JP2878484B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents
Processing method of silver halide color photographic light-sensitive materialInfo
- Publication number
- JP2878484B2 JP2878484B2 JP15399591A JP15399591A JP2878484B2 JP 2878484 B2 JP2878484 B2 JP 2878484B2 JP 15399591 A JP15399591 A JP 15399591A JP 15399591 A JP15399591 A JP 15399591A JP 2878484 B2 JP2878484 B2 JP 2878484B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- color developing
- silver halide
- solution
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 40
- -1 silver halide Chemical class 0.000 title claims description 36
- 229910052709 silver Inorganic materials 0.000 title claims description 31
- 239000004332 silver Substances 0.000 title claims description 31
- 238000003672 processing method Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 238000012545 processing Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 40
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 84
- 239000004094 surface-active agent Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 16
- 238000011161 development Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- 239000000693 micelle Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZFXPBTZXYNIAJW-UHFFFAOYSA-N 4-[2-(2-phenylethenyl)phenyl]triazine Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1C1=CC=NN=N1 ZFXPBTZXYNIAJW-UHFFFAOYSA-N 0.000 description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 102100033183 Epithelial membrane protein 1 Human genes 0.000 description 4
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000002704 decyl 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])* 0.000 description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-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
- 108010008594 epithelial membrane protein-1 Proteins 0.000 description 4
- 239000006081 fluorescent whitening agent Substances 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001400 nonyl 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])[H] 0.000 description 4
- 125000002347 octyl 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])[H] 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000002948 undecyl 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])[H] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- DNRUPOAHVJBDJE-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine;hydrochloride Chemical compound Cl.CN(C)C1=CC=C(N(C)C)C=C1 DNRUPOAHVJBDJE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 102100033176 Epithelial membrane protein 2 Human genes 0.000 description 1
- 108050009423 Epithelial membrane protein 2 Proteins 0.000 description 1
- 102100030146 Epithelial membrane protein 3 Human genes 0.000 description 1
- 101710143764 Epithelial membrane protein 3 Proteins 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WZULOGZDECNCPK-UHFFFAOYSA-L S(=O)([O-])O.[K+].[Cl-].[K+] Chemical compound S(=O)([O-])O.[K+].[Cl-].[K+] WZULOGZDECNCPK-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 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
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])[H] 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はハロゲン化銀カラー写真
感光材料の処理方法に関するものであり、詳しくは発色
現像補充液中に高濃度の発色現像主薬を溶解しても析出
を起こさず、従来よりも少ない補充量で迅速かつ安定な
現像処理を行うことができるハロゲン化銀写真感光材料
の処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically , the present invention relates to a method for dissolving a high concentration of a color developing agent in a color developing replenisher without causing precipitation. A silver halide photographic material that can perform rapid and stable development with less replenishment
In the processing method.
【０００２】[0002]
【発明の背景】一般にハロゲン化銀カラー写真感光材料
を処理してカラー写真画像を形成するには、該感光材料
を像様に露光し、パラフェニレンジアミン系発色現像主
薬を含有する発色現像液で現像する。この際、ハロゲン
化銀は銀に還元されると同時に現像主薬が酸化され、生
成した該酸化物と感光材料中のカプラーとが結合し、現
像された銀に対応する像様の色素が形成される。BACKGROUND OF THE INVENTION Generally, in order to form a color photographic image by processing a silver halide color photographic light-sensitive material, the light-sensitive material is exposed imagewise, and is exposed to a color developer containing a paraphenylenediamine-based color developing agent. develop. At this time, the silver halide is reduced to silver and the developing agent is oxidized at the same time as the developing agent is oxidized, and the generated oxide and the coupler in the photosensitive material are combined to form an image-like dye corresponding to the developed silver. You.
【０００３】発色現像液では、写真感光材料を現像処理
することによって、感光材料中から溶出する現像抑制物
質が蓄積する一方、発色現像主薬は消費され、その成分
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的に処理する現像処理
方法においては、成分濃度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の濃度
範囲に保つための手段が必要である。In a color developing solution, when a photographic light-sensitive material is subjected to development processing, a development inhibitor eluted from the light-sensitive material accumulates, while a color developing agent is consumed and its component concentration decreases. Therefore, in a development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic processor or the like, the components of the color developing solution are confined within a certain concentration range in order to avoid a change in development finish characteristics due to a change in the component concentration. Means are needed to keep
【０００４】かかる手段として通常は不足成分を補い、
不要な増加成分を希釈するための補充液を補充する方法
が採られている。この補充液の補充により必然的に多量
のオーバーフローが生じ、廃棄されるために、この方法
は経済上および公害上の大きな問題となっている。[0004] As such means, usually, the shortage component is supplemented,
A method of replenishing a replenisher for diluting unnecessary increasing components has been adopted. The replenishment of this replenisher inevitably results in a large amount of overflow and is discarded, so that this method is a major economic and pollution problem.
【０００５】それ故に近年では前記オーバーフロー液を
減少させるため、イオン交換樹脂や電気透析法により現
像液を再生する再生法、濃厚低補充法、あるいはオーバ
ーフローに再生剤を加え再び補充液として用いる方法等
が提案され実用化されている。[0005] Therefore, in recent years, in order to reduce the overflow solution, a regeneration method for regenerating the developer by ion exchange resin or electrodialysis, a concentrated low replenishment method, a method of adding a regenerating agent to the overflow and using it as a replenisher again, etc. Has been proposed and put into practical use.
【０００６】現像液の再生は、不要蓄積成分である臭化
物を除去して不足成分を補うことによって行われるが、
この方法（イオン交換樹脂法と電気透析法）は化学分析
によって現像液成分を定量し一定ならしめないと感光材
料の現像処理特性が損なわれるという欠点があり、煩雑
な管理を必要とするために、特別なスキルを持たない小
規模な現像所やミニラボ等では導入がほとんど不可能で
ある。さらにイニシャルコストが極めて高い欠点もあ
る。[0006] Regeneration of the developer is carried out by removing bromide which is an unnecessary accumulation component to make up for the deficient component.
This method (ion-exchange resin method and electrodialysis method) has a drawback that the development processing characteristics of the photosensitive material are impaired unless the developer components are quantified and made constant by chemical analysis. It is almost impossible to introduce it in small-scale laboratories and mini-labs without special skills. There is also a disadvantage that the initial cost is extremely high.
【０００７】さらにオーバーフロー液に再生剤を加え補
充液として再生使用する方法は特にスキルはいらないも
ののストックタンク等のスペースが必要であり、さらに
現像所にとっては煩雑である欠点を有しており、この方
法もミニラボ等への導入は難しい。Further, the method of adding a regenerant to the overflow solution and reusing it as a replenisher requires no special skills, but requires a space such as a stock tank, and has the disadvantage that it is complicated for a developer. It is difficult to introduce the method to mini labs.
【０００８】これに対し、感光材料の処理によって消費
される現像液成分を濃厚化し少量の補充液で補充する濃
厚低補充法は、特に新たな装置を必要とせず、処理管理
も容易なことから、ミニラボ等の小規模ラボには極めて
適した方法といえる。On the other hand, the concentrated low replenishment method in which the developer component consumed by processing of the light-sensitive material is concentrated and replenished with a small amount of replenisher does not require a new device, and the process management is easy. It is a very suitable method for small labs such as mini labs.
【０００９】また、近年の当業界の動向として、カラー
写真感光材料の迅速処理への要求が高まっている。即
ち、カラー写真感光材料は各現像所に設置された自動現
像装置によって処理されているが、現像を受け付けたそ
の日のうちに現像処理して顧客に現像済みの写真製品を
渡すことが要求され、近時では受付から数時間で行うこ
とさえ要求される。さらに、写真店の店頭での短時間処
理を売りものにするいわゆるミニラボが広まっており、
この傾向は益々強まってきている。[0009] As a recent trend in the industry, there is an increasing demand for rapid processing of color photographic materials. In other words, the color photographic light-sensitive material is processed by an automatic developing device installed in each developing station, but it is required to perform the developing process on the day of receiving the development and deliver the developed photographic product to the customer, In recent years, it is even required to do it within hours of reception. In addition, so-called mini labs that sell short-time processing at photo shop stores are becoming popular,
This trend is getting stronger.
【００１０】現像処理を短時間で行うための技術として
は、発色現像液の処理温度を上げる、ｐＨを上げる、現
像促進剤を加える、発色現像主薬の濃度を高める等の方
法が知られている。As a technique for performing the development processing in a short time, there are known methods of increasing the processing temperature of the color developing solution, increasing the pH, adding a development accelerator, and increasing the concentration of the color developing agent. .
【００１１】処理温度をあげる方法は簡便であるが、蒸
発による処理液の濃縮が起こり、写真性能に重大な影響
を与える。仮に蒸発を防止する手段を講じたとしても、
液中の発色現像主薬は空気による酸化を受けやすいため
に、温度により酸化反応が促進され、タール状の酸化物
による処理槽や搬送ローラーの汚染、さらには処理した
カラー写真感光材料の汚染が発生する。Although the method of raising the processing temperature is simple, concentration of the processing solution due to evaporation occurs, which seriously affects photographic performance. Even if you take measures to prevent evaporation,
Since the color developing agent in the solution is easily oxidized by air, the oxidation reaction is accelerated by the temperature, and contamination of the processing tank and transport rollers by the tar-like oxide, and further, contamination of the processed color photographic light-sensitive material occur. I do.
【００１２】発色現像液のｐＨを上げる方法では、ｐＨ
を一定に保つことが困難であり、ｐＨが徐々に低下する
ことから経時で安定した色素画像を得られない。In the method of increasing the pH of the color developing solution,
Is difficult to maintain constant, and the pH gradually decreases, so that a stable dye image cannot be obtained over time.
【００１３】さらにベンジルアルコールに代表される現
像促進剤の使用は、公害上の問題から好ましくない。Further, the use of a development accelerator represented by benzyl alcohol is not preferred because of the problem of pollution.
【００１４】以上の観点から、迅速処理を達成するため
には現像液中の発色現像主薬を高濃度化し、カラー感光
材料中のカプラーとの反応性を高めることが最も有効で
ある。自動現像機による連続処理で高濃度の発色現像液
を維持するためには、多量の補充を行う必要があるが、
多量の補充は結局オーバーフローによる廃液量を増大さ
せる結果となり、前述のように公害上および経済上から
好ましくない。From the above viewpoints, to achieve rapid processing, it is most effective to increase the concentration of the color developing agent in the developer and to increase the reactivity with the coupler in the color photographic material. In order to maintain a high concentration of color developer in continuous processing by an automatic processor, a large amount of replenishment must be performed,
A large amount of replenishment eventually results in an increase in the amount of waste liquid due to overflow, which is undesirable from the viewpoint of pollution and economy as described above.
