JPS6150140A - Treatment of silver halide color photographic sensitive material - Google Patents
Treatment of silver halide color photographic sensitive materialInfo
- Publication number
- JPS6150140A JPS6150140A JP17171984A JP17171984A JPS6150140A JP S6150140 A JPS6150140 A JP S6150140A JP 17171984 A JP17171984 A JP 17171984A JP 17171984 A JP17171984 A JP 17171984A JP S6150140 A JPS6150140 A JP S6150140A
- Authority
- JP
- Japan
- Prior art keywords
- group
- complex salt
- ferric complex
- acid ferric
- acid
- 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 82
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 50
- 239000004332 silver Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000011282 treatment Methods 0.000 title claims description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 134
- 238000012545 processing Methods 0.000 claims abstract description 50
- 238000004061 bleaching Methods 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 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 7
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 33
- 150000007524 organic acids Chemical class 0.000 claims description 29
- 238000011161 development Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000007844 bleaching agent Substances 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 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
- 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 4
- 125000003545 alkoxy group Chemical group 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
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-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
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 239000012086 standard solution Substances 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 150000001768 cations Chemical group 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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 claims 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims 1
- 239000012088 reference solution Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 abstract 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 2
- 239000005711 Benzoic acid Substances 0.000 abstract 1
- 235000010233 benzoic acid Nutrition 0.000 abstract 1
- 229960003512 nicotinic acid Drugs 0.000 abstract 1
- 235000001968 nicotinic acid Nutrition 0.000 abstract 1
- 239000011664 nicotinic acid Substances 0.000 abstract 1
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 210000003423 ankle Anatomy 0.000 description 3
- KZTASAUPEDXWMQ-UHFFFAOYSA-N azane;iron(3+) Chemical compound N.[Fe+3] KZTASAUPEDXWMQ-UHFFFAOYSA-N 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 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 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 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 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 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 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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 class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 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
- 239000000084 colloidal system Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 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
- 239000000975 dye 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 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
- 239000003755 preservative agent Substances 0.000 description 2
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical group O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 1
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 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
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000005283 halide glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011591 potassium Substances 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
- 159000000001 potassium salts Chemical class 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
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 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
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 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
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- G03C7/421—Additives other than bleaching or fixing agents
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。更に詳しくは迅速な銀漂白能力を有し、長期連
続処理に供してもイエロースティンの発生がなく、更に
漂白定着液の保存安定性を高めることができる、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, a method for processing a silver halide color photographic light-sensitive material that has rapid silver bleaching ability, does not generate yellow stain even when subjected to long-term continuous processing, and can further improve the storage stability of a bleach-fix solution. It is related to.
［従来技術］
一般に像様露光されたハロゲン化銀カラー写真感光材料
を処理してカラー画像を得るには、発色現像工程の後に
、生成された金属銀を漂白能を有する処理液で処理する
工程が設けられている。[Prior Art] Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development step, there is a step of treating the produced metallic silver with a processing solution having bleaching ability. is provided.
漂白能を有する処理液としては、乙７ｊ白液、漂白定着
液が知られている。漂白液が使用される場合は、通常漂
白工程に次いでハロゲン化銀を定着剤によって定着する
工程が付加えられるが、ｂア白定着液では漂白及び定着
が一工程で行われる。As processing solutions having bleaching ability, Otsu 7j white solution and bleach-fix solution are known. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added next to the bleaching step, but with a b-white fixing solution, bleaching and fixing are performed in one step.
ハロゲン化銀カラー写真感光材料の処理における漂白能
を有する処理液には、画像銀を漂白するための醇化剤と
して、赤血塩、重クロム酸塩等のｆｉ機の酸化剤が広く
用いられている。Fi-machine oxidizing agents such as red blood salt and dichromate are widely used as maceration agents for bleaching image silver in processing solutions with bleaching ability in processing silver halide color photographic light-sensitive materials. There is.
しかし、これらの無機の酸化剤を含有する漂白能を有す
る処理液には、いくつかの重大な欠点が指摘されている
０例えば赤血塩及び重クロム酸塩は画像銀の漂白刃とい
う点では比較的すぐれているが、光により分解して人体
に有害なシアンイオンや六価のクロムイオンを生成する
虞れがあり、公害防止上好ましくない性質を有している
。またこれらの酸化剤はその酸化力が極めて強いために
、チオ硫酸塩等のハロゲン化銀可溶化剤（定着剤）を同
一の処理液中に共存させることが困難で、漂白定着浴に
これらの酸化剤を用いることばほとんど不Ｕｆ能であり
、このため処理の迅速化及び簡素化という目的の達成を
難しくしている。さらにこれらの無機の酸化剤を含む処
理液は処理後の廃液を捨てることなく再生使用すること
が困難であるという欠点を有している。However, some serious drawbacks have been pointed out to the bleaching solutions containing these inorganic oxidizing agents. Although it is relatively good, it has undesirable properties in terms of pollution prevention, as it may decompose when exposed to light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers (fixing agents) such as thiosulfates in the same processing solution, and these agents are not used in bleach-fixing baths. The use of oxidizing agents is almost ineffective, making it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.
これに対し、公害上の問題も少なく、処理の迅速化、簡
素化及び廃液の再生使用可能等の要請にかなうものとし
て、アミノポリカルボン酸金属錯塩等の有機酸の金属錯
塩を酸化剤とした処理液が使用されるようになってきた
。しかし、有機酸の金属錯塩を使用した処理液（１：、
酸化力が緩慢なために、現像工程で形成された画像銀（
金属１！１１）の漂白速度（酸化速度）が遅いという欠
点を有している０例えば、アミノポリカルボン酸金属錯
塩の中で漂白刃が強いと考えられているエチレンジアミ
ン四酢酸鉄（ＩＩＩ）錯塩は一部で漂白液及び漂白定着
液として実用化されているが、臭化銀、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
ーパー及び撮影用のカラーネガティブフィルム、カラー
リバーサルフィルムでは漂白刃が不足し、長時間処理し
ても痕跡程度の画像銀が残り、脱銀性が不良となる。こ
の傾向は、酸化剤とチオ硫酸塩及び亜硫酸塩が共存する
漂白定着液では酸化還元電位が低下するため特に顕著に
現われる。On the other hand, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling recycling of waste liquid. Treatment liquids have come into use. However, a treatment solution using a metal complex salt of an organic acid (1:
Because the oxidizing power is slow, the image silver (
For example, iron(III) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has the disadvantage of slow bleaching rate (oxidation rate) of metal 1!11) has been put into practical use as a bleaching solution and a bleach-fixing solution in some areas, but it is also used in high-sensitivity silver halide color photographic light-sensitive materials based on silver bromide and silver iodobromide emulsions, especially when silver iodide is used as the silver halide. The color paper for photography, color negative film for photography, and color reversal film contained therein lack a bleaching blade, and traces of image silver remain even after long-term processing, resulting in poor desilvering properties. This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents and thiosulfates and sulfites coexist because the redox potential is lowered.
また、近年低コスト化及び低公害化の目的から処理液の
低補充化の動きがある。この場合、漂白液又は漂白定着
液中に感光材料に付着して混入する現像液成分の含有量
が増加し、かつ漂白液及び漂白定着液の滞留時間の長期
化が生じる。これにより感光材料の脱銀性能はさらに悪
くなるばかりでなく、長期保存時に、感光材料中に残留
する漂白剤や漂白定着液に混入した現像液成分に起因す
ると思われるイエロースティンの発生という別なる問題
を生じる。In addition, in recent years, there has been a movement toward lower replenishment of processing liquids for the purpose of lowering costs and reducing pollution. In this case, the content of developer components that adhere to and mix with the photosensitive material in the bleach or bleach-fix solution increases, and the residence time of the bleach and bleach-fix solutions becomes longer. This not only further deteriorates the desilvering performance of the photosensitive material, but also causes yellow stain, which is thought to be caused by bleach remaining in the photosensitive material and developer components mixed in the bleach-fix solution, to occur during long-term storage. cause problems.
［発明が解決しようとする問題点］
本発明は、迅速な銀源白刃をハｊ１え、長期連続処理に
供してもイエロースティンの発生がなく、更に漂白能を
有する処理液として醪：前液前液とじた場合に該漂白定
着液の保存安定性が優れた、ハロゲン化銀カラー写真感
光材料の処理方法を提供することを技術的課題とする。[Problems to be Solved by the Invention] The present invention provides a rapid silver source white blade, does not generate yellow stain even when subjected to long-term continuous processing, and uses a mortar preliquid as a processing liquid that has bleaching ability. It is an object of the present invention to provide a method for processing a silver halide color photographic material, in which the bleach-fix solution has excellent storage stability when the pre-solution is combined.
［発明の構成］
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、該ハロゲン化銀カラー写真感光材料が誘電
率３．５以上を有する高Ｗｌ＋点有機溶媒を少なくとも
１つ合有し、かつ前記漂白能を有する処理液が、漂白剤
として下記第２鉄錯塩群から選ばれる有機醜第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
貼溶液のＰＨが５．０〜８．０の間での酸化還元電位の
差が１００ｍＶ以内である有機酸第２鉄錯塩（Ｂ）の少
なくとも１つ、及び下記一般式［Ｉ］で示される化合物
及び／又は下記一般式［：ＩＩＩで示される化合物の少
なくとも１つを含有し、かつ表面張力が５！１ｄｙｎｅ
／ａｍ以下の漂白能を有する処理液で処理することによ
って、前記技術的課題（目的）が解決されることを見い
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 one high Wl+ point organic solvent having a dielectric constant of 3.5 or more, and the processing solution having bleaching ability contains the following ferric complex salt group as a bleaching agent: The difference in redox potential is within 100 mV when the pH of at least one of the organic ugly ferric complex salts (A) selected from the following or organic acid ferric complex salts is between 5.0 and 8.0. and at least one compound represented by the following general formula [I] and/or at least one compound represented by the following general formula [:III], and the surface Tension is 5!1 dyne
It has been found that the above technical problem (object) can be solved by processing with a processing solution having a bleaching ability of /am or less.
