JPS59166951A - Processing solution capable of bleaching silver halide color photosensitive material - Google Patents
Processing solution capable of bleaching silver halide color photosensitive materialInfo
- Publication number
- JPS59166951A JPS59166951A JP4063383A JP4063383A JPS59166951A JP S59166951 A JPS59166951 A JP S59166951A JP 4063383 A JP4063383 A JP 4063383A JP 4063383 A JP4063383 A JP 4063383A JP S59166951 A JPS59166951 A JP S59166951A
- Authority
- JP
- Japan
- Prior art keywords
- bleaching
- complex salt
- bleach
- color
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004061 bleaching Methods 0.000 title claims abstract description 54
- 238000012545 processing Methods 0.000 title claims abstract description 46
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 33
- -1 silver halide Chemical class 0.000 title claims description 57
- 239000000463 material Substances 0.000 title claims description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 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 claims description 11
- 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 claims description 6
- 239000007844 bleaching agent Substances 0.000 abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 4
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 abstract 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000011161 development Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- 238000005406 washing Methods 0.000 description 25
- 230000018109 developmental process Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 17
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229960003330 pentetic acid Drugs 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 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
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000011272 standard treatment Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical group O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OOXJLYWWZIPWKG-UHFFFAOYSA-I N'-(2-aminoethyl)ethane-1,2-diamine iron(5+) pentaacetate Chemical compound [Fe+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCN OOXJLYWWZIPWKG-UHFFFAOYSA-I 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- WZGNVVUXVXNNOX-UHFFFAOYSA-N [Fe+] Chemical compound [Fe+] WZGNVVUXVXNNOX-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MOOSBPSAZDOBSN-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O MOOSBPSAZDOBSN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 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 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical class O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 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
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OMDXFCRSKHYDTM-UHFFFAOYSA-J thorium(4+);tetrabromide Chemical compound Br[Th](Br)(Br)Br OMDXFCRSKHYDTM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
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の漂白能を
有する処理液に関する。更に詳しくは、種々の処理性能
及び液特性を改良した、効果的なハロゲン化銀カラー写
真感光材料用漂白液及び漂白定着液に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a processing solution having bleaching ability for silver halide color photographic materials. More specifically, the present invention relates to an effective bleaching solution and bleach-fixing solution for silver halide color photographic materials, which have improved various processing performance and solution properties.
一般に、像様露光されたハロゲン化銀カラー写真感光材
料を処理してカラー画像を得るには、発色現像工程の後
に、生成された金属銀を漂白能を有する処理液で処理す
る工程が設けられる。Generally, in order to obtain a color image by processing a silver halide color photographic light-sensitive material that has been imagewise exposed, a step is provided after the color development step to treat the generated metallic silver with a processing solution having bleaching ability. .
漂白能を有する処理液としては、漂白液、漂白定着液が
知られている。漂白液が使用される場合は、通常、漂白
工程に次いで−・ロゲン化銀を定着剤によって定着する
工程が付は加えられるが、漂白定着液では漂白及び定着
が一工程で行なわれる。Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, the bleaching step is usually followed by a step of fixing the silver halide with a fixing agent, but with a bleach-fixing solution, bleaching and fixing are carried out in one step.
ハロゲン化銀カラー写真感光材料の処理における漂白能
を有する処理液には、画像銀を漂白するだめの酸化剤と
して、赤血塩、重クロム酸塩等の無機の酸化剤が広く用
いられている。Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic materials. .
しかし、これらの無機の酸化剤を含有する漂白能を有す
る処理液には、いくつかの重大な欠点が指摘されている
。例えば赤血塩及び重クロム酸塩は画像銀の漂白刃とい
う点では比較的すぐれているが、光によシ分解して人体
に有害なシアンイオンや六価のクロムイオンを生成する
虞れがあシ、公害防止上好ましくない性質を有している
。またこれらの酸化剤はその酸化力が極めて強いために
、チオ硫酸塩等のハロゲン化銀溶化剤を同一の処理液中
に共存させることが困難で、漂白定着浴にこれらの酸化
剤を用いることはほとんど不可能であシ、このため処理
の迅速化および簡素化という目的の達成を難しくしてい
る。さらにこれらの無機の酸化剤を含む処理液は、処理
後の廃液を捨てることなく再生使用することが困雉であ
ると（ハう欠点を有している。However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively good at bleaching silver images, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. Reeds have unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizing agents such as thiosulfates in the same processing solution, making it difficult to use these oxidizing agents in bleach-fixing baths. is almost impossible, which makes it difficult to achieve the objective of speeding up and simplifying the process. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.
これに対し、公害上の問題も少すく、処理の迅速化、簡
素化、および廃液の再生使用可能等の要請にかなうもの
として、アミンポリカルボン酸金属錯塩等の有機酸の金
属錯塩を酸化剤とした処理液が使用されるようになって
きた。しかし、有機酸の金属錯塩を使用した処理液は、
酸化力が緩慢なために、現像工程で形成された画像銀（
金属銀）の漂白速度（酸化速度）が遅いという欠点を有
している。例えば、アミノポリカルボン酸金属錯塩の中
で漂白刃が強いと考えられているエチレンジアミン四酢
酸鉄（２）錯塩は、一部で漂白液および漂白定着液とし
て実用化されているが、臭化銀、ラー写真感光材料、特
にハロゲン化銀としてヨウ化銀を含有する撮影用カラー
ペーパー及び撮影用のカラーネガティブフィルム、カラ
ーリバーサルフィルムでは、漂白刃が不足し、長時間処
理しても痕跡程度の画像銀が残り、脱銀性が不良となる
。On the other hand, metal complex salts of organic acids, such as amine polycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the requirements of speeding up and simplifying treatment, and enabling the reuse of waste liquids. In recent years, treatment solutions have come to be used. However, treatment solutions using metal complex salts of organic acids are
Because the oxidizing power is slow, the image silver (
It has the disadvantage that the bleaching rate (oxidation rate) of silver (metallic silver) is slow. For example, ethylenediaminetetraacetic acid iron (2) complex salt, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleach solution and bleach-fix solution in some places, but silver bromide , color photographic light-sensitive materials, especially color paper for photography containing silver iodide as silver halide, color negative film for photography, and color reversal film, lack a bleaching blade, and even after long processing, the image remains only a trace. Silver remains and desilvering performance becomes poor.
この傾向は、酸化剤とチオ硫酸塩及び亜硫酸塩が共存す
る漂白定着液では酸化還元電位が低Ｆするために特に顕
著に表われる。This tendency is particularly noticeable in a bleach-fix solution in which an oxidizing agent and thiosulfate and sulfite coexist because the redox potential is low F.
一力、有機酸の金属錯塩を含有した漂白液または漂白定
着液の銀漂白刃を増加させるため、漂白促進剤の開発等
に多大な努力がなされたにもかかわらず、いまだに充分
な結果が得られていないのが実情である。Although great efforts have been made to develop bleach accelerators to increase the silver bleaching edge of bleach or bleach-fix solutions containing metal complexes of organic acids, satisfactory results have not yet been achieved. The reality is that this is not the case.