【００１５】このため高濃度に発色現像主薬を溶解した
補充液が必要となった。しかしながら、カラー写真感光
材料の現像に通常用いられる発色現像主薬は、色素形成
に必要なｐＨ領域において溶解度に限界があり、一定濃
度以上を添加した場合には現像主薬が析出するという問
題がある。Therefore, a replenisher in which a color developing agent is dissolved at a high concentration is required. However, the color developing agents usually used for developing color photographic light-sensitive materials have a limit in solubility in a pH range necessary for dye formation, and there is a problem that when a certain concentration or more is added, the developing agents are precipitated.
【００１６】このように処理時間の短縮及び補充量低減
のために、現像主薬を高濃度に溶解した発色現像液を用
いてカラー写真感光材料を処理したときには、イエロー
ステインの発生と現像主薬の析出が起こることがわかっ
た。また現像主薬の析出によって、補充タンクやポンプ
等を汚染し、写真処理の安定性を阻害することがわかっ
た。In order to shorten the processing time and reduce the replenishment amount, when a color photographic light-sensitive material is processed using a color developing solution in which a developing agent is dissolved at a high concentration, generation of yellow stain and precipitation of the developing agent are caused. Was found to happen. It was also found that the precipitation of the developing agent contaminates the replenishment tank and the pump and inhibits the stability of photographic processing.
【００１７】従って、本発明の目的は、第１に発色現像
主薬の析出を起こさない発色現像液を用いるハロゲン化
銀カラー写真感光材料の処理方法を提供することであ
り、第２に迅速処理及び低補充処理を行っても、写真性
能が安定し、現像主薬が析出せず補充タンクやポンプ等
を汚染することがない発色現像液を用いるハロゲン化銀
カラー写真感光材料の処理方法を提供することである。Accordingly, an object of the present invention is to firstly provide a halogenated solution using a color developing solution which does not cause precipitation of a color developing agent .
Secondly, to provide a processing method for silver color photographic light-sensitive materials . Even when rapid processing and low replenishment processing are performed, photographic performance is stable, and a developing agent does not precipitate and contaminates a replenishment tank or a pump. Silver halide using colorless developing solution
An object of the present invention is to provide a method for processing a color photographic light-sensitive material .
【００１８】[0018]
【課題を解決するための手段】本発明者らは上記目的を
達成するため、鋭意検討を重ねた結果、本発明に至った
ものである。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have accomplished the present invention.
【００１９】即ち、本発明に係るハロゲン化銀カラー写
真感光材料の処理方法は、下記一般式［ＳＩ］または
［ＳＩＩ］で示される化合物の少なくとも１種を含有
し、かつ１０〜２００ｇ／ｌの芳香族スルホン酸または
その塩を少なくとも１種含有する発色現像液でハロゲン
化銀カラー写真感光材料を処理する方法であって、その
補充量がハロゲン化銀カラー写真感光材料１ｍ ２ 当り１
２０ｍｌ以下であることを特徴とする。 一般式 ［ＳＩ］That is, the method for processing a silver halide color photographic light-sensitive material according to the present invention comprises a compound containing at least one compound represented by the following general formula [SI] or [SII] and having a content of 10 to 200 g / l . Halogen in a color developer containing at least one aromatic sulfonic acid or a salt thereof
A method for processing silver halide color photographic light-sensitive material, the method comprising:
Amount replenishment silver halide color photographic material 1 m 2 per
It is characterized by being 20 ml or less. General formula [SI]
【００２０】[0020]
【化６】 ［式中、Ａは１価の有機基を表す。Ｂ及びＣはそれぞれEmbedded image [In the formula, A represents a monovalent organic group. B and C are respectively
【００２１】[0021]
【化７】 を表し、同一であっても異なっていてもよい（ただし、
ａ、ｂおよびｃは各々０、１、２または３、ｄは０また
は１であり、Ｙは水素原子または水酸基である）。ｍ及
びｎは１〜１００の整数を表す。Ｘは水素原子、アルキ
ル基、アラルキル基またはアリール基を表す。］ 一般式 ［ＳＩＩ］Embedded image And may be the same or different (provided that
a, b and c are each 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group). m and n represent an integer of 1 to 100. X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. General formula [SII]
【００２２】[0022]
【化８】 ［式中、Ｍはアルカリ金属、水素原子、アンモニウム塩
またはアルカノールアミン塩を表し、ｎは１〜１００の
整数であり、Ａは１価の有機基を表す。］Embedded image [In the formula, M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt, n is an integer of 1 to 100, and A represents a monovalent organic group. ]
【００２３】本発明は、前記芳香族スルホン酸またはそ
の塩が下記一般式［１］または［２］で示される化合物
であることを特徴とする請求項１記載のハロゲン化銀カ
ラー写真感光材料の処理方法である。 一般式［１］According to the present invention, the aromatic sulfonic acid or a salt thereof is a compound represented by the following general formula [1] or [2] . Processing method . General formula [1]
【００２４】[0024]
【００２５】[0025]
【化９】 ［式中、Ａ〜Ｆは、そのうちの少なくとも１つがスルホ
ン酸基またはスルホン酸塩であり、残りは水素原子、ハ
ロゲン原子、飽和あるいは不飽和のアルキル基のいすれ
かを表す。］ 一般式［２］Embedded image [In the formula, A to F represent at least one of a sulfonic acid group and a sulfonate, and the rest represent any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. General formula [2]
【化１０】 ［式中、Ｇ〜Ｎは、そのうちの少なくとも１つがスルホ
ン酸基またはスルホン酸塩であり、残りは水素原子、ハ
ロゲン原子、飽和あるいは不飽和のアルキル基のいずれ
かを表す。］Embedded image [In the formula, at least one of G to N is a sulfonic acid group or a sulfonic acid salt, and the rest represent any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. ]
【００２６】更に本発明は、一般式［ＳＩ］または［Ｓ
ＩＩ］で示される化合物を０．０１ｇ／１〜２．０ｇ／
１の範囲で含有することを特徴とする請求項１または２
記載のハロゲン化銀カラー写真感光材料の処理方法であ
る。尚又、本発明は、パラフェニレンジアミン系発色現
像主薬を０．０２ｍｏｌ／１以上含有することを特徴と
する請求項１、２または３記載のハロゲン化銀カラー写
真感光材料の処理方法である。 Further, the present invention provides a compound represented by the general formula [SI] or [S
II] in an amount of 0.01 g / l to 2.0 g /
3. The composition according to claim 1, wherein the content is within the range of 1.
A method for processing the silver halide color photographic light-sensitive material described above. In addition, the present invention relates to a paraphenylenediamine-based color
It is characterized by containing 0.02 mol / 1 or more of the image agent
4. The silver halide color copying method according to claim 1, 2 or 3, wherein
This is a method for processing a true photosensitive material.
【００２７】[0027]
【作用】本発明は発色現像液に一般式［ＳＩ］または
［ＳＩＩ］で示される化合物の少なくとも１種を含有
し、かつ１０〜２００ｇ／ｌの芳香族スルホン酸または
その塩を少なくとも１種含有することにより、高濃度に
発色現像主薬を溶解した場合に生じる主薬析出の防止を
可能とし、補充量が１ｍ ２ 当り１２０ｍｌ以下という発
色現像補充液の濃厚化を実現したものである。According to the present invention, the color developing solution contains at least one compound represented by the general formula [SI] or [SII] and contains at least one aromatic sulfonic acid or a salt thereof at 10 to 200 g / l. By doing so, it is possible to prevent the precipitation of the color developing agent which occurs when the color developing agent is dissolved at a high concentration, and to realize a concentrated color developing replenisher having a replenishing amount of 120 ml or less per 1 m 2. is there.
【００２８】アルカリ水溶液にパラフェニレンジアミン
系発色現像主薬を高濃度に溶解させるために、ベンゼン
スルホン酸誘導体を用いる方法は、英国特許６６９５０
５号に開示されている。しかしながらこの方法では、本
発明の目的の１つにあるような濃厚低補充と迅速処理を
両立するために必要な発色現像主薬の濃度としては不十
分であり、かつまた低温で保存された場合の主薬析出を
防止するには至っていない。A method using a benzenesulfonic acid derivative for dissolving a paraphenylenediamine-based color developing agent at a high concentration in an aqueous alkali solution is disclosed in British Patent No. 66950.
No. 5. However, in this method, the concentration of the color developing agent necessary for achieving both the low concentration replenishment and the rapid processing, which is one of the objects of the present invention, is insufficient, and the concentration of the color developing agent when stored at a low temperature is also low. It has not been possible to prevent the precipitation of the main drug.
【００２９】また、発色現像液に水溶性界面活性剤を添
加することはすでに知られているが、その目的は現像液
中に発生するタール等を可溶化し、写真感光材料の着色
を防止することにあり、本発明のように発色現像主薬の
高濃度化を目的とするものではない。It is already known to add a water-soluble surfactant to a color developer, but the purpose is to solubilize tars and the like generated in the developer and prevent coloring of the photographic light-sensitive material. This is not intended to increase the concentration of the color developing agent as in the present invention.
【００３０】[0030]
【発明の具体的構成】一般式［ＳＩ］、［ＳＩＩ］につ
いて詳説する。一般式［ＳＩ］において、Ａは１価の有
機基、例えば炭素数が６〜５０、好ましくは６〜３５の
アルキル基（例えばヘキシル、ヘプチル、オクチル、ノ
ニル、デシル、ウンデシルまたはドデシル等の各基）ま
たは炭素数が３〜３５のアルキル基または炭素数が２〜
３５のアルケニル基で置換されたアリール基である。DETAILED DESCRIPTION OF THE INVENTION The general formulas [SI] and [SII] will be described in detail. In the general formula [SI], A is a monovalent organic group, for example, an alkyl group having 6 to 50, preferably 6 to 35 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) ) Or an alkyl group having 3 to 35 carbon atoms or 2 to 2 carbon atoms
An aryl group substituted with 35 alkenyl groups.
【００３１】アリール基上に置換する好ましい基として
は炭素数が１〜１８のアルキル基（例えばメチル、プロ
ピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチ
ル、ノニル、デシル、ウンデシルまたはドデシル等の非
置換アルキル基）、ベンジル、フェネチル等の置換アル
キル基または炭素数２〜２０のアルケニル基（例えばオ
レイル、セチル、アリル基等の非置換のアルケニル基）
が挙げられる。A preferred group to be substituted on the aryl group is an alkyl group having 1 to 18 carbon atoms (eg, unsubstituted alkyl such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). Group), a substituted alkyl group such as benzyl and phenethyl, or an alkenyl group having 2 to 20 carbon atoms (eg, an unsubstituted alkenyl group such as oleyl, cetyl, allyl, etc.)
