JPS6150145A - Treatment of silver halide color photographic sensitive material - Google Patents
Treatment of silver halide color photographic sensitive materialInfo
- Publication number
- JPS6150145A JPS6150145A JP17215484A JP17215484A JPS6150145A JP S6150145 A JPS6150145 A JP S6150145A JP 17215484 A JP17215484 A JP 17215484A JP 17215484 A JP17215484 A JP 17215484A JP S6150145 A JPS6150145 A JP S6150145A
- Authority
- JP
- Japan
- Prior art keywords
- group
- complex salt
- ferric complex
- acid ferric
- processing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 40
- 229910052709 silver Inorganic materials 0.000 title claims description 53
- 239000004332 silver Substances 0.000 title claims description 53
- 150000003839 salts Chemical class 0.000 claims abstract description 150
- 238000012545 processing Methods 0.000 claims abstract description 54
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- 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 abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 57
- 238000011161 development Methods 0.000 claims description 44
- 238000004061 bleaching Methods 0.000 claims description 37
- 150000007524 organic acids Chemical class 0.000 claims description 29
- 239000007844 bleaching agent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012086 standard solution Substances 0.000 claims description 3
- 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 claims description 2
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 2
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 5
- 229910021612 Silver iodide Inorganic materials 0.000 abstract description 5
- 229940045105 silver iodide Drugs 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 20
- 239000000975 dye Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 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 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- 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
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 3
- 239000012088 reference solution Substances 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 108010010803 Gelatin Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- KZTASAUPEDXWMQ-UHFFFAOYSA-N azane;iron(3+) Chemical compound N.[Fe+3] KZTASAUPEDXWMQ-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000003944 tolyl group Chemical group 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 1
- ASVZBRLVGGMTEN-UHFFFAOYSA-N 2-methylidenebenzimidazole Chemical compound C1=CC=CC2=NC(=C)N=C21 ASVZBRLVGGMTEN-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
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-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
- MTOCKMVNXPZCJW-UHFFFAOYSA-N 4-n-dodecyl-4-n-ethyl-2-methylbenzene-1,4-diamine Chemical compound CCCCCCCCCCCCN(CC)C1=CC=C(N)C(C)=C1 MTOCKMVNXPZCJW-UHFFFAOYSA-N 0.000 description 1
- QJNVAFZHBQNXJT-UHFFFAOYSA-N 4-n-ethyl-4-n-(2-methoxyethyl)-2-methylbenzene-1,4-diamine;4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.COCCN(CC)C1=CC=C(N)C(C)=C1 QJNVAFZHBQNXJT-UHFFFAOYSA-N 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101000767534 Arabidopsis thaliana Chorismate mutase 2 Proteins 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241001269524 Dura Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 101000986989 Naja kaouthia Acidic phospholipase A2 CM-II Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KTWNIUBGGFBRKH-UHFFFAOYSA-N [4-(dimethylamino)phenyl]azanium;chloride Chemical compound Cl.CN(C)C1=CC=C(N)C=C1 KTWNIUBGGFBRKH-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- AOGQQMWRSVSSEK-UHFFFAOYSA-M [Cl-].[Ag+].IBr Chemical compound [Cl-].[Ag+].IBr AOGQQMWRSVSSEK-UHFFFAOYSA-M 0.000 description 1
- JXHNPIOENFLSER-UHFFFAOYSA-L [Fe+2].CN(CC(=O)[O-])CC(=O)[O-] Chemical compound [Fe+2].CN(CC(=O)[O-])CC(=O)[O-] JXHNPIOENFLSER-UHFFFAOYSA-L 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- CKJBFEQMHZICJP-UHFFFAOYSA-N acetic acid;1,3-diaminopropan-2-ol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCC(O)CN CKJBFEQMHZICJP-UHFFFAOYSA-N 0.000 description 1
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000012790 adhesive layer Substances 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
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- FZERHIULMFGESH-UHFFFAOYSA-N methylenecarboxanilide Natural products CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 1
- BJXLHKJBRORJJJ-UHFFFAOYSA-N n-(pyridin-3-ylmethyl)aniline Chemical compound C=1C=CN=CC=1CNC1=CC=CC=C1 BJXLHKJBRORJJJ-UHFFFAOYSA-N 0.000 description 1
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 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
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 229910052700 potassium Inorganic materials 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
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はハロゲン化銀カラー写真感光材料の処理方法に
関する。更に詳しくは大巾に銀漂白能力が改良され、更
に処理時の顕色性も改良されたハロゲン化銀カラー写真
感光材料の処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials in which the silver bleaching ability is greatly improved and the color developing property during processing is also improved.
［従来技術］
従来、ハロゲン化銀カラー写真感光材料の画像銀を除去
するためのいわゆる漂白剤としては赤血塩、重クロム酸
塩、塩化鉄等の酸化剤が用いられてきたが、毒性や処理
機部材の腐食の点で問題があり、実用上充分満足できる
ものではない。[Prior Art] Oxidizing agents such as red blood salt, dichromate, and iron chloride have conventionally been used as bleaching agents to remove image silver from silver halide color photographic light-sensitive materials, but they are toxic and There is a problem in terms of corrosion of processing machine parts, and it is not completely satisfactory in practical terms.
近年、毒性に問題がないということから７ミノポリカル
ポン酸金属錯塩を漂白液又は漂白定着液の酸化剤として
用いる方法が行われてきている。In recent years, a method of using a 7-minopolycarboxylic acid metal complex salt as an oxidizing agent in a bleaching solution or a bleach-fixing solution has been carried out because there is no problem with toxicity.
しかしながら、アミノポリカルボン酸金属錯塩は酸化力
が弱く、従って画像銀の漂白速度が遅いという欠点を有
しており、このことは特に高感度ハロゲン化銀カラー写
真感光材料の迅速処理という目的から必要な一浴漂白定
着処理ができないという欠点をもたらしている。実際上
、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（Ｅ［Ｉ）
！塩（以下、ＥＤＴＡ−Ｆｅ （ＩＩＩ ） ｉｎ 塩
と呼ぶ）は、一部では漂白定着液としても実用化されて
いるが、臭化銀または沃臭化銀乳剤を主体とする高感度
ハロゲン化銀カラー写真感光材料、特にハロゲン化銀と
して沃化銀を含有する撮影用カラーペーパー及び撮影用
カラーネガティブフィルム、並びに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。また更には処
理液中の溶解、蓄積する銀塩や、沃素イオンのｆＱ度が
高まると著しく漂白刃が低下する。特にｐＨ４，０以上
の場合、可溶性銀イオン錯体として交当り５ｇを越える
溶解蓄積でＷＪ著に現われる。又ｐ８４．０以下では、
可溶性銀イオン錯体蓄積の漂白刃に与える影響は極めて
小さい、更にまた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下するために脱
銀不良か４’Ｆに顕著に上地われる。However, aminopolycarboxylic acid metal complex salts have the disadvantage of weak oxidizing power and therefore slow bleaching speed of image silver, which is especially necessary for the purpose of rapid processing of high-sensitivity silver halide color photographic materials. This brings about the disadvantage that a single-bath bleach-fixing process cannot be performed. In fact, iron ethylenediaminetetraacetate (E[I), which is considered to have the strongest bleaching edge among aminopolycarboxylic acid metal complex salts,
! Salt (hereinafter referred to as EDTA-Fe(III) in salt) is used as a bleach-fixing solution in some areas, but it is also used as a high-sensitivity silver halide emulsion based on silver bromide or silver iodobromide emulsions. Color photographic materials, especially color paper for photography, color negative film for photography, and color reversal film containing silver iodide as silver halide, lack a bleaching blade and leave only traces of image silver even after long processing. remains, resulting in poor desilvering properties. Moreover, when the fQ degree of dissolved and accumulated silver salts and iodide ions in the processing solution increases, the bleaching edge deteriorates significantly. In particular, when the pH is above 4.0, it appears as a soluble silver ion complex with a dissolved accumulation of more than 5 g per intersection, as reported by WJ. Also, below p84.0,
The effect of accumulation of soluble silver ion complexes on the bleaching blade is extremely small.Furthermore, in a bleach-fix solution in which an oxidizing agent, thiosulfate, and sulfite coexist, the redox potential decreases, resulting in poor desilvering, which is noticeable in 4'F. will be appointed.
従来これらの問題の解決のために特公昭４５−８０５６
号、同４６−５５６号、特開昭４６−２８０号、同４９
−５６３０号等に記載されているが如く、漂白促進剤を
主にＥＤＴＡφＦｅ（ｍ）錯塩を酸化剤とする漂白定着
液に加えて使用しているが、かならずしも満足しうる漂
白促進効果を得ていないか、もしくは銀が溶解蓄積する
と難溶性の沈超を生じる等の問題があり、とても高感度
ハロゲン化銀カラー写真感光材料の実用的な漂白定着液
として耐えうるものではなかった。Conventionally, in order to solve these problems, the special public
No. 46-556, JP-A No. 46-280, No. 49
As described in No.-5630, etc., a bleach accelerator is used in addition to a bleach-fixing solution that mainly uses EDTAφFe(m) complex salt as an oxidizing agent, but it is not always possible to obtain a satisfactory bleach accelerating effect. There are problems such as the formation of poorly soluble precipitation when the silver dissolves and accumulates, and cannot be used as a practical bleach-fixing solution for highly sensitive silver halide color photographic materials.
又別の方法と−しては、ＥＤＴＡ赤Ｆｅ （ＩＩＩ）錯
塩を用いた場合にその漂白刃が強く発揮されるような低
ｐｏ域で処理することが行われているが、共存するチオ
硫酸塩及び亜硫酪塩が分解し易く液の安定性が低い、又
発色色素特にシアン色素がロイコ化し易く充分顕色しな
いという重大な問題となることが知られている。Another method is to use EDTA red Fe (III) complex salt to perform treatment at a low po range where its bleaching power is strongly exerted, but the coexisting thiosulfuric acid It is known that salts and butysulfurous salts are easily decomposed and the stability of the liquid is low, and coloring dyes, particularly cyan dyes, are easily leucoized and do not develop colors sufficiently, which is a serious problem.
この問題を解決するために高ｐＨ側で処理するとシアン
のロイコ色票が少なくなるものの脱銀性がｐＨの上昇と
ともに低下し、又現像主薬の酸化体と残留カプラーとの
カプリングによる色素汚染（以下、スティンと呼び）を
生じる等の欠点が現われ、満足する漂白定着処理性能が
得られなかった。To solve this problem, processing at a high pH reduces the cyan leuco color patch, but the desilvering performance decreases as the pH increases, and dye contamination (hereinafter referred to as , staining) occurred, and satisfactory bleach-fixing performance could not be obtained.
従って、従来のＥＤＴＡ−Ｆｅ （ＩＩＩ）錯塩を酸化
剤とする漂白定着液を用いてｔｉｔ！影川高感用カラー
写真感光材料を処理する場合、感光材料の計時性を害さ
ず、実用上充分１酎えうる迅速な銀？ＩＪ自刃を有する
ことはほとんど不可能であった。Therefore, using a conventional bleach-fix solution containing EDTA-Fe (III) complex salt as an oxidizing agent, tit! Kagegawa: When processing high-sensitivity color photographic light-sensitive materials, is there a method that does not impair the timekeeping properties of the light-sensitive materials and can be processed quickly enough for practical use? It was almost impossible to have an IJ self-blade.
木発明者は前記問題点を解決するために鋭意研究した結
果、有機酸第２鉄錯塩の中でも本発明特有の漂白剤は銀
源白刃に優れ、高銀量でかつ高沃度のハロゲン化銀カラ
ー写真感光材料を処理する上で充分満足できる性能を有
していることを見い出した。更に本発明の漂白剤は銀漂
白反応が迅速であるにもかかわらず、直接漂白定着処理
したときのスティンの発生も少なく、液の保存安定性に
も優れているということを見い出した。As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention discovered that among organic acid ferric complex salts, the bleaching agent unique to the present invention is excellent in silver source white blades, and has a high silver content and high iodine content in silver halide color photographs. It has been found that it has sufficiently satisfactory performance in processing photosensitive materials. Furthermore, it has been found that although the bleaching agent of the present invention has a rapid silver bleaching reaction, it produces less staining when directly bleach-fixed and has excellent storage stability.
