-24547, No. 60-35731, No. 60-
Examples include those described in No. 37557 and the like.
本発明においては前記一般式(n)または(III)で
表されるシアンカプラーのうち、下記一般式(IT)、
(V)または(VI)で表されるシアンカプラーが更に
好ましい。In the present invention, among the cyan couplers represented by the general formula (n) or (III), the following general formula (IT),
Cyan couplers represented by (V) or (VI) are more preferred.
一般式(IV)
H
一般式(V)
H
一般式(1
一般式(rV)において、Rt3は置換、未置換のアリ
ール基(特に好ましくはフェニル基)である、該アリー
ル基が置換基を有する場合の置換基としては、S02
Rls、ハロゲン原子(フッ素、塩素、臭素等) 、
CF3 、−NO2、−CM、−CORti。General formula (IV) H General formula (V) H General formula (1) In the general formula (rV), Rt3 is a substituted or unsubstituted aryl group (particularly preferably a phenyl group), and the aryl group has a substituent. In this case, the substituent is S02
Rls, halogen atom (fluorine, chlorine, bromine, etc.),
CF3, -NO2, -CM, -CORti.
−COOIhs 、 −8020Rts 。-COOIhs, -8020Rts.
から選ばれる少なくとも1つの置換基が包含される。At least one substituent selected from is included.
ここで、 RIGはアルキル基、好ましくは炭素数1
〜20のアルキル2&i(例えばメチル、エチル。Here, RIG is an alkyl group, preferably a carbon number 1
~20 alkyl 2&i (e.g. methyl, ethyl.
tert−ブチル、ドデシルの各基等)、アルケニル基
、好ましくは炭素数2〜20のアルケニル基(アリル基
、ヘプタデセニル基等)、シクロアルキル基、好ましく
は5〜7員環基(例えばシクロヘキシル等)、アリール
基(例えばフェニル基、トリル基、ナフチル基等)を表
し、 Rlyは水素原子もしくはRuで表される基で
ある。tert-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (e.g. cyclohexyl, etc.) , represents an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), and Rly is a hydrogen atom or a group represented by Ru.
一般式(IV)で表される本発明のシアンカプラーの好
適な化合物は、Ruが置換ないし未置換のフェニル基で
あり、フェニル基への置換基としてシアノ、ニトロ、−
9O2RLI (Lmはアルキル基)、ハロゲン原子、
トリフルオロメチルであるような化合物である。In a preferred compound of the cyan coupler of the present invention represented by the general formula (IV), Ru is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -
9O2RLI (Lm is an alkyl group), halogen atom,
A compound that is trifluoromethyl.
一般式(V)及び(Vl)において、R14、Risは
アルキル基、好ましくは炭素数1〜20のアルキル基(
例えばメチル、エチル、tert−ブチル、ドデシルの
各基等)、アルケニル基、好ましくは炭素数2〜20の
アルケニル基(アリル基、オレイル基等)、シクロアル
キル基、好ましくは5〜7員環基(例えばシクロヘキシ
ル等)、アリール基(例えばフェニル基、トリル基、ナ
フチル基等)、ヘテロ環基(例えば窒素原子、酸素原子
、もしくはイオウ原子を1〜4個含む5員〜6員環のへ
テロ環が好ましく、例えばフリル基、チェニル基、ベン
ゾチアゾリル基等が挙げられる。)を表す。In general formulas (V) and (Vl), R14 and Ris are an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (
For example, methyl, ethyl, tert-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, oleyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups. (e.g. cyclohexyl, etc.), aryl groups (e.g. phenyl, tolyl, naphthyl, etc.), heterocyclic groups (e.g. 5- to 6-membered heterocyclic groups containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms) A ring is preferred, such as a furyl group, a chenyl group, a benzothiazolyl group, etc.).
前記Rt、R1?及び一般式(V)及び(VI)のR1
4、Raには、さらに任意の置換基を導入することがで
き、具体的には、一般式(It)及び(m)においてR
4またはRsに導入することのできるが如き置換基であ
る。そして置換基としては特にハロゲン原子(塩素原子
、フッ素原子等)が好ましい。Said Rt, R1? and R1 of general formulas (V) and (VI)
4. An arbitrary substituent can be further introduced into Ra. Specifically, in general formulas (It) and (m), R
4 or Rs. As a substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable.
一般式〔■〕、(V)及び(VI)においてZ及びR3
は各々一般式(II)及び(m)と同様の意味を有して
いる。 R:Iで表されるバラスト基の好ましい例は
、下記一般式(■〕で表される基である。In general formula [■], (V) and (VI), Z and R3
have the same meanings as in general formulas (II) and (m), respectively. A preferred example of the ballast group represented by R:I is a group represented by the following general formula (■).
一般式〔■〕
式中、Jは酸素原子、硫黄原子又はスルホニル基を表し
、には0〜4の整数を表し1文は0又はlを示し、Kが
2以上の場合2つ以上存在するRnは同一でも異なって
いてもよい、Rtは炭素数1〜20の直鎖又は分岐、及
びアリール基等の置換したアルキレン基を表し、Rnは
一価の基を表し、好ましくは水素原子、ハロゲン原子(
例えばクロム、ブロム)、アルキル基、好ましくは直鎖
又は分岐の炭素数1〜20のアルキル基(例えばメチル
、t−ブチル、t−ペンチル、t−オクチル、ドデシル
、ペンタデシル、ベンジル、フェネチル等の各基)、ア
リール基(例えばフェニル基)、複素環基(例えば含有
チッ素複素環基)アルコキシ基、好ましくは直鎖又は分
岐の炭素数1〜2oのアルコキシ基(例えばメトキシ、
エトキシ、t−ブチルオキシ、オクチルオキシ、デシル
オキシ、ドデシルオキシ等の各基)、アリールオキシ基
(例えばフェノキシ基)、ヒドロキシ基、アシルオキシ
基、好ましくはアルキルカルボニルオキシ基、アリール
カルボニルオキシ基(例えばアセトオキシ基、ベンゾイ
ルオキシ基)、カルボキシ、アルキルオキシカルボニル
基、好ましくは炭素数1〜20の直鎖又は分岐のフルキ
ルカルボニル基、好ましくはフェノキシカルボニル基、
アルキルチオ基、好ましくは炭素数1〜20のアシル基
、好ましくは炭素数1〜20の直鎖又は分岐のアルキル
カルボニル基、アシルアミノ基、好ましくは炭素数1〜
20の直鎖又は分岐のフルキルカルボ7ミド基、ベンゼ
ンカルボアミド基、スルホンアミド基、好ましくは炭素
数1〜20の直鎖又は分岐のフルキルスルホンアミド基
又はベンゼンスルホンアミド基、カルバモイル基、好ま
しくは炭素数1〜20の直鎖又は分岐のフルキルアミノ
カルボニル基又はフェニルアミノカルボニル基、スルフ
ァモイル基、好ましくは炭素a1〜20の直鎖又は分岐
のフルキルアミノスルホニル基又はフェニルアミノスル
ホニル基等を表す。General formula [■] In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, represents an integer from 0 to 4, one sentence represents 0 or l, and when K is 2 or more, two or more are present. Rn may be the same or different; Rt represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group; Rn represents a monovalent group, preferably a hydrogen atom or a halogen atom(
For example, chromium, bromine), alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.) ), aryl groups (e.g., phenyl groups), heterocyclic groups (e.g., nitrogen-containing heterocyclic groups), alkoxy groups, preferably linear or branched alkoxy groups having 1 to 2 o carbon atoms (e.g., methoxy,
ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (e.g. phenoxy groups), hydroxy groups, acyloxy groups, preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (e.g. acetoxy groups, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a straight-chain or branched furkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group,
Alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, acylamino group, preferably 1 to 20 carbon atoms
20 straight chain or branched furkylcarboamide group, benzenecarboxamido group, sulfonamide group, preferably straight chain or branched furkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonamide group, carbamoyl group, preferably Represents a straight or branched fluorylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a straight or branched fluorylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms. .
次に一般式(n)又は(III)で表されるシアンカプ
ラーの具体的な化合物例を示すが、これらに限定されな
い。Next, specific examples of cyan couplers represented by formula (n) or (III) will be shown, but the invention is not limited thereto.
以下余白 〔例示化合物〕 0 −2り OJ。Margin below [Exemplary compounds] 0 -2ri O.J.
0−ノケ −J5 −J7 C−シー C−ツク I C−りθ OH。0-noke -J5 -J7 C-C C-Tsuku I C-ri θ Oh.
C−弘1 −P2 C−幻 C−会ψ C−%” C−りl a−<x7 OH C−り? C−+り (t)OsHu 0−ダ1 H −f2 H H3 −1j C−f弘 C−fり t −sj −f7 H −si H 4H9 0−fメ l O−〆θ 06H。C-Hiro 1 -P2 C-Illusion C-kai ψ C-%” C-ril a-<x7 OH C-ri? C-+ri (t)OsHu 0-da1 H -f2 H H3 -1j C-f Hiromu C-fri t -sj -f7 H -si H 4H9 0-f mail l O-〆θ 06H.
f−1 C4H。f-1 C4H.
C−/2 ρI C−ρ j a−を侶 H 06H,。C-/2 ρI C-ρ j a- as a partner H 06H,.
c −1ap c−/;1 H 2H5 C−?1 H u c −7s O−りl O−’t8 c −’?’1 −SO (t)O,H。c-1ap c-/;1 H 2H5 C-? 1 H u c -7s O-ri l O-’t8 c-’? '1 -S.O. (t) O, H.
OCH20H20(3H。OCH20H20 (3H.
c−gb C−87 〇−分8 C−8? 0−’l。c-gb C-87 〇-minute 8 C-8? 0-'l.
H 04H。H 04H.
04H,”’ −qF H 2H5 0H (t)O,H,1 −1o0 H O−101 NH80,(3H。04H,”’ −qF H 2H5 0H (t)O,H,1 -1o0 H O-101 NH80, (3H.
a−(o3 2Hs O−10牛 H c −tOr 0−+o’b C−IOり p 04H,,5o2NB Oμ SO□NH (OH2)200 zHs o−/Iり t 0−/l弘 0−//、!; t O−//6 t O−/19 0−1zl。a-(o3 2Hs O-10 cow H c −tOr 0-+o'b C-IO p 04H,,5o2NB Oμ SO□NH (OH2)200zHs o-/Iri t 0-/l Hiro 0-//,! ; t O-//6 t O-/19 0-1zl.
H
r”
0− /2J
O−/2り
0−7.Z!
N
C−/2〆
N
−1z7
H
これら本発明のシアンカプラーは公知の方法によって合
成することができ、一般式〔■〕で表される化合物の場
合、例えば米国特許3,222,178号、同3,44
8.[t22号、同3,998,253号、英国特許1
.011,940号等に記載の合成法によって合成する
ことができる。また一般式(III)で表される化合物
の場合1例えば米国特許2,772,182号、同3,
758.308号、同3,880,881号、同4,1
24,3118号、英国特許975,773号、同8.
011,893号、同8,011,884号、特開昭4
7−21139号、同50−112038号、同55−
163537号、同56−29235号、同55−99
341号、同56−116030号、同52−6932
9号、同56−55945号、同56−80045号、
同50−134644号並びに英国特許1,011,9
40号、米国特許3,448,822号、同3,998
,253号、特開昭56−65134号、同57−20
4543号、同57−204544号、同57−204
545号、特願昭56−131309号、同56−13
1311号、同56−131312号、同56−131
313号、同56−131314号、同56−1304
59号、同57−149791号、特開昭59−146
050号、同59−166956号、同60−2454
7号、同60−35731号、同60−37557号等
に記載の合成法によって合成することができる。H r"0- /2J O-/2ri0-7.Z! N C-/2〆N -1z7 H These cyan couplers of the present invention can be synthesized by a known method, and have the general formula [■] In the case of compounds represented by, for example, U.S. Pat.
8. [T22, 3,998,253, British Patent 1
.. It can be synthesized by the synthesis method described in No. 011,940 and the like. In addition, in the case of a compound represented by general formula (III) 1, for example, U.S. Pat. No. 2,772,182;
758.308, 3,880,881, 4.1
No. 24,3118, British Patent No. 975,773, 8.
No. 011,893, No. 8,011,884, JP-A-4
No. 7-21139, No. 50-112038, No. 55-
No. 163537, No. 56-29235, No. 55-99
No. 341, No. 56-116030, No. 52-6932
No. 9, No. 56-55945, No. 56-80045,
No. 50-134644 and British Patent No. 1,011,9
No. 40, U.S. Patent No. 3,448,822, U.S. Patent No. 3,998
, No. 253, JP-A-56-65134, JP-A No. 57-20
No. 4543, No. 57-204544, No. 57-204
No. 545, Japanese Patent Application No. 56-131309, No. 56-13
No. 1311, No. 56-131312, No. 56-131
No. 313, No. 56-131314, No. 56-1304
No. 59, No. 57-149791, JP-A No. 59-146
No. 050, No. 59-166956, No. 60-2454
No. 7, No. 60-35731, No. 60-37557, etc.
一般式(I)、(n)又は(III)で表されるシアン
カプラーは1本発明の目的に反しない範囲において本発
明外のシアンカプラーと組合せて用いることができる。The cyan coupler represented by the general formula (I), (n) or (III) can be used in combination with a cyan coupler other than the one according to the invention to the extent that it does not contradict the object of the invention.
また、一般式CI)、(It)及び(m)のシアンカプ
ラーを1又は2以上併用することもできる。Furthermore, one or more cyan couplers of the general formulas CI), (It) and (m) can be used in combination.
一般式(I)〜(III)で表される本発明に係るシア
ンカプラーをハロゲン化銀乳剤層中に含有させるときは
、通常ハロゲン化銀1モル当り約0.005〜2モル、
好ましくは0,01〜1モルの範囲で用いられる。When the cyan coupler according to the present invention represented by general formulas (I) to (III) is contained in the silver halide emulsion layer, it is usually about 0.005 to 2 mol per mol of silver halide,
It is preferably used in a range of 0.01 to 1 mol.
本発明において、処理温度は色素の保存安定性よりむし
ろ短時間に現像を終了させるために上昇させるものであ
り、30℃以上、50℃以下であれば高い程短時間処理
が可能となりむしろ迅速性という点で好ましく、特に好
ましくは33℃以上、48℃以下であり、最も好ましく
は35℃以上、43℃以下で処理することである。In the present invention, the processing temperature is raised to complete the development in a short time rather than to maintain the storage stability of the dye.The higher the temperature is from 30°C to 50°C, the shorter the processing time, and the faster the process. From this point of view, the temperature is preferably 33°C or higher and 48°C or lower, and most preferably 35°C or higher and 43°C or lower.