Is mentioned.
【００３２】アリール基としてはフェニル、ビフェニル
またはナフチル等の各基が挙げられ、好ましくはフェニ
ル基である。アリール基に置換する位置としては、オル
ト、メタ、パラ位のいずれでもよく、複数の基が置換で
きる。Ｂ及びＣは各々Examples of the aryl group include groups such as phenyl, biphenyl and naphthyl, and a phenyl group is preferable. The position to be substituted with the aryl group may be any of the ortho, meta and para positions, and a plurality of groups can be substituted. B and C are each
【００３３】[0033]
【化１１】 を表し、同一であっても異なっていてもよい（ただし、
ａ、ｂおよびｃは各々０、１、２または３、ｄは０また
は１であり、Ｙは水素原子または水酸基である）。ｍ及
びｎは１〜１００の整数を表す。Ｘは水素原子、アルキ
ル基、アラルキル基またはアリール基であり、例えばＡ
で説明した基が挙げられる。Embedded image And may be the same or different (provided that
a, b and c are each 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group). m and n represent an integer of 1 to 100. X is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
And the groups described above.
【００３４】一般式［ＳＩＩ］において、Ｍはアルカリ
金属（例えばＮａ、Ｋ、Ｌｉ等）、水素原子、アンモニ
ウム塩またはアルカノールアミン塩を表し、ｎは１〜１
００の整数であり、Ａは１価の有機基、例えば炭素数が
６〜２０、好ましくは６〜１２のアルキル基（例えばヘ
キシル、ヘプチル、オクチル、ノニル、デシル、ウンデ
シルまたはドデシル等の各基）、または炭素数が３〜２
０のアルキル基で置換されたアリール基であり、置換基
として好ましくは炭素数が３〜１２のアルキル基（例え
ばプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、
オクチル、ノニル、デシル、ウンデシルまたはドデシル
等の各基）が挙げられ、アリール基としてはフェニル、
トリル、キシニル、ビフェニルまたはナフチル等の各基
が挙げられ、好ましくはフェニル基またはトリル基であ
る。In the general formula [SII], M represents an alkali metal (eg, Na, K, Li, etc.), a hydrogen atom, an ammonium salt or an alkanolamine salt, and n represents 1 to 1
A is an integer of 00, and A is a monovalent organic group, for example, an alkyl group having 6 to 20, preferably 6 to 12 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) Or 3 to 2 carbon atoms
An aryl group substituted with an alkyl group of 0, preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl, undecyl or dodecyl, etc.), and the aryl group is phenyl,
Examples include groups such as tolyl, xinyl, biphenyl, and naphthyl, and preferably a phenyl group or a tolyl group.
【００３５】アリール基にアルキル基が結合する位置と
しては、オルト、メタ、パラ位のいずれでもよい。The position at which the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions.
【００３６】以下に一般式［ＳＩ］、［ＳＩＩ］で示さ
れる化合物の例示化合物を挙げるが、これらに限定され
るものではない。Examples of the compounds represented by formulas [SI] and [SII] are shown below, but are not limited thereto.
【００３７】（一般式 [SI] で示される化合物）SI-1〜
SI-22 特願平2-178833号明細書第18頁〜19頁 I-1〜 I
-22 と同じ。(Compound represented by the general formula [SI])
SI-22 Japanese Patent Application No. 2-178833, pages 18 to 19 I-1 to I
Same as -22.
【００３８】[0038]
【化２０】 SI-24〜SI-27 特願平2-178833号明細書第20頁 I-24〜
I-27 と同じ。Embedded image SI-24 to SI-27 Japanese Patent Application No. 2-178833, page 20, I-24 to
Same as I-27.
【００３９】[0039]
【化２１】 SI-29〜SI-30 特願平2-178833号明細書第20頁 I-29〜I
-30 と同じ。Embedded image SI-29 to SI-30 Japanese Patent Application No. 2-178833, page 20, I-29 to I
Same as -30.
【００４０】[0040]
【化２２】 SI-35 特願平2-178833号明細書第21頁 I-35 と同じ。Embedded image SI-35 Same as I-35 on page 21 of Japanese Patent Application No. 2-178833.
【００４１】[0041]
【化２３】 SI-38 〜SI-46 特願平2-178833号明細書第22頁〜23頁
I-38 〜I-46と同じ。Embedded image SI-38 to SI-46 Japanese Patent Application No. 2-178833, pp. 22-23
Same as I-38 to I-46.
【００４２】[0042]
【化２４】 SI-48 〜SI-78 特願平2-178833号明細書第23頁〜27頁
I-48 〜I-78と同じ。Embedded image SI-48 to SI-78 Japanese Patent Application No. 2-178833, pp. 23-27
Same as I-48 to I-78.
【００４３】（一般式 [SII] で示される化合物） SII-1〜SII-7 特願平2-178833号明細書第31頁〜32頁 V
-1〜V-7 と同じ。(Compound represented by the general formula [SII]) SII-1 to SII-7 Japanese Patent Application No. 2-178833, pages 31 to 32 V
Same as -1 to V-7.
【００４４】[0044]
【化２５】 上記例示化合物の中で好ましいのは、SI-23 、SI-28 、
SI-31 、SI- 32、SI-33 、SI-34 、SI-36 、SI-37 、SI
-47 、SII-8、SII-9である。Embedded image Preferred among the above exemplified compounds are SI-23, SI-28,
SI-31, SI-32, SI-33, SI-34, SI-36, SI-37, SI
-47, SII-8 and SII-9.
【００４５】一般式［ＳＩ］、［ＳＩＩ］で示される化
合物の添加量は、０．０１ｇ／ｌ〜２．０ｇ／ｌの範囲
が主薬析出防止及びステイン防止の上で好ましい。The addition amount of the compounds represented by the general formulas [SI] and [SII] is preferably in the range of 0.01 g / l to 2.0 g / l from the viewpoint of preventing the precipitation of the principal drug and preventing the stain.
【００４６】また上記一般式［ＳＩ］、［ＳＩＩ］で示
される化合物（界面活性剤）は、発色現像液中での臨界
ミセル濃度の１／５〜１０倍の濃度範囲で含有すること
が好ましい。The compounds represented by the above general formulas [SI] and [SII] (surfactants) are preferably contained in a concentration range of 1/5 to 10 times the critical micelle concentration in the color developing solution. .
【００４７】ここでいう界面活性剤の臨界ミセル濃度と
は、界面活性剤濃度の増加に対して溶液の表面張力低下
が急激に小さくなるごく狭い濃度範囲で、発色現像液中
のような疎水性物質の存在下ではこの濃度範囲で表面張
力が極小値を示すこともあり、その場合には極小値の濃
度を臨界ミセル濃度とする。The critical micelle concentration of the surfactant herein means a very narrow concentration range in which the decrease in the surface tension of the solution sharply decreases as the concentration of the surfactant increases. In the presence of a substance, the surface tension sometimes shows a minimum value in this concentration range, and in such a case, the concentration of the minimum value is defined as the critical micelle concentration.
【００４８】発色現像主薬は概して水溶性に劣り、発色
現像液中で不安定に分散されているため、疎水性界面に
配向しやすく、液界面及び容器壁界面で顕著に析出す
る。界面活性剤は、疎水性界面に自ら配向し発色現像主
薬の界面析出を防止すると考えられる。このため界面活
性剤が発色現像液中での臨界ミセル濃度の１／５倍未満
では発色現像主薬の界面析出を防止する効果はうすく、
また臨界ミセル濃度の１０倍を越えると溶液中に多量の
界面活性剤がミセル状態で存在するため、かえって発色
現像主薬の溶解性を低下させる。Since the color developing agent is generally poor in water solubility and is unstablely dispersed in the color developing solution, it is easily oriented at the hydrophobic interface, and is remarkably precipitated at the liquid interface and the container wall interface. It is thought that the surfactant orients itself at the hydrophobic interface to prevent interfacial precipitation of the color developing agent. Therefore, when the surfactant is less than 1/5 times the critical micelle concentration in the color developing solution, the effect of preventing interfacial precipitation of the color developing agent is slightly reduced.
On the other hand, if the concentration exceeds 10 times the critical micelle concentration, a large amount of a surfactant is present in a micelle state in the solution, so that the solubility of the color developing agent is rather reduced.
【００４９】本発明でいう芳香族スルホン酸またはその
塩とは、芳香族性を示す不飽和共役環にスルホン酸塩が
直接結合している化合物を示す。スルホン酸基またはス
ルホン酸塩は、１つでも複数であってもよい。芳香族性
を示す環は、ヘテロ原子を含んでもよく、また任意の置
換基を有していてもよい。１つの化合物で芳香族性を示
す環を複数有していてもよく、ポリマーであってもよ
い。スルホン酸塩としてはリチウム、ナトリウム、カリ
ウム等のアルカリ金属塩、アンモニウム塩が挙げられ
る。The aromatic sulfonic acid or a salt thereof in the present invention refers to a compound in which a sulfonic acid salt is directly bonded to an unsaturated conjugated ring showing aromaticity. One or more sulfonic acid groups or sulfonic acid salts may be present. The ring showing aromaticity may contain a hetero atom and may have an optional substituent. One compound may have a plurality of aromatic rings, or may be a polymer. Examples of the sulfonate include alkali metal salts such as lithium, sodium and potassium, and ammonium salts.
【００５０】本発明で好ましく用いられる芳香族スルホ
ン酸またはその塩としては、前記一般式［１］または
［２］で示される化合物が挙げられる。The aromatic sulfonic acid or a salt thereof preferably used in the present invention includes a compound represented by the above general formula [1] or [2].
【００５１】一般式［１］または［２］において、Ａ〜
ＦまたはＧ〜Ｎを表す飽和あるいは不飽和のアルキル基
としては炭素数が１〜１０であることが好ましい。炭素
鎖は直鎖状であっても側鎖を持つものであってもよい。In the general formula [1] or [2], A to
The saturated or unsaturated alkyl group representing F or G to N preferably has 1 to 10 carbon atoms. The carbon chain may be linear or have a side chain.