しかしながら、前記のような優れた性能を有する本発明
の漂白剤を用いた漂白定着液で漂”内定着処理した場合
に思いもよらずマゼンタ色素の顕色性が悪いということ
が判った。このことは、Ｅ［！ＴＡ・Ｆｅ（ｍ）ｆｉ塩
を漂白剤とする漂白定着液では全く生じないということ
から本発明者にとって全く予想しえないことであった。However, it was unexpectedly found that the color development of the magenta dye was poor when the bleach-fixing solution using the bleach-fixing agent of the present invention, which has the above-mentioned excellent performance, was used for in-bleach fixing. This was completely unexpected to the inventors since it does not occur at all in a bleach-fix solution using E[!TA.Fe(m)fi salt as a bleaching agent.
特に漂白定着処理時間が８分以内の場合に顕色性が劣化
し易く、実用上重大な問題となるこｋが判った。In particular, it has been found that when the bleach-fixing treatment time is 8 minutes or less, the color development property tends to deteriorate, which poses a serious problem in practical use.
従って、本発明の漂白剤を用いて漂白定着液として使用
していくためには、マゼンタ色素の顕色性を改良し、か
つｆａ漂白能力、スティン耐性及び液保存性を損なわな
い技術の開発が望まれている。Therefore, in order to use the bleaching agent of the present invention as a bleach-fix solution, it is necessary to develop a technology that improves the color development of magenta dye and does not impair fa bleaching ability, stain resistance, and solution storage stability. desired.
［発明が解決しようとする問題点コ
本発明は、迅速な銀源白刃を備え、マゼンタ色素の顕色
性を改良及びスティンの防止、更に漂白定着液の保存安
定性が改良された。ハロゲン化銀カラー写真感光材料用
の処理方法を提供することを技術的課題とする。[Problems to be Solved by the Invention] The present invention is equipped with a rapid silver source white blade, improves the development of magenta dye, prevents staining, and improves the storage stability of the bleach-fix solution. It is an object of the present invention to provide a processing method for silver halide color photographic materials.
〔発明の構成コ
本発明者は鋭意研究した結果、ハロゲン化銀カラー写真
感光材料を像様露光後現像処理し、漂白能を有する処理
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、前記ハロゲン化銀カラー写真感光材料が少
なくとも下記一般式（Ｉ）及び／又は〔■〕で示される
マゼンタカプラーを含有し、前記漂白能を有する処理液
が、漂白剤として下記第２鉄鎖塩群から選ばれる有機酸
第２鉄錯塩（Ａ）の少なくとも１つ又は有機酸第２鉄錯
塩の下記基準溶液のｐＨが５．０〜９．０の間での酸化
還元電位の差がｌｏＯｍＶ以内である有機酸第２鉄錯塩
の少なくとも１つを含有することによって上記目的を達
成しうることを見い出した。[Structure of the Invention] As a result of intensive research, the present inventor has developed a method for processing a silver halide color photographic material, which involves developing the silver halide color photographic material after imagewise exposure and treating it with a processing solution having bleaching ability. , the silver halide color photographic light-sensitive material contains at least a magenta coupler represented by the following general formula (I) and/or [■], and the processing solution having bleaching ability contains the following ferric chain salt group as a bleaching agent. The difference in redox potential is within loOmV when the pH of at least one of the organic acid ferric complex salts (A) selected from the following or the following reference solution of the organic acid ferric complex salt is between 5.0 and 9.0. It has been found that the above object can be achieved by containing at least one ferric complex salt of a certain organic acid.
一般式（Ｉ）
式中、Ａｒはフェニル基である。Ｙｌは芳香族第１級ア
ミン発色現像主薬の酸化体とカプリングして色素が形成
されるとき離脱する基を表わす、Ｘはハロゲン原子、ア
ルコキシ基、アルキル基である。Ｒはベンゼン環に置換
可能な基を表わし、ｎは１又は２で表わす、ｎが２のと
きＲは同じでも異なっていてもよい。General Formula (I) In the formula, Ar is a phenyl group. Yl represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent, and X represents a halogen atom, an alkoxy group, or an alkyl group. R represents a group that can be substituted on the benzene ring, n is 1 or 2, and when n is 2, R may be the same or different.
一般式（ＩＩ ）
Ｍ Ｙｚ
式中、 Ｒｒ及びＲ２は夫々アルキル基又はアリール
基を示し、厩は水素原子又は発色現像主薬の酸化体との
カプリング反応時に離脱しうる基又は原子を表わす、又
Ｙ２は水素原子又はＲコ
−Ｎ０２又は−ＣＭを表わし、 Ｒ４は前記Ｒ３にお
いにＧ
Ｒｓはアルキル基を表わし、Ｒ６は水素原子、−０００
）１ 、−０Ｈ１−ＣＯＯＲｓ又は−Ｓ０３ Ｈを表わ
す、 Ｒ３とＲ４はそれぞれ同一の基でも異なる基で
もよい。General formula (II) M Yz In the formula, Rr and R2 each represent an alkyl group or an aryl group, and the stable represents a hydrogen atom or a group or atom that can be separated during a coupling reaction with an oxidized product of a color developing agent, and Y2 represents a hydrogen atom or R-N02 or -CM, R4 represents the above R3, Rs represents an alkyl group, R6 represents a hydrogen atom, -000
)1, -0H1-COORs or -S03H, R3 and R4 may be the same group or different groups, respectively.
［有機酸第２鉄鎖塩（Ａ）〕
（１）ジエチレントリアミン五酢酸第２鉄２ａＩＭ（２
）ジエチレントリアミン五メチレンホスホン酸第２鉄錯
塩
（３）シクロヘキサンジアミン四酢酸第２鉄錯塩（４）
シクロヘキサンジアミン四メチレンホスホン酸第２鉄錯
塩
（５）トリエチレンテトラミン六酢酸第２鉄錯塩（８）
トリエチレンテトラミン六メチレンホスホン酸第２鉄鎖
塩
（７）グリニールエーテルジアミン四酢酸第２鉄錯塩
（８）グリコールエーテルジアミン四メチレンホスホン
酸第２鉄錯１！！
（９） １．２−ジアミノプロパン四酢酸第２鉄錯塩（
１０）１．２−ジアミノプロパン四メチレンホスホン酩
第２鉄錯ｊム１
（１１）メチルイミノジ酢酸第２鉄錯塩（１２）メチル
イミノジメチレンホスホン酸第２鉄錯塩
（１３）１．３−ジアミノプロパン−２−オール四酢酸
第２鉄錯塩
（１４）１．３−ジアミノプロパン−２−オール四メチ
レンホスホン酸第２鉄鎖塩
（１５）エチレンジアミンジオルトヒドロキシフェニル
酢酸第２鉄錯塩
（ＩＢ）エチレンジアミンジオルトヒドロキシフェニル
メチレンホスホン酸第２鉄鎖塩
（１７）エチレンジアミン四メチレンホスホン酸第２鉄
鎖塩
［酸化還元電位測定用アミノポリカルボン酸等の有機酸
有機酸第２鉄鎖塩基準溶液］
塩化第２鉄 ０．２３Ｍアミノポ
リカルボン酸等の有ａｍ ０．３０５Ｍチオ硫酸ア
ンモニウム １．０Ｍ亜硫酸アンモニウム
０．１Ｍアンモニア水及び酢酸を用い
てｐＨをＷｆｆｉｔ、、酸イし還元電位を測定する。[Organic acid ferric chain salt (A)] (1) Ferric diethylenetriaminepentaacetic acid 2aIM (2
) diethylenetriaminepentamethylenephosphonic acid ferric complex salt (3) cyclohexanediaminetetraacetic acid ferric complex salt (4)
Cyclohexanediamine tetramethylenephosphonic acid ferric complex salt (5) Triethylenetetramine hexaacetic acid ferric complex salt (8)
Triethylenetetramine hexamethylene phosphonic acid ferric chain salt (7) Greenyl ether diamine tetraacetic acid ferric complex salt (8) Glycol ether diamine tetramethylene phosphonic acid ferric complex 1! ! (9) 1,2-diaminopropanetetraacetic acid ferric complex salt (
10) 1,2-diaminopropane tetramethylene phosphonic acid ferric complex 1 (11) Methyliminodiacetic acid ferric complex salt (12) Methylimino dimethylene phosphonic acid ferric complex salt (13) 1,3-diaminopropane -2-ol Tetraacetic acid ferric complex salt (14) 1.3-diaminopropan-2-ol tetramethylenephosphonic acid ferric chain salt (15) Ethylenediamine diorthohydroxyphenylacetic acid ferric complex salt (IB) Ethylenediamine diortho Hydroxyphenylmethylenephosphonic acid ferric chain salt (17) Ethylenediamine tetramethylenephosphonic acid ferric chain salt [Reference solution of organic acid ferric chain salt of aminopolycarboxylic acid, etc. for redox potential measurement] Ferric chloride 0. 23M aminopolycarboxylic acid, etc. am 0.305M ammonium thiosulfate 1.0M ammonium sulfite 0.1M Aqueous ammonia and acetic acid are used to adjust the pH and measure the reduction potential.
更には扉内定着処理時間が８分以内である場合に、特に
本発明の効果が顕著に現われることを見い出した。Furthermore, it has been found that the effects of the present invention are particularly noticeable when the in-door fixing processing time is 8 minutes or less.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
一般に、アミノポリカルボン酩金屈錯塩の中でも特にＥ
ＤＴＡ・Ｆｅ（ＤＩ）錯塩は、ｐＨの上昇と共に酸化還
元電位が卑となり実際に使用されるｐＨ領域ではほとん
ど銀源白刃が低下し、脱銀不良になるという特徴がある
。又はな；自足着液中に処理によって溶解蓄積する可溶
性銀イオン錯体の影響によっても急激に銀源白刃が低下
する。更に漂白定着液が高ｐＨ側で、かつ発色現像液は
ｂ１１定着液に充分混入した場合はスティンが発生しや
すい、更に又チオ硫酸塩の分解による硫化、特に高ｐＨ
側で起り易い等の種々の欠点があるのに対し、有機酸第
２鉄錯塩の中でも本発明のｔフ（白側を用いた場合には
」−記のような欠点を全く示さないことを本発明者は発
見した。In general, among the aminopolycarbonate complex salts, especially E
DTA/Fe(DI) complex salt has a characteristic that the redox potential becomes base as the pH increases, and in the pH range where it is actually used, the silver source white edge almost decreases, resulting in poor desilvering. Or, the silver source white blade rapidly decreases due to the influence of soluble silver ion complexes that dissolve and accumulate during treatment during self-sufficient liquid deposition. Furthermore, staining is likely to occur if the bleach-fix solution is on the high pH side and the color developer is sufficiently mixed with the B11 fixer.Furthermore, sulfurization due to decomposition of thiosulfate, especially at high pH.
On the other hand, among the organic acid ferric complex salts, the present invention does not exhibit any of the drawbacks as described above (when using the white side). The inventor discovered this.
しかしながら、かかる特徴を示す本発明の漂白剤はＥＤ
ＴＡ ｌｌＦｅ （ＩＩＩ） 錯塩にはほとんど見られ
ないマゼンタ色素の顕色性が低下するということが本発
明者の検討により明らかになった。However, the bleaching agent of the present invention exhibiting such characteristics has an ED
The inventor's studies have revealed that the color development of magenta dye, which is rarely seen in TA llFe (III) complex salts, is reduced.
一般にＥＤＴＡ・Ｆｅ（ＩＩＩ）錯塩によるの顕色性不
良は感光材料中及び／又は漂白定着液中のＥＯＴＡ−Ｆ
ｅ（ＩＩ ）錯塩の生成、蓄積等によって生じ１色素が
二元され易いことが知られているが、その場合にもっば
ら問題になるのは、シアン色素のロイコ体生成による顕
色性の低下であり、マゼンタ色素の顕色性は全く問題な
いか又は若干顕色性の低下がみられたとしても感光材料
の性能上、特にカラーバランス的に全く問題にならない
程度のものであった。In general, poor color development due to EDTA/Fe(III) complex salts is caused by EOTA-F in light-sensitive materials and/or bleach-fix solutions.
It is known that one dye is likely to become binary due to the formation and accumulation of e(II) complex salts, but in this case, the main problem is the decrease in color development due to the formation of the leuco form of the cyan dye. Therefore, there was no problem with the color development of the magenta dye, or even if there was a slight decrease in the color development, it was such that it did not cause any problem in terms of the performance of the light-sensitive material, especially in terms of color balance.
しかるに漂白剤を用いた漂白定着液で処理した場合には
マゼンタ色素の顕色性が不良となり、色再現性等、写真
性能上重大な問題となることがわかった。このことは本
発明者にとって全く予期せざる驚くべきことであった。However, it has been found that when processed with a bleach-fix solution containing a bleaching agent, the color development of the magenta dye becomes poor, resulting in serious problems in terms of photographic performance such as color reproducibility. This was completely unexpected and surprising to the inventor.