本発明者らは、アミンポリカルボン酸金属錯塩の中でも
特に優れた酸化力を有する酸化剤として、ジエチレント
リアミン五酢酸鉄（加錯塩を見い出した。ジエチレント
リアミン五酢酸鉄（！ｉ）錯塩を酸化剤とする漂白液お
よび漂白定着液は、銀漂白反応が迅速で、直接漂白処理
したときのスティンの発生が少なく、更に漂白定着液の
保存安定性が良いという極めて優れた性能を有している
。しかしながら、この漂白液もしくは漂白定着液を使用
し、自動現像機によって連続的に処理した際に、ロイコ
化したシアン色素が、漂白又は漂白定着処理によシ充分
に顕色しない、いわゆる復色不良が発生することが明ら
かとなった。との復色不良は、特に長時間に亘って連続
的に処理した際に著しく発生する。従って、この漂白液
及び漂白定着液を実用化するためには、上記の有利な特
性を維持しながら、しかも連続処理をした際、復色不良
を起さない技術が強く望まれている。The present inventors have discovered diethylenetriamine iron pentaacetate (addition complex salt) as an oxidizing agent that has particularly excellent oxidizing power among amine polycarboxylic acid metal complex salts. The bleaching solution and the bleach-fixing solution have extremely excellent performance in that the silver bleaching reaction is rapid, there is little staining when directly bleached, and the bleach-fixing solution has good storage stability.However, When this bleaching solution or bleach-fixing solution is used and processed continuously in an automatic processor, the leuco-converted cyan dye does not develop sufficiently during bleaching or bleach-fixing processing, so-called color recovery failure occurs. It has become clear that poor color recovery occurs particularly when continuous processing is carried out over a long period of time.Therefore, in order to put this bleach and bleach-fix solution into practical use, the above-mentioned There is a strong desire for a technology that maintains the advantageous properties of chromium oxide and does not cause defective color restoration during continuous processing.
本発明の目的は、迅速な銀漂白刃を備え、長期連続処理
に供してもシアン色素のロイコ化及びスティンの発生が
なく、更に漂白能を有する処理液として漂白定着液とし
た場合においても該漂白定着液の保存安定性がすぐれた
、ハロゲン化銀カラー写真感光材料用の漂白能を有する
処理液を提供する事にある。The object of the present invention is to provide a quick silver bleaching blade, to prevent cyan dye from becoming leuco and to cause staining even when subjected to long-term continuous processing, and to be able to be used as a bleach-fixing solution as a processing solution having bleaching ability. It is an object of the present invention to provide a processing solution having bleaching ability for silver halide color photographic light-sensitive materials, which has excellent storage stability as a bleach-fix solution.
本発明者らは鋭意研究した結果、前記目的は、ジエチレ
ントリアミン五酢酸鉄０）錯塩を酸化剤として含有し、
かつとドロキシエチルエチレンジアミン三酢酸および／
又はヒドロギシエテルエチレンジアミン三酢酸鉄（ＩＩ
Ｄ錯塩を含有する漂白液及び漂白定着液によって達成さ
れることを見い出した。As a result of intensive research by the present inventors, the above object contains diethylenetriaminepentaacetic acid iron 0) complex salt as an oxidizing agent,
Katsuto Droxyethylethylenediaminetriacetic acid and/or
or iron hydroxyethyl ethylene diamine triacetate (II
It has been found that this can be achieved by a bleach solution and a bleach-fix solution containing a D complex salt.
一般にシアン色素のロイコ化は、銀漂白反応によシ生成
した鉄（「）錯塩が色素を還元して起るといわれている
。ロイコ化した色素は、一般には拡散によって乳剤中の
鉄ＧＩＤ錯塩の温度が上昇するにつれて、鉄（２）錯塩
によって再酸化され色素に復色する。しかしながら、連
続処理によって画像銀を多量に酸化する事で漂白液もし
くは漂白定着液中の鉄（［Ｄ＃塩が蓄積した場合、ロイ
コ化した色素が光分に顕色せず、いわゆる復色不良とい
う現象になって表われる。It is generally said that the leuco conversion of cyan dyes occurs when the dye is reduced by the iron complex salt produced by the silver bleaching reaction.The leuco conversion of the cyan dye is generally carried out by diffusion into the iron GID complex salt in the emulsion. As the temperature of When this accumulates, the leuco-formed dye does not develop color under light, resulting in a phenomenon called poor color recovery.
ジエチレン？ ＩＪアミン五酢酸鉄Ｉ錯塩は、従来漂白
剤としてよく使用されているエチレンジアミン四酢酸鉄
（至）錯塩にくらべ、ロイコ化した色素の色素への酸化
力が高く、シかも対応する鉄（［Ｄ錯塩は、色素をロイ
コ化しにくいという、基本的にはシアン色素のロイコ化
が起シにく層特性を有しているにもかかわらず、自動現
像機によって連続的に処理した際、著しい復色不良が発
生した。かかる原因について検討を重ねた結果、ジエチ
レントリアミン五酢酸鉄（［）錯塩は、空気酸化速度が
極めて遅く、連続的に処理した際、液中に鉄（［Ｄ錯塩
が蓄積するために復色不良が発生することが明らかとな
った。すなわち、一般に自動現像機によって処理した場
合、漂白反応によって生成した鉄（ｒｉ）錯塩は、自動
現像機の処理液タンク中の液を循環するために設けられ
た循環ポンプに引き込まれた空気によって、あるいは強
制的にエアーバブリングを行なうことによって、鉄（２
）錯塩に酸化されるが、ジエチレン） ＩＪアミン五酢
酸鉄（［１）錯塩は空気酸化速度が極めて遅いために、
こうした通常の空気酸化力法では充分に酸化されないこ
とがわかった。Diethylene? IJ amine pentaacetic acid iron I complex salt has a higher ability to oxidize leuco-formed pigments to pigments than ethylenediaminetetraacetic acid iron complex salt, which is commonly used as a bleaching agent. Although complex salts have a layer characteristic that basically makes it difficult for cyan dyes to undergo leuco conversion, when they are continuously processed using an automatic processor, they exhibit significant color regeneration. As a result of repeated investigations into the causes of this problem, we found that diethylenetriaminepentaacetic acid iron ([) complex salt has an extremely slow air oxidation rate, and when processed continuously, iron ([D complex salt accumulates in the liquid. It has become clear that defective color restoration occurs in the automatic processor.In other words, when processing is generally carried out using an automatic processor, the iron (ri) complex salt produced by the bleaching reaction is circulated through the solution in the processing solution tank of the automatic processor. Iron (2
) is oxidized to a complex salt, but diethylene) IJ amine iron pentaacetate ([1) Since the air oxidation rate of complex salts is extremely slow,
It was found that this conventional air oxidation method did not oxidize sufficiently.