〔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’５２ 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（
１０）１．２−ジアミノプロパン四メチレンホスホン酸
ｆＪＳ２鉄錯塩
（１１）メチルイミノジ酩酊第２鉄錯塩（１２）メチル
イミノジメチレンホスホン酸第２結？ｊシ塩
（１３） １．３−ジアミノプロパン−２−オール四番
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ｆＪ５２鉄錯塩
（１Ｂ）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アミノポリカルボン酸等の有機酸
布ａ酸第２鉄錯塩基準溶液］
塩化第２鉄 ０．２３Ｍアミノポ
リカルボン酩等の有機酸 ０．３０５Ｍチオ硫酸アン
モニウム １．ＯＭ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。[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 '52 Iron complex salt (8) Glycol ether diamine tetramethylene phosphonic acid ferric complex salt (9) 1.2-Diaminopropane tetraacetic acid ferric salt Iron complex salt (
10) 1.2-diaminopropane tetramethylene phosphonic acid fJS2 iron complex salt (11) Methyliminoditoxic ferric complex salt (12) Methyliminodimethylene phosphonic acid secondary ? J salt (13) 1.3-diaminopropan-2-ol ferric acid complex salt (14) 1.3-diaminopropan-2-ol ferric tetramethylenephosphonic acid complex salt (15) Ethylenediamine diortho Hydroxyphenylacetic acid fJ52 iron complex salt (1B) Ethylenediamine diorthohydroxyphenylmethylenephosphonic acid ferric complex salt (17) Ethylenediamine tetramethylene phosphonic acid ferric complex salt [organic acid cloth a acid such as aminopolycarboxylic acid for redox potential measurement Ferric complex salt standard solution] Ferric chloride 0.23M Organic acid such as aminopolycarbonate 0.305M ammonium thiosulfate 1. OM ammonium sulfite
The pH is adjusted using 0.1M ammonia water and acetic acid, and the redox potential is measured.
一般式 ［エコ
式中、Ｒ１、Ｒ２、Ｒ３はそれぞれ水素原子、置換基を
有してもよいアルキル基、アルケニル基、水酸基、ハロ
ゲン原子、アミノ基、アミド基、又はメルカプト基を表
わす０Ｍは水素原子又は−価のカチオン基を表わす。ｍ
はＯｌ又は２の整数であり、ｎは１，２又は３の整数で
ある。General formula [In the Eco formula, R1, R2, and R3 each represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group, a hydroxyl group, a halogen atom, an amino group, an amide group, or a mercapto group; 0M is hydrogen Represents an atom or a -valent cationic group. m
is an integer of Ol or 2, and n is an integer of 1, 2 or 3.
一般式［１１］
式中、Ｒ４、Ｒ５、Ｒ６及びＲ７はそれぞれ水素原子、
置換基を有してもよいアルキル基、アルケニル基、水酸
基、アミ７基、アミド基、スルホン酸基、アルコキシ基
、ニトロ基、ハロゲン原子、メルカプト基又はカルボキ
シ基を表わす。Ｋは一般式［Ｉ］と同義である。General formula [11] In the formula, R4, R5, R6 and R7 are each a hydrogen atom,
It represents an alkyl group, an alkenyl group, a hydroxyl group, an amide group, an amide group, a sulfonic acid group, an alkoxy group, a nitro group, a halogen atom, a mercapto group, or a carboxy group which may have a substituent. K has the same meaning as in general formula [I].
本発明の好ましい実施態様としては、前記漂白能を有す
る処理液が漂白定着液であることがあげられ、これによ
り本発明の目的をより効果的に達成しうることを本発明
者は見い出した。In a preferred embodiment of the present invention, the processing solution having bleaching ability is a bleach-fixing solution, and the inventors have found that the object of the present invention can be achieved more effectively by this.
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.
本発明者は、長期保存時のイエロースティンの改良と、
脱銀性能の両方を改良する技術を種々検討する中で、あ
る特定の誘電率を有する高沸点有機溶媒を含む感光材料
を、ある特定の有機酸第２鉄錯塩とニコチン酩誘導体及
び／又は安恋、酩誘導体を含有する漂白定着液で、かつ
該漂白定着液の表面張力がある特定の範囲のものであれ
ば、驚くべきことに前記目的が達成できることを見い出
したものである。この効果はこれまで考えられてきたこ
とからは、全く予想もできない驚くべき効果であった。The present inventor aims to improve yellow stain during long-term storage,
While investigating various techniques for improving both desilvering performance, we discovered that a photosensitive material containing a high-boiling point organic solvent with a certain dielectric constant, a certain organic acid ferric complex salt, a nicotine intoxicant derivative and/or an alcoholic material, etc. It has been surprisingly discovered that the above object can be achieved by using a bleach-fix solution containing a Koi-dou derivative and having a surface tension within a certain range. This effect was a surprising one that could not have been predicted based on what had been considered so far.
本発明に係る有機溶媒は誘電率３．５以上の化合物であ
ればいずれでも用いることができる０例えば誘電率３．
５以上のフタル酸エステル、燐酸エステル等のエステル
類、有機酸アミド類、ケトン類、炭化水素化合物等であ
る。好ましくは？Ａ電車４．０〜８．５の高沸点有機溶
媒である。より好ましくは、該高沸点有機溶媒中のフタ
ル酸エステル類或いは燐酸エステル類である。なお、本
発明に用いられる有機溶媒は、２種以上のｇ合物であっ
てもよく、この場合は混合物の誘電率３．５以上であれ
ばよい６なお、本発明での誘電率とは、３０°Ｃにおけ
る誘電率を示している。As the organic solvent according to the present invention, any compound having a dielectric constant of 3.5 or more can be used.
These include esters such as 5 or more phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably? It is a high boiling point organic solvent with an A train of 4.0 to 8.5. More preferred are phthalate esters or phosphoric esters in the high boiling point organic solvent. The organic solvent used in the present invention may be a mixture of two or more kinds of g, and in this case, the dielectric constant of the mixture may be 3.5 or more. , shows the dielectric constant at 30°C.
本発明において右利に用いられるフタル酸エステルとし
ては、下記一般式［Ｉ［［］で示されるものが挙げられ
る。Examples of the phthalate esters used in the present invention include those represented by the following general formula [I[[].
一般式［ｍ］
式中、 Ｒ８及びＲ９はそれぞれアルキル基、アルケニ
ル基又はアリール基を表わす、但し、 Ｒｅ及びＲｇで
表わされる基の炭素数の総和は２〜３６である。より好
ましくは炭素数の総和が６〜２４である。General formula [m] In the formula, R8 and R9 each represent an alkyl group, an alkenyl group, or an aryl group, provided that the total number of carbon atoms in the groups represented by Re and Rg is 2 to 36. More preferably, the total number of carbon atoms is 6 to 24.
本発明において、前記一般式［ｍ］のＲｉ及びＲ９で表
わされるアルキル基は、直鎖もしくは分岐のものであり
、例えばブチル基、ペンチル基、ヘキシル基、ヘプチル
基、オクチル基、ノニル基、デシル基、ウンデシル基、
ドブダル基、トリデシル基、テトラデシル基、ペンタデ
シル基、ヘキサデシル基、ヘプタデシル基、オクタデシ
ル基等である。Ｒ８及びＲｓで表わされるアリール基は
フェニル基、ナフチル基等であり、アルケニル基及びア
リール基は単一もしくは複数の置換基を有していてもよ
い、アルキル基及びアルケニル基の置換基としては、例
えばハロゲン原子、アルコキシ基、アリール基、アリー
ルオキシ基、アルケニル基、アルコキシカルボニル基等
が挙げられる。アリール基の置換基としては、例えばハ
ロゲン原子、アルキル基、アルコキシ基、アリール基、
アリールオキシ基、アルケニル基、アルコキシカルボニ
ル基等が挙げられる。これらの置換基の２つ以上がアル
キル基、アルケニル基又はアリール基に導入されていて
もよい。In the present invention, the alkyl group represented by Ri and R9 in the general formula [m] is a linear or branched one, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. group, undecyl group,
These include Dovdal group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like. The aryl group represented by R8 and Rs is a phenyl group, a naphthyl group, etc., and the alkenyl group and aryl group may have a single or multiple substituents.Substituents for the alkyl group and alkenyl group include: Examples include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, and the like. Examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups,
Examples include an aryloxy group, an alkenyl group, an alkoxycarbonyl group, and the like. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.
本発明において有利に用いられる燐酸エステルとしては
、下記一般式［ＩＶ］で示されるものが挙げられる。Phosphoric esters advantageously used in the present invention include those represented by the following general formula [IV].
一般式［■］ 。General formula [■].
式中、ｔ？ｌｏ、 Ｒｕ及びＲｔｚはそれぞれアルキ
ル基、アルケニル基又はアリール基を表わす。但し、
Ｒｌａ、Ｒｎ及びＲ１２で表わされる基の炭素数の総和
は３〜５４である。During the ceremony, t? lo, Ru and Rtz each represent an alkyl group, an alkenyl group or an aryl group. however,
The total number of carbon atoms in the groups represented by Rla, Rn and R12 is 3 to 54.
