JPH03284748A - Processing liquid for silver halide color photographic sensitive material and processing method using this liquid - Google Patents
Processing liquid for silver halide color photographic sensitive material and processing method using this liquidInfo
- Publication number
- JPH03284748A JPH03284748A JP8555090A JP8555090A JPH03284748A JP H03284748 A JPH03284748 A JP H03284748A JP 8555090 A JP8555090 A JP 8555090A JP 8555090 A JP8555090 A JP 8555090A JP H03284748 A JPH03284748 A JP H03284748A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- color photographic
- processing
- group
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- -1 silver halide Chemical class 0.000 title claims description 98
- 229910052709 silver Inorganic materials 0.000 title claims description 77
- 239000004332 silver Substances 0.000 title claims description 77
- 238000012545 processing Methods 0.000 title claims description 69
- 238000003672 processing method Methods 0.000 title description 7
- 238000005406 washing Methods 0.000 claims abstract description 64
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 48
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- 238000004061 bleaching Methods 0.000 claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 24
- 238000011161 development Methods 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000007844 bleaching agent Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 2
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910006146 SO3M1 Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 238000011282 treatment Methods 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 12
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 235000011118 potassium hydroxide Nutrition 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 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 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 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 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229960003330 pentetic acid Drugs 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- WZTQWXKHLAJTRC-UHFFFAOYSA-N benzyl 2-amino-6,7-dihydro-4h-[1,3]thiazolo[5,4-c]pyridine-5-carboxylate Chemical compound C1C=2SC(N)=NC=2CCN1C(=O)OCC1=CC=CC=C1 WZTQWXKHLAJTRC-UHFFFAOYSA-N 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 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 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 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 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 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 2
- 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 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 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 2
- 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 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- FITNPEDFWSPOMU-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-b]pyridin-5-one Chemical compound OC1=CC=C2NN=NC2=N1 FITNPEDFWSPOMU-UHFFFAOYSA-N 0.000 description 1
- TYFSYONDMQEGJK-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid Chemical compound OC(O)CNCC(O)=O TYFSYONDMQEGJK-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
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- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 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
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 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
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 101150052401 slc44a1 gene Proteins 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
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハロゲン化銀カラー写真感光材料用処理液及び
それを用いた処理方法に関し、更に詳しくは定着処理後
の水洗代替安定浴に発生する固着現象を防止し、感光材
料のスリキズの発生を大巾に防止可能な処理技術に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a processing solution for silver halide color photographic light-sensitive materials and a processing method using the same, and more specifically, the present invention relates to a processing solution for silver halide color photographic light-sensitive materials and a processing method using the same. The present invention relates to a processing technology that can prevent sticking phenomena and largely prevent the occurrence of scratches on photosensitive materials.
一般にハロゲン化銀写真感光材料は画像露光後1発色現
像工程と脱銀工程とを基本工程とする一連の写真処理に
より色素画像が形成される。In general, in silver halide photographic materials, a dye image is formed by a series of photographic processes whose basic steps are a one-color development step and a desilvering step after image exposure.
発色現像工程では発色現像主薬の酸化体が共存するカラ
ーカプラーとカプリング反応することによって1画像模
様の色素画像を形成すると同時に還元銀が生成される。In the color development step, the oxidized form of the color developing agent undergoes a coupling reaction with the coexisting color coupler, thereby forming a dye image of one image pattern and simultaneously producing reduced silver.
ここに生成された銀は。The silver produced here.
引き続く脱銀工程において、漂白剤により酸化され、定
着剤の作用を受けて可溶性の銀錯体にされた後、溶解し
除去される。In the subsequent desilvering process, the silver is oxidized by a bleaching agent and converted into a soluble silver complex by the action of a fixing agent, which is then dissolved and removed.
かかる現像処理工程を有する自動現像機において、近年
、低公害化を目的とした無水洗処理技術が導入され、現
在ではミニラボのほとんどが無水洗処理タイプの自動現
像機を用いるようになってきている。その理由としては
、ミニラボ市場では処理の簡易化、設置面積の減少化の
ニーズが高く、配管が不要の無水洗処理タイプがこのニ
ーズに合っていたからと考えられる。In recent years, waterless washing processing technology has been introduced in automatic processing machines that have such a processing process for the purpose of reducing pollution, and now most minilabs are using waterless washing processing type automatic processing machines. . The reason for this is thought to be that in the minilab market there is a strong need for simplified processing and a reduction in installation space, and the waterless cleaning type, which does not require piping, met these needs.
かかる無水洗処理タイプの自動現像機においては、水洗
に替えて水洗代替安定浴が用いられ、また、この水洗代
替安定浴とは別に従来タイプのホルマリン含有の安定浴
が設けられている場合がある。In such a waterless washing processing type automatic developing machine, a water washing alternative stabilizing bath is used instead of water washing, and a conventional type formalin-containing stabilizing bath may be provided separately from the water washing alternative stabilizing bath. .
前者の水洗代替安定浴による処理は、スーパースタビラ
イザーによる処理であり、本明細書では水洗代替安定化
処理と称し、従来タイプの安定化処理と区別する。The former process using a stabilizing bath instead of washing is a process using a super stabilizer, and is referred to herein as a stabilizing process instead of washing, and is distinguished from the conventional stabilization process.
しかるに、かかる無水洗処理タイプの自動現像機がミニ
ラボ市場に導入されて以降、カラーネガフィルム用の自
動現像機において、定着処理後の水洗代替安定浴で固着
物が発生し、そのためカラーフィルムに度々スリ傷が発
生したり、ひどい時にはカラーフィルムの搬送が出来ず
ジャミングが発生するという問題があることが判った。However, since such waterless washing processing type automatic processing machines were introduced to the minilab market, in automatic processing machines for color negative films, fixed substances were generated in the washing substitute stabilizing bath after fixing processing, and as a result, color films were often scratched. It has been found that there is a problem in that when scratches occur or are severe, the color film cannot be conveyed and jamming occurs.
上記問題はカラーネガフィルムの商品的価値を著しく下
げ、顧客のカラーネガフィルムを傷つけたり、フィルム
そのものを駄目にしたりし、ミニラボ店の信用を著しく
傷つけるという意味で早急にその解決が求められていた
。The above problem significantly lowers the commercial value of color negative film, damages the customer's color negative film, or ruins the film itself, and seriously damages the credibility of the minilab store, so there is an urgent need for a solution to the problem.
そこで、本発明の目的とするところは、水洗代替安定浴
における固着現象の発生を防止し、感光材料のスリ傷や
ジャミングの発生を防止できるハロゲン化銀カラー写真
感光材料用処理液及びそれを用いた処理方法を提供する
ことにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a processing solution for silver halide color photographic light-sensitive materials that can prevent the occurrence of sticking phenomena in a water-washing alternative stabilizing bath, and prevent scratches and jamming of light-sensitive materials, and a processing solution using the same. The objective is to provide a processing method that is
〔課題を解決するための手段及び作用〕本発明者等は上
記課題を解決する為に、鋭意検討を重ねた結果、スリ傷
の発生やジャミングの発生の状況を検討してみると、無
水洗処理タイプの自動現像機をミニラボに導入後、約3
ケ月位から徐々にカラーネガフィルム用の自動現像機に
上記の問題が発生していること、カラーペーパー用の自
動現像機や大規模に集中処理している所謂大ラボにおい
ては上記の様な問題が全く皆無であること、又上記問題
は水洗代替安定浴において多発していることが判明した
。[Means and effects for solving the problem] In order to solve the above problem, the inventors of the present invention have made extensive studies and found that waterless washing After introducing a processing type automatic processing machine to the minilab, approximately 3
The above-mentioned problems have been gradually occurring in automatic processors for color negative film since about a month ago, and the above-mentioned problems have been occurring in automatic processors for color paper and so-called large laboratories that carry out intensive processing on a large scale. It was found that there were no such problems at all, and that the above-mentioned problems frequently occurred in water washing alternative stabilizing baths.
また本発明者等は、実際にスリ傷やジャミングが発生し
た自動現像機、更にはカラーペーパー用の自動現像機や
大ラボのカラーネガフィルム用大型自動現像機を調査、
解析したところ、水洗代替安定浴の液外のラック、ギア
に大量の固い付着物が発生しており、それが原因でスリ
傷やジャミングが発生していることが判った。In addition, the present inventors investigated automatic processors in which scratches and jamming actually occurred, as well as automatic processors for color paper and large automatic processors for color negative film in a large laboratory.
Analysis revealed that a large amount of hard deposits had formed on the racks and gears outside of the water washing alternative stabilizing bath, and that this was causing scratches and jamming.
また水洗代替安定浴に発生する固着が前浴成分であるチ
オ硫酸塩の分解によって生じ、特に後浴がホルマリン浴
である場合に固着の程度が更に悪化することが判った。It has also been found that the sticking that occurs in the water-washing alternative stabilizing bath is caused by the decomposition of thiosulfate, which is a component of the pre-bath, and that the degree of sticking becomes even worse when the post-bath is a formalin bath.
さらにカラーペーパー用自動現像機については若干発生
はしているもののカラーネガ用自動現像機に比べ付着物
の程度が比較的軽微であることが判った。これはカラー
ペーパーの処理では高濃度の第2鉄塩が一浴漂白定着か
らそれに続く安定液に持ち込まれ、この第2鉄塩が固着
に対して抑制作用を呈しているからと思われる。Furthermore, it was found that the degree of deposits in the automatic processor for color paper was relatively small compared to the automatic processor for color negatives, although some occurred. This is thought to be because in color paper processing, a high concentration of ferric salt is carried into the subsequent stabilizing solution from the one-bath bleach-fixing process, and this ferric salt exerts an inhibitory effect on fixation.
ざらに又、大ラボのカラーネガフィルム用の自動現像機
はハンガー(吊下)方式とシネ方式があり、ハンガ一方
式の場合には吊下による搬送方法をとっている為上記問
題は全くなく、一方シネ方式の場合は若干固着物がある
もののミニラボ用自動現像機と比べるとかなり少なく、
しかもノ\ンガ一方式と同様市場からのクレームとはな
っていないことが判った。大ラボにおいてジャミングや
スリ傷が生じにくい理由と°しては、水洗代替安定浴に
固着は生じるものの、大ラボでは、毎日あるいは定期的
に搬送用ラックや渡りラックを洗n1するなどの処理液
の管理がきちんと行なわれているのに対し、ミニラボ市
場では自動現像機内でトラブルがない限り自動現像機の
フタをあけ、洗浄することはほとんどなく、液管理が全
く行なわれていない為と考えられる。Zaranimata's automatic developing machines for color negative films come in two types: a hanger (hanging) type and a cine type.In the case of a hanger type, the above-mentioned problem does not occur at all because the hanging method is used. On the other hand, in the case of the cine method, although there are some adherents, it is much less compared to automatic developing machines for minilabs.
Moreover, it was found that there were no complaints from the market like the Nonga one-way type. The reason why jamming and scratches are less likely to occur in large laboratories is that although the stabilizing bath used as an alternative to water washing does cause sticking, in large laboratories, treatment liquids such as washing transport racks and transfer racks daily or periodically are used. In contrast, in the minilab market, unless there is a problem inside the automatic processor, the lid of the automatic processor is rarely opened and cleaned, and this is thought to be because liquid management is not carried out at all. .
本発明は以上の知見に基き完成されたものであり、本発
明に係るハロゲン化銀カラー写真感光材ネ4用処理液は
1発色現像浴、漂白浴、定着浴、水洗代替安定浴及び安
定浴を有する処理工程における前記水洗代替安定浴に用
いられる水洗代替安定液が下記一般式(1)又は一般式
(II )で示される水溶性界面活性剤を含有すること
を特徴とする。The present invention has been completed based on the above knowledge, and the processing solution for silver halide color photographic light-sensitive materials according to the present invention includes a color developing bath, a bleaching bath, a fixing bath, a water-washing substitute stabilizing bath, and a stabilizing bath. The water washing alternative stabilizing solution used in the water washing alternative stabilizing bath in the treatment step is characterized in that it contains a water-soluble surfactant represented by the following general formula (1) or general formula (II).
一般式〔I〕 ^、−〇+B+−+cヤX。General formula [I] ^, -〇+B+-+cyaX.
[式中、 A?は1価の有機基、B又はCはエチレンオ
キシド又はプロピレンオキシド又は+CH2HCH九丁
子CH2±「0−
1
H
を表わす(但し、旧、ml及びi+lfそれぞれ0、l
、2又は3である)。[In the formula, A? represents a monovalent organic group, B or C represents ethylene oxide or propylene oxide or +CH2HCH9chojiCH2±'0-1H (however, old, ml and i+lf are respectively 0 and l
, 2 or 3).
m及びnはθ〜100の整数を表わす。m and n represent integers from θ to 100.
XIは水素原子、SO3M+、 PO3M2 (Ml、
)hl*水素原子、アルカリ金属又はアンモニウムを
表す、)、アルキル基、アラルキル基、アリール基であ
る。XI is a hydrogen atom, SO3M+, PO3M2 (Ml,
)hl*represents a hydrogen atom, an alkali metal or ammonium, ), an alkyl group, an aralkyl group, an aryl group.
一般式(n)
R’ X 2−f E ’ +F+E ’ +i−r+
E ”七TR2[式中 1111は水素原子、脂肪族基
、アシル基を表わし 92は水素原子、脂肪族基を表わ
す。General formula (n) R' X 2-f E'+F+E' +i-r+
E''7TR2 [In the formula, 1111 represents a hydrogen atom, an aliphatic group, or an acyl group, and 92 represents a hydrogen atom or an aliphatic group.
El、E2及びE3はエチレンオキシド又11プロピレ
ンオキシドを表わし、 X2は酸素原子、−ト基で
R3は脂肪族基、水素原子又t±3
(El−)Tr+E2九丁(43)丁R4を表わし、
R1よ水素原子又は脂肪族基を表わす。El, E2 and E3 represent ethylene oxide or 11 propylene oxide, X2 is an oxygen atom, -to group
R3 represents an aliphatic group, a hydrogen atom, or t±3 (El-)Tr+E29 (43) R4;
R1 represents a hydrogen atom or an aliphatic group.
jLz、J13.@2、−3.n?、B3は各々0〜2
00の整数を表わす。jLz, J13. @2, -3. n? , B3 are each 0 to 2
Represents an integer of 00.
また本発明の好ましい態様としては、前記安定浴がホル
マリンを含有していること、前記/Xロゲン化銀カラー
写真感光材料が撮影用l\ロゲン化銀カラー写真感光材
料であること、前記定着浴が少なくとも0.4モル/l
のチオ硫酸塩を含有すること、前記定着浴が少なくとも
0.5モル/lのチオシアン酸塩を含有することである
。Further, in a preferred embodiment of the present invention, the stabilizing bath contains formalin, the /X silver halide color photographic light-sensitive material is a silver halide color photographic light-sensitive material for photographing, and the fixing bath is at least 0.4 mol/l
of thiosulfate, and the fixing bath contains at least 0.5 mol/l of thiocyanate.
更に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、ハロゲン化銀カラー写真感光材料を像様露光
した後1発色現像、漂白処理し。Further, in the method for processing a silver halide color photographic light-sensitive material according to the present invention, the silver halide color photographic light-sensitive material is subjected to imagewise exposure, followed by one-color development and bleaching treatment.
その後定着液で処理し、引続き水洗代替安定液で処理し
た後、ホルマリン含有安定液で処理するハロゲン化銀カ
ラー写真感光材料の処理方法において、前記水洗代替安
定液が前記一般式〔I〕又は(H)で示される水溶性界
面活性剤を含有することを特徴とする。In a method for processing a silver halide color photographic light-sensitive material, which is then treated with a fixing solution, followed by a washing substitute stabilizer, and then treated with a formalin-containing stabilizer, the washing substitute stabilizer has the formula [I] or ( It is characterized by containing a water-soluble surfactant represented by H).
又好ましい態様としては、上記処理方法において、前記
ハロゲン化銀カラー写真感光材料が撮影用ハロゲン化銀
カラー写真感光材料であること。Further, in a preferred embodiment, in the above-mentioned processing method, the silver halide color photographic light-sensitive material is a silver halide color photographic light-sensitive material for photographing.