【００５２】以下に、一般式［１］または［２］で示さ
れる化合物の具体例を挙げるが、これらに限定されな
い。なお例示化合物はすべてナトリウム塩で示したが、
その一部又は全部がスルホン酸又は他の塩であってもよ
い。Hereinafter, specific examples of the compound represented by the general formula [1] or [2] are shown, but the invention is not limited thereto. In addition, all the exemplified compounds are shown as sodium salts,
Some or all of them may be sulfonic acids or other salts.
【００５３】[0053]
【化３０】 Embedded image
【００５４】[0054]
【化３１】 Embedded image
【００５５】本発明の発色現像液に用いられる芳香族ス
ルホン酸またはその塩の添加量は１０〜２００ｇ／ｌの
範囲であり、好ましくは２０〜１００ｇ／ｌの範囲であ
る。１０ｇ／ｌ未満では可溶化効果はほとんどなく、本
発明の目的を達成できない。The amount of the aromatic sulfonic acid or salt thereof used in the color developing solution of the present invention is 10 to 200 g / l.
Range, preferably in the range of 20 to 100 g / l.
You. If it is less than 10 g / l, there is almost no solubilizing effect and the object of the present invention cannot be achieved.
【００５６】発色現像液に用いられる発色現像主薬とし
ては、本発明においては、水溶性基を有するp-フェニレ
ンジアミン系化合物が好ましい。かかる水溶性基は、p-
フェニレンジアミン系化合物のアミノ基またはベンゼン
核上に少なくとも１つ有するものであればよい。As the color developing agent used in the color developing solution, a p-phenylenediamine compound having a water-soluble group is preferred in the present invention. Such a water-soluble group is p-
Any compound having at least one on the amino group or benzene nucleus of the phenylenediamine compound may be used.
【００５７】具体的な水溶性基としては、-(CH2)n-CH2O
H 、 -(CH2)m-NHSO2-(CH2)n-CH3、-(CH2)m-O-(CH2)n-C
H3、-(CH2CH2O)nCmH2m+1（m 及びn はそれぞれ０以上の
整数を表す。）、-COOH 基、-SO3H 基等が好ましいもの
として挙げられる。Specific water-soluble groups include-(CH 2 ) n -CH 2 O
H,-(CH 2 ) m -NHSO 2- (CH 2 ) n -CH 3 ,-(CH 2 ) m -O- (CH 2 ) n -C
H 3 , — (CH 2 CH 2 O) n C m H 2m + 1 (m and n each represent an integer of 0 or more), a —COOH group, a —SO 3 H group, and the like are preferable.
【００５８】本発明に好ましく用いられる発色現像主薬
の具体例としては、特願平2-178833号明細書第６６〜６
９頁に記載のＡ−１〜１６が挙げられる。Specific examples of the color developing agent preferably used in the present invention are described in Japanese Patent Application No. 2-178833, Nos. 66-6.
A-1 to 16 described on page 9 are mentioned.
【００５９】上記例示した発色現像主薬の中でも本発明
に用いて好ましいのは例示No.(Ａ−１) 、(Ａ−２）、
（Ａ−３）、(Ａ−４）、(Ａ−６）、(Ａ−７）及び（Ａ−
15）で示した化合物であり、特に好ましくはNo.(Ａ−
１) である。Among the color developing agents exemplified above, those preferably used in the present invention are exemplified by Nos. (A-1), (A-2) and
(A-3), (A-4), (A-6), (A-7) and (A-
15), and particularly preferably No. (A-
1).
【００６０】上記発色現像主薬は通常、塩酸塩、硫酸
塩、p-トルエンスルホン酸塩等の塩のかたちで用いられ
る。発色現像主薬の塩がp-トルエンスルホン酸等の芳香
族スルホン酸である場合には本発明はより好ましい効果
が得られる。しかしながら本発明は発色現像主薬の塩と
して芳香族スルホン酸を含有することを特徴とするもの
ではなく、発色現像主薬に対して当量以上に芳香族スル
ホン酸および／又はスルホン酸塩を含有することによっ
て効果を発揮するものである。The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate and p-toluenesulfonate. In the case where the salt of the color developing agent is an aromatic sulfonic acid such as p-toluenesulfonic acid, the present invention provides more preferable effects. However, the present invention is not characterized by containing an aromatic sulfonic acid as a salt of a color developing agent, but by containing an aromatic sulfonic acid and / or sulfonic acid salt in an equivalent amount or more with respect to the color developing agent. It is effective.
【００６１】本発明の目的である低補充と迅速処理の両
方を達成するためには、p-フェニレンジアミン系化合物
は、発色現像液１リットル当り 2.0×10-2モル以上であ
ることが好ましく、より好ましくは 2.2×10-2モル以上
である。In order to achieve both low replenishment and rapid processing which are the objects of the present invention, the amount of the p-phenylenediamine compound is preferably 2.0 × 10 -2 mol or more per liter of color developing solution. It is more preferably at least 2.2 × 10 -2 mol.
【００６２】本発明の発色現像液には、高濃度に溶解し
た発色現像主薬の空気酸化を防ぐために、従来保恒剤と
して用いられているヒドロキシルアミンに代えて、特開
昭63−146043号、同63−146042号、同63−146041号、同
63−146040号、同63−135938号、同63−118748号記載の
ヒドロキシルアミン誘導体及び特開昭64−62639 号記載
のヒドロキサム酸類、ヒドラジン類、ヒドラジド類、フ
ェノール類、α−ヒドロキシケトン類、α−アミノケト
ン類、糖類、モノアミン類、ジアミン類、４級アンモニ
ウム塩類、ニトロキシラジカル類、アルコール類、オキ
シム類、ジアミド化合物類、縮環式アミン類などが有機
保恒剤として好ましく用いられる。特に下記一般式
［Ｂ］又は［Ｃ］で示される化合物を含有させた場合
に、迅速処理及びブルーイングの軽減に好ましく、又発
色現像液槽の液面の結晶折出についても良好となり、別
なる効果も奏するため、本発明のより好ましい態様の一
つとして挙げられる。 一般式［Ｂ］In order to prevent the color developing agent dissolved at a high concentration from being oxidized by air, the color developing solution of the present invention is disclosed in Japanese Patent Application Laid-Open No. Sho 63-146043 instead of hydroxylamine which has been conventionally used as a preservative. 63-146042, 63-146041, same
Nos. 63-146040, 63-135938, 63-118748 and hydroxylamine derivatives, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α -Amino ketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are preferably used as organic preservatives. In particular, when a compound represented by the following general formula [B] or [C] is contained, it is preferable for rapid processing and reduction of bluing, and the crystal surface of the color developing solution tank is excellent in crystal deposition, and Since such an effect is also exhibited, it is mentioned as one of the more preferred embodiments of the present invention. General formula [B]
【００６３】[0063]
【化３２】 一般式［Ｃ］Embedded image General formula [C]
【００６４】[0064]
【化３３】 Embedded image
【００６５】一般式［Ｂ］又は一般式［Ｃ］の詳細な説
明は特願平2-178833号明細書第50頁、 54頁、 55頁に記載
の一般式［Ａ］又は一般式［Ｂ］の説明と同義である。The general formula [B] or the general formula [C] is described in detail in the specification of Japanese Patent Application No. 2-178833, pages 50, 54 and 55. ] Is the same as described above.
【００６６】一般式［Ｂ］の例示化合物 Ｂ−１〜３９ 特願平2-178833号明細書第51頁〜第53
頁Ａ−１〜３９と同じ 一般式［Ｃ］の例示化合物 Ｃ−１〜３３ 特願平2-178833号明細書第55〜58頁Ｂ
−１〜３３と同じ 一般式［Ｂ］又は一般式［Ｃ］で示される化合物は、通
常遊離のアミン、塩酸塩、硫酸塩、シュウ酸塩、リン酸
塩、酢酸塩等の形で用いられる。Illustrative compounds of the general formula [B] B-1 to 39: Japanese Patent Application No. 2-178833, pages 51 to 53
Exemplified compound of the general formula [C] same as pages A-1 to A-39 C-1 to 33-B.
Compounds represented by the same general formula [B] or general formula [C] as -1 to 33 are usually used in the form of free amine, hydrochloride, sulfate, oxalate, phosphate, acetate and the like. .
【００６７】発色現像液中の［Ｂ］及び一般式［Ｃ］で
示される化合物の濃度は、通常 0.2g/l 〜50g/l 、好ま
しくは 0.5g/l 〜30g/l 、さらに好ましくは1g/ l 〜15
g/lである。また、一般式［Ｂ］又は一般式［Ｃ］で示
される化合物と、従来より用いられているヒドロキシル
アミン及び有機保恒剤を組み合わせて用いることもでき
るが、好ましくはヒドロキシルアミンを用いない方が現
像性の上から好ましい。The concentration of the compound represented by the formula [B] or the compound represented by the formula [C] in the color developing solution is usually 0.2 g / l to 50 g / l, preferably 0.5 g / l to 30 g / l, and more preferably 1 g. / l to 15
g / l. In addition, the compound represented by the general formula [B] or [C] can be used in combination with a conventionally used hydroxylamine and an organic preservative, but it is preferable to use no hydroxylamine. It is preferable from the viewpoint of developability.
【００６８】本発明の発色現像液には、下記一般式
［Ｄ］又は一般式［Ｅ］で示される化合物を含有する際
に、発色現像液の溶解性向上及び空気酸化に対しても改
良効果を示し、しかも漂白定着液に混入してもほとんど
悪影響を与えないため好ましく用いられる。 一般式［Ｄ］When the color developing solution of the present invention contains a compound represented by the following formula [D] or [E], the solubility of the color developing solution is improved and the effect of improving air oxidation is also improved. The compound is preferably used because it has almost no adverse effect even when mixed in a bleach-fixing solution. General formula [D]
【００６９】[0069]
【化３４】 一般式［Ｅ］Embedded image General formula [E]
【００７０】[0070]
【化３５】 Embedded image
【００７１】一般式［Ｄ］又は一般式［Ｅ］の詳細な説
明は特願平2-178833号明細書第59頁、 60頁、 61頁に記載
の一般式［Ｃ］又は一般式［Ｄ］の説明と同義である。The general formula [D] or the general formula [E] is described in detail in the specification of Japanese Patent Application No. 2-178833, pages 59, 60 and 61. ] Is the same as described above.