本発明において、前記一般式［ＩＶ］のＲｈｏ、Ｒｕ及
びＲ１２で表わされるアルキル基は、直鎖もしくは分岐
のものであり、例えばブチル基、ペンチル基、ヘキシル
基、ヘプチル基、オクチル基。In the present invention, the alkyl groups represented by Rho, Ru, and R12 in the general formula [IV] are linear or branched, such as a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
ノニル基、デシル基、ウンデシル基、ドデシル基、トリ
デシル基、テトラデシル基、ペンタデシル基、ヘキサデ
シル基１（、ヘキサデシル基、（、オクタデシル基、ノ
ナデシル基等である。Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group 1 (, hexadecyl group, (, octadecyl group, nonadecyl group, etc.).
これらのアルキル基、アルケニル基及びアリール基は単
一もしくは複数の置換基を有していてもよい、好ましく
はＲｒａ、 Ｒｔｔ及びＲｔｚはアルキル基であり、
例えばｎ−ブチル基、２−エチルヘキシル基、ｎ−オク
チル基、３，５．５−）リメチルヘキシル基、ｎ−ノニ
ル基、ｎ−デシル基、５ｅａ−デシル基、５ｅｃ−ドデ
シル基、ｔ−オクチル基等が挙げられる。These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents, preferably Rra, Rtt and Rtz are alkyl groups,
For example, n-butyl group, 2-ethylhexyl group, n-octyl group, 3,5.5-)limethylhexyl group, n-nonyl group, n-decyl group, 5ea-decyl group, 5ec-dodecyl group, t-octyl group. Examples include groups.
アルケニル基としてはエチレン基、アリル基、ブテン基
等が挙げられ、またアリール基としてはフェニル基、ト
リル基、キシリル基等が挙げられる。Examples of the alkenyl group include ethylene group, allyl group, and butene group, and examples of the aryl group include phenyl group, tolyl group, and xylyl group.
以下に本発明に係る誘電率３．５以上の高沸点有機溶媒
の具体例を示すが本発明はこれらに限定されるものでは
ない。Specific examples of the high boiling point organic solvent having a dielectric constant of 3.5 or more according to the present invention are shown below, but the present invention is not limited thereto.
以下余白
〔例示化合物〕
Ａ’−ＩＡ’−２
Ａ’−３Ａ’−４
ＡＩ−５Ａ４−６
に−７、・＼、′−８
に−９Ｎ−１０
Ａ−１１Ａ−１２
Ａ １３ Ａ’ １４Ａ’
−１５＆−１６
ｉ（−１７Ａ’−１８
２Ｈ５
２Ｈ５
Ａ’−２０
（Ｊ１３にＨ３
Ａ−２１〕＼′−２２
Ａ’ −２３Ａ −２４
Ａ’−２５Ａ−２６
Ａ−２７Ａ−２８
Ａ′−２Ｑ Ａ’−３０Ａ’−３
１Ａ−３２
Ａ−３３Ａ’−３４
０Ｃ２Ｈ５
０Ｈ２０Ｈ（ＯＨ２） ３０Ｈ。The following margins [exemplary compounds] A'-IA'-2 A'-3A'-4 AI-5A4-6 ni-7, \,'-8 ni-9N-10 A-11A-12 A 13 A' 14A '
-15 & -16 i (-17A'-18 2H5 2H5 A'-20 (H3 A-21 to J13)\'-22 A' -23A -24 A'-25A-26 A-27A-28 A'-2Q A'-30A'-3
1A-32 A-33A'-34 0C2H5 0H20H (OH2) 30H.
２Ｈ５
Ａ’ −３５八′−３６
０＝Ｐ−ＯＣ８Ｈ，９（ｎ） Ｏ＝Ｐ −０−
０，、ｌ−１□３（ｉ）０ ０ｇＨ，ｇ（ｎ）
ＯＣ１１Ｈ２３（ｔ
）Ａ−３７Ａ’−３８
０”Ｐ ０−Ｃ４ｏＨ２１（ｉ） ０＝Ｐ
０−０１２Ｈ２５（ｉ）Ｏ−０１ｏＨ２１（ｉ）
０ ０＋２１■ｚｓ（１）Ａ’−３９
０−（３，ｏＨ２１（ｎ）
０＝Ｐ−０−Ｃ１１Ｈ２３（ｎ）
ｏ−ｃ１ｏＨ２、（ｎ）
本発明に係る話電車３．５以上である高廓点有機溶媒と
しては、上記の溶媒の他に、例えばマロン酸ジエチル、
マレイン酪ジエチル、γ−ブチロラクトン、安息香酸メ
チル、ベンジルアルコール。2H5 A'-358'-36 0=P-OC8H,9(n) O=P -0-
0,,l-1□3(i)0 0gH,g(n)
OC11H23(t
)A-37A'-38 0"P 0-C4oH21(i) 0=P
0-012H25(i)O-01oH21(i)
0 0+21■zs(1)A'-39 0-(3,oH21(n) 0=P-0-C11H23(n) o-c1oH2,(n) In addition to the above-mentioned solvents, for example, diethyl malonate,
Diethyl malein butyrolactone, γ-butyrolactone, methyl benzoate, benzyl alcohol.
ｌ−オクタノール等を挙げることができる。Examples include l-octanol and the like.
本発明に係るこれらの高柳点有機溶媒は１例えば酢酸エ
チル等の如き公知の低沸点有機溶媒と併用することもで
きる。These high-point organic solvents according to the present invention can also be used in combination with known low-boiling point organic solvents such as ethyl acetate.
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−浴漂白定着液により、処理することを意味
するが、本発明の効果をより良好に奏するのは、−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-fix solution, but the effect of the present invention is better achieved when a -bath bleach-fix treatment 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は、漂白剤として有機酸第２鉄錯
塩（Ａ）又は（Ｂ）が含有される。The bleach-fix solution of the present invention contains an organic acid ferric complex salt (A) or (B) as a bleaching agent.
有機酸第２鉄錯塩（Ａ）は上記１７種のうちから任意に
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。As the organic acid ferric complex salt (A), one type can be arbitrarily selected from the above 17 types, and two or more types can also be used in combination as necessary.
′４４機酸第２鉄錯塩（Ａ）の上記１７種の゛化合物の
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 above 17 kinds of compounds of the ferric acid complex salt (A), the following are particularly preferred.
（Ｉ）ジエチレントリアミン五酢酸第２＃錯塩（ＩＩ）
シクロヘキサンジアミン四酩酊第ジ鉄錯塩（ｍ）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１ｉ
Ｘ（Ｂ）は酸化還元電位により規制された複数の有４２
酸ｆｆ１２鉄錯塩群で、これらのうちから任意にｉＭｌ
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。(I) Diethylenetriaminepentaacetic acid #2 complex salt (II)
Cyclohexanediamine tetradrunk ferric complex salt (m) Triethylenetetramine hexaacetic acid ferric complex salt Organic acid ferric complex 1i
X(B) has multiple atoms regulated by redox potential 42
In the group of acid ff12 iron complex salts, iMl can be arbitrarily selected from among these.
These can be selected and used, and two or more types can also be used in combination if necessary.
本発明においてアミノポリカルボン酸等の有機酸第２鉄
錯塩の；！ｉ！ｉ準溶液の酸化還元電位は基準溶滴を２
５°Ｃ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Ｊｉｌｔ
定したものである。In the present invention, ferric complex salts of organic acids such as aminopolycarboxylic acids;! i! The redox potential of the i quasi-solution is 2
Measurements were made at 5°C using a platinum electrode using an ordinary electrometer, and a calomel electrode was used as the reference electrode.
It has been established.
アミノポリカルボン酪等の有機酸第２鉄錯塩の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。しかしながら本発明の漂白定着基準溶液で４
１１定したときに広いｐ）Ｉ領域に亘って酸化還元電位
の差が少ないアミノポリカルボ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、駕くべき発見であった。Regarding the relationship between pH and potential of organic acid ferric complex salts such as aminopolycarbonyl butylene, data for ferric complex salts alone are known. However, with the bleach-fixing standard solution of the present invention,
It is completely unknown that the favorable effects of the present invention are exhibited only in organic acids such as aminopolycarboxylic acids, which have a small difference in redox potential over a wide p)I region when It was a remarkable discovery.
本発明の範囲の酸化還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。Specific examples of organic acid complex salts such as aminopolycarboxylic acids having a redox potential within the scope of the present invention include, but are not limited to, the following.
［有機酸第２鉄錯塩（Ａ）コ
（１）ジエチレントリアミン五酩酊第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は第２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ｔｉｘ） 、ナトリウム塩、カリウム塩、すチウム塩
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ＪｉＸ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ＩＪＩ当り０．０１モル以上で使用でき、好まし
くは０．０５〜０．６モルで使用される。なお、補充液
においてはＧ４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。[Organic acid ferric complex salt (A) (1) diethylenetriamine penta-drunk ferric complex salt (2) diethylenetriamine pentamethylene phosphonic 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 Hexamethylene phosphone is a ferric complex salt The ferric complex salt of an organic acid according to the present invention is a free acid (hydrogen tix), an alkali metal salt such as a sodium salt, a potassium salt, a stium salt, or an ammonium salt. , or water-soluble amine salts such as triethanolamine salts, preferably potassium salts, sodium salts and ammonium JiX. 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. For example,
It can be used in an amount of 0.01 mol or more per working solution IJI, preferably 0.05 to 0.6 mol. In addition, in order to reduce G4 replenishment, it is desirable to use the replenisher in a highly concentrated form with the highest solubility.