前記漂白液に含有される漂白剤が下記一般式〔A〕又は
CB)で示される第2鉄錯塩を含有すること、前記定着
液が少なくとも0.4モJし/lのチオ硫酸塩を含有す
ること、前記定着液が少なくとも0.5モル/lのチオ
シアン酸塩を含有することである。The bleaching agent contained in the bleaching solution contains a ferric complex salt represented by the following general formula [A] or CB), and the fixing solution contains at least 0.4 moJ/l of thiosulfate. and that the fixer contains at least 0.5 mol/l of thiocyanate.
一般式〔A〕
[式中、Ar”Asはそれぞれ同一でも異ってもよ<
、 −〇〇20H、−GOON又は−P031111
M2を表す。General formula [A] [In the formula, Ar''As may be the same or different.
, -〇〇20H, -GOON or -P031111
Represents M2.
N 、 Ml、 M2はそれぞれ水素原子、アルカリ金
属又はアンモニウムを表す、Xは炭素数3〜6の置換、
未置換のアルキレン基を表す、]一般式〔B〕
[式中、A!〜A4は前記一般式〔A〕で定義したちの
°と同義であり、nは1〜8の整数を表す、またBl及
びB2は同一でも異なっていてもよく、それぞれ炭素数
2〜5の置換、未置換のフルキレン基を表す、]
なお、界面活性剤を処理液に用いることは公知であり、
例えば発色現像液においては特開昭62−42154号
公報、同82−42155号公報にアルキルベンゼン系
の界面活性剤が開示されており、更には漂白定着液又は
安定液においては、特開平1−154153号公報にエ
チレンオキサイド系のノニオン界面活性剤を含有する技
術が開示されており、更には水洗又は無水洗処理後の物
性改良、画像保存性改良を目的として安定浴に特開昭5
8−199348号公報、同59−17551号公報に
ノニオン、アニオン及びカチオン系界面活性剤を用いる
技術が開示されている。N, Ml, M2 each represent a hydrogen atom, an alkali metal or ammonium, X is a substitution having 3 to 6 carbon atoms,
Represents an unsubstituted alkylene group] General formula [B] [wherein A! ~A4 has the same meaning as ° defined in the above general formula [A], n represents an integer of 1 to 8, and Bl and B2 may be the same or different, each having 2 to 5 carbon atoms. [represents a substituted or unsubstituted fullkylene group] It is known that a surfactant is used in the treatment liquid,
For example, alkylbenzene-based surfactants are disclosed in JP-A-62-42154 and JP-A-82-42155 in color developing solutions, and JP-A-1-154153 in bleach-fix solutions or stabilizers. A technology containing an ethylene oxide-based nonionic surfactant is disclosed in Japanese Patent Application Laid-open No. 5 (1973).
No. 8-199348 and No. 59-17551 disclose techniques using nonionic, anionic, and cationic surfactants.
しかしながら、特開昭58−199348号、同581
7551号公報には、現像液の溶解性改良やフィルム面
での水滴ムラ防止の為に少量の界面活性剤を用いる方法
が開示されているだけであり1本発明の構成又は効果に
ついては全く記載されていない。However, JP-A-58-199348 and JP-A-581
Publication No. 7551 only discloses a method of using a small amount of a surfactant to improve the solubility of a developer and prevent unevenness of water droplets on the film surface, and does not describe the structure or effects of the present invention at all. It has not been.
又、特開平1−154153号公報には、漂白定着液又
は無水洗安定液に界面活性剤を用いることで低補充処理
であってもカラーネガフィルムとカラーペーパーの混合
処理が可能になる方法が開示されているが、水洗代替安
定浴に発生する固着が前浴成分であるチオ硫酸塩の分解
によって生じ、特に後浴がホルマリン浴である場合に固
着の程度が更に悪化するという技術的課題について何ら
示唆しておらず、しかも本発明のようにカラー写真感光
材料用処理液に界面活性剤を用いることにより、水洗代
替安定浴のラックに処理液成分が付着固化することを防
止できることについては全く開示されておらず、従来の
知見からは予想しがたいものであった。Furthermore, JP-A-1-154153 discloses a method that uses a surfactant in a bleach-fix solution or an anhydrous wash stabilizer to enable mixed processing of color negative film and color paper even in low replenishment processing. However, there is no technical problem that the sticking that occurs in the water washing alternative stabilizing bath is caused by the decomposition of thiosulfate, which is a component of the pre-bath, and that the degree of sticking becomes even worse especially when the post-bath is a formalin bath. Moreover, it does not disclose at all that by using a surfactant in the processing liquid for color photographic light-sensitive materials as in the present invention, it is possible to prevent the processing liquid components from adhering and solidifying on the rack of the water-washing alternative stabilizing bath. This was difficult to predict based on conventional knowledge.
以下、本発明について詳説する。 The present invention will be explained in detail below.
はじめに一般式(I)で示される水溶性界面活性剤につ
いて説明する。First, the water-soluble surfactant represented by general formula (I) will be explained.
一般式〔I〕において、 A2は1価の有機基。In general formula [I], A2 is a monovalent organic group.
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、ウンデシル又はドデシル等の各基)又は炭素
数が3〜35のアルキル基又は炭素数が2〜35のアル
ケニル基で置換されたアリール基である。For example, carbon number is 6 to 50. Preferably, it is an alkyl group having 6 to 35 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), an alkyl group having 3 to 35 carbon atoms, or an alkenyl group having 2 to 35 carbon atoms. It is a substituted aryl group.
アリール基上に置換する好ましい基としては。Preferred groups to be substituted on the aryl group include:
炭素数が1−18のアルキル基(例えば、メチル。An alkyl group having 1 to 18 carbon atoms (for example, methyl).
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、ウンデシル又はドデシル等の
非置換アルキル基)、ベンジル。unsubstituted alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), benzyl.
フェネチル等の置換アルキル基又は炭素数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、スチリル基等の置換されたアル
ケニル基)が挙げられる。Examples include substituted alkyl groups such as phenethyl, and alkenyl groups having 2 to 20 carbon atoms (for example, unsubstituted alkenyl groups such as oleyl, cetyl, allyl groups, substituted alkenyl groups such as styryl groups).
アリール基としてはフェニル、ビフェニル又はナフチル
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。Examples of the aryl group include phenyl, biphenyl, naphthyl, and the like, with phenyl being preferred. The aryl group may be substituted at any of the ortho, meta, and para positions, and a plurality of groups can be substituted.
B又はCはエチレンオキシド又はプロピレンオキシド又
は +CH2+1i−r+CH九丁子CI(2±rro
−H
を表わす(但し、 nl、s+1及びl+はそれぞれ0
.1.2又は3である)。B or C is ethylene oxide or propylene oxide or +CH2+1i-r+CH nine cloves CI (2±rro
-H (however, nl, s+1 and l+ are each 0
.. 1.2 or 3).
m及びnはθ〜100の整数を表わす。m and n represent integers from θ to 100.
xlは水素原子、S03MI、P03M2 (L、A2
は水素原子、アルカリ金属又はアンモニウムを表す、)
、アルキル基、アラルキル基、アリール基である。xl is a hydrogen atom, S03MI, P03M2 (L, A2
represents a hydrogen atom, an alkali metal or ammonium)
, an alkyl group, an aralkyl group, and an aryl group.
アルキル基、アリール基の具体例としては1例えばA2
で説明した基が挙げられる。Specific examples of alkyl groups and aryl groups include 1, such as A2
Examples include the groups explained in .
一般式〔I!〕
R’ X 2+E ’ +7r+E 2+i−r+E
’9TT R2式中、R1は水素原子、脂肪族基、アシ
ル基を表わし、 R2は水素原子、脂肪族基を表わす。General formula [I! ] R' X 2+E' +7r+E 2+i-r+E
'9TT R2 In the formula, R1 represents a hydrogen atom, an aliphatic group, or an acyl group, and R2 represents a hydrogen atom or an aliphatic group.
[il、 R2及びR3はエチレンオキシド、又はプロ
ピレンオキシドを表わし、x2は酸素原子、N−基で
R3は脂肪族基、水素原子又は3
(El+−Ir−+E2九dE% R4を表わし R4
は水素原子又は脂肪族基を表わす。[il, R2 and R3 represent ethylene oxide or propylene oxide, x2 is an oxygen atom, an N-group
R3 represents an aliphatic group, a hydrogen atom, or 3 (El+-Ir-+E29dE% R4)
represents a hydrogen atom or an aliphatic group.
12.13、 ff12 、 m3. R2,r3は各
々0〜200の整数を表わす。12.13, ff12, m3. R2 and r3 each represent an integer from 0 to 200.
以下に一般式(I)及び(II )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 compounds represented by formulas (I) and (II) are listed below, but the invention is not limited thereto.
(一般式(1)で表される化合物)
1−1
C,、+1□−〇(−C,11,O七、I+■−2
C,11,1−0(−C,11,0→π11−3
CJI+e O+CII+40−+vSOJa−4
C+ollt+
0−(−CIl+40升PO3Na*
■−22
C1山、0−C−C山0−)−11
5llt
−14
C,、II□O+Cl11.O→−11■−15
C,II、@−0−(−C,11,O→−、I+!
6
C1゜11□−0−(−C,11,0−)π11−23
+−24
!−25
−26
菖−27
Csll+s O+ C*l1−0へτ11C111
1? 0(−CIl+40男7゜C2゜11□−0+
C,II、Oへ711CBII*a O+ Ctl1
40士711C1−11*5−0−ec*I1.oうi
ll■
34
−35
6
■
7
7
8
■
9
0
■
1
■
2
11
01]
01!
11
υ11
−41
■
2
■
3
■
4
−60
(n)C,all、、−0−(CIltCILO)Tl
ll−75
1−76
11
−74
■−82
■−86
■
8
(一般式(u)で表される化合物)
11−5
l13
7−1
C+*Il□Coo + Ca1140→i11−6
C,、+1□−NIICIIfCI+10111−2
C*II+5COO+ Ctll、o−+v11−3
Cl tlltsNll + C*lI40禿11−4
C,、l+□1111−e C,Il、O→i11■−
10
−1
Il−12
+1O−f−C111CI+tC11,0−)−7云C
I1.CIl、O→漬τ11110 + Cl1CIl
*C11−0七丁÷CI1.CIl*O→7π!Ill
a
+1(−0C11,CIl、 −)−f 0C11,C
l1ICI+、−)−i−=千〇CII 、ell l
bo11前記一般式〔I〕又は(n )で示される水
溶性界面活性剤は、水洗代替安定液IJ1あたり0.0
5〜408の範囲で使用することが好ましく、より好ま
しくは0.1〜20gの範囲である。(Compound represented by general formula (1)) 1-1 C,, +1□-〇(-C,11,O7, I+■-2 C,11,1-0(-C,11,0→ π11-3 CJI+e O+CII+40-+vSOJa-4 C+ollt+ 0-(-CIl+40 square PO3Na* ■-22 C1 mountain, 0-C-C mountain 0-)-11 5llt -14 C,, II□O+Cl11.O→-11■ -15 C, II, @-0-(-C,11,O→-,I+! 6 C1゜11□-0-(-C,11,0-)π11-23 +-24 !-25 -26 Iris-27 Csll+s O+ C*l1-0 to τ11C111
1? 0(-CIl+40m7゜C2゜11□-0+
To C, II, O 711CBII*a O+ Ctl1
40shi711C1-11*5-0-ec*I1. oui
ll ■ 34 -35 6 ■ 7 7 8 ■ 9 0 ■ 1 ■ 2 11 01] 01! 11 υ11 -41 ■ 2 ■ 3 ■ 4 -60 (n)C,all,, -0-(CIltCILO)Tl
ll-75 1-76 11 -74 ■-82 ■-86 ■ 8 (Compound represented by general formula (u)) 11-5 l13 7-1 C++*Il□Coo + Ca1140→i11-6 C,, +1□-NIICIIIfCI+10111-2 C*II+5COO+ Ctll, o-+v11-3 Cl tlltsNll + C*lI40bald11-4 C,, l+□1111-e C, Il, O→i11■-
10 −1 Il-12 +1O-f-C111CI+tC11,0-)-7云C
I1. CIl, O → dipping τ11110 + Cl1CIl
*C11-0 7th block ÷ CI1. CIl*O→7π! Ill
a +1(-0C11,CIl, -)-f 0C11,C
l1ICI+,-)-i-=1000CII, ell l
bo11 The water-soluble surfactant represented by the above general formula [I] or (n) is 0.0 per water washing alternative stabilizer IJ1
It is preferably used in a range of 5 to 408 g, more preferably in a range of 0.1 to 20 g.
又、一般式〔I〕又は(11)で示される水溶性界面活
性剤の濃度はハロゲン化銀感光材料から溶出してくる界
面活性剤も含めて0.05〜40g/lの範囲にあれば
良いが、上記添加量をあらかじめ水洗代替安定液に添加
しておく方が本発明の効果を奏する上で特に好ましい、
すなわち、感光材料から溶出してくる水溶性界面活性剤
は連続処理により少量ではあるが蓄積してくるものであ
り、あらかじめ水洗代替安定液に添加されている場合の
効果とは顕著な差がある。Further, the concentration of the water-soluble surfactant represented by general formula [I] or (11), including the surfactant eluted from the silver halide photosensitive material, is in the range of 0.05 to 40 g/l. However, in order to achieve the effects of the present invention, it is particularly preferable to add the above amount to the water washing alternative stabilizing liquid in advance.
In other words, the water-soluble surfactant eluted from the photosensitive material accumulates, albeit in a small amount, through continuous processing, and there is a marked difference in the effect when it is added to the water-washing alternative stabilizing solution in advance. .
本発明に用いられる水溶性界面活性剤は少なくとも1種
含有するが2種以上併用してもよく、要は0.05〜4
0g/lの範囲で含有していれば良い。The water-soluble surfactant used in the present invention contains at least one kind, but two or more kinds may be used in combination, and in short, 0.05 to 4
It is sufficient if the content is within the range of 0 g/l.
本発明において、定着液は少なくとも0.4モル/fL
のチオ硫酸塩を含有することが好ましく、より好ましく
は0.5〜3.0モル/l含有する(とであり、特に好
ましくは0.8〜2.5モル/l含有スることにより本
発明の効果がより顕著となる0本発明の界面活性剤を水
洗代替安定液に含まない場合にはチオ硫酸塩を0.4モ
ル/i以上含有すると固着状態は短期間に急激に劣化す
るが1本発明の界面活性剤を水洗代替安定液に添加する
と長期間の処理でチオ硫酸塩を0.4モル/i以上含有
していても固着状態が良好となる。In the present invention, the fixer is at least 0.4 mol/fL
It is preferable to contain thiosulfate, more preferably 0.5 to 3.0 mol/l, and particularly preferably 0.8 to 2.5 mol/l. The effect of the invention becomes more pronounced.0 If the surfactant of the present invention is not included in the water washing alternative stabilizing solution, if thiosulfate is contained at 0.4 mol/i or more, the fixed state will deteriorate rapidly in a short period of time. 1. When the surfactant of the present invention is added to a water-washing substitute stabilizing solution, the fixing state becomes good even if it contains 0.4 mol/i or more of thiosulfate during long-term treatment.
本発明において漂白液に用いられる漂白剤は前記一般式
〔A〕又は〔B〕で表わされる有機酸の第2鉄錯塩及び
後記A′−1〜18等で示される例示化合物の第2鉄錯
塩が挙げられるが、好ましくは前記一般式〔A〕又は〔
B〕で表わされる有機酸の第2鉄錯廖である。The bleaching agent used in the bleaching solution in the present invention is a ferric complex salt of an organic acid represented by the general formula [A] or [B], and a ferric complex salt of an exemplified compound represented by A'-1 to A'-18 below. Preferably, the general formula [A] or [
B] is a ferric complex of an organic acid.
以下に一般式〔A〕で示される化合物について詳述する
。The compound represented by the general formula [A] will be explained in detail below.