本発明は、ジエチレントリアミン五酢酸鉄（２）錯塩が
もつ種々の優れた特性を維持しながら、対応する鉄（Ｉ
ｆ）錯塩の鉄（２）錯塩への空気酸化を促進する方法を
種々検討した結果達成されたものであり、詳細な機構は
未だ明らかではない。しかしながら敢えて考察するなら
ば、ジエチレントリアミン五酢酸鉄（［０錯塩から鉄（
２）錯塩への酸化は、主としてとドロキシエチルエチレ
ンジアミン三酢酸鉄■錯塩によってなされ、これによっ
て生成したヒドロキシエチルエチレンジアミン三酢酸鉄
（［１）錯塩は、極めて空気酸化を受けやすいために簡
単に鉄（ｊＤ錯塩に酸化される。すなわちヒドロキシエ
チルエチレンジアミン三酢酸鉄（Ｉ）錯塩が触媒的に作
用するものと考えられる。The present invention maintains various excellent properties of the diethylenetriaminepentaacetic acid iron (2) complex salt, while maintaining the corresponding iron (I) complex salt.
f) This was achieved as a result of various studies on ways to promote the air oxidation of complex salts to iron(2) complex salts, and the detailed mechanism is not yet clear. However, if we dare to think about it, we will find that from iron diethylenetriaminepentaacetate ([0 complex salt to iron (
2) The oxidation to the complex salt is mainly carried out by the hydroxyethylethylenediamine iron triacetate complex, and the hydroxyethylethylenediamine iron triacetate ([1) complex salt produced by this is extremely susceptible to air oxidation and is therefore easily oxidized to iron. (It is oxidized to a jD complex salt. In other words, it is thought that the hydroxyethylethylenediamine triacetate iron (I) complex salt acts catalytically.
すなわち本発明は、ヒドロキシエチルエチレンジアミン
三酢酸鉄（「）錯塩が、空気酸化を受けやすいこと、及
び空気酸化によシ生成したヒドロキシエチルエチレンジ
アミン三酢酸鉄（４）錯塩とジエチレン） ＩＪアミン
五酢酸鉄（［Ｄ錯塩との間の電子授受が立体的に円滑に
なされることが必要十分条件であシ、あくまでもジエチ
レントリアミン五酢酸鉄（至）錯塩トヒドロキシエチル
エチレンジアミン三酢酸及ヒ／又はヒト０キシエチルエ
ナレンジアミン三酢酸鉄（４）錯塩の組み合わせに於い
て達成されたものである。このことは、例えばエチレン
シアミン四酢酸鉄（ｌｌＤ錯塩にヒドロキシエチルエチ
レンジアミン三酢酸及び／又はヒドロキシエチルエチレ
ンジアミン三酢酸鉄（ＪｆＤ錯塩を添加しても、対応す
る鉄（Ｉｔ）錯塩の空気酸化速度を全く促進しないこと
からも明らかである。That is, the present invention discloses that hydroxyethylethylenediamine iron triacetate (4) complex salt is susceptible to air oxidation, and that the hydroxyethylethylenediamine iron triacetate (4) complex salt and diethylene IJ amine iron pentaacetate complex salt produced by air oxidation are (It is a necessary and sufficient condition that the electron transfer between D and the complex salt is sterically smooth, and the only condition is that the electron exchange between the complex salt and the diethylenetriaminepentaacetate complex salt, hydroxyethylethylenediaminetriacetic acid, and/or human oxyethyl This has been achieved in combinations of enalediamine iron (4) triacetate complex salts. This is also clear from the fact that the addition of iron (JfD complex salt) does not promote the air oxidation rate of the corresponding iron (It) complex salt at all.
本発明に係るジエチレントリアミン五酢酸鉄■錯塩は、
フリーの酸（水素塩）、ナ） ＩＪウム塩、カリウム塩
、リチウム塩等のアルカリ金属塩、もしくはアンモニウ
ム塩、又は水溶性アミン塩例えばトリエタノールアミン
塩等として使われる。これらの鉄（９）錯塩は少なくと
も１種用いればよいが、２種以上を併用することも出来
る。使用量は任意に選ぶ事が出来、処理する感光材料の
銀量及びＩ・ロゲン化銀組成等によって選択する必要が
あるが、一般に酸化力が高いため他のアミノポリカルボ
ン酸塩より低濃度で使用出来る。例えば、使用液１１当
、！ｌＪＯ，０１モル以上で使用出来、好１しくは０．
０５モル以上で使用される。なお、補光液においては濃
厚低補充化のために溶解度いっばいに濃厚化して使用す
る事が望せしい。The diethylenetriaminepentaacetic acid iron complex salt according to the present invention is
Free acid (hydrogen salt), n) Used as alkali metal salts such as aluminum salts, potassium salts, and lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine salts. At least one type of these iron(9) complex salts may be used, but two or more types can also be used in combination. The amount to be used can be selected arbitrarily and must be selected depending on the amount of silver in the photosensitive material to be processed and the composition of I/silver halide, but in general, it should be used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. Can be used. For example, 11 servings of liquid used! It can be used in an amount of 0.01 mol or more, preferably 0.01 mol or more.
It is used in amounts of 0.05 mol or more. In addition, it is desirable to use the brightening solution in a concentrated state with the highest solubility in order to reduce the concentration and replenishment.
本発明に係るとドロキシエテルエチレンジアミン三酢酸
鉄（２）錯塩およびヒドロキシエチルエチレンジアミン
三酢酸は、フリーの酸、ナトリウム塩、カリウム塩、リ
チウム塩等のアルカリ金属塩、もしくはアンモニウム塩
、又は水溶性アミン塩例えばトリエタノールアミン塩等
として使われる。これらは少なくとも１種用いればよい
が２種以上を併用する事も出来る。使用量は漂白主剤で
あるジエチレントリアミン五酢酸鉄（２）錯塩の優れた
特性を阻害しない程度に使用することが好捷しく、ジエ
チレントリアミン五酢酸鉄（２）錯塩１モルに対して０
．０１モルから１モルが好ましく、特に好ましくは０．
０５モルから０．５モルの範囲で使用する。According to the present invention, droxyethylethylenediaminetriacetic acid iron (2) complex salt and hydroxyethylethylenediaminetriacetic acid are free acids, alkali metal salts such as sodium salts, potassium salts, lithium salts, or ammonium salts, or water-soluble amines. It is used as a salt such as triethanolamine salt. At least one type of these may be used, but two or more types can also be used in combination. It is preferable to use the amount in an amount that does not impede the excellent properties of diethylenetriaminepentaacetate iron (2) complex salt, which is the main bleaching agent, and is 0 per mole of diethylenetriaminepentaacetate iron (2) complex salt.
．． 0.01 to 1 mole is preferred, particularly preferably 0.01 to 1 mole.
It is used in a range of 0.05 mol to 0.5 mol.
本発明の漂白液及び漂白定着液は、ｐＨ０，２から９．
５で使用出来、好ましくは４．０以上、より好１しくけ
５．０以上で用いられ、また、最も好菫し込ｐＨ範囲は
５．５以上８．５以下である。処理の温度は８０℃以下
で使用されるが、望１しくけ５５℃以下で蒸発等を抑え
て使用する。The bleaching solution and bleach-fixing solution of the present invention have a pH of 0.2 to 9.
It can be used at a pH of 5.5, preferably 4.0 or higher, more preferably 5.0 or higher, and the most preferable pH range for stirring is 5.5 or higher and 8.5 or lower. The treatment temperature is 80° C. or lower, but preferably 55° C. or lower to prevent evaporation.
本発明の漂白液は、前記の如き漂白剤としてのジエチレ
ントリアミン五酢酸鉄（［）錯塩、ヒドロキシエチルエ
チレンジアミン三酢酸及び／又ハソノ鉄（ＩＩＤ錯塩を
含有するとともに、種々の添加剤を含むことができる。The bleaching solution of the present invention contains diethylenetriaminepentaacetate iron ([) complex salt, hydroxyethylethylenediaminetriacetic acid and/or hasonoteric acid (IID complex salt) as a bleaching agent as described above, and may also contain various additives. .