【００７２】一般式［Ｄ］の例示化合物 Ｄ−１〜１７ 特願平2-178833号明細書第60〜61頁Ｃ−
１〜１７と同じ。 一般式［Ｅ］の例示化合物 Ｅ−１〜３３ 特願平2-178833号明細書第62〜64頁Ｄ−
１〜３３と同じ。一般式［Ｄ］又は一般式［Ｅ］で示さ
れる化合物は、空気酸化防止の点から、発色現像液１リ
ットル 当り1g〜100gの範囲で好ましく用いられ、より
好ましくは2g〜 30gの範囲で用いられる。Illustrative Compounds of the General Formula [D] D-1-17 Japanese Patent Application No. 2-178833, pages 60-61 C-
Same as 1-17. Illustrative compounds of the general formula [E] E-1 to 33 Japanese Patent Application No. 2-178833, pages 62 to 64 D-
Same as 1-33. The compound represented by the general formula [D] or the general formula [E] is preferably used in an amount of 1 g to 100 g, more preferably 2 g to 30 g per liter of the color developing solution from the viewpoint of preventing air oxidation. Can be
【００７３】本発明の発色現像液には蛍光増白剤を含有
させることが好ましい。蛍光増白剤は感光材料の未露光
部の白地性能を改善するのみならず、本発明の発色現像
液に添加して結晶析出防止に良好な結果をもたらす。The color developing solution of the present invention preferably contains a fluorescent whitening agent. The fluorescent whitening agent not only improves the white background performance of the unexposed area of the light-sensitive material, but also has a good effect on the prevention of crystal precipitation when added to the color developing solution of the present invention.
【００７４】蛍光増白剤としては、トリアジニルスチル
ベン系のものが好ましく、特に下記一般式［Ｆ］で示さ
れる化合物が好ましい。 一般式［Ｆ］As the fluorescent whitening agent, a triazinylstilbene-based compound is preferable, and a compound represented by the following general formula [F] is particularly preferable. General formula [F]
【００７５】[0075]
【化３６】 Embedded image
【００７６】一般式［Ｆ］の詳細な説明は特願平2-1788
33号明細書第73頁〜75頁に記載の一般式［Ｅ］の説明と
同義である。The detailed description of the general formula [F] is disclosed in Japanese Patent Application No. 2-1788 / 1990.
It has the same meaning as that of the description of general formula [E] described in page 33, pages 73 to 75 of the specification.
【００７７】一般式［Ｆ］の例示化合物 Ｆ−１〜４５ 特願平2-178833号明細書第76〜82頁Ｅ−
１〜４５と同じ。トリアジニルスチルベン系増白剤は、
例えば化成品工業協会編「蛍光増白剤」（昭和５１年８
月発行）８頁に記載されている通常の方法で合成するこ
とができる。Illustrative compounds of the general formula [F] F-1 to 45: Japanese Patent Application No. 2-178833, pages 76 to 82 E-
Same as 1-45. Triazinyl stilbene brighteners are
For example, "The Optical Brightener" edited by The Chemical Industry Association of Japan (August 1978
It can be synthesized by the usual method described on page 8 of the publication.
【００７８】例示化合物の中で特に好ましく用いられる
のはＦ−４、Ｆ−24、Ｆ−34、Ｆ−35、Ｆ−36、Ｆ−3
7、Ｆ−41である。Among the exemplified compounds, F-4, F-24, F-34, F-35, F-36 and F-3 are particularly preferably used.
7, F-41.
【００７９】トリアジニルスチルベン系増白剤は発色現
像液１リットル当り0.2 〜 10gの範囲であることが好ま
しく、更に好ましくは 0.4 〜 5g の範囲である。The amount of the triazinylstilbene-based brightener is preferably in the range of 0.2 to 10 g, more preferably in the range of 0.4 to 5 g per liter of the color developing solution.
【００８０】さらに、発色現像液には、必要に応じて、
エチレングリコール、メチルセロソルブ、メタノール、
アセトン、ジメチルホルムアミド、β−シクロデキスト
リン、その他特公昭47-33378号、同44-9509 号各公報記
載の化合物を現像主薬の溶解度を上げるための有機溶剤
として使用することができる。Further, if necessary, a color developing solution may be used.
Ethylene glycol, methyl cellosolve, methanol,
Acetone, dimethylformamide, β-cyclodextrin and other compounds described in JP-B-47-33378 and JP-B-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.
【００８１】更に、現像主薬とともに補助現像剤を使用
することもできる。これらの補助現像剤としては、例え
ばＮ−メチル -p-アミノフェノールヘキサルフェート
（メトール）、フェニドン、Ｎ，Ｎ’- ジエチル -p-ア
ミノフェノール塩酸塩、Ｎ，Ｎ，Ｎ’，Ｎ’- テトラメ
チル -p-フェニレンジアミン塩酸塩等が知られており、
その添加量としては通常0.01〜1.0g／l が好ましい。Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexaulfate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known,
Usually, the addition amount is preferably 0.01 to 1.0 g / l.
【００８２】さらにまた、その他ステイン防止剤、スラ
ッジ防止剤、重層効果促進剤等各種添加剤を用いること
ができる。Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.
【００８３】また、本発明の発色現像液には、下記一般
式［Ｋ］で示されるキレート剤が添加されることが本発
明の目的を効果的に達成する観点から好ましい。 一般式［Ｋ］It is preferable to add a chelating agent represented by the following general formula [K] to the color developing solution of the present invention from the viewpoint of effectively achieving the object of the present invention. General formula [K]
【００８４】[0084]
【化３７】 Embedded image
【００８５】一般式［Ｋ］の詳細な説明は、特願平2-17
8833号明細書第84頁〜85頁に記載の一般式［Ｋ］の説明
と同義である。The detailed description of the general formula [K] is described in Japanese Patent Application No. 2-17 / 1990.
Synonymous with the description of the general formula [K] described in JP-A-8833, pages 84 to 85.
【００８６】一般式［Ｋ］の例示化合物 Ｋ−１〜２２ 特願平2-178833号明細書第85〜89頁Ｋ−
１〜２２と同じ。Illustrative compounds of the general formula [K] K-1 to 22 Japanese Patent Application No. 2-178833, pages 85 to 89
Same as 1-22.
【００８７】上記発色現像液の各成分は、一定の水に、
順次添加、撹拌して調製することができる。この場合水
に対する溶解性の低い成分はトリエタノールアミン等の
前記有機溶媒等と混合して添加することができる。また
より一般的には、それぞれが安定に共存し得る複数の成
分を濃厚水溶液、または固体状態で小容器に予め調製し
たものを水中に添加、撹拌して調製し、本発明の発色現
像液として得ることができる。Each component of the color developing solution is prepared by adding
It can be prepared by sequentially adding and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state, is added to water and prepared by stirring to prepare a color developing solution of the present invention. Obtainable.
【００８８】本発明においては、上記発色現像液を任意
のpH域で使用できるが、迅速処理の観点からpH 9.5〜1
3.0であることが好ましく、より好ましくはpH 9.8〜12.
0で用いられる。処理温度は、一般に30℃以上、好まし
くは33℃以上、特に好ましくは35℃〜65℃であり、処理
時間は、90秒以内が好ましく、より好ましくは 3秒以上
60秒以内であり、特に好ましくは 3秒以上45秒以内であ
る。In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range.
It is preferably 3.0, more preferably pH 9.8 to 12.
Used with 0. The processing temperature is generally 30 ° C. or higher, preferably 33 ° C. or higher, particularly preferably 35 ° C. to 65 ° C., and the processing time is preferably 90 seconds or less, more preferably 3 seconds or more.
It is 60 seconds or less, particularly preferably 3 seconds or more and 45 seconds or less.
【００８９】本発明においては、低補充である場合に本
発明の効果を良好に奏することから、発色現像液の補充
量は、１２０ｍｌ／ｍ２以下であり、好ましくは１１０
ｍｌ／ｍ２以下であり、特に好ましくは１００ｍｌ／ｍ
２以下である。In the present invention, the replenishment rate of the color developing solution is 120 ml / m 2 or less , preferably 110
ml / m 2 or less, particularly preferably 100 ml / m 2
2 or less.
【００９０】本発明の処理方法においては、上記の発色
現像液による処理以外については公知の処理工程及び処
理液を採用できる。In the processing method of the present invention, known processing steps and processing liquids can be employed except for the processing using the color developing solution described above.
【００９１】本発明の発色現像液及び処理方法が適用さ
れる感光材料は特に限定されず、感光材料中にカプラー
を含有する所謂内式現像方式で処理される感光材料であ
れば、カラーペーパー、カラーネガフィルム、カラーポ
ジフィルム、スライド用カラー反転フィルム、映画用カ
ラー反転フィルム、ＴＶ用カラー反転フィルム、反転カ
ラーペーパー等任意の感光材料に適用することができる
が、最も好ましくは塩化銀主体のカラーペーパーに適用
することである。The light-sensitive material to which the color developing solution and the processing method of the present invention are applied is not particularly limited. If the light-sensitive material contains a coupler in the light-sensitive material and is processed by a so-called internal developing method, color paper, It can be applied to any photosensitive material such as a color negative film, a color positive film, a color reversal film for a slide, a color reversal film for a movie, a color reversal film for a TV, and a reversal color paper. Is to apply.
【００９２】[0092]
【実施例】以下、本発明を実施例によりさらに具体的に
説明するが、本発明の実施の態様がこれに限定されるも
のではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.
【００９３】実施例１ 下記の組成の発色現像補充液を調製した。 発色現像補充液 トリエタノールアミン １４．０ｇ エチレングリコール ８．０ｇ Ｎ，Ｎ−ジエチルヒドロキシルアミン ７．１ｇ ジエチレントリアミン五酢酸 ３．０ｇ 亜硫酸カリウム ３．５×１０-3ｍｏｌ 炭酸カリウム ３３．０ｇ ユビテックスＭＳＴ（チバガイギー社製） ２．３ｇ チノパールＳＦＰ（チバガイギー社製） １．８ｇ スルホン酸またはスルホン酸塩（例示化合物、表１記載） ５０ｇ 界面活性剤（例示化合物、表１記載） ０．１ｇ 発色現像主薬（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）−アニリン硫酸塩） 表１に記載 水を加えて全量を１リットルとすると共に、水酸化ナト
リウムまたは硫酸でｐＨ１０．５０に調整した。３０ｍ
ｌガラスびんに上記発色現像液を２５ｍｌずつ入れて密
封し、−５℃の恒温槽中で２週間保存し、保存後の主薬
析出物の有無を観察した。結果を表１に示すが、評価は
下記の基準に従って行った。Example 1 A color developing replenisher having the following composition was prepared. Replenisher for color development Triethanolamine 14.0 g Ethylene glycol 8.0 g N, N-diethylhydroxylamine 7.1 g Diethylenetriaminepentaacetic acid 3.0 g Potassium sulfite 3.5 × 10 -3 mol Potassium carbonate 33.0 g Ubitex MST ( 2.3 g Tinopearl SFP (manufactured by Ciba Geigy) 1.8 g Sulfonic acid or sulfonate (exemplary compound, described in Table 1) 50 g Surfactant (exemplary compound, described in Table 1) 0.1 g Color developing agent ( 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) Table 1 Add water to make the total volume 1 liter, and adjust the pH to 10 with sodium hydroxide or sulfuric acid. Adjusted to .50. 30m
25 ml of the above color developing solution was placed in a glass bottle, sealed and stored in a constant temperature bath at -5 ° C for 2 weeks, and the presence or absence of the precipitate of the main drug after storage was observed. The results are shown in Table 1. The evaluation was performed according to the following criteria.
