JPH0140340B2 - - Google Patents
Info
- Publication number
- JPH0140340B2 JPH0140340B2 JP54106401A JP10640179A JPH0140340B2 JP H0140340 B2 JPH0140340 B2 JP H0140340B2 JP 54106401 A JP54106401 A JP 54106401A JP 10640179 A JP10640179 A JP 10640179A JP H0140340 B2 JPH0140340 B2 JP H0140340B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- coupler
- synthesis example
- couplers
- synthesis
- 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.)
- Expired
Links
- -1 aromatic primary amine Chemical class 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 37
- 239000004332 silver Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000001043 yellow dye Substances 0.000 claims description 7
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000004421 aryl sulphonamide group Chemical group 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 63
- 238000003786 synthesis reaction Methods 0.000 description 62
- 239000010410 layer Substances 0.000 description 31
- 238000011161 development Methods 0.000 description 23
- 239000000975 dye Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 238000000921 elemental analysis Methods 0.000 description 17
- 238000001308 synthesis method Methods 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- RHSBOLDDBPDRPZ-UHFFFAOYSA-N 1-benzylimidazolidine-2,4-dione;potassium Chemical compound [K].O=C1NC(=O)CN1CC1=CC=CC=C1 RHSBOLDDBPDRPZ-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- XVNKRRXASPPECQ-UHFFFAOYSA-N phenyl n-phenylcarbamate Chemical compound C=1C=CC=CC=1OC(=O)NC1=CC=CC=C1 XVNKRRXASPPECQ-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SXVDLDJIEMVEHA-UHFFFAOYSA-N 1-(2-hydroxyphenyl)decan-1-one Chemical compound CCCCCCCCCC(=O)C1=CC=CC=C1O SXVDLDJIEMVEHA-UHFFFAOYSA-N 0.000 description 3
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GADUASLYYYXIGK-UHFFFAOYSA-N (4,4-dimethyl-3-oxopentan-2-yl) acetate Chemical compound CC(=O)OC(C)C(=O)C(C)(C)C GADUASLYYYXIGK-UHFFFAOYSA-N 0.000 description 2
- PKEQJRNMFGPHMC-UHFFFAOYSA-N 1-(4-hydroxyphenyl)decan-1-one Chemical compound CCCCCCCCCC(=O)C1=CC=C(O)C=C1 PKEQJRNMFGPHMC-UHFFFAOYSA-N 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- 229940018563 3-aminophenol Drugs 0.000 description 2
- IWLGXPWQZDOMSB-UHFFFAOYSA-N 4-chloro-3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC(C(Cl)=O)=CC=C1Cl IWLGXPWQZDOMSB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 description 2
- 150000003938 benzyl alcohols Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer 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
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009467 reduction Effects 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