本発明において有効な現像主薬はトヒドロキシアルキル
置換−p−フェニレンジアミン化合物の第4級アンモニ
ウム塩、特に下記一般式で表すことができるものである
。An effective developing agent in the present invention is a quaternary ammonium salt of a hydroxyalkyl-substituted p-phenylenediamine compound, particularly one that can be represented by the following general formula.
式中、R1は水素原子、1〜4個の炭素原子を有するア
ルキル基、または1〜4個の炭素原子を有するアルコキ
シ基であり、R2は水素原子、または1〜4個の炭素原
子を有するアルキル基であり、R3は水票基を有しても
よい1〜4個の炭素原子を有するアルキル基であり、
Aは少なくとも1つの水酸基を有し、かつ分岐を有して
もよいアルキル基であり、より好ましくは
である、 R4、R5、R6はそれぞれ水素原子、水
酸基又は水酸基を有してもよい1〜3個の炭素原子を有
するアルキル基を表し、 R4、Rs 、 R6の少な
くとも1つは水酸基又は水酸基を有するアルキル基であ
るonl、R2、R3はそれぞれO,l、2又は3であ
り、モしてHXは塩酸、硫酸、P−)ルエンスルホン酸
、硝酸または燐酸を表す。In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R2 is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. is an alkyl group, R3 is an alkyl group having 1 to 4 carbon atoms which may have a water group,
A is an alkyl group that has at least one hydroxyl group and may have a branch, and is more preferably R4, R5, and R6 are each a hydrogen atom, a hydroxyl group, or 1 to 1 that may have a hydroxyl group. represents an alkyl group having 3 carbon atoms, at least one of R4, Rs, R6 is a hydroxyl group or an alkyl group having a hydroxyl group, R2, R3 are each O, l, 2 or 3, and where HX represents hydrochloric acid, sulfuric acid, P-)luenesulfonic acid, nitric acid or phosphoric acid.
このようなP−7工ニレンジアミン発色現像主薬はその
i離のアミンでは不安定であり、一般には塩として使用
されている(最も普遍的には上記式で特定されたもので
ある)、典型的な例としては4−アミノ−3−メチル−
N−エチル−N−(β−ヒドロキシエチル)−アニリン
塩や4−アミノ−N−エチル−N−(β−ヒドロキシエ
チル)−アニリン塩が挙げられる。Such P-7 nylenediamine color developing agents are unstable with their amines and are commonly used as salts (most commonly those specified by the formula above), typical An example is 4-amino-3-methyl-
Examples include N-ethyl-N-(β-hydroxyethyl)-aniline salt and 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline salt.
好ましくは、本発明においては4−アミ7−3−メチル
ートエチル−N−(β−ヒドロキシエチル)−アニリン
硫酸塩−水和物[これはCD−4とい名称で重版されて
おり、大部分のカラー写真方式において(例えばイース
トマンコダック社C41方式や、小西六写真工業社CN
K−4方式のようなカラーネガフィルムを現像するため
に)使1されている1が特に有効であることが認められ
た。Preferably, in the present invention, 4-amino-7-3-methyltoethyl-N-(β-hydroxyethyl)-aniline sulfate hydrate [which has been reprinted under the name CD-4 and is mostly In the color photographic system of
1, which is used for developing color negative films such as the K-4 system, has been found to be particularly effective.
本発明に使用する好ましいN−ヒドロキシフルキルこ換
−p−7工ニレンジアミン誘導体は以下のものが挙げら
れるが、これら例示化合物に限定されるものではない。Preferred N-hydroxyfurkyl substituted-p-7-functional nylene diamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.
H2
H2
H2
H2
(や
N1−12
H2
以下余白
上記(1)〜(8)の化合物の塩酸、硫酸、p−トルエ
ンスルホン酸塩か特に好ましい。H2 H2 H2 H2 (or N1-12 H2 Space below) Hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salts of the compounds (1) to (8) above are particularly preferred.
これら例示化合物の中てもNo、(1)、(2) 、
(6) 。Among these exemplified compounds, No., (1), (2),
(6).
(7)及び(8)が好ましく用いられ、特にNo、(1
)、(2)及び(6)か好ましく用いられる。さらに、
とりわけ特にNo、(1)が、本発明においては好まし
く用いられる
本発明の発色現像主薬の水に対する溶解度は著しく高い
ためその使用量は処理液11当り1g〜100 gの範
囲で使用することが好ましく、より好ましくは2g〜3
0gの範囲で使用される。(7) and (8) are preferably used, especially No., (1
), (2) and (6) are preferably used. moreover,
In particular, No. (1) is preferably used in the present invention.Since the solubility of the color developing agent of the present invention in water is extremely high, the amount used is preferably in the range of 1 g to 100 g per 11 of the processing solution. , more preferably 2g to 3
Used in the range of 0g.
これら本発明のN−ヒドロキシアルキル置換−p−フェ
ニレンジアミン誘導体はジャーナル オブアメリカン
ケミカル ソサイアティー73巻、3100頁(195
1年)に記載の方法で容易に合成できる。These N-hydroxyalkyl-substituted-p-phenylenediamine derivatives of the present invention are described in the Journal of American
Chemical Society Vol. 73, p. 3100 (195
It can be easily synthesized by the method described in 1).
本発明に係る発色現像主薬にはN−ヒドロキシアルキル
置換−p−フェニレンジアミン誘導体現像主薬の他に、
p−フェニレンジアミン系のものが用いられ1次のもの
が好ましい例として挙げられる。In addition to the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent, the color developing agent according to the present invention includes:
A p-phenylene diamine type is used, and a primary type is mentioned as a preferable example.
4−アミノ−N、N−ジエチルアニリン、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−メトキシエチルアニ
リン、3−メチル−4−アミノ−N−エチル−N−β−
メタンスルホンアミドエチルアニリン、3−メトキシ−
4−アミノ−N−エチル−N−β−メトキシエチルアニ
リン、3−アセトアミド−4−アミノ−N、N−ジメチ
ルアニリン、N−エチル−N−β−(β−(β−メトキ
シエトキシ)エトキシ)エチル−3−メチル−4−アミ
ノアニリン、N−エチル−N−β−(β−メトキシエト
キシ)エチル−3−メチル−4−アミノアニリンや、こ
れらの塩例えば硫酸塩、塩酸塩、亜硫酸塩、p−トルエ
ンスルホン酸塩、リン酸塩等てある。好ましくは、ツー
メチル−4−アミノ−N−エチル−N−β−メタンスル
ホンアミドエチルアニリンが先祖色性の上から有用であ
る。4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methoxy-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N-ethyl-N-β-(β-(β-methoxyethoxy)ethoxy) Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, Examples include p-toluenesulfonate and phosphate. Preferably, dimethyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline is useful from the viewpoint of chromaticity.
さらに1例えば特開昭48−64932号、同50−1
31526号、同51−95849号およびベント等の
ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサエ
ティー、73巻、3100〜3125頁(1951年)
記載のものも代表的なものとして挙げられる。Further 1, for example, JP-A No. 48-64932, JP-A No. 50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.
本発明においては、N−ヒドロキシアルキル置換−p−
フェニレンジアミン誘導体は少なくとも発色現像液中の
p−フェニレンジアミン発色現像主薬全量に対し30モ
ル%以上、好ましくは40モル%以上含有することか迅
速処理や処理安定性に対して有効に作用する。In the present invention, N-hydroxyalkyl substituted -p-
The phenylenediamine derivative has an effective effect on rapid processing and processing stability when it is contained at least 30 mol% or more, preferably 40 mol% or more, based on the total amount of p-phenylenediamine color developing agent in the color developer.
本発明の発色現像液は、実質的にベンジルアルコールが
フリーであることが必要であり、最も好ましくは発色現
像液11当りOであることが画像保存性の上から好まし
いか、画像保存性に余り影響を与えない程度のベンジル
アルコールは添加することかできる。具体的には発色現
像液ti当り5II1文以下、好ましくは2+*Jl以
下が本発明を実施する上で好ましい。又実質的にベンジ
ルアルコールをフリーにすることて更なる濃厚低補充化
やキットサイズのコンパクト化が可能てあり、無公害性
やコストの上からも好ましい。The color developing solution of the present invention needs to be substantially free of benzyl alcohol, and most preferably it is O per 11 parts of the color developing solution, or it is preferable from the viewpoint of image preservation, or if the content is too much for image preservation. Benzyl alcohol can be added to an extent that does not have any effect. Specifically, in carrying out the present invention, it is preferable to use 5II1 or less, preferably 2+*Jl or less, per color developer ti. Furthermore, by substantially freeing benzyl alcohol, it is possible to further reduce the concentration and replenishment and make the kit size more compact, which is preferable from the viewpoint of non-polluting properties and cost.
本発明の発色現像液は臭化物イオン濃度が5×10−″
rモル以上であることが好ましか、本発明では臭化物は
高い程補充量が下げられるため好ましい。従来の現像方
式では臭化物は現像反応を抑制し低い程好ましいとされ
ていたが1本発明のカラー写真感光材料と現像液の組合
せては全く逆に臭化物は高い程好ましく、より本発明の
目的が達成される。換言すれば本発明では臭化物の影響
を受けにくいために補充量が下げられることがてきるよ
うになった。The color developing solution of the present invention has a bromide ion concentration of 5 x 10-''
It is preferable that the amount is r moles or more, and in the present invention, the higher the bromide, the lower the replenishment amount, so it is preferable. In conventional development methods, bromide inhibits the development reaction, and the lower the bromide content, the better; however, in the combination of the color photographic light-sensitive material and developer of the present invention, the higher the bromide content, the more preferable it is. achieved. In other words, in the present invention, the amount of replenishment can be reduced because it is less susceptible to the effects of bromide.
臭化物は好ましくはl x 10−2モル以上、特に好
ましくは1.sx 10−2モル以上てあり、臭化物イ
オン濃度かあまり高いと現像が抑制されるため臭化物イ
オン濃度の影響かではじめる6 x 10−2モル以上
ては好ましくない。なお塩化物の濃度は影響しない。The bromide is preferably present in an amount of l x 10-2 mol or more, particularly preferably 1. If the bromide ion concentration is too high, development will be inhibited, so it is not preferable to have a bromide ion concentration of 6 x 10-2 mol or more due to the influence of the bromide ion concentration. Note that the concentration of chloride has no effect.
本発明のカラー写真感光材料は青感性乳剤層、緑感性乳
剤層、赤感性乳剤層の各々を含む3層以上の多層カラー
写真感光材料において、その膜膨潤時間か最大となる迄
の時間の172即ち膜膨潤速度T l/2か30秒以下
である時に最大の効果を発揮するが、その金膜の厚みは
乾燥時に147ts以下。The color photographic light-sensitive material of the present invention is a multilayer color photographic light-sensitive material having three or more layers including each of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. That is, the maximum effect is exhibited when the membrane swelling rate T l/2 is 30 seconds or less, but the thickness of the gold membrane when dry is 147 ts or less.
好ましくは13%−以下、特に好ましくは12gm以下
であるが、いずれの場合にもT l/2は30秒以下で
あることが好ましい。It is preferably 13% or less, particularly preferably 12 gm or less, but in any case it is preferred that T l/2 is 30 seconds or less.
本発明の写真感光材料の処理方式は、前記本発明に係わ
る発色現像主薬を含有する発色現像浴を用いることが可
能である。また、浴処理を始めとして他の各種の方法1
例えば処理液を噴霧状にするスプレ一方式、又は処理液
を含浸させた担体との接触によるウェッブ方式、あるい
は粘性処理液による現像方法等各種の処理方式を用いる
ことができる。In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing bath containing the color developing agent according to the present invention. In addition, various other methods including bath treatment 1
For example, various processing methods can be used, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid.
上記の他、本発明の写真感光材料の処理方法については
特に側限はなく、あらゆる処理方法が適用できる0例え
ば、その代表的なものとしては。In addition to the above, there are no particular limitations on the processing method for the photographic light-sensitive material of the present invention, and any processing method can be applied.
発色現像後、漂白定着処理を行い必要ならさらに水洗お
よび/または水洗代替安定処理を行う方法5発色現像後
、漂白と定着を分離して行い、必要に応じさらに水洗お
よび/または安定処理を行う方法;あるいは前硬膜、中
和、発色現像、停止定着、水洗、漂白、定着、水洗、後
硬膜、水洗の順で行う方法、発色現像、水洗、補足発色
現像、停止、P:4白、定着、水洗、安定の順で行う方
法。After color development, bleach-fixing is performed, and if necessary, washing with water and/or stabilizing treatment as an alternative to washing is performed. Method 5: After color development, bleaching and fixing are performed separately, and if necessary, washing with water and/or stabilizing treatment are performed. ; or a method of performing in the order of pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water, color development, washing with water, supplementary color development, stop, P: 4 white; Method of fixing, washing with water, and stabilizing in that order.
発色現像によって生じた現像銀をハロゲネーションブリ
ーチをしたのち、再度発色現像をして生成色素量を増加
させる現像方法等、いずれの方法を用いて処理してもよ
い。The developed silver produced by color development may be subjected to halogenation bleaching, and then color development may be performed again to increase the amount of produced dye, or any other method may be used for processing.
本発明において水洗代替安定液に好ましく用いられる化
合物としては鉄イオンに対するキレート安定度定数が6
以上であるキレート剤が挙げられ、これらは本発明の目
的を達成する上で好ましく用いられる。In the present invention, compounds preferably used in the water washing alternative stabilizer have a chelate stability constant of 6 for iron ions.
The above-mentioned chelating agents are mentioned, and these are preferably used to achieve the object of the present invention.
ここにキレート安定度定数とは、L、G、5illen
・A−E、Martell 著、 ” 5tabi
lity Con5tants of Meta
l−ion Complexes” 、 The
Chemical 5ociety、London
(1964)、 S、Chaberek−A、E、Ma
rtell著、” OrganicSequester
ing Agents″、 Wiley(1959)等
により一般に知られた定数を意味する。Here, the chelate stability constants are L, G, 5illen
・A-E, Martell, “5tabi
ity Con5tants of Meta
l-ion Complexes”, The
Chemical 5ociety, London
(1964), S., Chaberek-A., E., Ma.
"Organic Sequester" by Rtell
ing Agents'', a constant commonly known by Wiley (1959) and others.
本発明の水洗代替安定液に好ましく用いられる鉄イオン
に対するキレート安定度定数が6以上であるキレート剤
としては、有機カルボン酸キレート剤、有機リン酸キレ
ート剤、無機リン酸キレート剤、ポリヒドロキシ化合物
等が挙げられる。なお1記鉄イオンとは、第2鉄イオン
(Fe”)を意味する。Examples of chelating agents having a chelate stability constant of 6 or more for iron ions that are preferably used in the water washing alternative stabilizer of the present invention include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. can be mentioned. Note that 1. Iron ion means ferric ion (Fe'').