A1−A4はそれぞれ同一でも異っていてもよく、−C
H20)1、−GOON又は−P03MIM2を表し、
X1M亀、M2はそれぞれ水素原子、アルカリ金属(例
えばナトリウム、カリウム)又はアンモニウムを表す、
Xは炭素数3〜6の置換、未置換のアルキレン基(例え
ばプロピレン2ブチレン、ペンタメチレン等)を表す、
置換基としては水酸基、炭素数1〜3のアルキル基が挙
げられる。A1-A4 may be the same or different, and -C
H20) 1, -GOON or -P03MIM2,
X1M and M2 each represent a hydrogen atom, an alkali metal (e.g. sodium, potassium) or ammonium,
X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (e.g. propylene 2-butylene, pentamethylene, etc.),
Examples of the substituent include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.
以下に、前記一般式〔A〕で示される化合物の好ましい
具体例を示す。Preferred specific examples of the compound represented by the general formula [A] are shown below.
(A−1)
(A−7)
(A−2)
(A−8)
(A−3)
(A−9)
(A−4;)
(A−10)
(A−5)
(A−11)
(A −12)
(A−6)
これら(A−1)〜(A−12)の化合物の第2鉄錯塩
としては、これらの第2鉄錯塩のナトリウム塩、カリウ
ム塩又はアンモニウム塩を任意に用いることができる0
本発明の目的の効果及び溶解度の点からは、これらの第
2鉄錯塩のアンモニウム塩が好ましく用いられる。(A-1) (A-7) (A-2) (A-8) (A-3) (A-9) (A-4;) (A-10) (A-5) (A-11 ) (A-12) (A-6) As the ferric complex salts of these compounds (A-1) to (A-12), sodium salts, potassium salts, or ammonium salts of these ferric complex salts may be optionally used. 0 can be used for
From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.
前記化合物例の中で1本発明において特に好ましく用い
られるものは、(A−1)、(A−3)、(A−4)、
(A−5)、(A−9)であり、とりわけ特に好ましい
ものは(A−1)である。Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-3), (A-4),
(A-5) and (A-9), and particularly preferred is (A-1).
次に一般式CB)で示される化合物について詳述する。Next, the compound represented by the general formula CB) will be explained in detail.
^1〜A4は前記と同義であり、nは1〜8の整数を表
す、Bl及びB2は同一でも異っていてもよく、それぞ
れ炭素数2〜5の置換、未置換のフルキレン基((Mえ
ifエチレン、プロピレン、ブチレン、ペンクメチレン
等)を表す、置換基としては水酸基、炭素数1〜3の低
級アルキル基(メチル基。^1 to A4 have the same meanings as above, n represents an integer of 1 to 8, Bl and B2 may be the same or different, and each represents a substituted or unsubstituted fullkylene group having 2 to 5 carbon atoms (( Examples of substituents include hydroxyl group and lower alkyl group having 1 to 3 carbon atoms (methyl group).
エチル基、プロピル基)等が挙げられる。ethyl group, propyl group), etc.
以下に、前記一般式CB)で示される化合物の好ましく
具体例を示す。Preferred specific examples of the compound represented by the general formula CB) are shown below.
(B−1)
(B −2)
(B−3)
(B−4)
(B−5)
(E−6)
(B −7)
これら(B−1)〜(B−7)の化合物の第2欽錯塩は
、これらの化合物の第2鉄錯塩のナトリウム1…、カリ
ウム塩又はアンモニウム塩を任意に用いることができる
0本発明においては、前記漂白剤の酸化力が十分高いこ
と、漂白刃ブリはアンモニウム塩の場合に発生し易いこ
とから、アンモニウム塩は50モル%以下、好ましくは
20モル%以下、特に好ましくは10モル%以下が本発
明を実施する上で好ましい態様である。(B-1) (B-2) (B-3) (B-4) (B-5) (E-6) (B-7) These (B-1) to (B-7) compounds As the ferric complex salt, sodium 1..., potassium salt, or ammonium salt of the ferric complex salt of these compounds can be optionally used. In the present invention, the oxidizing power of the bleaching agent is sufficiently high, and Since yellowtail tends to occur in the case of ammonium salts, it is a preferred embodiment for carrying out the present invention that the ammonium salt content is 50 mol% or less, preferably 20 mol% or less, particularly preferably 10 mol% or less.
前記化合物例の中で1本発明において特に好ましく用い
られるものは、特に(E−1)、(B−2)、(B−7
)であり、とりわけ特に好ましいのは(B−1)である
。Among the above compound examples, one particularly preferably used in the present invention is (E-1), (B-2), (B-7).
), and particularly preferred is (B-1).
有機酸第2鉄!塩の添加量は漂白液1文当り0.1モル
〜2.0モルの範囲で含有することが好ましく、より好
ましくは0.15〜1.5モル/旦の範囲である。Ferric organic acid! The amount of salt added is preferably in the range of 0.1 mol to 2.0 mol per liter of bleaching solution, more preferably in the range of 0.15 to 1.5 mol/day.
漂白液において、上記一般式〔A〕又はCB)で示され
る化合物以外の好ましい漂白剤としては下記化合物の第
2鉄鎖塩(例えばアンモニウム。In the bleaching solution, preferable bleaching agents other than the compounds represented by the above general formula [A] or CB) include ferric chain salts of the following compounds (for example, ammonium).
ナトリウム、カリウム、トリエタノールアミン等の塩)
が例示されるがこれらに限定されない。salts of sodium, potassium, triethanolamine, etc.)
Examples include, but are not limited to.
(A′−1) エチレンジアミン四酢酸〔A′−2)
)ランス−1,2−シクロヘキサンジアミン四酢
醜
(A′−3) ジヒドロキシエチルグリシン酸〔A′
−4〕 エチレンジアミンテトラキスメチレンホスホン
酸
(A’−5) ニトリロトリスメチレンホスホン猷(
A′−6) ジエチレントリアミンペンタキスメチレ
ンホスホン酸
(A’−7) ジエチレントリアミン五酢酸(A′−
8) エチレンジアミンジオルトヒドロキジフェニル
酢酸
(A”−9) ヒドロキシエチルエチレンジアミン三
酢酸
(A”−10) エチレンジアミンジプロピオン酸〔
^’−11) エチレンジアミンジ酢酸(A’−12
) ヒドロキシエチルイミノジ酢酸(A”−13)
ニトリロトリ酢酸
〔^’−14) ニトリロ三プロピオン酸〔ム’−1
5) )リエチレンテトラミン六酢酸(A’−18
) エチレンジアミン四プロピオン酸漂白液には、前
記一般式〔A〕又は(E)で示される化合物の第2鉄錯
塩に、前記A”−1−18の化合物の第2鉄錯塩の1種
又は2種以上を組合せて使用〒きる。(A'-1) Ethylenediaminetetraacetic acid [A'-2)
) Lance-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycinate [A'
-4] Ethylenediaminetetrakismethylenephosphonic acid (A'-5) Nitrilotrismethylenephosphonic acid (A'-5)
A'-6) Diethylenetriaminepentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-
8) Ethylenediaminediorthohydroxydiphenylacetic acid (A”-9) Hydroxyethylethylenediaminetriacetic acid (A”-10) Ethylenediaminedipropionic acid [
^'-11) Ethylenediamine diacetic acid (A'-12
) Hydroxyethyliminodiacetic acid (A”-13)
Nitrilotriacetic acid [^'-14] Nitrilotripropionic acid [Mu'-1
5)) Liethylenetetraminehexaacetic acid (A'-18
) The ethylenediaminetetrapropionic acid bleaching solution contains one or two of the ferric complex salts of the compound represented by A''-1-18 in addition to the ferric complex salt of the compound represented by the general formula [A] or (E). You can use more than one species in combination.
有機融第2鉄錯塩を2種以上を組合せて使用する場合は
、本発明の効果をより良好に奏するという点から前記一
般式〔A〕又はCB)で示される化合物の第2鉄錯塩が
70%(モル換算)以上占めることが好ましく、より好
ましくは80%以上であり、特に好ましくは90%以上
であり、最も好ましくは95%以上である。When using two or more types of organic molten ferric complex salts in combination, the ferric complex salt of the compound represented by the general formula [A] or CB) is 70% % (in terms of mole) or more, more preferably 80% or more, particularly preferably 90% or more, most preferably 95% or more.
有機酸鉄(m)錯塩は錯塩の形で使用してもよいし、鉄
1)塩、例えば!酸第2鉄、塩化第2鉄、酢酸第2鉄、
硫#第2鉄アンモニウム。Organic acid iron (m) complex salts may be used in the form of complex salts, iron 1) salts, for example! ferric acid, ferric chloride, ferric acetate,
Sulfur #ferric ammonium.
燐酸第2鉄などと7ミノボリカルボン酸またはその塩を
用いて溶液中で鉄(III)イオン錯塩を形成させても
よい、また錯塩の形で使用する場合は、1種類の錯塩を
用いてもよいし、また2種類以上の錯塩を用いてもよい
、さらに第2鉄塩と7ミノポリカルボン酸を用いて溶液
中で錯塩を形成する場合は第2鉄塩を1種類または2種
類以上使用してもよい、更にまたアミノポリカルボン酸
を1種類または2種類以上使用してもよい。An iron (III) ion complex salt may be formed in a solution using ferric phosphate, etc. and 7-minobolycarboxylic acid or its salt, or when used in the form of a complex salt, one type of complex salt may be used. Alternatively, two or more types of complex salts may be used. Furthermore, when forming a complex salt in a solution using a ferric salt and a 7-minopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used.
また、いずれの場合にもアミノポリカルボン酸な鉄(m
)イオン錯塩を形成する以上に過剰に用いてもよい。In both cases, aminopolycarboxylic acid iron (m
) It may be used in excess of the amount required to form an ionic complex salt.
また上記の鉄1)イオン錯体を含む漂白定着液ないし漂
白液には鉄以外のコバルト、銅、ニッケル、亜鉛等の金
属イオン錯塩が入っていてもよい。Further, the bleach-fix solution or bleaching solution containing the above-mentioned iron 1) ion complex may contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc.
漂白液には、特願昭83−48931号明細書に記載の
イミダゾール及びその誘導体又は同明細書記載の一般式
(I)〜(EX)で示される化合物及びこれらの例示化
合物の少なくとも一種を含有することにより迅速性に対
して効果を奏しうる。The bleaching solution contains imidazole and its derivatives described in Japanese Patent Application No. 83-48931, or compounds represented by general formulas (I) to (EX) described therein, and at least one of these exemplified compounds. This can have an effect on speed.
上記の漂白促進剤の他、特願昭60−2835118号
明細書の第51頁から第115頁に記載の例示化合物及
び特開昭63−17445号明細書の第22頁から第2
5頁に記載の例示化合物、特開昭53−95830号、
同53−28428号公報記載の化合物等も同様に用い
ることができる。In addition to the bleaching accelerators mentioned above, the exemplified compounds described on pages 51 to 115 of Japanese Patent Application No. 60-2835118 and pages 22 to 2 of Japanese Patent Application Laid-open No. 17445/1982
Exemplary compounds described on page 5, JP-A-53-95830,
Compounds described in Publication No. 53-28428 can also be used in the same manner.
これらの漂白促進剤は単独で用いてもよいし、21ii
以上を併用してもよく、鰯加量は一般に漂白液l皇′当
り約0.01〜100gの範囲が好ましく、より好まし
くは0.05〜50gであり、特に好ましくは0.05
〜15gである。These bleach accelerators may be used alone or 21ii
The above may be used in combination, and the amount of sardine added is generally preferably in the range of about 0.01 to 100 g per liter of bleaching solution, more preferably 0.05 to 50 g, particularly preferably 0.05 g.
~15g.
漂白促進剤を添加する場合には、そのまま添加溶解して
もよいが、水、アルカリ、有機酸等に予め溶解して添加
するのが一般的であり、必要に応じてメタノール、エタ
ノール、アセトン等の有機溶媒を用いて溶解して添加す
ることもできる。When adding a bleaching accelerator, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add methanol, ethanol, acetone, etc. as necessary. It can also be added after being dissolved in an organic solvent.
漂白液の温度は20℃〜50℃で使用されるのがよいが
、望ましくは25℃〜45℃である。The temperature of the bleaching solution is preferably 20°C to 50°C, preferably 25°C to 45°C.
漂白液のpalは6.0以下が好ましく、より好ましく
は1.0以上5.5以下にすることである。The pal of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less.
なお、漂白液のp)Iはハロゲン化銀感光材料の処理時
の処理槽のpHであり、いわゆる補充液のpHとは明確
に区別されうる。Note that p)I of the bleaching solution is the pH of the processing tank during processing of the silver halide photosensitive material, and can be clearly distinguished from the pH of the so-called replenisher.
漂白液には、臭化アンモニウム、臭化カリウム、臭化ナ
トリウムの如きハロゲン化物を通常添加して用いる。又
、各種の蛍光増白剤や消泡剤あるいは界面活性剤を含有
せしめることもできる。Halides such as ammonium bromide, potassium bromide, and sodium bromide are usually added to the bleaching solution. Further, various optical brighteners, antifoaming agents, or surfactants can be contained.
漂白液の好ましい補充量はハロゲン化銀カラー写真感光
材料1m″当り500mJl以下であり、好ましくハフ
0鳳見ないし400膳9であり、最も好ましくは40−
見ないし350腸皇であり、低補充量になればなる程、
本発明の効果がより顕著となる。The preferred replenishment amount of the bleaching solution is 500 mJl or less per 1 m'' of silver halide color photographic light-sensitive material, preferably from 0 to 400, most preferably 40 -
It's 350 intestines, and the lower the supplementation amount, the more
The effects of the present invention become more significant.
本発明においては漂白液の活性度を高める為に処理浴中
及び処理補充液貯蔵タンク内で所望により空気の吹き込
み、又は酸素の吹き込みを行ってよく、或いは適当な酸
化剤、例えば過酸化水素、臭素酸塩、過硫酸塩等を適宜
添加してもよい。In the present invention, in order to increase the activity of the bleaching solution, air or oxygen may be blown into the processing bath and the processing replenisher storage tank, if desired, or a suitable oxidizing agent such as hydrogen peroxide, Bromates, persulfates, etc. may be added as appropriate.
次に漂白工程後に採用される定着工程にお(する定着液
に用いられる定着剤としては、前述の如く少なくとも0
.4モル/lのチオ硫酸塩が用いられるが、チオシアン
酸塩を混合使用すると、本発明の課題である固着の問題
を改善できる。チオシアン酸塩の添加量としては少なく
とも0.5モル/1が好ましく、 0.1〜3.0モ
ル/すがより好ましく、特に好ましくは0.2〜2.5
モル/lの範囲である。Next, in the fixing step adopted after the bleaching step, the fixing agent used in the fixing solution is at least 0.
.. Although 4 mol/l of thiosulfate is used, the admixture of thiocyanate can improve the problem of sticking, which is an object of the present invention. The amount of thiocyanate added is preferably at least 0.5 mol/1, more preferably 0.1 to 3.0 mol/1, particularly preferably 0.2 to 2.5 mol/1.
The range is mol/l.
定着液には、これら定着剤の他に更に硼酸、硼砂、水酸
化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸
カリウム、重炭酸ナトリウム、重炭酸カリウム、酢酸、
酢酸ナトリウム、水酸化アンモニウム等の各種の塩から
成るpH緩衝剤を単独或いは2種以上含むことができる
。In addition to these fixing agents, the fixing solution also contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
It may contain one or more types of pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide.
更にアルカリハライドまたはアンモニウムハライド、例
えば臭化カリウム、臭化ナトリウム、塩化ナトリウム、
臭化アンモニウム等の再ハロゲン化剤を多量に含有させ
ることが望ましい、また硼酸塩、蓚酸塩、酢酸塩、炭酸
塩、燐酸塩等のp)II衝剤、アルキルアミン類、ポリ
エチレンオキサイド類等の通常定着液に添加することが
知られている化合物を適宜添加することができる。Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain large amounts of rehalogenating agents such as ammonium bromide, and p) II buffering agents such as borates, oxalates, acetates, carbonates, phosphates, alkylamines, polyethylene oxides, etc. Compounds known to be usually added to fixers can be added as appropriate.
又、定着液においては、アンモニウムイオンが全カチオ
ンの50モル%以下、好ましくは20モル%以下、特に
好ましくは0−1oモル%が漂白液から直接定着処理さ
れる場合のスティンを防止でき。In addition, in the fixing solution, ammonium ions account for 50 mol % or less, preferably 20 mol % or less, particularly preferably 0-10 mol % of the total cations, which can prevent staining when the fixing solution is directly fixed from the bleaching solution.