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YIMPSLVALVKLGH-UHFFFAOYSA-N 1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione;potassium Chemical compound [K].C=1C=CC=CC=1CN1C(=O)NC(=O)N1C1=CC=CC=C1 YIMPSLVALVKLGH-UHFFFAOYSA-N 0.000 description 1
- VJUNTPRQTFDQMF-UHFFFAOYSA-N 1-benzylimidazolidine-2,4-dione Chemical compound O=C1NC(=O)CN1CC1=CC=CC=C1 VJUNTPRQTFDQMF-UHFFFAOYSA-N 0.000 description 1
- HRBLHUVHOWWBEN-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine;hydrochloride Chemical compound Cl.CCNC1=CC=C(NCC)C=C1 HRBLHUVHOWWBEN-UHFFFAOYSA-N 0.000 description 1
- PXJHVKRLFWZUNV-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine;hydron;dichloride Chemical compound Cl.Cl.CNC1=CC=C(NC)C=C1 PXJHVKRLFWZUNV-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NBINSWOYIKLKGL-UHFFFAOYSA-N 2-dodecylbenzenesulfonyl chloride Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(Cl)(=O)=O NBINSWOYIKLKGL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 description 1
- VYCUUOHOBUPEPJ-UHFFFAOYSA-N 2-phenoxybutanamide Chemical group CCC(C(N)=O)OC1=CC=CC=C1 VYCUUOHOBUPEPJ-UHFFFAOYSA-N 0.000 description 1
- SANDYHMGZOWTMT-UHFFFAOYSA-N 3-dodecoxyphenol Chemical compound CCCCCCCCCCCCOC1=CC=CC(O)=C1 SANDYHMGZOWTMT-UHFFFAOYSA-N 0.000 description 1
- ZSWMSPXXQKJONO-UHFFFAOYSA-N 3-dodecylsulfonyl-2-methylpropanoyl chloride Chemical compound CCCCCCCCCCCCS(=O)(=O)CC(C)C(Cl)=O ZSWMSPXXQKJONO-UHFFFAOYSA-N 0.000 description 1
- WHZFOCFKEQZOFG-UHFFFAOYSA-N 3-oxo-n-phenylprop-2-enamide Chemical compound O=C=CC(=O)NC1=CC=CC=C1 WHZFOCFKEQZOFG-UHFFFAOYSA-N 0.000 description 1
- YRAANFWGKAQTGC-UHFFFAOYSA-N 4-dodecyl-n-(3-hydroxyphenyl)benzenesulfonamide Chemical compound C1=CC(CCCCCCCCCCCC)=CC=C1S(=O)(=O)NC1=CC=CC(O)=C1 YRAANFWGKAQTGC-UHFFFAOYSA-N 0.000 description 1
- MTOCKMVNXPZCJW-UHFFFAOYSA-N 4-n-dodecyl-4-n-ethyl-2-methylbenzene-1,4-diamine Chemical compound CCCCCCCCCCCCN(CC)C1=CC=C(N)C(C)=C1 MTOCKMVNXPZCJW-UHFFFAOYSA-N 0.000 description 1
- IJJSFSXLZYFTKV-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine;hydrochloride Chemical compound Cl.CNC1=CC=C(N)C=C1 IJJSFSXLZYFTKV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical group NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- JIANLLWEEGSVTA-UHFFFAOYSA-N C(CCCCCCCCCCC)S(=O)(=O)C(C(=O)N)C Chemical compound C(CCCCCCCCCCC)S(=O)(=O)C(C(=O)N)C JIANLLWEEGSVTA-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241000907661 Pieris rapae Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- MPLZNPZPPXERDA-UHFFFAOYSA-N [4-(diethylamino)-2-methylphenyl]azanium;chloride Chemical compound [Cl-].CC[NH+](CC)C1=CC=C(N)C(C)=C1 MPLZNPZPPXERDA-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical class NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical group 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 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