上記本発明の漂白剤を用いた漂白定着液で処理した場合
に生ずるマゼンタ色素の顕色性の不良は漂白定着処理時
間によって顕色性の程度が異なるが、 ８分以内で処理
した場合に特に顕色性不良の程度が大きいことが判った
。The degree of poor color development of the magenta dye that occurs when processed with a bleach-fix solution using the bleaching agent of the present invention differs depending on the bleach-fixing processing time, but it is particularly noticeable when processing is performed within 8 minutes. It was found that the degree of poor color development was large.
このことは、ハロゲン化銀カラー写真感光材料の迅速処
理を目的とした場合やカラー自動現像処理機のコンパク
ト化を考えたときに重大な問題である。This is a serious problem when considering the rapid processing of silver halide color photographic materials and the miniaturization of automatic color processing machines.
本発明は、特有の第２鉄錯塩のもつ優れた銀源白刃及び
スティン防止効果、良１１ｆな液保存性等の特性を維持
しながら、本発明の漂白剤を使用したときのマゼンタ色
素の顕色性を改良し、処理の迅速化を実現する方法を種
々検討した結果到達したものである。The present invention aims to improve the visibility of magenta dye when using the bleaching agent of the present invention, while maintaining the characteristics of the unique ferric complex salt, such as the excellent silver source white blade, stain prevention effect, and good liquid storage stability. This was achieved as a result of various studies on methods for improving color properties and speeding up processing.
本発明において漂白能を有する処理液で処理するとは、
漂白液又は−浴漂自足着俄により、処理することを意味
するが、本発明の効果を良好に奏するのは、−浴漂白定
着処理を行った場合である。以下の説明は主にこの一浴
漂白定着処理について行う。In the present invention, processing with a processing solution having bleaching ability means
This means processing with a bleach solution or a -bath bleach-fixing process, but the effect of the present invention is best achieved when a -bath bleach-fixing process is performed. The following explanation will mainly be made regarding this one-bath bleach-fixing process.
本発明の漂白定着液にば、漂白剤として有機酸第２鉄詰
塩（Ａ）又は（Ｂ）が含有される。The bleach-fix solution of the present invention contains organic acid ferric salt (A) or (B) as a bleaching agent.
有機酸第２鉄錯１１！（Ａ）は上記１７種のうちから任
意に１Ｍ！を選んで用いることができ、また必要に応じ
て２種以上を組合せ使用することもできる。Organic acid ferric complex 11! (A) is 1M from the above 17 types! These can be selected and used, and two or more types can also be used in combination if necessary.
有機酸第２鉄錯塩（Ａ）の上記１７種のうち特に好まし
いものとしては下記のものが挙げられる。Among the 17 types of organic acid ferric complex salts (A), the following are particularly preferred.
ＣＩ）ジエチレントリアミン五酢酸第２鉄錯塩（ＩＩ
）シクロヘキサンジアミン四酢酸第２鉄錯塩（■）トリ
エチレンテトラミン六酢酸第２鉄錯塩有機酸第２鉄錯１
１！（Ｂ）は酸化還元電位により規制された複数の有機
酸ｆｆ１２鉄錯塩群で、これらのうちから任意に１種を
選んで用いることができ、また必要に応じて２種以上を
組合せ使用することもできる。CI) Diethylenetriaminepentaacetic acid ferric complex salt (II
) Cyclohexanediaminetetraacetic acid ferric complex salt (■) Triethylenetetraminehexaacetic acid ferric complex salt Organic acid ferric complex 1
1! (B) is a group of a plurality of organic acid ff12 iron complex salts regulated by redox potential, and one type can be arbitrarily selected and used from these, and two or more types can be used in combination as necessary. You can also do it.
本発明においてアミノポリカルボン酸等の有機酪第２鉄
鎖塩の基準溶液の酸化還元電位は基準溶液を２５°０で
通常の電位計を用い白金電極を用いて測定したものであ
り、比較電極はカロメル電極を用いて測定したものであ
る。In the present invention, the oxidation-reduction potential of a reference solution of an organic butyric ferric chain salt such as an aminopolycarboxylic acid is measured using a platinum electrode using an ordinary electrometer at 25°0. This was measured using a calomel electrode.
アミノポリカルボン酸等の有機酸第２鉄詰塩のＰＨと電
位の関係については第２鉄錯塩単独でのデーターは知ら
れている。しかしなから本）ｉ、すＪの漂白定着基準溶
Ｉαで測定したときに広いｐＨ領域に互って酸化ａ元電
位の差が少ないアミノポリカルホン酸等の有機酸にのみ
本発明のような好ましい効果が発揮されることは全く知
られておらず、驚くべき発見であった・
本発明の範囲の酸化ぶ元電位を有する具体的アミノポリ
カルボン酸等の有機酸錯塩としては下記のものが挙げら
れるがこれらに限定されるものではない。Regarding the relationship between PH and potential of ferric-packed salts of organic acids such as aminopolycarboxylic acids, data for ferric complex salts alone are known. However, the method of the present invention is applicable only to organic acids such as aminopolycarphonic acids, which have a small difference in oxidation a source potential over a wide pH range when measured with the bleach-fixing standard solution Iα of Book I) and SuJ. This was a surprising discovery as it was not known at all that a favorable effect would be exhibited.Specific organic acid complex salts such as aminopolycarboxylic acids having an oxidizing potential within the range of the present invention include the following: These include, but are not limited to.
（１）ジエチレントリアミン五酢酸第２鉄錯塩（２）ジ
エチレントリアミン五メチレンホスホン酸第２鉄錯塩
（３）シクロヘキサンジアミングア醜第２鉄錯塩（４）
シクロヘキサンジアミン四メチレンホスホン酸第２鉄錯
塩
（５）トリエチレンテトラミン六酢酸第２鉄錯塩（８）
トリエチレンテトラミン六メチレンホスホン酸ｆＪＳ２
鉄錯塩
本発明に係わる有機酸の第２鉄錯塩は、フリーの酸（水
素塩）、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、または水溶性
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
るが、好ましくはカリウム塩、ナトリウム塩及びアンモ
ニウム塩が使われる。これらの第２鉄錯塩は少なくとも
１種用いればよいが、２種以上を併用することもできる
。その使用量は任意に選ぶことができ、処理する感光材
料の銀量及びハ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できる０例えば、使用液１ｆ
Ｌ当り０．０１モル以上で使用でき、好ましくは０．０
５モル〜０．６モルで使用される。なお、補充液におい
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
使用することが望ましい。(1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriaminepentaacetic acid ferric complex salt (3) Cyclohexane diamingua ugly ferric complex salt (4)
Cyclohexanediamine tetramethylenephosphonic acid ferric complex salt (5) Triethylenetetramine hexaacetic acid ferric complex salt (8)
Triethylenetetramine hexamethylenephosphonic acid fJS2
Iron complex salts The ferric complex salts of organic acids according to the present invention include free acids (hydrogen salts), alkali metal salts such as sodium salts, potassium salts, and lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine. Although it is used as a salt, potassium salt, sodium salt and ammonium salt are preferably used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. Possible 0 For example, working liquid 1f
It can be used in an amount of 0.01 mol or more per L, preferably 0.0
It is used in amounts of 5 mol to 0.6 mol. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.
本発明の漂白能を有する処理液は表面張力が５５ｄｙｎ
ｅ／ｃｍ以下であることが好ましく、より好ましくは５
０ｄｙｎｅ／ｃｍ以下、最も好ましくは４０ｄｙｎｅ／
ａｍ以下である。The treatment liquid having bleaching ability of the present invention has a surface tension of 55 dyn.
It is preferably less than e/cm, more preferably 5
0 dyne/cm or less, most preferably 40 dyne/cm
am or less.
本発明の処理に用いられる漂白能を有する処理液の表面
張力は、「界面活性剤の分析と試験法」（北原文雄、早
野茂夫、原一部共著、■８８２年３月１日発行、■講談
社発行）等に記載されである一般的な測定方法でＪ１１
定され、本発明では２０°Ｃにおける通常の測定方法に
よる表面張力の値である。The surface tension of the treatment liquid with bleaching ability used in the treatment of the present invention can be determined from "Analysis and Testing Methods of Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published on March 1, 1982, J11 using the general measurement method described in Kodansha (published by Kodansha) etc.
In the present invention, it is a value of surface tension determined by a conventional measurement method at 20°C.
本発明においては、漂白能を有する処理液の表面張力を
５５ｄｙｎｅ／ｃｍ以下にする方法は任意であり、いか
なるものを用いてもよいが、界面活性剤が好ましく用い
られる。これらの漂白能を有する処理液の表面張力を５
５ｄｙｎｅ／ ｃｒｓ以下にする界面活性剤は、補充液
よりタンク液に添加されてもよいし、あるいは前浴より
感光材料に付着させて添加させてもよい。さらに、該界
面活性剤を感光材林木発明の界面活性剤の中でも、とり
わけ本発明の目的の効果に対する点から下記一般式（１
）〜（４）で示される化合物が好ましく用いられる。In the present invention, any method may be used to reduce the surface tension of the treatment liquid having bleaching ability to 55 dyne/cm or less, and any method may be used, but surfactants are preferably used. The surface tension of these processing solutions with bleaching ability is 5
The surfactant to be reduced to 5 dyne/crs or less may be added to the tank liquid from the replenisher, or may be added by being attached to the photosensitive material from the pre-bath. Furthermore, among the surfactants of the photosensitive material Rinki invention, the following general formula (1
) to (4) are preferably used.
一般式（１）
％式％：
式中、Ｒ１及びＲ２のうち一方は水素原子、他方は式−
Ｓ（ｈＭ（Ｍは水素原子又は−価の陽イオンを表わす、
）で表わされる基を表わす、 Ａｒは酸素原子又は式
−ＮＲ５−（Ｒｓは水素原子又は炭素原子数１〜８のア
ルキル基を表わす、）で表わされる基を表わす、Ｒ３及
びＲ４は、それぞれ炭素原子数４〜１Ｂのアルキル基を
表わす、但し、Ｒ３、Ｒ４又はＲｓで表わされるアルキ
ル基はフッ素原子によって置換されていてもよい。General formula (1) % formula %: In the formula, one of R1 and R2 is a hydrogen atom, and the other is a formula -
S (hM (M represents a hydrogen atom or a -valent cation,
), Ar represents an oxygen atom or a group represented by the formula -NR5- (Rs represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), R3 and R4 each represent a carbon It represents an alkyl group having 4 to 1 B atoms, provided that the alkyl group represented by R3, R4 or Rs may be substituted with a fluorine atom.
一般式（２）
％式％
式中、 Ａ２は一価の有機基、例えば炭素原子数が６〜
２０、好ましくは８〜１２のアルキル基（例えば、ヘキ
シル、ヘプチル、オクチル、ノニル、デシル、ウンデシ
ル又はドデシル等の各基）、又は炭素原子数が３〜２０
のアルキル基で置換されたアリール基であり、置換基と
して好ましくは炭素原子数が３〜１２のアルキル基（例
えば、プロピル、ブチルペンチル、ヘキシル、ヘプチル
、オクチル、ノニル、デシル、ウンデシル又はドデシル
等の各基）が挙げられ、アリール基としてはフェニル、
トリル、キシニル、ビフェニル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又はトリル基である。General formula (2) % formula % In the formula, A2 is a monovalent organic group, for example, a group having 6 to 6 carbon atoms.
20, preferably 8 to 12 alkyl groups (e.g., hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl groups), or 3 to 20 carbon atoms
It is an aryl group substituted with an alkyl group, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butylpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.). each group), and the aryl group includes phenyl,
Examples include tolyl, xynyl, biphenyl, and naphthyl groups, with phenyl group or tolyl group being preferred.
アリール基にアルキル基が結合する位置としては、オル
ト、メタ、パラ位のいずれでもよい、Ｂはエチレンオキ
シド又はプロピレンオキサイドを表わし、ｍは４〜５０
の整数を表わす、Ｘエバ水素原子、ＳＯ３Ｙ又はＰＯ３
Ｙ ｚを示シ。The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions, B represents ethylene oxide or propylene oxide, and m is 4 to 50.
Xeva hydrogen atom, SO3Y or PO3, representing an integer of
Show Y z.
Ｙ ＃学は水素原子、アルカリ金属原子（Ｎａ、 Ｋ又
はＬｉ等）又はアンモニウムイオンを表わす。Y represents a hydrogen atom, an alkali metal atom (such as Na, K or Li), or an ammonium ion.