第2鉄イオンとのキレート安定度定数が6以上であるキ
レート剤の具体的化合物例としては、下記化合物が挙げ
られるが、これらに限定されるものてはない、即ち、エ
チレンジアミンジオルトヒトロキシフェニル酢酸、ジア
ミノプロパン四酢酸、ニトリロ三酢酸、ヒドロキシエチ
レンジアミン三酢酸、ジヒドロキシエチルグリシン、エ
チレンジアミンニ酢酸、エチレンジアミンニプロピオン
酸、イミノニ酢酸、ジエチレントソアミン五酢酸、ヒト
ロキシエチルイミノニ酢酸、ジアミノプロパノール四酢
酸、トランスシクロヘキサンジアミン四酢酸、グリコー
ルエーテルジアミン四酢酸、エチレンジアミンテトラキ
スメチレンホスホン酸、ニトリロトリメチレンホスホン
酸、l−ヒドロキシエチリデン−1,1−ジホスホン酸
、■、1−ジホスホノエタンー2−カルボン酸、2−ホ
スホノブタン−1,2,4−トリカルボン酸、1−ヒド
ロキシ−1−ホスホノプロパン−1,2,3−トリカル
ボン酸、カテコール−3,5−ジホスホン酸、ピロリン
酸ナトリウム、テトラポリリン酸ナトリウム、ヘキサメ
タリン酸ナトリウムが挙げられ、特に好ましくはジエチ
レントリアミン五酢酸、ニトリロ三酢酸、■−ヒドロキ
シエチリデンー1.1−ジホスホン酸等であり、中でも
l−ヒドロキシエチリデン−1,1−ジホスホン酸か最
も好ましく用いられる。Specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with ferric ions include, but are not limited to, the following compounds: ethylenediaminediorthohydroxyphenyl Acetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetosoaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, Trans-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, ■, 1-diphosphonoethane-2-carboxylic acid, 2 -Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexamethalin Particularly preferred are diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and -hydroxyethylidene-1,1-diphosphonic acid, among which l-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.
上記キレート剤の使用量は水洗代替安定液1交当り0.
01〜50gが好ましく、より好ましくは0.05〜2
0gの範囲である。The amount of the above-mentioned chelating agent used is 0.00.
01-50g is preferable, more preferably 0.05-2
It is in the range of 0g.
本発明の水洗代替安定液の補充量が、単位面植当り前浴
からの持ち込み量の0.5倍より少ない場合は1本発明
の水洗代替安定液中に蓄積する前浴成分が多くなり、写
真色素画像の保存安定性が悪化し、一方、50倍より多
い場合は本発明の目的の効果が小さくなる。このために
、本発明においては、0.5〜50倍の範囲で用いるこ
とか好ましい。If the amount of replenishment of the water washing alternative stabilizer of the present invention is less than 0.5 times the amount brought in from the prebath per unit planting area, the prebath components will accumulate in the water washing alternative stabilizer of the present invention, and the photo The storage stability of the dye image deteriorates, and on the other hand, if it is more than 50 times, the desired effect of the present invention becomes smaller. For this reason, in the present invention, it is preferable to use the amount in a range of 0.5 to 50 times.
特に2〜30倍の範囲で用いる際には、前記本発明の目
的の効果をとりわけ、良好に奏し得る。特に感光材料1
m″当り 20005M以下を添加するのが好ましい。In particular, when used in a range of 2 to 30 times, the desired effects of the present invention can be particularly well achieved. Especially photosensitive material 1
It is preferable to add 20005 M or less per m''.
本発明の水洗代替安定液の槽は、l槽でもよいが、2〜
lO槽程度までは槽の数を増やすことができ、かつ槽増
加によって本発明の目的の効果も大きくなるため、この
範囲内で槽数な増やしてもよい。また、前記水洗代替安
定液に補充する補充液は何ケ所かに分けて補充してもよ
いが、好ましくは、なるべく感光材料の処理の流れから
見て後の槽へ補充して、そのオーバーフロー(種間を液
面下に位置する管で連通させた場合、鎖管を浴液が通る
場合を含む、)を核種の前の槽に流入させる型式にする
のが好ましい、更に好ましくは、2槽以上の水洗代替安
定液で、最後の該安定槽へ水洗代替安定補充液を補充し
て、オーバーフローを順次前の槽へ移入し、定着能を有
する液の次の水洗代替安定液からのオーバーフロー液の
一部又は全部は全て廃棄してもよいし、あるいは、該定
着能を有する液を流し込んでもよい。The tank for the water washing alternative stabilizing solution of the present invention may be 1 tank, but may be 2 to 1 tank.
The number of tanks can be increased up to about 1O2 tank, and the effect of the present invention becomes greater as the number of tanks increases, so the number of tanks may be increased within this range. Further, the replenisher to be added to the water-washing alternative stabilizing solution may be replenished in several places, but it is preferable to replenish it to a later tank as far as possible in terms of the processing flow of the photosensitive material, so that the overflow ( When the species are communicated by a tube located below the liquid surface, it is preferable to use a type in which the bath liquid (including the case where the bath liquid passes through a chain tube) flows into a tank in front of the nuclide, and more preferably two tanks. With the above-mentioned washing alternative stabilizer, replenish the washing alternative stabilizing replenisher to the last stabilizing tank, transfer the overflow to the previous tank sequentially, and collect the overflow from the washing alternative stabilizer after the solution with fixing ability. A part or all of the liquid may be discarded, or a liquid having the fixing ability may be poured into the liquid.
本発明に用いられる水洗代替安定液に防パイ性を付与す
る手段としては、防パイ性を付与する化学的手段及び物
理的手段が挙げられる。Means for imparting anti-spill properties to the water-washing alternative stabilizer used in the present invention include chemical means and physical means for imparting anti-spill properties.
防パイ性を付与する化学的手段の具体例としては、本発
明の水洗代替安定液に防パイ剤を含有させることが挙げ
られる。好ましく用いられる防ハイ剤は、ソルビン酸、
安息香酸系化合物、フェノール系化合物、チアゾール系
化合物、ピリジン系化合物、グアニジン系化合物、カー
バメイト系化合物1モルホリン系化合物、四級ホスホニ
ウム系化合物、アンモニウム系化合物、尿素系化合物、
イソキサゾール系化合物、プロパツールアミノ系化合物
、スルファミド系化合物、ピロノン系化合物及びアミノ
酸系化合物である。A specific example of chemical means for imparting anti-spill properties is to include an anti-spill agent in the water washing alternative stabilizing solution of the present invention. Preferably used anti-high agents include sorbic acid,
Benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds 1 Morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds,
These are isoxazole-based compounds, propatoolamino-based compounds, sulfamide-based compounds, pyronone-based compounds, and amino acid-based compounds.
前記安息香酸系化合物は、サルチル酸、ヒドロキシ安息
香酸及びヒドロキシ安息香酸のエステル化合物としてメ
チルエステル、エチルエステル、プロピルエステル、ブ
チルエステル等があるが。The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, propyl ester, and butyl ester.
好ましくは、ヒドロキシ安息香酸のn−ブチルエステル
、イソブチルエステル、プロピルエステル及びサルチル
酸であり、より好ましくは前記ヒドロキシ安息香酸エス
テル3種の混合物である。Preferred are n-butyl ester, isobutyl ester, propyl ester and salicylic acid of hydroxybenzoic acid, and more preferred is a mixture of the three hydroxybenzoic acid esters.
フェノール系化合物は、ハロゲン原子、ニトロ基、水酸
基、カルボン酸基、アミノ基、アルキル基(特に、アル
キル基がCt−Sのアルキル21i)゛又はフェニル基
等を置換基として持ってもよい化合物であり、好ましく
はオルトフェニルフェノール及びオルトシクロヘキシル
フェノール、ニトロフェノール、クロロフェノール、ク
レゾール、グアヤコール、アミノフェノール、フェノー
ル等である。The phenolic compound is a compound which may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (especially alkyl 21i where the alkyl group is Ct-S), or a phenyl group as a substituent. Among them, preferred are ortho-phenylphenol, ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like.
チアゾール系化合物は、五員環に窒素原子及びイオウ原
子を持つ化合物であり、好ましくは1.2−ベンツイソ
チアゾリン3−オン、 2−メチル−4−イソチアゾリ
ン3−オン、2−才クチル−4−イソチアゾリン3−オ
ン、5−クロロ−2−メチル−4−イソチアシリ3−ノ
ン、2−クロロ−チアゾリル−ベンツイミダゾールであ
る。The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-benzisothiazolin 3-one. These are isothiazolin 3-one, 5-chloro-2-methyl-4-isothiacyli-3-one, and 2-chloro-thiazolyl-benzimidazole.
ピリジン系化合物は具体的には、2.トジメチルピリジ
ン、2,4.6−ドリメチルピリシン、ラジウム−2−
ピリジンチオール−1−オキサイト等があるが、好まし
くはラジウム−2−ピリジンチオール−1−オキサイド
である。Specifically, pyridine compounds include 2. dimethylpyridine, 2,4,6-drimethylpyridine, radium-2-
Examples include pyridinethiol-1-oxide, but radium-2-pyridinethiol-1-oxide is preferred.
グアニジン系化合物は具体的には、シクロへキシジン、
ポリへキサメチレンビグアニジン塩酩塩、ドデシルグア
ニジン塩酸塩等があり、好ましくはドデシルグアニジン
及びその塩である。Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine salt, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.
カーバメイト系化合物は具体的には、メチル−1−(プ
チルカーバモイル)−2−ベンツイミダゾールカーバメ
イト、メチルイミダゾールカーバメイト等がある。Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.
モルホリン系化合物は具体的には: 4−(:l−二ト
ロブチル)モルホリン、 4−(3−ニトロブチル)モ
ルホリン等がある。Specific examples of morpholine compounds include: 4-(:l-nitrobutyl)morpholine, 4-(3-nitrobutyl)morpholine, and the like.
四級ホスホニウム系化合物は、テトラアルキルホスホニ
ウム塩、テトラアルコキシホスホニウム塩等があるが、
好ましくは、テトラアルキルホスホニウム塩であり、更
に具体的な好ましい化合物はトリーnブチル−テトラデ
シルホスホニウムクロライト及びトリーフェニル・ニト
ロフェニルホスホニウムクロライドである。Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chlorite and triphenyl-nitrophenylphosphonium chloride.
四級アンモニウム系化合物は具体的には、ベンザルコニ
ウム塩、ベンゼトニウム塩、テトラアルキルアンモニウ
ム塩、アルキルピリジウム塩等があり、更に具体的には
ドデシルジメチルベンジルアンモニウムクロライド、ド
デシルジメチルアンモニウムクロライド、ラウリルピリ
ジニウムクロライド等がある。Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium. There are chloride etc.
尿素系化合物は具体的には、N−(:1.4−ジクロロ
フェニル)−N7−(4−クロロフェニル)尿素、N−
(:l−トリフルオロメチル)−N”−(4−クロロフ
ェニル)尿素等がある。Specifically, the urea-based compounds include N-(:1,4-dichlorophenyl)-N7-(4-chlorophenyl)urea, N-
(:l-trifluoromethyl)-N''-(4-chlorophenyl)urea and the like.
インキサゾール系化合物は具体的には、3−ヒドロキシ
−5−メチル−イソキサゾール等がある。Specific examples of inxazole compounds include 3-hydroxy-5-methyl-isoxazole.
プロパツールアミノ系化合物は、n−プロパツール類と
イソプロパツール類があり、具体的にはDL−2−ベン
ジルアミノ−1−プロパツール、3−ジエチルアミノ−
1−プロパツール、2−ジメチルアミノ−2−メチル−
■−プロパツール、3−アミノ−1−プロパツール、イ
ドプロパツールアミン、ジイソプロパツールアミン、N
、N−ジメチル−イソプロパツールアミン等がある。Proptool amino compounds include n-proptools and isoproptools, specifically DL-2-benzylamino-1-proptool, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
■-Propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
, N-dimethyl-isopropanolamine, and the like.
スルファミド系化合物は具体的には、0−ニトロベンゼ
ンスルファミド、p−アミノベンゼンスルファミド、フ
ッ素化スルファミド、4−クロロ−3,5−ジニトロベ
ンゼンスルファミド、α−アブミノーp−トルエンスル
ファミドスルファニルアミド、アセトスルファグアニジ
ン、スルファチアゾール、スルファジアジン、スルファ
メラジン、スルファメタシン、スルファインオキサゾー
ル、ホモスルファミン、スルファミジン、スルファグア
ニジン、スルファメチゾール、スルファピラジン、フタ
ルイソスルファチアゾール、スクシニルスルファチアゾ
ール等がある。Specifically, the sulfamide-based compounds include 0-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-abminor p-toluenesulfamide. Dosulfanilamide, acetosulfaguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethacine, sulfaine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfa There are thiazoles, etc.
ピロノン系化合物としては具体的には、デヒドロ酢酸等
がある。Specific examples of pyronone compounds include dehydroacetic acid and the like.
アミノ酸系化合物は具体的には、N−ラウリル−β−ア
ラニンがある。A specific example of the amino acid compound is N-lauryl-β-alanine.
なお上記防パイ剤のなかで本発明において好ましく用い
られる化合物はチアゾール系化合物、スルファミド系化
合物、ピロノン系化合物等である。Among the anti-spill agents mentioned above, compounds preferably used in the present invention include thiazole compounds, sulfamide compounds, and pyronone compounds.
水洗代替安定液への防パイ剤の添加量は、水洗代任安定
液1!L当り0.001〜30gの範囲で用いられるこ
とが好ましく、より好ましくは0−003g〜5gの範
囲て使用される。The amount of anti-piping agent added to the washing substitute stabilizer is 1! It is preferably used in a range of 0.001 to 30 g per L, more preferably in a range of 0-003 g to 5 g.
一方、物理的手段としては水洗代替安定液に紫外線照射
したり、磁場を通すことによる防パイ性付与か挙げられ
る。On the other hand, physical means include irradiating the water washing alternative stabilizer with ultraviolet rays or passing it through a magnetic field to impart anti-piping properties.
本発明において水洗代替安定液に磁場を通すとは磁場の
正極と負極の間に発生する磁場に水洗代替安定液を通過
させることであり、感光材料は磁場を通過しても、しな
くてもよい。In the present invention, passing a magnetic field through the water-washing alternative stabilizer means passing the water-washing alternative stabilizer through a magnetic field generated between the positive and negative poles of the magnetic field, and the photosensitive material may pass through the magnetic field or not. good.