且つアンモニウムイオンの減少等により、低公害化がは
かれる上で好ましい実施態様であるが、アンモニウムイ
オンを減少させると定着性に影響がでることもあり、好
ましくはチオシアン酸塩を0.4モル/l以上3.0モ
ル以下程度併用して使用するか、又はチオ硫酸塩の濃度
を0.5モル/1以上、好ましくは1.0モル/1以上
、特に好ましくは1.2モル/文〜2.5モル/又とす
ることが好ましい実施態様である。This is a preferred embodiment because it reduces pollution by reducing ammonium ions, but reducing ammonium ions may affect fixing properties, so it is preferable to reduce the amount of thiocyanate to 0.4 mol/l. The above 3.0 mol or less is used in combination, or the concentration of thiosulfate is 0.5 mol/1 or more, preferably 1.0 mol/1 or more, particularly preferably 1.2 mol/1 to 2 In a preferred embodiment, the amount is .5 mol/mole.
なお、定着液から公知の方法で銀回収してもよい0例え
ば電気分解法(仏閣特許2,299,887号明細書記
載)、沈殿法(特開昭52−73037号公報記載、壮
図特許2,331,220号明細書記載)、イオン交換
法(特開昭51−17114号公報記載、壮図特許2.
548,237号りj細書記載)及び金属置換法(英国
特許1,353,805号明細書記載)等が有効に利用
できる。Incidentally, silver may be recovered from the fixing solution by a known method. For example, electrolysis method (described in Buddhist Patent No. 2,299,887), precipitation method (described in JP-A-52-73037, Sozu Patent) 2,331,220), ion exchange method (described in JP-A-51-17114, Sozu Patent 2.
548,237) and the metal substitution method (described in British Patent No. 1,353,805), etc. can be effectively used.
これら銀回収はタンク液中から電解法又はアニオン交換
樹脂を用いてインラインで銀回収すると、迅速処理適性
がさらに良好となるため、特に好ましいが、オーバーフ
ロー廃液から銀回収し。It is particularly preferable to recover silver from the tank solution in-line using an electrolytic method or an anion exchange resin, since the suitability for rapid processing becomes even better, but silver recovery from the overflow waste solution is particularly preferable.
再生使用してもよい。May be recycled and used.
定着液の補充量は感光材料1rn’当り 1200m文
以下が好ましく、より好ましくは感光材料1rn’当り
20腸文〜1000s見であり、特に好ましくは50膳
見〜800膳見である。The amount of replenishment of the fixing solution is preferably 1,200 microns or less per rn' of the light-sensitive material, more preferably 20 microns to 1,000 microns per rn' of the light-sensitive material, particularly preferably 50 microns to 800 microns per rn' of the photosensitive material.
定着液のpHは4〜8の範囲が好ましい。The pH of the fixer is preferably in the range of 4 to 8.
定着液に、特願昭83−48931号明細書第56頁に
記載の一般式[FA]で示される化合物及びこの例示化
合物を添加してもよく、漂白定着液又は、定着液を用い
て、少量感光材料を長期間にわたって処理する際に発生
するスラッジが極めて少ないという別なる効果がえられ
る。A compound represented by the general formula [FA] described on page 56 of Japanese Patent Application No. 83-48931 and exemplified compounds thereof may be added to the fixing solution, and using a bleach-fixing solution or a fixing solution, Another advantage is that the amount of sludge generated when processing a small amount of light-sensitive material over a long period of time is extremely small.
同明細書記載の一般式[FAIで示される化合物は米国
特許3,335,181号明細書及び米国特許3,28
0,718号明細書に記載されている如き一般的な方法
で合成できる。これら、前記一般式[FAIで示される
化合物はそれぞれ単独で用いてもよく、また2種以上組
合せて用いてもよい。The compound represented by the general formula [FAI] described in the same specification is described in U.S. Patent No. 3,335,181 and U.S. Patent No. 3,28
It can be synthesized by a general method as described in US Pat. No. 0,718. These compounds represented by the general formula [FAI] may be used alone or in combination of two or more.
また、これら一般式[FAIで示される化谷物の添加量
は処理液1fL当り0.1g〜200gの範囲で好結果
が得られる。Further, good results can be obtained when the amount of chemical compounds represented by the general formula [FAI] ranges from 0.1 g to 200 g per 1 fL of the treatment liquid.
定着液には亜硫酸塩及び亜硫酸放出化合物を用いてもよ
い、これらの具体的例示化合物としては、亜硫酸カリウ
ム、亜硫酸ナトリウム、亜硫酸アンモニウム、亜硫酸水
素アンモニウム、亜硫酸水素カリウム、亜硫酸水素ナト
リウム、メタ重亜硫酸カリウム、メタ重亜硫酸ナトリウ
ム、メタ重亜硫酸アンモニウム等が挙げられる。さらに
特願昭[13−48931号明細書第BO頁記載の一般
式[B−13又は[B−2]で示される化合物も包含さ
れる。Sulfites and sulfite-releasing compounds may be used in the fixer; specific exemplary compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, potassium metabisulfite. , sodium metabisulfite, ammonium metabisulfite, and the like. Furthermore, compounds represented by the general formula [B-13 or [B-2] described in Japanese Patent Application No. 13-48931, page BO are also included.
これらの亜硫酸塩及び亜硫酸放出化合物は、定着液II
L当り亜硫酸イオンとして少なくとも0.05モル必要
であるが、 0.08モル/又〜0.65モル/lの範
囲が好ましく、0.1θモル/l〜0.50モル/文の
範囲が特に好ましい、とりわけ特に0.■2モル/l〜
0.40モル/lの範囲が好ましい。These sulfites and sulfite-releasing compounds are present in Fixer II
At least 0.05 mol of sulfite ion is required per L, but the range of 0.08 mol/l to 0.65 mol/l is preferred, and the range of 0.1θ mol/l to 0.50 mol/l is particularly preferred. Preferably, especially 0. ■2 mol/l~
A range of 0.40 mol/l is preferred.
本発明に係わる漂白液及び定着液による処理時間は任意
であるが、各々6分30秒以下であることが好ましく、
より好ましくは10秒〜4分20秒、特に好ましくは2
0秒〜3分20秒の範囲である。The processing time with the bleaching solution and fixing solution according to the present invention is arbitrary, but each is preferably 6 minutes and 30 seconds or less,
More preferably 10 seconds to 4 minutes 20 seconds, particularly preferably 2
The range is from 0 seconds to 3 minutes and 20 seconds.
本発明の処理方法においては、漂白液、定着液に強制的
液撹拌を付与することが本発明の実施態様として好まし
い、この理由は本発明の目的の効果をより良好に奏する
のみならず、迅速処理適性の観点からである。ここに強
制的液撹拌とは1通常の液の拡散移動ではなく、攪拌手
段を付加して強制的に攪拌することを意味する0強制的
撹拌手段としては、特願昭83−48930号及び特開
平1−20B343号に記載の手段を採用することがで
きる。In the processing method of the present invention, it is preferred as an embodiment of the present invention to provide the bleaching solution and the fixing solution with forcible stirring. This is from the viewpoint of processing suitability. Forcible stirring of the liquid here means 1. It means adding a stirring means to forcibly stir the liquid, rather than the normal diffusion movement of the liquid. The means described in JP-A-1-20B343 can be adopted.
又、本発明においては、発色現像槽から漂白槽等、各検
量のクロスオーバー時間が10秒以内、好ましくは7秒
以内が本発明とは別なる効果である漂白刃ブリに対して
効果があり、更にはダックヒル弁等を設置して感光材料
により持ち込まれる処理液を少なくする方法も本発明を
実施する上で好ましい態様である。In addition, in the present invention, the cross-over time for each calibration from the color developing tank to the bleach tank, etc. is within 10 seconds, preferably within 7 seconds, which is effective against bleaching blade blur, which is a different effect from the present invention. Furthermore, a method of installing a duck hill valve or the like to reduce the amount of processing liquid brought in by the photosensitive material is also a preferred embodiment of the present invention.
本発明においては、感光材料は定着処理工程に引き続い
て水洗代替安定化処理工程及び従来タイプの安定化処理
工程で処理される。In the present invention, the photographic material is subjected to a fixing process followed by a washing alternative stabilization process and a conventional type stabilization process.
前者の水洗代替安定化処理は、スーパースタビライザー
による処理であり、後者の従来タイプの安定化処理はホ
ルマリン含有の安定浴による安定化処理である。The former stabilization treatment alternative to washing with water is a process using a super stabilizer, and the latter conventional type stabilization treatment is a stabilization treatment using a formalin-containing stabilization bath.
連続処理における水洗代替安定液の補充量は処理する撮
影用カラー写真感光材料の単位面積当り前浴からの持ち
込み量の0.5〜50倍が好ましい。In continuous processing, the amount of replenishment of the water-washing substitute stabilizer is preferably 0.5 to 50 times the amount brought in from the pre-bath per unit area of the color photographic light-sensitive material to be processed.
前浴からの持ち込み量は感光材料の種類、自動現像機の
搬送速度、搬送方式、感光材ネ4表面のスクイズ方式等
により異なる。撮影用カラー感光材料の場合通常持ち込
み量は50mJl/In’〜150■皇/rn’であり
、この持ち込み量に対する効果的な補充量は25seJ
l / rn’ 〜7.5jL / m’の範囲であり
、特に効果が顕著な補充量は200騰皇/ば〜1500
mi/ばの範囲にある。The amount brought in from the pre-bath varies depending on the type of photosensitive material, the conveying speed of the automatic processor, the conveying method, the method of squeezing the surface of the photosensitive material 4, etc. In the case of color photosensitive materials for photography, the normal amount of carry-in is 50 mJl/In' to 150 ■K/rn', and the effective replenishment amount for this carry-in amount is 25 seJ.
l / rn' ~ 7.5jL / m' range, and the particularly effective replenishment amount is 200 Tenghuang / Ba ~ 1500
It is in the range of mi/ba.
水洗代替安定化槽は複数の檜より構成されることが好ま
しく、好ましくは2槽以上6槽以下にすることであり、
特に好ましくは2〜3槽、更に好ましくは2槽としカウ
ンターカレント方式(後浴に供給して前浴からオーバー
フローさせる方式)にすることが好ましい。It is preferable that the water washing alternative stabilization tank is composed of a plurality of cypress trees, preferably 2 tanks or more and 6 tanks or less,
It is particularly preferable to use 2 to 3 tanks, more preferably 2 tanks, and use a countercurrent system (a system in which the water is supplied to the rear bath and overflows from the front bath).
水洗代替安定液による処理の処理温度は15〜80℃が
好ましく、より好ましくは20〜45℃の範囲がよい。The treatment temperature for the treatment with the water washing substitute stabilizer is preferably 15 to 80°C, more preferably 20 to 45°C.
水洗代替安定液のPH値としては、画像保存性を向上さ
せる目的でpH4,0〜9.0の範囲が好ましく、より
好ましくはp)I 4.5〜9.0の範囲であり、特に
好ましくはP)+ 5.0〜8.5の範囲である。The pH value of the water washing alternative stabilizer is preferably in the range of pH 4.0 to 9.0, more preferably in the range of p)I 4.5 to 9.0, particularly preferably in the range of pH 4.0 to 9.0 for the purpose of improving image storage stability. P)+ ranges from 5.0 to 8.5.
水洗代替安定液はキレート剤と併用して金属塩を含有す
ることが好ましい、かかる金属塩としては、Ba、 C
a、 Ce、 Go、 In、La、 Mn、 Mi、
Bi、 Pb。It is preferable that the water washing alternative stabilizer contains a metal salt in combination with a chelating agent. Such metal salts include Ba, C,
a, Ce, Go, In, La, Mn, Mi,
Bi, Pb.
Sn、 Zn、 Ti、 Zr、 Ng、 An又は
5rc7)金属塩があり、ハロゲン化物、水酸化物、硫
酸塩、炭酸塩。Sn, Zn, Ti, Zr, Ng, An or 5rc7) Metal salts include halides, hydroxides, sulfates, carbonates.
リン酸塩、酢酸塩等の無機塩又は水溶性キレート剤とし
て供給できる。使用量としては水洗代替安定液In当り
IX 10−4〜IX 10−1モルノ範囲が好まし
く、より好ましくは4X 10−4〜2X 10−2千
ルの範囲である。It can be supplied as an inorganic salt such as phosphate or acetate or as a water-soluble chelating agent. The amount used is preferably in the range of IX 10-4 to IX 10-1 mol per In of the water-washing alternative stabilizer, more preferably in the range of 4X 10-4 to 2X 10-2,000 mol.
水洗代替安定液には、有機酸塩(クエン酸、酢酸、コハ
ク酸、シュウ触4安息香酸等) 、 pH調整剤(リン
酸塩、ホウ酸塩、塩酸、硫酸塩等)、界面活性剤、防腐
剤等を添加することができる。これら化合物の添加量は
水洗代替安定浴のPHを維持するに必要でかつカラー写
真画像の保存時の安定性と沈殿の発生に対し悪影響を及
ぼさない範囲の量をどのような組み合わせで使用しても
さしつかえない。Water washing alternative stabilizers include organic acid salts (citric acid, acetic acid, succinic acid, sulfuric acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), surfactants, Preservatives etc. can be added. The amount of these compounds to be added is necessary to maintain the pH of the water-washing alternative stabilizing bath, and the amount is within the range that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. I can't help it.
水洗代替安定液に好ましく用いられる防パイ剤は、ヒド
ロキシ安息香酸エステル化合物、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、インキサゾール系化合物、プロパツールア
ミン系化合物、スルファミド系化合物、アミノ酸系化合
物、活性ハロゲン放出化合物及びペンツトリアゾール系
化合物である。Preferably used anti-pecking agents in the water-washing alternative stabilizer include hydroxybenzoic acid ester compounds, phenolic compounds,
Thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds 1 morpholine compounds,
These include quaternary phosphonium compounds, ammonium compounds, urea compounds, inxazole compounds, propatoolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds, and penttriazole compounds.
なお上記防パイ剤の中で好ましく用いられる化合物は、
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、四級アンモニウム系化合
物、活性ハロゲン放出化合物、ペンツトリアゾール系化
合物である。更に。In addition, the compounds preferably used among the above-mentioned anti-spill agents are:
These are phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen-releasing compounds, and penttriazole compounds. Furthermore.
特に好ましくは液保存性の上からフェノール系化合物、
チアゾール系化合物、活性ハロゲン放出化合物及びペン
ツトリアゾール系化合物である。Particularly preferred are phenolic compounds from the viewpoint of liquid storage stability.
These are thiazole-based compounds, active halogen-releasing compounds, and penztriazole-based compounds.
水洗代替安定液への防パイ剤の添加量は、水洗代替安定
液11当り0.001〜50gの範囲が好ましく、より
好ましくは0.005〜10gの範囲で使用される。The amount of the anti-piping agent added to the washing alternative stabilizing liquid is preferably in the range of 0.001 to 50 g, more preferably in the range of 0.005 to 10 g per 11 of the washing alternative stabilizing liquid.
本発明の処理においては水洗代替安定液からも前述の方
法で銀回収してもよい、また、水洗代替安定液をイオン
交換処理、電気透析処理(特願昭59−98352号参
照)や逆浸透処理(特願昭59−118532号参照)
等してもよい、又、水洗代替安定液に使用する水を予め
脱イオン処理したものを使用することも好ましい、即ち
安定液の防パイ性や安定液の安定性及び画像保存性向上
がはかれるからである。脱イオン処理の手段としては、
処理後の水洗水のCa、 Mgイオンを5PP履以下に
するものであればいかなるものでもよいが1例えばイオ
ン交換樹脂や逆浸透膜による処理を単独或いは併用する
ことが好ましい、イオン交換樹脂や逆浸透膜については
公開接摺87−1984号に詳細に記載されている。In the treatment of the present invention, silver may be recovered from the water washing alternative stabilizing solution by the above-mentioned method, and the water washing alternative stabilizing solution may be subjected to ion exchange treatment, electrodialysis treatment (see Japanese Patent Application No. 59-98352) or reverse osmosis. Processing (see Japanese Patent Application No. 118532/1983)
It is also preferable to use water that has been deionized in advance for the water-washing alternative stabilizing solution.In other words, the anti-spill properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage properties are improved. It is from. As a means of deionization treatment,
Any material may be used as long as it reduces the Ca and Mg ions in the washed water after treatment to 5 PP or less. For example, it is preferable to use ion exchange resin or reverse osmosis membrane treatment alone or in combination. The permeable membrane is described in detail in Kokka Sukuri No. 87-1984.