一般式（３）
式中 、 Ｒｓ、Ｒ７、Ｒ８及びＲ９はそれぞれ水素
原子、アルキル基、フェニル基を示すが、Ｒ６、Ｒ７、
Ｒ８及びＲ９の炭素原子数の合計が３〜５０である。
Ｘｚはハロゲン原子、水酸基、硫酪基、炭酩基、硝酢
基、酢酸基、ｐ−トルエンスルホン酸基等の７ニオンを
示す。General formula (3) In the formula, Rs, R7, R8 and R9 each represent a hydrogen atom, an alkyl group, or a phenyl group, but R6, R7,
The total number of carbon atoms in R8 and R9 is 3 to 50.
Xz represents a 7-ion such as a halogen atom, a hydroxyl group, a butysulfur group, a carbonate group, a nitrate group, an acetate group, or a p-toluenesulfonic acid group.
一般式（４）
式中、ＲＩＯｌＲｌｌ、ＲＬ２、及びＲ１１はそれぞれ
水素原子又はアルキル基を表わし、Ｎは一般式（１）と
同義である。ｎ及びｐはそれぞれＯ又は１〜４の整数を
示し、 １≦ｎ＋ｐ≦８を満足する値である。General formula (4) In the formula, RIOlRll, RL2, and R11 each represent a hydrogen atom or an alkyl group, and N has the same meaning as in general formula (1). n and p each represent O or an integer from 1 to 4, and are values satisfying 1≦n+p≦8.
表面張力が低い程、エアレーションを強制的に行わなく
ても第１鉄錯塩の酸化がすみやかに行われ好ましい、エ
アレーションを行う場合にもエアー量が著しく低くても
泡の径が小さく表面積が大となるため、酸化が極めて効
率よく行われ１表面張力が低い漂白液又は漂白定着液な
いし槽の組合せは最も好ましいことである。The lower the surface tension, the more quickly the oxidation of the ferrous complex salt occurs even without forced aeration, which is preferable. Even when aeration is performed, the bubble diameter is small and the surface area is large even if the amount of air is extremely low. Therefore, it is most preferable to use a combination of a bleach solution or a bleach-fix solution or tank in which oxidation is carried out extremely efficiently and the surface tension is low.
本発明の漂白液及び漂白定着液は、 ｐＨ０，２から８
．５で使用でき、好ましくは４〜９、より好ましくは５
．５〜８．５で用いられる。処理の温度は８０℃以下で
使用されるが、債ましくは５５℃以下、最も好ましくは
４５℃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 8.
．． 5, preferably 4 to 9, more preferably 5
．． 5 to 8.5. The treatment temperature is 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower to prevent evaporation.
処理時間は８分以内が好ましく、より好ましくは６分以
内である。即ち、 ８分以内とすることにより本発明の
有４ｉｊ！、酸第２鉄錯１１１によるスティン発生を著
しく抑えられる。The treatment time is preferably within 8 minutes, more preferably within 6 minutes. In other words, the present invention can be achieved by making it within 8 minutes! , the generation of stain due to the ferric acid complex 111 can be significantly suppressed.
本発明の１７Ｚ白液は、前記の如き漂白剤としての有ａ
酩第２鉄錯ＪＪ４とともに種々の添加剤を含むことがで
きる。添加剤としては、特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、沃化カリウ
ム、沃化ナトリウム、沃化アンモニウム等を含有させる
ことが望ましい、また硼酸用、蓚酸塩、酢酸１ｕ、炭酸
Ｊｌ、燐酸塩等のｐ）Ｉ緩衝剤、トリエタノールアミン
等の可溶化剤、アセチルアセトン、ホスホノカルボン酸
、ポリリン酸、有機ホスホン酸、オギシカルポン酸、ポ
リカルボン酸、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が知られているも
のを適宜添加することができる。The 17Z white liquor of the present invention can be used as a bleaching agent as described above.
Various additives can be included along with the ferric complex JJ4. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. , p) I buffers such as oxalate, 1U acetic acid, JL carbonate, phosphate, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, Those known to be commonly added to bleaching solutions, such as alkylamines and polyethylene oxides, can be added as appropriate.
本発明の漂白定着液には、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
化合物との組合せ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-fix solution of the present invention includes a bleach-fix solution containing a small amount of a halogen compound such as potassium bromide, or conversely a bleach-fix solution containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a fixing solution, as well as a special bleach-fixing solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide.
前記のハロゲン化合物としては臭化カリウムの他に１１
化水素酸、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、沃化カリウム、沃化ナトリウム、
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 11
Hydrohydric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide,
Ammonium iodide and the like can also be used.
本発明の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１例えばチオ硫
酸カリウム、チオ硫酸ナトリウム、チオ硫醜アンモニウ
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、チオシアンＮアンモニウムの如きチオ
シアン＃ 塩、 チオ尿素、チオエーテル、高Ｃ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５ｇ／ＩＪ：Ａ上、好ましくは５０ｇ／又以上
、より好ましくは７０ｇ／ １以上溶解できる範囲の量
で使用できる。The silver halide fixing agents to be included in the bleach-fixing solution of the present invention include compounds 1 which react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanine salts such as potassium thiocyanate, sodium thiocyanate, and N-ammonium thiocyanate, thioureas, thioethers, high C bromides, and iodides. These fixing agents can be used in an amount that can dissolve 5 g/IJ:A, preferably 50 g/1 or more, more preferably 70 g/1 or more.
なお未発ＩＪの漂白定着液には漂白Ｉαの場合とｌｒｉ
様に、ｉｊｌ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、酪酸ナトリウム、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、８種の蛍光増白剤や消泡剤あるいは界面活性
剤や防ばい剤を含有せしめることもできる。またとドロ
キシアミン、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
、アセチルアセトン、ホスホノカルボン酸、ポリリン酸
、有機ホスホン酸、オキシカルボン酸、ポリカルシボン
酢、ジカルボン酸及びアミノポリカルボンｍ等の″＃槻
キレート剤あるいはニトロアルコール、硝酸塩等の安定
剤、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
チルホルムアミド、ジメチルスルホ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, the bleach-fix solution for undeveloped IJ includes bleach Iα and lri.
Similarly, pH buffers consisting of various salts such as ijl acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium butyrate, ammonium hydroxide, etc. They can be contained alone or in combination of two or more. Furthermore, eight kinds of optical brighteners, antifoaming agents, surfactants, and antifungal agents can also be contained. Also, droxyamine, hydrazine, sulfites, isomeric bisulfites,
Preservatives such as bisulfite adducts of aldehydes and ketone compounds, chelating agents such as acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarcibon vinegar, dicarboxylic acids, and aminopolycarboxylic m Alternatively, stabilizers such as nitro alcohol and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be appropriately contained. .
本発明の処理液を用いる処理方法では、発色現像後直ち
に漂白もしくは漂白定着することが最も好ましい処理方
式であるが、発色現像後直洗又はリンス又は停止等の処
理を行った後、漂白もしくは漂白定着処理してもよく、
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よい。In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. It may be fixed,
A prebath containing a bleach accelerator may also be used as a processing solution prior to bleaching or bleach-fixing.
漂白及び定着（又は漂白定着）後は、水洗を行わず安定
処理することもできるし、水洗処理し、その後安定処理
してもよい０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
付加えられてもよい、好ましい処理方法の代表的具体例
を挙げると、下記の諸工程が含まれる。After bleaching and fixing (or bleach-fixing), stabilizing treatment may be performed without washing with water, or washing with water and subsequent stabilizing processing may be performed.In addition to 0 or more steps, hardening, neutralization, black and white development,
Typical examples of preferred processing methods include the following steps, in which known auxiliary steps such as inversion and washing with a small amount of water may be added as necessary.
（１）発色現像→ｔπ白定自足水洗
（２）発色現像→漂白定着→少量水洗呻水洗（３）発色
現像→漂白定着→水洗→安定（４）発色現像→ｔπ白定
自足安定
（５２発色現像→漂白自足→第１安定＋ｆｆ５２安定（
６）発色現像→水洗（又は安定）→漂白定着→水洗（又
は安定）
（７）発色現像→停止呻漂自足着→水洗（又は安定）（
８）発色現像→ｈ＝白→水洗神定着→水洗→安定（８）
発色現像→漂白→定着→水洗→安定（ｌＯ）発色現像→
ゐＲ白→定若→ｉｌ安定→ｆ５２安定（１１）発色現像
→漂白呻少量水洗→定着→少量水洗→水洗→安定
（１２）発色現像→少量水洗→漂白→少量水洗→定看→
少量水洗→水洗→安定
（１３）発色現像→停止→漂白→少量水洗→定着→少量
水洗→水洗→安定
（１４）黒白現像→水洗（又は安定）→反転呻発色現像
−４−膿白→定着峠水洗（又は省略）→安定（１５）前
硬膜→中和呻黒白現像→停止→発色現像→漂白→定着→
水洗（又は省略）→安定
これらの処理工程の中でも、本発明の効果がより顕著に
表われるため、（１） 、（２） 、（３） 、（４）
、（５） 。(1) Color development → tπ white fixation Self-sufficient water washing (2) Color development → bleach fixing → small amount of water washing (3) Color development → bleach fixing → water washing → stable (4) Color development → tπ white fixation self-sufficient stability (52 color development Development → Bleach self-sufficiency → 1st stability + ff52 stability (
6) Color development → washing with water (or stable) → bleaching and fixing → washing with water (or stable) (7) Color development → stop bleaching → washing with water (or stable) (
8) Color development → h = white → washing with water, fixation → washing with water → stable (8)
Color development → Bleaching → Fixing → Washing → Stable (1O) color development →
ゐR white → constant youth → stable → f52 stable (11) color development → bleaching, washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stable (12) color development → washing with a small amount of water → bleaching → washing with a small amount of water → regular maintenance →
Wash with a small amount of water → Wash with water → Stable (13) Color development → Stop → Bleach → Wash with a small amount of water → Fix → Wash with a small amount of water → Wash with water → Stabilize (14) Black and white development → Wash with water (or stable) → Reversal Color development - 4-Pustula → Fix Washing with water (or omitting) → Stabilization (15) Before dura → Neutralization Black and white development → Stop → Color development → Bleaching → Fixation →
Water washing (or omission) → stability Among these treatment steps, the effects of the present invention are more pronounced, so (1), (2), (3), (4)
, (5).
（６）及び（７）の漂白定着工程を有する処理工程が本
発明ではより好ましく用いられる。The processing steps (6) and (7) having the bleach-fixing steps are more preferably used in the present invention.
本発明の漂白定着液には、各種の無機金属塩を添加する
ことが好ましい、これらの無機金属塩は各種のキレート
剤とともに金属ｆｆｉ塩と成した後、添加することも好
ましい方法である。It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. It is also preferable to add these inorganic metal salts after forming them into metal ffi salts together with various chelating agents.
本発明の漂白定着１夜には本発明外のキレート剤及び／
又はその第２鉄錯塩を添加することが好ましい。しかし
ながら本発明以外の第２鉄錯塩は本発明の有機酩第２鉄
錯塩を１モル％としたとき０．４５モル％以下で使用す
ることが好ましい。During the bleach-fixing process of the present invention, a chelating agent other than the present invention and/or
or a ferric complex salt thereof is preferably added. However, it is preferable to use the ferric complex salt other than the present invention in an amount of 0.45 mol% or less when the organic ferric complex salt of the present invention is 1 mol%.
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及び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り安
定のため一般°に塩の形、例えば１１Ａ／ｊ６塩または
硫酸ＪＪＡ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１ｆＬについて約０．１ｇ〜約３０
ｇの濃度、更に好ましくは１文について約１ｇ〜約１５
ｇ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 may be any of the known aromatic primary amine color developing agents that are widely used in various color photographic processes. Included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as the 11A/j6 salt or sulfuric acid JJA, since they are more stable than in the free state. In addition, these compounds are generally used in an amount of about 0.1 g to about 30 g per 1 fL of color developer.
g concentration, more preferably from about 1 g to about 15 g per sentence.
Use at a concentration of g.
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−アミンフェノール、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−ジメチルベンゼン等が
含まれる。Examples of amine phenol developers include 0-aminophenol, p-aminephenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.
特に有用な芳香族第１級アミン発色現像剤はＫ。A particularly useful aromatic primary amine color developer is K.