本発明に用いる磁場は、強磁性体の鉄、コバルト、ニッ
ケルからなる永久磁石等を使用することにより得られ、
又はコイル等に直流を流すことによっても得ることかて
きるが、特に限定されず、磁場を形成しうる全での手段
を用いることかてきる。なお、磁場は1個の磁石を用い
て磁力線を形成するようにしてもよいし、2個(正極と
負極)の磁石を対向させて対向磁石間に磁力線を形成す
るようにしてもよい。The magnetic field used in the present invention is obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel.
Alternatively, it can be obtained by passing a direct current through a coil or the like, but there is no particular limitation, and any means capable of forming a magnetic field can be used. Note that the magnetic field may be formed by using one magnet to form lines of magnetic force, or by opposing two magnets (a positive pole and a negative pole) to form lines of magnetic force between the opposing magnets.
本発明に用いる水洗代替安定液を磁場に通す方法として
は、磁場を形成する永久磁石等を使用して安定液中及び
/又は液外に設けた永久磁石を移動(回転を含む)させ
るか、又は水洗代替安定液を攪拌又は循環により水洗代
替安定液を移動する等の方法がある。特に望ましい方法
としては、循環系パイプの内部又は外部の一部又は全部
に永久磁石を固定し安定液を循環させる方法である。The method of passing the water-washing alternative stabilizing solution used in the present invention through a magnetic field includes moving (including rotation) a permanent magnet that is placed inside and/or outside the stabilizing solution using a permanent magnet that forms a magnetic field. Alternatively, there is a method of moving the washing alternative stabilizing liquid by stirring or circulating the washing alternative stabilizing liquid. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of the circulation system pipe and circulate the stabilizing liquid.
個々にパイプ全部に永久磁石を固定するとはパイプ自体
が永久磁石てあってもよいし、該永久磁石を該パイプ全
部に取付けてもよい。When permanent magnets are individually fixed to all of the pipes, the pipes themselves may be permanent magnets, or the permanent magnets may be attached to all of the pipes.
自動現像機の場合には水洗代替安定浴に永久磁石等を設
置することて目的は達成せられるか、前述のように安定
浴の循環系(″Oa環パイプに限らず、途中のタンクそ
の他の部材を含む。)に設置することが好ましい。また
水洗代替安定化処理工程か多段安定浴の場合、全水洗代
替安定浴の安定液を磁場に通すことが最も好ましいが、
定着能を有する処理液に最も近い水洗代替安定浴以外の
安定浴の安定液を磁場に通すことも好ましいことである
。なお、水洗代替安定浴自体、好ましくは水洗代替安定
浴内面に、!!力線を発生可能な素材を含有せしめた樹
脂ライニングを施してもよく、このライニングは循環系
に施すこともできる。このようにして安定液を磁場に通
すことができる。In the case of an automatic developing machine, is it possible to achieve the purpose by installing a permanent magnet etc. in the stabilizing bath instead of washing with water? In the case of a water washing alternative stabilization treatment process or a multi-stage stabilization bath, it is most preferable to pass the stabilizing solution of the all water washing alternative stabilization bath through a magnetic field.
It is also preferable to pass the stabilizing liquid of a stabilizing bath other than the water washing alternative stabilizing bath closest to the processing liquid having fixing ability through the magnetic field. In addition, the washing alternative stabilizing bath itself, preferably the inner surface of the washing alternative stabilizing bath! ! A resin lining containing a material capable of generating lines of force may be applied, and this lining can also be applied to the circulation system. In this way the stabilizing liquid can be passed through a magnetic field.
本発明において水洗代替安定液に紫外線を照射する方法
は、一般に重版されている紫外線ランプ又は紫外線照射
装置等によって行なわれ、好ましくは紫外線ランプの出
力は5〜aoow (管出力)のものが好ましいが、こ
れに限定されるものではない。In the present invention, the method of irradiating the washing alternative stabilizer with ultraviolet rays is generally carried out using a reprinted ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5 to aoow (tube output). , but is not limited to this.
また、本発明の好ましい実施態様によれば紫外線の波長
が220nm〜350n■の範囲のものである。According to a preferred embodiment of the present invention, the wavelength of the ultraviolet rays is in the range of 220 nm to 350 nm.
更に、照射方法としては、水洗代替安定液中又は水洗代
替安定液外に設置し直接照射する方法がある。Further, as an irradiation method, there is a method of placing the product in the washing substitute stabilizing solution or outside the washing substitute stabilizing solution and irradiating it directly.
本発明において用いられる発色現像液には、更に通常添
加されている種々の成分、例えば水酸化ナトリウム、炭
酸ナトリウム等のアルカリ剤、アルカリ金属亜硫酸塩、
アルカリ金属亜硫酸水素塩、アルカリ金属チオシアン酸
塩、アルカリ金属ハロゲン化物、ベンジルアルコール、
濃厚化剤および現像促進剤等を任意に含有させることも
てきる。The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A thickening agent, a development accelerator, etc. may optionally be included.
更に本発明においては下記一般式(IT)、(V)及び
(VI)で表されるキレート剤は本発明の低補充化及び
処理安定性に対する効果を更に奏する上で好ましく用い
られる。Further, in the present invention, chelating agents represented by the following general formulas (IT), (V), and (VI) are preferably used because they further exhibit the effects of the present invention on low replenishment and processing stability.
一般式(TV ) A−COOM 一般式〔V〕0 B −P−82 B。General formula (TV) A-COOM General formula [V] 0 B-P-82 B.
一般式(VI) ¥ :c−on
式中、Aは一価の有機残基、B、B+ 及びB2は各
々−価の有機残基もしくは原子を表し、無機物であ っ
てもよいし、有機物であってもよい。General formula (VI) ¥:c-on In the formula, A is a monovalent organic residue, B, B+ and B2 each represent a -valent organic residue or atom, which may be an inorganic substance or an organic substance. It may be.
Dは置換基を有してもよい芳香族環、複素環を表し、M
は水素原子又はアルカリ金属原子を表す。D represents an aromatic ring or heterocycle which may have a substituent, and M
represents a hydrogen atom or an alkali metal atom.
本発明に添加される面記一般式([V)、(V)又は(
VL)で示されるキレート剤の中でも、本発明に好まし
いキレート剤は下記一般式〔■〕〜(XVOI)のいず
れかで示される化合物である。Surface general formula ([V), (V) or (
Among the chelating agents represented by VL), preferred chelating agents for the present invention are compounds represented by any of the following general formulas [■] to (XVOI).
一般式〔■) MIIIPI110301一般式〔
■) Mn+ tPnosn + を一般式(fK
) A+ Rt Z Rt C00H一般
式(X)
式中、Eは置換又は未置換のアルキレン基、シクロアル
キレン基、フェニレン基、−Rt−0R7−、−Rt−
OR?OR,−又は−RtZR,−を表し、Zは> N
−Rv A *又は>N−A、を表し、R,〜R7
は各々置換又は未置換のアルキレン基を表し、A1〜八
〇は各々水素原子、−08,−COOM又は−POpM
xを表し、Mは水素原子又はアルカリ金属原子を表し、
mは3〜6の整数、nは2〜20の整数を表す。General formula [■] MIIIPI110301 general formula [
■) Mn+ tPnosn + is expressed by the general formula (fK
) A+ Rt Z Rt C00H General Formula (X) In the formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -Rt-0R7-, -Rt-
OR? Represents OR,- or -RtZR,-, where Z is > N
-Rv A * or >N-A, R, ~R7
each represents a substituted or unsubstituted alkylene group, A1 to 80 are each a hydrogen atom, -08, -COOM or -POpM
represents x, M represents a hydrogen atom or an alkali metal atom,
m represents an integer of 3 to 6, and n represents an integer of 2 to 20.
一般式〔尺) RsN(CIItPOaM’t)を式
中、R1は低級アルキル基、アリール基、アラルギル基
、含窒素6員環基〔置換基として一0t−r、−OR,
−COOM)を表し、Mは水素原子、アルカリ金属原子
を表す。General formula [scale] RsN (CIItPOaM't), where R1 is a lower alkyl group, an aryl group, an aralgyl group, a nitrogen-containing 6-membered ring group [as a substituent: 10t-r, -OR,
-COOM), and M represents a hydrogen atom or an alkali metal atom.
一般式(1)
%式%
式中、R,〜R1は水素原子、−〇H1低級アルキル(
未置換又は置換基として−OH,−COOM。General formula (1) %Formula% In the formula, R, ~R1 are hydrogen atoms, -〇H1 lower alkyl (
-OH, -COOM, unsubstituted or as a substituent.
P OsM t)を表し、81〜B、は水素原子、−O
tl−COOM、−PO3M!、−NJzを表し、Jは
水素原子、低級アルキル基、C! H40[4、−PO
,Mオを表し、Mは水素原子、アルカリ金属を表し、n
、mは0又は1を表ず。P OsM t), 81 to B are hydrogen atoms, -O
tl-COOM,-PO3M! , -NJz, where J is a hydrogen atom, a lower alkyl group, and C! H40[4,-PO
, M represents a hydrogen atom or an alkali metal, n
, m does not represent 0 or 1.
一般式(XII) OM R,、−0−P−ORIs ■ 式中、RI!及びR13は水素原子、アルカリ金属。General formula (XII) OM R,,-0-P-ORIs ■ During the ceremony, RI! and R13 is a hydrogen atom or an alkali metal.
01〜C11のアルキル基、アルケニル基環状アルキル
基を表す。01 to C11 alkyl group, alkenyl group represents a cyclic alkyl group.
一般式(XN)
式中、RoはCI〜1.のアルキル基、C1〜Iオのア
ルコキシ基、C,X、、のモノアルキルアミノ基、C1
〜、、のジアルキルアミノ基、アミノ基、CI〜2.の
アリロキシ基、C1〜、4のアリールアミノ基及びアミ
ルオキシ基を表し、Q、〜Q、は−OH。General formula (XN) In the formula, Ro is CI~1. an alkyl group of C1 to Io, a monoalkylamino group of C,X, , C1
~, dialkylamino group, amino group, CI~2. represents an aryloxy group, a C1-4 arylamino group, and an amyloxy group, and Q and ~Q are -OH.
C1〜、4のアルコキシ基、アラルキルオキシ基、アミ
ルオキシ基、−0M 3 (Mはカチオン)、アミノ基
、モルホリノ基、環状アミノ基、アルキルアミノ基、ジ
アルキルアミノ基、アリールアミノ基アルキルオキシ基
を示す。C1 to 4 alkoxy group, aralkyloxy group, amyloxy group, -0M3 (M is a cation), amino group, morpholino group, cyclic amino group, alkylamino group, dialkylamino group, arylamino alkyloxy group .
一般式(X’/)
一般式〔願〕
式中、n 4g、R+*、Rr7及びR1,はそれぞれ
水素原子、ハロゲン原子、スルホン酸基、置換又未置換
の素原子数1〜7のアルキル基、
もしくは未置換のフェニル基を表す。General formula (X'/) General formula [application] In the formula, n 4g, R++, Rr7 and R1 are each a hydrogen atom, a halogen atom, a sulfonic acid group, or a substituted or unsubstituted alkyl having 1 to 7 atoms. or unsubstituted phenyl group.
Rl#+ Rtar R*r及びR11はそれぞれ水素
原子又は炭素原子数1〜18のアルキル基を表す。Rl#+ Rtar R*r and R11 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
式中、Rt、及びR1,は水素原子、ハロゲン原子又は
スルホン酸基を表す。In the formula, Rt and R1 represent a hydrogen atom, a halogen atom, or a sulfonic acid group.
一般式〔X■〕
式中、R1゜及びR2゜はそれぞれ水素原子、リン酸基
、カルボン酸基、−Cl1tCOOII、 −CIl*
PO51(*又はそれらの塩を表し、xlは水酸基又は
その塩を表し、W、、Z、及びY、はそれぞれ水素原子
、ハロゲン原子、水酸基、シアノ基、カルボン酸基、リ
ン酸基、スルホン酸基もしくはそれらの塩、アルコキシ
氏或はアルキル基を表す。またIllは0又はl。General formula [X■] In the formula, R1゜ and R2゜ are respectively a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -Cl1tCOOII, -CIl*
PO51 (* or a salt thereof; xl represents a hydroxyl group or a salt thereof; W, Z, and Y each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group) represents a group or a salt thereof, an alkoxy group, or an alkyl group. Ill is 0 or l.
nlは1〜4の整数、[1は!又は2、plは0〜3の
整数、qlはO〜2の整数を表す。nl is an integer from 1 to 4, [1 is! or 2, pl represents an integer of 0 to 3, and ql represents an integer of 0 to 2.
前記一般式〔■〕〜〔X■〕で示されるキレート剤の具
体例としては次のものがあげられる。Specific examples of the chelating agents represented by the general formulas [■] to [X■] include the following.
〔例示キレート剤〕;
(1) Na5P*0ta (2) Na
5P30゜(3) II−how (4)
Ir5PsO+。[Exemplary chelating agent]; (1) Na5P*0ta (2) Na
5P30゜(3) II-how (4)
Ir5PsO+.
(5) Na5P*0ta
CIl、C00I+
CIls
(15) (+10Cヨ■4)ヨNCIIINC
llIC0OI
I(16
)(2I
)(22)(lx
(OON (24)PG!I
AI POIIIz(29)
(3G)POllt2
CH2−POllt2POIIl、
PO,II。(5) Na5P*0ta CIl, C00I+ CIls (15) (+10Cyo ■4) YoNCIIINC
llIC0OI I (16 ) (2I ) (22) (lx (OON (24) PG!I
AI POIIIz (29)
(3G) POllt2
CH2-POllt2POIIl,
P.O., II.
CII2POilb po=I+
。CII2POilb po=I+
.
PG、II、 Cll
2COOIIPO1ff2
POlltCII2P(hlh
POilhPO,11゜
(51) (52) (52′
)PO112(Ill
0il
0ilOll
■
11yOiP−C−POJlh
■
C2110]
+IOC12CI(011)−CII2G−P−(ON
m)2l
110CII2C1hO−P−(Ollh110C11
2CI−0−P−(ONa)2cn、ot+
110−C112−CIl−C1lz−0−P−(Ol
l)201!
++00C−C1l−C112−0−P−(011)。PG, II, Cll
2COOIIPO1ff2
POlltCII2P(hlh
POilhPO, 11° (51) (52) (52'
) PO112 (Ill 0il
0ilOll ■ 11yOiP-C-POJlh ■ C2110] +IOC12CI(011)-CII2G-P-(ON
m) 2l 110CII2C1hO-P-(Ollh110C11
2CI-0-P-(ONa)2cn, ot+ 110-C112-CIl-C1lz-0-P-(Ol
l) 201! ++00C-C11-C112-0-P-(011).