- 238000004061 bleaching Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- YNTDWRYEWSWDON-UHFFFAOYSA-N ethene;2-hydroxyacetic acid Chemical compound C=C.OCC(O)=O.OCC(O)=O YNTDWRYEWSWDON-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 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 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 1
- IPCKADOBKNUJMU-UHFFFAOYSA-N n-[2-(4-aminoanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCNC1=CC=C(N)C=C1 IPCKADOBKNUJMU-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- HERBOKBJKVUALN-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O HERBOKBJKVUALN-UHFFFAOYSA-K 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- G03C7/32—Colour coupling substances
- G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
Description
本発明は、ハロゲン化銀写真感光材料に関し、
更に詳しくは特定の基を有するカプラーを含有さ
せることにより、発色性、画像保存性を高めたハ
ロゲン化銀カラー写真感光材料に関する。
減色法に基づくカラー写真画像の形成は、一般
にハロゲン化銀カラー写真感光材料をシアンカプ
ラー、マゼンタカプラーおよびイエローカプラー
の存在下に芳香族第１アミン系現像主薬を用いて
発色現像することによつて行なわれ、その際露光
されたハロゲン化銀カラー写真感光材料のハロゲ
ン化銀粒子は現像主薬によつて還元され、同時に
生成する現像主薬の酸化生成物は、各カプラーと
カツプリング反応して、シアン色素、マゼンタ色
素およびイエロー色素からなるカラー写真画像を
形成する。
ところで、近年、ハロゲン化銀カラー写真感光
材料の画像形成処理量が非常に増大し、その迅速
処理がきわめて強く要望されている。この迅速処
理を図るための一手段としては、従来発色現像液
中にベンジルアルコール類を添加することによ
り、現像主薬の浸透性を向上して、カプラーの発
色効率を高めることが行われている。しかし、ベ
ンジルアルコール類の添加は、例えば現像廃液中
のB.O.D.（生物化学的酸素要求量）値を増加させ
る等、環境汚染上好ましくなく、その添加量の減
少ないしはこの添加を除去することが望まれてい
る。
一方、シアン、マゼンタおよびイエロー各カプ
ラーとしては、そのそれぞれをハロゲン化銀カラ
ー写真感光材料中の赤、緑および青各感光性乳剤
層中に内蔵せしめた、いわゆる内式カプラーが主
に用いられており、この内式カプラーは、乳剤層
間の拡散が起こらないようにするために、いわゆ
る拡散阻止基を具えている。例えば、マゼンタカ
プラーは、一般に、ピラゾロンあるいはピラゾリ
ノベンツイミダゾール型母核構造を有し、これら
の活性点の隣接炭素原子にイミノ基、アミド基等
を介し結合するアリール基上に親油性基が結合
し、このアリール基と親油性基とで拡散阻止基が
構成されている。又、イエローカプラーでは、一
般に、アシルアセトアニリド型母核構造を有し、
このアシルアセトアニリドのベンゼン環に親油性
基が結合する構造を有する。
このようなマゼンタまたはイエローカプラーに
おける拡散阻止基の親油性基としては、従来、英
国特許第1040710号明細書、同第1077874号明細
書、米国特許第3408194号明細書、同第3519429号
明細書、特開昭48−66834号公報、同50−13229号
公報等に記載されているような、ジーターシヤリ
―フエノキシブチロアミド基等のアリールオキシ
アルキルアシルアミド基が広く使用されている。
しかし、このような拡散阻止基を有するマゼンタ
またはイエローカプラーは、発色現像液中のベン
ジルアルコールを除去あるいは減少すると、現像
主薬の酸化生成物との反応性（カツプリング性）
が極度に悪くなり、発色不良を生じることにな
り、又通常それを感光性乳剤層中に含有せしめる
にあたり用いる高沸点有機溶媒のわずかな量変化
によつて、写真特性が大きく影響を受けることに
なる。
これに対し、マゼンタまたはイエローカプラー
の拡散阻止基の親油性基としては、特公昭42−
5582号公報、同48−16374号公報、特開昭49−
123034号公報、同49−74028号公報等に記載され
ているような、テトラデシルオキシカルボニル基
やヘキサデシルオキシカルボニル基等のモノアル
キルエステル基が、カプラーの発色効率を高める
ことが知られている。しかし、このモノアルキル
エステル型の親油性基でも、発色現像液中のベン
ジルアルコールを減少あるいは除去すると、カツ
プリング性は悪くなり、発色効率は十分でなく、
得られる画像の最大濃度が十分でなく、加えて、
上述のアリールオキシアルキルアシルアミド型の
親油性基と比較して画像保存性、特に耐光性がき