添加剤としては、とくにアルカリハライドまたはアンモ
ニウム゛ハライド、たとえば臭化カリウム、臭化すトリ
ウム、塩化ナトリウム、臭化アンモニウム等、沃化カリ
ウム、沃化ナトリウム、沃化アンモニウム、チオ尿素等
を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ｐＨ緩衝剤、トリエタノール
アミン等の可溶化剤、アミノポリカルボン酸もしくはそ
の塩、アルキルアミン類、ポリエチレンオキサイド類等
の通常漂白液に添加することカ知られているものを適宜
添加することができる。As additives, in particular, alkali halides or ammonium halides such as potassium bromide, thorium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, thiourea, etc. may be included. desirable. Also, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, solubilizing agents such as triethanolamine, ordinary bleaching agents such as aminopolycarboxylic acids or their salts, alkylamines, and polyethylene oxides. It is possible to appropriately add substances that are known to be added to.
本発明の漂白定着液としては前記の如き漂白剤としての
ジエチレントリアミン五酢酸鉄ＣＩ）錯塩、ヒドロキシ
エチルエチレンジアミン三酢酸及び／チオシアン酸塩、
チオ尿素、チオエーテル類等のハロゲン化銀定着剤を含
有する組成の液が適用される。また、本発明の漂白剤と
前記のハロゲン化銀定着剤の他に臭化カリウムの如きハ
ロゲン化合物を少量添加した組成からなる漂白定着液、
あるいは逆に臭化カリウムや臭化アンモニウムの如きハ
ロゲン化合物を多量に添加した組成からなる漂白定着液
、さらには本発明の漂白剤と多量の臭化カリウムの如き
ハロゲン化合物との組合、ピからなる組成の特殊な漂白
定着液等も用いることができる。The bleach-fixing solution of the present invention includes diethylenetriaminepentaacetic acid iron CI) complex salt, hydroxyethylethylenediaminetriacetic acid and/or thiocyanate as bleaching agents as described above;
A liquid having a composition containing a silver halide fixing agent such as thiourea or thioethers is applied. Further, a bleach-fixing solution comprising a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to the bleaching agent of the present invention and the above-mentioned silver halide fixing agent;
Or, conversely, a bleach-fix solution consisting of a composition containing a large amount of a halogen compound such as potassium bromide or ammonium bromide, or a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide; A bleach-fixing solution with a special composition can also be used.
前記のハロゲン化合物としては臭化カリウムの他に塩化
水床酸、臭化水素酸、臭化リチウム、臭化ナトリウム、
臭化アンモニウム、沃化ナトリウム、沃化カリウム、沃
化アンモニウム等も使用することができる。In addition to potassium bromide, the halogen compounds mentioned above include aqueous chloride acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used.
漂白定着液に含ませるハロゲン化銀定着剤としては通常
の定着処理に用いられるようなハロゲン化銀と反応して
水溶性の錯塩を形成する化合物、たとえばチオ硫酸カリ
ウム、チオ硫酸ナトリウム、チオ硫酸アンモニウムの如
きチオ硫酸塩、チオシアン酸カリウム、チオシアン酸ナ
トリウム、チオシフ７６アンモニウムの如きチオシアン
酸塩、あるいはチオ尿素、チオエーテル、高濃度の臭化
物、ヨウ化物等がその代表的なものである。これらの定
着剤は５ ｇ／を以上、溶解できる範囲の量で使用でき
る。Silver halide fixing agents to be included in the bleach-fix solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiosif-76, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount of 5 g/m or more as long as they can be dissolved.
なお漂白定着液には漂白液の場合と同様に硼酸、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、酢酸す） １７ウム、水酸化アンモニウム等の各種
の塩からなるｐＨ緩衝剤を単独であるいは２種以上組合
せて含有せしめることができる。さらにまた、各種の螢
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。The bleach-fix solution contains boric acid, borax, and
Sodium hydroxide, potassium hydroxide, sodium carbonate,
pH buffering agents consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, ammonium hydroxide, etc. can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained.
また、ヒドロキシルアミン、ヒドラジン、亜硫酸塩、異
性重亜硫酸塩、アルデヒドやケトン化合物の重亜硫酸付
加物等の保恒剤、アミノポリカルボン酸等の有機キレー
ト剤あるいはニトロアルコール硝酸塩等の安定４１、ア
ルカノールアミン等の可溶化剤、有機アミン等のスティ
ン防止剤、その他の添加剤や、メタノール、ジメチルフ
ォルムアミド、ジメチルスルフオキシド等の有機溶媒を
適宜含有せしめることができる。In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol nitrates, alkanolamines, etc. , etc., stain inhibitors such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.
本発明の処理液を用いる処理力法では、発色現像後直ち
に漂白もしくは漂白定着する事が最も好ましい処理力式
であるが、発色現像後直洗又はリンス及び停止等の処理
を行なった後、漂白もしくは漂白定着処理しても良く、
゛又漂白促進剤を含ませた前浴を漂白もしくは漂白定着
に先立つ処理液として用いても良い。In the processing power method using the processing solution of the present invention, the most preferable processing power method is to perform bleaching or bleach-fixing immediately after color development. Alternatively, it may be bleach-fixed,
Also, a prebath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing.
漂白および定着（又は漂白定着）後は、水洗を行なわず
安定処理する事も出来るし、水洗処理し、その後安定処
理しても良い。以上の工程の他に硬膜、中和、黒白現像
、反転、少量水洗工程等、必要に応じて既知の補助工程
が付は加えられても良い。好ましい処理力法の代表的具
体例を挙げると、下記の諸工程が含まれる。After bleaching and fixing (or bleach-fixing), stabilization treatment may be performed without washing with water, or washing with water may be performed and then stabilization treatment may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. A typical example of a preferred processing power method includes the following steps.
＋１３ 発色現像→漂白定着→水洗
（２）発色現像→漂白定着→少量水洗→水洗（３）発色
現像→漂白定着→水洗→安定（４）発色現像→漂白定着
→安定
（５）発色現像→水洗→漂白定着→水洗（６）発色現像
→停止→漂白定着→水洗（力 発色現像→漂白→水洗→
定着→水洗→安定（８）発色現像→漂白→足着→水洗→
安定（９）発色現像→漂白→少量水洗→定着→少量水洗
→水洗→安定
Ｑｌ 発色現像→少量水洗→漂白→少量水洗→定着→
少量水洗→水洗→安定
（１１）発色現像→停止→漂白→少童水洗→定着→少愈
水洗→水洗→安定
（１３黒白現像→水洗→反転→発色現像→漂白→定着→
水洗→安定
α騰 前硬膜→中和→黒白現像→停止→発邑現像→漂白
→定着→水洗→安定
本発明の漂白能を有する処理液による処理の前に使用さ
れる黒白現像液は通常知られているカラー写真感光材料
の処理に用いられる黒白第１現像液と呼ばれるもの、も
しくは黒白写真感光材料の処理に用いられるものであり
、一般に黒白現像液に添加される各種の添加剤を含有せ
しめることができる。+13 Color development → bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stabilization (4) color development → bleach fixing → stable (5) color development → water washing → Bleach and fix → Wash with water (6) Color development → Stop → Bleach and fix → Wash with water (Power Color development → Bleach → Wash with water →
Fixing → Washing → Stabilization (8) Color development → Bleaching → Footwear → Washing →
Stable (9) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stable Ql Color development → washing with a small amount of water → bleaching → washing with a small amount of water → fixing →
Small amount of water washing → Water washing → Stable (11) Color development → Stop → Bleach → Small amount of water washing → Fixing → Small amount of water washing → Water washing → Stable (13 Black and white development → Water washing → Reversal → Color development → Bleaching → Fixing →
Washing with water → stable α rise Pre-hardening → neutralization → black and white development → stop → development → bleaching → fixing → washing with water → stability The black and white developer used before processing with the processing solution having bleaching ability of the present invention is usually This is the so-called black-and-white first developer used in the processing of known color photographic materials, or the one used in the processing of black-and-white photographic materials, and contains various additives that are generally added to black-and-white developers. You can force it.