(67) (6g)COO
に C00I+112
N−CII2CI+2−OP−(OH)2l211−C
oo−P−(OK)2
HIC−COO−P−(01112
IIooC−Cl12CI12NllC−Cll0II
−C−Cl120− P−(OH)tl11
0K 0+1
C21160−P−0CzH&
NaOONm
011 0i1
(8【)
Oll 011 011Oll
011 011Oll 011
0i+
OCIl、 OCIl。(67) (6g) COO
to C00I+112
N-CII2CI+2-OP-(OH)2l211-C
oo-P-(OK)2 HIC-COO-P-(01112 IIooC-Cl12CI12NllC-Cll0II
-C-Cl120- P-(OH)tl11 0K 0+1 C21160-P-0CzH& NaOONm 011 0i1 (8[) Oll 011 011Oll
011 011Oll 011
0i+ OCIl, OCIl.
01+ 0il
(8g) (89)C1
に0011 CIItCOOllCIgCOOII
CIzCOOHCIl、C00II Cl
l2COOIICOOII C
OO11CIIzPChN幻
CII2COONa CI12COONmCl12
C
OON、COOff CIItCOOllCTo
COONa CIlzCOCllzCOON
C1l、C00II
本発明において一般式〔■〕、(Vff[)、(IX)
(X)、(Xl)、(XII)、(XV)及び〔X■〕
て示されるキレート剤を用いることか有効である。01+ 0il (8g) (89)C1
ni0011 CIItCOOllCIgCOOII
CIzCOOHCIl, C00II Cl
l2COOIICOOII C
OO11CIIzPChNphantom CII2COONa CI12COONmCl12
C OON, COOff CIItCOOllCTo
COONa CIlzCOCllzCOON C1l, C00II In the present invention, general formula [■], (Vff[), (IX)
(X), (Xl), (XII), (XV) and [X■]
It is effective to use chelating agents shown in
本発明に用いられる上記一般式(IV)〜(Vl)のい
ずれかて示されるキレート剤は安定液ifL当りi x
to−’モル−1モルの範囲で添加することかてき、
好ましくは2 X 10−’モル〜l X 10−’モ
ルの範囲で添加することかてき、更に好ましくは5XI
O−4モル〜s x to−2モルの範囲で添加するこ
とかてきる。The chelating agent represented by any of the above general formulas (IV) to (Vl) used in the present invention has an amount of i x per stable liquid ifL.
It can be added in the range of to-'mol-1 mole,
Preferably, it is added in a range of 2 x 10-' mol to 1 x 10-' mol, more preferably 5XI
It can be added in the range of O-4 mol to s x to-2 mol.
前記発色現像液に添加される上記以外の添加剤としては
1例えば臭化カリウム、臭化ナトリウム等の臭化物、沃
化アルカリ、ニトロペンゾイミタソール、メルカプトベ
ンゾイミタゾール、5−メチル−ベンゾトリアゾール、
l−フェニル−5−メルカプトテトラゾール等の迅速処
理液用化合物を始めとして、スティン防止剤、スラッジ
防W剤、保恒剤、重層効果促進剤、キレート剤等がある
。Examples of additives other than the above that may be added to the color developing solution include bromides such as potassium bromide and sodium bromide, alkali iodide, nitropenzimitazole, mercaptobenzimitazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing solutions such as l-phenyl-5-mercaptotetrazole, there are anti-stain agents, anti-sludge W agents, preservatives, interlayer effect promoters, chelating agents, and the like.
漂白工程の漂白液もしくは漂白定性液に用いられる漂白
剤としては、アミノポリカルボン酸または蓚酸、クエン
酸等の有機酸で鉄、コバルト、銅等の全屈イオンを配位
したものが一般に知られている。そして上記のアミノポ
リカルボン酸の代表的な例としては次のものを挙げるこ
とができる。As bleaching agents used in bleaching solutions or bleaching qualitative solutions in the bleaching process, those in which total ion such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid are generally known. ing. Representative examples of the above aminopolycarboxylic acids include the following.
エチレンジアミンテトラ酢酸
ジエチレントリアミンペンタ酢酸
プロピレンジアミンテトラ酢酸
ニトリロトリ酢酸
イミノジ酢酸
グリコールエーテルジアミンテトラ酢酸エチレンジアミ
ンテトラプロビオン酸
エチレンジアミンテトラ酢酸ジナトリウム塩ジエチレン
トリアミンペンタ酢酸ペンタナトリウム塩
ニトリロトリ酢酸ナトリウム塩
漂白液は上記の漂白剤と共に種々の添加剤を含有しても
よい。また漂白工程に漂白定着液を用いる場合には、前
記漂白剤のほかにハロゲン化銀定着剤を含有する組成の
液が適用される。また漂白定着液には更に例えば臭化カ
リウムの如きハロゲン化合物を含有させてもよい。そし
て前記の漂白液の場合と同様に、その他の各社の添加剤
、例えばpu緩衝剤、蛍光増白剤、消泡剤、界面活性剤
、保恒剤、キレート剤、安定剤、有機溶媒等を添加、含
有させてもよい。Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol etherdiaminetetraacetic acidethylenediaminetetraprobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may also contain additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the bleach solution mentioned above, additives from other companies such as PU buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. It may be added or contained.
なおハロゲン化銀定着剤としては、例えばチオ硫酸ナト
リウム、チオ硫酸アンモニウム、チオシアン酸カリウム
、チオシアン酸ナトリウム、またはチオ尿素、チオエー
テル等の通常の定着処理に用いられるようなハロゲン化
銀と反応して水溶性の銀塩を形成する化合物を挙げるこ
とができる。The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.
本発明のハロゲン化銀カラー写真感光材料の発色現像以
外の処理、例えば漂白定着(又は漂白、定着)、更に必
要に応じて行われる水洗、安定化等の各種処理工程の処
理温度についても迅速処理の見地から30℃以上で行わ
れるのが好ましい。Processing processes other than color development of the silver halide color photographic light-sensitive material of the present invention, such as bleach-fixing (or bleaching, fixing), as well as various processing steps such as water washing and stabilization as necessary, are also rapidly processed. From this point of view, it is preferable to carry out the process at a temperature of 30°C or higher.
本発明のハロゲン化銀カラー写真感光材料は特開昭58
−14834号、同5B−105145号、同58−1
34634号及び同5B−18631号並びに特願昭5
8−2709号及び同59−89288号等に示される
ような水洗代替安定化処理を行ってもよい。The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 5B-105145, 58-1
No. 34634 and No. 5B-18631 and patent application No. 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.
本発明のハロゲン化銀カラー写真感光材料の写真構成層
には、水溶性または発色現像液て脱色する染料(AI染
料)を添加することがてき、該AI染料としては、オキ
ソノール染料、ヘミオキソノール染料、メロシアニン染
料及びアゾ染料が包含される。中でもオキソノール染料
、ヘミオキソノール染料及びメロシアニン染料等が有用
である。用い得るAI染料の例としては、英国特許58
4.509号、同1,277.429号、特開昭48−
85130号、同49−99620号、同49−114
420号、同49−129537号、同52−1081
15号、同59−25845号、同59−111640
号、同59−111641号、米国特許2,274,7
82号、同2,533,472号、同2,956,87
9号、同:l、125,448号、同:1.148,1
87号、同3,177.078号、同 :l、247,
127号、同 3,260,601号、同3.540,
887号、同 1,575,704号、同 :l、65
3,905号、同3,718,472号、同4,071
.:112号、同4,070.352号に記載されてい
るものを挙げることがてきる。The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that is decolorized by a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 58
No. 4.509, No. 1,277.429, Japanese Unexamined Patent Publication No. 1977-
No. 85130, No. 49-99620, No. 49-114
No. 420, No. 49-129537, No. 52-1081
No. 15, No. 59-25845, No. 59-111640
No. 59-111641, U.S. Patent No. 2,274,7
No. 82, No. 2,533,472, No. 2,956,87
No. 9, same: l, 125,448, same: 1.148,1
No. 87, No. 3,177.078, No. 87, No. 3,177.078, Same: l, 247,
No. 127, No. 3,260,601, No. 3.540,
No. 887, No. 1,575,704, No. 1, 65
No. 3,905, No. 3,718,472, No. 4,071
.. :112 and No. 4,070.352.
これらのAI染料は、一般に乳剤層中の銀1モル当り2
X 10−’〜5 X 10−’モル用いることが好
ましく、より好ましくはl x 10−”〜l X t
o−’モルを用いる。These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-' to 5 X 10-' moles, more preferably l x 10-'' to l X t
o-' moles are used.
ハロゲン化銀粒子の結晶は、正常晶ても双晶てもその他
でもよく、[1,0,0]面と[1,1,1]面の比率
は任意のものが使用てきる。更に、これらのハロゲン化
銀粒子の結晶構造は、内部から外部まで均一なものであ
っても、内部と外部か異質の層状構造(コア・シェル型
)をしだものてあってもよい。また、これらのハロゲン
化銀は潜像を主として表面に形成する型のものでも、粒
子内部に形成する型のものてもよい。ざらにモ板状ハロ
ゲン化銀粒子(特開昭58−113934号、特願昭5
9−170070号参照)を用いることもてきる。The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,1] planes may be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Roughly plate-shaped silver halide grains (Japanese Patent Application Laid-open No. 113934/1982, Japanese Patent Application No. 1983)
9-170070) may also be used.
本発明に特に好ましく用いられるハロゲン化銀粒子は、
実質的に単分散性のものであり、これは、酸性法、中性
法またはアンモニア法等のいずれの調製法により得られ
たものでもよい。Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.
また例えば種粒子を酸性法でつくり、更に、成長速度の
速いアンモニア法により成長させ、所定の大きさまで成
長させる方法てもよい。ハロゲン化銀粒子を成長させる
場合に反応釜内のpH、PAg等をコントロールし、例
えば特開昭5.4−48521号に記載されているよう
なハロゲン化銀粒子の成長速度に見合った量の銀イオン
とハライドイオンを逐次同時に注入混合することが好ま
しい。Alternatively, for example, seed particles may be produced using an acid method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH, PAg, etc. in the reaction vessel are controlled, and an amount suitable for the growth rate of silver halide grains is controlled, for example, as described in JP-A-5.4-48521. It is preferable to simultaneously implant and mix silver ions and halide ions.
本発明に係わるハロゲン化銀粒子の調製は以上のように
して行われるのが好ましい、該ハロゲン化銀粒子を含有
する組成物を、本明細書においてハロゲン化銀乳剤とい
う。Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.
これらのハロゲン化銀乳剤は、活性ゼラチン:硫黄増感
剤例えばアリルチオカルバミド、チオ尿素、シスチン等
の硫黄増感剤;セレン増感剤:還元増感剤例えば第1ス
ズ塩、二酸化チオ尿素、ポリアミンkg:貴金属増感剤
例えば金増感剤、具体的にはカリウムオーリチオシアネ
ート、カリウムクロロオーレート、2−オーロチオー3
−メチルベンゾチアゾリウムクロライド等あるいは例え
ばルテニウム、パラジウム、白金、ロジウム、イリジウ
ム等の水溶性塩の増感剤、具体的にはアンモニウムクロ
ロバラデート、カリウムクロロオーレ−トおよびナトリ
ウムクロロパラデート(これらの成る種のものは量の大
小によって増感剤あるいはカブリ抑制剤等として作用す
る。)等により単独であるいは適宜併用(例えば金増感
剤と硫黄増感剤の併用、金増感剤とセレン増感剤との併
用等)して化学的に増感されてもよい。These silver halide emulsions contain active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers: reduction sensitizers such as stannous salts, thiourea dioxide, Polyamine kg: Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol 3
- Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these They act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer).
本発明に係わるハロゲン化銀乳剤は、含硫黄化合物を添
加して化学熟成し、この化学熟成する前、熟成中、又は
熟成後、少なくとも1種のヒドロキシテトラザインデン
およびメルカプト基を有する含窒素へテロ環化合物の少
なくとも1種を含有せしめてもよい。The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.
本発明に用いられるハロゲン化銀は、各々所望の感光波
長域に感光性を付与するために、適当な増感色素をハロ
ゲン化itモルに対して5 X 10−’〜3 X 1
0−’モル添加して光学増感させてもよい。The silver halide used in the present invention contains an appropriate sensitizing dye in an amount of 5 x 10-' to 3 x 1 per mole of halide in order to impart photosensitivity to a desired wavelength range.
Optical sensitization may be achieved by adding 0-'mol.
増感色素としては種々のものを用いることができ、また
各々増感色素を1種又は2種以上組合せて用いることか
てきる0本発明において有利に使用される増感色素とし
ては例えば次の如きものを挙げることがてきる。Various sensitizing dyes can be used, and each sensitizing dye may be used alone or in combination. Examples of the sensitizing dyes advantageously used in the present invention include the following: I can list things like this.
即ち、青感性ハロゲン化銀乳剤に用いられる増感色素と
しては、例えば西独特許929,080号、米国特許2
,231,658号、同2,493,748号、同2.
50:1.776号、同2,519,001号、同2,
912,329号、同 3.556,959号、同3,
672,897号、同:l、694,217号、同41
ロ25,349号、同4,046,572号、英国特許
1,242.588号、特公昭44−14030号、同
52−24844号等に記載されたものを挙げることか
てきる。また緑感性ハロゲン化銀乳剤に用いられる増感
色素としては、例えば米国特許1,9:19,201号
、同2,072,908号、同2,739,149号、
同2,945.763号、英国特許505,979号等
に記載されている如きシアニン色素、メロシアニン色素
または複合シアニン色素をその代表的なものとして挙げ
ることができる。さらに、赤感性ハロゲン化銀乳剤に用
いられる増感色素としては、例えば米国特許2.2[i
9,234号、同2,270,378号、同2,442
,710号、同2,454,629号、同2,776.
280号等に記載されている如きシアニン色素、メロシ
アニン色素または複合シアニン色素をその代表的なもの
として挙げることかてきる。更にまた米国特許2,21
3,995号、同2,493,748号、同2,519
,001号、西独特許929.080号等に記載されて
いる如きシアニン色素、メロシアニン色素または複合シ
アニン色素を緑感性ハロゲン化銀乳剤または赤感性ハロ
ゲン化銀乳剤に有利に用いることかできる。That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2.
50:1.776, 2,519,001, 2,
No. 912,329, No. 3.556,959, No. 3,
No. 672,897, same: l, No. 694,217, same: 41
Examples include those described in Japanese Patent Publication No. 25,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, and the like. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 2,945.763 and British Patent No. 505,979. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, US Pat.
No. 9,234, No. 2,270,378, No. 2,442
, No. 710, No. 2,454,629, No. 2,776.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 280 and the like. Furthermore, U.S. Patent 2,21
No. 3,995, No. 2,493,748, No. 2,519
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat.
これらの増感色素は単独で用いてもよく、またこれらを
組合せて用いてもよい。These sensitizing dyes may be used alone or in combination.