本発明の漂白定着液には一ヒ記有ＰＬ酸第２鉄錯塩以外
に前記一般式［１１及び／又は一般式［ＩＩ ］で表わ
される化合物が含有せしめられる。The bleach-fix solution of the present invention contains a compound represented by the above general formula [11] and/or general formula [II] in addition to the PL acid ferric complex salt described above.
本発明に係わる一般式（ｊ」で表わされる化合物の中で
本発明において好ましく用いられる具体的例示化合物を
以下に示すがこれらに限定されるものではない。Among the compounds represented by the general formula (j) according to the present invention, specific exemplary compounds preferably used in the present invention are shown below, but the invention is not limited thereto.
０ＯＨ
ＯＨＵｕｕＭ
本発明に係わる一般式（ＩＩ）で表わされる化合物の中
で、本発明において好まし、く用いられる具体的例示化
合物を以下に示すが、これらに限定されるものではない
。0OH OHUuuM Among the compounds represented by the general formula (II) according to the present invention, specific exemplary compounds that are preferably and often used in the present invention are shown below, but the compounds are not limited thereto.
Ｎｌ（００（：！Ｉ（、Ｂｔ６ｃｏｏＨ０Ｈ３
Ｂ−１９Ｃｏｏｌ（Ｂ−２２Ｃ００Ｈ
Ｃ３Ｈ７
以下余白
これら本発明に係る前記一般式［１］又［ＩＩ］で表わ
される化合物は、本発明の漂白能を有する処理液（漂白
定着＃ｆＺ ）中に０．１ｇ／文〜５０ｇ／文の範囲で
添加される際に本発明の効果を良好に奏し、さらに好ま
しくはＩｇ／ｌ〜１０ｇ／！；Ｌの範囲で用いる際に、
より良好な効果を奏する。Nl (00 (:! (Bleach-fixing #fZ) When added in the range of 0.1g/liter to 50g/liter, the effects of the present invention are exhibited well, and more preferably in the range of Ig/l to 10g/!L Occasionally,
Provides better effects.
本発明の漂白能を有する処理液は表面張力が５５ｄｙｎ
ｅ／ｃｍ以下であり、好ましくは５０ｄｙｎｅ／ａｍ以
下、最も好ましくは４０ｄｙｎｅ／ ｃｍ以下である。The treatment liquid having bleaching ability of the present invention has a surface tension of 55 dyn.
e/cm or less, preferably 50 dyne/am or less, most preferably 40 dyne/cm 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、１８８２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ｘｔ１
１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 solution with bleaching ability used in the treatment of the present invention is determined from "Analysis and Testing Methods for Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1882, Kodansha xt1 using the general measurement method described in
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／ ｃｒａ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そもよいし、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
面活性剤を感光材料中に含有させて本発明の漂白能を有
する処理液に溶出添加させてもよい。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/cra 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 prebath. It may also be dissolved and added to the treatment solution having bleaching ability according to the present invention.
本発明の界面活性剤の中でも、とりわけ本発明の効果に
対する点から下記一般式［Ｖ］〜［■］で示される化合
物が好ましく用いられる。Among the surfactants of the present invention, compounds represented by the following general formulas [V] to [■] are preferably used from the viewpoint of the effects of the present invention.
一般式［Ｖ］
Ｒ１３−ＯＨ−ＣＯＡ＋Ｒ＋！ｆ
夏
Ｒ１４−ＯＨ−Ｃ００Ｒｔｓ
式中、Ｒ’１３及びＲ１４のうち一方は水素原子、他方
は式−Ｓ０３ＭＣＭ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。 Ａ＋ は酩素原子
又は式−ＮＲ＋７− （Ｒ１７は水素原子又は炭素数１
〜８のアルキル基を表わす、）で表わされる基を表わす
。ＲＩＳ及びＲｌｇは、それぞれ炭素数４〜１６のアル
キル基を表わす。但し、 ＲＬＳ、 Ｒｔａ又はＲＩ７
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 [V] R13-OH-COA+R+! f Summer R14-OH-C00Rts In the formula, one of R'13 and R14 is a hydrogen atom, and the other represents a group represented by the formula -S03MCM represents a hydrogen atom or a -valent cation. A+ is a hydrogen atom or the formula -NR+7- (R17 is a hydrogen atom or a carbon number of 1
-8 represents an alkyl group, represents a group represented by ). RIS and Rlg each represent an alkyl group having 4 to 16 carbon atoms. However, RLS, Rta or RI7
The alkyl group represented by may be substituted with a fluorine atom.
一般式［ＶＩ］
Ａｚ −０−（Ｂ）ｆＬ−ｘ１
式中、Ａ２は一価有ａ！！基、例えば炭素数が８〜２０
、好ましくは６〜１２のアルキル基（例えば、ヘキシル
、ヘプチル、オクチル、ノニル、デシル、ウンデシル又
はドデシル等の各基）、又は炭素数が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。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。General formula [VI] Az -0-(B)fL-x1 In the formula, A2 is monovalent a! ! group, e.g. having 8 to 20 carbon atoms
, preferably an aryl group substituted with an alkyl group having 6 to 12 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), or an alkyl group having 3 to 20 carbon atoms, The substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butylpentyl, hexyl, heptyl, octyl,
Examples of the aryl group include phenyl, tolyl, xynyl, biphenyl, and naphthyl, with phenyl or tolyl being preferred. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions.
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、文は４〜５０の整数を表わすｍ Ｘｔは水素原子
、ＳＯ３Ｙ又はＰＯ３Ｙ ２を示し、Ｙ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。B represents ethylene oxide or propylene oxide, and the sentence represents an integer from 4 to 50. represents.
一般式［■］
式中−１Ｒ＋ａ 、 Ｒ１９、Ｒ２１１及びＲ２Ｌは
それぞれ水素原子、アルキル基、フェニル基を示すが、
Ｒｕ、 Ｒｔｓ、Ｒｚｏ及びＲ２１の炭素数の合計が３
〜５０である。 Ｘｚはハロゲン原子、水酸基、硫酸
基、炭酸基、硝酸基、酢は基、Ｐ−）ルエンスルホン酸
基等のアニオンを示ス。General formula [■] In the formula, -1R+a, R19, R211 and R2L each represent a hydrogen atom, an alkyl group, or a phenyl group,
The total number of carbon atoms in Ru, Rts, Rzo and R21 is 3
~50. Xz represents an anion such as a halogen atom, a hydroxyl group, a sulfuric acid group, a carbonic acid group, a nitric acid group, an acetic acid group, or a P-)luenesulfonic acid group.
一般式［ＶＩ［］
式中、Ｒ２２、Ｒ２２，Ｒ２４、及びＲ２５はそれぞれ
水素原子ヌはアルキル基を表わし、には一般式［Ｖ］
と同義である。ｎ及びｐはそれぞれ０又は１〜４の整数
を示し、 ｌ≦ｎ＋ｐ≦８を満足する値である。General formula [VI[] In the formula, R22, R22, R24, and R25 each represent a hydrogen atom and an alkyl group, and the general formula [V]
is synonymous with n and p each represent 0 or an integer from 1 to 4, and are values satisfying l≦n+p≦8.
以下に一般式［Ｖ］〜［■］で表わされる化合物の具体
例を挙げるがこれらに限定されるものではない。Specific examples of compounds represented by general formulas [V] to [■] are listed below, but the invention is not limited thereto.
以下余白
（一般式ＬＶ）で表わされる化合物）
（面 Ｃ２Ｈ５
（ｘ） Ｃｓ１□０００Ｃ！）１２＋０Ｆ２０Ｆ２）
３Ｈ薯
ｅＦｉｃＯＯＯＨ２＋ＣＦ２０Ｆ２） ３Ｈ？
０３Ｎａ
（ＸＤ （ｊＩＩ２Ｃ０００ＰＦ１７Ｃ１−１０００
０８Ｆ 、７
と０３：ＩＺ
０３Ｎａ
（一般式ＣＵＴ）で表わされる化合物）（１） Ｄ、
２１（□、ｏ（Ｃ２Ｈ４０）、ｏｔｌ（４） Ｃ３）（
１７０（０３Ｈ６０） ＋ｓＨ（：ｉｉ） Ｃ９Ｈ１
９０（０２１１４０）４ＳＯ３Ｎａ（＋ｖ） Ｃ１ｏ
Ｉ−１２１０（０２Ｈ４０）１５ＰＯ３Ｎａ２３Ｈ７
（一般式〔■〕で表わされる化合物）
ＣＨ３
ＣＨ３
２Ｈ５
Ｃ２ニー１５
ＣＨ３
ＣＨ３
ＣＨ。A compound represented by the blank below (general formula LV)) (face C2H5 (x) Cs1□000C!)12+0F20F2)
3H?FicOOOH2+CF20F2) 3H? 03Na (XD (jII2C000PF17C1-1000
08F, 7 and 03: IZ 03Na (compound represented by general formula CUT)) (1) D,
21(□, o(C2H40), otl(4) C3)(
170 (03H60) +sH (:ii) C9H1
90(021140)4SO3Na(+v) C1o
I-1210(02H40)15PO3Na23H7 (Compound represented by general formula [■]) CH3 CH3 2H5 C2ney15 CH3 CH3 CH.