【００９４】◎ 全く析出なし ○ ほとんど析出物が認められない △ 結晶性の析出物が少量認められる × 結晶性の析出物が多量に認められる◎ No precipitation ○ Almost no precipitates △ Small amount of crystalline precipitates × Large amount of crystalline precipitates
【００９５】[0095]
【表１】 [Table 1]
【００９６】表１より本発明の組合せによってはじめて
主薬析出防止効果が認められる。From Table 1, it can be seen that the combination of the present invention has the effect of preventing precipitation of the active ingredient for the first time.
【００９７】実施例２ 実施例１と同じ発色現像補充液で、スルホン酸塩として
例示化合物（１−２）を添加し、発色現像主薬０．０２
８ｍｏｌ／ｌで、同様の保存実験を行った。結果を表２
に示す。評価基準は実施例１と同様である。Example 2 The same color developing replenisher as in Example 1 was used, except that Exemplified Compound (1-2) was added as a sulfonate, and the color developing agent was 0.02.
A similar storage experiment was performed at 8 mol / l. Table 2 shows the results
Shown in The evaluation criteria are the same as in Example 1.
【００９８】[0098]
【表２】 [Table 2]
【００９９】表２から界面活性剤の添加量は０．０１〜
２．０ｇ／ｌが好ましく、また臨界ミセル濃度の１／５
〜１０倍がより好ましいことがわかる。また、例示化合
物（ＳＩ−２３）、（ＳＩ−２８）、（ＳＩ−３２）、
（ＳＩ−３３）、（ＳＩ−３６）、（ＳＩ−４７）につ
いても同様の結果を得た。From Table 2, it is found that the amount of the surfactant added is 0.01 to
2.0 g / l is preferable, and 1/5 of the critical micelle concentration.
It turns out that 10 to 10 times is more preferable. In addition, the exemplified compounds (SI-23), (SI-28), (SI-32),
Similar results were obtained for (SI-33), (SI-36) and (SI-47).
【０１００】実施例３ 実施例２においてスルホン酸塩の例示化合物（１−２）
を例示化合物（１−１）、（１−５）、（１−７）、
（１−１４）、（１−１８）、（２−４）、（２−
６）、（２−８）に代えて同様に実験を行ったところ、
同様の結果を得た。Example 3 Exemplified compound (1-2) of sulfonic acid salt in Example 2
Are exemplified compounds (1-1), (1-5), (1-7),
(1-14), (1-18), (2-4), (2-
When the same experiment was performed instead of (6) and (2-8),
Similar results were obtained.
【０１０１】実施例４ 実施例１記載の発色現像補充液にスルホン酸塩として例
示化合物（１−２）、界面活性剤として（ＳＩ−３７）
を添加した。このうちトリエタノールアミン、エチレン
グリコールを各々除いた液を用意し、同様の保存実験を
行った。また、ユビテックスＭＳＴとチノパールＳＦＰ
の両方を除き、代わりに一般式［Ｆ］で表される次の化
合物を各々添加し、同様の保存実験を行った。結果を表
３に示す。評価基準は実施例１と同様である。Example 4 Exemplified compound (1-2) as a sulfonate and (SI-37) as a surfactant in the color developing replenisher described in Example 1.
Was added. Among them, liquids from which triethanolamine and ethylene glycol were respectively removed were prepared, and the same storage experiment was performed. Also, Ubitex MST and Chino Pearl SFP
, Except that the following compounds represented by the general formula [F] were added instead, and a similar storage experiment was performed. Table 3 shows the results. The evaluation criteria are the same as in Example 1.
【０１０２】[0102]
【外１】 [Outside 1]
【０１０３】[0103]
【表３】 [Table 3]
【０１０４】表３より、トリエタノールアミン、エチレ
ングリコールの添加が本発明に好ましい結果をもたらし
ていることがわかる。また、トリアジニルスチルベン系
蛍光増白剤の添加により、現像主薬の析出がより効果的
に防止できることがわかる。From Table 3, it can be seen that the addition of triethanolamine and ethylene glycol has provided favorable results in the present invention. Further, it can be seen that the addition of the triazinylstilbene-based fluorescent whitening agent can more effectively prevent the deposition of the developing agent.
【０１０５】実施例５ 実施例１と同じ発色現像補充液で、界面活性剤として例
示化合物（ＳＩ−３７）を０．２ｇ／ｌ添加し、スルホ
ン酸塩（１−２）の添加量を表４のように変化させ、同
様の保存実験を行った。結果を表４に示すが、評価基準
は実施例１と同様である。Example 5 The same color developing and replenishing solution as in Example 1 was used, and 0.2 g / l of the exemplified compound (SI-37) was added as a surfactant. 4 and the same preservation experiment was performed. The results are shown in Table 4, and the evaluation criteria are the same as in Example 1.
【０１０６】[0106]
【表４】 [Table 4]
【０１０７】表４より芳香族スルホン酸塩の添加量が１
０〜２００ｇ／ｌで好ましい効果が得られ、２０〜１０
０ｇ／ｌでより顕著な効果が現れることがわかる。Table 4 shows that the amount of the aromatic sulfonate was 1
A preferable effect is obtained at 0 to 200 g / l, and 20 to 10 g / l.
It can be seen that a more remarkable effect appears at 0 g / l.
【０１０８】同じ実験を芳香族スルホン酸塩を例示化合
物（１−１４）、（２−８）に代えて行ったところ同様
の結果を得た。また、界面活性剤を例示化合物（ＳＩ−
３４）、（ＳＩＩ−８）に代えて行ったところ同様の結
果を得た。The same experiment was carried out except that the aromatic sulfonate was replaced with the exemplified compounds (1-14) and (2-8), and similar results were obtained. Further, a surfactant is used as an example compound (SI-
34) and (SII-8), and similar results were obtained.
【０１０９】実施例６ 紙支持体の片面にポリエチレンを、別の面の第１層側に
酸化チタンを含有するポリエチレンをラミネートした支
持体上に以下に示す構成の各層を塗設し、多層カラー感
光材料を作成した。塗布液は下記のごとく調製した。 第１層塗布液 イエローカプラー（Ｙ−１）２６．７ｇ、色素画像安定
化剤（ＳＴ−１）１０．０ｇ、（ＳＴ−２）６．６７
ｇ、添加剤（ＨＱ−１）０．６７ｇを高沸点溶剤（ＤＮ
Ｐ）６．６７ｇに酢酸エチル６０ｍｌを加え溶解し、こ
の溶液を２０％界面活性剤（ＳＵ−１）７ｍｌを含有す
る１０％ゼラチン水溶液２２０ｍｌに超音波ホモジナイ
ザーを用いて乳化分散させてイエローカプラー分散液を
作製した。この分散液を下記条件にて作製した青感性ハ
ロゲン化銀乳剤（銀１０ｇ含有）と混合し第１層塗布液
を調製した。Example 6 Each layer having the following constitution was applied on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer. A photosensitive material was prepared. The coating solution was prepared as described below. First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g, additive (HQ-1) 0.67 g with a high boiling solvent (DN)
P) To 6.67 g, 60 ml of ethyl acetate was added and dissolved. This solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to disperse the yellow coupler. A liquid was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.
【０１１０】第２層〜第７層塗布液も上記第１層塗布液
と同様に調製した。The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer.
【０１１１】また、硬膜剤として第２層及び第４層に
（Ｈ−１）を、第７層に（Ｈ−２）を添加した。塗布助
剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を
添加し、表面張力を調整した。 下記のハロゲン化銀カ
ラー写真感光材料用を作成した。As a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The following silver halide color photographic materials were prepared.
【０１１２】[0112]
【外２】 [Outside 2]
【０１１３】[0113]
【外３】 [Outside 3]
【０１１４】[0114]
【化３８】 Embedded image
【０１１５】[0115]
【化３９】 Embedded image
【０１１６】[0116]
【化４０】 Embedded image
【０１１７】[0117]
【化４１】 Embedded image
【０１１８】［青感性ハロゲン化銀乳剤の調製方法］４
０℃に保温した２％ゼラチン水溶液１０００ｍｌ中に下
記（Ａ液）及び（Ｂ液）をｐＡｇ＝６．５、ｐＨ＝３．
０に制御しつつ３０分かけて同時添加し、更に下記（Ｃ
液）及び（Ｄ液）をｐＡｇ＝７．３、ｐＨ＝５．５に制
御しつつ１８０分かけて同時添加した。[Method for Preparing Blue-Sensitive Silver Halide Emulsion]
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C.
0 and added simultaneously over 30 minutes.
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.
【０１１９】このとき、ｐＡｇの制御は特開昭５９−４
５４３７号記載の方法により行い、ｐＨの制御は硫酸ま
たは水酸化ナトリウムの水溶液を用いて行った。 （Ａ液） 塩化ナトリウム ３．４２ｇ 臭化カリウム ０．０３ｇ 水を加えて ２００ｍｌ （Ｂ液） 硝酸銀 １０ｇ 水を加えて ２００ｍｌ （Ｃ液） 塩化ナトリウム １０２．７ｇ 臭化カリウム １．０ｇ 水を加えて ６００ｍｌ （Ｄ液） 硝酸銀 ３００ｇ 水を加えて ６００ｍｌAt this time, the control of pAg is described in JP-A-59-4.
The pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add silver nitrate 10 g Water 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water 600 ml (D solution) 300 g of silver nitrate Add water to 600 ml
【０１２０】添加終了後、花王アトラス社製デモールＮ
の５％水溶液と硫酸マグネシウムの２０％水溶液を用い
て脱塩を行った後、ゼラチン水溶液と混合して平均粒径
０．８５μｍ、変動係数（σ／ｒ）＝０．０７、塩化銀
含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１を
得た。After completion of the addition, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (σ / r) = 0.07, and a silver chloride content. A 99.5 mol% monodisperse cubic emulsion EMP-1 was obtained.