代表的な添加剤としてＦｉｌ−フェニル−３−ピラゾリ
ドン、メトールおよびハイドロキノンのような現像主薬
、亜硫酸塩のような保恒剤、水酸化ナトリウム、炭酸ナ
トリウム、炭酸カリウム等のアルカリから成る促進剤、
臭化カリウムや、２−メチルベンツイミダゾール、′メ
チルベンツチアゾール等の無機性、もしくは有機性の抑
制剤、ポリリン酸塩のような硬水軟化剤、微量のヨウ化
物やメルカプト化合物から成る表面過現像防止剤等を挙
げることができる。Typical additives include developing agents such as Fil-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.
Surface overdevelopment prevention consisting of potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole, 'methylbenzthiazole, water softeners such as polyphosphates, and trace amounts of iodide and mercapto compounds. Agents, etc. can be mentioned.
本発明の漂白能を有する処理液による処理の前に使用さ
れるカラー現像液に用いられる芳香族第１級アミン発色
現像主薬は種々のカラー写真プロセスにおいて広範囲に
使用されている公知のものが包含される。これらの現像
剤はアミノフェノール系およびｐ−フェニレンジアミン
系誘導体が含まれる。これらの化合物は遊離状態よ多安
定のため一般に塩の形、例えば塩酸塩または硫酸塩の形
で使用される。また、これらの化合物は、一般に発色現
像液Ｘｔについて約０．１ｇ〜約３０ｇの濃度、更に好
ましくは、発色現像液１ｔについて約１ｇ〜約１５ｇの
濃度で使用する。The aromatic primary amine color developing agent used in the color developer used before processing with the processing solution having bleaching ability of the present invention includes known ones that are widely used in various color photographic processes. be done. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more multistable than the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. Further, these compounds are generally used at a concentration of about 0.1 g to about 30 g per ton of color developer Xt, more preferably about 1 g to about 15 g per 1 t of color developer.
アミンフェノール系現像剤としては例えば、０−アミノ
フェノール、ｐ−アミノフェノール、５−アミノ−２−
オキシ−トルエン、２−アミノ−３−オキシ−トルエン
、２−オキシ−３−アミノ−１，４−ジメチル−ベンゼ
ンなどが含まれる。Examples of the amine phenol developer include 0-aminophenol, p-aminophenol, 5-amino-2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.
特に有用な第１級芳香族アミノ系発色現像剤はＮ、Ｎ−
ジアルキル−ｐ−フェニレンジアミン系化合物であシ、
アルキル基およびフェニル基は置換されていても、ある
いは置換されていなくてもよい。その中でも特に有用な
化合物例としてはＮ、Ｎ−ジエチル−ｐ−フェニレンジ
アミン塩酸塩、Ｎ−メチル−ｐ−７二二レンジアミンｔ
Ｊ［塩、Ｎ、Ｎ−ジメチル−ｐ−）二二レンジアミン塩
酸塩、２−アミノ−５−〔Ｎ−エチル−Ｎ−ドデシルア
ミノコ−トルエン、Ｎ−エチル−Ｎ−β−メタンスルホ
ンアミドエチル−３−メチル−４−アミ／アニリン硫酸
＆ Ｎ−エチル−Ｎ−β−ヒドロキシエチルアミ／アニ
リン、４−アミノ−３−メチル−Ｎ、Ｎ−ジエナルアニ
リン、４−アミノ−Ｎ−（２−ノドキシエテル）−Ｎ−
エテル−３−メチルアニリン−ｐ−）ルエンスルホネー
トナトヲ挙げることができる。Particularly useful primary aromatic amino color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-72-2-diamine t
J[salt, N,N-dimethyl-p-)2-diamine hydrochloride, 2-amino-5-[N-ethyl-N-dodecylaminocortoluene, N-ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-amiline/aniline sulfate & N-ethyl-N-β-hydroxyethylamine/aniline, 4-amino-3-methyl-N,N-dienalaniline, 4-amino-N-( 2-nodoxy ether)-N-
Ether-3-methylaniline-p-)luenesulfonate may be mentioned.
本発明の漂白能を有する処理液による処理の前に使用さ
れるアルカリ性発色現像液は、前記第１級芳香族アミン
系発色現像剤に加えて、更に、発色現像液に通常添加さ
れている種々の成分、例えば水酸化ナトリウム、炭酸ナ
トリウム、炭酸カリウムなどのアルカリ削、アルカリ金
属亜硫酸塩、アルカリ金属重亜硫酸塩、アルカリ金属チ
オシアン酸塩、アルカリ金属ハロゲン化物、ベンジルア
ルコール、ジエチレントリアミン五酢酸、１−ヒドロキ
シエチリデン−１，１−ジホスホン酸等の水軟化剤およ
び濃厚化剤などを任意に含有することもできる。この発
色現像液のｐＨ値は、通常７以上であシ、最も一般的に
は約１０〜約１３である。In addition to the above-mentioned primary aromatic amine-based color developer, the alkaline color developer used before the treatment with the processing solution having bleaching ability of the present invention contains various types of color developer that are usually added to the color developer. Ingredients such as alkaline sulfates such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxy Water softeners and thickeners such as ethylidene-1,1-diphosphonic acid can also be optionally included. The pH value of the color developing solution is usually 7 or higher, most commonly about 10 to about 13.
本発明の漂白能を有する処理液を適用できるハロゲン化
銀カラー写真感光材料は、発色剤が感光材料中に含まれ
ている内式現像方式（米国特許第２．３７６．６７９号
、同第２，８０１，１７１号ＥＪＡ組書参照）のほか、
発色剤が現像液中に含まれている外式現像方式（米国特
許第２，２５２，７１８号、同第２，５９２．２４３号
、同第２，５９０，９７０号明細書参照）のものであっ
てもよい。また発色剤は農業界で一般に知られている任
意のものが使用できる。例えばシアン発色剤としてはす
７トールあるいはフェノール構造を基本とし、カップリ
ングによりインドアニリン色素を形成するもの、マゼン
タ発色剤としては活性メチレン基を有する５−ピラゾロ
ン環を骨格構造として有するもの、イエロー発色剤とし
ては活性メチレン鎖を有するベンゾイルアセドアニライ
ド、ビバリルアセトアニライド、アシルアセドアニライ
ド構造のものなどでカップリング位置に置換基を有する
もの、治しないもののいずれも使用できる。このように
発色剤としては、所謂２貫量型カプラーおよび４当量型
カプラーのいずれをも適用できる。使用し得るー・ロゲ
ン化銀乳剤としては塩化銀、臭化銀、沃化銀、塩臭化銀
、塩沃化銀、沃臭化銀、塩沃臭化銀、寸たけこれらの混
合物の如きいずれのハロゲン化銀を用いたものであって
もよい。また、これ等のノ・ログン化銀の保護コロイド
としては、ゼラチン等の天然物の他合成によって得られ
る種々のものが使用できる。ハロゲン化銀乳剤には、安
定剤、増感剤、硬膜剤、増感色素、界面活性剤等通富の
写真用添加剤が含まれてもよい。The silver halide color photographic light-sensitive material to which the processing solution having bleaching ability of the present invention can be applied is an internal development method (U.S. Pat. No. 2,376,679, U.S. Pat. , No. 801, 171 EJA), as well as
External development method (see U.S. Pat. No. 2,252,718, U.S. Pat. No. 2,592.243, and U.S. Pat. No. 2,590,970) in which a color former is contained in the developer. There may be. Further, as the coloring agent, any coloring agent generally known in the agricultural industry can be used. For example, cyan color formers are based on a lotus 7-tall or phenol structure and form indoaniline dyes through coupling, magenta color formers have a skeletal structure of 5-pyrazolone rings with active methylene groups, and yellow color formers. As the agent, those having a benzoylacedoanilide, bivalylacetanilide, or acylacedoanilide structure having an active methylene chain, and either those having a substituent at the coupling position or those not curing can be used. Thus, as the coloring agent, both so-called two-equivalent couplers and four-equivalent couplers can be used. Silver chloride emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof. Any silver halide may be used. Furthermore, as protective colloids for these silver oxides, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion may contain commonly used photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.