Ｎ−ジアルキル−ｐ−フェニレンジアミン系化合物であ
り、アルキル基及びフェニル基は置換されていても、あ
るいは；δ換されていなくてもよい、その中でも特に有
用な化合物としてはＮ、Ｎ−ジエチル−ｐ−フェニレン
ジアミン塩酸塩、Ｎ−メチル−ｐ−フェニレンジアミン
１１１ Ｍ 塩、Ｎ、Ｎ−ジメチル−ｐ−フェニレンジ
アミン塩酸塩、２−アミノ−５−（Ｎ−エチル−Ｎ−ド
デシルアミノ）−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−アミノアニ
リン硫酸塩、トエチルーＮ−β−ヒドロキシエチルアミ
ノアニリン、４−アミノ−３−メチル−Ｎ、Ｎ−ジエチ
ルアニリン、４−アミノ−Ｎ−（２−メトキシエチル）
−Ｎ−エチル−３−メチルアニリン−ｐ−トルエンスル
ホネート等を挙げることができる。It is an N-dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted; among them, a particularly useful compound is N,N-diethyl- p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine 111 M salt, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene , N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, toethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-toluenesulfonate and the like.
前記バラフェニレンジアミン発色現像主薬は、本発明の
漂白定着液に混入されることが好ましいものである。The above-mentioned phenylenediamine color developing agent is preferably mixed into the bleach-fix solution of the present invention.
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、前記芳香族第１級アミン
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、炭酸カリウム等のアルカリ剤、アルカリ金属亜
ＶＬｓ塩、アルカリ金属重亜硫＃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
エメ畳“ソー１．１−ジホスホン酸等の水軟化剤及び濃
厚化剤等を任意に含有することができる。この発色現像
液のｐＨは、通常７以上であり、最も一般的には約１０
〜約１３である。The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention contains, in addition to the above-mentioned aromatic primary amine color developing agent, various types of color developing solutions that are usually added to color developing solutions. Ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sub-VLs salts, alkali metal bisulfite salts, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1 A water softener and a thickening agent such as 1.1-diphosphonic acid can be optionally contained.The pH of this color developing solution is usually 7 or higher, and most commonly about 10
〜about 13.
本発明に係るハロゲン化銀カラー写真感光材料は、一般
式（Ｉ）及び／又は一般式（ＩＩ ）で表わされるマゼ
ンタカプラーを含有する。The silver halide color photographic light-sensitive material according to the present invention contains a magenta coupler represented by the general formula (I) and/or the general formula (II).
ｙ−４下本発明で用いられる一般式［０又は一般式ｌで
表わされるマゼンタカプラーについて詳述する。y-4 Below, the magenta coupler represented by the general formula [0 or general formula 1] used in the present invention will be described in detail.
先ず一般式〔ＵにおけるＡｒ 、 Ｙ 、 Ｘ 、几の
各基について以下に具体的１ｃ Ｘ！？明する。First, for each group of Ar, Y, X, and 几 in the general formula [U, specific 1c ? I will clarify.
Ａｒ：フェニル輌であり、行ＩＣＩご置換されたフェニ
ル基である。Ar: phenyl, a phenyl group substituted with ICI.
置換基としてはハロゲン原子、アルキル基、１ルコギ゛
７基、アリールオキシ基、アルコキンカルボニルＪ１１
５．ンアノ基、カルバそイル基、スルファモイル基、ス
ルホニル基、スルホンアミド７！＋１１、アフルアミノ
基でちり、Ａｒで表わされるフェニルジとに２個以上の
置換基を有してもよい。Substituents include halogen atom, alkyl group, 1-alcotylene group, aryloxy group, alkoxycarbonyl J11
5. Ano group, carbamoyl group, sulfamoyl group, sulfonyl group, sulfonamide 7! +11, afuramino group, and the phenyl group represented by Ar may have two or more substituents.
以下に置換基の具（４・的な例を誉げる。Below are some examples of substituents.
ハロゲン原子：工ぶ累、臭ぶ、フッ索
アルキル茫：メチル賃、エチル基、 １ｓｏ−プロピ
ル基、ブチル基、ｔ−ブチル基、１−ペンチル基等であ
るが４；ｆに炭素原子数１〜５のアルキル７！＋シが好
２１−い。Halogen atom: Accumulated, odor, fluorocarbon alkyl: Methyl group, ethyl group, 1-so-propyl group, butyl group, t-butyl group, 1-pentyl group, etc., but 4; f has 1 carbon atom ~Alkyl 7 of 5! +shi is good 21-.
アルコキシ基よ一二メトギ、／λζ、エトキノ基、ブト
キシ基、５ｅａ−ブトキシ基、１ｓｏ−ペンチルメ・Ａ
−ン基等であるが、特に炭素原子数１〜５のアルコキシ
基が好ましい。Alkoxy group, 12methoxy, /λζ, ethquino group, butoxy group, 5ea-butoxy group, 1so-pentylmethoxy, A
Among these, an alkoxy group having 1 to 5 carbon atoms is particularly preferred.
アリールオキシ、Ｖ； ：フェノキシ基、β−ナフトキ
シ基等で必るが、このアリール部分には更ＫＡｒで示さ
れるフェニル基に挙げていると同様ン上置換基を有して
もよい。Aryloxy, V: Necessary for phenoxy group, β-naphthoxy group, etc., but this aryl moiety may further have a substituent as mentioned for the phenyl group represented by KAr.
アルコキシカルボニル基：上述したアルコキシ基の付い
たカルボニル基であシ、メトキシカルボニル基、ペンチ
ルオキシカルボニル基等のアルギル部分の炭素原子数が
１〜５のものが好ましい。Alkoxycarbonyl group: A carbonyl group with an alkoxy group as described above, preferably one in which the argyl moiety has 1 to 5 carbon atoms, such as a methoxycarbonyl group or a pentyloxycarbonyl group.
カルバモイル基：カルバモイル基、ジメチルカルバモイ
ル基等のアルキルカルバモイル基
スルファモイル基：スルファモイル基、メチルスルファ
モイル基、ジメチルスルファモイル基、メチルスルファ
モイル基等のアルキルスルファモイル基
スルホニル基二メタンスルホニル基、エタンスルホニル
基、ブタンスルホニル基等アルキルスルホニ／Ｉ／ （
！ｉ’；
スルホンアξト’２＋、：メタンスルホンアミド基、ト
ルエンスルｉＩ；ンア＜ ｌ” ａ 等ノアｋ ＄ ル
スルホンアミド左、アリールスルホンアミド基等
アシルアミノ基ニア七ドアミノ基、ピバロイルアミノ基
、ベンズアミド基等
特に好ましくはハロゲン原子であシ、その中でも塩素が
最も好ましい。Carbamoyl group: Alkylcarbamoyl group such as carbamoyl group, dimethylcarbamoyl group Sulfamoyl group: Alkylsulfamoyl group such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, methylsulfamoyl group, sulfonyl group, dimethanesulfonyl group , ethanesulfonyl group, butanesulfonyl group, etc., alkylsulfony/I/ (
! i'; sulfonate ξto'2+, : methanesulfonamide group, toluenesul iI; n<l'' a, etc. $ sulfonamide left, arylsulfonamide group, etc. acylamino group, near hepta-amino group, pivaloylamino group, benzamide group Particularly preferred are halogen atoms, among which chlorine is most preferred.
Ｙ：芳香族第１級アミン発色ＴＡ作主薬の酸化体とカッ
プリングして色水が形成されるときに離脱する基を表わ
す。Y: Represents a group that leaves when a colored water is formed by coupling with an oxidized product of an aromatic primary amine color-forming TA agent.
具体的には例えばハロゲン原子、アルコキク基、アリー
ルオキシ基、アシルオキシ基、アリールチオ基、アルキ
ルチオ基、−ＮＺ（Ｚは窒尤原子と共に炭素原子、酸素
原子。Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, -NZ (Z is a nitrogen atom, a carbon atom, or an oxygen atom.
窒素原子、イオウ原子の中から選ばれた原子と５ないし
６Ｊ［ｔを形成する忙要する原子群を表わす）
以下ＫＡ体的な例を挙ける。An atom selected from a nitrogen atom, a sulfur atom, and 5 to 6 J [representing a group of atoms that form t]. An example of a KA body is given below.
ハロクン原子：塩素、臭諧、フッ累
アルコキーシ基：エトキシ基、ベンジルオキシ基、メト
ーＩ−７エチルカルバモイルメトキシ基、テト２デンル
力ルバモイルメトキシ基等
アリールオキシ基：フェノキシ基、４−メトキシフェノ
キシ基、４−二トロフェノキシ基等
アクルオキシ基：アセトキシ基、ミリストイルオキ７基
、ベンゾイルオキ７基等
アリールチオＭ：フェニルチオ基、２−ブトキシ−５−
オクチルフェニルチオ基、２．５−ジヘキシルオキ７フ
ェニルチオ基等
アルキルチオ基：エチルチオ基、オクチルチオ基、ヘキ
テデシルテオ基、ベンジルチオ基％ ２−（ジエチルア
ミノ）エチルチオ基、エトキシカルボニルメチルチオ基
、エトキシエチルチオ基、フェノキシエチルチオ基等
トリアゾリル基、テトラゾリル基等
Ｘ：ハロゲン原子、アルコキシ基、アルキル基な表わす
。Halokun atom: chlorine, odor, fluorine alkoxy group: ethoxy group, benzyloxy group, methoxycarbamoylmethoxy group, tetoxycarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group , 4-nitrophenoxy group, etc. Acryloxy group: acetoxy group, myristoyloki 7 group, benzoyloxy 7 group, etc. Arylthio M: phenylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexylthio group, 7phenylthio group: ethylthio group, octylthio group, hexatedecylthio group, benzylthio group% 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group, ethoxyethylthio group, phenoxyethyl A triazolyl group such as a thio group, a tetrazolyl group, etc. X: represents a halogen atom, an alkoxy group, an alkyl group.
具体的な例を以下忙挙げる。Specific examples are listed below.
ハロゲン原子：ｊ、−素％臭紫、フッ累アルコキシ基：
メトキシ基、エトキシ基、ブトキシ基、 ａｅｃ−ブ
トキシ基、１ｓｏ−ベンジルオキシ基等の炭素原子数が
１〜５のアルコキ・／基が好セしい、。Halogen atom: j, - element% odor purple, fluorine alkoxy group:
Alkoxy groups having 1 to 5 carbon atoms such as methoxy group, ethoxy group, butoxy group, aec-butoxy group, and 1so-benzyloxy group are preferred.
アルキル基二メチル基、エチル基、 １ｓｏ−プロピ
ル基、ブチル基、ｔ−ブチル基、１−ペンチル基等の炭
水原子数が１〜５のアルギル基が好ましい。Alkyl groups Argyl groups having 1 to 5 carbon atoms, such as dimethyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, and 1-pentyl group, are preferable.
特に好ましくはハロゲン原子でおり、中でも塩；）うが
好ましい。Particularly preferred are halogen atoms, and salts are particularly preferred.
几：ベンゼン環に１１１換可能な基を表わし、ｎは１又
は２からなる整数を表わす、ｌｎが２のときＩＬ ｌ−
を同じでもＹへなっていてもよい。几: Represents a group capable of converting 111 to a benzene ring, n represents an integer consisting of 1 or 2, and when ln is 2, IL l-
may be the same or Y.
Ｒで示されるべ〕・ゼンｊ、７Ｊに置換可能な基として
は、ハロゲン原子、几’ −Ｉ Ｒ’Ｏ−１几’、ＩＩ
Ｌ“、几″′はそれぞれ１司−でも異なりていでもよく
、水ネ原子まれはそれぞれ置換基を有してもよいアルキ
ル基、アルケニル基もしくけアリール基を表わす。これ
らの中でも好でおる。Groups that can be substituted for be], zenj, and 7J represented by R include halogen atom,
L" and 几"' may each be 1- or different, and each of the water atoms and rare atoms represents an alkyl group, an alkenyl group, or a aryl group, each of which may have a substituent. Among these, I like it.
欠（（マゼンタ力ダラーの具体例を示すがこれらに限定
されない。Missing ((Specific examples of magenta power dollar are shown, but are not limited to these.
ＯＣ４Ｉ−１９０ｔ
ａｔ
上記式中の几としては下記のもの（Ｍ−１〜Ｍ−７）が
挙げられる。OC4I-190t in the above formula include the following (M-1 to M-7).
Ｍ −１−ＮＨＯＯｏ、５Ｈ３゜
Ｍ −２−ＮＨＯＯＯ１４）１２゜
１２Ｈ２５
１０Ｈ２１
ａｔ
上記式中Ｙとしては下記のもの（Ｍ−８〜λ（−２５）
が挙げられる。M -1-NHOOo, 5H3゜M -2-NHOOO14) 12゜12H25 10H21 at In the above formula, Y is the following (M-8 ~ λ (-25)
can be mentioned.
０８Ｈ１フ
ｈ４−１１ −８ｏ１□ｌ１２５
Ｍ−１２−８ＯＨ２００２Ｃ２１１゜
八Ｉ −１３−８ｏｉ１２０００Ｈ
Ｍ−１５−３ＣＩ−１□ＯＯＮ１１２
Ｍ−１６−８ｏｌ−１□ＣＩ−１Ｃｌ−１２００２Ｆ１
５ −８ＯＨ２０）［２０Ｈ
００８Ｈ，７
Ｍ −２０−８ＯＨ２ＣＨ２ＮＨ５Ｏ□０Ｈ３Ｃ）Ｉ３
以上は置換基な代入して例示化合物が得られるが、以下
はそれ自体具体的例示化合物を示す。08H1 h4-11 -8o1□l125 M-12-8OH2002C211゜8I -13-8oi12000H M-15-3CI-1□OON112 M-16-8ol-1□CI-1Cl-12002F1
5 -8OH20)[20H 008H,7 M -20-8OH2CH2NH5O□0H3C)I3 The above examples can be substituted with substituents to obtain exemplified compounds, and the following themselves show specific exemplified compounds.
Ｍ −２６ ■２ ０Ｈ３ ００００１２Ｈ２５ ＳＯ□Ｏ，Ｈ。M-26 ■2 0H3 000012H25 SO□O,H.
Ｎ１１８０２Ｃ〕Ｈ３０２１ｋ
次に一般式（６）におけるＩＬＩ ＋ Ｒ２＋ Ｍ ＋
Ｙ２の各基についてβｊ、明する。N11802C]H3021k Next, ILI + R2+ M + in general formula (6)
βj for each group of Y2 will be explained.
几、及び几２は夫々直換又はシト置換のアルキル基又は
アリール基を表わすが、アルキル基は炭素数１〜８の直
ｆ、ｆＪ又は分岐のアルキル基が好ましく、例えばメチ
ル基、メトキシメチル基、エチル基。几 and 几2 each represent a direct or cytosubstituted alkyl group or aryl group, and the alkyl group is preferably a straight f, fJ or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group or a methoxymethyl group. , ethyl group.
ｔｅｒｔ−ブチル基、オクチル基等が挙げられる。アリ
ール基は好ましくはフェニル基でらシ該フェニル基は置
換基を有していてもよく、置換基としては、ハロゲン原
子、アルコキン基、アシルアミノ基等が挙げられる。そ
して几２としては好ましくはアリール基が置換したアル
キル基が挙げられ、特に一般式叩で表わされるマゼンタ
カプラーに耐拡散性を付与し得るパラスト化されたアル
キル基が好ましい。Examples include tert-butyl group and octyl group. The aryl group is preferably a phenyl group, and the phenyl group may have a substituent, and examples of the substituent include a halogen atom, an alkokene group, and an acylamino group. Preferably, the phosphor 2 is an alkyl group substituted with an aryl group, and a pallasted alkyl group that can impart diffusion resistance to the magenta coupler represented by the general formula is particularly preferable.
体的卒＃≠ミにはハロゲン原子（例えば塩素原子、ＪＱ
水素原子沃素原子、フック１１１−子等）、ブリールオ
キシハ（例えばフェノキシ基、ｐ−メトキシンエノキシ
基、ｐ−ブタンスルホンアミドフェノキシ基、 ｐ
−ｔａｒｔ−ブチルカルボアミドフェノキシ茫等）アリ
ールチオ基（例えばフェニルチオ基＠）へテロ環基（例
え杜ｌ−エチルテトラゾールー５−チオイルｉＦ ）
ａｙＦが挙げられる。Physically, #≠Mi is a halogen atom (e.g. chlorine atom, JQ
hydrogen atom iodine atom, hook 111-child, etc.), bryloxyha (e.g. phenoxy group, p-methoxyenoxy group, p-butanesulfonamidophenoxy group, p
-tart-butylcarboamidophenoxy, etc.) arylthio group (e.g., phenylthio group @), heterocyclic group (e.g., l-ethyltetrazole-5-thioyl iF)
For example, ayF.
Ｙ２Ｆｉ水塁原子又は−Ｃ１ｍ３Ｂ＋ ＪＪ’、’を表
わし、ｒＬ３−ＣＯＯＨ、−Ｎｏ□又は−ＯＮを表わし
、几、は前記Ｒ３わす、なお几５はアルキル基を表わし
、好ましくは炭Ｗｅ数１−１０の直鎖又は分岐のアルキ
ル基を表わし、このアルキル基は置換基を有していてよ
く、１ζむ換晶としては例えばカルボン酸基、スルホン
酸９１（及び水酸基等が孕げられる一Ｉｔ６は水素原子
。Y2Fi represents a water base atom or -C1m3B+ JJ','; rL3-COOH, -No□ or -ON; 10 represents a straight-chain or branched alkyl group, and this alkyl group may have a substituent. Examples of conversion crystals containing 1ζ include carboxylic acid groups, sulfonic acids 91 (and hydroxyl groups, etc.). hydrogen atom.
−０ＯＯＨ、−０ｉｌ 、−ｅ（１）ｏＩＬ、を表わし
、１（，３と几、はそれぞれ回−の尤でも異なる基でも
よいが、好ましく几６
一般式叩で表わされる化合物の具体例を記載するが、本
発明はこれによシ限定されるものではない。-0OOH, -0il, -e(1)oIL, and 1(,3 and 几 may each be different groups, but preferably 几6) Specific examples of compounds represented by the general formula However, the present invention is not limited thereto.
＋Ｖ、ｌ −３７ ０１２Ｎ２〜 Ｃ，献１２１ ０．２Ｈ２５ ０、Ｈｌ、（ｔ） １５Ｈ３１ λ１−４５ ０□■（５ Ｃ２Ｉ（５ ｋｌ ５２ Δ１−５４ Δ１−５６ ０４Ｈ。+V, l -37 012N2～ C, dedication 121 0.2H25 0, Hl, (t) 15H31 λ1-45 0□■(5 C2I(5 kl 52 Δ1-54 Δ1-56 04H.
Ｍ−５７ ０２Ｈ。M-57 02H.
ＣＩＤ’２１
Ｍ−６０
００，８１１，フ
八１−６２
本発明において一般式（Ｉ］又は一般式ａ」で表わされ
るマゼンタカプラーは、ネ発明の目的に反しない範囲に
おいて、従来公知のマゼンタカプラーと組み合わせて用
いることができる。CID'21 M-60 00,811, F8 1-62 In the present invention, the magenta coupler represented by general formula (I) or general formula a'' may be a conventionally known magenta coupler, to the extent that it does not contradict the purpose of the invention. Can be used in combination with
更に本釦明に併用し得る無呈色カプラーとしては、英国
特許８６１．１３８号、同９１４，１４５号、同１．
ｌ Ｏ９，９６３−：、特公昭４５−１４０３３号、米
国特許３．５８０，７２２号およびミットタイルンゲン
アウスデン フォルフェニンゲス ッポントリー エ
ンデア アグファ レベルキエー七ン４巻 ３５２〜３
６７頁（１９６４年）等に記載のものから遣ぶことがで
きる。Furthermore, as colorless couplers that can be used in combination with this button light, British Patent No. 861.138, British Patent No. 914,145, British Patent No. 1.
l O9,963-:, Japanese Patent Publication No. 45-14033, U.S. Patent No. 3,580,722, and Mitteilungen Ausden Forfeningesuppontrie Endea Agfa Rebelkie 7, Vol. 4, 352-3
67 (1964) etc. can be used.
一般式１刀又は一般式［ｎＪで表わされる本発明に係る
マゼンタカプラーを）・ロゲン化銖乳剤層中に含有させ
るときは、通常ノ・ロゲン化傾１モル自り約０．００５
〜２モル、好ましくは０．０１〜１モルの範囲で用いら
れる。When the magenta coupler according to the present invention represented by the general formula 1 or the general formula [nJ] is contained in the halogenated emulsion layer, 1 mole of the halogenation gradient is usually about 0.005
-2 mol, preferably 0.01-1 mol.
カラー写ｆ（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。Color photographic f (referred to as a black-and-white first developer used in the processing of photosensitive materials, or used in the processing of black-and-white photographic materials, and containing various additives that are generally added to black-and-white developers) I can do it.
代表的な添加剤としてはｌ−フェニル−３−ピラゾリド
ン、メト−ル及びパイトロキノンのような現。Typical additives include l-phenyl-3-pyrazolidone, methol and pytroquinone.
像下県、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、炭酸カリウム等のフルカリからなる促
進剤、臭化カリウムや２−メチレン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、微量の沃
化物やメルカプト化合物からなる表面過現像防止剤等を
挙げることができる。preservatives such as sulfites, sodium hydroxide,
Accelerants consisting of potassium carbonate, potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylenebenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, trace amounts of Examples include surface overdevelopment inhibitors made of iodides and mercapto compounds.
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２．３７８．８７９号、
同２，８０１，１７１号参照）のほか１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２，２５２，
７１８号、同２．５１１２，２４３号、同２，５９０，
９７０号参照）のものであってもよい、また発色剤は本
発明のマゼンタカプラー以外に当業界で一般に知られて
いる任意のものが使用できる０例えばシアン発色剤とし
ては、ナフトールあるいはフェノール構造を基本とし、
カプリングによりインドアニリン色素を形成するもの、
イエロー発色剤とドアニライド、ピバリルアセトアニラ
イド詮γシルアセトアニライド４１Ｔ造のもの等でカプ
リング位置に置換ノ１（を有するもの、イ１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当量型カプラー及び４当−１−型カプラーのいずれ
をも適用できる。使用しえるハロゲン化銀乳剤としては
塩化銀、臭化銀、沃化銀、１１Ｘ臭化銀、塩沃化銀、沃
臭化銀、塩沃臭化銀または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
れらのハロゲ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。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 in which a color former is contained in the light-sensitive material (U.S. Pat. No. 2,378,879,
2,801,171), as well as an external development method in which one color former is included in the developer (see U.S. Pat. No. 2,252,
No. 718, No. 2.5112, 243, No. 2,590,
In addition to the magenta coupler of the present invention, any coloring agent generally known in the art may be used.For example, as a cyan coloring agent, a naphthol or phenolic structure may be used. Basically,
those that form indoaniline dyes by coupling;
Yellow color formers and doanilide, pivalyl acetanilide (gamma cylacetanilide 41T), etc., with or without substitution at the coupling position can be used.As a color former, , so-called 2-equivalent type couplers and 4-equivalent-1-type couplers can be applied.Silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, 11X silver bromide, and silver chloroiodide. Any silver halide such as silver iodobromide, silver chloride iodobromide, or a mixture thereof may be used.Also, as a protective colloid for these silver halides, natural products such as gelatin may be used. In addition, various compounds obtained by synthesis can be used.
ハロゲン化銀乳剤には、°安定剤、硬膜剤、増感色素、
界面活性剤等通常の写真用添加剤が含まれてもよい。Silver halide emulsions include ° stabilizers, hardeners, sensitizing dyes,
Common photographic additives such as surfactants may also be included.
本発明に係わるハロゲン化銀カラー写真感光材料中には
コロイド銀分散層があることが好まし−い、該コロイド
銀分散層はフィルタ一層やハレーション防Ｗ層であって
もよく、さらに乳剤層中に分散されたものであってもよ
い、これらコロイド銀分散物のつくり方としては特公昭
４３−２７７４０号、同４９−４３２０１号、回４５−
１４８９０号、特開１１／（５１−８９７２２号及び英
国特許１．０３２．．８７ｉ号等に記載の一般的な方法
で合成され、塗設される。It is preferable that the silver halide color photographic light-sensitive material of the present invention has a colloidal silver dispersion layer.The colloidal silver dispersion layer may be a filter layer or an anti-halation W layer, and may also be an emulsion layer. How to make these colloidal silver dispersions, which may be dispersed in
14890, Japanese Unexamined Patent Application Publication No. 11-89722, and British Patent No. 1.032..87i, etc., it is synthesized and coated.
本発明に係わる漂白能及び漂白定若液は、カラーペーパ
ー、カラーネガフィルム、カラーポジフィルム、スライ
ド用カラー反転フィルム、映画用カラー反転フィルム、
ＴＶ用カラー反転フィル・ ム、反転カラーペーパー等
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
きるが、特に沃化銀を０．１モル％以上含有する沃臭化
銀又は塩沃臭化銀で総塗布銀量が２θＩ１ｇ／ｄｍ″以
上である高感度カラー写真感光材料の処理に最も適して
いる。The bleaching ability and bleaching fixative according to the present invention are applicable to color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to silver halide color photographic materials such as color reversal films for TVs and reversal color papers, but especially silver iodobromide or chloroiobromide containing 0.1 mol% or more of silver iodide. It is most suitable for processing high-sensitivity color photographic materials in which the total amount of silver coated is 2θI1 g/dm'' or more.
［実施例］
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態様が限定されるものではない。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.
実施例 １
トリアセテートフィルムベース上にハレーション防止層
及びゼラチン層を設け、この上に赤感性ハロゲン化銀乳
剤層、緑感性ハロゲン化銀乳剤層、黄色コロイド銀を含
有するフィルタ一層及び青感性ハロゲン化銀乳剤層、保
ｄ（（層を順次塗設し、総体の銀量が１０ｆｌｃｒｎ’
当り７Ｏ＠Ｈになるようにした。上記の乳剤層は沃化銀
のモル９６が約４．５％の沃臭化銀であり、この際、青
感性ハロゲン化銀乳剤層に下記イエローカプラー（Ｙ−
１）を、緑感性ハロゲン化銀乳剤層には表１に記載した
比較のマゼンタカプラー（Ｍ−１）〜（Ｍ−３）及び本
発明のマゼンタカプラーを、更に赤感性ハロゲン化銀乳
剤層には下記シアンカプラー（ｃ−ｉ）を用いた。Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and on top of this are a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer. Emulsion layer, adhesive layer
I made it so that the hit was 7O@H. The above emulsion layer is made of silver iodobromide with a mole of silver iodide of about 4.5%. At this time, the following yellow coupler (Y-
1), the comparative magenta couplers (M-1) to (M-3) listed in Table 1 and the magenta coupler of the present invention were added to the green-sensitive silver halide emulsion layer, and the magenta couplers of the present invention were added to the red-sensitive silver halide emulsion layer. The following cyan coupler (c-i) was used.
更にそれぞれ高沸点溶媒、増感色素、硬１１ｇ剤及び延
展割等通常の添加剤を用いた。このようにして作られた
カラーネガフィルムを常法によりウエッヂ露光をした後
、下記の現像処理を行った。Further, conventional additives such as a high boiling point solvent, a sensitizing dye, a hardening agent, and a spreading agent were used. The color negative film thus produced was subjected to wedge exposure in a conventional manner and then subjected to the following development treatment.
比較マセンタカグ２−（八４−１）
シアンカプラー（０−１）
比較マゼンタカプラーＣＭ−２）
比較マゼンタカプラー（Ｍ−３）
処理工程 処理温度（°Ｃ） 処理時間１発色現像
３７．８ ３分１５秒２漂白定着
３７．８ ３分１５秒３水 洗 ３０〜
３４ ２分４安 定 ３０〜３４
１分５乾 燥 ４０〜６０
発色現像液、漂白定着液及び安定液は以下のものを使用
した。Comparative magenta coupler 2-(84-1) Cyan coupler (0-1) Comparative magenta coupler CM-2) Comparative magenta coupler (M-3) Processing process Processing temperature (°C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 bleach fixing
37.8 3 minutes 15 seconds 3 water wash 30~
34 2 minutes 4 stable 30~34
Drying for 1 minute and 5 minutes 40-60 The following color developing solution, bleach-fixing solution and stabilizing solution were used.
［発色現像液］
炭酸カリウム ３０ｇ亜硫酸カリ
ウム ２．０ｇジエチレントリア
ミン五酢酸 ２．０ｇヒドロキシアミン硫酸塩
２．５ｇ臭化ナトリウム
１．３ｇ水酸化カリウム １
．４ｇＮ−エチル−Ｎ−β−ヒドロキシエチル−３−メ
チル−４アミノアニリ７ａ酸塩 ４．６ｇ水を加
えてＩｆＬに仕上げ、５０％硫酸及び水酸化ナトリウム
にてｐＨ１０，０に調整した。[Color developer] Potassium carbonate 30g Potassium sulfite 2.0g Diethylenetriaminepentaacetic acid 2.0g Hydroxyamine sulfate 2.5g Sodium bromide
1.3g potassium hydroxide 1
．． 4gN-ethyl-N-β-hydroxyethyl-3-methyl-4aminoanili7a salt 4.6g water was added to prepare IfL, and the pH was adjusted to 10.0 with 50% sulfuric acid and sodium hydroxide.
［漂白定着液〕
有機酸鉄（ｍ）錯塩 ０．３モル亜硫酸ア
ンモニウム １０．０ｇチオ硫酸アンモニ
ウム １５０．０ｇアンモニア水（２８％溶
液） １０＋ａ文水を加えて１４Ｑ、に仕上
げ、酢酸及びアンモニア水にてｐＨ７，０に調整した。[Bleach-fix solution] Organic acid iron (m) complex salt 0.3 mol Ammonium sulfite 10.0 g Ammonium thiosulfate 150.0 g Aqueous ammonia (28% solution) Add 10+a water to give 14Q, and finish with acetic acid and aqueous ammonia The pH was adjusted to 7.0.
［安定液コ
ホルマリン（３５％水溶液） ７ｍ文水を加
えてｌｆＬに仕上げる。[Stabilizing liquid coformalin (35% aqueous solution) Add 7ml of water to make lfL.
処理後の試料は顕色性を拡大してみるために６０℃、８
０％ＲＨの条件で１日放置し、その後サクラ光電濃度計
ＰＤＡ−８５（小西六写真工業社製）で最高Ｈ度ＬＩ３
のマゼンタ色素ｅ度を測定し、サクラ力う−ネガ処理の
ＣＮＫ−４基準処理におけるマゼンタ色素濃度との比か
ら顕色性を求めた。After processing, the sample was incubated at 60°C at 8°C to expand the color development.
Leave it for one day under the condition of 0% RH, and then measure the maximum H degree LI3 with Sakura Photodensitometer PDA-85 (manufactured by Konishiroku Photo Industry Co., Ltd.).
The magenta dye concentration was measured, and the color developability was determined from the ratio of the magenta dye density in the CNK-4 standard processing of the cherry blossom negative processing.
６０℃、８０％ＲＨ１日放置後の ＣＮＫ−４基準処理における マゼンタ色素最高濃度 更に最高濃度部の残存銀量を蛍光Ｘ線にて測定した。After being left at 60℃ and 80%RH for 1 day In CNK-4 standard processing Maximum magenta dye density Furthermore, the amount of residual silver in the highest density area was measured using fluorescent X-rays.
以上の結果を表１に示す。The above results are shown in Table 1.
なお本実施例において、ＥＤＴＡｅＦｅ （ｍ） 、
ＤＴＰＡ・Ｆｅ（ｍ）、ＣｙＤＴＡ−Ｆｅ （ｍ） 、
ＴＴＨＡ−Ｆｅ （ＩＩＩ）、ＧＥＤＴＡ ・Ｆｅ
（ｍ） 、 ＤＴＰＰｌｌＦｅ （ｍ）、ＣＦＤＴＰ−
Ｆｅ（ＤＩ） 、 ＴＴＨＰ−Ｆｅ （ｍ） 、 ＭＩ
ＤＡｌｌＦｅ （ｍ） 、 ＭｅＥＤＴＡ・Ｆｅ（ＤＩ
）はそれぞれ、次のものの略号である。In this example, EDTAeFe (m),
DTPA・Fe (m), CyDTA-Fe (m),
TTHA-Fe (III), GEDTA ・Fe
(m), DTPPllFe (m), CFDTP-
Fe(DI), TTHP-Fe(m), MI
DAllFe (m), MeEDTA・Fe(DI
) are abbreviations for the following:
ＥＤＴＡ・Ｆｅ（ＩＩＩ）；エチレンジアミン四酢酸鉄
（ｍ）アンモニウム塩。EDTA.Fe(III); ethylenediaminetetraacetic acid iron(m) ammonium salt.
ＤＴＰＡ争Ｆｅ （ＩＩＩ） ；ジエチレントリアミ
ン五酢酸鉄（ｍ）アンモニウム塩。DTPA Fe(III); diethylenetriaminepentaacetic acid iron (m) ammonium salt.
ＣｙＤＴＡ＠Ｆｅ （ＤＩ） ； １，２−シクロヘキ
サンジアミン四酢酸鉄（ｍ）アンモニウム塩。CyDTA@Fe (DI); 1,2-cyclohexanediaminetetraacetic acid iron (m) ammonium salt.
ＴＴＨＡＩＩＦｅ （ｍ） ； トリエチレンテトラ
ミン六酢酸鉄（ｍ）アンモニウム塩。TTHAIIFe (m); triethylenetetraminehexaacetic acid iron (m) ammonium salt.
ＧＥＤＴＡＩＩＦｅ （ｍ） ；グリコールエーテルジ
アミン四酢酸鉄（ＩＩＩ）アンモニウム塩。GEDTAIIFe (m); glycol ether diamine tetraacetic acid iron (III) ammonium salt.
ＤＴＰＰｌｌＦｅ（■）；ジエチレントリアミン五メチ
レンホスホン酸鉄（ｍ）アンモニ
ラム塩。DTPPllFe (■); diethylenetriaminepentamethylenephosphonic acid iron (m) ammonium salt.
ＣｙＤＴＰｌｌＦｅ （ＩＩＩ） ； １，２−シク
ロヘキサンジアミン四メチレンホスホン酸鉄（ｍ）
アンモニウム塩。CyDTPllFe (III); 1,2-cyclohexanediaminetetramethylenephosphonic acid iron(m) ammonium salt.
ＴＴＨＰｌｌＦｅ （ｍ） ； トリエチレンテトラ
ミン六メチレンホスホンｌｌｉ（ｍ）アンモ
ニウム塩。TTHPllFe (m); triethylenetetramine hexamethylene phosphone lli (m) ammonium salt.
ＭＩＤＡ−Ｆｅ （ｍ） ；メチルイミノジ酢酸鉄（
ｍ）アンモニウム塩。MIDA-Fe (m); iron methyliminodiacetate (
m) ammonium salts.
ＭｅＥＤＴＡ・Ｆｅ （ＩＩＩ） ； １．２−ジア
ミノプロノくン四酢酸鉄（ＩＩＩ）アンモニウム１１２
・
以下余白
表 １
表１より有機酸鉄（ｍ）錯塩としてＥＤＴＡ・Ｆｅ（ｍ
）を用いた場合はカプラーの種類にかかわらず顕色性に
優位差はなく、良好な顕色性を示している反面、多量の
残存銀量がある。しかるに本発明の有機酸鉄（ｍ）錯塩
を用いた場合、脱銀性は十分満足いく結果を得ているも
のの本）Ａ切外のカプラーである比較（Ｍ−１）〜（Ｍ
−３）を使用すると顕色性が低下しているのに対し、本
発明のカプラー（Ｍ−１，Ｍ−８、Ｍ−１１）との組合
せにおいては良好な顕色性を示している。MeEDTA・Fe(III); 1,2-diaminopronotetraacetate iron(III) ammonium 112
・ Below is a blank table 1 From Table 1, EDTA・Fe(m) is used as an organic acid iron(m) complex salt.
), there is no superiority in color development regardless of the type of coupler, and while good color development is shown, there is a large amount of residual silver. However, when using the organic acid iron (m) complex salt of the present invention, although sufficiently satisfactory results were obtained in desilvering property, comparisons (M-1) to (M
-3), the color development property deteriorates, whereas the combination with the couplers of the present invention (M-1, M-8, M-11) shows good color development property.
従って、本発明の有機酸鉄（ＩＩＩ）錯ｊＩＡと本発明
のマゼンタカプラーを用いた場合にのみ、顕色性及び脱
銀性が十分満足のいく結果になるということは明らかで
ある。なお実施例１記載以外の本発明の漂白剤について
も検討したが、上記と同様良好な結果を得た。Therefore, it is clear that only when the organic acid iron(III) complex jIA of the present invention and the magenta coupler of the present invention are used, sufficiently satisfactory color developing properties and desilvering properties can be obtained. It should be noted that bleaching agents of the present invention other than those described in Example 1 were also investigated, and good results were obtained similar to the above.
実施例 ２
実施例１で使用した有ｖ１酸鉄（ｍ）錯１１１を漂白剤
とする漂白定着液をガラスビーカーにて、４０°Ｃにて
放置し、硫化物の生成迄のＵ数を観δｌ（した。Example 2 A bleach-fix solution containing v1 iron (m) complex 111 used in Example 1 as a bleaching agent was left in a glass beaker at 40°C, and the U number until sulfide formation was observed. δl(did.
その結果、有機酸鉄（ＩＩＩ）錯塩としてＥＤＴＡ−Ｆ
ｅを用いた場合は１４日で硫化物が生成したのに対し、
本発明の有機酸鉄（ｍ）錯塩を用いると５０日以上でも
硫化物の発生がみられなかった。特に［］ＴＰＡΦＦｅ
（ｍ）、ＣｙＤＴＡ １１Ｆｅ （ｍ）が良好であった
。As a result, EDTA-F was found as an organic acid iron(III) complex salt.
When using e, sulfide was generated in 14 days, whereas
When the organic acid iron (m) complex salt of the present invention was used, no generation of sulfide was observed even after 50 days or more. Especially []TPAΦFe
(m) and CyDTA 11Fe (m) were good.
実施例 ３
実施例１で用いた試料Ｎ００１．４．７．ｔｏ、１３．
１６を用いて漂白定着処理時間を代え、漂白定着処理時
間（分）と顕色性、脱銀性との関係をみた。Example 3 Sample N001.4.7. used in Example 1. to, 13.
Using No. 16, the bleach-fixing treatment time was varied, and the relationship between the bleach-fixing treatment time (minutes), color developing property, and desilvering property was examined.
評価方法の中で６０℃、８０％ＲＨ１日放置の条件を２
日にした以外は実施例１と同様の方法で行った。In the evaluation method, the condition of leaving for 1 day at 60℃ and 80% RH is 2.
The same method as in Example 1 was carried out except that the day was changed.
結果を表２に示す。The results are shown in Table 2.
表２より明らかなように実施例１の詰果と同様、本発明
の有機酸鉄（ｍ）錯塩と比較カプラーとの組合せにおい
てのみ顕色性が低下しているのがわかる。又漂白定着処
理時間を代えた場合、８分を顕色性の下限としているこ
とがわかる。As is clear from Table 2, similar to the filling of Example 1, the color development is reduced only in the combination of the organic acid iron (m) complex salt of the present invention and the comparative coupler. It can also be seen that when the bleach-fixing treatment time was changed, the lower limit of color development was 8 minutes.
更に脱水性についても評価したが、本発明の有機酸鉄（
ＩＩＩ）錯塩を用いた場合はＤＴＰＡ−Ｆｅで３分、
Ｃｙ口ＴＡ＊Ｆｅで３分３０秒で完全に脱銀されている
のに対し、ＥＤＴＡ＠Ｆｅは１０分以上も脱銀されなか
った。Furthermore, the dehydration properties were also evaluated, and the organic acid iron of the present invention (
III) When using a complex salt, 3 minutes with DTPA-Fe;
While Cy-TA*Fe was completely desilvered in 3 minutes and 30 seconds, EDTA@Fe was not desilvered for more than 10 minutes.
Claims (1)
像処理し、漂白能を有する処理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、前記ハロゲ
ン化銀カラー写真感光材料が少なくとも下記一般式〔
I 〕及び／又は〔II〕で示されるマゼンタカプラーを含
有し、前記漂白能を有する処理液が、漂白剤として下記
第２鉄鎖塩群から選ばれる有機酸第２鉄錯塩（Ａ）の少
なくとも１つ又は有機酸第２鉄錯塩の下記基準溶液のｐ
Ｈが５．０〜９．０の間での酸化還元電位の差が１００
ｍＶ以内である有機酸第２鉄錯塩の少なくとも１つを含
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。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 式中、Ａｒはフェニル基である。Ｙ＿１芳香族第１級ア
ミン発色現像主薬の酸化体とカプリングして色素が形成
されるとき離脱する基を表わす。Ｘはハロゲン原子、ア
ルコキシ基、アルキル基である。Ｒはベンゼン環に置換
可能な基を表わし、ｎは１又は２を表わす。ｎが２のと
きＲは同じでも異なっていてもよい。 一般式〔II〕 ▲数式、化学式、表等があります▼ 式中、Ｒ＿１及びＲ＿２は夫々アルキル基又はアリール
基を示し、Ｍは水素原子又は発色現像主薬の酸化体との
カプリング反応時に離脱しうる基又は原子を表わす。又
Ｙ＿２は水素原子又は ▲数式、化学式、表等があります▼基を表わし、Ｒ＿３
はＲ＿５−ＯＣＯ−、Ｒ＿５−ＣＯ−、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼、−ＣＯＯＨ、−ＮＯ＿２又は−ＣＮを表わし、Ｒ＿
４は前記Ｒ＿３において定義された基又は▲数式、化学
式、表等があります▼を表わし、 Ｒ＿５はアルキル基を表わし、Ｒ＿６は水素原子、−Ｃ
ＯＯＨ、−ＯＨ、−ＣＯＯＲ＿５又は−ＳＯ＿３Ｈを表
わす。Ｒ＿３とＲ＿４はそれぞれ同一の基でも異なる基
でもよい。 ［有機酸第２鉄錯塩（Ａ）］ （１）ジエチレントリアミン五酢酸第２鉄錯塩（２）ジ
エチレントリアミン五メチレンホスホン酸第２鉄錯塩 （３）シクロヘキサンジアミン四酢酸第２鉄錯塩（４）
シクロヘキサンジアミン四メチレンホスホン酸第２鉄錯
塩 （５）トリエチレンテトラミン六酢酸第２鉄錯塩（６）
トリエチレンテトラミン六メチレンホスホン酸第２鉄錯
塩 （７）グリコールエーテルジアミン四酢酸第２鉄錯塩 （８）グリコールエーテルジアミン四メチレンホスホン
酸第２鉄錯塩 （９）１，２−ジアミノプロパン四酢酸第２鉄錯塩（１
０）１，２−ジアミノプロパン四メチレンホスホン酸第
２鉄錯塩 （１１）メチルイミノジ酢酸第２鉄錯塩 （１２）メチルイミノジメチレンホスホン酸第２鉄錯塩 （１３）１，３−ジアミノプロパン−２−オール四酢酸
第２鉄錯塩 （１４）１，３−ジアミノプロパン−２−オール四メチ
レンホスホン酸第２鉄錯塩 （１５）エチレンジアミンジオルトヒドロキシフェニル
酢酸第２鉄錯塩 （１６）エチレンジアミンジオルトヒドロキシフェニル
メチレンホスホン酸第２鉄錯塩 （１７）エチレンジアミン四メチレンホスホン酸第２鉄
錯塩 ［酸化還元電位測定用有機酸第２鉄錯塩基準溶液］塩化
第２鉄 ０．２３Ｍ 有機酸 ０．３０５Ｍ チオ硫酸アンモニウム １．０Ｍ 亜硫酸アンモニウム ０．１Ｍ アンモニア水及び酢酸を用いてｐＨを調整し、酸化還元
電位を測定する。 （２）漂白能を有する処理液の表面張力が５５ｄｙｎｅ
／ｃｍ以下であることを特徴とする特許請求の範囲第１
項記載のハロゲン化銀カラー写真感光材料の処理方法。 （３）有機酸第２鉄錯塩がジエチレントリアミン五酢酸
第２鉄錯塩、シクロヘキサンジアミン四酢酸第２鉄錯塩
又はトリエチレンテトラミン六酢酸第２鉄錯塩であるこ
とを特徴とする特許請求の範囲第１項又は第２項記載の
ハロゲン化銀カラー写真感光材料の処理方法。 （４）漂白能を有する処理液が漂白定着液であることを
特徴とする特許請求の範囲第１項、第２項又は第３項記
載のハロゲン化銀カラー写真感光材料の処理方法。 （５）漂白定着液による一浴漂白定着処理が発色現像処
理に続いて直接行われることを特徴とする特許請求の範
囲第４項記載のハロゲン化銀カラー写真感光材料の処理
方法。Scope of Claims: (1) A method for processing a silver halide color photographic material, which comprises developing the silver halide color photographic material after imagewise exposure and treating it with a processing solution having bleaching ability, comprising: The color photographic material has at least the following general formula [
The processing solution containing the magenta coupler represented by [I] and/or [II] and having bleaching ability contains at least one organic acid ferric complex salt (A) selected from the following ferric chain salt group as a bleaching agent. p of the following standard solution of ferric or organic acid ferric complex salt
The difference in redox potential between H is 5.0 and 9.0 is 100
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that it contains at least one organic acid ferric complex salt having a ferric iron complex salt having a ferric iron complex salt having a voltage of 1.0 mV or less. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar is a phenyl group. Y_1 Represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. X is a halogen atom, an alkoxy group, or an alkyl group. R represents a group that can be substituted on the benzene ring, and n represents 1 or 2. When n is 2, R may be the same or different. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent an alkyl group or an aryl group, and M can be separated during a coupling reaction with a hydrogen atom or an oxidized form of a color developing agent. Represents a group or an atom. In addition, Y_2 represents a hydrogen atom or a ▲ group that has a mathematical formula, chemical formula, table, etc., and R_3
represents R_5-OCO-, R_5-CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COOH, -NO_2 or -CN, and R_
4 represents the group defined in R_3 above or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_5 represents an alkyl group, R_6 represents a hydrogen atom, -C
Represents OOH, -OH, -COOR_5 or -SO_3H. R_3 and R_4 may be the same group or different groups. [Organic acid ferric complex salt (A)] (1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriaminepentamethylenephosphonic acid ferric complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (4)
Cyclohexanediamine tetramethylene phosphonic acid ferric complex salt (5) Triethylenetetramine hexaacetic acid ferric complex salt (6)
Triethylenetetramine hexamethylenephosphonic acid ferric complex salt (7) Glycol ether diamine tetraacetic acid ferric complex salt (8) Glycol ether diamine tetramethylene phosphonic acid ferric complex salt (9) 1,2-diaminopropane tetraacetic acid ferric complex salt Iron complex salt (1
0) 1,2-diaminopropane tetramethylenephosphonic acid ferric complex salt (11) methyliminodiacetic acid ferric complex salt (12) methylimino dimethylene phosphonic acid ferric complex salt (13) 1,3-diaminopropane-2- All-tetraacetic acid ferric complex salt (14) 1,3-diaminopropan-2-ol tetramethylenephosphonic acid ferric complex salt (15) Ethylenediamine diorthohydroxyphenylacetic acid ferric complex salt (16) Ethylenediamine diorthohydroxyphenylmethylene Ferric phosphonic acid complex salt (17) Ethylenediamine tetramethylene phosphonic acid ferric complex salt [Organic acid ferric complex salt standard solution for redox potential measurement] Ferric chloride 0.23M Organic acid 0.305M Ammonium thiosulfate 1.0M Adjust the pH using ammonium sulfite 0.1M ammonia water and acetic acid, and measure the redox potential. (2) The surface tension of the processing liquid with bleaching ability is 55 dyne.
/cm or less
A method for processing a silver halide color photographic light-sensitive material as described in . (3) Claim 1, wherein the organic acid ferric complex salt is diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. Or the method for processing a silver halide color photographic light-sensitive material according to item 2. (4) The method for processing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing solution having bleaching ability is a bleach-fix solution. (5) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that a one-bath bleach-fix treatment using a bleach-fix solution is carried out directly following the color development treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17215484A JPS6150145A (en) | 1984-08-18 | 1984-08-18 | Treatment of silver halide color photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17215484A JPS6150145A (en) | 1984-08-18 | 1984-08-18 | Treatment of silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6150145A true JPS6150145A (en) | 1986-03-12 |
Family
ID=15936564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17215484A Pending JPS6150145A (en) | 1984-08-18 | 1984-08-18 | Treatment of silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6150145A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS642048A (en) * | 1987-06-25 | 1989-01-06 | Konica Corp | Method for processing silver halide color photographic sensitive material |
| JPH01197754A (en) * | 1988-02-01 | 1989-08-09 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036126A (en) * | 1973-07-13 | 1975-04-05 | ||
| JPS5999437A (en) * | 1982-10-28 | 1984-06-08 | Fuji Photo Film Co Ltd | Color photosensitive silver halide material |
| JPS59125732A (en) * | 1983-01-07 | 1984-07-20 | Fuji Photo Film Co Ltd | Color photographic sensitive silver halide material |
-
1984
- 1984-08-18 JP JP17215484A patent/JPS6150145A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5036126A (en) * | 1973-07-13 | 1975-04-05 | ||
| JPS5999437A (en) * | 1982-10-28 | 1984-06-08 | Fuji Photo Film Co Ltd | Color photosensitive silver halide material |
| JPS59125732A (en) * | 1983-01-07 | 1984-07-20 | Fuji Photo Film Co Ltd | Color photographic sensitive silver halide material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS642048A (en) * | 1987-06-25 | 1989-01-06 | Konica Corp | Method for processing silver halide color photographic sensitive material |
| JPH01197754A (en) * | 1988-02-01 | 1989-08-09 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
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