【０１２１】上記乳剤ＥＭＰ−１に対し、下記化合物を
用い５０℃にて９０分化学熟成を行い、青感性ハロゲン
化銀乳剤（Ｅｍ−Ｂ）を得た。The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).
【０１２２】 チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ 塩化金酸 ０．５ｍｇ／モルＡｇＸ 安定剤（ＳＴＡＢ−１） ６×１０−４モル／モルＡｇＸ 増感色素（ＢＳ−１） ４×１０−４モル／モルＡｇＸ 〃 （ＢＳ−２） １×１０−４モル／モルＡｇＸSodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer (STAB-1) 6 × 10 −4 mol / mol AgX Sensitizing dye (BS-1) 4 × 10 −4 Mol / mol AgX〃 (BS-2) 1 × 10 −4 mol / mol AgX
【０１２３】［緑感性ハロゲン化銀乳剤の調製方法］
（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）
の添加時間を変更する以外はＥＭＰ−１と同様にして、
平均粒径０．４３μｍ、変動係数（σ／ｒ）＝０．０
８、塩化銀含有率９９．５モル％の単分散立方体乳剤Ｅ
ＭＰ−２を得た。[Method for Preparing Green-Sensitive Silver Halide Emulsion]
(Solution A) and (solution B) addition time and (solution C) and (solution D)
Except for changing the addition time of EMP-1,
Average particle size 0.43 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained.
【０１２４】ＥＭＰ−２に対し、下記化合物を用いて５
５℃で１２０分化学熟成を行い、緑感性ハロゲン化銀乳
剤（Ｅｍ−Ｇ）を得た。The following compound was used for EMP-2.
Chemical ripening was performed at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).
【０１２５】 チオ硫酸ナトリウム １．５ｍｇ／モルＡｇＸ 塩化金酸 １．０ｍｇ／モルＡｇＸ 安定剤（ＳＴＡＢ−１） ６×１０−４モル／モルＡｇＸ 増感色素（ＧＳ−１） ４×１０−４モル／モルＡｇＸSodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer (STAB-1) 6 × 10 −4 mol / mol AgX Sensitizing dye (GS-1) 4 × 10 −4 Mol / mol AgX
【０１２６】［赤感性ハロゲン化銀乳剤の調製方法］
（Ａ液）と（Ｂ液）の添加時間及び（Ｃ液）と（Ｄ液）
の添加時間を変更する以外はＥＭＰ−１と同様にして、
平均粒径０．５０μｍ、変動係数（σ／ｒ）＝０．０
８、塩化銀含有率９９．５モル％の単分散立方体乳剤Ｅ
ＭＰ−３を得た。[Method for Preparing Red-Sensitive Silver Halide Emulsion]
(Solution A) and (solution B) addition time and (solution C) and (solution D)
Except for changing the addition time of EMP-1,
Average particle size 0.50 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-3 was obtained.
【０１２７】ＥＭＰ−３に対し、下記化合物を用いて６
０℃で９０分化学熟成を行い、赤感性ハロゲン化銀乳剤
（Ｅｍ−Ｒ）を得た。EMP-3 was synthesized using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).
【０１２８】 チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ 塩化金酸 ２．０ｍｇ／モルＡｇＸ 安定剤（ＳＴＡＢ−１） ６×１０−４モル／モルＡｇＸ 増感色素（ＲＳ−１） ４×１０−４モル／モルＡｇＸSodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 −4 mol / mol AgX sensitizing dye (RS-1) 4 × 10 −4 Mol / mol AgX
【０１２９】[0129]
【化４２】 Embedded image
【０１３０】この試料を常法に従って露光後、次の処理
工程と処理液を使用して処理を行った。This sample was exposed according to a conventional method, and then processed using the following processing steps and processing solutions.
【０１３１】 処理工程 処理温度 処理時間 補充量 （１）発色現像 表５に記載 表５に記載 表５に記載 （２）漂白定着 ３５．０±０．５℃ ４５秒 ２２０ｍｌ／ｍ２ （３）安定 ３０〜３４℃ ９０秒 ２５０ｍｌ／ｍ２ （３槽カスケード） （４）乾燥 ６０〜８０℃ ３０秒 −Processing Step Processing Temperature Processing Time Replenishment Amount (1) Color Development Described in Table 5 Described in Table 5 Described in Table 5 (2) Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 220 ml / m 2 (3) Stable 30-34 ° C 90 seconds 250 ml / m 2 (3 tank cascade) (4) Drying 60-80 ° C 30 seconds −
【０１３２】発色現像タンク液 トリエタノールアミン １０ｇ エチレングリコール ５．６ｇ Ｎ，Ｎ−ジエチルヒドロキシルアミン ５．０ｇ ジエチレントリアミン五酢酸 ２．１ｇ 塩化カリウム 表５に記載 亜硫酸カリウム ２．５×１０−３モル 炭酸カリウム ２３ｇ ユビテックスＭＳＴ（チバガイギー社製） １．６ｇ チノパールＳＦＰ（チバガイギー社製） １．３ｇ スルホン酸またはスルホン酸塩（例示化合物、表６に記載） ３５ｇ 界面活性剤（例示化合物、表６に記載） ０．１ｇ 発色現像主薬（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)-アニリン硫酸塩） 表５に記載 水を加えて全量を１リットルとするとともに、水酸化カ
リウム又は硫酸でｐＨ１０．１０に調整した。 Color developing tank liquid Triethanolamine 10 g Ethylene glycol 5.6 g N, N-diethylhydroxylamine 5.0 g Diethylenetriaminepentaacetic acid 2.1 g Potassium chloride Potassium sulfite 2.5 × 10 -3 mol Potassium carbonate described in Table 5 23 g Ubitex MST (manufactured by Ciba-Geigy) 1.6 g Tinopearl SFP (manufactured by Ciba-Geigy) 1.3 g Sulfonic acid or sulfonate (exemplary compound, described in Table 6) 35 g Surfactant (exemplary compound, described in Table 6) 0.1 g color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) Table 5 Add water to make the total volume 1 liter, The pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid.
【０１３３】発色現像補充液 トリエタノールアミン １４ｇ エチレングリコール ８．０ｇ Ｎ，Ｎ−ジエチルヒドロキシルアミン ７．１ｇ ジエチレントリアミン五酢酸 ３．０ｇ 亜硫酸カリウム ３．５×１０-3モル ユビテックスＭＳＴ（チバガイギー社製） ２．３ｇ チノパールＳＦＰ（チバガイギー社製） １．８ｇ スルホン酸またはスルホン酸塩（例示化合物、表６に記載） ５０ｇ 界面活性剤（例示化合物、表６に記載） ０．１ｇ 発色現像主薬（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)-アニリン硫酸塩） 表５に記載 水を加えて全量を１リットルとするとともに、水酸化カ
リウムまたは硫酸でｐＨ１０．５０に調整した。 Color developing replenisher triethanolamine 14 g Ethylene glycol 8.0 g N, N-diethylhydroxylamine 7.1 g Diethylenetriaminepentaacetic acid 3.0 g Potassium sulfite 3.5 × 10 -3 mol Ubitex MST (manufactured by Ciba Geigy) 2.3 g Tinopearl SFP (manufactured by Ciba Geigy) 1.8 g Sulfonic acid or sulfonic acid salt (exemplary compound, described in Table 6) 50 g Surfactant (exemplary compound, described in Table 6) 0.1 g Color developing agent (3- Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate described in Table 5 Water was added to make up to 1 liter, and the pH was 10.50 with potassium hydroxide or sulfuric acid. Was adjusted.
【０１３４】漂白定着タンク液及び補充液 エチレンジアミン四酢酸第２鉄アンモニウム塩 ５３ｇ エチレンジアミン四酢酸 ３．０ｇ チオ硫酸アンモニウム（７０％溶液） １２３ｇ 亜硫酸アンモニウム（４０％溶液） ５１ｇ 臭化アンモニウム ４０ｇ アンモニア水又は氷酢酸でｐＨ６．５に調整するととも
に水を加えて全量を１リットルとする。 Bleaching-fixing tank solution and replenisher ferric ammonium ammonium salt of ethylenediaminetetraacetic acid 53 g ethylenediaminetetraacetic acid 3.0 g ammonium thiosulfate (70% solution) 123 g ammonium sulfite (40% solution) 51 g ammonium bromide 40 g ammonia water or glacial acetic acid The pH is adjusted to 6.5 and water is added to bring the total volume to 1 liter.
【０１３５】安定タンク液及び補充液 オルトフェニルフェノール ０．１ｇ ユビテックス（チバガイギー社製） １．０ｇ ＺｎＳＯ4 ・７Ｈ2 Ｏ ０．１ｇ 亜硫酸アンモニウム（４０％溶液) ５．０ｍｌ １−ヒドロキシエチリデン−１，１−ジホスホン酸（６０％溶液） ３．０ｇ エチレンジアミン四酢酸 １．５ｇ アンモニア水又は硫酸でｐＨ７．８とすると共に水で１リットルとする。[0135] stabilizing tank solution and replenisher o-phenylphenol 0.1g Uvitex (Ciba Geigy) 1.0g ZnSO 4 · 7H 2 O 0.1g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene--1 , 1-diphosphonic acid (60% solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid and make up to 1 liter with water.
【０１３６】作成したカラーペーパー及び処理液を用い
て、ランニング処理を行った。ランニング処理は自動現
像機に上記の発色現像タンク液を満すとともに、漂白定
着タンク液及び安定タンク液を満し、前記カラーペーパ
ー試料を処理しながら上記した発色現像補充液と漂白定
着補充液と安定補充液を定量ポンプを通じて補充しなが
ら行った。A running process was performed using the prepared color paper and the processing solution. In the running process, the automatic developing machine is filled with the color developing tank solution, the bleach-fixing tank solution and the stabilizing tank solution are filled, and while the color paper sample is being processed, the color developing replenisher and the bleach-fix replenisher described above are used. This was performed while the stable replenisher was being replenished through a metering pump.
【０１３７】ランニング処理は発色現像液中に補充され
た発色現像液の量が発色現像タンク液の容量の３倍にな
るまで、１日当り０．０５Ｒの連続処理を行った。In the running process, a continuous process of 0.05 R per day was performed until the amount of the color developing solution replenished in the color developing solution became three times the capacity of the color developing tank solution.
【０１３８】なお１Ｒというのは発色現像タンク容量分
の発色現像補充液が補充されることを意味する。Note that 1R means that the color developing replenisher for the capacity of the color developing tank is replenished.