本発明の写真感光材料は必要に応してシアニン或はメロ
シアニン色素の単用又は組合せによる分光増感法にて所
望の波長域に光学増感かなされていてもよい。The photographic material of the present invention may be optically sensitized to a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.
特に好ましい分光増感法としては代表的なものは例えば
、ベンズイミダゾロカルボシアニンとベンゾオキサゾロ
カルボシアニンとの組合せに関する特公昭43−493
6号、同43−22884号、同45−18433号、
同47−37443号、同48−28293号、同49
−6209号、同53−12375号、特開昭52−2
3931号、同52−51932号、同54−8011
8号、同58−153926号、同59−116646
号、同59−116647号等に記載の方法が挙げられ
る。A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like.
又、ベンズイミダゾール核を有したカルボシアニンと他
のシアニン或はメロシアニンとの組合せに関するものと
しては例えば特公昭45−25831号、同47−11
114号、同47−25379号、同48−38406
号、同48−38407号、同54−34535号、同
55−1569号、特開昭50−33220号、同50
−38526号、同51−107127号、同5t−t
15820号、同51−135528号、同52−10
4916号、同52−104917号等が挙げられる。Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 5t-t
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like.
さらにベンゾオキサゾロカルボシアニン(オキサ・カル
ボシアニン)と他のカルボシアニンとの組合せに関する
ものとしては例えば特公昭44−32753号、同46
−11627号、特開昭57−1483号、メロシアニ
ンに関するものとしては例えば特公昭48−38408
号、同48−41204号、同50−40662号、特
開昭56−25728号、同58−10753号、同5
8−91445号、同59−116645号、同50−
33828号等か挙げられる。Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828, etc. may be mentioned.
又、チアカルボシアニンと他のカルボシアニンとの組合
せに関するものとしては例えば特公昭43−4932号
、同43−4933号、同45−、:6470号、同4
6−18107号、同47−8741号、特開昭59−
114533号等かあり、さらにゼロメチン又はジメチ
ンメロシアニン、モノメチン又はトリメチンシアニン及
びスチリール染料を用いる特公昭49−6207号に記
載の方法を有利に用いることができる。Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications No. 43-4932, No. 43-4933, No. 45-, No. 6470, No. 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.
これらの増感色素を本発明に係るハロゲン化銀乳剤に添
加するには予め色素溶液として例えばメチルアルコール
、エチルアルコール、アセトン、ジメチルフォルムアミ
ド、或は特公昭50−40659号記載のフッ素化アル
コール等の親水性有機溶媒に溶解して用いられる。In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.
添加の時期はハロゲン化銀乳剤の化学熟成開始時、熟成
中、熟成終了時の任意の時期でよく、場合によっては乳
剤塗布直前の工程に添加してもよい。The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.
本発明に係わるハロゲン化銀乳剤層にはそれぞれカプラ
ー、即ち、発色現像主薬の酸化体と反応して色素を形成
し得る化合物を含有させることがてきる。Each of the silver halide emulsion layers according to the present invention may contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.
本発明において使用できる上記カプラーとしては各杼イ
エローカプラー、マゼンタカプラーおよびシアンカプラ
ーを特別の制限なく用いることがてきる。これらのカプ
ラーはいわゆる2当量型てあってもよいし4当量型カプ
ラーてあってもよく、またこれらのカプラーに組合せて
、拡散性色素放出型カプラー等を用いることも可能であ
る。As the above-mentioned couplers that can be used in the present invention, yellow couplers, magenta couplers and cyan couplers can be used without any particular limitations. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers.
前記イエローカプラーとしては、開鎖ケトメチレン化合
物さらにいわゆる2当量型カプラーと称される活性点−
〇−アリール置換カプラー、活性点−〇−アシル置換カ
プラー、活性点ヒダントイン化合物置換カプラー、活性
点ウラゾール化合物置換カプラーおよび活性点コハク酸
イミド化合物置換カプラー、活性点フッ素コ換カプラー
、活性点塩素あるいは臭素置換カプラー、活性点−〇−
スルホニル置換カプラー等か有効なイエローカプラーと
して用いることかできる。用い得るイエローカプラーの
具体例としては、米国特許2,875.057号、同:
l、265,506号、同3,408,194号、同3
.551,155号、同 1,582.:122号、同
3,725,072号、同3,891,445号、西
独特許1,547,868号、西独出願公開2,219
,917号、同2,261.:161号、同2,414
.006号、英国特許1,425,020号、特公昭5
1−10783号、特開昭47−26133号、同48
−73147号、同51−102636号、同50−6
341号、同50−123342号、同50−1304
42号、同51−21827号、同50−87650号
、同52−82424号、同52−115219号、同
58−95346号等に記載されたものを挙げることが
できる。The yellow coupler includes an open-chain ketomethylene compound and a so-called two-equivalent type coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine co-substituted coupler, active point chlorine or bromine Substituted coupler, active point -〇-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875.057;
l, No. 265,506, No. 3,408,194, No. 3
.. No. 551,155, 1,582. : No. 122, No. 3,725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2,219
, No. 917, 2,261. : No. 161, 2,414
.. No. 006, British Patent No. 1,425,020, Special Publication No. 5
No. 1-10783, JP-A-47-26133, JP-A No. 48
-73147, 51-102636, 50-6
No. 341, No. 50-123342, No. 50-1304
42, No. 51-21827, No. 50-87650, No. 52-82424, No. 52-115219, No. 58-95346, and the like.
また本発明において用いられるマゼンタカプラーとして
は、ピラゾロン系、ピラゾロトリアゾール系、ピラゾリ
ノベンツイミダゾール系、インダシロン系の化合物を挙
げることができる。これらのマゼンタカプラーはイエロ
ーカプラーと同様4当量型カプラーだけでなく、2当量
型カプラーであってもよい、マゼンタカプラーの具体例
としては米国特許2,600,788号、同2,983
,608号、同3,062,653号、同3,127,
269号、同:l、:Ill、476号、同3,419
.コ91号、同:l、519,429号、同3.558
.119号、同 コ、51112.:122号、同:l
、615,506号。Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3,062,653, No. 3,127,
No. 269, Ill., No. 476, No. 3,419.
.. Co No. 91, same: l, 519,429, same 3.558
.. No. 119, same, 51112. : No. 122, same: l
, No. 615,506.
同3,834,908号、同3,891,445号、西
独特許1,810.464号、西独特許出願(OL S
) 2,408,565号、同2,417,945
号、同2,418,959号、同2,424.467号
、特公昭40−6031号、特開昭51−20826号
、同52−58922号、同49−129538号、同
49−74027号、同50−159336号、同52
−42121号、同49−74028号、同50−60
233号、同51−26541号、同53−55122
号、特願昭55−110943号等に記載されたものを
挙げることができる。No. 3,834,908, No. 3,891,445, West German Patent No. 1,810.464, West German Patent Application (OL S
) No. 2,408,565, No. 2,417,945
No. 2,418,959, No. 2,424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826/1982, No. 52-58922, No. 49-129538, No. 49-74027 , No. 50-159336, No. 52
-42121, 49-74028, 50-60
No. 233, No. 51-26541, No. 53-55122
and Japanese Patent Application No. 55-110943.
本発明において特に好ましく用いられるマゼンタカプラ
ーは2当量型カプラーであるが、処理安定性及び画像保
存性の上から最も好ましくは特願昭60−169226
号等に記載された下記一般式(XX)又は(XX)で示
されるマゼンタカプラーが本発明の効果を奏する上で有
用である。The magenta coupler particularly preferably used in the present invention is a 2-equivalent type coupler, but from the viewpoint of processing stability and image storage stability, it is most preferably
Magenta couplers represented by the following general formula (XX) or (XX) described in No. 1, etc. are useful in achieving the effects of the present invention.
一般式(XIX)
[式中、Zは含窒木裏素環を形成するに必要な非金属原
子群を表し、該Zにより形成される環は置換基を有して
もよい。Xは水素原子または発色現象主薬の酸化体との
反応により離脱しうる置換基を表す。またRは水素原子
または置換基を表す。]一般式(XX)
■
Ar
式中、Arはフェニル基てあり1置換されたフェニル基
を含む、YはN−ヒドロキシアルキル置換−p−フェニ
レンジアミン誘導体発色主薬の酸化体とカブリンクして
色素か形成されるときに離脱する基を表す。Rはアシル
アミノ基、アニリノ基、ウレイド基を表す。General Formula (XIX) [In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing wood ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a coloring agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula (XX) ■ Ar In the formula, Ar is a phenyl group and includes a monosubstituted phenyl group, and Y is an N-hydroxyalkyl-substituted p-phenylenediamine derivative that is linked with an oxidized form of a coloring agent to form a pigment. represents a group that leaves when a compound is formed. R represents an acylamino group, anilino group, or ureido group.
本発明のハロゲン化銀乳剤層、その他の写真構成層中に
は非拡散性DIR化合化合物シカラードマゼンタシアン
カプラー、ポリマーカプラー、拡散性DIR化合物等の
カプラーを併用してもよい、非拡散性DIR化合化合物
シカラードマゼンタシアンカプラーについては本出願人
による特願昭59−193611号の記載を、またポリ
マーカプラーについては本出願人による特願昭59−1
72151号の記載を各々参照できる。In the silver halide emulsion layer of the present invention and other photographic constituent layers, couplers such as a non-diffusible DIR compound, a sicard magenta cyan coupler, a polymer coupler, and a diffusible DIR compound may be used in combination. The chemical compound Sicard magenta cyan coupler is described in Japanese Patent Application No. 59-193611 by the present applicant, and the polymer coupler is described in Japanese Patent Application No. 59-198 by the present applicant.
72151 can be referred to.
本発明に使用できる上記カプラーを本発明の写真構成層
中に添加する方法は従前通りであり、また上記カプラー
の添加量は限定的ではないが、銀1モル当りI X 1
0−”〜5モルか好ましく、より好ましくはl x 1
0−2〜5 x 10−’である。The method of adding the above coupler that can be used in the present invention into the photographic constituent layer of the present invention is the same as before, and the amount of the above coupler added is not limited, but I x 1 per mole of silver.
0-” to 5 mol is preferable, more preferably l x 1
0-2 to 5 x 10-'.
本発明の感光材料には他に各種の写真用添加剤を含有せ
しめることがてきる1例えばリサーチ・ディスクロージ
ャー誌1764:1号に記載されているかぶり防止剤、
安定剤、紫外線吸収剤、色汚染防止剤、蛍光増白剤、色
画像褪色防止剤、帯電防止剤、硬膜剤、界面活性剤、可
塑剤、湿潤剤等を用いることかてきる。The light-sensitive material of the present invention may contain various other photographic additives.
Stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like may be used.
本発明のハロゲン化銀カラー写真感光材料において、乳
剤を調製するために用いられる親水性コロイドには、ゼ
ラチン、誘導体ゼラチン、ゼラチンと他の高分子とのグ
ラフトポリマー、アルブミン、カゼイン等の蛋白質、ヒ
ドロキシエチルセルロース誘導体、カルボキシメチルセ
ルロース等のセルロース誘導体、澱粉誘導体、ポリビニ
ルアルコール、ポリビニルイミダゾール、ポリアクリル
アミド等の単一あるいは共重合体の合成親水性高分子等
の任意のものが包含される。In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.
本発明のハロゲン化銀カラー写真感光材料の支持体とし
ては、例えばバライタ紙、ポリエチレン被覆紙、ポリプ
ロピレン合成紙、反射層を併設した。又は反射体を併用
する透明支持体、例えばガラス板、セルロースアセテー
ト、セルロースナイトレート又はポリエチレンテレフタ
レート等のポリエステルフィルム、ポリアミドフィルム
、ポリカーボネートフィルム、ポリスチレンフィルム等
が挙げられ、その他通常の透明支持体であってもよい、
これらの支持体は感光材料の使用目的に応じて適宜選択
される。Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a reflective layer. Or a transparent support used in combination with a reflector, such as a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and other ordinary transparent supports. Good too,
These supports are appropriately selected depending on the intended use of the photosensitive material.
本発明において用いられるハロゲン化銀乳剤層及びその
他の写真構成層の塗設には、ディッピング塗布、エアー
ドクター塗布、カーテン塗布、ホッパー塗布等種々の塗
布方法を用いることかてきる。また米国特許2,761
,791号、同2,941,898号に記載の方法によ
る2層以上の同時塗布法を用いることもてきる。The silver halide emulsion layer and other photographic constituent layers used in the present invention can be coated using various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941,898 may be used to coat two or more layers simultaneously.
本発明においては各乳剤層の塗設位置な任意に定めるこ
とができる0例えばフルカラーの印画紙用感光材料の場
合には、支持体側から順次青感性ハロゲン化銀乳剤層、
緑感性ハロゲン化銀乳剤層、赤感性ハロゲン化銀乳剤層
の配列とすることが好ましい、これらの感光性ハロゲン
化銀乳剤層は各々2以上の層から成っていてもよい。そ
して、これら全ての感光性乳剤層が実質的に塩臭化銀乳
剤から成るときに本発明の効果か大である。In the present invention, the coating position of each emulsion layer can be determined arbitrarily.For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion layer,
It is preferable to arrange a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. Each of these light-sensitive silver halide emulsion layers may consist of two or more layers. The effect of the present invention is most significant when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.
本発明の感光材料に3いて、目的に応じて適当な厚さの
中間層を設けることは任意であり、更にフィルタ一層、
カール防止層、保護層、アンチハレーション層等の種々
の居を構r&層として適宜組合せて用いることかてきる
。これらの構成層には結合剤として前記のような乳剤層
に用いることのできる親水性コロイドを同様に用いるこ
とができ、またその層中には前記の如き乳剤層中に含有
せしめることができる種々の写真用添加剤を含有せしめ
ることができる。In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as a structural layer. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.
[発明の効果]
本発明によれば、発色現像液を用いて低補充量で処理し
ても臭化物イオン濃度の変化を受けず常に一定の適正な
写真性能が長期に亘って維持でき、かつ得られた発色色
素や未発色部か長期に保存しても褪色したり変色したり
しない迅速で安定な感光材料の処理方法を提供すること
できる。更に又低公害化しうる処理方法を提供すること
できる。[Effects of the Invention] According to the present invention, even when processed using a color developing solution at a low replenishment amount, the bromide ion concentration does not change and constant appropriate photographic performance can be maintained over a long period of time. To provide a rapid and stable method for processing a photosensitive material in which colored dyes and uncolored areas do not fade or change color even when stored for a long period of time. Furthermore, a treatment method capable of reducing pollution can be provided.