本発明の漂白液及び漂白定着液は、カラーベーハー、カ
ラーネガフィルム、カラーポジフィルム、スライド用カ
ラー反転フィルム、映画用カラー反転フィルム、ＴＶ用
カラー反転フィルム、反転カラーペーパーなどのハロゲ
ン化銀カラー写真感光材料に適用することができる。The bleaching solution and bleach-fixing solution of the present invention can be used for silver halide color photographic materials such as color substrates, color negative films, color positive films, color reversal films for slides, color reversal films for movies, color reversal films for TVs, and reversal color papers. Can be applied.
以下、実施例によって本発明の詳細な説明するが、これ
により本発明の実施の態様カニ限定されるものではない
。Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby.
実施例１ 洋白定着液を以下の様に調整した。Example 1 A nickel silver fixer was prepared as follows.
〔漂白定着液（１）〕
〔漂白定着液（２）〕
〔漂白定着液（３）〕
〔漂白定着液（４）〕
〔漂白定着液（５）〕
漂白定着液（１）〜（５）を窒素気流中で漂白定着液１
を当シ９ｇの銀粉末を加え鉄（Ｊ！Ｄ錯塩の一部を鉄（
ＩＴ）錯塩に変換した後、上澄液者５０−を２００ゴビ
ーカーに入れ室温で静置し、エチレンジアミン四酢酸鉄
（社）錯塩及びジエチレン） ＩＪアミン五酢酸鉄（ｆ
ｉｔ）錯塩を定量することにょシ、それぞれ対応する鉄
（「ン錯塩の空気酸化速度を測定した。[Bleach-fix solution (1)] [Bleach-fix solution (2)] [Bleach-fix solution (3)] [Bleach-fix solution (4)] [Bleach-fix solution (5)] Bleach-fix solution (1) to (5) Bleach-fix solution 1 in a nitrogen stream
Add 9g of silver powder to the mixture and add some iron (J!D complex salt to iron (
After converting the supernatant into a complex salt (IT), the supernatant (50-) was placed in a 200-gover beaker and allowed to stand at room temperature to convert it into ethylenediaminetetraacetate complex salt and diethylene) IJaminetetraacetate iron (f).
In order to quantify the complex salts, the air oxidation rate of the corresponding iron complex salts was measured.
この結果を■記第１表に示す。The results are shown in Table 1 marked (■).
以下余白
第１表
上記第１表から明らかなように、ジエチレントリアミン
五酢酸鉄（［Ｄ錯塩は、通常エテレンジアミヒドロキシ
エチルエナレンジアミン三酢酸を添加しても、鉄（ｎ）
錯塩の空気酸化が促進されないが、本発明の漂白定着液
では、エチレンジアミン四酢酸鉄（ｆｆ）錯塩より以上
の空気酸化速度定数を持っていることがわかる。Table 1 in the margin below.
Although the air oxidation of the complex salt is not promoted, it can be seen that the bleach-fix solution of the present invention has a higher air oxidation rate constant than the ethylenediaminetetraacetic acid iron (ff) complex salt.
次に、漂白定着液（１１〜（５）の亜硫酸アンモニウム
及びチオ硫酸アンモニウムに代えて、−８化アンモニウ
ム１４０ｇ／７を添加し、ｐＨを６．５に調整した漂白
液（１）〜（５）を作成し、β１様に突気酸化速度定数
を測定したが、はぼ同様の結果が得られた。Next, in place of ammonium sulfite and ammonium thiosulfate in bleach-fix solutions (11 to (5)), 140 g/7 of ammonium -8 oxide was added, and the pH was adjusted to 6.5. Bleach solutions (1) to (5) was prepared and the sudden oxidation rate constant was measured in the same manner as β1, but almost the same results were obtained.
実施例２
サクラカラーａフィルム〔小西六写真工業■製］１００
０Ｆ７１′をコニカＦＳ−１［小西六写真工業■製〕を
用いて撮影した後、次の処理ＪＸ程に従って自動現像機
にて連続補充処理（以下、自現ランニング処理と称する
）した。Example 2 Sakura color a film [manufactured by Konishiroku Photo Industry ■] 100
After photographing 0F71' using a Konica FS-1 [manufactured by Konishiroku Photo Industry ■], it was subjected to continuous replenishment processing (hereinafter referred to as automatic development running processing) using an automatic developing machine according to the following processing JX procedure.
自動現像機は、／−リツ鋼機製吊Ｆ式フィルム自動現像
機タイプＨ４−２２０Ｗ−２を改造して使用した。The automatic developing machine used was a modified hanging F-type film automatic developing machine type H4-220W-2 manufactured by Ritsu Koki Co., Ltd.
処理工程（３８℃） 槽数 処理時間使用した処
理液の組成は次のとおりである。Treatment process (38°C) Number of tanks Treatment time The composition of the treatment liquid used is as follows.
〔発色現像補充液〕
〔漂白定着液及び漂白定着補光液（１）〕〔漂白定着液
及び漂白定着補光液（２）〕〔漂白定着液及び漂白定着
補光液（３）〕〔漂白定着液及び漂白定着補充液（４）
〕〔安定液〕
〔安定補光液〕
発色現像補光液は、カラーネガフィルム１００ｄ蟲シ１
５−発色埃像浴に補光され、漂白定着補光液は、カラー
ネガフィルム】００ｃ１／ｌ当、１９ｍ漂白漂白浴に補
光され、さらに安定補光液は、カラーネガフィルム】０
０ｄ当り１１−安定浴に補充された。また、水洗浴には
、水がカラーネガフィルム１００ｃｒＩ当シ】５〇−流
された。[Color development replenisher] [Bleach-fix solution and bleach-fix auxiliary solution (1)] [Bleach-fix solution and bleach-fix auxiliary solution (2)] [Bleach-fix solution and bleach-fix auxiliary solution (3)] [Bleach Fixer and bleach-fix replenisher (4)
] [Stabilizer] [Stable brightener] Color developing brightener is a color negative film 100d Mushi 1
5- The light is supplemented to the color developing dust image bath, the bleach-fixing auxiliary solution is supplemented to the color negative film]00c1/l, the light is supplemented to the 19m bleaching bath, and the stable light auxiliary solution is added to the color negative film]0
11-stabilization bath was replenished per 0 d. In addition, water was poured into the washing bath with a color negative film of 100 crI.