ＣＨ３
ＣＨ３
（ＯＨ２０Ｈ２Ｏ−）−２Ｈ
（一般式（Ｖ’ｌ）で表わされる化合物）（４）
−〇３Ｈ，７
８０３Ｎａ
ＳＯｌＩＩ
ＳＯ３に
本発明のｔフ！白液及び漂白定着液は、ｐＨ０，２〜９
．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、望ましくは５５°Ｃ以下、最も好ましく
は４５°Ｃ以下で蒸発等を抑えて使用する。CH3 CH3 (OH20H2O-)-2H (compound represented by general formula (V'l)) (4)
-〇3H,7 803Na SOlII The t-fu of the present invention is added to SO3! White liquor and bleach-fix solution have a pH of 0.2 to 9.
．． 5, preferably 4 to 9, more preferably 5
．． 5 to 8.5. The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation and the like.
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。８分以内とすることにより本発明の有機酸第
２鉄錯塩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. By setting the heating time to within 8 minutes, the generation of stain due to the organic acid ferric complex salt of the present invention can be significantly suppressed.
本発明の漂白液は、前記の如き漂白剤としての有機酸第
２鉄錯塩、上記一般式［１１及び／又はｉｆ＞式［Ｉｔ
］で表わされる化合物及び界面活性剤とともに種々の
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、また硼酸塩、砂
酸塩、酢酸塩１次酸塩、燐酩塩等のｐｏ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
ホノカルホン酸、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 bleaching solution of the present invention comprises an organic acid ferric complex salt as a bleaching agent as described above, the general formula [11 and/or if> formula [It
] Various additives can be included together with the compound represented by and the surfactant. 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. , sand salts, primary acetate salts, PO buffers such as phosphorous salts, solubilizers such as triethanolamine, acetylacetone, phosphonocarphonic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, 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ｔ１）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 halogen compound such as potassium bromide with a multi-t1) content.
前記のハロゲン化合物としては臭化カリウムの他に塩化
水素酸、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
化アンモニウム尊も使用することができる。In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide can also be used.
本発明の漂白定着液に含ませるハロゲン化銀足首剤とし
ては通常の宝刀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、例えばチオ硫
酸カリウム、チオ硫酸ナトリウム、チオ硫酸アンモニウ
ムの如きチオ硫酸用、チオシアン酪カリウム、チオシア
ン酸ナトリウム、チオシアン盾アンモニウムの如きチオ
シアン酸塩、チオ尿素、チオエーテル、高濃度の臭化物
、ヨウ化物等がその代表的なものである。これらの定着
剤は５ｇ／ｉ以上、好ましくは５０ｇ／ １以上、より
好ましくは７０ｇ／ ｆＬ以上溶解できる範囲の量で使
用できる。Silver halide additives to be included in the bleach-fixing solution of the present invention include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as butypotassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount that can dissolve at least 5 g/i, preferably at least 50 g/fL, more preferably at least 70 g/fL.
なお本発明の漂白定着液には前記漂白液の場合と同様に
、硼酸、硼砂、水酸化ナトリウム、水酸化カリウム、炭
酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、亜炭
酸カリウム、酢酸、酢酸ナトリウム、水酸化アンモニウ
ム等の各種の塩からなるｐＨ１街剤を単独であるいは２
種以上組合せて含有せしめることができる。さらにまた
、各種の蛍光増白剤や消泡剤あるいは防ぽい剤を含有せ
しめることもできる。またヒドロキシルアミン、ヒドラ
ジン、並値酢塩、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、有機ホスホン酢、
オキシカルボンＱＬ ポリカルボン酸、ジカルボン酸
及びアミノポリカルボン酸等の有機キレート剤あるいは
ニトロアルコール、硝酸塩等の安定剤、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。Note that the bleach-fix solution of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium subcarbonate, acetic acid, sodium acetate, and water, as in the case of the bleach solution described above. A pH 1 pH stabilizer consisting of various salts such as ammonium oxide may be used alone or at pH 2.
A combination of two or more types can be contained. Furthermore, various optical brighteners, antifoaming agents, or antifoaming agents can be contained. In addition, preservatives such as hydroxylamine, hydrazine, average acetate, isomeric bisulfite, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic vinegar,
Oxycarboxylic QL Organic chelating agents such as polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, and other additives. , methanol, dimethylformamide,
An organic solvent such as dimethyl sulfoxide can 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１１り、中和、黒白現
像１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。々ｆ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), stabilization processing may be performed without washing with water, or washing may be performed and stabilization processing may be performed after that.In addition to the above steps, hardening, neutralization, black and white development may be performed. Known auxiliary steps such as one inversion and a small amount of water washing may be added as necessary. Typical specific examples of the most desirable treatment methods include the following steps.
（１）発色現像→漂前液７？→水洗
（２）発色現像→漂白定着→少量水洗→水洗（３）発色
現像→漂白定着→水洗→安定（４）発色現像→漂白定着
→安定
（５）発色現像→漂白定着→第１安定→ｆ：ＪＪ２安定
（６）発色現像後直洗（又は安定）→漂白定着→水洗（
又は安定）
（７）発色現像→停止→漂前液着→水洗（又は安定）（
８）発色現像→漂白→水洗→定着→水洗→安定（９）発
色現像→漂白→足首峠水洗→安定（１０）発色現像→漂
白→定着→第１安定→第２安定（１１）発色現像→漂白
→少量水洗→定着→少量水洗→水洗→安定
（１２）発色現像→少量水洗→漂白呻少量水洗→定着→
少量水洗→水洗→安定
（１３）発色現像→停止→漂白→少量水洗→足首呻少量
水洗→水洗→安定
（１４）黒白現像→水洗（又は安定）→反転→発色現像
→漂白→定着→水洗（又は省略）→安定（１５）前＆’
ｉ ＨＱ→中和→黒白現像→停止→発色現像→漂白→定
若足首水洗（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 → Bleach solution 7? →Water wash (2) Color development → Bleach-fix → Small amount of water wash → Water wash (3) Color development → Bleach-fix → Water wash → Stable (4) Color development → Bleach-fix → Stable (5) Color development → Bleach-fix → First stabilization → f: JJ2 stable (6) Direct washing after color development (or stable) → bleach fixing → washing with water (
(or stable) (7) Color development → stop → bleaching liquid → washing with water (or stable) (
8) Color development → bleaching → washing with water → fixing → washing with water → stable (9) color development → bleaching → washing with water at Ankle Pass → stable (10) color development → bleaching → fixing → first stable → second stable (11) color development → Bleach → Wash with a small amount of water → Fix → Wash with a small amount of water → Wash with water → Stable (12) Color development → Wash with a small amount of water → Bleach, wash with a small amount of water → Fix →
Wash with a small amount of water → Wash with water → Stabilize (13) Color development → Stop → Bleach → Wash with a small amount of water → Wash ankles with a small amount of water → Wash with water → Stable (14) Black and white development → Wash with water (or stabilize) → Invert → Color development → Bleach → Fix → Wash with water ( or omitted) → stable (15) before &'
i HQ → Neutralization → Black and white development → Stop → Color development → Bleaching → Constant young ankle washing (or omitted) → Stability Among these processing steps, the effects of the present invention are more noticeable, 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ＦＡ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
ト剤とともに金属錯塩と成した後。It is preferable to add various inorganic gold FA salts to the bleach-fix solution of the present invention. After forming these inorganic metal salts into metal complex salts with various chelating agents.
添加することも好ましい方法である。Addition is also a preferred method.
本発明の醒；自足前液には本発明外のキレート剤及び／
又はその第２鉄鎖１１１を添加することが好ましい、し
かじながら本発明以外の第２鉄錯塩は本発明の有機酸第
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。According to the present invention, a chelating agent other than the present invention and/or
or its ferric chain 111 is preferably added; however, the ferric complex salt other than the present invention is used in an amount of 0.45 mol% or less when the organic acid ferric complex salt of the present invention is 1 mol%. It is preferable.
本発明の処理に用いられる黒白現像液は通常知られてい
るカラー写真感光材料の処理に用いられる黒白第１現像
液と呼ばれるもの、もしくは黒白写真感光材料の処理に
用いられるものであり、一般に黒白現像液に添加される
各種の添加剤を含有せしめることができる。The black-and-white developer used in the processing of the present invention is a so-called black-and-white first developer used in the processing of color photographic materials, or a black-and-white developer used in the processing of black-and-white photographic materials. Various additives added to the developer can be included.
代表的な添加剤としてはｌ−フェニル−３−ピラゾリド
ン、メトール及びハイドロキノンのような現像主薬、亜
硫酸塩のような保恒剤、水耐化ナトリウム、炭酸ナトリ
ウム、炭酸カリウム等のアルカリからなる促進剤、臭化
カリウムや２−メチルベンツイミダゾール、メチルベン
ツチアゾール等の無機性、もしくは有機性の抑制剤、ポ
リリン耐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。Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators made of alkalis such as water-resistant sodium, sodium carbonate, and potassium carbonate. , inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphorus salt-resistant, surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds, etc. can be mentioned.
本発明の漂白能を有する処理液による処理の前に使用さ
れる発色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
剤はアミンフェノール系及び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、例えば塩酸塩または硫酸塩の形で
使用される。また、これらの化合物は、一般に発色現像
液１ｆＬについて約０．１ｇ〜約３０ｇの儂度、更に好
ましくはＩ！；Ｌについて約１ｇ〜約１５ｇの濃度で使
用する。The aromatic primary amine color developing agent used in the color developing solution 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 amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a strength of about 0.1 g to about 30 g per 1 fL of color developer, more preferably I! ; Used at a concentration of about 1 g to about 15 g per L.