[実施例コ
以下に本発明の具体的実施例を述べるか、本発明の実施
の態様はこれらに限定されない。[Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
実施例 l
ポリエチレンをラミネートした紙支持体上に、下記の各
層を支持体側より順次塗設し、ハロゲン化銀カラー写真
感光材料試料No、1〜25を作成した。Example 1 Silver halide color photographic light-sensitive material samples Nos. 1 to 25 were prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.
層1−−−1.2g/rn’のゼラチン、 0.:l
Og/rn’(銀換算、以下同じ)の青感性ハロゲン化
銀ゼラチン乳剤(ハロゲン化銀組成及び平均粒径は表1
に示す。) 、0.50g/rn’のジオクチルフタレ
ートに溶解した0、85g/rn’のイエローカプラー
(Y−■)を含有する青感性ハロゲン化銀乳剤層。Layer 1---1.2 g/rn' gelatin, 0. :l
Blue-sensitive silver halide gelatin emulsion of Og/rn' (in terms of silver, the same applies hereinafter) (silver halide composition and average grain size are shown in Table 1)
Shown below. ), a blue-sensitive silver halide emulsion layer containing 0.85 g/rn' of yellow coupler (Y-■) dissolved in 0.50 g/rn' dioctyl phthalate.
層2−−−0.70g /m’のゼラチン、lflog
/m’のイラジェーション防止染料(AI−1)、So
+g/rn’の(AI−2)からなる中間層。Layer 2---0.70 g/m' gelatin, lflog
/m' anti-irradiation dye (AI-1), So
Intermediate layer consisting of (AI-2) of +g/rn'.
層3−−− 1.25g/rn’のゼラチン、 O,:
lOg/ rn’の緑感性ハロゲン化銀ゼラチン乳剤(
ハロゲン化銀組成及びモ均粒径は表1に示す。) 、
Q、:lOg/rrr’のジオクチルフタレートに溶解
した0、62g/m’のマゼンタカプラー(M−1)及
びジブチルフタレートに溶解した0、04g/m’の酸
化防止剤(AO−1)を含有する緑感性ハロゲン化銀乳
剤層。Layer 3---1.25g/rn' gelatin, O,:
lOg/rn' green-sensitive silver halide gelatin emulsion (
The silver halide composition and average grain size are shown in Table 1. ),
Q: Contains 0.62 g/m' of magenta coupler (M-1) dissolved in lOg/rrr' of dioctyl phthalate and 0.04 g/m' of antioxidant (AO-1) dissolved in dibutyl phthalate. green-sensitive silver halide emulsion layer.
層4・・・1.2g/rn’のゼラチン及びジブチルフ
タレートに溶解した0、O5g/rn’の色にごり防止
剤(As−1)からなる中間層。Layer 4: Intermediate layer consisting of gelatin at 1.2 g/rn' and anti-tarnishing agent (As-1) at 0,05 g/rn' dissolved in dibutyl phthalate.
層5−−−1.4g/rn’のゼラチン、 0.25g
/rr+′の赤感性ハロゲン化銀ゼラチン乳剤(ハロゲ
ン化銀組成及び平均粒径は表1に示す、)、 0.20
g/m’のジオクチルフタレートに溶解した0、45g
/rn’のシアンカプラー(C−1)及び0.15g/
ゴのシアンカプラー(C−2)を含有する赤感性ハロゲ
ン化銀乳剤層。Layer 5---1.4g/rn' gelatin, 0.25g
/rr+' red-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.20
0.45 g dissolved in g/m' dioctyl phthalate
/rn' cyan coupler (C-1) and 0.15g/
A red-sensitive silver halide emulsion layer containing a black cyan coupler (C-2).
層6・・・0.50g /rn’のゼラチン及び紫外線
吸収剤(UV−1)を含有する保護層。Layer 6: Protective layer containing 0.50 g/rn' of gelatin and ultraviolet absorber (UV-1).
尚、青感性ハロゲン化銀乳剤層、緑感性ハロゲン化銀乳
剤層、赤感性ハロゲン化銀乳剤層それぞれのハロゲン化
銀は一般的増感色素により色増加したものを使用した。The silver halide in each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer was one whose color had been increased by a general sensitizing dye.
(Y−1)
t
t
(1)・(示化合狗C−に)
(U−2)
t
(AI−1)
Nap3SCH2NHO0H
(AI−2)
(AO−1)
H
(As−+)
(UV−1)
05H,、(t)
なお、硬膜剤として、2.4−ジクロロ−6−ヒトロキ
シーS−t−リアジンナトリウムを層2.4及び6中に
、それぞれゼラチンIg当り0.02:Igになるよう
に添加し、乾燥後下記発色現像液を用いて30℃にてゼ
ラチン膜*111速度TI/2を測定した結果約6秒で
あった。測定はレベンゾンy!1膨潤度計を用いた。(Y-1) t t (1)・(Indicative dog C-) (U-2) t (AI-1) Nap3SCH2NHO0H (AI-2) (AO-1) H (As-+) (UV- 1) 05H,, (t) As a hardening agent, 2.4-dichloro-6-hydroxysodium S-t-riazine was added in layers 2.4 and 6 at a rate of 0.02 per gelatin Ig, respectively. After drying, the gelatin film*111 speed TI/2 was measured at 30°C using the following color developing solution, and the result was about 6 seconds. Measured using Lebenzon Y! 1. A swelling degree meter was used.
表1に示す感光材料試料No、1〜25各々を光学ウェ
ッジを通して露光後、次の工程て処理した。Each of the photosensitive material samples Nos. 1 to 25 shown in Table 1 was exposed through an optical wedge and then processed in the following steps.
処理工程(38℃)
発色現像 150秒
漂白定着 60秒
水洗 60秒
乾燥 60〜80℃ 120秒各処理液
の組成は下記の通りである。Processing steps (38°C) Color development 150 seconds Bleach-fixing 60 seconds Washing 60 seconds Drying 60-80°C 120 seconds The composition of each processing solution is as follows.
[発色現像液]
塩化ナトリウム 1.0g亜硫酸
カリウム 2.0gトリエタノー
ルアミン 2.0g発色現像主薬(下記
に示す) 0.030モルl−ヒドロキシエチリ
デン−1,1−ジホスホン酸(60%水溶液)
1.5a+交塩化マグネシウム
0.3g炭酸カリウム
32gKaycoll−PK−Conc(ケイコール−
PK−rンク)(蛍光増白剤、新日曹化工社製)
2m文純水を加えて1Mとし20%水酸化カリウム又
は10%希硫酸でpH=lO115に調整する。[Color developer] Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g Color developing agent (shown below) 0.030 mol l-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution)
1.5a+magnesium exchange chloride
0.3g potassium carbonate
32gKaycoll-PK-Conc
PK-rink) (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.)
Add 2M pure water to make it 1M, and adjust the pH to 115 with 20% potassium hydroxide or 10% dilute sulfuric acid.
[PM白定着液]
純水 550a文エチレ
ンジアミン四酢酸鉄(TI[)
アンモニウム塩 65gチオ硫酸
アンモニウム(70%水溶液)85g亜硫酸水素ナトリ
ウム 10gメタ重亜硫酸ナトリウム
2gエチレンジアミン四酢酸−2ナトリウ
ム20g純水を加えて141とし、アンモニア水又は希
硫酸にてpH= 7.0に調整する。[PM white fixer] Pure water 550a Iron ethylenediaminetetraacetate (TI) Ammonium salt 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium bisulfite 10g Sodium metabisulfite
Add 2g ethylenediaminetetraacetic acid-disodium 20g pure water to make 141, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.
別に、上記発色現像液の臭化カリウム濃度0.6g/l
を1.5g/又及び1.5g/見とすることのみ異なら
せた発色現像液を用いて、上記と同じ試料No、1〜2
5の各々を現像処理した。Separately, the potassium bromide concentration of the above color developer is 0.6 g/l.
The same sample No. 1 to 2 as above was prepared using a color developing solution with the only difference that the amount was 1.5 g/or and 1.5 g/view.
Each of No. 5 was subjected to development processing.
得られた各試料について常法によってセンシトメトリー
を行った。臭化カリウム濃度0.6g/ lのときの各
試料の濃度1.0付近の露光域の濃度を100とし、臭
化カリウム濃度を変動させたときの濃度の動きを表1に
示した。尚発色濃度の比はシアン濃度のみを表1に示し
た。Sensitometry was performed on each sample obtained by a conventional method. When the potassium bromide concentration was 0.6 g/l, the concentration of each sample in the exposed region around the concentration of 1.0 was set as 100, and Table 1 shows the concentration changes when the potassium bromide concentration was varied. As for the color density ratio, only the cyan density is shown in Table 1.
[発色現像主薬]
現像主薬(例示化合物(1)の硫酸塩)とCD−3の混
合物てモル比は
例示化合物(1) : CD−3= 1 : 1[C
D−3]
: 3 / 2 H2SO4・ト■20表1の結果か
らも明らかな通り、ハロゲン化銀か実質的に塩臭化銀て
ない場合の試料No、lないしNo、I2に比べ、実質
的に塩臭化銀である場合の試料No、l:lないしNo
、25は発色現像液中の臭化物イオン濃度かO,6gl
交、 1.5g/i、3.5g/文と変化しても発色濃
度にあまり変化かみられず処理安定性か高いことがわか
る。尚、表1は臭化物イオン濃度が高くなるにつれ補充
量か少ない量で処理されたことを示しているため1本発
明処理ては補充量を著しく少なくてきることを示してい
る。[Color developing agent] A mixture of a developing agent (sulfate of exemplified compound (1)) and CD-3, the molar ratio of which is exemplified compound (1): CD-3 = 1: 1 [C
D-3]: 3/2 H2SO4・T ■20 As is clear from the results in Table 1, compared to Samples No. 1 to No. 12, which contain substantially no silver halide or silver chlorobromide, Sample No., l:l or No. when it is silver chlorobromide
, 25 is the bromide ion concentration in the color developer, O, 6gl
It can be seen that even when changing from 1.5 g/i to 3.5 g/i, there was not much change in color density, indicating high processing stability. Table 1 shows that as the bromide ion concentration increases, the amount of replenishment is reduced, which indicates that the amount of replenishment can be significantly reduced in the treatment of the present invention.
実施例 2
実施例1のハロゲン化銀写真感光材料試料No、21を
用いて実施例1の発色現像主薬又はペンシルアルコール
を表2のようにした以外は同じ処理液を用いて同様に露
光を与え現像処理した。処理温度は38℃にて行った。Example 2 Using the silver halide photographic light-sensitive material sample No. 21 of Example 1, exposure was carried out in the same manner using the same processing solution as in Example 1 except that the color developing agent or pencil alcohol was changed as shown in Table 2. Developed. The treatment temperature was 38°C.
得られた試料を75°C相対湿度90%R11に保存し
シアン濃度の変化を測定した。その際発色現像主薬トシ
てC[l−3を用い、発色現像液11当りベンジルアル
コールを20ni用いた場合の試料初期濃度1.0が約
0.3程度劣化したときの他の発色現像液て処理した試
料の同じ濃度域の濃度低下を測定し表2に示した。この
とき同じ試料の未露光部のイ缶曇1スティン濃度を測定
し同様に表2に示した。The obtained sample was stored at 75° C. and relative humidity 90% R11, and changes in cyan concentration were measured. At that time, when using the color developing agent Toshi C[l-3 and using 20 ni of benzyl alcohol per 11 color developing solutions, the sample initial concentration of 1.0 deteriorated by about 0.3. The concentration reduction in the same concentration range of the treated samples was measured and shown in Table 2. At this time, the 1-stain density of the unexposed portion of the same sample was measured and is also shown in Table 2.
又上記と同様に発色現像主薬としてCD−3を用い、ベ
ンジルアルコールを2hJl用いた場合の最大発色濃度
(D訃ajをlOOとしてそれぞれの試料の最大発色濃
度を測定した。Further, in the same manner as above, the maximum color density of each sample was measured using CD-3 as a color developing agent and 2 hJl of benzyl alcohol.
以下余白
表2の結果からも明らかな通り、ベンジルアルコールが
1oe12,20−と存在すれば発色現像主薬がCD−
3又はCD−4又はCD−3とCD−4の混合物であっ
ても退色性は余りかわらず特にCD−一4にベンジルア
ルコールを多量に用いると退色性が特に大きいことがわ
かる。このことは未露光部のスティン濃度(D m1n
)についてもいえる。As is clear from the results in Margin Table 2 below, if benzyl alcohol is present at 1oe12,20-, the color developing agent is CD-
3 or CD-4 or a mixture of CD-3 and CD-4, the discoloration property is not much different, and it can be seen that the discoloration property is particularly large when a large amount of benzyl alcohol is used in CD-14. This means that the stain density of the unexposed area (D m1n
).
ところがベンジルアルコールが5−以下の場合、特に2
+a12以下の場合、退色性及び未露光部のスティン濃
度(Dmin)も顕著に改良されている。このことは発
色現像主薬が特にCD−4の場合ベンジルアルコールに
よって膜中に残留しやすいということを示していると予
測される。However, when benzyl alcohol is 5- or less, especially 2-
In the case of +a12 or less, the fading property and stain density (Dmin) of the unexposed area are also significantly improved. This is predicted to indicate that the color developing agent, especially in the case of CD-4, tends to remain in the film due to benzyl alcohol.
又最大発色濃度についてもCD−3使用の場合ベンジル
アルコール量に大きく依存するが、CD−3/CD−4
=2/1程度ではベンジルアルコール量に大きく依存す
ることなく良好な発色濃度を示している。Also, the maximum color density depends largely on the amount of benzyl alcohol when using CD-3, but when CD-3/CD-4
When the ratio is about 2/1, good color density is exhibited without being greatly dependent on the amount of benzyl alcohol.
実施例3
実施例2の試料No、26 No、40を使用し、青、
緑、赤感性乳剤層の銀塗布量が実施例1と同じになるよ
うなハロゲン化銀量を用いて硬膜剤の添加量を種々に変
化させた試料を作成した。乾燥後の試料を前記発色現像
液を用い、レベンゾン型膨潤度計によって膜膨潤速度T
1/2を測定した。膜膨潤速度TI/2が2秒、5秒、
10秒、15秒、30秒、40秒、60秒となった試料
を選び実験に用いた。この試料を実施例1と同様に露光
を与え実施例1と同じ処理液にて処理した。38℃にて
10分間発色現像したときの最大濃度をlOOとし、最
大濃度が80となるに必要な処理時間を表3に示した。Example 3 Using sample No. 26 No. 40 of Example 2, blue,
Samples were prepared in which the amount of silver halide in the green and red-sensitive emulsion layers was the same as in Example 1, and the amount of hardener added was varied. The membrane swelling rate T of the sample after drying was measured using the above-mentioned color developer using a Lebenzon type swelling meter.