漂白定着及び漂白定着補光液＋１１〜（４）を使用し、
フィルムを各々１０００ｍ連続補充処理した。各自現ラ
ンニング処理終了後、鯛白定着タンク液を密栓冷蔵庫保
存した。すべての自現ランニング処理終了後、漂白定着
タンク液１１）〜（４）のｐＫ’を第２表の値に調整し
、ピース用処理装置を用いて処理（以丁、手現処理と称
する）を行ない、脱銀完了時間即ちクリアリングタイム
を測定し７、更に３０分間漂白定着処理して得られたフ
ィルムの赤色最高濃度（シアン色票濃度）と緑色最低濃
度（マゼンタスティン）を測定し、その結果を第２表に
示した。Using bleach-fixing and bleach-fixing brightening solution +11 to (4),
Each film was continuously replenished for 1000 m. After completing each self-development process, the Taishiro fixing tank solution was stored in a tightly closed refrigerator. After all the self-development running processes are completed, adjust the pK' of bleach-fix tank solutions 11) to (4) to the values shown in Table 2, and process using a piece processing device (referred to as hand processing). The desilvering completion time, that is, the clearing time, was measured7, and the maximum red density (cyan color patch density) and minimum green density (magenta tin) of the film obtained by bleach-fixing for 30 minutes were measured. The results are shown in Table 2.
なお、処理条件は漂白足滝の処理時間以外は自現ランニ
ング処理と同一の処理条件とし、使用した処理液は漂白
定着液以外は、自現ランニング処理と同一の組成の処理
液を使用した。１だ処理した試料は、サクラカラーａフ
ィルム〔小西六写真工業■製〕をピースに断裁し、常法
に従って倶型露光を与えたものを用いた。The processing conditions were the same as those for the Jigen Running process except for the processing time for the bleaching footfall, and the processing solution used had the same composition as the Jigen Running process, except for the bleach-fix solution. The single-processed sample was obtained by cutting Sakura Color A film (manufactured by Konishiroku Photo Industry) into pieces and subjecting it to cross-shaped exposure according to a conventional method.
冑、比較として基準処理であるサクラ力う−ネガプロセ
スＣＮＫ−４で処理した試料を同様に測定した。但し脱
銀処理時間は漂白処理６分３０秒と定着処理６分３０秒
を行なった。For comparison, a sample treated with the standard treatment, Sakura Force Negative Process CNK-4, was measured in the same manner. However, the desilvering treatment time was 6 minutes 30 seconds for bleaching and 6 minutes 30 seconds for fixing.
以下余白
第２表の結果から明らかなように、本発明の漂白定着液
（３）および（４）では、りＩＪアリングタイムも短く
、赤色最高濃度も基準処理の２．６２とほぼ一致し、緑
色最低濃度も基準処理の０５８に近く実質的に問題ない
ことがわかる。As is clear from the results in Table 2 below, in the bleach-fix solutions (3) and (4) of the present invention, the IJ ringing time was short, and the maximum red density was almost the same as 2.62 of the standard treatment. It can be seen that the minimum green density is close to 058 of the standard treatment and there is no substantial problem.
一力、本発明以外の漂白定着液（１１、（２１では、ク
リアリングタイム、赤色最高濃度及び緑色最低濃度のす
べてを満足する事ができない。However, the bleach-fix solutions (11 and 21) other than those of the present invention cannot satisfy all of the requirements of clearing time, maximum red density, and minimum green density.
次に、処理後の液をガラスビーカーにて３８℃にて放置
し、硫化銀の生成迄の日数を観測した。Next, the treated solution was left in a glass beaker at 38° C., and the number of days until silver sulfide was formed was observed.
結果を第３表に示した。The results are shown in Table 3.
以下余白
第３表の結果よシ明らかのように、エチレンジアミン四
酢酸鉄（ＩＩＤ錯塩を漂白剤とする漂白定着液（１）は
、比較的短時間で硫化銀が発生するのに対し、本発明の
漂白定着液＋３） 、 ＋４）は、ヒドロキシエチルエ
チレンジアミン三酢酸および／又はヒドロキシエチルエ
チレンジアミンミ酢酸鉄（ＩＩＤ錯塩を離別しない漂白
定着液（２）と同様に極めて安定であることがわかる。As is clear from the results in Table 3 below, the bleach-fix solution (1) using iron ethylenediaminetetraacetate (IID complex salt) as a bleaching agent generates silver sulfide in a relatively short time, whereas the present invention It turns out that the bleach-fix solutions +3) and +4) are very stable, as is the bleach-fix solution (2) which does not dissociate the hydroxyethylethylenediaminetriacetic acid and/or hydroxyethylethylenediaminemyacetate iron (IID) complex salts.
実施例３
白色顔料としてアナターゼ型の酸化チタンを含むポリエ
テレン層によって、表面を′＄、扮した紙支持体上にコ
ロナ放電による前処理を施こした後、次の各層を順次塗
設してカラー印画紙を作った。Example 3 A paper support whose surface was coated with a polyethylene layer containing anatase titanium oxide as a white pigment was pretreated by corona discharge, and then the following layers were sequentially applied to produce color. I made photographic paper.
第１層：イエローカプラーとしてα−〔４−（１−ベン
ジル−２−フェニル−３，５−ジオキン−１，２，４−
１リアシリシル）〕−〕α−ピバリルー２−クロロー５
−γ−（２，４−ジ−ｔ−アミルフェノキシ）ブナルア
ミド〕アセトアニリドを含有し、５モル係の塩化銀を含
む青感性塩臭化銀乳剤層。1st layer: α-[4-(1-benzyl-2-phenyl-3,5-dioquine-1,2,4-
1 riasilicyl)]-]α-pivalru 2-chlororu 5
- A blue-sensitive silver chlorobromide emulsion layer containing γ-(2,4-di-t-amylphenoxy)bunalamide] acetanilide and containing 5 moles of silver chloride.
第２層：紫外線吸収剤を含有するゼラチン中間層。Second layer: gelatin intermediate layer containing UV absorbers.
第３層：マゼンタカプラーとしてＩ −（２，４，６−
ドリクロロフエニル）−３−（２−クロロ−５−オクタ
テセニルサクシンイミドアニリノ）−５＝ピラゾロンを
含有し、１５モル係の塩化銀を含む緑感性塩臭化銀乳剤
層。Third layer: I-(2,4,6-
A green-sensitive silver chlorobromide emulsion layer containing pyrazolone (dolichlorophenyl)-3-(2-chloro-5-octatecenylsuccinimidoanilino)-5=pyrazolone and containing 15 moles of silver chloride.
第４層：第２層と同じゼラチン中間層。4th layer: Gelatin middle layer same as 2nd layer.
第５層ニジアンカプラーとして２，４−ジクロロ−３−
メチル−６−〔γ−（２，４−シアミルフェノキシ）ブ
ナルアミド〕フェノールヲ含有Ｌ、１５モル係の塩化銀
を含む赤感性塩臭化銀乳剤層。2,4-dichloro-3- as the fifth layer nitrogen coupler
A red-sensitive silver chlorobromide emulsion layer containing methyl-6-[γ-(2,4-cyamylphenoxy)bunalamido]phenol and 15 moles of silver chloride.