水洗代替安定液中の塩濃度は+000pp■以下が好ま
しく、より好ましくは800ppm以下である。The salt concentration in the water washing alternative stabilizing solution is preferably +000 ppm or less, more preferably 800 ppm or less.
水洗代替安定液の処理時間は2分以下が好ましく、より
好ましくは1分30秒以下、特に迅速処理という観点か
ら好ましくは1分以下である。The processing time of the water washing substitute stabilizing solution is preferably 2 minutes or less, more preferably 1 minute 30 seconds or less, particularly preferably 1 minute or less from the viewpoint of rapid processing.
水洗代替安定液中には本発明外の界面活性剤を本発明の
界面活性剤と組合せて含有することができる。界面活性
剤としては、特開昭82−2504411号公報記載の
一般式[I]〜[II ]で表される化合物及び水溶性
有機シロキサン系化合物等が挙げられる。The water washing substitute stabilizing solution may contain a surfactant other than the one according to the invention in combination with the surfactant according to the invention. Examples of the surfactant include compounds represented by formulas [I] to [II] described in JP-A-82-2504411, water-soluble organic siloxane compounds, and the like.
発色現像処理工程に用いられる発色現像主薬としては、
アミノフェノール系化合物及びp−フェニンレンジアミ
ン系化合物があるが1本発明においては、水溶性基を有
するp−フェニンレンジアミン系化合物が好ましい。Color developing agents used in the color development process include:
Although there are aminophenol compounds and p-phenylene diamine compounds, p-phenylene diamine compounds having a water-soluble group are preferred in the present invention.
かかる水溶性基は、p−7工ニレンジアミン系化合物の
7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、具体的な水溶性基としては、−(C)lz)e−
CH20H。Such a water-soluble group has at least one on the 7-mino group or benzene nucleus of the p-7-functional nylene diamine compound, and a specific water-soluble group is -(C)lz)e-
CH20H.
−(CH2)a−NH9Oz−(CH2)*−CH3゜
−(CIlz)*−0−(GHz)n−CHs、−(C
I2CHpO)ncsH2m、+ (m及びnはそれぞ
れ0以上の整数を表す、 ) 、−COOH基、−9o
3H基等が好ましいものとして挙げられる。-(CH2)a-NH9Oz-(CH2)*-CH3゜-(CIlz)*-0-(GHz)n-CHs, -(C
I2CHpO) ncsH2m, + (m and n each represent an integer of 0 or more, ), -COOH group, -9o
Preferred examples include 3H group.
本発明に好ましく用いられる発色現像主薬の具体的例示
化合物を以下に示す。Specific examples of color developing agents preferably used in the present invention are shown below.
[例示発色現像主薬]
(A−1)
0″I・\10・Il、Nll5O・011・(A−2
)
0・11・\10・1・011
(A−3)
0山\10・11・Oll
以下余白
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N00(^−1)、(^−2)、(A−3
)、(A−4)、 (^−6)、(A−7)及び(^−
15)で示した化合物であり、特に(^−1)又は(A
−3)である。[Example color developing agent] (A-1) 0″I・\10・Il, Nll5O・011・(A-2
) 0・11・\10・1・011 (A-3) 0山\10・11・Oll Below margin Among the color developing agents exemplified above, preferred ones for use in the present invention are exemplified N00 (^-1), (^-2), (A-3
), (A-4), (^-6), (A-7) and (^-
15), especially (^-1) or (A
-3).
上記発色現像主薬は通常、塩酸塩、硫酸塩。The color developing agent mentioned above is usually a hydrochloride or a sulfate.
p−トルエンスルホン酸塩等の塩のかたちで用いられる
。It is used in the form of salts such as p-toluenesulfonate.
発色現像処理工程に用いられる発色現像液は、現像液に
通常用いられるアルカリ剤1例えば水酸化ナトリウム、
水酸化カリウム、水酸化アンモニウム、炭酸ナトリウム
、炭酸カリウム、硫酸ナトリウム、メタホウ酸ナトリウ
ム又は硼砂等を含むことができる。更に種々の添加剤1
例えばベンジルアルコール、ハロゲン化アルカリ、例え
ば臭化カリウム又は塩化カリウム等、あるいは現像調節
剤として例えばシトラジン酸等、保恒剤としてヒドロキ
シルアミン、ヒドロキシルアミン訪導体(例えばジエチ
ルヒドロキシルアミン)、ヒドラジン誘導体(例えばヒ
ドラジン誘導体)又は亜硫酸塩等を含むことができる。The color developing solution used in the color development processing step contains alkaline agents commonly used in developing solutions, such as sodium hydroxide,
Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, and the like can be included. Furthermore, various additives 1
Examples include benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, development regulators such as citradinic acid, preservatives such as hydroxylamine, hydroxylamine conductors (e.g. diethylhydroxylamine), hydrazine derivatives (e.g. hydrazine), etc. derivatives) or sulfites.
さらにまた、各種消泡剤や界面活性剤を、またメタノー
ル、ジメチルフォルムアミド又はジメチルスルフオキシ
ド等の有機溶剤等を適宜含有せしめることができる。Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.
発色現像液のpHは通常7以上であり、好ましくは約9
〜13である。The pH of the color developer is usually 7 or higher, preferably about 9.
~13.
発色現像液には必要に応じて酸化防止剤として、テトロ
ン酸、テトロンイミド、2−アニリノエタノール、ジヒ
ドロキシアセトン、芳香族第2アルコール、ヒドロキサ
ム酸、ペントースまたはヘキソース、ピロガロール−1
,3−ジメチルエーテル等が含有されてもよい。The color developing solution contains antioxidants such as tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1 as necessary.
, 3-dimethyl ether, etc. may be contained.
発色現像液中には、金属イオン封鎖剤として、種々なる
キレート剤を併用することができる1例えば該キレート
剤としてエチレンジアミン四酢酸、ジエチレントリアミ
ン五酢酸等の7ミノポリカルボン酸、1−ヒドロキシエ
チリデン−1,1−ジホスホン酸等の有機ホスホン酸、
アミノトリ(メチレンホスホン酸)もしくはエチレンジ
アミンテトラリン酸等の7ミノポリホスホン酸、クエン
酸もしくはグルコン酸等のオキシカルボン酸、2−ホス
ホノブタン−1,2,4−)リカルボン酸等のホスホノ
カルボン酸、トリポリリン酸もしくはヘキサメタリン酸
等のポリリン酸等が挙げられる。In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents.1 For example, the chelating agents include 7-minopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1 , organic phosphonic acids such as 1-diphosphonic acid,
7minopolyphosphonic acid such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-)licarboxylic acid, tripolyline Examples include acids and polyphosphoric acids such as hexametaphosphoric acid.
連続処理における発色現像液の好ましい補充量はカラー
ネガティブフィルムについては感光材料100cは当り
15.OmJl以下が好ましく、より好ましくは2.
5層1〜B、01m1であり、更に好ましくは3.0m
l〜7.0腸見である。カラーペーパーの処理の場合は
0,2〜3.0−見、好ましくは0.3〜1゜6〜lで
ある。The preferred replenishment amount of color developer in continuous processing is per photosensitive material 100c for color negative film.15. OmJl or less is preferable, more preferably 2.
5 layers 1 to B, 01 m1, more preferably 3.0 m
1 ~ 7.0 gut readings. In the case of color paper processing, it is 0.2-3.0 mm, preferably 0.3-1.6-l.
ハロゲン化銀カラー写真感光材料(以下、必要により「
感光材料」又は「感材」と略す)に用いられるハロゲン
化銀粒子は塩化銀、塩臭化銀、沃臭化銀、塩沃臭化銀い
ずれでもよい。Silver halide color photographic material (hereinafter referred to as “
The silver halide grains used in the "photosensitive material" or "sensitive material" may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.
感光材料中の全ハロゲン化銀乳剤の平均粒径は2.0g
m以下が好ましく、より好ましくは0.1〜l・2μ層
である。The average grain size of all silver halide emulsions in the light-sensitive material is 2.0 g.
The layer thickness is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm.
ハロゲン化銀乳剤が粒径/粒子の厚さの平均値が5未満
である粒子を含む場合には粒子サイズ分布が単分散性で
あることが脱−性の上から好ましい。When the silver halide emulsion contains grains having an average value of grain size/grain thickness of less than 5, it is preferable for the grain size distribution to be monodisperse from the viewpoint of de-leaving properties.
単分散性ハロゲン化銀乳剤とは、平均粒grを中心に±
20%の粒径範囲内に含まれるハロゲン化銀重量が全ハ
ロゲン化銀粒子重量の60%以上であるものを言い、好
ましくは70%以上、更に好ましくは80%以上である
。A monodisperse silver halide emulsion is a monodisperse silver halide emulsion with ±
The weight of silver halide contained within the 20% grain size range is 60% or more of the total weight of silver halide grains, preferably 70% or more, and more preferably 80% or more.
ここに、平均粒径rは1粒径riを有する粒子の頻度n
iとri3との1lniXri3が最大となるときの粒
径「iと定義する(有効数字3桁、最小桁数字は4捨5
人する)。Here, the average particle size r is the frequency n of particles having 1 particle size ri.
The particle size when 1lniXri3 of i and ri3 is maximum is defined as "i" (3 significant figures, minimum digit is 5 to 40)
people).
ここで言う粒径とは1球状のI\ロゲン化銀粒子の場合
は、その直径、また球状以外の形状の粒子の場合は、そ
の投影像を同面積の円像に換算した時の直径である。In the case of a spherical I\silver halide grain, the grain size referred to here is the diameter, or in the case of a grain with a shape other than spherical, the diameter when its projected image is converted into a circular image of the same area. be.
粒径は例えば該粒子を電子IQIt鏡で1万倍から5万
倍に拡大して撮影し、そのプリント上の粒子直径又は投
影時の面積を実測することによって得ることができる(
測定粒子個数は無差別に1000個以上あることとする
)。The particle size can be obtained, for example, by photographing the particle with an electronic IQIt mirror at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.
The number of particles to be measured is assumed to be 1000 or more indiscriminately).
特に好ましい高度の単分散乳剤は
平均粒径
によって定義した分布の広さが20%以下のものであり
、更に好ましくは15%以下のものである。Particularly preferred highly monodisperse emulsions are those in which the breadth of the distribution defined by the average grain size is 20% or less, more preferably 15% or less.
ハロゲン化銀粒子の結晶は、正常晶でも双晶でもその他
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できる。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、内部と外部が異質の層状構造(コア・シェル
型)をしたものであってもよい、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でもよい、さらに平板状ハ
ロゲン化銀粒子(特開昭58−113934号、特願昭
59−170070号参照)を用いることもできる。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 can be used. Furthermore, 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. These silver halides are of the type that mainly forms latent images on the surface,
It is also possible to use tabular silver halide grains (see JP-A-58-113934 and Japanese Patent Application No. 59-170070).
ハロゲン化銀粒子は、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。The silver halide grains may be obtained by any preparation method such as an acid 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
長させる方法でもよい、ハロゲン化銀粒子を成長させる
場合に反応釜内のPH,pl’1g等をコントロールし
、例えば特開昭54−48521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 grains may be produced using an acidic method, and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size. It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521.
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1
本明細書においてハロゲン化銀乳剤という。Preparation of silver halide grains is preferably carried out as described above.
In this specification, it is referred to 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WIJ
lスズ塩、二酸化チオ尿素、ポリアミン等;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
ロロパラデート、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かぶり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 WIJ.
tin salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc.; or, for example, ruthenium, Sensitizers of water-soluble salts such as palladium, platinum, rhodium, and iridium, specifically ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadate (these types can be sensitized depending on the amount) ), alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). may be sensitized.
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 is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group is added. At least one kind may be contained.
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、増感色素をハロゲン化銀1モルに対して例
えば5 X 10−8〜3 X 10−3モル添加して
光学増感させてもよい、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ができる。Silver halide can be optically sensitized by adding a sensitizing dye, for example, in an amount of 5 x 10-8 to 3 x 10-3 mol per mol of silver halide, in order to impart photosensitivity to a desired wavelength range. Various sensitizing dyes may be used, and each sensitizing dye may be used alone or in combination of two or more.
また感光材料は、赤感性ハロゲン化銀乳剤層、青感性ハ
ロゲン化銀乳剤層及び緑感性ハロゲン化銀乳剤層にそれ
ぞれカプラ、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たものが好ましい。In addition, the light-sensitive material contains a coupler, that is, a compound capable of reacting with an oxidized form of a color developing agent to form a dye, in a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer, respectively. Preferably, it contains.
使用できるイエローカプラとしては、閉鎖ケトメチレン
化合物さらにいわゆる2当量カプラと称される活性点−
〇−アリール置換カブラ、活性点−〇−アシル置換カプ
ラ、活性点ヒダントイン化合物M換カプラ、活性点ウラ
ゾール化合物置換カプラおよび活性点コハク酸イミド化
合物置換カプラ、活性点フッ素置換カプラ、活性点塩素
あるいは臭素を換カプラ、活性点−〇−スルホニル置換
カプラ等が有効なイエローカプラとして用いることがで
5る。用い得るイエローカプラの具体例としては、米国
特許2,875,057号、同3,265,508号、
同3.408,194号、同3,551,155号、同
3,582.322号、同3,725,072号、同3
,891,445号、同3.933501号、同4,0
22,820号、同4,328,024号、同4,40
1,752号、***特許1.547.888号、***出
願公開2,219,917号、同2,281,381号
、同2,414,006号、英国特許1,425,02
0号、同1.478,760号、特公昭51−1078
3号、特開昭4726133号、同48−73147号
、同51−102838号、同50−8341号、同5
0−123342号、同50−130442号。Yellow couplers that can be used include closed ketomethylene compounds and active point -so-called 2-equivalent couplers.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound M-substituted coupler, active point urazole compound substituted coupler, active point substituted coupler with succinimide compound, active point fluorine substituted coupler, active point chlorine or bromine substituted coupler Couplers substituted with , active point -0-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent Nos. 2,875,057 and 3,265,508;
3.408,194, 3,551,155, 3,582.322, 3,725,072, 3
, No. 891,445, No. 3.933501, No. 4,0
No. 22,820, No. 4,328,024, No. 4,40
No. 1,752, West German Patent No. 1.547.888, West German Patent Application No. 2,219,917, No. 2,281,381, No. 2,414,006, British Patent No. 1,425,02
No. 0, No. 1.478,760, Special Publication No. 1978-1078
No. 3, JP-A-4726133, JP-A No. 48-73147, JP-A No. 51-102838, JP-A No. 50-8341, JP-A No. 5
No. 0-123342, No. 50-130442.
同51−21827号、同50−878509号、同5
2−82424号。No. 51-21827, No. 50-878509, No. 5
No. 2-82424.
同52−115219号、同58−95348号、特開
平1−180542号等に記載されたものを挙げること
ができる。Examples include those described in JP-A-52-115219, JP-A-58-95348, and JP-A-1-180542.
カラー写真感光材料が陰画用感光材料の場合。When the color photographic light-sensitive material is a negative light-sensitive material.
好ましいイエローカプラーとしては、ベンゾイルアセト
アニリド系イエローカプラーが挙げられる。Preferred yellow couplers include benzoylacetanilide yellow couplers.
ベンゾイルアセトアニリド系イエローカプラーはいかな
るベンゾイルアセトアニリド銹導体をも含むが、好まル
いものは、下記一般式(VB−1)で表される化合物で
ある。The benzoylacetanilide yellow coupler includes any benzoylacetanilide conductor, but preferred is a compound represented by the following general formula (VB-1).