1/2 was measured. Membrane swelling rate TI/2 is 2 seconds, 5 seconds,
Samples that took 10 seconds, 15 seconds, 30 seconds, 40 seconds, and 60 seconds were selected and used in the experiment. This sample was exposed to light in the same manner as in Example 1 and treated with the same processing solution as in Example 1. The maximum density when color development was performed at 38° C. for 10 minutes was defined as lOO, and the processing time required to reach the maximum density of 80 is shown in Table 3.
この結果は現像完了点の迅速性を示している。This result shows the rapidity of the development completion point.
以下余白
表3
表3の結果からも明らかな通り、本発明の発色現像主薬
を用い、かつ膜膨潤速度T1/2が30秒以下の場合に
は極めて速い現像完了(到達)時間を示し、迅速現像処
理が可能であることがわかる。Margin Table 3 below As is clear from the results in Table 3, when the color developing agent of the present invention is used and the film swelling rate T1/2 is 30 seconds or less, the development completion time is extremely fast, and the development is completed quickly. It can be seen that development processing is possible.
実施例4
実施例1で用いた感光材料のシアンカプラー(例示化合
物C−8)にかえ本発明の例示化合物C−2、C−36
−1C−86、C−111及び比較カプラー(下記)に
ついて実施例2のNo、39の処理方法で評価した。結
果は表4に示す、丸\゛し全を業場主濃っCD−3fA
c(Cr)−午′l七lレヒヒ1工1;1静した。Example 4 Exemplary compounds C-2 and C-36 of the present invention were used in place of the cyan coupler (exemplified compound C-8) of the photosensitive material used in Example 1.
-1C-86, C-111 and comparative couplers (described below) were evaluated using the treatment method No. 39 of Example 2. The results are shown in Table 4.
c(Cr)-17lLehich1tech1;1quiet.
r:−レ佼ンアy々フ)−
〇CH2CH25o2cH3
表4の結果より明らかな様に、本発明のシアンカプラー
を用いた場合、退色性及び未露光部のシアンスティン(
D akin)が改良されている。r:-RayenAyyyf)- 〇CH2CH25o2cH3 As is clear from the results in Table 4, when the cyan coupler of the present invention is used, the fading property and the cyan stain in the unexposed area (
Dakin) has been improved.
実施例5
実施例1で用いた水洗処理の代わりに水洗代替安定液(
下記組成)を用いて実施例2と同様の評価を行ったが、
水洗処理に比べ退色性は約0.03、未露光部のスティ
ンは0.01〜0.02改良された。Example 5 Instead of the water washing treatment used in Example 1, a water washing substitute stabilizing solution (
The same evaluation as in Example 2 was conducted using the following composition, but
Compared to washing with water, the fading property was improved by about 0.03, and the stain in the unexposed area was improved by 0.01 to 0.02.
5−クロロ−2−メチル−4〜
イソチアゾリン−3−オン 0.02g2−メ
チル−4−イソチアゾリン
=3−オン 0.02gエ
チレングリコール 1g2 オクチル−
4−イソチアゾリン
−3−オン 0.01g例
示キレート剤(1112) 3.0gB
I CQコ(45%水溶液) 0.6
5gアンモニア水
(水酸化アンモニウム25%水溶液) 3.0g例示
キレート剤(44) 1.5g水で!Q
とし、Ht S O4とKOHでpH8,0とする。5-Chloro-2-methyl-4~Isothiazolin-3-one 0.02g2-Methyl-4-isothiazolin=3-one 0.02gEthylene glycol 1g2 Octyl-
4-Isothiazolin-3-one 0.01g Exemplary chelating agent (1112) 3.0gB
I CQco (45% aqueous solution) 0.6
5g ammonia water (ammonium hydroxide 25% aqueous solution) 3.0g exemplary chelating agent (44) 1.5g water! Q
and adjust the pH to 8.0 with HtSO4 and KOH.
実施例6
実施例1で用いたマゼンタカプラーの代りに下記マゼン
タカプラーを用い比較として下記比較マゼンタカプラー
を用いて実施例5と同様の評価を行ったが、比較マゼン
タカプラーに比べ実施例1及び下記マゼンタカプラーを
用いた場合、イエロースティンを減少させるのに効果が
あった。Example 6 The following magenta coupler was used instead of the magenta coupler used in Example 1, and the same evaluation as in Example 5 was performed using the following comparative magenta coupler as a comparison, but compared to the comparative magenta coupler, Example 1 and the following When a magenta coupler was used, it was effective in reducing yellow stain.
t 〔比較マゼンタカプラー〕 t [Comparison magenta coupler]
第1図はバインダーの膜膨潤速度T I/2を示すグラ
フである。FIG. 1 is a graph showing the membrane swelling rate T I/2 of the binder.
Claims (13)
方法において、少なくとも1層の感光性乳剤層のハロゲ
ン化銀乳剤が実質的に塩臭化銀乳剤であり、バインダー
の膜膨潤速度T1/2が30秒以下で、かつ下記一般式
( I )、(II)又は(III)で表されるシアンカプラー
を少なくとも1種含有するハロゲン化銀カラー写真感光
材料を、N−ヒドロキシアルキル置換−p−フェニレン
ジアミン誘導体を発色現像液中のp−フェニレンジアミ
ン発色現像主薬に対し30モル%以上含有し、かつ実質
的にベンジルアルコールを含有しない発色現像液を用い
て30℃以上で現像処理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の処理方法。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 式中、R及びR_1は一方が水素原子であり、他方が少
なくとも炭素数2〜12の直鎖又は分岐のアルキル基で
あり、Xは水素原子又はN−ヒドロキシアルキル置換−
p−フェニレンジアミン系発色現像主薬の酸化体とのカ
プリング反応により離脱しうる基を表し、R_2はバラ
スト基を表す。 一般式〔II〕 ▲数式、化学式、表等があります▼ 一般式〔III〕 ▲数式、化学式、表等があります▼ 式中、Yは−COR_4、 ▲数式、化学式、表等があります▼、−SO_2R_4
、▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、−COHHCOR
_4または−COHHSO_2R_4(但しR_4はア
ルキル基、アルケニル基、シクロアルキル基、アリール
基またはヘテロ環基を表し、R_5は水素原子、アルキ
ル基、アルケニル基、シクロアルキル基、アリール基ま
たはヘテロ環基を表し、R_4とR_5とが互いに結合
して5〜6員のヘテロ環を形成してもよい。)を表し、
R_3はバラスト基を表し、Zは水素原子又はN−ヒド
ロキシアルキル置換−p−フェニレンジアミン系発色現
像主薬の酸化体とのカプリング反応により離脱しうる基
を表す。(1) In a method for developing a silver halide color photographic light-sensitive material, the silver halide emulsion in at least one photosensitive emulsion layer is substantially a silver chlorobromide emulsion, and the film swelling rate of the binder is T1/2. is 30 seconds or less and contains at least one cyan coupler represented by the following general formula (I), (II) or (III). A color developing solution containing a phenylenediamine derivative at 30 mol % or more based on p-phenylenediamine color developing agent in a color developer and substantially free of benzyl alcohol is used for development processing at 30°C or higher. A method for processing a silver halide color photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, one of R and R_1 is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is Hydrogen atom or N-hydroxyalkyl substitution-
R_2 represents a ballast group. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, Y is -COR_4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, - SO_2R_4
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COHHCOR
_4 or -COHHSO_2R_4 (where R_4 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, and R_5 represents a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group) , R_4 and R_5 may combine with each other to form a 5- to 6-membered heterocycle.),
R_3 represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an N-hydroxyalkyl-substituted p-phenylenediamine color developing agent.
剤が、臭化銀含有率が90モル%以下の塩臭化銀乳剤で
あることを特徴とする特許請求の範囲第1項記載のハロ
ゲン化銀カラー写真感光材料の処理方法。(2) The silver halide emulsion of at least one photosensitive emulsion layer is a silver chlorobromide emulsion having a silver bromide content of 90 mol% or less. A method for processing silver halide color photographic materials.
臭化物を含有することを特徴とする特許請求の範囲第1
項又は第2項のいずれかに記載のハロゲン化銀カラー写
真感光材料の処理方法。(3) Claim 1, characterized in that the color developer contains at least 5 x 10^-^3 moles of bromide.
2. A method for processing a silver halide color photographic light-sensitive material according to either item 1 or 2.
る化合物を含有することを特徴とする特許請求の範囲第
1項〜第3項のいずれかに記載のハロゲン化銀カラー写
真感光材料の処理方法。 一般式(IV)A−COOM 一般式(V)▲数式、化学式、表等があります▼ 一般式(VI)▲数式、化学式、表等があります▼ [式中、Aは一価の有機残基、B、B_1及びB_2は
各々一価の有機残基もしくは原子を表わし、無機物であ
ってもよいし、有機物であってもよい。 Dは置換基を有してもよい芳香族環、複素環を形成する
に必要な非金属原子群を表し、Mは水素原子又はアルカ
リ金属原子を表す。](4) The silver halide according to any one of claims 1 to 3, wherein the color developer contains a compound represented by the following general formulas (IV) to (VI). A method of processing color photographic materials. General formula (IV) A-COOM General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is a monovalent organic residue , B, B_1 and B_2 each represent a monovalent organic residue or atom, and may be an inorganic substance or an organic substance. D represents a nonmetallic atom group necessary to form an aromatic ring or heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. ]
膜膨潤速度T1/2が20秒以下であることを特徴とす
る特許請求の範囲第1項〜第4項のいずれかに記載のハ
ロゲン化銀カラー写真感光材料の処理方法。(5) The halogen according to any one of claims 1 to 4, wherein the film swelling rate T1/2 of the photographic constituent layer of the silver halide color photographic light-sensitive material is 20 seconds or less. Processing method for silver chemical color photographic materials.
アミン系発色現像主薬が発色現像液中のp−フェニレン
ジアミン発色現像主薬の■量に対し40モル%以上含有
することを特徴とする特許請求の範囲第1項〜第5項の
いずれかに記載のハロゲン化銀カラー写真感光材料の処
理方法、(6) A claim characterized in that the N-hydroxyalkyl-substituted p-phenylenediamine color developing agent is contained in an amount of 40 mol% or more based on the amount of the p-phenylenediamine color developing agent in the color developer. A method for processing a silver halide color photographic material according to any one of items 1 to 5;
1l当り5ml以下であることを特徴とする特許請求の
範囲第1項〜第6項のいずれかに記載のハロゲン化銀カ
ラー写真感光材料の処理方法。(7) The silver halide color photographic light-sensitive material according to any one of claims 1 to 6, characterized in that the amount of benzyl alcohol in the color developer is 5 ml or less per 1 liter of the color developer. Processing method.
1l当り2ml以下であることを特徴とする特許請求の
範囲第1項〜第7項のいずれかに記載のハロゲン化銀カ
ラー写真感光材料の処理方法。(8) The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the benzyl alcohol in the color developer is 2 ml or less per 1 liter of the color developer. Processing method.
現像液で処理することを特徴とする特許請求の範囲第3
項記載のハロゲン化銀カラー写真感光材料の処理方法。(9) Claim 3, characterized in that processing is performed with a color developing solution containing 1 x 10^-^2 moles or more of bromide.
A method for processing a silver halide color photographic light-sensitive material as described in .
る発色現像液で処理することを特徴とする特許請求の範
囲第3項記載のハロゲン化銀カラー写真感光材料の処理
方法。(10) A method for processing a silver halide color photographic light-sensitive material according to claim 3, which comprises processing with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide.
ジアミン系発色現像主薬が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塩である
こと特徴とする特許請求の範囲第1項〜第10項のいず
れかに記載のハロゲン化銀カラー写真感光材料の処理方
法。(11) N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent is 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline salt.The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 10.
が250ml/m^2以下で処理すること特徴とする特
許請求の範囲第1項〜第11項のいずれかに記載のハロ
ゲン化銀カラー写真感光材料の処理方法。(12) The silver halide color according to any one of claims 1 to 11, characterized in that the color photographic material is processed at a replenishment amount of 250 ml/m^2 or less during continuous processing. Method of processing photographic materials.
が200ml/m^2以下で処理すること特徴とする特
許請求の範囲第12項記載のハロゲン化銀カラー写真感
光材料の処理方法。(13) A method for processing a silver halide color photographic material according to claim 12, wherein the color photographic material is processed at a replenishment amount of 200 ml/m^2 or less during continuous processing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP976586A JPH0675179B2 (en) | 1986-01-20 | 1986-01-20 | Processing method of silver halide color photographic light-sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP976586A JPH0675179B2 (en) | 1986-01-20 | 1986-01-20 | Processing method of silver halide color photographic light-sensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62166336A true JPS62166336A (en) | 1987-07-22 |
JPH0675179B2 JPH0675179B2 (en) | 1994-09-21 |
Family
ID=11729362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP976586A Expired - Fee Related JPH0675179B2 (en) | 1986-01-20 | 1986-01-20 | Processing method of silver halide color photographic light-sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0675179B2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62172349A (en) * | 1986-01-24 | 1987-07-29 | Fuji Photo Film Co Ltd | Color image forming method |
JPS62276546A (en) * | 1986-05-23 | 1987-12-01 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
JPS6311941A (en) * | 1986-01-23 | 1988-01-19 | Fuji Photo Film Co Ltd | Processing method for silver halide color photosensitive material |
JPS63100454A (en) * | 1986-01-23 | 1988-05-02 | Fuji Photo Film Co Ltd | Color image forming method |
JPH0268546A (en) * | 1988-09-02 | 1990-03-08 | Konica Corp | Image forming method for silver halide color photographic sensitive material |
JPH0321947A (en) * | 1989-06-19 | 1991-01-30 | Fuji Photo Film Co Ltd | Ultra high speed processable color photographic sensitive material and color image forming method |
-
1986
- 1986-01-20 JP JP976586A patent/JPH0675179B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6311941A (en) * | 1986-01-23 | 1988-01-19 | Fuji Photo Film Co Ltd | Processing method for silver halide color photosensitive material |
JPS63100454A (en) * | 1986-01-23 | 1988-05-02 | Fuji Photo Film Co Ltd | Color image forming method |
JPS62172349A (en) * | 1986-01-24 | 1987-07-29 | Fuji Photo Film Co Ltd | Color image forming method |
JPS62276546A (en) * | 1986-05-23 | 1987-12-01 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
JPH0268546A (en) * | 1988-09-02 | 1990-03-08 | Konica Corp | Image forming method for silver halide color photographic sensitive material |
JPH0321947A (en) * | 1989-06-19 | 1991-01-30 | Fuji Photo Film Co Ltd | Ultra high speed processable color photographic sensitive material and color image forming method |
Also Published As
Publication number | Publication date |
---|---|
JPH0675179B2 (en) | 1994-09-21 |
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