第６．鳴：ゼラチン保護層。6th. Sound: Gelatin protective layer.
上記の各感光性乳剤層は、総体の銀量が１００ｄ当シ１
０■となるように律布した。また各感光性乳剤層に用い
たハロゲン化銀写真乳剤はそれぞれチオ硫酸ナトリウム
によシ化学増感を施し、安定剤、増感色素等通常の添加
剤を加えた。またすべての層の塗布液には硬膜剤及び延
展剤を添加した。Each of the above photosensitive emulsion layers has a total silver content of 100 d/1
It was set so that it was 0 ■. The silver halide photographic emulsions used in each light-sensitive emulsion layer were chemically sensitized using sodium thiosulfate, and conventional additives such as stabilizers and sensitizing dyes were added. Further, a hardening agent and a spreading agent were added to the coating solution for all layers.
以上のようにして作ったカラー印画紙（ロール状）を絵
焼プリント後、ロール自動現像機で連続補光処理した。The color photographic paper (in roll form) produced as described above was printed with engravings and then subjected to continuous light supplementation processing using an automatic roll developing machine.
処理液の組成は次の通シである。 The composition of the treatment liquid is as follows.
〔発色現像補光液〕
〔漂白液及び漂白補充液（１）〕
〔漂白液及び漂白補光液（２）〕
〔漂白液及び漂白補光液（３）〕
〔漂白液及び漂白補充液（４）〕
〔定着液〕
〔定着補充液〕
発色現像補光液及び漂白補充液は、カラー印画紙１００
ｉ当シ３．２−がそれぞれ発色現像浴に補充され、定着
補光液はカラー印画紙１００ｃ１１当シ０．７−補光さ
れ、水洗浴には、水がカラー印画紙１００ｆｆｌ当シ１
ｏｏ−流された。またｉｔ工白浴及び定着浴前後のスク
イーズを調整し、カラー印画紙１ （１０ａ／を当シの
液の持ち込み及び持ち出し量を０．５−とした。[Color development brightener solution] [Bleach solution and bleach replenisher (1)] [Bleach solution and bleach replenisher (2)] [Bleach solution and bleach replenisher (3)] [Bleach solution and bleach replenisher ( 4)] [Fixer] [Fixer replenisher] Color developing light replenisher and bleach replenisher should be used on color photographic paper 100.
The color developing bath is replenished with 3.2 - of each color, the fixing auxiliary liquid is supplemented with 0.7 - of light per 100 c of color photographic paper, and the water is added to the washing bath with 1 of 100 ffl of color photographic paper.
oo-washed away. In addition, the squeezing before and after the IT process white bath and fixing bath was adjusted, and the amount of liquid carried in and taken out of color photographic paper 1 (10 a/) was set to 0.5-.
禄白液及び漂白補光液ｆｉｌ〜（４）を使用し、各々漂
白補充液の使用量が漂白浴のタンク容量の４倍になるま
で自現ランニング処理を行なつ＆、各自現ランニング処
理終了後、漂白タンク液を密栓冷蔵庫保存した。すべて
の自現ランニング処理終了後、漂白タンク液＋ＩＪ〜（
４）のｐＨを第４表の値に調整し、手現処理を行ない、
脱銀完了時間即ちクリアリングタイムを測定し、更に２
分間漂白処理して得られたカラー印画紙の赤色最高透過
濃度〔シアン色票濃度〕と緑色最低反射濃度（マゼンタ
スティン）を測定し、その結果を第４表に示した。なお
、処理条件は漂白の処理時間以外は、自現ランニング処
理と同一の処理条件とし使用した処理液は漂白液以外は
、自現ランニング処理と同一の組成の処理液を使用した
。また処理した試料は、自現ランニング処理に用いたカ
ラー印画紙をピースに断裁し、常法に従って模型露光を
与えたものを用いた。Using Rokuhaku liquid and bleach replenisher fil~(4), perform the self-development running process until the usage amount of each bleach replenisher becomes 4 times the tank capacity of the bleach bath &, each process is completed. Afterwards, the bleach tank solution was stored in a tightly closed refrigerator. After all the jibun running processes are completed, bleach tank solution + IJ ~ (
Adjust the pH of 4) to the value shown in Table 4, perform manual treatment,
Measure the desilvering completion time, that is, the clearing time, and then
The maximum red transmission density (cyan color patch density) and minimum green reflection density (magentastin) of the color photographic paper obtained by bleaching for minutes were measured, and the results are shown in Table 4. The processing conditions were the same as those for the automatic running process, except for the bleaching time, and the processing liquid used had the same composition as the automatic running process, except for the bleaching solution. The processed sample used was one in which the color photographic paper used in the free running process was cut into pieces and pattern exposure was applied in accordance with a conventional method.
以下余白
第４表の結果から明らかなように、本発明の漂白液（３
）および（４）ではクリアリングタイムも短く赤色最高
透過濃度も高いし、四に條色最低反射濃度も低く極めて
良好な性能を有していることがわかる。−力、本発明以
外の卵白液（ＩＩ 、 （２＋ではクリアリングタイム
、赤色最高透過濃度及び緑色最低反射濃度のすべてを満
足する事ができない。As is clear from the results in Table 4 below, the bleaching solution of the present invention (3
) and (4) have short clearing times and high red maximum transmission densities, and fourthly, low color minimum reflection densities and have extremely good performance. In contrast, egg white liquids other than those of the present invention (II, (2+) cannot satisfy all of the clearing time, red maximum transmission density, and green minimum reflection density.
Claims (1)
ドロキシエチルエチレンジアミン三酢酸および／又はヒ
ドロキシエチルエチレンジアミン三酢酸鉄ＩＤ錯塩を含
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
料用の漂白能を有する処理液。A processing solution having bleaching ability for silver halide color photographic light-sensitive materials, characterized in that it contains a diethylenetriaminepentaacetate iron I complex salt, and hydroxyethylethylenediaminetriacetic acid and/or a hydroxyethylethylenediaminetriacetate iron ID complex salt. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4063383A JPS59166951A (en) | 1983-03-14 | 1983-03-14 | Processing solution capable of bleaching silver halide color photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4063383A JPS59166951A (en) | 1983-03-14 | 1983-03-14 | Processing solution capable of bleaching silver halide color photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59166951A true JPS59166951A (en) | 1984-09-20 |
| JPH0565865B2 JPH0565865B2 (en) | 1993-09-20 |
Family
ID=12585948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4063383A Granted JPS59166951A (en) | 1983-03-14 | 1983-03-14 | Processing solution capable of bleaching silver halide color photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59166951A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61117541A (en) * | 1984-11-13 | 1986-06-04 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5151940A (en) * | 1974-10-31 | 1976-05-07 | Fuji Photo Film Co Ltd | KARAASHASHINZAIRYONO SHORIHOHO |
-
1983
- 1983-03-14 JP JP4063383A patent/JPS59166951A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5151940A (en) * | 1974-10-31 | 1976-05-07 | Fuji Photo Film Co Ltd | KARAASHASHINZAIRYONO SHORIHOHO |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61117541A (en) * | 1984-11-13 | 1986-06-04 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0565865B2 (en) | 1993-09-20 |
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