アミノフェノール系現像剤としては１例えば〇−アミノ
フェノール、ｐ−７ミノフエノール、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 aminophenol-based developers include 1, for example, 〇-aminophenol, p-7 minophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.
特に有用なｐ−フェニレンジアミン系発色現像剤は少な
くとも１つの水溶性を有するアミノ基を有した芳香族第
１級アミン発色現像剤であり、特に好ましくは下記一般
式［ＩＫ］で示される化合物である。A particularly useful p-phenylenediamine color developer is an aromatic primary amine color developer having at least one water-soluble amino group, and particularly preferably a compound represented by the following general formula [IK]. be.
一般式［ＩＸ］
式中、Ｒ２Ｇは水素原子、ハロゲン原子又はアルキル基
を表わし、このアルキル基は直鎖又は分岐の炭素数１〜
５のアルキル基を表わし、置換基を有していてもよい、
Ｒ２７及びＲ２１１は水素原子又はアルキル基又はアリ
ール基を表わすが、これらの基は置換基を有していても
よく、アルキル基の場合アリール基が置換したアルキル
基が好ましい。General formula [IX] In the formula, R2G represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group is a straight-chain or branched alkyl group having 1 to 1 carbon atoms.
5 represents an alkyl group, which may have a substituent,
R27 and R211 represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable.
そしてＲ２？及びＲ２１の少なくとも１つは水酸基、カ
ルボン酸基、スルホン酸基、アミノ基、スルホンアミド
基等の水溶性基が置換したアルキル基又は−（−＋Ｃ）
ｌｚ％；−０雪７Ｒｚツである。このアルキル基は更に
置換基を有していてもよい。And R2? and at least one of R21 is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or -(-+C)
lz%; -0 snow 7Rztsu. This alkyl group may further have a substituent.
なお、 Ｒ２１は水素原子又はアルキル基を表わし、
このアルキル基としては直鎖又は分岐の炭素数１〜５の
アルキル基を表わし、を及びｒは１〜５の整数を表わす
。In addition, R21 represents a hydrogen atom or an alkyl group,
The alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 5.
次に前記一般式［ＩＸ］で示される化合物の代表的具体
例を挙げるが、これらに限定されるものではない。Next, typical examples of the compound represented by the general formula [IX] will be listed, but the invention is not limited thereto.
〔例示化合′１！）〕
（Ｅ−１）
（Ｅ−２）
Ｈ２
（Ｅ−３）
Ｈ２
（Ｅ−４）
Ｎ１（２
（ＩＧ−５）
Ｈ２
（Ｅ−６）
ｌｌ２
（Ｅ−７）
Ｎ１−１□
（Ｘ；−８）
Ｈ２
（Ｅ−９）
Ｎｉ１２
（Ｅ−１０）
Ｈ２
（Ｅ−１１）
Ｈ２
（Ｅ−１２）
Ｈ２
（Ｅ−１３）
Ｈ２
（Ｅ−１４）
Ｈ２
（Ｅ−１５）
トＩＨ２
（Ｅ−１６）
ＮＨ□
これら一般式［■］で示されるｐ−フェニレンジアミン
誘導体は有機酸及び無機酸の塩として用いることができ
１例えば塩酸塩、硫酸塩、燐酸塩、Ｐ４ルエンスルホン
酸塩、亜硫酸塩、シュウ酸塩、ベンゼンジスルホン酸塩
等を用いることができる。[Exemplary compound '1! )] (E-1) (E-2) H2 (E-3) H2 (E-4) N1(2 (IG-5) H2 (E-6) ll2 (E-7) N1-1□ (X ;-8) H2 (E-9) Ni12 (E-10) H2 (E-11) H2 (E-12) H2 (E-13) H2 (E-14) H2 (E-15) IH2 (E -16) NH□ These p-phenylenediamine derivatives represented by the general formula [■] can be used as salts of organic acids and inorganic acids. For example, hydrochloride, sulfate, phosphate, P4 luenesulfonate, sulfite. Salts, oxalates, benzenedisulfonates, etc. can be used.
本発明において、これら一般式［ＩＸ］で示され６Ｐ−
フェニレンジアミン誘導体の中でもＲ２７及ヒ／又はＲ
２１１が一＋＋ＣＨｚ→−０＋−Ｒ２９（ｔ 、 ｒ及
び七ｒ
Ｒ２９は前記と同義。）で示されるものである際に、と
りわけ本発明の効果を良好に奏する。In the present invention, 6P-
Among the phenylenediamine derivatives, R27 and/or R
The effects of the present invention are particularly effective when 211 is 1++CHz→-0+-R29 (t, r, and 7rR29 have the same meanings as above).
前記ｐ−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 p-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
ている秤々の成分１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、アルカリ全１工
亜硫酸塩、アルカリ金Ｂ重亜硫酸塩、アルカリ金属チオ
シアン酸塩、アルカリ金属ハロゲン化物、ベンジルアル
コール、ジエチレントリアミン五酢酸、１−ヒドロキシ
エチリデン−１，１−ジホスホン酸等の水軟化剤及び濃
厚化剤等を任意に含宥することができる。In addition to the aromatic primary amine color developer, the alkaline color developer used before the treatment with the processing solution having bleaching ability of the present invention further contains an amount of the amount normally added to the color developer. Ingredients 1 For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkaline total sulfites, alkali gold B bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, Water softeners and thickeners such as 1-hydroxyethylidene-1,1-diphosphonic acid can optionally be included.
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１ｆｌ〜約１３である。The pH of this color developer is usually 7 or higher, most commonly about 1 fl to about 13.
本発明の漂白能を有する処理液を適用できるハロゲン化
銀ガラ−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２，５９２，２４３号、同２．５ｉ３０．
９７０号参照）のものであってもよい、また発色剤は当
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、マゼンタ発色剤としては、活性メ
チレン基を有する５−ピラゾロン環を骨格構造として有
するもの、イエロー発色剤としては、活性メチレン鎖を
イアするベンゾイルアセドアニライド、ピへリルアセト
アニライドの如きアシルアセドアニライド構造のもの等
でカプリング位置に置換基を有するもの、有しないもの
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当是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、塩臭化銀、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
。ハロゲン化銀乳剤には、安定剤、硬ｎｇ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。The silver halide glass 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. 2,592,243, No. 2.5i30.
For example, the cyan coloring agent is based on naphthol or phenol structure, and indaniline is formed by coupling. Those that form pigments, magenta coloring agents include those having a 5-pyrazolone ring having an active methylene group as a backbone structure, and yellow coloring agents include benzoylacedoanilide and pyherylacetoanilide containing active methylene chains. Those having an acylacedoanilide structure, such as anilide, with or without a substituent at the coupling position can be used. Thus, as the coloring agent, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be used. Silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Any silver halide such as silver chloroiodobromide or a mixture thereof may be used. Protective colloids for these silver halides include natural products such as gelatin, as well as synthetically obtained colloids. A variety of materials can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, hardening agents, sensitizing dyes, and surfactants.
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。８にコロイド
銀分散層はフィルタ一層やハレーション防止層であって
もよく５さらに乳剤層中に分１我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４”９−４３２０１号、同４
５−１４８９０号、特開昭５１−８９７２２号及び芙国
特許１．０３２，８７１号等に記載の一般的な方法で合
成され、塗設される。The silver halide color photographic light-sensitive material according to the present invention preferably has a colloidal silver dispersion layer. 8. The colloidal silver dispersion layer may be a single filter layer or an antihalation layer.5 It may also be dispersed in an emulsion layer. How to make these colloidal silver dispersions is described in Japanese Patent Publication No. 43-1989. No. 27740, No. 4”9-43201, No. 4
5-14890, Japanese Patent Application Laid-Open No. 51-89722, Fukoku Patent No. 1.032,871, etc., and is synthesized and coated.
本発明に係わる漂白液及び漂白定着液は、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ｆｒｉ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２０ｍｇ／ｄｒｎ’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 solution and bleach-fixing solution according to the present invention include 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 color reversal papers, but especially silver iodobromide or silver chloroiodobromide containing 0.1 mol% or more of fri iodide. It is most suitable for processing high-sensitivity color photographic materials having a total coating silver amount of 20 mg/drn' 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 ｌ
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を総体
の銀量が１００ｃゴ当り８５ｍｇになるよう塗布した。Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and thereon 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. The layers were coated for a total silver content of 85 mg per 100 cm.
上記の乳剤層は沃化銀のモル％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は黄色カ
プラーとしてα−（４−ニトロフェノキシ）−α−ピバ
リルー５−〔γ−（２，４−ジ−ｔ−アミノフェノキシ
）ブチルアミド］−２−クロロアセトアニリドを用い、
緑感性ｌ＼ロゲン化銀乳剤層には、マゼンタカプラーと
して１−（２，４，６−トリクロロフェニル）−３−（
［α−（２，４−ジーし一アミルフェノキシ）−７セト
アミド］ベンズアミド）−３−ピラゾロン及び１−（２
，４，８−）リクロロフェニル）−３−（［α−（２，
４−ジ−ｔ−アミルフェノキシ）−アセトアミド］ベン
ズアミド） −４−（４−メトキシフェニルアゾ）−５
−ピラゾロンを用い、赤感性Ｉ＼ロゲン化銀乳剤層には
シアンカプラーとしてｌ−ヒドロキシ−Ｎ−（α−（２
，４−ｔ−アミルフェノキシ）ブチル）−２−ナフトア
ミドを用い、各乳剤層にはそれぞれ増感色素、硬膜剤等
の通常の添加剤を加えた。但し、高沸点溶媒として例示
化合物（Ａ’−２５） （誘電率７．５）を用いた。The above emulsion layer is made of silver iodobromide with a molar percentage of silver iodide of about 4.5%, and the blue-sensitive silver halide emulsion layer has a yellow coupler of α-(4-nitrophenoxy)-α. - pivalyl 5-[γ-(2,4-di-t-aminophenoxy)butyramide]-2-chloroacetanilide,
The green-sensitive l\silver halide emulsion layer contains 1-(2,4,6-trichlorophenyl)-3-( as a magenta coupler.