【０１３９】連続処理の後、イエロー最大発色濃度（Ｄ
ｍａｘＹ）、未露光部のイエローステイン、補充タンク
内の析出物の有無を評価した。イエローステインは、未
露光部におけるイエロー反射濃度を測定した。また、結
晶析出評価は下記の基準に従って行った。After the continuous processing, the yellow maximum color density (D
maxY), the unexposed portion of yellow stain, and the presence of precipitate in the replenishment tank were evaluated. For the yellow stain, the yellow reflection density in the unexposed area was measured. The evaluation of crystal precipitation was performed according to the following criteria.
【０１４０】◎ ： 全く析出なし △ ： 補充タンクの壁面にわずかの析出物が認められ
る × ： 補充タンクの壁面にかなりの析出物が認められ
る ××： 補充タンクの壁面に加え、底にも多量の結晶が
見られる 結果を表６に示す。◎: No precipitation at all △: Slight precipitates are observed on the wall of the replenishment tank ×: Considerable precipitates are observed on the wall of the replenishment tank XX: A large amount is present on the bottom of the replenishment tank The results are shown in Table 6.
【０１４１】[0141]
【表５】 [Table 5]
【０１４２】[0142]
【表６】 [Table 6]
【０１４３】処理時間の短縮および補充量の低減によっ
て発色現像主薬の必要量が増加し、これにともなってイ
エローステインの発生と主薬の析出が起こっている。１
ｍ ２ 当り１２０ｍｌ以下と本発明の組み合わせによって
イエローステインの改善と析出防止に効果が認められ
る。The required amount of the color developing agent is increased by shortening the processing time and reducing the replenishing amount, and accordingly, yellow stain is generated and the main agent is precipitated. 1
effect is observed in the deposition prevention and improvement of yellow stain by a combination of m 2 per 120ml or less and present invention.
【０１４４】また、発色現像主薬の析出によりタンク液
中の実質的な主薬濃度が低下し、現像性の低下が認めら
れ、特にイエローの最大発色濃度が低下するが、１ｍ ２
当り１２０ｍｌ以下と本発明の組み合わせはこれを防止
していることがわかる。[0144] Also, the substantial agent concentration in the tank solution by precipitation of the color developing agent is decreased, lowering of developability is observed, especially the maximum color density of yellow drops, 1 m 2
It can be seen that the combination of the present invention with 120 ml or less per unit prevents this.
【０１４５】同じ実験をスルホン酸塩を例示化合物（１
−１４）、（２−６）、（２−８）に代えて行ったとこ
ろ、ほぼ同様な結果を得た。The same experiment was conducted using the sulfonate as an example compound (1).
-14), (2-6) and (2-8) were performed, and almost the same results were obtained.
【０１４６】また、界面活性剤を例示化合物（ＳＩ−３
４）、（ＳＩＩ−８）に代えて同じ実験を行ったとこ
ろ、ほぼ同様の結果を得た。Further, the surfactant may be exemplified compound (SI-3)
When the same experiment was performed in place of (4) and (SII-8), almost the same results were obtained.
【０１４７】さらに、保恒剤として、Ｎ，Ｎ−ジエチル
ヒドロキシルアミンに代えて、ヒドラジノジ酢酸を発色
現像タンク液に８．３ｇ／ｌ、補充液に１１．８ｇ／ｌ
添加したところ、同様に良好な結果を得た。Further, as a preservative, hydrazinodiacetic acid was used in place of N, N-diethylhydroxylamine in a color developing tank solution of 8.3 g / l and a replenisher solution of 11.8 g / l.
When added, similarly good results were obtained.
【０１４８】[0148]
【発明の効果】本発明によれば、第１に発色現像主薬の
析出を起こさない発色現像液を用いるハロゲン化銀カラ
ー写真感光材料の処理方法を提供することができ、第２
に迅速処理及び低補充処理を行っても、写真性能が安定
し、現像主薬が析出せず補充タンクやポンプ等を汚染す
ることがない発色現像液を用いるハロゲン化銀カラー写
真感光材料の処理方法を提供することができる。According to the present invention, firstly, a silver halide color using a color developing solution which does not cause precipitation of a color developing agent.
-It is possible to provide a method for processing photographic light-sensitive materials,
Silver halide color transfer using a color developing solution that stabilizes photographic performance even when rapid processing and low replenishment processing are performed, and does not precipitate developing agents and contaminate replenishment tanks and pumps.
A method for processing a true photosensitive material can be provided.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−234161（ＪＰ，Ａ) 特開 昭62−242938（ＪＰ，Ａ) 特開 昭62−105140（ＪＰ，Ａ) 特開 昭62−42154（ＪＰ，Ａ) 特開 昭54−107345（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) G03C 7/407 G03C 7/413 G03C 7/44 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-62-234161 (JP, A) JP-A-62-242938 (JP, A) JP-A-62-105140 (JP, A) JP-A 62-234140 42154 (JP, A) JP-A-54-107345 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) G03C 7/407 G03C 7/413 G03C 7/44
Claims (4)
される化合物の少なくとも１種を含有し、かつ１０〜２
００ｇ／ｌの芳香族スルホン酸またはその塩を少なくと
も１種含有する発色現像液でハロゲン化銀カラー写真感
光材料を処理する方法であって、その補充量がハロゲン
化銀カラー写真感動材料１ｍ ２ 当り１２０ｍｌ以下であ
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 ［ＳＩ］ 【化１】 ［式中、Ａは１価の有機基を表す。Ｂ及びＣはそれぞれ 【化２】 を表し、同一であっても異なっていてもよい（ただし、
ａ、ｂおよびｃは各々０、１、２または３、ｄは０また
は１であり、Ｙは水素原子または水酸基である）。ｍ及
びｎは１〜１００の整数を表す。Ｘは水素原子、アルキ
ル基、アラルキル基またはアリール基を表す。］ 一般式［ＳＩＩ］ 【化３】 ［式中、Ｍはアルカリ金属、水素原子、アンモニウム塩
またはアルカノールアミン塩を表し、ｎは１〜１００の
整数であり、Ａは１価の有機基を表す。］[Claim 1] contains at least one compound represented by the following general formula [SI] or [SII], and 10 to 2
Color developing solution containing at least one of 00 g / l of aromatic sulfonic acid or a salt thereof and a silver halide color photographic
A method for treating optical materials, wherein the replenishment amount is halogen.
Halide color photographic impression material 1m 2 per 120ml or less der
Of silver halide color photographic light-sensitive materials,
Processing method. General formula [SI] [In the formula, A represents a monovalent organic group. B and C are respectively And may be the same or different (provided that
a, b and c are each 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group). m and n represent an integer of 1 to 100. X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. General formula [SII] [In the formula, M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt, n is an integer of 1 to 100, and A represents a monovalent organic group. ]
一般式［１］または［２］で示される化合物であること
を特徴とする請求項１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［１］ 【化４】 ［式中、Ａ〜Ｆは、そのうちの少なくとも１つがスルホ
ン酸基またはスルホン酸塩であり、残りは水素原子、ハ
ロゲン原子、飽和あるいは不飽和のアルキル基のいずれ
かを表す。］ 一般式［２］ 【化５】 ［式中、Ｇ〜Ｎは、そのうちの少なくとも１つがスルホ
ン酸基またはスルホン酸塩であり、残りは水素原子、ハ
ロゲン原子、飽和あるいは不飽和のアルキル基のいずれ
かを表す。］2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein said aromatic sulfonic acid or a salt thereof is a compound represented by the following general formula [1] or [2]. . General formula [1] [In the formula, at least one of A to F is a sulfonic acid group or a sulfonic acid salt, and the rest represent any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. General formula [2] [In the formula, at least one of G to N is a sulfonic acid group or a sulfonic acid salt, and the rest represent any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. ]
る化合物を０．０１ｇ／１〜２．０ｇ／１の範囲で含有
することを特徴とする請求項１または２記載のハロゲン
化銀カラー写真感光材料の処理方法。3. The silver halide according to claim 1, wherein the compound represented by the general formula [SI] or [SII] is contained in the range of 0.01 g / 1 to 2.0 g / 1. Processing method for color photographic light-sensitive materials.
０．０２ｍｏｌ／１以上含有することを特徴とする請求Claims characterized by containing 0.02 mol / 1 or more
１、２または３記載のハロゲン化銀カラー写真感光材料A silver halide color photographic light-sensitive material as described in 1, 2, or 3 above.
の処理方法。Processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399591A JP2878484B2 (en) | 1991-05-29 | 1991-05-29 | Processing method of silver halide color photographic light-sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399591A JP2878484B2 (en) | 1991-05-29 | 1991-05-29 | Processing method of silver halide color photographic light-sensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04350855A JPH04350855A (en) | 1992-12-04 |
| JP2878484B2 true JP2878484B2 (en) | 1999-04-05 |
Family
ID=15574617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15399591A Expired - Fee Related JP2878484B2 (en) | 1991-05-29 | 1991-05-29 | Processing method of silver halide color photographic light-sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2878484B2 (en) |
-
1991
- 1991-05-29 JP JP15399591A patent/JP2878484B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04350855A (en) | 1992-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0477894B2 (en) | ||
| JP2819487B2 (en) | Photographic processing composition and processing method | |
| US20010012602A1 (en) | Calcium ion stable photographic color developing composition and method of use | |
| JP3009432B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JPH0640216B2 (en) | Method of replenishing color development replenisher | |
| JP2878484B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP3025368B2 (en) | Color developer for silver halide color photographic materials | |
| JPH0743524B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP2811117B2 (en) | Color developer for silver halide color photographic materials | |
| JP2949879B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| US5314791A (en) | Processing solution for light-sensitive silver halide color photographic material and processing method using the same | |
| US5955248A (en) | Concentrated photographic fixer additive and fixing compositions containing triazinylstilbene and method of photographic processing | |
| JP2955881B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP3021878B2 (en) | Color developing solution for silver halide color photographic material and processing method | |
| JP3048462B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP3065775B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP2876157B2 (en) | Color developing replenisher for silver halide color photographic materials | |
| JPS60162253A (en) | Method for processing silver halide color photosensitive material | |
| JP2673698B2 (en) | Color developer for silver halide color photographic materials | |
| JP2887881B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP2863870B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| US5811226A (en) | Method of processing a silver halide photographic element which reduces fog | |
| JP2673257B2 (en) | Processing method of silver halide color photographic light-sensitive material | |
| JP2794325B2 (en) | Stabilizing solution for silver halide color photographic light-sensitive material and processing method | |
| JPH0233142A (en) | Method and apparatus for processing silver halide color photographic sensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |