JPS62257154A - Processing method for silver halide color photographic sensitive material - Google Patents
Processing method for silver halide color photographic sensitive materialInfo
- Publication number
- JPS62257154A JPS62257154A JP10020286A JP10020286A JPS62257154A JP S62257154 A JPS62257154 A JP S62257154A JP 10020286 A JP10020286 A JP 10020286A JP 10020286 A JP10020286 A JP 10020286A JP S62257154 A JPS62257154 A JP S62257154A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- general formula
- present
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 149
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 72
- 239000004332 silver Substances 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000003672 processing method Methods 0.000 title description 8
- 238000012545 processing Methods 0.000 claims abstract description 40
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 70
- 239000000839 emulsion Substances 0.000 description 62
- 239000000975 dye Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 32
- 238000011161 development Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- 238000004061 bleaching Methods 0.000 description 13
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 108010010803 Gelatin Proteins 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
- 235000011852 gelatine desserts Nutrition 0.000 description 10
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- PYWQACMPJZLKOQ-UHFFFAOYSA-N 1,3-tellurazole Chemical class [Te]1C=CN=C1 PYWQACMPJZLKOQ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001556 benzimidazoles Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical class O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-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
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- USYCQABRSUEURP-UHFFFAOYSA-N 1h-benzo[f]benzimidazole Chemical compound C1=CC=C2C=C(NC=N3)C3=CC2=C1 USYCQABRSUEURP-UHFFFAOYSA-N 0.000 description 1
- FITNPEDFWSPOMU-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-b]pyridin-5-one Chemical compound OC1=CC=C2NN=NC2=N1 FITNPEDFWSPOMU-UHFFFAOYSA-N 0.000 description 1
- AXCGIKGRPLMUDF-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one;sodium Chemical compound [Na].OC1=NC(Cl)=NC(Cl)=N1 AXCGIKGRPLMUDF-UHFFFAOYSA-N 0.000 description 1
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 1
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GCSVNNODDIEGEX-UHFFFAOYSA-N 2-sulfanylidene-1,3-oxazolidin-4-one Chemical class O=C1COC(=S)N1 GCSVNNODDIEGEX-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- HCCNHYWZYYIOFM-UHFFFAOYSA-N 3h-benzo[e]benzimidazole Chemical class C1=CC=C2C(N=CN3)=C3C=CC2=C1 HCCNHYWZYYIOFM-UHFFFAOYSA-N 0.000 description 1
- WFFZGYRTVIPBFN-UHFFFAOYSA-N 3h-indene-1,2-dione Chemical class C1=CC=C2C(=O)C(=O)CC2=C1 WFFZGYRTVIPBFN-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- MVVFUAACPKXXKJ-UHFFFAOYSA-N 4,5-dihydro-1,3-selenazole Chemical class C1CN=C[Se]1 MVVFUAACPKXXKJ-UHFFFAOYSA-N 0.000 description 1
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- GKIFPROMYBQIHS-UHFFFAOYSA-N 4-n-ethyl-2-methoxy-4-n-(2-methoxyethyl)benzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(OC)=C1 GKIFPROMYBQIHS-UHFFFAOYSA-N 0.000 description 1
- OOMLOTQQQVXPLN-UHFFFAOYSA-N 4-n-ethyl-2-methylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(N)C(C)=C1 OOMLOTQQQVXPLN-UHFFFAOYSA-N 0.000 description 1
- FFAJEKUNEVVYCW-UHFFFAOYSA-N 4-n-ethyl-4-n-(2-methoxyethyl)-2-methylbenzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(C)=C1 FFAJEKUNEVVYCW-UHFFFAOYSA-N 0.000 description 1
- HPIVZWOZEIGINZ-UHFFFAOYSA-N 4-n-ethyl-4-n-[2-(2-methoxyethoxy)ethyl]-2-methylbenzene-1,4-diamine Chemical compound COCCOCCN(CC)C1=CC=C(N)C(C)=C1 HPIVZWOZEIGINZ-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
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- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical compound NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
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- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
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- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical class C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- MWGUHVCAWGDKNU-UHFFFAOYSA-N benzo[f][1,3]benzoselenazole Chemical compound C1=CC=C2C=C([se]C=N3)C3=CC2=C1 MWGUHVCAWGDKNU-UHFFFAOYSA-N 0.000 description 1
- GYTPOXPRHJKGHD-UHFFFAOYSA-N benzo[f][1,3]benzoxazole Chemical compound C1=CC=C2C=C(OC=N3)C3=CC2=C1 GYTPOXPRHJKGHD-UHFFFAOYSA-N 0.000 description 1
- BVVBQOJNXLFIIG-UHFFFAOYSA-N benzo[g][1,3]benzoxazole Chemical compound C1=CC=CC2=C(OC=N3)C3=CC=C21 BVVBQOJNXLFIIG-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
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- 229940006460 bromide ion Drugs 0.000 description 1
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- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
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- 238000012937 correction Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 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 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- PDXVZGTYXXBEQV-UHFFFAOYSA-N n'-acetylpropanehydrazide Chemical compound CCC(=O)NNC(C)=O PDXVZGTYXXBEQV-UHFFFAOYSA-N 0.000 description 1
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 description 1
- PEIVHTCIMKJVJF-UHFFFAOYSA-N n-[2-amino-5-(dimethylamino)phenyl]acetamide Chemical compound CN(C)C1=CC=C(N)C(NC(C)=O)=C1 PEIVHTCIMKJVJF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000004095 oxindolyl group Chemical class N1(C(CC2=CC=CC=C12)=O)* 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000008130 triterpenoid saponins Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
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】
し産業上の利用分野〕
本発明はハロゲン化銀カラー写真感光材料（以下写真要
素という。）の発色現像処理方法に関し、詳しくは処理
迅速性に優れ、増感色素による残色が少なく、高感度で
かつカブリ濃度が低い写真要素の処理方法に関する。[Detailed Description of the Invention] Industrial Application Field] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as photographic elements). The present invention relates to a method for processing photographic elements with little residual color, high sensitivity, and low fog density.
［発明の背景１
写真要素の発色現像処理における処理時間を短縮するこ
とは重要な課題である。すなわち、写真要素は各ラボラ
トリ−に設けられた自動現像様にてランニング処理が行
なわれている。このことは、ユーザーに対するサービス
向上の一環として、現像受付日のその日の内に現像処理
してユーザーに返還することが要求されているためで有
り、近時では、受付から数時間、数十分で現像処理して
返還することさえも要求されるようになり、写真要素の
短時間処理は、納期の短縮という点で強く要請されてい
る。BACKGROUND OF THE INVENTION 1 Reducing processing time in color development processing of photographic elements is an important issue. That is, photographic elements are subjected to running processing in an automatic development system installed in each laboratory. This is because, as part of improving services for users, it is required that the images be processed and returned to the user within the same day that they are received. There is now even a demand for photographic elements to be processed and then returned, and there is a strong demand for short-time processing of photographic elements in order to shorten delivery times.
その結果、現在カラー印画紙においては、現像時間を９
０秒程度以下にする事が強く要望されるようになって来
た。As a result, the development time for current color photographic paper is 9
There has been a strong demand to reduce the time to about 0 seconds or less.
しかしこのように現像時間が短縮されると、感光材料中
の増感色素の溶出が充分行われないうちに現像が終了し
、溶出されないままの多聞の増感色素が感光層中に残っ
てしまう場合が多い。このように溶出されないままの増
感色素は、写真要素の白地を損い、商品ｌｉ！Ｉｉ値を
大きく低下させてしまうため、写真要素の短時間処理に
おいて、大きな問題となっていた。However, when the development time is shortened in this way, development ends before the sensitizing dye in the photosensitive material is sufficiently eluted, and a large amount of uneluted sensitizing dye remains in the photosensitive layer. There are many cases. Sensitizing dyes that remain uneluted in this way will degrade the white background of the photographic element and cause product liability! This has been a major problem in short-term processing of photographic elements since it greatly reduces the Ii value.
このような増感色素の写真要素中での残留を低減するた
め、種々の検討がなされて来た。最も容易な方法は、用
いられる増感色素の添加量を減ｌすることであるが、こ
れでは写真要素の感度が所望の感度より低下してしまう
ため単に増感色素を′ｇ伍するだけでは写真要素の短時
間処理に起る問題の解決にならない。一方、蛍光増白剤
を現像処理液中に添加することにより増感色素が感光層
中から処理液中に溶出するのを促進し、写真要素の白地
における増感色素による残色がある程度低減されること
が知られている。Various efforts have been made to reduce the residual amount of such sensitizing dyes in photographic elements. The easiest method is to reduce the amount of sensitizing dye used, but this would reduce the sensitivity of the photographic element below the desired sensitivity, so simply adding 100 ml of sensitizing dye is not enough. It does not solve the problem of short-term processing of photographic elements. On the other hand, adding an optical brightener to the processing solution promotes the elution of the sensitizing dye from the photosensitive layer into the processing solution, reducing to some extent the residual color caused by the sensitizing dye on the white background of the photographic element. It is known that
しかし、現在のように極めて短時間のうちに処理を完了
さけることが要望されるようになると、もはや上記の蛍
光増白剤のみの促進効果によっては、充分に写真要素の
白地における増感色素による残色除去の要求を満足でき
ないのが現状である。However, as it is now required to complete processing in an extremely short period of time, the accelerating effect of the above-mentioned optical brightener alone is no longer sufficient to increase the effectiveness of the sensitizing dye on the white background of the photographic element. At present, it is not possible to satisfy the requirements for removing residual color.
［発明の目的］
そこで本発明の目的は、迅速現像において、感度を低下
させることなく写真要素の白地における、残色の少ない
ハロゲン化銀写真感光材料の処理方法を提供することで
ある。[Object of the Invention] Accordingly, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material in which the white background of a photographic element has little residual color during rapid development without reducing the sensitivity.
［発明の構成〕
本発明の上記目的は、下記一般式［Ａ］の増感色素を含
有するハロゲン化銀写真感光材料を下記一般式［Ｉ］の
化合物を含有する処理液によって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より達成された。[Structure of the Invention] The above object of the present invention is to process a silver halide photographic light-sensitive material containing a sensitizing dye of the following general formula [A] with a processing solution containing a compound of the following general formula [I]. This was achieved by a method for processing silver color photographic materials.
一般式［Ａ］
（Ｘｌ、、
［式中、ｚｌ及びｚ２はそれぞれ同一でも相違してもよ
く、各々へテロ環を形成するに必要な原子群を表わし、
Ｒ１はカルボキシ基で置換されたアルキル基を表わす。General formula [A]
R1 represents an alkyl group substituted with a carboxy group.
Ｒ２はＲ１と同一でも相違していてもよく、アルキル基
、アリール基、アルケニル基またはアラルキル基を表わ
す。Ｒ３−Ｒ６は各々水素原子、炭素数４以下のアルキ
ル基、アリール基、アラルキル基又は複素環基を表わし
、Ｒ２とＲｓ（ｑ＝２の場合）又はＲ３とＲｓ （ｍ
−２、ｑ−２の場合）が連結して５又は６員環となるア
ルキレン架橋を形成しても良い。ｌ、ｍ、ｎＳＱ及びｒ
は、それぞれ１又は２を表わす。R2 may be the same as or different from R1 and represents an alkyl group, an aryl group, an alkenyl group or an aralkyl group. R3-R6 each represent a hydrogen atom, an alkyl group having 4 or less carbon atoms, an aryl group, an aralkyl group, or a heterocyclic group, and R2 and Rs (when q=2) or R3 and Rs (m
-2, q-2) may be connected to form an alkylene bridge that becomes a 5- or 6-membered ring. l, m, nSQ and r
represent 1 or 2, respectively.
Ｘ〜はアニオンを表わす。］
一般式［Ｉ］
ＹＮ
基、または、Ｒ５−Ｃｏ−基を表わす。（ここで、Ｒ７
、ＲａおよびＲ９は、それぞれ、ヒドロキシル基、ハロ
ゲン原子、モルホリノ基、アルコキシ基、アリールオキ
シ基、アルキル基、アリール基、アミノ基、アルキルア
ミＬＬまたはアリールアミノ基を表わす。Ｍは１価の陽
イオンを表わす。）］
［発明の具体的構成］
以下本発明について具体的に説明する。X~ represents an anion. ] General formula [I] represents a YN group or an R5-Co- group. (Here, R7
, Ra and R9 each represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, an alkylamino LL or an arylamino group. M represents a monovalent cation. )] [Specific Structure of the Invention] The present invention will be specifically described below.
本発明のハロゲン化銀写真感光材料に含有される前記一
般式［Ａ］で表わされる増感色素において２１及びｚ２
は同一でも相違してもよく、各々へテロ環を形成するに
必要な原子群を表わす。具体的にはオキサゾリン核、オ
キサゾール核、ベンゾオキサゾール核、ナフトオキサゾ
ール核（例えば、ナフト［２，１−ｄ ］オキサゾール
、ナフトＮ、２−ｄ ］オキサゾール、ナフト［２，３
−ｄ］オキサゾール）、チアゾリン核、チアゾール核、
ベンゾチアゾール核、ナフトチアゾール核（例えば、ナ
フト［１，２−ｄ ］ｌチアゾールナフト［２，１−ｄ
］ｌチアゾールナフト［２，３−ｄ ｌチアゾール）
、セレナゾリン核、セレナゾール核、ベンゾセレナゾー
ル核、ナフトセレナゾール核（〃１えばナフトＮ、２−
ｄ ］セレナゾール、ナフトＣ２，１−ｄ ］セレナゾ
ール、ナフト［２，３−ｄ ］セレナゾール）、テルラ
ゾール核、ペンゾテルラゾール核、ナフトテルラゾール
咳（例えばナフト［２，１−ｄｌテルラゾール、ナフト
［１，２−ｄ ］テルラゾール）、イミダゾール核、ベ
ンゾイミダゾール核、ナフトイミダゾール核（例えばナ
フト［１，２−ｄコイミダゾール、ナフト［２，３−ｄ
］イミダゾール）、ピリジン核、ピロリジン核、テト
ラゾール核、キノリン咳を形成するのに必要な原子群を
表わす。In the sensitizing dye represented by the general formula [A] contained in the silver halide photographic material of the present invention, 21 and z2
may be the same or different, and each represents an atomic group necessary to form a heterocycle. Specifically, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus (for example, naphtho[2,1-d]oxazole, naphthoN,2-d]oxazole, naphtho[2,3
-d]oxazole), thiazoline nucleus, thiazole nucleus,
benzothiazole nucleus, naphthothiazole nucleus (e.g. naphtho[1,2-d]lthiazolenaphtho[2,1-d
]lthiazolenaphtho[2,3-dlthiazole)
, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus (1, for example, naphtho-N, 2-
d]selenazole, naphthoC2,1-d]selenazole, naphtho[2,3-d]selenazole), tellurazole nucleus, penzotelllazole nucleus, naphthotellazole cough (e.g. naphtho[2,1-dltellazole, naphtho[ 1,2-d ] Tellurazole), imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus (e.g. naphtho[1,2-d coimidazole, naphtho[2,3-d
] imidazole), pyridine nucleus, pyrrolidine nucleus, tetrazole nucleus, represents the atomic group necessary to form quinoline cough.
上記のへテロ環の核のうち好ましい咳はベンゾチアゾー
ル核、ベンゾイミダゾール核、ベンゾオキサゾール核で
ありそのうち特に好ましいものはベンゾチアゾール核で
ある。Preferred among the above-mentioned heterocyclic nuclei are benzothiazole nucleus, benzimidazole nucleus, and benzoxazole nucleus, and among these, benzothiazole nucleus is particularly preferable.
上記のへテロ環の核はその環上に１または２以上の種々
の置換基が存在してもよい。One or more various substituents may be present on the ring of the above heterocyclic ring.
このような置換基の好ましい例としては、ヒドロキシ基
、ハロゲン原子、（例えば、フッ素原子、クロル原子、
ブロム原子）、無置換及び置換アルキル基（例えば、メ
チル、エチル、ブＯピル、イソプロピル
チル、クロロエチル、メトキシメチル等の各基）、アリ
ール基又は置換アリール基（例えばフェニル、トリル、
アニシル、クロロフェニル、１−ナフチル、２−ナフチ
ル、カルボキシフェニル等の各基）、複素環基（例えば
、２−チェニル、２−フリル、２−ピリジル等の各基）
、アラルキル基（例えば、ベンジル、フェネチル、２−
フリルメチル等の各基）、アルコキシ基（例えば、メト
キシ、エトキシ、ブトキシ等の各基）、アルキルチオ基
（例えば、メチルチオ、エチルチオ等の各Ｍ）、カルボ
キシ基、アルコキシカルボニル基（例えば、メトキシカ
ルボニル、エトキシカルボニル、ブトキシカルボニル等
の各基）、アシルアミノ基（例えば、アセチルアミノ、
プロピオニルアミン、ベンゾイルアミノ等の各基）、メ
チレンジオキシ基、テトラメチレン基、シアン基、カル
バモイル基（例えば、ジメチルカルバモイルチルカルバ
モイル
基）、アシル基（例えば、アセチル、プロピオニル、ベ
ンゾイル等の各基）、アルキルスルホニル基（例えば、
メチルスルホニル、エチルスルホニル等の各基）、アル
キルスルフィニル基（例えば、メチルスルフィニル、エ
チルスルフィニル等の各基）、アリールスルホニル基（
例えば、フェニルスルホニル、０−トリルスルホニル等
の各基）、スルファモイル基（メチルスルファモイル、
エチルスルファモイル等の各基）等が挙げられる。Preferred examples of such substituents include hydroxy group, halogen atom, (e.g. fluorine atom, chlorine atom,
bromine atom), unsubstituted and substituted alkyl groups (e.g., methyl, ethyl, butyl, isopropyl, chloroethyl, methoxymethyl, etc.), aryl or substituted aryl groups (e.g., phenyl, tolyl,
anisyl, chlorophenyl, 1-naphthyl, 2-naphthyl, carboxyphenyl, etc.), heterocyclic groups (e.g., 2-chenyl, 2-furyl, 2-pyridyl, etc.)
, aralkyl groups (e.g. benzyl, phenethyl, 2-
furylmethyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, butoxy, etc.), alkylthio groups (e.g., methylthio, ethylthio, etc.), carboxy groups, alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), acylamino groups (e.g. acetylamino,
propionylamine, benzoylamino, etc.), methylenedioxy group, tetramethylene group, cyan group, carbamoyl group (e.g., dimethylcarbamoylthylcarbamoyl group), acyl group (e.g., acetyl, propionyl, benzoyl, etc.) , an alkylsulfonyl group (e.g.
methylsulfonyl, ethylsulfonyl, etc.), alkylsulfinyl groups (for example, methylsulfinyl, ethylsulfinyl, etc.), arylsulfonyl groups (
For example, phenylsulfonyl, 0-tolylsulfonyl, etc.), sulfamoyl group (methylsulfamoyl,
Examples include various groups such as ethylsulfamoyl.
Ｒ１はカルボキシ基で置換されたフルキル基を表わし例
えば、カルボキシメチル、２−カルボキシエチル、３−
カルボキシメチル等の各基を挙げることができる。この
Ｒ１は、好ましくは炭素数が５以下のアルキル基がカル
ボキシ基で買換されたものである。R1 represents a furkyl group substituted with a carboxy group, such as carboxymethyl, 2-carboxyethyl, 3-
Examples include various groups such as carboxymethyl. This R1 preferably has an alkyl group having 5 or less carbon atoms replaced with a carboxy group.
Ｒ２はアルキル基、アリール基、アルケニル基、又はア
ラルキル基を表わし、これらは未置換でも置換されてい
てもよいが、スルホ基で置換されたアルキル基が好まし
い。Ｒ２の具体例としては、メチル、エチル、プロピル
、ブチル、イソプロピル、ペンチル、ヘキシル、２−ヒ
ドロキシエチル、３−ヒドロキシプロピル、２−（２−
ヒドロキシエトキシ）エチル、エトキシカルボニルメチ
ル２−スルホエチル、３−スルホプロピル、３−スルホ
ブチル、４−スルホブチル、２−ヒドロキシ−３−スル
ホプロピル、２−クロロ−３−スルホプロピル、２−（
３−スルホプロピルオキシ）エチル、２−サルファトエ
チル、３−サルファトブロピル、３−チオサルファドブ
０ピル、２−ホスホノエチル、２−りＯロエチル、２．
２．２−トリフルオロエチル、２．２，３．３−テトラ
フルオロプロピル、２−カルバモイルエチル、３−力ル
バモイルブロピル、メトキシエチル、エトキシエチル、
メトキシプロピル、フリル、フェニル、ｉ〜リル、カル
ボキシフェニル、スルホフェニル、ナフチル、スルホナ
フチル、ベンジル、フェネチル、ｐ−スルホフェネチル
、ｍ−スルホエチル、ｐ−カルボキシフェネチル等が挙
げられる。R2 represents an alkyl group, an aryl group, an alkenyl group, or an aralkyl group, which may be unsubstituted or substituted, but preferably an alkyl group substituted with a sulfo group. Specific examples of R2 include methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-(2-
hydroxyethoxy)ethyl, ethoxycarbonylmethyl 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-chloro-3-sulfopropyl, 2-(
3-sulfopropyloxy)ethyl, 2-sulfatoethyl, 3-sulfatobropyl, 3-thiosulfadobutyl, 2-phosphonoethyl, 2-diOloethyl, 2.
2.2-trifluoroethyl, 2.2,3.3-tetrafluoropropyl, 2-carbamoylethyl, 3-trifluoroethyl, methoxyethyl, ethoxyethyl,
Examples include methoxypropyl, furyl, phenyl, i-lyl, carboxyphenyl, sulfophenyl, naphthyl, sulfonaphthyl, benzyl, phenethyl, p-sulfophenethyl, m-sulfoethyl, p-carboxyphenethyl, and the like.
また、一般式［ＡｌにおいてＲ３ 、Ｒ崎、Ｒ５及びＲ
６は各々水素原子、炭素原子数４以下のアルキル基、ア
ラルキル基、アリール基または複素環基を表わす。In addition, in the general formula [Al, R3, Rzaki, R5 and R
6 each represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, an aralkyl group, an aryl group, or a heterocyclic group.
アルキル基の具体例としてはメチル、エチル、プロピル
、ブチル等の各基が挙げられ、アラルキル基としてはベ
ンジル、フェネチル等の各基が挙げられ、アリール基と
してはフェニル、ｏ−トリル等の各基が挙げられる。Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, etc., aralkyl groups include benzyl, phenethyl, etc., and aryl groups include phenyl, o-tolyl, etc. can be mentioned.
また、複素環基としてはチェニル、フリル等の芳香族複
素環基あるいは下記一般式（Ｂ）で示される酸性複素環
基が挙げられる。Examples of the heterocyclic group include aromatic heterocyclic groups such as chenyl and furyl, and acidic heterocyclic groups represented by the following general formula (B).
一般式＜８）におけるＱは例えばごラゾロン誘導体、イ
ソオキサシロン誘導体、オキサシロン誘導体、２．４．
６−ドリケトへキサヒドロピリミジン誘導体、２−チオ
−２．４．６−ドリケトへキサヒドロピリミジン誘導体
、ローダニン誘導体、２、４−チアゾリジンジオン誘導
体、２−チオ−２、４−オキサゾリジンジオン誘導体、
チアナフチノン誘導体、ヒダントインＭ導体、インダン
ジオン誘導体、オキシインドール誘導体等から選ばれる
５員または６員の複素環核を形成するに必要な非金属原
子群を表わす。Ｒ２とＲｓ（Ｑ＝２の場合）又はＲ３と
ＲＳ（Ｉｌｌ−２、Ｑ−２の場合）が連結して５又は６
員環となるアルキレン架橋を形成しても良い．Ｒ３ 、
Ｒ４ 、Ｒｓ及びＲ６で表わされる水素原子、アルキル
基、アラルキル基、アリール基、複素環のうち、好まし
いものは水素原子又はアルキル基が挙げられる。Q in the general formula <8) is, for example, a lazolone derivative, an isoxacilone derivative, an oxacilone derivative, 2.4.
6-drichetohexahydropyrimidine derivative, 2-thio-2.4.6-drichetohexahydropyrimidine derivative, rhodanine derivative, 2,4-thiazolidinedione derivative, 2-thio-2,4-oxazolidinedione derivative,
Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic nucleus selected from thianafuthynone derivatives, hydantoin M conductors, indandione derivatives, oxindole derivatives, etc. R2 and Rs (in the case of Q=2) or R3 and RS (in the case of Ill-2, Q-2) are connected to 5 or 6
It is also possible to form an alkylene bridge that becomes a membered ring. R3,
Among the hydrogen atom, alkyl group, aralkyl group, aryl group, and heterocycle represented by R4, Rs, and R6, preferred are a hydrogen atom or an alkyl group.
１、ｍ 、 ｎ 、 ｑとｒは１又は２を表わし、好ま
しくはｑは１を表わし、更に好ましくはｍ１ｑともに１
を表わす。1, m, n, q and r represent 1 or 2, preferably q represents 1, more preferably m1q both represent 1
represents.
以下に本発明の一般式［Ａｌで表わされる増感色素の具
体例を示すが本発明はこれらに限定されない。Specific examples of the sensitizing dye represented by the general formula [Al] of the present invention are shown below, but the present invention is not limited thereto.
一般式［Ａｌの化合物例
Ａ−７
Ｃ０ＯＨ
Ａ−３５
Ａ−３６
ＣＨ２ＣＵ○Ｈ
Ｈ３
Ａ−５８
Ａ−５９
ｔＨｓ
Ａ−８１
Ａ−８２
２Ｈ５
２Ｈ６
２Ｈ５
薯
Ｃ２Ｈ５（工”〕
（ＣＨ２）２ＣＯＯＨ
ＣＨ２Ｃ０ＯＨ
（ＣＨ２）２ＣＯＯＨ
Ａ−９７
Ａ−９８
Ａ １００
２Ｈ５
八−１０８
ＣＨ２ＣＯＯＨ
Ａ−１１３
Ａ−１１４
２Ｈ５
（： Ｍ２１．； Ｕ Ｕ ｔｉ
Ｃｃｔ ｏ？〕
一般式［Ａ］で表わされる本発明に使用される増感色素
は公知であり、エフ エム バーマー。General formula [Al compound example A-7 C0OH A-35 A-36 CH2CU○H H3 A-58 A-59 tHs A-81 A-82 2H5 2H6 2H5 薯C2H5(工”) (CH2)2COOH CH2C0OH (CH2 )2COOH A-97 A-98 A 100 2H5 8-108 CH2COOH A-113 A-114 2H5 (: M21.; U U ti Cct o?) Sensitization used in the present invention represented by general formula [A] The dyes are known and manufactured by F.M. Balmer.
ザ ケミストリイ オブ へテロサイクリックコンパウ
ンズ ボリューム１８ ザ シニアンダイズ アンド
リレイティッド コンパウンズ。The Chemistry of Heterocyclic Compounds Volume 18 The Senior Dies and
Related Compounds.
エイ、パイセルガー、エディジョン インターサイエン
ス、ニューヨーク、 １９６４．７”イー エムスター
マー、ザ ケミストリイ オブ へテロサイクリック
コンボンズ、ボリューム３０．エイ。Peiselger, E., Edition Interscience, New York, 1964.7” E. M. Starmer, The Chemistry of Heterocyclics.
Combons, Volume 30. Stingray.
パイセルガー アンド イー シー ティラーエディシ
ョンズ ジョン ウィリレイ、ニューヨーク、 １９７
７、ページ４４１
（Ｆ、 Ｍ、 Ｈａｍｅｒ、 Ｔｈｅ Ｃｈｅｌｓｔ
ｒｙ ｏｆ）−１ｅｔｅｒｏｃｙｃｌｉｃ Ｃｏｍｐｏ
ｕｄｓ 、 Ｖｏｌｌ ８ 、 ＴｈｅＣｙａｎｉｎｅ
［）ｙｅｓ ａｎｄ Ｒｅ１ａｔｅｄ Ｑｏａ＋
ｐｏｕｎｄｓ、 Ａ。Peiserger and E.C. Tiller Editions John Williley, New York, 197
7, page 441 (F. M. Hamer, The Chelst
ry of)-1eterocyclic Compo
uds, Vol 8, TheCyanine
[)yes and Re1ated Qoa+
Pounds, A.
Ｗｅｉｓｓｅｒｏｅｒ ｅｄ、、 Ｉ ｎｔｅｒｓｃ
ｉｅｎｃｅ 、 ＮｅｗＹｏｒｋ 、 １９６４． Ｄ
、 Ｍ、 Ｓｔｕｒｇ＋ｅｒ、 ＴｈｅＣｈｅｍｉｓｔ
ｒｙ Ｏｆ Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃ０ｆｌｌｌ
）ＯＬＩｎｄＳ。Weisseroer ed., Intersc.
ience, New York, 1964. D
, M. Sturg+er, TheChemist
ry Of Heterocyclic C0flll
)OLIndS.
Ｖｏ１３０． Ａ、 Ｗｅｉｓｓｅｒｇｅｒ ａｎｄ
Ｅ、Ｃ０Ｔａｙ＋ｏｒ ｅｄｓ 、 、 ＪＯｈｎ Ｗ
ｉｌｅｙ、 Ｎｅｗ Ｙｏｒｋ 。Vo130. A. Weisserger and
E, C0Tay+or eds, , JOhn W
iley, new york.
１９７７、 ｐ、４４１ ）等に記載されており、これ
らを参照すれば合成できる。1977, p. 441), etc., and can be synthesized by referring to these.
本発明に用いられる一般式［Ａ］で表わされる上記増感
色素の乳剤中への添加時期としては、ハロゲン化銀乳剤
の化学熟成（第２熟成とも呼ば机る）開始時、熟成進行
中、熟成終了後、または乳剤塗布に先立つ適切な時期等
側れの工程でも差支えない。The timing of adding the sensitizing dye represented by the general formula [A] used in the present invention to the emulsion is at the beginning of chemical ripening (also called second ripening) of the silver halide emulsion, during the progress of ripening, It is also possible to carry out the step at a later stage, such as after the completion of ripening or at an appropriate time prior to emulsion coating.
また本発明に係わる増感色素を上記写真乳剤に添加する
方法としては従来から提案されている種々の方法が適用
できる。例えば米国特許第３．４６９８９８１号に記載
された如く、増感色素を揮発性有機溶媒に溶解し、該溶
液を親水性コロイド中に分散し、この分散物を乳剤に添
加する方法により行なってもよい。またざらに、本発明
に係わる増感色素は、国々に、同一または異なる溶媒に
溶解し、乳剤に添加する前に、これらの溶液を混合する
か、別々に添加することができる。Furthermore, as a method for adding the sensitizing dye according to the present invention to the above-mentioned photographic emulsion, various methods conventionally proposed can be applied. For example, as described in U.S. Pat. No. 3,469,8981, it may be carried out by dissolving a sensitizing dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion. good. Additionally, the sensitizing dyes according to the invention can be dissolved in the same or different solvents and these solutions can be mixed or added separately before being added to the emulsion.
本発明に係わる増感色素をハロゲン化銀乳剤に添加する
ときの溶媒としては、例えばメチルアルコール、エチル
アルコール、アセトン等の水混和性有機溶媒が好ましく
用いられる。As a solvent for adding the sensitizing dye according to the present invention to a silver halide emulsion, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol, acetone, etc. is preferably used.
本発明に係わる増感色素をハロゲン化銀乳剤に添加せし
める場合の添加量は、増感色素を添加するハロゲン化銀
乳剤層中のハロゲン化銀１モル当り、ｌＸ１０−５モル
ないし２．５ｘ １０−２−Ｅ−ル、好ましくはｉ、ｏ
ｘ ｉ ｏ→モルないし１．０Ｘ１０’モルである。When the sensitizing dye according to the present invention is added to a silver halide emulsion, the amount to be added is 1×10 −5 mol to 2.5× 10 mol per 1 mol of silver halide in the silver halide emulsion layer to which the sensitizing dye is added. -2-E-le, preferably i, o
x io→mol to 1.0×10′ mole.
本発明に係わる増感色素は、本発明の効果をそこなわな
い範囲で更に他の増感色素または強色増感剤と併用する
こともできる。The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes or supersensitizers as long as the effects of the present invention are not impaired.
次に本発明の処理液中に含有される下記一般式［Ｉ］で
表わされる化合物について説明する。Next, the compound represented by the following general formula [I] contained in the treatment liquid of the present invention will be explained.
一般式［Ｉ］
ＹＮ
基、または、Ｒ９−Ｃ〇−基を表わす。ここで、Ｒ７、
ＲａおよびＲ９は、それぞれ、ヒドロキシル基、ハロゲ
ン原子（塩素、臭素等）、モルホリノ基、アルコキシ基
（例えばメトキシ基、エトキシ基、メトキシエトキシ基
等）、アリールオキシ基（例えばフェノキシ基、ｐ−ス
ルホフェノキシ基等）、アルキル基（例えばメチル基、
エチル基等）、アリール基（例えば、フェニル基、メト
キシフェニル基等）、アミノ基、アルキルアミノ基（例
えばメチルアミノ基、エチルアミン基、プロピルアミノ
基、ジメチルアミン基、シクロヘキシルアミノ基、β−
ヒドロキシエチルアミノ基、ジ（β−ヒドロキシエチル
）アミン基、β−スルホエチルアミムＩ、Ｎ−ＣＢ−ス
ルホエチル）−Ｎ′−メチルアミノ基、Ｎ−（β−ヒド
ロキシエチル−Ｎ′−メチルアミノ基等）、またはアリ
ールアミノ基（例えば、アニリへ！！、Ｏ、ｍ 。General formula [I] represents a YN group or an R9-C〇- group. Here, R7,
Ra and R9 each represent a hydroxyl group, a halogen atom (chlorine, bromine, etc.), a morpholino group, an alkoxy group (e.g., methoxy group, ethoxy group, methoxyethoxy group, etc.), an aryloxy group (e.g., phenoxy group, p-sulfophenoxy group, etc.). groups), alkyl groups (e.g. methyl groups,
ethyl group, etc.), aryl group (e.g., phenyl group, methoxyphenyl group, etc.), amino group, alkylamino group (e.g., methylamino group, ethylamine group, propylamino group, dimethylamine group, cyclohexylamino group, β-
Hydroxyethylamino group, di(β-hydroxyethyl)amine group, β-sulfoethylamine I, N-CB-sulfoethyl)-N'-methylamino group, N-(β-hydroxyethyl-N'-methylamino groups), or arylamino groups (e.g., ani!!, O, m.
ｐ−スルホアニリへＬｏ−１ｍ −、ｐ−クロロアニリ
ムｉ、ｏ−，ｍ−，ｐ−トルイジノ基、ｏ −、ｍ −
、ｐ−カルボキシアニリノ基、０−。Lo-1m-, p-chloroanirimi, o-, m-, p-toluidino group, o-, m- to p-sulfoanily
, p-carboxyanilino group, 0-.
鳳−１ρ−ヒドロキシアニリノ基、スルホナフチルアミ
ノ基、ｏ −、ｍ ＋、 ｐ−アミノアニリノ基、ｏ
−、ｍ ＋、 ｐ−アニシジン等）を表わす。Ｍは１価
の陽イオンを表わす。Otori-1ρ-hydroxyanilino group, sulfonaphthylamino group, o −, m +, p-aminoanilino group, o
-, m +, p-anisidine, etc.). M represents a monovalent cation.
以下に一般式［工］で表わされる化合物の具体例を示ず
が本発明はこれらの化合物のみによって限定されるもの
ではない。Although specific examples of the compounds represented by the general formula [E] are not shown below, the present invention is not limited only to these compounds.
Δ辺冨白
１」−・→
％＋Ｊ
−Ｊ一一一
１＋７ １＋７
Ｕ會 Ｕ
口し’
ｕ
ＩＪ本発明において一般式［Ｉ］の化合物を含有する
処理液とは発色現像液、漂白液、漂白定着液および水洗
代替安定化液をいう。Δside Tomihaku 1”−・→ %+J
-J1111+7 1+7
U meeting U
Mouth'
u
IJ In the present invention, the processing solution containing the compound of general formula [I] refers to a color developing solution, a bleaching solution, a bleach-fixing solution, and a water-washing substitute stabilizing solution.
一般式［Ｉ］で表される化合物（以下蛍光増白剤ともい
う。）は現像液中に添加されても良いし、漂白液又は漂
白定着液中に添加されても良いし、または水洗代替安定
化液中に添加されても良いが、゛現像液中に添加するの
が好ましい。The compound represented by the general formula [I] (hereinafter also referred to as an optical brightener) may be added to the developer, the bleach or bleach-fix solution, or as an alternative to washing with water. Although it may be added to the stabilizing solution, it is preferably added to the developing solution.
本発明の蛍光増白剤は現像液１２当り０．２＋ＩＩ〜１
５（ｌ添加されるが好ましくは１〜５ｇが添加される。The optical brightener of the present invention is 0.2+II to 1 per 12 developer solution.
5 (l), preferably 1 to 5 g.
本発明の蛍光増白剤が添加されている現像液は通常の発
色現像処理と同様な発色現像処理に適用される。The developer to which the fluorescent brightener of the present invention is added can be applied to the same color development treatment as ordinary color development treatment.
本発明の写真要素は青感性ハロゲン化銀乳剤層、緑感性
ハロゲン化銀乳剤層、赤感性ハロゲン化銀乳剤層の各々
を含む少なくとも３層の多層カラー用写真要素において
、その写真構成層（感光性乳剤層のみならず、中間層、
オーバーコート層、下引層等、感光性乳剤層を塗設した
側の全ての親水性コロイド層をいう。本明細書において
は同じ意味である。）の金膜の厚みは乾燥時に１４μ鶴
以下が好ましく、より好ましくは１３μｍ以下、特に好
ましくは１２μ信以下である。The photographic element of the present invention is a multilayer color photographic element having at least three layers including each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. Not only the emulsion layer but also the intermediate layer,
Refers to all hydrophilic colloid layers on the side coated with the photosensitive emulsion layer, such as overcoat layers and subbing layers. They have the same meaning in this specification. ) The thickness of the gold film when dried is preferably 14 μm or less, more preferably 13 μm or less, particularly preferably 12 μm or less.
本発明の写真要素の処理方法には、発色現像処理を含有
する発色現像浴が用いられる。また、浴処理を始めとし
て他の各種の方法、例えば処理液を噴霧状にするスプレ
一方式、又は処理液を含浸させた担体との接触によるウ
ェッブ方式、あるいは粘性処理液による現像方法等各種
の処理方式を用いることができる。The method of processing photographic elements of the present invention employs a color development bath containing a color development treatment. In addition, various other methods including bath processing, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, etc. Processing schemes can be used.
上記の他、本発明の写真要素の処理方法については特に
υ１限はな（、あらゆる処理方法が通用できる。例えば
、その代表的なものとしては、発色現象後、漂白定着処
理を行い必要ならさらに水洗および／または安定処理を
行う方法、発色現ａｍ、漂白と定着を分離して行い、必
要に応じざらに水洗および／または安定処理を行う方法
または水洗代替安定化液を用いる方法；あるいは前Ｉｉ
！膜、中和、発色現像、停止定着、水洗、漂白、定着、
水洗、後硬膜、水洗の順で行う方法、発色現象、水洗、
補足発色現像、停止、漂白、定着、水洗、安定の順で行
う方法、発色現像によって生じた現像銀をハロゲネーシ
ョンブリーチをしたのち、再度発色現像をして生成色素
量を増加させる現像方法等、いずれの方法を用いて処理
してもよい。In addition to the above, there is no particular limit to the processing method for the photographic element of the present invention (but any processing method can be used. For example, a typical method is to carry out a bleach-fixing treatment after the coloring phenomenon and further processing if necessary. A method of performing water washing and/or stabilization treatment, a method of performing color development, bleaching and fixing separately, and carrying out rough water washing and/or stabilization treatment as necessary, or a method of using a stabilizing solution as an alternative to water washing;
! Film, neutralization, color development, stop fixing, water washing, bleaching, fixing,
Method of washing with water, postdural mater, washing with water in order, coloring phenomenon, washing with water,
Supplementary color development, stopping, bleaching, fixing, washing, and stabilizing in that order; a development method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye produced, etc. The treatment may be performed using any method.
本発明の処理方法に用いられる発色現像液には、一般式
［Ｉ］で表わされる化合物及びＮ−ヒドロキシアルキル
置換−ｐ−フェニレンジアミン誘導体現像生薬が用いら
れる。また、Ｎ−ヒドロキシルアルキル置換−ｐ−フェ
ニレンジアミン誘導体現像主薬の他に下記の発色現像主
薬を使用できる。A compound represented by the general formula [I] and an N-hydroxyalkyl-substituted p-phenylenediamine derivative developing crude drug are used in the color developing solution used in the processing method of the present invention. In addition to the N-hydroxylalkyl-substituted p-phenylenediamine derivative developing agent, the following color developing agents can be used.
４−アミノ−Ｎ、Ｎ−ジエチルアニリン、３−メチル−
４−アミノ−Ｎ、Ｎ−ジエチルアニリン、３−メチル−
４−アミノ−Ｎ−エチル−Ｎ−β−メトキシエチルアニ
リン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−
メタンスルホンアミドエチルアニリン、３−メトキシ−
４−アミノ−Ｎ−エチル−Ｎ−β−メトキシエチルアニ
リン、３−アセトアミド−４−アミノ−Ｎ、Ｎ−ジメチ
ルアニリン、Ｎ−エチル−Ｎ−β−［β−（β−メトキ
シエトキシ）エトキシ］エチルー３−メチル−４−アミ
ノアニリン、Ｎ−エチル−Ｎ−β−（β−メトキシエト
キシ）エチル−３−メチル−４−アミノアニリンや、こ
れらの塩例えば硫酸塩、塩酸塩、亜硫酸塩、ｐ−トルエ
ンスルホン酸塩、リン酸塩等である。4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methoxy-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy] Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochlorides, sulfites, p -Toluenesulfonate, phosphate, etc.
ざらに、例えば特開昭４８−６４９３２号、同５０−１
３１５２６号、同５１−９５８４９号およびベント等の
ジャーナル・オブ・ジ・アメリカン・ケミカル・ソサエ
ティー、７３巻、３１００〜３１２５頁（１９５１年）
記載のものも代表的なものとして挙げられる。For example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.
本発明において用いられる発色現像液には、前記発色現
象主薬及び本発明の一般式［Ｉ］で示される化合物のほ
かに更に通常添加されている種々の成分、例えば水酸化
ナトリウム、炭酸ナトリウム等のアルカリ剤、アルカリ
金属亜硫酸塩、アルカリ金属亜硫酸水素塩、アルカリ金
工チオシアン酸塩、アルカリ今風ハロゲン化物、ベンジ
ルアルコール、水軟化剤、濃厚化剤および現象促進剤等
を任意に含有させることもできる。In addition to the color developing agent and the compound represented by the general formula [I] of the present invention, the color developing solution used in the present invention contains various components that are usually added, such as sodium hydroxide, sodium carbonate, etc. Alkali agents, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali modern halides, benzyl alcohol, water softeners, thickeners, phenomenon accelerators, and the like may optionally be included.
前記発色現像液に添加される上記以外の添加剤としては
、例えば臭化カリウム、臭化ナトリウム等の臭化物、沃
化アルカリ、ニトロベンゾイミダゾール、メルカプトベ
ンゾイミダゾール、５−メチル−ベンゾトリアゾール、
１−フェニル−５−メルカプトテトラゾール等の迅速処
理液用化合物を始めとして、スティン防止剤、スラッジ
防止剤、保恒剤、ｆｆ１Ｊｉ効果促進剤、キレート剤等
がある。Examples of additives other than the above added to the color developer include bromides such as potassium bromide and sodium bromide, alkali iodides, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing solutions such as 1-phenyl-5-mercaptotetrazole, there are anti-stain agents, anti-sludge agents, preservatives, ff1Ji effect promoters, chelating agents, and the like.
臭化物イオン濃度は好ましくはｌＸ１０−２モル以上、
特に好ましくは１．５Ｘ１０’モル以上、６Ｘ １０−
２モル以下である。The bromide ion concentration is preferably 1×10−2 mol or more,
Particularly preferably 1.5X10'mol or more, 6X10-
It is 2 moles or less.
本発明における発色現像の処理は３０℃以上で行われる
が、好ましくは３３℃以上、１２０秒以下、最も好まし
くは３５℃以上、９０秒以下で処理することであり、３
０’Ｃ以上、１５０秒以上の処理を行うときには発色現
像された色素の保存安定性が悪化する。特に処理湿度よ
り処理時間が重要であり １５０秒を越えるとシアン色
素の光褪色性が著しく上昇し好ましくない。処理温度は
色素の保存安定性よりむしろ短時間に現像を終了させる
ために上昇させるものであり、３０℃以上、５０℃以下
であれば高い方が、短時間処理が可能となりむしろ好ま
しく、特に好ましくは３３℃以上、４８℃以下であり、
最も好ましくは３５℃以上、４３℃以下で処ｗＡするこ
とである。The color development process in the present invention is carried out at 30°C or higher, preferably at 33°C or higher and 120 seconds or less, most preferably at 35°C or higher and 90 seconds or less.
When processing is carried out at 0'C or higher and for 150 seconds or longer, the storage stability of the color-developed dye deteriorates. In particular, the processing time is more important than the processing humidity; if it exceeds 150 seconds, the photofading property of the cyan dye increases significantly, which is undesirable. The processing temperature is raised to complete the development in a short time rather than to maintain the storage stability of the dye, and a higher temperature of 30° C. or higher and 50° C. or lower is preferable since it enables short processing time, and is particularly preferred. is 33°C or higher and 48°C or lower,
Most preferably, the treatment is performed at a temperature of 35°C or higher and 43°C or lower.
発色現像液のｐＨは通常７以上が好ましく、より好まし
くは９〜１３の範囲である。The pH of the color developing solution is usually preferably 7 or more, more preferably in the range of 9 to 13.
また、本発明の一般式［Ｉ］で表わされる化合物を、前
記発色現像液に添加する代りに漂白工程の漂白液もしく
は漂白定着液に添加してもよい。Further, the compound represented by the general formula [I] of the present invention may be added to the bleaching solution or bleach-fixing solution in the bleaching step instead of being added to the color developing solution.
この漂白液もしくは漂白定着液に用いられる漂白剤とし
ては、アミノポリカルボン酸または’ｆＪＦｉ、クエン
酸等の有機酸で鉄、コバルト、銅等の全屈イオンを配位
したものが一般に知られている。そして上記のアミノポ
リカルボン酸の代表的な例としては次のものを挙げるこ
とができる。Bleaching agents used in this bleaching solution or bleach-fixing solution are generally known to include aminopolycarboxylic acids, 'fJFi, and organic acids such as citric acid that coordinate total ions such as iron, cobalt, and copper. There is. Representative examples of the above aminopolycarboxylic acids include the following.
エチレンジアミンテトラ酢酸
ジエチレントリアミンペンタ酢酸
ブＯピレンジアミンテトラ酢酸
ニトリロトリ酢酸
イミノジ酢酸
グリコールエーテルジアミンテトラ酢酸エチレンジアミ
ンテトラブＯピオン駁
エチレンジアミンテトラ酢酸ジナトリウム塩ジエチレン
トリアミンペンタ酢酸ペンタナトリウム塩
二１〜リロトリ酢酸ナトリウム塩
漂白液は上記の漂白剤と共に種々の添加剤を含有しても
よい。また漂白工程に漂白定着液を用いる場合には、前
記漂白剤のほかにハロゲン化銀定着剤を含有する組成の
液が適用される。また漂白定着液には更に例えば臭化カ
リウムの如きハロゲン化合物を含有させてもよい。そし
て前記の漂白液の場合と同様に、その他の各種の添加剤
、例えば１）ＨａｉｖｊＪ剤、蛍光増白剤、消泡剤、界
面活性剤、保恒剤、キレート剤、安定剤、有機溶媒等を
添加、含有させてもよい。Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidbutylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol etherdiaminetetraacetic acidethylenediaminetetrabuOpione ethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium salt 2-lilotriacetic acid sodium saltThe bleaching solution is the above may contain various additives along with the bleaching agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the above-mentioned bleaching solution, various other additives, such as 1) Haivj agent, optical brightener, antifoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. may be added or contained.
なおハロゲン化銀定着剤としては、例えばチオＩａ ｉ
ｆｆナトリウム、チオ＠酸アンモニウム、チオシアン酸
カリウム、チオシアン酸ナトリウム、またはチオ尿素、
チオエーテル等の通常の定着処理に用いられるようなハ
ロゲン化銀と反応して水溶性の銀塩を形成する化合物を
挙げることができる。As the silver halide fixing agent, for example, Thio Ia i
ff sodium, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, or thiourea,
Mention may be made of compounds which react with silver halides to form water-soluble silver salts, such as those used in conventional fixing processes, such as thioethers.
本発明の写真要素の発色現像以外の処理、例えば漂白窓
＠（又は漂白、定着）、更に必要に応じて行われる水洗
、安定化等の各種処理工程の処理温度についても迅速処
理の見地から３０℃以上で行われるのが好ましい。From the viewpoint of rapid processing, the processing temperature of various processing steps other than color development of the photographic element of the present invention, such as bleaching window @ (or bleaching, fixing), washing with water, stabilization, etc. as necessary, is also 30%. Preferably, the reaction is carried out at a temperature of 0.degree. C. or above.
本発明の写真要素は特開［５８−１４８３４号、同５８
−１０５１４５号、同５８−１３４６３４号及び同５８
−１８６３１号並びに特願昭５８−２７０ｅ号及び同５
９−８９２８８号等に示されるような水洗代替安定化処
理を行ってもよい。この水洗代替安定化処理に本発明の
一般式ＣＩ］で示される化合物を含有せしめることがで
きる。The photographic element of the present invention is disclosed in Japanese Patent Publication Nos. 58-14834 and 58-14834.
-105145, 58-134634 and 58
-18631 and Japanese Patent Application No. 58-270e and 58-58
A stabilization treatment as an alternative to water washing as shown in No. 9-89288 or the like may be performed. A compound represented by the general formula CI of the present invention can be included in this water washing alternative stabilization treatment.
本発明の写真要素の写真構成層の１又は２以上の層には
、水溶性または発色現像液で脱色する染料（ＡＩ染料）
を添加することができ、該ＡＩ染料としては、オキソノ
ール染料、ヘミオキソノール染料、メロシアニン染料及
びアゾ染料が包含される。中でもオキソノール染料、ヘ
ミオキソノール染料及びメロシアニン染料等が有用であ
る。用い得るＡＩ染料の例としては、英国特許５８４，
６０９号、同１，２２７，４２９号、特開昭４８−８５
１３０号、同４９−９９６２０号、同 ４９−１１４４
２０号、同 ４９−１２９５３７号、同 ５２−１０８
１１５号、同５９−２５８４５号、同 ５９−１１１６
４０号、同５９−１１１６４１号、米国特許２，２７４
，７８２号、同２，５３３．４７２号、同 ２．９５６
．８７９号、同 ３，１２５，４４８号、同 ３、１４
８．１８７号、同 ３，１７７．０７８号、同 ３，２
４７，１２７号、同３．２６０．６０１号、同３．５４
０．８８７号、同３，５７５，７０４号、同３，６５３
，９０５号、同３，７１８，４７２号、同４，０７１．
３１２号、同４，０７０，３５２＠に記載されているも
のを挙げることができる。In one or more of the photographic constituent layers of the photographic element of the present invention, a dye (AI dye) that is water-soluble or decolorable with a color developing solution is used.
can be added, and the AI dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 584,
No. 609, No. 1,227,429, Japanese Unexamined Patent Publication No. 48-85
No. 130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 52-108
No. 115, No. 59-25845, No. 59-1116
No. 40, No. 59-111641, U.S. Patent No. 2,274
, No. 782, No. 2,533.472, No. 2.956
．． No. 879, No. 3,125,448, No. 3, 14
8.187, 3,177.078, 3,2
No. 47,127, No. 3.260.601, No. 3.54
No. 0.887, No. 3,575,704, No. 3,653
, No. 905, No. 3,718,472, No. 4,071.
No. 312, No. 4,070,352@.
これらのＡＩ染料は、一般に乳剤層中の銀１モル当り２
Ｘ １０−３〜５Ｘ１０−１モル用いることが好まし
く、より好ましくはｌＸ１０−２〜１×１０−１モルを
用いる。These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X10-3 to 5X10-1 mol, more preferably 1X10-2 to 1x10-1 mol.
本発明の写真要素を構成するハロゲン化銀乳剤層は少な
くともその一層が、実質的な塩臭化銀乳剤から成ること
が好ましく、更に感光性乳剤層の全てが塩臭化銀乳剤か
ら成ることが好ましい。Preferably, at least one of the silver halide emulsion layers constituting the photographic element of the present invention consists essentially of a silver chlorobromide emulsion, and more preferably all of the light-sensitive emulsion layers consist of a silver chlorobromide emulsion. preferable.
本発明の写真要素が青感性ハロゲン化銀乳剤層、緑感性
ハロゲン化銀乳剤層、赤感性ハロゲン化銀乳剤層から構
成される場合、これらの乳剤層は、各々２居以上からな
っていてもよい。そして、本発明において青感性ハロゲ
ン化銀乳剤層、緑感性ハロゲン化銀乳剤層、赤感性ハロ
ゲン化銀乳剤層の各層中に占める塩化銀含有率は１０モ
ル％以上が好ましく、特に２０モル％以上が好ましい。When the photographic element of the present invention is composed of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, each of these emulsion layers may consist of two or more layers. good. In the present invention, the silver chloride content in each of the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer is preferably 10 mol% or more, particularly 20 mol% or more. is preferred.
本発明において青感性ハロゲン化銀乳剤層に含まれるハ
ロゲン化銀は平均粒径（平均粒子サイズ）は限定されな
いが、好ましくは０．２０〜０．５５μｍ、より好まし
くは０．３０−０．５０μ屯である。In the present invention, the average grain size (average grain size) of the silver halide contained in the blue-sensitive silver halide emulsion layer is not limited, but is preferably 0.20 to 0.55 μm, more preferably 0.30 to 0.50 μm. It's a ton.
処理安定性の点で平均粒径０．５５μ以下が好ましく、
一方、感度およびマゼンタの色濁り防止の点で平均粒径
０．２０μｍ以上がよい。In terms of processing stability, the average particle size is preferably 0.55μ or less,
On the other hand, from the viewpoint of sensitivity and prevention of magenta color turbidity, the average particle diameter is preferably 0.20 μm or more.
緑感性ハロゲン化銀乳剤層と赤感性ハロゲン化銀乳剤層
に含まれるハロゲン化銀の平均粒径も、特に限定されな
いが、０．１〜２μｍが好ましく、更に好ましくは０．
２〜１μｍ、特に好ましくは０．２５〜０．８μｎ＋で
ある。The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is also not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.1 to 2 μm.
It is 2 to 1 μm, particularly preferably 0.25 to 0.8 μn+.
ハロゲン化銀の平均粒径は、上記の目的のために当該技
術分野において一般に用いられる各種の方法によってこ
れを測定することができ、該ハロゲン化銀の平均粒径は
、立方体のハロゲン化銀粒子の場合は、その−辺の長さ
、また立方体以外の形状の場合は、同一体積を有する立
方体に換算したときの一辺の長さである。The average grain size of silver halide can be measured by various methods commonly used in the art for the above purpose, and the average grain size of silver halide is defined as cubic silver halide grains. In the case of , it is the length of its -side, and in the case of a shape other than a cube, it is the length of one side when converted to a cube having the same volume.
本発明の写真要素における塗布根囲は小さい方が、臭化
物の増加に対する現像の遅れがなくかつ短時間でも充分
な色素形成が行える点で好ましく、０．３〜１ （１／
ｒ 、特ニ０．４〜０．８０ ／ｆが好マシい。The coating radius in the photographic element of the present invention is preferably small, since there is no delay in development due to an increase in bromide and sufficient dye formation can be achieved in a short time;
r, especially 0.4 to 0.80/f is better.
本発明の写真要素に用いられるハロゲン化銀は、平均粒
子サイズが広い範囲に分布している多分散乳剤でもよい
が、実質的な単分散乳剤の方が好ましい。The silver halide used in the photographic elements of this invention may be a polydisperse emulsion with average grain sizes distributed over a wide range, but substantially monodisperse emulsions are preferred.
上記実質的な単分散性のハロゲン化銀粒子とは、電子顕
微鏡写真により乳剤をＩＩ！察したときに大部分のハロ
ゲン化銀粒子が同一形状に見え、粒子サイズが揃ってい
て、かつ下記式で定義される如き粒径分布を有するもの
である。即ち、粒径の分布の標準偏差Ｓを平均粒径Ｔで
割ったとき、その（直が０．１５以下のものをいう。The above-mentioned substantially monodisperse silver halide grains can be seen in the emulsion II! When observed, most of the silver halide grains appear to have the same shape, are uniform in grain size, and have a grain size distribution as defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size T, the value (() is 0.15 or less.
ここでいう粒径とは、前記平均粒径について述べた粒径
と同義である。The particle size here has the same meaning as the particle size described above regarding the average particle size.
ハロゲン化銀粒子の結晶は、正常晶でも双晶でもその他
でもよく、［１００］面と［１１１］面の比率は任意の
ものが使用できる。更に、これらのハロゲン化銀粒子の
結晶構造は、内部から外部まで均一なものであっても、
内部と外部が異質の層状構造（コア・シェル型）をした
ものであってもよい。また、これらのハロゲン化銀は潜
像を主として表面に形成する型のものでも、粒子内部に
形成する型のものでもよい。さらに平板状ハロゲン化銀
粒子（特開昭５８−１１３９３４号、特ＸＩ ！！［１
５９−１７００７０号参照）を用いることもできる。The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [100] planes to [111] planes can be used. Furthermore, even though the crystal structure of these silver halide grains is uniform from the inside to the outside,
It may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains (JP-A-58-113934, Special Edition XI!![1
59-170070) can also be used.
本発明に特に好ましく用いられるハロゲン化銀粒子は、
実質的に単分散のものであり、これは、酸性法、中性法
またはアンモニア法のいずれの調製法により得られたも
のでもよい。Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any of the acidic, neutral, and ammonia methods.
また例えば種粒子を酸性法でつくり、更に、成長速度の
速いアンモニア法により成長させ、所定の大きさまで成
長させる方法でもよい。ハロゲン化銀粒子を成長させる
場合に反応釜内のｐＨｌｏＡｇ等をコントロールし、例
えば特開昭５４−４８５２１号に記載されているような
ハロゲン化銀粒子の成長速度に見合った農の銀イオンと
ハライドイオンを逐次同時に注入混合することが好まし
い。Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, pHloAg etc. in the reaction vessel are controlled, and silver ions and halide are adjusted to match the growth rate of silver halide grains as described in JP-A No. 54-48521. It is preferable to implant and mix the ions sequentially and simultaneously.
本発明に係わるハロゲン化銀粒子のＩＩ製は以上のよう
にして行われるのが好ましい。該ハロゲン化銀粒子を含
有する組成物を、本明細書においてハロゲン化銀乳剤と
いう。II production of silver halide grains according to the present invention is preferably carried out as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.
これらのハロゲン化銀乳剤は、活性ゼラチン；硫黄増感
剤例えばアリルチオカルバミド、チオ尿素、シスチン等
の硫黄増感剤；セレン増感剤；還元増感剤例えば第１ス
ズ塩、二酸化チオ尿素、ポリアミン等：、ｉｌ＊ｆｆ増
感剤例えば金増感剤、具体的にはカリウムオーリチオシ
アネート、カリウムクロロオーレート、２−オー０チオ
−３−メチルベンゾチアゾリウムクロライド等あるいは
例えばルテニウム、パラジウム、白金、ロジウム、イリ
ジウム等の水溶性塩の増感剤、具体的にはアンモニウム
クロロバラデート、カリウムクロロオーレ−トおよびナ
トリウムクロロパラデート（これらの成る種のものは］
の大小によって増感剤あるいはカブリ抑制剤等として作
用する。）等により単独であるいは適宜併用（例えば金
増感剤と硫黄増感剤の併用、金増感剤とセレン増感剤と
の併用等）して化学的に増感されてもよい。These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc., il*ff sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-00thio-3-methylbenzothiazolium chloride, etc., or, for example, ruthenium, palladium, Sensitizers of water-soluble salts such as platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadate (the types consisting of these)
It acts as a sensitizer or a fog suppressant depending on the size of the substance. ) or the like alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.).
本発明に係わるハロゲン化銀乳剤は、含硫黄化合物を添
加して化学熟成し、この化学熟成する前、熟成中、又は
熟成後、少なくとも１種のヒドロキシテトラザインデン
およびメルカプト塁を有する含窒素へテロ環化合物の少
なくとも１種を含有せしめてもよい。The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.
本発明に係わるハロゲン化銀乳剤層にはそれぞれカプラ
ー、即ち、発色現像主薬の酸化体と反応して色素を形成
し得る化合物を含有させることができる。Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.
本発明において使用できる上記カプラーとしては各種イ
エローカプラー、マゼンタカプラーおよびシアンカプラ
ーを特別の制限なく用いることができる。これらのカプ
ラーはいわゆる２当量型であってもよいし４当伍型カプ
ラーであってもよく、またこれらのカプラーに組合せて
、拡散性色素放出型カプラー等を用いることも可能であ
る。As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent couplers or 4-equivalent couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing couplers.
前記イエローカプラーとしては、開鎖ケトメチレン化合
物さらにいわゆる２当母型カプラーと称される活性点−
〇−アリール置換カプラー、活性点−〇−アシル置換カ
プラー、活性点ヒダントイン化合物置換カプラー、活性
点ウラゾール化合物置換カプラーおよび活性点コハク酸
イミド化合物置換カプラー、活性点フッ素誼換カプラー
、活性点塩素あるいは臭素置換カプラー、活性点−〇−
スルホニル置換カプラー等が有効なイエローカプラーと
して用いることができる。用い得るイエローカプラーの
具体例としては、米国特許２．８７５．０５７号、同
３，２６５，５０６号、同 ３，４０８，１９４号、同
３，５５１、１５５号、同 ３，５８２，３２２号、
同 ３，７２５，０７２号、同３．８９１，４４５号、
西独特許１．５４７．１３６８号、西独出願公開２，２
１９，９１７号、同２，２６１，３６１号、同２，４１
４，００６号、英国特許１，４２５，０２０号、特公昭
５１−１０７８３号、特開昭４７−２６１３３号、同４
８−７３１４７号、同５１−１０２６３６号、同５０−
６３４１号、同５０−１２３３４２号、同５０−１３０
４４２号、同５１−２１８２７号、同５０−８７６５０
号、同５２−８２４２４号、同５２−１１５２１９号、
同５８−９５３４６号等に記載されたものを挙げること
ができる。The yellow coupler includes an open-chain ketomethylene compound and an active point coupler called a two-terminal coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine-converted coupler, active point chlorine or bromine Substituted coupler, active point -〇-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3,265,506, No. 3,408,194, No. 3,551, 155, No. 3,582,322,
No. 3,725,072, No. 3.891,445,
West German Patent No. 1.547.1368, West German Application Publication 2,2
No. 19,917, No. 2,261,361, No. 2,41
4,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, 4
No. 8-73147, No. 51-102636, No. 50-
No. 6341, No. 50-123342, No. 50-130
No. 442, No. 51-21827, No. 50-87650
No. 52-82424, No. 52-115219,
Examples include those described in No. 58-95346.
また本発明において用いられるマゼンタカプラーとして
はピラゾロン系、ピラゾロトリアゾール系、ピラゾリノ
ベンツイミダゾール系、インダシロン系の化合物を挙げ
ることができる。これらのマゼンタカプラーはイエロー
カプラーと同様４当ｌ型カプラーだけでなく、２当量型
カプラーであってもよい。マゼンタカプラーの具体例と
しては米国特許２，６００．７８８号、同２，９８３，
６０８号、同３．０６２．６５３号、同 ３，１２７，
２６９号、ｊＩｉｌ ３，３１１，４７６号、晦３．
４１９，３９１号、同 ３，５１９，４２９号、同 ３
，５５８，３１９号同３．５８２．３２２号、同３，６
１５，５０６号、同３，８３４，９０８号、同３．８９
１．４４５号、西独特許１，８１０，４６４号、西独特
許比Ｘｉ （ＯＬ Ｓ ） ２，４０８，６６５号、
同２，４１７，９４５号、同２．４１８．９５９号、同
２．４２４．４６７号、特公昭４０−６０３１号、特開
昭５１−２０８２６号、同５２−５８９２２号、同 ４
９−１２９５３８号、同４９−７４０２７号、同 ５（
１−１５９３３６号、同５２−４２１２１Ｍ、同４９−
７４０２８号、同５０−６０２３３号、同５１−２６５
４１号、同５３−５５１２２号、特願昭５５−１１０９
４３号等に記載されたものを挙げることができる。Examples of magenta couplers used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patent No. 2,600.788, U.S. Pat.
No. 608, No. 3.062.653, No. 3,127,
No. 269, jIil No. 3,311,476, Akira 3.
No. 419,391, No. 3,519,429, No. 3
, 558, 319 No. 3.582.322, No. 3, 6
No. 15,506, No. 3,834,908, No. 3.89
1.445, West German Patent No. 1,810,464, West German Patent Xi (OL S) No. 2,408,665,
No. 2,417,945, No. 2.418.959, No. 2.424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1982, No. 52-58922, No. 4
No. 9-129538, No. 49-74027, No. 5 (
No. 1-159336, No. 52-42121M, No. 49-
No. 74028, No. 50-60233, No. 51-265
No. 41, No. 53-55122, patent application No. 55-1109
Examples include those described in No. 43 and the like.
さらに本発明において用いられる有用なシアンカプラー
としては、例えばフェノール系、ナフトール系カプラー
等を挙げることができる。そしてこれらのシアンカプラ
ーはイエローカプラーと同様４当田型カプラーだけでな
く、２当量型カプラーであってもよい。シアンカプラー
の具体例としては米国特許２，３６９，９２９号、同２
，４３４，２７２号、同２．４７４，２９３号、同 ２
，５２１，９０８号、同 ２．８９５．８２６号、同３
，０３４，８９２号、同３，３１１，４７６号、同３，
４５８，３１５号、同３．４７６、５６３号、同３．５
８３．９７１号、同３．５９１．３８８号、同 ３．７
６７、４１１号、同 ３，７７２，００２号、同 ３．
９３３，４９４号１、同４．００４．９２９号、西独特
許出願（ＯＬ Ｓ ） ２，４１４Ｊ３Ｑ号、Ｊｉｉ
ｌ ２．４５４．３２９Ｍ、特開昭４８−５９８３８号
、同５１−２６０３４号、同４８−５０５５号、同５１
−１４６８２７号、同５２−６９６２４号、同５２−９
０９３２号、同５８−９５３４６号、特公昭４９−１１
５７２号等に記載のものを挙げることができる。Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. Similar to the yellow coupler, these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2.
, No. 434,272, No. 2.474,293, No. 2
, No. 521,908, No. 2.895.826, No. 3
, No. 034,892, No. 3,311,476, No. 3,
No. 458,315, No. 3.476, No. 563, No. 3.5
83.971, 3.591.388, 3.7
67,411, 3,772,002, 3.
933,494 No. 1, 4.004.929, West German Patent Application (OL S) No. 2,414J3Q, Jii
l 2.454.329M, JP-A-48-59838, JP-A No. 51-26034, JP-A No. 48-5055, JP-A No. 51
-146827, 52-69624, 52-9
No. 0932, No. 58-95346, Special Publication No. 1978-11
Examples include those described in No. 572 and the like.
本発明のハロゲン化銀乳剤層、その他の写真構成層中に
は非拡散性ＤＩＲ化合物、カラードマぜンタ又はシアン
カプラー、ポリマーカプラー、拡散性ＤＩＲ化合物等の
カプラーを併用してもよい。Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers.
非拡散性ＤＩＲ化合物、カラードマゼンタ又はシアンカ
プラーについては本出願人による特願昭５９−１９３６
１１号の記載を、またポリマーカプラーについては本出
願人による特願昭５９−１７２１５１号の記載を各々参
照できる。Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, patent application filed in 1983-1936 by the present applicant
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 172151/1983 filed by the present applicant.
本発明に使用できる上記カプラーを本発明の写真構成層
中に添加する方法は従前通りでよく、また上記カプラー
の添加伍は限定的ではないが、銀１モル当りｌＸｌ０−
３〜５モルが好ましく、より好ましくは１ Ｘ １０−
２〜５ Ｘ １０−１である。The above-mentioned coupler that can be used in the present invention may be added to the photographic constituent layer of the present invention by any conventional method, and the number of additions of the above-mentioned coupler is not limited.
Preferably 3 to 5 mol, more preferably 1 X 10-
It is 2-5×10−1.
本発明の写真要素には上記の他に各種の写真用添加剤を
含有せしめることができる。例えばリサーチ・ディスク
ロージャー誌１７６４３号に記載されているかぶり防止
剤、安定剤、紫外線吸収剤、色汚染防止剤、色画像褪色
防止剤、帯電防止剤、硬膜剤、界面活性剤、可塑剤、湿
潤剤等を用いることができる。The photographic elements of the present invention may contain various photographic additives in addition to those mentioned above. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, and wetting agents described in Research Disclosure No. 17643. Agents etc. can be used.
本発明ハロゲン化銀乳剤層は、塗布助剤、帯電防止、ス
ベリ性改良、乳化分散、接着防止及び写真性改良（例え
ば現像促進、硬調化、増感）など種々の目的で種々の公
知の界面活性剤を含んでもよい。The silver halide emulsion layer of the present invention has various known interfaces for various purposes such as a coating aid, antistatic properties, improvement of slipperiness, emulsification dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). It may also contain an activator.
すなわち、米国特許第２，２４０，４７２号、同２，８
３１．７６６号、同 ３，１５８，４８４号、同３．２
１０．１９１号、同 ３．２９４，５４０号、同３．５
０７．６６０号、英国特許１，０１２，４９５号、同
１，０２２，８７８号、同 １，１７９，２９０号、同
１，１９８、４５０号、米国特許２．７３９．８９１
号、同２，８２３．１２３号、同１，１７９，２９０号
、同１，１９８，４５０号、同２，７３９．８９１号、
同２．８２３．１２３号、同３．０６８．１０１号、同
３．４１５，６４９号、同 ３．６６６、４７８号、同
３．７５６．８２８号、英国特許１．３９７．２１８
号、同３．１１３．８１６号、同３，４１１、４１３号
、同 ３，４７３．１１４号、同 ３．３４５．９７４
号、同３、７２６．６８３号、同３．８４３．３６８号
、ベルギー特許１３１、１２６号、英国特許１．４３８
，５１４号、同 １，１５９，８２５号、同１．３７４
．７８０号、米国特許２，２７１，６２３号、同２．２
８８，２２６号、同 ２．９４４．９００号、同 ３，
２３５，９１９号、同３．６７１．２４７号、同３．，
７７２，０２１号、同３．５８９．９０６号、同３．６
６６、４７８号、同３．７５４．９２４号、西独出願公
開（ＯＬ Ｓ ’） １，９６１，６８３号及び特開
昭５０−１１７４１４号、同５０−５９０２５号、特公
昭４０−３７８号、同４０−３７’３号、同４３−１３
８２２号に記載されている例えばサポニン、（ステロイ
ド系）、アルキレンオ本サイド誘導体く例えばポリエチ
レングリコール、ポリエチレングリコール／ポリプロピ
レングリコール縮合物、ポリエチレングリコールアルキ
ルまたはアルキルアリールエーテル頚、ポリエチレング
リコールエステル類、ポリエチレングリコールソルビタ
ンエステル類、ポリアルキレングリコールアルキルアミ
ンまたはアミド類、シリコーンのポリエチレンオキサイ
ド付加物類）、グリシドール誘導体（例えばアルケニル
コハク酸ポリグリセリド、アルキルフェノールポリグリ
セリド）、多価アルコールの脂肪酸エステル類、糖のア
ルキルエステル類、同じくウレタン類またはエーテル類
などの非イオン性界面活性剤、トリテルペノイド系サポ
ニン、アルキルカルボン酸塩、アルキルベンゼンスルホ
ン酸塩、アルキルナフタレンスルホン酸塩、アルキル硫
酸エステル類、アルキルリン酸エステル類、Ｎ−アシル
−Ｎ−アルキルタウリン類、スルホコハク酸エステル類
、スルホアルキルポリオキシエチレンアルキルフェニル
エーテル類、ポリオキシエチレンアルキルリン酸エステ
ル類などのようなカルボキシ基、スルホ基、ホスホ基、
硫酸エステル基、リン酸エステル基等め酸性基を含むア
ニオン界面活性剤、アミノ酸類、アミノアルキルスルホ
ン酸類、アミノ、アルキル硫酸またはリン酸エステル類
、アルキルベタイン類、アミンイミド類、アミンオキシ
ド類などの両性界面活性剤、アルキルアミン塩類、脂肪
族或いは芳香族第４扱アンモニウム塩類、ピリジウム、
イミダゾリウムなどの複素環第４綴アンモニウム塩類及
び脂肪族または′ａ素環を含むスルホニウムまたはスル
ホニウム塩類などのカチオン界面活性剤を用いることが
できる。That is, U.S. Patent Nos. 2,240,472 and 2,8
31.766, 3,158,484, 3.2
10.191, 3.294,540, 3.5
No. 07.660, British Patent No. 1,012,495,
No. 1,022,878, No. 1,179,290, No. 1,198,450, U.S. Patent No. 2.739.891
No. 2,823.123, No. 1,179,290, No. 1,198,450, No. 2,739.891,
2.823.123, 3.068.101, 3.415,649, 3.666, 478, 3.756.828, British Patent 1.397.218
No. 3.113.816, No. 3,411, 413, No. 3,473.114, No. 3.345.974
No. 3, 726.683, 3.843.368, Belgian Patent No. 131, 126, British Patent No. 1.438
, No. 514, No. 1,159,825, No. 1.374
．． No. 780, U.S. Patent No. 2,271,623, 2.2
No. 88,226, No. 2.944.900, No. 3,
No. 235,919, No. 3.671.247, No. 3. ，
No. 772,021, No. 3.589.906, No. 3.6
No. 66,478, No. 3.754.924, OLS' No. 1,961,683, Japanese Patent Application Publication No. 50-117414, No. 50-59025, Japanese Patent Publication No. 40-378, 40-37'3, 43-13
No. 822, for example, saponins, (steroids), alkylene derivatives such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan. esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, Similarly, nonionic surfactants such as urethanes or ethers, triterpenoid saponins, alkyl carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl- Carboxy groups, sulfo groups, phospho groups such as N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, amino, alkyl sulfate or phosphate esters, alkyl betaines, amine imides, and amine oxides; Surfactants, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium and sulfonium or sulfonium salts containing aliphatic or 'a' rings can be used.
本発明のハロゲン化根乳剤層には、現像促進剤として、
前記の界面活性剤の他に西独出願公開（ＯＬ Ｓ ）
２，００２，８７１号、同２．４４５．６１１号、同
２．３６０，８７８号、英国特許１，３５２，１９６号
などに記載されているイミダゾール類、チオエーテル類
、セレノエーテル類などを含有してもよい。In the halogenated root emulsion layer of the present invention, as a development accelerator,
In addition to the above-mentioned surfactants, OLS
Contains imidazoles, thioethers, selenoethers, etc. described in No. 2,002,871, No. 2.445.611, No. 2.360,878, British Patent No. 1,352,196, etc. It's okay.
本発明の写真要素において、乳剤を調製するために用い
られる親水性コロイドには、ゼラチン、誘導体ゼラチン
、ゼラチンと池の高分子とのグラフトポリマー、アルブ
ミン、カゼイン等の蛋白質、ヒトＯキシエチＪレセルロ
ース誘導体、カルボキシメチルセルロース等のセルロー
ス誘導体、澱粉誘導体、ポリビニルアルコール、ポリビ
ニルイミダゾール、ポリアクリルアミド等の単一あるい
は共重合体の合成親水性高分子等の任意のものが包含さ
れる。In the photographic elements of this invention, the hydrophilic colloids used to prepare the emulsions include gelatin, derivative gelatins, graft polymers of gelatin and polymers, proteins such as albumin, casein, and human O-oxyethyl cellulose. Examples include derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.
本発明の写真要素の支持体としては、例えばバライタ紙
、ポリエチレン被覆紙、ポリプロピレン合成紙、反射層
を併設した、又は反射体を併用する透明支持体、例えば
ガラス板、セルロースアセテート、セルロースナイトレ
ート又はポリエチレンテレフタレート等のポリエステル
フィルム、ポリアミドフィルム、ポリカーボネートフィ
ルム、ポリスチレンフィルム等が挙げられ、その他通常
の透明支持体であってもよい。これらの支持体は写真要
素の使用目的に応じて適宜選択される。Supports for the photographic elements of the invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflector, such as glass plates, cellulose acetate, cellulose nitrate, or Examples include polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, and other common transparent supports. These supports are appropriately selected depending on the intended use of the photographic element.
本発明において用いられるハロゲン化銀乳剤層及びその
他の写真構成層の塗設には、ディッピング塗布、アエー
ドクター塗布、カーテン塗布、ホッパー塗布等種々の塗
布方法を用いることができる。また米国特許２，７６１
，７９１号、同２，９４１，８９８号に記載の方法によ
る２層以上の同時塗布法を用いることもできる。For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, various coating methods such as dipping coating, A-doctor coating, curtain coating, and hopper coating can be used. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941,898 can also be used to simultaneously coat two or more layers.
本発明においては各乳剤層の塗設位置を任意に定めるこ
とができる。例えばフルカラープリント用のペーパーの
場合には、支持体側から順次青感性ハロゲン化銀乳剤層
、緑感性ハロゲン化銀乳剤層、赤感性ハロゲン化銀乳剤
層の配列とすることが好ましい。これらの感光性ハロゲ
ン化銀乳剤層は各々２以上の層から成っていてもよい。In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of paper for full color printing, it is preferable to arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer sequentially from the support side. Each of these photosensitive silver halide emulsion layers may consist of two or more layers.
そして、これら全ての感光性乳剤層が本発明の塩臭化銀
乳剤から成るときに本発明の効果が大である。The effects of the present invention are most significant when all of these photosensitive emulsion layers are composed of the silver chlorobromide emulsion of the present invention.
本発明の写真要素において、目的に応じて過当な厚さの
中間層を設けることは任意であり、更にフィルタ一層、
カール防止層、保護層、アンチハレーション層等の種々
の層を、写真構成層として適宜組合せて用いることがで
きる。これらの構成層には結合剤として前記のような乳
剤層に用いることのできる親水性コロイドを同様に用い
ることができ、またその層中には前記の如き乳剤層中に
含有せしめることができる種々の写真用添加剤を含有せ
しめることができる。In the photographic element of the present invention, it is optional to provide an intermediate layer having an excessive thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as photographic constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.
以下・、余白
一２−
Ｃ９＃電−
［実施例］
以下に本発明の具体的実施例を述べるが、本発明の実施
の態様はこれらに限定されない。Below, margin 12-C9# [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.
実施例１
ポリエチレンで両面ラミネートした紙支持体上に、下記
の各層を支持体側より順次塗設し、写真要素試料Ｎ０．
１を作成した。Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to form photographic element sample No.
1 was created.
Ｂ １ ・−１，２０／ｌ’ （Ｄセｙチン、１ｌｆｆ
ｉカ０．３２り／ｆ（銀換算、以下同じ）の表−１の増
感色素により増感された青感性塩臭化銀乳剤（臭化銀含
有率８０モル％）、０．５０（１／ ｆのジオクチルフ
タレートに溶解した０、８０ｇ／ｗ’のイエローカプラ
ー（Ｙ−１）を含有する層。B 1 ・-1,20/l' (D seytin, 1lff
A blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%) sensitized with the sensitizing dyes shown in Table 1 with i/f (in terms of silver, the same applies hereinafter), 0.50 ( A layer containing 0.80 g/w' of yellow coupler (Y-1) dissolved in 1/f dioctyl phthalate.
層２−０．７０Ｑ／ｆのゼラチン、１２１１／ｉ’のイ
ラジェーション防止染料（Ａ Ｉ −１＞ 、６＋１１
０／ｍ”の（ＡＩ−２）からなる中間層。Layer 2 - 0.70Q/f gelatin, 1211/i' anti-irradiation dye (A I -1>, 6+11
0/m'' (AI-2).
層３・・・１．２５＋ｊ／ｖ’のゼラチン、銀量が０．
２５（１／ｆの２．５Ｘ １０−畔ｍｏ！ ／ｍｏｌ
ＡＱ Ｘの下記色素Ｂ−１により分光増感された緑感性
塩臭化銀乳剤（臭化銀含有率７０モル％）、０．３０（
１／ ｒのジオクチルフタレートに溶解した０、 ６２
（１／−ｔ’のマゼンタカプラー（Ｍ−’１）を含有す
る層。Layer 3: Gelatin of 1.25+j/v', silver amount 0.
25 (2.5X of 1/f 10-mo!/mol
Green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%) spectrally sensitized with the following dye B-1 of AQ X, 0.30 (
0,62 dissolved in 1/r dioctyl phthalate
(Layer containing magenta coupler (M-'1) of 1/-t'.
層４・・・１．２０（１／ｆのゼラチンからなる中間層
。Layer 4: Intermediate layer made of 1.20 (1/f) gelatin.
層５・１．２０Ｑ／ｆ（１）セラチン、ＩＩが０．３０
Ｑ／’ｆの２．５ｘ１１’ｍｏｌ ／ｍｏｌ ＡｇＸの
下記色素Ｂ−２により分光増感された赤感性塩臭化銀乳
剤（臭化銀含有率７０モル％）、０．２０１Ｊ／、Ｊの
ジオクチルフタレートに溶解した０、４５ｇ／ｌ’のシ
アンカプラー（Ｃ−１）を含有する層。Layer 5・1.20Q/f(1) Ceratin, II is 0.30
Red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%) spectrally sensitized with the following dye B-2 of 2.5 x 11' mol / mol of Q/'f AgX, 0.201 J/, of J Layer containing 0.45 g/l' of cyan coupler (C-1) dissolved in dioctyl phthalate.
層６・・・１．ｏｏｇ／ｆのゼラチン及び０．２０ｑ／
、、２のジオクチルフタレートに溶解した０、３００／
１２の紫外線吸収剤（ＵＶ−１）を含有す枦り
層７・・・０．５００／ ｆのゼラチンを含有する層。Layer 6...1. oog/f gelatin and 0.20q/
, 0,300/dissolved in dioctyl phthalate of 2
Layer 7 containing ultraviolet absorber (UV-1) of 12: Layer containing gelatin of 0.500/f.
なお、５！膜剤として、２，４−ジクロロ−６−ヒドロ
キシ−ｓ−トリアジンナトリウムを層２．４及び６中に
、それぞれゼラチン１ｇ当り ０．０１７ｇになるよう
に添加した。In addition, 5! As a membrane agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2.4 and 6 in an amount of 0.017 g per 1 g of gelatin, respectively.
以く■ｂ白
（Ｙ−１）
ＣＩ
（Ｃ−１）
（ＡＩ−１）
（ＡＩ−２）
（ＵＶ−１）
し、ルｕ（ｔ）
上記試料を光学ウェッジを通して露光後、次の工程で処
理した。After exposing the above sample to light through an optical wedge, the next step is Processed with.
処理工程（３８℃）
発色現像 １分３０秒
漂白定着 、 １分３０秒
水 洗 １分
乾 燥 ６０〜８０℃ ２分各
処理液の組成は上記の通りである。Processing steps (38°C) Color development 1 minute 30 seconds Bleach-fixing, 1 minute 30 seconds washing with water 1 minute drying 60-80°C 2 minutes The composition of each processing solution is as described above.
［発色現像液］
純水 ８００城ベンジ
ルアルコール １５−硫酸ヒドロキシ
アミノ ２．０ｇ臭化カリウム
０．６６塩化ナトリウム
１，０ｇ亜硫酸カリウム
２．Ｑ Ｏトリエタノールアミン ２
．０ｇ発色現像主薬（表−１に示す通り＞ ６．０
ｇ１−ヒドロキシエチリデン−１，１
−ジホスホン酸（６０％水溶液） １．５ｉＲ
炭酸カリウム ３２１７表−１
に記載の一般式［Ｉ］の化合物
（添加機は表−１に記載）
純水を加えて１１とし２０％水酸化カリウム又は１０％
希硫酸でｐ）（−１１，０に調整する。[Color developer] Pure water 800% benzyl alcohol 15-hydroxyamino sulfate 2.0g Potassium bromide
0.66 sodium chloride
1.0g potassium sulfite
2. Q O triethanolamine 2
．． 0g color developing agent (as shown in Table-1 > 6.0
g1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5iR
Potassium carbonate 3217 Table-1
Compound of general formula [I] described in (adding machine is listed in Table 1) Add pure water to make 11 and 20% potassium hydroxide or 10%
Adjust to p)(-11.0 with dilute sulfuric acid.
［ｉ１！白定着液］
純水 ５５（ｈｅエチ
レンジアミン四酢酸鉄（Ｉ［［）
アンモニウム塩 ６５ Ｑチオ硫
酸アンモニウム ８５ （１亜＠酸水素
ナトリウム １０ ｇメタ重亜１ｉｉＩ
酸ナトリウム ２ｇエチレンジアミン四
酢！−２
ナトリウム ２０ （１臭化ナ
トリウム １０ （１純水を加え
て１２とし、アンモニア水又は希硫酸にて ｐｌ−１−
７，０に調整する。[i1! White fixer] Pure water 55 (he ethylenediaminetetraacetic acid iron (I
Sodium acid 2g ethylenediaminetetra vinegar! -2 Sodium 20 (1 Sodium bromide 10 (1) Add pure water to make 12, add ammonia water or dilute sulfuric acid pl-1-
Adjust to 7.0.
上記処理後の各試料について、サクラデンシトメーター
ＰＤＡ−６５を用いて、青色光により濃度漬り定を行っ
た。感度はカブリ＋０．５の濃度を得るのに必要な露光
量の逆数より求め、表−１にその相対値を示した。For each sample after the above-mentioned treatment, the concentration was determined using blue light using a Sakura densitometer PDA-65. The sensitivity was determined from the reciprocal of the exposure amount required to obtain a density of fog + 0.5, and the relative values are shown in Table 1.
一方、処理後の各試料の未露光部分の分光反射率より、
４３５ｎｌにおける吸光度を求め表−１に吸光度の相対
値を示した。なお、この相対値は支持体の吸光度を０と
したときのものである。On the other hand, from the spectral reflectance of the unexposed part of each sample after processing,
The absorbance at 435 nl was determined and the relative values of absorbance are shown in Table 1. Note that this relative value is based on the absorbance of the support being 0.
表−１の比較用色素Ｂ−３の化学構造を下記に示す。The chemical structure of comparative dye B-3 in Table 1 is shown below.
表−１の結果から、本発明の写真要素を、現像液中に一
般式［Ｉ］で示される化合物を含有する現像液中で処理
すると、写真要素の感度を低下させることなく、しかも
写真要素の白地部分の残色性を低減させることができる
ことが判る。これに対して比較の試料は、写真要素のい
ずれも残色性が大きく、白地部分が増感色素で着色され
ていることが判る。なお、比較の試料においては、現像
液中に本発明の一般式［Ｉ］で表わされる化合物を含有
する現像液で処理しても、わずかに残色性が改善される
にすぎない。From the results in Table 1, it is clear that when the photographic element of the present invention is processed in a developer containing the compound represented by the general formula [I], the sensitivity of the photographic element is not reduced, and the photographic element It can be seen that it is possible to reduce the residual color in the white background area. On the other hand, in the comparative samples, all of the photographic elements had a large residual color, indicating that the white background areas were colored with the sensitizing dye. In addition, in the comparative sample, even if the sample was treated with a developer containing the compound represented by the general formula [I] of the present invention, the residual color was only slightly improved.
実施例−２
実施例−１に示した１１で使用するハロゲン化銀乳剤を
８ ’−３によって分光温感された塩臭化銀乳剤（臭化
銀含有率８０モル％）に変え、実施例−１で示した層３
で使用するハロゲン化銀乳剤を、表−２に示される増感
色素によって増感された塩化銀乳剤（臭化銀含有＄７０
モル％）にすること以外は実施例−１と同様の方法によ
り試料を作製し、緑色光で測定した以外は実ＩＭｒ！Ａ
−１と同様の方法で感度を求めた。なお残色性は５３０
ｎＩｌの吸光度より求めた。これらの結果を表−２に示
した。なお、表−２の吸光度の相対値は支持体の吸光度
を０と表−２の結果から、本発明の増感色素を緑感光性
ハロゲン化銀乳剤層中に含有する本発明の試料を本発明
の処理法に従って現像処理したものは、感度の低下を引
き起こすことなくしかも残色性がすぐれていることが判
る。これに対し、比較の試料はいずれも残色性が劣り、
処理液中に一般式［Ｉ］で示される化合物を含有するも
ので処理しても残色性はほとんど改善されないことが判
る。Example 2 The silver halide emulsion used in 11 shown in Example 1 was changed to a silver chlorobromide emulsion (silver bromide content 80 mol%) spectrally and temperature sensitive by 8'-3, and Example 1 was prepared. Layer 3 indicated by -1
The silver halide emulsion used in Table 2 was a silver chloride emulsion sensitized with the sensitizing dye shown in Table 2 (silver bromide containing $70
A sample was prepared in the same manner as in Example-1, except that it was made into mol%), and the actual IMr! was measured using green light. A
Sensitivity was determined in the same manner as in -1. The residual color is 530.
It was determined from the absorbance of nIl. These results are shown in Table-2. Note that the relative values of absorbance in Table 2 are based on the absorbance of the support being 0 and the results in Table 2. It can be seen that those developed according to the processing method of the invention do not cause a decrease in sensitivity and have excellent residual color. On the other hand, all comparative samples had poor color retention;
It can be seen that even if the treatment solution contains a compound represented by the general formula [I], the residual color property is hardly improved.
実施例−３
層３で使用するハロゲン化銀乳剤を８−１によって分光
増感された塩臭化銀乳剤（臭化銀含有率７０モル％）に
変え、層５で使用するハロゲン化銀乳剤を表３で示され
る増感色素によって増感された塩臭化銀乳剤（臭化銀含
有率７０モル％）にすること以外は実施例−２と同様の
方法にて試料を作製し、赤色光で濃度測定を行った以外
は実施例−２と同様の方法で感度を求めた。Example-3 The silver halide emulsion used in layer 3 was changed to a silver chlorobromide emulsion (silver bromide content 70 mol%) spectrally sensitized by 8-1, and the silver halide emulsion used in layer 5 was changed. A sample was prepared in the same manner as in Example 2, except that silver chlorobromide emulsion (silver bromide content 70 mol%) was sensitized with the sensitizing dye shown in Table 3. Sensitivity was determined in the same manner as in Example 2, except that the concentration was measured using light.
なお残色性は６５０ｎ＋＋＋の吸光度より求めた。これ
らの結果を表−３に示した。Incidentally, residual color was determined from the absorbance at 650n+++. These results are shown in Table-3.
表−３の結果より本発明の増感色素によって増感された
ハロゲン化銀写真感光材料を、蛍光増白剤を含有する現
像液によって処理することにより、感度を低下させるこ
となく、残色性を改良することができた。The results in Table 3 show that by processing the silver halide photographic light-sensitive material sensitized with the sensitizing dye of the present invention with a developer containing a fluorescent whitening agent, it is possible to reduce residual color without reducing sensitivity. was able to improve.
一方、本発明の増感色素によってハロゲン化銀写真感光
材料が増感されていても、現像液中に蛍光増白剤を含有
しなかった場合や、現像液中に蛍光増白剤が含有されて
いても、ハロゲン化銀写真感光材料が本発明外の増感色
素によって増感されている場合には残色性の改良はほん
のわずかであり、このことから本発明の効果を予想する
ことは困難である。On the other hand, even if the silver halide photographic light-sensitive material is sensitized by the sensitizing dye of the present invention, there may be cases where the developer does not contain a fluorescent brightener or the developer does not contain a fluorescent brightener. However, if the silver halide photographic light-sensitive material is sensitized with a sensitizing dye other than the present invention, the improvement in residual color is only slight, and from this fact it is difficult to predict the effect of the present invention. Have difficulty.
特許出願人 小西六写真工業株式会社
手続省１】正置 （方式）
％式％
２、発明の名称
ハロゲン化銀ノＪラー写真感光材ｆ３１の処理方法３、
補正をする者
事件との関係 特ｎ出願人
住所 東京都新宿区西新宿１丁目２６番２号名称
（１２７＞ 小西六写真工業株式会社代表取締役
井手 恵生
４、代理人 〒１０２
住所 東京都千代田区九段北４丁目１番１号。Patent applicant Roku Konishi Photo Industry Co., Ltd. Ministry of Procedure 1] Formal placement (method) % formula % 2, Name of the invention Processing method for silver halide J-Ra photographic light-sensitive material f31 3,
Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127> Representative Director of Roku Konishi Photo Industry Co., Ltd.
Keio Ide 4, Agent 102 Address 4-1-1 Kudankita, Chiyoda-ku, Tokyo.
（発送日） 昭和６１年０７月２９８
手続？ｒｌｉ ｉＥ書 （０允）
１イ１和６１年特訂願 第１００２０２号２、発明の名
称
ハロゲン化銀カラー写真感光材料の処理方法３、補正を
マ゛る考
事件との関係 特許出願人
住所 東京都新１６区西新１６１丁目２６番２号名称
（１２７） 小西六写真工業株式会社代表取締役
井手 忠生
４、代理人 〒１０２
住所 東京都千代田区九段北４丁目１番１号九段−ロ
坂ビル電話２６３−９５２４
Ｎ１和６１年８月２１日付提出の手続補正１ｊに添６、
補正の内容
（１）明ｍｔｕ第２４頁例示化合物ＮＯ，Ａ−／１１の
構造式を以下の如く補正Ｊる。(Shipping date) July 298, 1985 Procedure? rli iE book (0 允) 1-1 Special revision application No. 100202 of 1961 2. Name of the invention Processing method for silver halide color photographic light-sensitive materials 3. Relationship with the case involving amendments Patent applicant address 161-26-2 Nishijin, Shin 16-ku, Tokyo Name (127) Konishiroku Photo Industry Co., Ltd. Representative Director Tadao Ide 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 N1 Attachment 6 to procedural amendment 1j submitted on August 21, 1961,
Contents of correction (1) The structural formula of exemplified compound NO, A-/11, page 24 of MTU, is corrected as follows.
（ｃＲヘー〕 以 上(cR hee) that's all
Claims (1)
真感光材料を下記一般式［ I ］の化合物を含有する処
理液によって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。 一般式［Ａ］ ▲数式、化学式、表等があります▼ ［式中、Ｚ＿１及びＺ＿２はそれぞれ同一でも相違して
もよく、各々ヘテロ環を形成するに必要な原子群を表わ
し、Ｒ＿１はカルボキシ基で置換されたアルキル基を表
わす。Ｒ＿２はＲ＿１と同一でも相違していてもよく、
アルキル基、アリール基、アルケニル基またはアラルキ
ル基を表わす。Ｒ＿３〜Ｒ＿６は各々水素原子、炭素数
４以下のアルキル基Ｒ＿２とＲ＿６（ｑ＝２の場合）又
はＲ＿３とＲ＿５（ｍ＝２、ｑ＝２の場合）が連結して
５又は６員環となるアルキレン架橋を形成しても良い。 ｌ、ｍ、ｎ、ｑ及びｒは、それぞれ１又は２を表わす。 Ｘ＾−はアニオンを表わす。］ 一般式［ I ］ ▲数式、化学式、表等があります▼ ［式中、Ｘ＿２およびＸ＿３は、それぞれ▲数式、化学
式、表等があります▼基、または、Ｒ＿９−ＣＯ−基を
表わす。（ここで、Ｒ＿７、Ｒ＿８およびＲ＿９は、そ
れぞれ、ヒドロキシル基、ハロゲン原子、モルホリノ基
、アルコキシ基、アリールオキシ基、アルキル基、アリ
ール基、アミノ基、アルキルアミノ基、またはアリール
アミノ基を表わす。Ｍは１価の陽イオンを表わす。）］[Scope of Claims] A silver halide photographic material containing a sensitizing dye of the following general formula [A], which is characterized in that it is processed with a processing solution containing a compound of the following general formula [I]. A method of processing color photographic materials. General Formula [A] ▲ Numerical formulas, chemical formulas, tables, etc. represents an alkyl group substituted with R_2 may be the same as or different from R_1,
Represents an alkyl group, aryl group, alkenyl group or aralkyl group. R_3 to R_6 are each a hydrogen atom, an alkyl group having 4 or less carbon atoms R_2 and R_6 (in the case of q=2), or R_3 and R_5 (in the case of m=2, q=2) are connected to form a 5- or 6-membered ring. Alternatively, an alkylene bridge may be formed. l, m, n, q and r each represent 1 or 2. X^- represents an anion. ] General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_2 and X_3 each represent a ▲ Numerical formula, chemical formula, table, etc. ▼ group or R_9-CO- group. (Here, R_7, R_8 and R_9 each represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, an alkylamino group, or an arylamino group.M represents a monovalent cation)]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10020286A JPS62257154A (en) | 1986-04-30 | 1986-04-30 | Processing method for silver halide color photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10020286A JPS62257154A (en) | 1986-04-30 | 1986-04-30 | Processing method for silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62257154A true JPS62257154A (en) | 1987-11-09 |
Family
ID=14267717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10020286A Pending JPS62257154A (en) | 1986-04-30 | 1986-04-30 | Processing method for silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62257154A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02843A (en) * | 1988-01-28 | 1990-01-05 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| JPH0228649A (en) * | 1988-06-06 | 1990-01-30 | Eastman Kodak Co | Photographic processing |
| JPH0250151A (en) * | 1988-05-09 | 1990-02-20 | Fuji Photo Film Co Ltd | Development processing method for silver halide photosensitive material |
| JPH0250155A (en) * | 1987-06-18 | 1990-02-20 | Fuji Photo Film Co Ltd | Color image forming method |
| JPH02275948A (en) * | 1989-01-19 | 1990-11-09 | Fuji Photo Film Co Ltd | Processing liquid for silver halide photographic sensitive material, silver halide photographic sensitive material and processing method |
| EP0631185A1 (en) | 1993-06-11 | 1994-12-28 | Fuji Photo Film Co., Ltd. | Method for continuously processing silver halide color photosensitive material |
| US5395742A (en) * | 1993-05-18 | 1995-03-07 | Fuji Photo Film Co., Ltd. | Diaminostilbene series compound and a method for forming an image using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5949537A (en) * | 1982-09-14 | 1984-03-22 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide photosensitive material |
| JPS60136738A (en) * | 1983-12-22 | 1985-07-20 | Fuji Photo Film Co Ltd | Photosensitive silver halide material |
| JPS6177843A (en) * | 1984-09-25 | 1986-04-21 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
| JPS62215272A (en) * | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | Color image forming method |
-
1986
- 1986-04-30 JP JP10020286A patent/JPS62257154A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5949537A (en) * | 1982-09-14 | 1984-03-22 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide photosensitive material |
| JPS60136738A (en) * | 1983-12-22 | 1985-07-20 | Fuji Photo Film Co Ltd | Photosensitive silver halide material |
| JPS6177843A (en) * | 1984-09-25 | 1986-04-21 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
| JPS62215272A (en) * | 1986-02-17 | 1987-09-21 | Fuji Photo Film Co Ltd | Color image forming method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0250155A (en) * | 1987-06-18 | 1990-02-20 | Fuji Photo Film Co Ltd | Color image forming method |
| JPH02843A (en) * | 1988-01-28 | 1990-01-05 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| JPH0250151A (en) * | 1988-05-09 | 1990-02-20 | Fuji Photo Film Co Ltd | Development processing method for silver halide photosensitive material |
| JPH0228649A (en) * | 1988-06-06 | 1990-01-30 | Eastman Kodak Co | Photographic processing |
| JPH02275948A (en) * | 1989-01-19 | 1990-11-09 | Fuji Photo Film Co Ltd | Processing liquid for silver halide photographic sensitive material, silver halide photographic sensitive material and processing method |
| US5395742A (en) * | 1993-05-18 | 1995-03-07 | Fuji Photo Film Co., Ltd. | Diaminostilbene series compound and a method for forming an image using the same |
| EP0631185A1 (en) | 1993-06-11 | 1994-12-28 | Fuji Photo Film Co., Ltd. | Method for continuously processing silver halide color photosensitive material |
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