[α-(2,4-di-amylphenoxy)-7cetamido]benzamide)-3-pyrazolone and 1-(2
,4,8-)lichlorophenyl)-3-([α-(2,
4-di-t-amylphenoxy)-acetamido]benzamide) -4-(4-methoxyphenylazo)-5
- Pyrazolone was used as a cyan coupler in the red-sensitive I\silver halide emulsion layer, and l-hydroxy-N-(α-(2
, 4-t-amylphenoxy)butyl)-2-naphthamide, and conventional additives such as sensitizing dyes and hardeners were added to each emulsion layer. However, exemplified compound (A'-25) (dielectric constant 7.5) was used as a high boiling point solvent.
このようにして得られたハロゲン化銀カラーネガ感光材
料をフィルム試料（１）とし、さらに、この高沸点溶媒
（ｐ！ −２５）の代わりに、流動パラフィン（誘電率
２．２）を用いて同様なフィルム試料（２）を作成した
。The silver halide color negative light-sensitive material thus obtained was used as film sample (1), and the same procedure was carried out using liquid paraffin (dielectric constant 2.2) instead of this high boiling point solvent (p! -25). A film sample (2) was prepared.
これらの試お）を常法により露光を施した後、下記の処
理を行った。After exposing these samples in a conventional manner, the following treatments were performed.
処理工程 処理温度（”Ｏ） 処理時間１発色現像
３７．８ ３分１５秒２漂白定着
３７．８ 表１に記載３水 洗 ３０
〜３４ ２分４安 定 ３０〜３４
１分５乾 燥
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。Processing process Processing temperature (O) Processing time 1 color development 37.8 3 minutes 15 seconds 2 bleach fixing
37.8 Listed in Table 1 3Wash 30
~34 2 minutes 4 stable 30~34
Drying for 1 minute and 5 minutes 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亜硫酸ナト
リウム ２・Ｑｇヒドロキシルアミ
ンｇ、酸塩 ２．２８臭化カリウム
１・２ｇジエチレントリアミン五酢ｍ
２ 、 Ｏｇ水酸化ナトリウム
３．４ｇＮ−エチレン−Ｎ−β−ヒドロキシ
エチル−３−メチル−４−アミノアニリンａ ｍ、 塩
ａ −ｅ ｇ水を加えて１０１００Ｏに仕上げ、水酸化
ナトリウムにてｐＨＩＱ、（１８に調整した。[Color developer] Potassium carbonate 30g Sodium sulfite 2.Qg Hydroxylamine g, Acid acid 2.28 Potassium bromide
1.2g diethylenetriamine pentavinegar m
2, Og sodium hydroxide
3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline am, salt a-e g Water was added to adjust to 10100O, and pHIQ was adjusted to 18 with sodium hydroxide.
［漂白定着液］
有機酸第２鉄錯塩 ０．３１モルニト
リロトリ酢酸 ５．０ｇ亜硫酸
アンモニウム（５０％溶液） １０ｍ１チオ硫酸
アンモニウム（７０％溶液） ２００ｍｆＬ発色現像
液（上記） ｌ００ａｌ水を加えて１
０００＋ｏ！ｌに仕上げ、アンモニア水（２８％溶液）
にてｐＨ７，０に調整した。[Bleach-fix solution] Organic acid ferric complex salt 0.31 mol Nitrilotriacetic acid 5.0 g Ammonium sulfite (50% solution) 10 ml Ammonium thiosulfate (70% solution) 200 mfL color developer (above) Add 100 al water and 1
000+o! Finished with aqueous ammonia (28% solution)
The pH was adjusted to 7.0.
［安定液〕
ホルマリン（３５％水溶液） ７．０ｍｍ氷
水加えて１０１００Ｏに仕上げる。[Stabilizing solution] Formalin (35% aqueous solution) Add 7.0 mm of ice water and adjust to 10100O.
但し、上記漂白定着液中に有機酸第２鉄錯塩を下記表１
に示す各第２鉄錯塩を用い、更に前記一般式［Ｉ］及び
／又は［ＩＩ ］で示され化合物を５ｇ／ｌ及び本発明
に係る界面活性剤を下記表１に示す組合せで添加して用
いた。However, the organic acid ferric complex salt contained in the above bleach-fix solution as shown in Table 1 below.
Using each of the ferric complex salts shown in Table 1 below, further adding 5 g/l of the compound represented by the general formula [I] and/or [II] and the surfactant according to the present invention in the combination shown in Table 1 below. Using.
フィルム試料について、フィルム試料中の残留銀星が０
．５ｒｎｇ／ｄｍ’になるまでの漂白足前処理工程の時
間を求めた。更に処理後のフィルム試料を６０℃、湿度
８０％ＲＨの状態で２週間保存し、保存後の未露光部の
イエロースティンを濃度計にて測定した。その結果を表
１にまとめて示す。Regarding the film sample, the residual silver star in the film sample is 0.
．． The time required for the bleaching foot pretreatment process to reach 5rng/dm' was determined. Further, the processed film sample was stored for two weeks at 60° C. and 80% RH, and the yellow stain in the unexposed area after storage was measured using a densitometer. The results are summarized in Table 1.
以下余白
（注１）表中、 ＥＤＴＡ ｅＦｅ、 ＤＴＰＡ ＠Ｆ
ｅ、ＣｙＤＴＡ ＠ＦｅＴＴ）ＩＡ −Ｆｅ、 ＧＥ
ＤＴＡ １１Ｆｅはそれぞれ、次のも（７）（７）略号
である。Below margin (Note 1) In the table, EDTA eFe, DTPA @F
e, CyDTA @FeTT)IA-Fe, GE
DTA 11Fe is the following abbreviation (7) (7), respectively.
ＥＤＴＡ−Ｆｅ ；エチレンジアミン四酢酸＃（ｍ）
アンモニウム。以下同じ。EDTA-Fe; ethylenediaminetetraacetic acid #(m)
Ammonium. same as below.
ＤＴＰＡａＦｅ ；ジエチレントリアミン五酢な鉄（
Ｉｌｌ）アンモニウム、以下同じ。DTPAaFe; diethylenetriaminepentaacetic iron (
Ill) Ammonium, the same shall apply hereinafter.
ＧｙＤＴＡ ＠ Ｆｅ ； １．２−シクロへ午すンジ
アミン四酢酸＃、（ＩＩＩ）アンモニウム、以下同じ。GyDTA@Fe; 1.2-cyclodiaminetetraacetic acid #, (III) ammonium, the same hereinafter.
ＴＴＨＡ・Ｆｅ；トリエチレンテトラミン六酢酷鉄（Ｉ
ＩＩ）アンモニウム、以下同じ。TTHA・Fe; triethylenetetraminehexaacetic iron (I
II) Ammonium, the same shall apply hereinafter.
ＧＥＤＴＡ １ｌＦｅ ；グリコールエーテルジアミン
四酢酸鉄（ＩＩＩ）アンモニウム、以下同じ。GEDTA 1lFe; iron (III) ammonium glycol ether diamine tetraacetate, the same hereinafter.
上記表１より明らかなように、有機酸第２鉄錯塩が従来
より用いられているＥＤＴＡ−Ｆｅの如きものでは脱銀
性能は十分ではなく、さらに本発明のＩＩＴＰＡ＊Ｆｅ
を単独で用いてもかなりの脱銀性能が得られるが、長期
保存時のイエロースティンが不十分である。また漂白定
着液中に前記一般式［１１及び／又は［ＩＩ ］の化合
物及び本発明の界面活性剤が組合せて使用されない場合
は、本発明の効果を達成するのが難しく、感光材料中に
、一定の誘電率を与える高沸点溶媒を用い、かつｔ７（
内定着液中に本発明の有機酸第２鉄錯塩、一般式［ＩＩ
及び／又は［Ｉｌｌの化合物及び表面張力５５ｄｙｎｅ
／ｃｍ以下を与える界面活性剤を組合せて使用した場合
にのみ駕〈べきことに十分な脱銀性能を得ることができ
、かつ保存後のイエロースティンが良好なることが判る
。As is clear from Table 1 above, the desilvering performance is not sufficient with conventionally used organic acid ferric complex salts such as EDTA-Fe;
Even when used alone, considerable desilvering performance can be obtained, but the yellow stain during long-term storage is insufficient. Furthermore, if the compound of general formula [11 and/or [II] and the surfactant of the present invention are not used in combination in the bleach-fix solution, it is difficult to achieve the effects of the present invention, and A high boiling point solvent giving a constant dielectric constant is used, and t7(
The organic acid ferric complex salt of the present invention, general formula [II
and/or [Ill compound and surface tension 55 dyne
It can be seen that sufficient desilvering performance can be obtained and the yellow stain after storage is good only when a combination of surfactants that give a silver density of /cm or less are used.