一般式(VB−1)
式中、R1−R1及び曽は水素原子又は置換基であり、
好ましくはRI+R2+及びR3は同−及び異なったも
の双方を含み、各々水素原子、ハロゲン原子、アルキル
基、アリール基、アルコキシ基、アシルアミノ基、カル
バモイル基、アルコキシカルボニル基、スルホンアミド
基またはスルファモイル基を表す。General formula (VB-1) In the formula, R1-R1 and So are hydrogen atoms or substituents,
Preferably, RI+R2+ and R3 include both the same and different ones, and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, or a sulfamoyl group. .
R4* R5* Rs 、及びR1は同−及び異なった
もの双方を含み、好ましくは、各々水素原子、アルキル
基、アルコキシ基、アリールオキシ基、アシルアミノ基
またはスルホンアミド基を表す。R4*R5*Rs and R1 include both the same and different groups, and each preferably represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, or a sulfonamide group.
賛は好ましくはハロゲン原子、アルキル基、アルコキシ
基、アリールオキシ基またはジアルキルアミノ基を表す
。Preferred represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a dialkylamino group.
xlは水素原子、または脱離可能な基を表す。xl represents a hydrogen atom or a detachable group.
こレラペンゾイルアセトアニリド系イエローカプラーは
、米国特許2,875,057号、同3,725,07
2号、同3.8i91,445号、特公昭51−107
83号、特開昭48−73147号、同50−8341
号、同51−102836号。Thisrapenzoylacetanilide yellow coupler is disclosed in U.S. Pat. Nos. 2,875,057 and 3,725,07.
No. 2, 3.8i91, 445, Special Publication No. 1984-107
No. 83, JP-A-48-73147, JP-A No. 50-8341
No. 51-102836.
同52−115219号、同54−21448号、同5
8−95237号。No. 52-115219, No. 54-21448, No. 5
No. 8-95237.
同59−1511183号、同511−174838号
、同59−208835号、特開平1−187580号
、同1−207748号、同l−207748号、同1
−214848号、同1−227152号、同l−23
1050号、同1−295258号、同1−30905
7号、同1−341240号、同1−318745号に
記載された化合物を含み、且つ記載された方法により合
成される。No. 59-1511183, No. 511-174838, No. 59-208835, No. 1-187580, No. 1-207748, No. 1-207748, No. 1
-214848, 1-227152, 1-23
No. 1050, No. 1-295258, No. 1-30905
No. 7, No. 1-341240, No. 1-318745, and is synthesized by the method described.
イエローカプラーの添加量は総量で通常ハロゲン化銀1
モル当り 1.OX 10−3モル〜1.0モル。The total amount of yellow coupler added is usually 1 silver halide.
Per mole 1. OX 10-3 mole to 1.0 mole.
好ましくは5.OX 10−3モル〜B、OX 10−
1モルの範囲である。Preferably 5. OX 10-3 mol ~ B, OX 10-
It is in the range of 1 mole.
一方カラー写真感光材料が陽画用写真感光材料の場合、
好ましいイエローカプラーとしては、下記一般式(Y−
I)で示される化合物が挙げられる。On the other hand, if the color photographic material is a positive photographic material,
A preferred yellow coupler has the following general formula (Y-
Examples include compounds represented by I).
一般式(Y−1)
^1
1式中、R1はアルキル基、シクロアルキル基またはア
リール基を表わし、R2はアルキル基、シクロアルキル
基、アリール基またはアシル基を表わし、R3はベンゼ
ン環に置換可能な基を表わす、nは0またはlを表わす
、XIは現像主薬の酸化体とのカップリング時に離脱し
得る基を表わし、Ylは有機基を表わす、】
前記一般式(Y−1)で示されるイエローカプラーは、
好ましくはハロゲン化銀1モル当たりI X 10−3
モル〜1モル、より好ましくはlXl0−2モル−8X
10−1モルの範囲で用いることができる。General formula (Y-1) ^1 In formula 1, R1 represents an alkyl group, cycloalkyl group, or aryl group, R2 represents an alkyl group, cycloalkyl group, aryl group, or acyl group, and R3 is substituted with a benzene ring. In the general formula (Y-1), The yellow coupler shown is
Preferably I x 10-3 per mole of silver halide
mol to 1 mol, more preferably lXl0-2 mol-8X
It can be used in a range of 10-1 mol.
使用できるマゼンタカプラとしては、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はイエローカプラと同様4当量型
カプラだけでなく。Examples of magenta couplers that can be used include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. These magenta couplers are not only 4-equivalent couplers like the yellow couplers.
2当量カプラであってもよい、使用できるマゼンタカプ
ラの具体例としては、米国特許2,800,788号、
同2.1183,808号、同3.082.853号、
同3.127,289号2同3,311,478号、同
3,419,391号、同3,519,429号、同3
,558,319号、同3.582,322号、同3,
815,508号、同3,834,908号、同3.8
111,445号、同4,310,819号、同4.3
51,811?号、同4,500,630号、同4,5
40.1154号、***特許1,810,484号、西
独特許出願(OtS)2.408,885号、同2.4
I7,945号、同2,424,487号、特公昭40
−8031号、特開昭51−20828号、同52−5
81122号、同49−129538号、同48−74
027号、同50−159338号、同52−4212
1号、同411−74028号、同50〜80233号
、同51−2804号、同53−55122号、同6O
−43E159号、欧州特許73.Et3e号等に記載
されたものを挙げることができる。Specific examples of magenta couplers that may be used, which may be 2-equivalent couplers, include U.S. Pat. No. 2,800,788;
2.1183,808, 3.082.853,
3.127,289 No.2 3.311.478, 3.419.391, 3.519.429, 3.
, No. 558,319, No. 3.582,322, No. 3,
No. 815,508, No. 3,834,908, No. 3.8
No. 111,445, No. 4,310,819, No. 4.3
51,811? No. 4,500,630, No. 4,5
40.1154, West German Patent No. 1,810,484, West German Patent Application (OtS) No. 2.408,885, West German Patent Application No. 2.4
No. I7,945, No. 2,424,487, Special Publication No. 1977
-8031, JP-A-51-20828, JP-A-52-5
No. 81122, No. 49-129538, No. 48-74
No. 027, No. 50-159338, No. 52-4212
No. 1, No. 411-74028, No. 50-80233, No. 51-2804, No. 53-55122, No. 6O
-43E159, European Patent 73. Examples include those described in Et3e and the like.
好ましく用いられるマゼンタカプラーとしては下記一般
式(M−I)で示されるマゼンタカプラーが挙げられる
。Preferably used magenta couplers include magenta couplers represented by the following general formula (M-I).
一般式(M−I)
一般式(M−I)において、Zは含窒素複素環を形成す
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。General formula (M-I) In general formula (M-I), Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. good.
又は水素原子又は発色現像主薬の酸化体との反応により
離脱しうる基を表す。Alternatively, it represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.
またRは水素原子又は置換基を表す。Moreover, R represents a hydrogen atom or a substituent.
一般式(M−I)で示されるマゼンタカプラーは特開昭
83−108855号明細書26頁に記載されており、
具体的例示化合物は同明細1i29〜34頁に記載のN
001〜N0.77が挙げられる。The magenta coupler represented by the general formula (M-I) is described on page 26 of JP-A-83-108855,
Specific example compounds include N described on pages 29-34 of the same specification 1i.
001 to N0.77.
上記マゼンタカプラーは通常ハロゲン化銀1モル当りI
X 10−3モル〜1モル、好ましくは1x10−2
モル−8X10−1モルの範囲で用いることができる。The above magenta couplers are usually I per mole of silver halide.
X 10-3 mol to 1 mol, preferably 1x10-2
It can be used in the range of -8 x 10 -1 moles.
使用できるシアンカプラとしては、例えばフェノール系
、ナフトール系カプラを挙げることができる。そしてこ
れらのシアンカプラはイエローカプラと同様4当量型カ
ブラだけでなく、2当量カプラであってもよい、使用で
きるシアンカプラの具体例としては、米国特許2,36
9,828号、同2.434,272号、同2,474
.293号、同2,521,908号、同2.8115
,828号、同3,034,892号、同3.311,
478号、同3,458,315号、同3,478,5
83号、同3,583,171号、同3,591,38
3号、同3.767.411号、同3,772.002
号、同3.1133,494号、同4,004,111
29号、同4,052,212号、同4.148,39
B号、同4,228,233号、l?il 4,298
,200号、同4,334,001号、同4,327,
173号、同4.451,559号、同4,427,7
87号、欧州特許1213135A号、同181826
A号、***特許出願(OLS)2.414,830号、
同2,454,329号、特開昭48−5983号、同
51−28034号、同4B−5055号、同51−+
4[1[127号、同52−89824号、同52−9
0932号、同5B−95348号、特公昭49−11
572号等に記載されたものを挙げることができる。Examples of cyan couplers that can be used include phenolic and naphthol couplers. These cyan couplers may be not only 4-equivalent type couplers like the yellow couplers, but also 2-equivalent couplers. Specific examples of cyan couplers that can be used include U.S. Pat.
No. 9,828, No. 2.434,272, No. 2,474
.. No. 293, No. 2,521,908, No. 2.8115
, No. 828, No. 3,034,892, No. 3.311,
No. 478, No. 3,458,315, No. 3,478,5
No. 83, No. 3,583,171, No. 3,591,38
No. 3, No. 3.767.411, No. 3,772.002
No. 3.1133,494, No. 4,004,111
No. 29, No. 4,052,212, No. 4.148,39
No. B, No. 4,228,233, l? il 4,298
, No. 200, No. 4,334,001, No. 4,327,
No. 173, No. 4,451,559, No. 4,427,7
No. 87, European Patent No. 1213135A, European Patent No. 181826
No. A, West German Patent Application (OLS) No. 2.414,830,
JP-A No. 2,454,329, JP-A No. 48-5983, JP-A No. 51-28034, JP-A No. 4B-5055, JP-A No. 51-+
4[1[No. 127, No. 52-89824, No. 52-9
No. 0932, No. 5B-95348, Special Publication No. 49-11
Examples include those described in No. 572 and the like.
カラー写真感光材料が陰画用感光材料の場合。When the color photographic light-sensitive material is a negative light-sensitive material.
好ましいシアンカプラーとしては、下記一般式%式% 化合物が挙げられる。As a preferable cyan coupler, the following general formula % formula % Examples include compounds.
一般式(C−A)
一般式(C−B)
式中、R+はアルキル基、フルヶニル基、シクロアルキ
ル基、アリール基又はヘテロ環基を表し、Yは
で表される基であり(但しR2はアルキル基、アルクこ
ル基、シクロアルキル基、アリール又はへテロ環基な表
し、 R3は水素原子もしくはR2で表される基を表
す、 R2と R3は同じでも異っていてもよく、互い
に結合して5〜6員のへテロ環を形成していてもよい、
)、Zは水素原子又は芳香族第1級アミン系発色現像主
薬の酸化体とのカップリング反応により離脱し得る基を
表す。General formula (C-A) General formula (C-B) In the formula, R+ represents an alkyl group, a fluganyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y is a group represented by (However, R2 represents an alkyl group, an alkyl group, a cycloalkyl group, an aryl or a heterocyclic group; R3 represents a hydrogen atom or a group represented by R2; R2 and R3 may be the same or different; May be combined to form a 5- to 6-membered heterocycle,
), Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
一般式(C−C)
0H
(式中、R1は−CONR4R5,−NHCORs 、
−NHCOOR&。General formula (C-C) 0H (wherein, R1 is -CONR4R5, -NHCORs,
-NHCOOR&.
−NH9O2Ri、−NHCONRaRs又は−NH3
Q2HR4R5を表し、R2は1価基、 R3は置換基
を表し、Xは水素原子又は芳香族第1級アミン現像主薬
酸化体との反応により離脱する基を表し、見は0又は1
を表し、■はθ〜3の整数を表し、R4及びR5は各々
水素原子、芳香族基、脂肪族基又はへテロ環基を表し。-NH9O2Ri, -NHCONRaRs or -NH3
Q2HR4R5, R2 is a monovalent group, R3 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, and the number is 0 or 1.
, ■ represents an integer of θ to 3, and R4 and R5 each represent a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group.
R6は芳香族基、脂肪族基又はヘテロ環基を表す。R6 represents an aromatic group, an aliphatic group or a heterocyclic group.
層が2又は3のとき、各々のR3は同一でも異なっても
よく、互いに結合して環を形成してもよく。When there are two or three layers, each R3 may be the same or different, or may be bonded to each other to form a ring.
又R4とR5,R2とR3、R2とXは結合して環を形
成してもよい、但し1文が0のとき騰はO,R+は−C
0NHR7であり、R1は芳香族基を表す、)具体的な
例としては、米国特許3,741,583号、特開昭4
7−37425号、特公昭4B−38894号、特開昭
50−10135号、同50−117422号、同50
−130441号、同51−108841号、同50−
120334号、同52−18315号。Also, R4 and R5, R2 and R3, and R2 and
0NHR7 and R1 represents an aromatic group) Specific examples include U.S. Pat.
7-37425, Japanese Patent Publication No. 4B-38894, Japanese Patent Publication No. 10135-1987, Japanese Patent Publication No. 50-117422, Japanese Patent Publication No. 50-117425
-130441, 51-108841, 50-
No. 120334, No. 52-18315.
同 53−105228号、同54−14736号、同
54−48237号、同55−32071号、同55−
85957号、同5G−1838号、同5B−1284
3号、同5B−27147号、同5111−14805
0号、同59−188958号、同80−24547号
、同80−35731号、同80−37557号、等の
各公報に記載されているものが挙げられる。No. 53-105228, No. 54-14736, No. 54-48237, No. 55-32071, No. 55-
No. 85957, No. 5G-1838, No. 5B-1284
No. 3, No. 5B-27147, No. 5111-14805
Examples include those described in publications such as No. 0, No. 59-188958, No. 80-24547, No. 80-35731, and No. 80-37557.
一般式(C−C)で表されるカプラーの具体例は特開昭
60−237448号、同81−153840号、同1
11−145557号、同82−85242号、同48
−15529号、同50−117422号、同52−1
8315号、同52−90932号、同53−5242
3号、同54−48237号2同54−68129号、
同55−32071号、同55−851157号、同
55−105228号。Specific examples of couplers represented by the general formula (C-C) are JP-A-60-237448, JP-A No. 81-153840, JP-A No. 1
No. 11-145557, No. 82-85242, No. 48
-15529, 50-117422, 52-1
No. 8315, No. 52-90932, No. 53-5242
No. 3, No. 54-48237 No. 2 No. 54-68129,
No. 55-32071, No. 55-851157, No. 55-851157, No. 55-851157, No.
No. 55-105228.
同 5B−11338号、同5B−12843号、同5
B−27147号。5B-11338, 5B-12843, 5
B-27147.
同5B−128832号、同5B−1115348号及
び米国特許3.488,193号等に記載されており、
これらに記載の方法により合成できる。It is described in 5B-128832, 5B-1115348, and U.S. Patent No. 3.488,193, etc.
It can be synthesized by the methods described in these.
カプラーの添加量は通常ハロゲン化銀1モル当り 1.
OX 10−3モル〜1.0モル、好ましくは5.0×
10−3モル−8,0X10−1モルの範囲である2次
にカラー写真感光材料が陽画用感光材料の場合、好まし
いシアンカプラーとしては、下記一般式(C−1)で示
されるものが挙げられる。The amount of coupler added is usually per mole of silver halide.1.
OX 10-3 mol to 1.0 mol, preferably 5.0×
When the secondary color photographic light-sensitive material in the range of 10-3 mol - 8.0 x 10-1 mol is a positive light-sensitive material, preferred cyan couplers include those represented by the following general formula (C-1). It will be done.
一般式(C−1)
11
シアンカプラーとしては(c−i)で示されるカプラー
と2.5−ジアシルアミノ系シアンカプラーを併用する
ことが好ましい。General formula (C-1) 11 As the cyan coupler, it is preferable to use a coupler represented by (ci) in combination with a 2,5-diacylamino cyan coupler.
2.5−ジアシルアミノフェノール系シアンカプラーと
しては、下記一般式(C−2)
1
[式中、R1はバラスト基を表し、 R2は炭素数2以
上のアルキル基を表す、 Zlは水素原子又は発色現像
主薬酸化体との反応により離脱する原子又は基を表す、
]
具体例は、特公昭49−11572号、特開昭81−3
142号、同81−9852号、同81−9853号、
同81−39045号、同81−50138号、同83
−99141号、同61−105545号等に記載され
ている。The 2.5-diacylaminophenol cyan coupler has the following general formula (C-2) 1 [wherein, R1 represents a ballast group, R2 represents an alkyl group having 2 or more carbon atoms, and Zl represents a hydrogen atom or Represents an atom or group that leaves due to reaction with an oxidized color developing agent;
] Specific examples include Japanese Patent Publication No. 49-11572 and Japanese Patent Publication No. 81-3.
No. 142, No. 81-9852, No. 81-9853,
No. 81-39045, No. 81-50138, No. 83
-99141, No. 61-105545, etc.
前記一般式(C−1)で示されるシアン色素形成カプラ
ーは1通常ハロゲン化銀1モル当りl×1O−3モル〜
1モル、好ましくはlXl0−2モル−8XIO−1モ
ルの範囲で用いることができる。The cyan dye-forming coupler represented by the general formula (C-1) is usually 1×1 O −3 mol to 1 mol per mol of silver halide.
It can be used in a range of 1 mol, preferably 1XIO-2 mol to 8XIO-1 mol.
[式中、R1はアルキル基、アリール基を表すaR2は
アルキル基、シクロアルキル基、アリール基又は複素環
基を表す、 R1は水素原子、ハロゲン原子、アルキ
ル基、アルコキシ基を表す、 R3はR1と共同して
環を形成してもよい、Zは水素原子又は芳香族第1級ア
ミン系発色現像主薬の酸化体とのカップリング反応によ
り離脱し得る原子又は基を表す。[In the formula, R1 represents an alkyl group or an aryl group; aR2 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group; R1 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; R3 represents R1 Z may form a ring in conjunction with Z, and Z represents a hydrogen atom or an atom or group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
上述のシアンカプラーの具体例としては更に例えば、特
願昭61−21853号明細書第26〜35頁、特開昭
80−225155号公報第7頁左下の欄〜第10頁右
下の欄、特開昭80−222853号公報第6頁左上の
欄〜第8頁右下の欄及び特開昭59−185135号公
報第6頁左下の欄〜89頁左上の欄に記載された2、5
−ジアシルアミノ系シアンカプラーを含み、これらの明
細書及び公報に記載されている方法に従って合成するこ
とができる。Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61-21853, pages 26-35, JP-A-80-225155, lower left column on page 7 to lower right column on page 10, 2 and 5 described in JP-A-80-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185135, page 6, lower left column to page 89, upper left column.
- diacylamino cyan couplers, and can be synthesized according to the methods described in these specifications and publications.
前記一般式[C−2]で示されるシアン色素形成カプラ
ーは、通常ハロゲン化銀1モル当り1×■0−3〜1モ
ル、好ましくはI X 10−2モル−8×10−1モ
ルの範囲で用いることができる。The cyan dye-forming coupler represented by the general formula [C-2] usually has an amount of 1 x 0-3 to 1 mol, preferably I x 10-2 mol - 8 x 10-1 mol per mol of silver halide. Can be used within a range.
前記一般式[C−1]で示されるシアンカプラーと一般
゛式[C−2] で示されるシアンカプラーを併用する
場合の混合比率としてはモル比で1:9〜9:lが好ま
しく、特に7:3〜3ニアが好ましい。When the cyan coupler represented by the general formula [C-1] and the cyan coupler represented by the general formula [C-2] are used together, the mixing ratio is preferably 1:9 to 9:l in terms of molar ratio, particularly 7:3 to 3 near is preferred.
ハロゲン化銀乳剤層、その他の写真構成層中にはカラー
ドマゼンタ又はカラードシアンカプラーポリマーカプラ
等のカプラを併用してもよい、カラードマゼンタ又はカ
ラードシアンカブラについては本出願人による特願昭5
9−193811号(特開昭81−72235号参照)
の記載を、またポリマーカプラについては本出願人によ
る特願昭58−172151号(特開昭81−5014
3号参照)の記載を各々参照できる。In the silver halide emulsion layer and other photographic constituent layers, a coupler such as a colored magenta or colored cyan coupler or a polymer coupler may be used together.
No. 9-193811 (see Japanese Patent Application Laid-open No. 81-72235)
Regarding polymer couplers, please refer to Japanese Patent Application No. 58-172151 (Japanese Unexamined Patent Publication No. 81-5014) filed by the present applicant.
(Refer to No. 3).
更に迅速性、脱銀性に効果のある特願昭Et3−325
01号記載(P232一記載78)のB −A R化合
物(例示化合物(1)〜(77))及び銀塩タイプの漂
白促進剤を用いることも本発明の好ましい実施態様であ
る。Patent application Sho Et3-325 which is more effective in rapidity and desilvering performance
It is also a preferred embodiment of the present invention to use the B-A R compounds (exemplary compounds (1) to (77)) described in No. 01 (P232-Description 78) and a silver salt type bleaching accelerator.
高塩化銀含有感光材料を用いる場合には含窒素複素環メ
ルカプト化合物を組合せて用いることがp了ましい。When using a photosensitive material containing high silver chloride, it is preferable to use a nitrogen-containing heterocyclic mercapto compound in combination.
これら含窒素複素環メルカプト化合物の具体例としては
、特開昭83−106E155号明細書、第42〜45
頁記載の(I′−1)〜(I ′−87)が挙げられる
。Specific examples of these nitrogen-containing heterocyclic mercapto compounds include JP-A-83-106E155, Nos. 42-45.
Examples include (I'-1) to (I'-87) described on page 1.
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
とができる1例えばリサーチφディスクロージャー誌1
7843号に記載されているがぶり防止剤、安定剤、紫
外線吸収剤、色汚染防止剤、蛍光増白剤、色画像退色防
止剤、帯電防止剤、硬膜剤、界面活性剤、可塑剤、湿潤
剤等を用いることができる。The light-sensitive material may contain various other photographic additives.For example, Research φ Disclosure Magazine1.
Antifog agents, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, as described in No. 7843; Wetting agents and the like can be used.
感光材料において、乳剤を調製するために用いられる親
木性コロイドは、ゼラチンが好ましく。In light-sensitive materials, the wood-philic colloid used to prepare emulsions is preferably gelatin.
他にも、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−ス
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 addition, derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, carboxymethyl cellulose, starch derivatives, monomers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are also available. Any synthetic hydrophilic polymers such as mono- or copolymers are included.
感光材料の支持体としては、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、バライ
タ紙やポリエチレン被覆紙、ポリプロピレン合成紙、反
射層を併用する透明支持体,例えばガラス板等が挙げら
れ。Supports for photosensitive materials include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and transparent supports with a reflective layer. , for example, a glass plate.
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。Other ordinary transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material.
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、エアードクタ塗4ノ、カーテン塗
布,ホッパー塗布等の種々の塗布方法を用いることがで
きる.また米国特許2、781,781号、同2,94
1,898号に記載の方法による2層以上の同時塗布法
を用いることもできる。Various coating methods can be used to coat the silver halide emulsion layer and other photographic constituent layers, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent Nos. 2,781,781 and 2,94
It is also possible to use a simultaneous coating method of two or more layers according to the method described in No. 1,898.
各乳剤層の塗設位にを任意に定めることができる.例え
ばフルカラーの撮影用カラーネガ写真感光羽料の場合に
は、支持体から順次赤感光性ハロゲン化銀乳剤層,緑感
光性ハロゲン化銀乳剤層。The coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color color negative photographic feather material, a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer are sequentially applied from the support.
青感光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
層からなっていてもよい。It is preferable to arrange the blue-sensitive silver halide emulsion layer. Each of these photosensitive silver halide emulsion layers may consist of two or more layers.
本発明で処理される感光材料において、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
ルター層、カール防止層。In the photosensitive material processed according to the present invention, an intermediate layer having an appropriate thickness may be optionally provided depending on the purpose, and may further include a filter layer and an anti-curl layer.
保;If アンチハレーション層等の種々の層を構成層
として適宜組合せて用いることができる。If various layers such as an antihalation layer can be used in appropriate combination as constituent layers.
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。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.
本発明の感光材料の処理方法においては、感光材料とし
て、感光材料中にカプラ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、カラーネガフィルム、カ
ラーペーパー、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、中でも撮影用ハロゲン化銀カラ
ー写真感光材料が好ましい。In the method for processing a photosensitive material of the present invention, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method, color negative film, color paper, color positive film, color for slides, etc. It can be applied to any light-sensitive material such as reversal film, color reversal film for movies, color reversal film for TV, and reversal color paper, among which silver halide color photographic light-sensitive materials for photography are preferred.
(発明の効果〕
本発明によれば、水洗代替安定浴における固着現象の発
生を防止し、感光材料のスリ傷やジャミングの発生を防
止できる感光材料用処理液及びそれを用いた処理方法を
提供できる。(Effects of the Invention) According to the present invention, there is provided a processing liquid for photosensitive materials that can prevent the occurrence of sticking phenomenon in a washing alternative stabilizing bath and prevent the occurrence of scratches and jamming on photosensitive materials, and a processing method using the same. can.
以下、本発明の実施例を挙げて本発明を更に詳説するが
1本発明はこれらの実施例によって限定されるものでは
ない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例1 下記水洗代替安定液を作成した。Example 1 The following water washing alternative stabilizing solution was prepared.
5−クロロ−2−メチル−4−
イソチアゾリン−3−オン 0.05g2−
メチル−4−イソチアゾリン−3−オン 0.02゜水
溶性界面活性剤(表1記載) 0.35゜pH
を7.80に調整し、Illに仕上げる。5-chloro-2-methyl-4-isothiazolin-3-one 0.05g2-
Methyl-4-isothiazolin-3-one 0.02゜Water-soluble surfactant (listed in Table 1) 0.35゜pH
Adjust to 7.80 and finish to Ill.
上記水洗代替安定液0.1鵬皇をポリ塩化ビニルの樹脂
板上に滴下する。これらを50℃湿度50%の条件で1
0日間保存し、その後表面を水で湿らせたペーパータオ
ルで拭き取り、表面の固着状態を観測した。結果を表1
に示す。0.1 Penghuang of the above water washing alternative stabilizing solution was dropped onto a polyvinyl chloride resin plate. 1 at 50°C and 50% humidity.
After storing for 0 days, the surface was wiped with a paper towel moistened with water, and the adhesion state of the surface was observed. Table 1 shows the results.
Shown below.
評価基準は下記の方法に基づいた。The evaluation criteria were based on the following method.
O表面の固着、変質が全くない。There is no adhesion or deterioration of the O surface.
O表面にわずかに固着するが1強くこすると取れる。It sticks slightly to the O surface, but can be removed by rubbing it hard.
Δ 表面にかなり固着するが1強くこすると取れる。Δ It sticks to the surface quite a bit, but it can be removed by rubbing it hard.
× 表面に固着し2強くこすってもわずかしか取れない
。× It sticks to the surface and only a small amount can be removed even if you rub it hard.
××表面に固着し1強くこすっても取れない。XX It sticks to the surface and cannot be removed even if you rub it hard.
表1 比較I 比較2 alls 比較3 CI+ 。Table 1 Comparison I Comparison 2 alls Comparison 3 CI+.
表1より明らかに本発明の一般式〔I〕、(II)で表
される水溶性界面活性剤を用いると固着性が改良されて
いることがわかった。Table 1 clearly shows that the use of the water-soluble surfactants represented by formulas [I] and (II) of the present invention improves adhesion.
実施例2
実施例1で使用した水溶性界面活性剤以外にI−3,8
,12,20,24,41,49,59,ll−1につ
いても検討したが、はぼ実施例1と同様の効果を得るこ
とができた。Example 2 In addition to the water-soluble surfactant used in Example 1, I-3,8
, 12, 20, 24, 41, 49, 59, and ll-1 were also investigated, and the same effects as in Example 1 could be obtained.
実施例3
実施例1の水洗代替安定液を7ニオン交換樹脂及びカチ
オン交換樹脂を充填した装置に水道水を通したイオン交
検水で調整し、それからジクロロインジアール酸20鵬
g添加し、水洗代替安定液を調整し、実施例1と同様の
検討をしたところ、はぼ実施例1と同様の効果を得るこ
とができた。Example 3 The water washing alternative stabilizing solution of Example 1 was adjusted with ion exchange water passed through tap water through a device filled with 7 anion exchange resin and cation exchange resin, then 20 g of dichloroindialic acid was added, and water washing was carried out. When an alternative stabilizing solution was prepared and the same study as in Example 1 was conducted, the same effects as in Example 1 could be obtained.
実施例4
コニカGX−11100(コニカ■製)、ゴールド10
0(イーストマンコダック社製)及びスーパーHR−I
I 100 (フジフィルム縛製)のカラーネガフィ
ルムを撮影後、各々2:1:2の割合でカラーネガ用自
動現像機KP−40(コニカ■製)を用いて、1日当り
20本(24枚撮り)2ケ月間処理を行った。Example 4 Konica GX-11100 (manufactured by Konica ■), Gold 10
0 (manufactured by Eastman Kodak) and Super HR-I
After shooting I 100 (manufactured by Fuji Film Taipei) color negative film, 20 films (24 shots) were taken per day using an automatic developing machine for color negatives KP-40 (manufactured by Konica ■) at a ratio of 2:1:2. The treatment was carried out for two months.
なお、処理条件及び処理液組成は下記に示す通りである
。The treatment conditions and treatment liquid composition are as shown below.
く処理条件〉
発色現像 3分15秒 38土0.3 1480漂
白 3分15秒 25〜38 2
70定 着 3分15秒 20〜38 92
B安 定 45秒 20〜38
92B乾 燥 2分5秒 45〜8゜
本 水洗代替安定液は2槽カウンターカレントになって
いる。感材による持込み量は50mJl /ゴである。Processing conditions> Color development 3 minutes 15 seconds 38 soil 0.3 1480 bleaching 3 minutes 15 seconds 25-38 2
70 fixed 3 minutes 15 seconds 20-38 92
B stable 45 seconds 20-38
92B drying 2 minutes 5 seconds 45-8゜ bottles The water washing alternative stabilizer is a 2-tank counter current. The amount brought in by the photosensitive material is 50 mJl/go.
λ伍里叉羞
炭酸カリウム 30g炭酸水
素ナトリウム 2.7gヨウ化カリ
ウム 1.2騰g亜硫酸カリウ
ム 2.8g臭化ナトリウム
1.3gヒドロキシルアミン硫@
tj4 3.2g塩化ナトリウム
0,6g4−アミノ−3−メチルートエ
チルート(β−ヒドロキシルエチル)アニリン硫酸塩4
.68ジエチレントリアミン五酢酸3.0g
水酸化カリウム 1.3g水を加
えてInとし、水酸化カリウムまたは20%硫酸を用い
てpH10,01に調整する。Potassium carbonate 30g Sodium bicarbonate 2.7g Potassium iodide 1.2g Potassium sulfite 2.8g Sodium bromide
1.3g hydroxylamine sulfur @
tj4 3.2g sodium chloride
0,6g 4-amino-3-methyltoethyl (β-hydroxylethyl) aniline sulfate 4
.. 68 Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.3g Add water to make In, and adjust to pH 10.01 using potassium hydroxide or 20% sulfuric acid.
是−曳!蓋人羞
炭酸カリウム 40g炭酸
水素ナトリウム 3g亜硫酸カリ
ウム 7g臭化ナトリウム
0.8gヒドロキシルアミン硫酸塩
3.2g
4−アミノ−3−メチル−N−エチルート (βヒドロ
キシルエチル)アニリン硫酸t18.Ogジエチレント
リアミン五酢酸3.0g
水酸化カリウム 2g水を加
えて1文とし、水酸化カリウムまたは20%硫酸を用い
てpo 10.12に調整する。Come on! Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite 7g Sodium bromide
0.8g hydroxylamine sulfate 3.2g 4-amino-3-methyl-N-ethyroot (β-hydroxylethyl)aniline sulfate t18. Og diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 2g Add water to make one sentence and adjust to po 10.12 using potassium hydroxide or 20% sulfuric acid.
票白液及び漂白補充液
エチレンジアミン四酢酸第2鉄アンモニウム0.25モ
ル
エチレンジアミンテトラ酢酸2ナトリウムg
臭化アンモニウム 120゜氷酢
酸 4o−文硝醜アン
モニウム 40g3−メルカプト
−1,2,4−)リアシーk 0.5g水を加えて
11とし、アンモニア水または氷酢酸をJ’nイテPH
5,8ニaI!lt6゜清液び若 液
チオ硫酸アンモニウム 200g無水
重亜硫酸ナトリウム 20gメタ重亜硫
酸ナトリウム 4.0gエチレンジアミン
テトラ酢酸2ナトリウム1.0g
水を加えて700mJlとし、氷酢酸とアンモニア水を
用いてpH8,5に調整する。Whitening solution and bleach replenisher ferric ammonium ethylenediaminetetraacetate 0.25 mol disodium ethylenediaminetetraacetate g ammonium bromide 120° glacial acetic acid 40-bunishio ammonium 40 g 3-mercapto-1,2,4-) rear sea k Add 0.5g water to make 11, add ammonia water or glacial acetic acid to J'nitePH
5,8 Ni aI! lt6゜Clear liquid Ammonium thiosulfate 200g Anhydrous sodium bisulfite 20g Sodium metabisulfite 4.0g Ethylenediaminetetraacetic acid disodium 1.0g Add water to make 700mJl, and adjust to pH 8.5 using glacial acetic acid and aqueous ammonia. do.
水(安液び補液
5−クロロ−2−メチル−4−
イソチアゾリン−3−オン 0.05g2−
メチル−4−イソチアゾリン−3−オン 0.0211
界面活性剤(表2記載) 0.1 g
ホルムアルデヒド(37%溶液) 3.0ml
処理後、水洗代替安定浴のラックの固着状態を観察し、
実施例1と同様の方法で評価した。Water (weak solution) 5-chloro-2-methyl-4-isothiazolin-3-one 0.05g2-
Methyl-4-isothiazolin-3-one 0.0211
Surfactant (listed in Table 2) 0.1 g
Formaldehyde (37% solution) 3.0ml
After treatment, observe the fixation of the rack in the water washing alternative stabilization bath,
Evaluation was made in the same manner as in Example 1.
表2
上記表2より明らかな様に、実際のランニング処理にお
いても本発明の効果、すなわち1本発明の水溶性界面活
性剤を添加することによって固着が防止されていること
がわかる。Table 2 As is clear from Table 2 above, it can be seen that the effect of the present invention is achieved even in actual running treatment, that is, the addition of the water-soluble surfactant of the present invention prevents sticking.
実施例5
実施例4で使用した感光材料を用いて1発色現像から水
洗代替安定化処理まで実施例4と同様の処理液、処理条
件で処理した後、最絆浴である安定浴を取りのぞいた状
態で処理し、実施例4と同様の評価を行った。Example 5 The photosensitive material used in Example 4 was processed from one-color development to water washing alternative stabilization treatment using the same processing solution and processing conditions as in Example 4, and then the stabilizing bath, which is the most bonding bath, was removed. The same evaluation as in Example 4 was performed.
結果を表3に示す。The results are shown in Table 3.
表3
表3より明らかなように実際のランニング処理において
も本発明の効果、すなわち本発明の水溶性界面活性剤を
添加することによって固着が防止されていることがわか
るが、実質的にホルマリンを含まない処理において本発
明外の界面活性剤でも効果があり、特に実施例4で示し
た様なホルマリン安定液を含む処理の場合に本発明の界
面活性剤を用いた効果が顕著に表れることがわかる。Table 3 As is clear from Table 3, it can be seen that the effect of the present invention is achieved even in actual running treatment, that is, sticking is prevented by adding the water-soluble surfactant of the present invention. Even surfactants other than the present invention are effective in treatments that do not contain formalin stabilizers, and the effects of using the surfactants of the present invention are particularly noticeable in treatments that include formalin stabilizing solutions as shown in Example 4. Recognize.
実施例6
実施例4で使用した感光材料を用いて漂白液を下記のよ
うに変化させて、実施例4と同様の処理液、処理条件に
おいて処理し、実施例4と同様の評価を行った。但し処
理期間は4ケ月にわたって処理した。Example 6 Using the photosensitive material used in Example 4, the bleaching solution was changed as shown below, and the material was processed using the same processing solution and processing conditions as in Example 4, and the same evaluation as in Example 4 was performed. . However, the treatment period was 4 months.
漂白液及び漂白補
可溶性第2欽塩(表4 ) 0.25モ
ルエチレンジ7ミンテトラ酢m2ナトリウム2g臭化ア
ンモニウム 120g氷酢m
40*見3−メルカプ
ト−1,2,4−)リアゾール 0.5g硝酸アン
モニウム 408水を加えてl
ILとし、アンモニア水又は氷酢酸を用いてpH5,8
にする。Bleach solution and bleach co-soluble sulfur salt (Table 4) 0.25 mol ethylenedi7minetetravinegar m2 Sodium 2g Ammonium bromide 120g Ice vinegar m
40*3-Mercapto-1,2,4-) Riazole 0.5g Ammonium nitrate Add 408 water and l
IL and pH 5.8 using aqueous ammonia or glacial acetic acid.
Make it.
結果を表4に示す。The results are shown in Table 4.
表4
EDTA Fs(m) :
エチレンジアミン四酢酸第2鉄アンモニウム塩PDTA
Fe(III) :
1.3−ジアミノプロパン四酢酸第2鉄アンモニウム塩
(例示化合物A−1の第2鉄1jりDTPA Fe(m
) ニ
ジエチレントリアミン五酢酸第2鉄アンモニウム塩
表4より明らかな様に漂白液の可溶性有機酸第2鉄の種
類により固着に対し、抑制効果に違いが認められるが、
有機酸第2鉄塩としてPD丁A Feを用いることで固
着状態がより改良されていることがわかる。Table 4 EDTA Fs (m): Ethylenediaminetetraacetic acid ferric ammonium salt PDTA
Fe(III): 1,3-diaminopropanetetraacetic acid ferric ammonium salt (ferric 1j-DTPA Fe(m
) Nidiethylenetriaminepentaacetic acid ferric ammonium salt As is clear from Table 4, there are differences in the inhibitory effect on sticking depending on the type of soluble organic acid ferric in the bleaching solution.
It can be seen that the fixation state is further improved by using PD-A Fe as the organic acid ferric salt.
実施例7
実施例4で使用した感光材料を用いて定着液のチオ硫酸
塩の量を変化させて実施例4と同様の処理液、処理条件
において処理し、実施例4と同様の評価を行った。その
結果を表5に示す。Example 7 Using the photosensitive material used in Example 4, the material was processed in the same processing solution and processing conditions as in Example 4 by changing the amount of thiosulfate in the fixer, and the same evaluation as in Example 4 was conducted. Ta. The results are shown in Table 5.
表5
実施例8
実施例4で使用した感光材料を用いて定着液にチオシア
ン酸塩を添加して実施例4と同様の処理液、処理条件に
おいて処理し、実施例4と同様の評価を行った。但し処
理期間は4ケ月である。Table 5 Example 8 Using the photosensitive material used in Example 4, thiocyanate was added to the fixing solution and the material was processed using the same processing solution and processing conditions as in Example 4, and the same evaluation as in Example 4 was conducted. Ta. However, the processing period is 4 months.
その結果を表6に示す。The results are shown in Table 6.
表6
表5より明らかな様に定着液中のチオ硫酸塩の量によっ
て、固着に対し抑制効果が認められるが、チオ硫酸塩が
0.4モル/文以上である場合に本発明の水溶性界面活
性剤による固着防止効果が発揮されることがわかる。Table 6 As is clear from Table 5, the amount of thiosulfate in the fixer has a suppressive effect on fixation, but when the amount of thiosulfate is 0.4 mol/liter or more, the water-soluble properties of the present invention It can be seen that the surfactant has an anti-sticking effect.
表6より明らかな様に定着液中にチオシアン酸塩を添加
していくと固着に対し、抑制効果が認められ、特にチオ
シアン酸が0.5モル/1以上ある場合に固着防止効果
があることがわかる。As is clear from Table 6, the addition of thiocyanate to the fixer has a suppressive effect on sticking, and in particular, when thiocyanate is present at 0.5 mol/1 or more, there is a sticking preventing effect. I understand.
又、実施例8において水溶性界面活性剤の併用1−5
/ I −47= O,1g70.1g添加も検討した
が実施例8とほぼ同様の効果を得ることができた。In addition, in Example 8, the combined use of water-soluble surfactants 1-5
/I-47=O, 1g Addition of 70.1g was also considered, but almost the same effect as in Example 8 could be obtained.
Claims (10)
び安定浴を有する処理工程における前記水洗代替安定浴
に用いられる水洗代替安定液が下記一般式〔 I 〕又は
一般式〔II〕で示される水溶性界面活性剤を含有するこ
とを特徴とするハロゲン化銀カラー写真感光材料用処理
液。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ [式中、A_2は1価の有機基、B又はCはエチレンオ
キシド又はプロピレンオキシド又は ▲数式、化学式、表等があります▼ を表わす(但し、n_1、m_1、及びl_1はそれぞ
れ0、1、2又は3である)。 m及びnは0〜100の整数を表わす。 X_1は水素原子、SO_3M_1、PO_3M_2(
M_1、M_2は水素原子、アルカリ金属又はアンモニ
ウムを表す。)、アルキル基、アラルキル基、アリール
基である。 一般式〔II〕 ▲数式、化学式、表等があります▼ [式中、R^1は水素原子、脂肪族基、アシル基を表わ
し、R^2は水素原子、脂肪族基を表わす。 E^1、E^2及びE^3はエチレンオキシド又はプロ
ピレンオキシドを表わし、X_2は酸素原子、▲数式、
化学式、表等があります▼基で、R^3は脂肪族基、水
素原子又は▲数式、化学式、表等があります▼を表わし
、R^4は 水素原子又は脂肪族基を表わす。 l_2、l_3、m_2、m_3、n_2、n_3は各
々0〜200の整数を表わす。(1) The washing substitute stabilizing solution used in the washing substitute stabilizing bath in a processing step having a color developing bath, a bleaching bath, a fixing bath, a washing substitute stabilizing bath, and a stabilizing bath has the following general formula [I] or general formula [II]. 1. A processing solution for silver halide color photographic materials, characterized by containing a water-soluble surfactant represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_2 is a monovalent organic group, B or C is ethylene oxide or propylene oxide, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, , n_1, m_1, and l_1 are 0, 1, 2, or 3, respectively). m and n represent integers from 0 to 100. X_1 is a hydrogen atom, SO_3M_1, PO_3M_2 (
M_1 and M_2 represent a hydrogen atom, an alkali metal or ammonium. ), alkyl groups, aralkyl groups, and aryl groups. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 represents a hydrogen atom, an aliphatic group, or an acyl group, and R^2 represents a hydrogen atom or an aliphatic group. E^1, E^2 and E^3 represent ethylene oxide or propylene oxide, X_2 is an oxygen atom, ▲ formula,
There are chemical formulas, tables, etc. in the ▼ group, R^3 represents an aliphatic group, a hydrogen atom, or ▲ there are numerical formulas, chemical formulas, tables, etc.▼, and R^4 represents a hydrogen atom or an aliphatic group. l_2, l_3, m_2, m_3, n_2, and n_3 each represent an integer from 0 to 200.
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
料用処理液。(2) The processing solution for silver halide color photographic materials according to claim 1, wherein the stabilizing bath contains formalin.
ロゲン化銀カラー写真感光材料であることを特徴とする
請求項1又は2記載のハロゲン化銀カラー写真感光材料
用処理液。(3) The processing liquid for a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the silver halide color photographic light-sensitive material is a silver halide color photographic light-sensitive material for photographing.
酸塩を含有することを特徴とする請求項1、2又は3記
載のハロゲン化銀カラー写真感光材料用処理液。(4) The processing solution for silver halide color photographic light-sensitive materials according to claim 1, 2 or 3, wherein the fixing bath contains at least 0.4 mol/l of thiosulfate.
アン酸塩を含有することを特徴とする請求項1、2、3
又は4記載のハロゲン化銀カラー写真感光材料用処理液
。(5) The fixing bath contains at least 0.5 mol/l of thiocyanate.
or 4. The processing liquid for silver halide color photographic light-sensitive materials.
後、発色現像、漂白処理し、その後定着液で処理し、引
続き水洗代替安定液で処理した後、ホルマリン含有安定
液で処理するハロゲン化銀カラー写真感光材料の処理方
法において、前記水洗代替安定液が請求項1に記載の一
般式〔 I 〕又は〔II〕で示される水溶性界面活性剤を
含有することを特徴とするハロゲン化銀カラー写真感光
材料の処理方法。(6) Halogenation in which a silver halide color photographic light-sensitive material is imagewise exposed, then subjected to color development and bleaching, then treated with a fixing solution, then treated with a water-washing alternative stabilizer, and then treated with a formalin-containing stabilizer. A method for processing a silver color photographic material, wherein the water-washing alternative stabilizing solution contains a water-soluble surfactant represented by the general formula [I] or [II] according to claim 1. A method of processing color photographic materials.
ロゲン化銀カラー写真感光材料であることを特徴とする
請求項6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 method for processing a silver halide color photographic material according to claim 6, wherein the silver halide color photographic material is a silver halide color photographic material for photographing.
〕又は〔B〕で示される第2鉄錯塩を含有することを特
徴とする請求項6又は7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〔A〕 ▲数式、化学式、表等があります▼ [式中、A_1〜A_4はそれぞれ同一でも異ってもよ
く、−CH_2OH、−COOM又は−PO_3M_1
M_2を表す。 M、M_1、M_2はそれぞれ水素原子、アルカリ金属
又はアンモニウムを表す、Xは炭素数3〜6の置換、未
置換のアルキレン基を表す。] 一般式〔B〕 ▲数式、化学式、表等があります▼ [式中、A_1〜A_4は前記一般式〔A〕で定義した
ものと同義であり、nは1〜8の整数を表す。またB_
1及びB_2は同一でも異なっていてもよく、それぞれ
炭素数2〜5の置換、未置換のアルキレン基を表す。](8) The bleaching agent contained in the bleaching solution has the following general formula [A
The method for processing a silver halide color photographic light-sensitive material according to claim 6 or 7, further comprising a ferric complex salt represented by ] or [B]. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_1
Represents M_2. M, M_1, and M_2 each represent a hydrogen atom, an alkali metal, or ammonium, and X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1 to A_4 have the same meaning as defined in the above general formula [A], and n represents an integer from 1 to 8. Also B_
1 and B_2 may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms. ]
酸塩を含有することを特徴とする請求項6、7又は8記
載のハロゲン化銀カラー写真感光材料の処理方法。(9) The method for processing a silver halide color photographic material according to claim 6, 7 or 8, wherein the fixing solution contains at least 0.4 mol/l of thiosulfate.
シアン酸塩を含有することを特徴とする請求項6、7、
8又は9記載のハロゲン化銀カラー写真感光材料の処理
方法。(10) Claims 6 and 7, characterized in that the fixer contains at least 0.5 mol/l of thiocyanate;
10. The method for processing a silver halide color photographic light-sensitive material according to 8 or 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8555090A JPH03284748A (en) | 1990-03-30 | 1990-03-30 | Processing liquid for silver halide color photographic sensitive material and processing method using this liquid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8555090A JPH03284748A (en) | 1990-03-30 | 1990-03-30 | Processing liquid for silver halide color photographic sensitive material and processing method using this liquid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03284748A true JPH03284748A (en) | 1991-12-16 |
Family
ID=13861947
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8555090A Pending JPH03284748A (en) | 1990-03-30 | 1990-03-30 | Processing liquid for silver halide color photographic sensitive material and processing method using this liquid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03284748A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005040916A1 (en) * | 2003-10-22 | 2005-05-06 | Konica Minolta Photo Imaging, Inc. | Stabilizer solution and method of processing silver halide color photographic sensitive material therewith |
-
1990
- 1990-03-30 JP JP8555090A patent/JPH03284748A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005040916A1 (en) * | 2003-10-22 | 2005-05-06 | Konica Minolta Photo Imaging, Inc. | Stabilizer solution and method of processing silver halide color photographic sensitive material therewith |
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