実施例 ２
実施例１．実験９のＧＥＤＴＡ −ＦｅをＮ−メチルイ
ミノジ計酸鉄（ＩＩＩ）アンモニウム塩、１．２−ジア
ミノプロパン四酢酸鉄（ＩＩＩ）アンモニウム塩及びジ
エチレントリアミン五メチレンホスホン酸鉄（ｍ）アン
モニウム塩にそれぞれ代えて実施例１（実験９）と同様
の実験を行ったところ、実験９とほぼ同じような結果を
得た。Example 2 Example 1. Experiment 9 was carried out by replacing GEDTA-Fe with N-methyliminodicate iron(III) ammonium salt, 1,2-diaminopropanetetraacetic acid iron(III) ammonium salt, and diethylenetriaminepentamethylenephosphonate iron(m) ammonium salt. When an experiment similar to Example 1 (Experiment 9) was conducted, almost the same results as Experiment 9 were obtained.
実施例 ３
実施例１の一般式［ＩＩ及び／又は［■］の化合物（Ａ
−３）をそれぞれ（Ａ−４）、ＣＢ−６）、 （Ｂ−
１６）、（Ｂ−２０）に代えて同様の実験を行ったとこ
ろ、実施例１と同様の結果を得た。Example 3 Compound of general formula [II and/or [■] of Example 1 (A
-3) respectively (A-4), CB-6), (B-
16) and (B-20), the same results as in Example 1 were obtained.
実施例 ４
実施例１の界面活性剤Ｖ −’（ＸＩ［）をそれぞれＶ
−（Ｖ）、■−〇ＣＩ） 、■−（Ｘｌｆｆ） 、 Ｖ
ｌｌｒ−（ＩＩ）に代えて同様な実験を行ったところ、
実施例１と同様の結果を得た。Example 4 The surfactant V −'(XI[) of Example 1 was replaced with V
-(V), ■-○CI), ■-(Xlff), V
When a similar experiment was performed in place of llr-(II),
The same results as in Example 1 were obtained.
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、該ハロゲン
化銀カラー写真感光材料が誘電率３．５以上を有する高
沸点有機溶媒を少なくとも１つ含有し、かつ前記漂白能
を有する処理液が、漂白剤として下記第２鉄錯塩群から
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１００ｍＶ以内である有
機酸第２鉄錯塩の少なくとも１つ、及び下記一般式［
I ］で示される化合物及び１又は下記一般式［II］で示
される化合物の少なくとも１つを含有し、かつ表面張力
が５５ｄｙｎｅ／ｃｍ以下の該漂白能を有する処理液で
処理することを特徴とするハロゲン化銀カラー写真感光
材料の処理方法。 ［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。 一般式［ I ］ ▲数式、化学式、表等があります▼ 式中、Ｒ＿１、Ｒ＿２、Ｒ＿３はそれぞれ水素原子、置
換基を有してもよいアルキル基、アルケニル基、水酸基
、ハロゲン原子、アミノ基、アミド基、又はメルカプト
基を表わす。Ｍは水素原子又は一価のカチオン基を表わ
す。ｍは０、１又は２の整数であり、ｎは１、２又は３
の整数である。 一般式［II］ ▲数式、化学式、表等があります▼ 式中、Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ＿７はそれぞれ水
素原子、置換基を有してもよいアルキル基、アルケニル
基、水酸基、アミノ基、アミド基、スルホン酸基、アル
コキシ基、ニトロ基、ハロゲン基、メルカプト基又はカ
ルボキシ基を表わす。Ｍは一般式［ I ］と同義である
。 （２）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項記載のハロゲン化
銀カラー写真感光材料の処理方法。 （３）誘電率３．５以上を有する高沸点有機溶媒が下記
一般式［III］又は［IV］示される化合物であることを
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。 一般式［III］ ▲数式、化学式、表等があります▼ 式中、Ｒ＿８及びＲ＿９はそれぞれアルキル基、アルケ
ニル基又はアリール基を表わす。 一般式［IV］ ▲数式、化学式、表等があります▼ 式中、Ｒ＿１＿０、Ｒ＿１＿１及びＲ＿１＿２はそれぞ
れアルキル基、アルケニル基又はアリール基を表わす。 （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 a silver halide color photographic material after imagewise exposure and treating it with a processing solution having bleaching ability, comprising: The color photographic light-sensitive material contains at least one high-boiling point organic solvent having a dielectric constant of 3.5 or more, and the processing liquid having bleaching ability contains organic acid ferric acid selected from the group of ferric complex salts below as a bleaching agent. The pH of the following reference solution of at least one iron complex salt (A) or an organic acid ferric complex salt is 5.0 to 9.
0 and at least one organic acid ferric complex salt having a redox potential difference of 100 mV or less, and the following general formula [
I] and at least one of the compounds represented by 1 or the following general formula [II], and has a surface tension of 55 dyne/cm or less and has a bleaching ability. A method for processing silver halide color photographic materials. [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. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, and R_3 are each a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group, a hydroxyl group, a halogen atom, an amino group, Represents an amide group or a mercapto group. M represents a hydrogen atom or a monovalent cation group. m is an integer of 0, 1 or 2, and n is 1, 2 or 3
is an integer. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_4, R_5, R_6, and R_7 are each a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group, a hydroxyl group, an amino group, an amide group, etc. group, sulfonic acid group, alkoxy group, nitro group, halogen group, mercapto group or carboxy group. M has the same meaning as the general formula [I]. (2) Claim 1, characterized in that the organic acid ferric complex salt is diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. A method for processing the silver halide color photographic light-sensitive material described above. (3) The halogen according to claim 1 or 2, wherein the high boiling point organic solvent having a dielectric constant of 3.5 or more is a compound represented by the following general formula [III] or [IV]. Processing method for silver chemical color photographic materials. General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_8 and R_9 each represent an alkyl group, an alkenyl group, or an aryl group. General formula [IV] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_0, R_1_1 and R_1_2 each represent an alkyl group, an alkenyl group or an aryl group. (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 |
|---|---|---|---|
| JP17171984A JPS6150140A (en) | 1984-08-19 | 1984-08-19 | Treatment of silver halide color photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17171984A JPS6150140A (en) | 1984-08-19 | 1984-08-19 | Treatment of silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6150140A true JPS6150140A (en) | 1986-03-12 |
Family
ID=15928399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17171984A Pending JPS6150140A (en) | 1984-08-19 | 1984-08-19 | Treatment of silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6150140A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6462643A (en) * | 1987-09-03 | 1989-03-09 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material |
| JPH03150563A (en) * | 1989-11-08 | 1991-06-26 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
| US5250402A (en) * | 1991-06-26 | 1993-10-05 | Fuji Photo Film Co., Ltd. | Photographic bleaching composition and a processing method therewith |
| US5460924A (en) * | 1992-12-14 | 1995-10-24 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
| US5550009A (en) * | 1995-04-17 | 1996-08-27 | Eastman Kodak Company | Stabilized peroxide bleaching solutions and their use for processing of photographic elements |
| EP0747765A1 (en) * | 1995-05-31 | 1996-12-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material |
| EP0750226A1 (en) * | 1995-06-09 | 1996-12-27 | Fuji Photo Film Co., Ltd. | A method for processing a silver halide color photographic light-sensitive material |
| EP0859276A1 (en) * | 1997-02-13 | 1998-08-19 | Eastman Kodak Company | Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition |
| JP2008144419A (en) * | 2006-12-07 | 2008-06-26 | Free Kogyo Kk | Structure of manhole |
| JP2008291563A (en) * | 2007-05-25 | 2008-12-04 | Hanex Co Ltd | Floating preventive manhole bottom slab, and prefabricated manhole constituted of floating preventive manhole bottom slab |
-
1984
- 1984-08-19 JP JP17171984A patent/JPS6150140A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6462643A (en) * | 1987-09-03 | 1989-03-09 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material |
| JPH03150563A (en) * | 1989-11-08 | 1991-06-26 | Fuji Photo Film Co Ltd | Method for processing silver halide color photographic sensitive material |
| US5250402A (en) * | 1991-06-26 | 1993-10-05 | Fuji Photo Film Co., Ltd. | Photographic bleaching composition and a processing method therewith |
| US5460924A (en) * | 1992-12-14 | 1995-10-24 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
| US5536625A (en) * | 1992-12-14 | 1996-07-16 | Eastman Kodak Company | Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts |
| US5550009A (en) * | 1995-04-17 | 1996-08-27 | Eastman Kodak Company | Stabilized peroxide bleaching solutions and their use for processing of photographic elements |
| EP0747765A1 (en) * | 1995-05-31 | 1996-12-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material |
| EP1001310A1 (en) * | 1995-05-31 | 2000-05-17 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material |
| EP0750226A1 (en) * | 1995-06-09 | 1996-12-27 | Fuji Photo Film Co., Ltd. | A method for processing a silver halide color photographic light-sensitive material |
| EP1365285A1 (en) * | 1995-06-09 | 2003-11-26 | Fuji Photo Film Co., Ltd. | A method for processing a silver halide color photographic light-sensitive material |
| EP0859276A1 (en) * | 1997-02-13 | 1998-08-19 | Eastman Kodak Company | Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition |
| JP2008144419A (en) * | 2006-12-07 | 2008-06-26 | Free Kogyo Kk | Structure of manhole |
| JP2008291563A (en) * | 2007-05-25 | 2008-12-04 | Hanex Co Ltd | Floating preventive manhole bottom slab, and prefabricated manhole constituted of floating preventive manhole bottom slab |
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