わめて悪いという欠点を有している。
本発明は、このような従来のマゼンタまたはイ
エローカプラーの欠点に鑑みてなされたものであ
つて、発色性が良好で、ベンジルアルコールの添
加量を減少させた発色現像液で処理したときにも
十分な色素画像が得られ、しかも画像保存性のよ
い新規なマゼンタまたはイエローカプラーを含有
するハロゲン化銀写真感光材料を提供することを
主たる目的とする。
本発明者らは、このような目的につき種々検討
を行つた結果本発明をなすに至つたものである。
すなわち、本発明は、ハロゲン化銀写真感光材
料において、下記一般式〔〕で示される芳香族
第１級アミン現像主薬の酸化生成物とカツプリン
グしてマゼンタまたは、イエロー色素を生成する
カプラーであつて、活性メチレン基または活性メ
チン基を一つ有するカプラーを含有することを特
徴とするハロゲン化銀写真感光材料。
一般式〔１〕
（式中R1は水素原子またはハロゲン原子を、
R2は、アルキル基、アルキルカルボニルアミノ
基、アリールスルホンアミド基、アルコキシ基、
アルキルカルボニル基、またはコハク酸イミド―
１―イル基を表わし、Coupはカプラー残基を、
ｌは０またはｌ、ｍは１または２を表わす。）
本発明におけるマゼンタまたはイエローカプラ
ーは、従来のカプラーと比較して、色素形成速度
が早く、発色性にすぐれ、又カプラーから形成さ
れる色素は光、熱、湿度等に対してすぐれた耐久
性を示す。従つて、このカプラーを含有する本発
明のハロゲン化銀写真感光材料は、ベンジルアル
コール量を減少した発色現像液で処理したときに
も感度、最大濃度ともにきわめて高く、又耐光
性、耐湿性、耐熱性等の画像保存性もきわめて良
好である。この本発明のハロゲン化銀写真感光材
料の優秀性は、後記実施例における、従来から拡
散阻止基用親油性基として広く使用されてきたア
リールオキシアルキルアミド基や、本発明におけ
ると同様エステル構造をとるもアルキルエステル
で構成される親油性基を拡散阻止基中に有するカ
プラーとの比較実験によつて明白になるであろ
う。
これらに加えて、本発明におけるカプラーは、
溶解性、分散性にすぐれ、それをプロテクト分散
するに際し用いる高沸点有機溶媒の量変化によつ
て写真特性上大きな影響を受けることはなく、安
定した発色性を示す。又、発色現像処理によつて
本発明におけるカプラーから得られたマゼンタま
たはイエロー色素は、すぐれた分光吸収特性を示
し、カプラーのすぐれた発色性と相俟つて、カプ
ラーを内蔵する感光性乳剤層をより薄膜化するこ
とができ、従つて本発明のハロゲン化銀写真感光
材料はすぐれた画像鮮鋭度および解像力と現像性
を示す。更に、発色性が向上するにも拘らず、色
汚染は生じず、カブリ濃度も増大しない。
以下、本発明のハロゲン化銀写真感光材料を更
に詳細に説明する。
本発明におけるカプラーは一般式〔〕で示さ
れる事を特徴とし、一般式〔〕のCoupで示さ
れるカプラー残基は芳香族第１級アミン現像主薬
の酸化生成物とカツプリングしてマゼンタまたは
イエロー色素を生成することができればいかなる
基であつてもよい。一般式〔〕のR2基は親油
性基であり、
基が拡散阻止基として機能し、Coup―基で示さ
れるカプラー残基がカプラー母核として機能する
ことになる。カプラー母核を構成するカプラー残
基Coupとしては、前述のごとくカツプリング反
応によりマゼンタまたはイエロー色素を生成する
ことができるものであればよいが、一般に、ピラ
ゾロン型マゼンタカプラー、ピラゾリノベンツイ
ミダーゾール型マゼンタカプラーおよびアシルア
セトアニリド型イエローカプラーからなるカプラ
ー群から選ばれたカプラーの拡散阻止基を除いた
残基であることが好ましい。
本発明において前期一般式〔〕で示される基
と結合する時に好ましいカプラー残基Coupは次
の一般式〔〕，〔〕または〔〕で表わされ
る。
一般式〔〕
一般式〔〕
一般式〔〕
上記一般式〔〕〜〔〕中ｎは１〜５の整数
を表わし、Ｘは水素原子、ハロゲン原子、アルキ
ル基（メチル基など）、アルコキシ基（メトキシ
基など）、アリールオキシ基（フエノキシ等）、ス
ルホンアミド基（フエニルスルホンアミド基等）、
アルコキシカルボニル基（ドデシルオキシカルボ
ニル基等）、アリールオキシカルボニル基（フエ
ノキシカルボニル基等）等を表わし、Y1および
Y2は水素原子、活性点置換基を表わし、Ｗは置
換または非置換のベンゾイル基又はピバロイル基
を表わし、この場合の置換基としては、ハロゲン
原子、アルキル基（メチル基など）、アルコキシ
基（メトキシ基など）アリールオキシ基（フエノ
キシ基など）、スルホニル基（メチルスルホニル
基、イソプロピルスルホニル基、フエニルスルホ
ニル基、ベンジルスルホニル基など）等から選択
される基が一般的であり、これら置換基は更に同
様の他の置換基で置換されていてもよい。但し一
般式〔〕に於いては、Ｗで表わされる基が置換
または非置換のピバロイル基の場合はY2が水素
であることはない。
以下に一般式〔〕，〔〕および〔〕におい
て、Y1およびY2がとりうる活性点置換基の代表
例を挙げる。
本発明における、前記一般式〔〕の構造を有
する基を具え、芳香族第１級アミン現像主薬の酸
化生成物とカツプリングしてマゼンタまたはイエ
ロー色素を形成するカプラーには、前記したとこ
ろから明らかなようにカプラー母核中の活性点に
水素原子を有する４当量カプラーおよびこの活性
点に発色現像主薬との反応系に於いて離脱しやす
い基、いわゆるスプリツトオフ基を有する２当量
カプラーのいずれも含まれる。又、前記スプリツ
トオフ基が離脱した場合に現像を抑制するカプラ
ー、いわゆる現象抑制剤放出型カプラー（DIRカ
プラー）、あるいはこのスプリツトオフ基に色素
部分を含ませ離脱した色素が受像層に色素像を形
成する拡散性色素放出カプラー（DDRカプラー）
も本発明におけるカプラーに含まれる。
次に本発明におけるカプラーの代表的具体例を
挙げるが、本発明はこれらに限定されるものでは
ない。
本発明におけるカプラーは、通常のカプラー母
核に拡散阻止基として
基が結合してなるものであるので、公知のマゼン
タまたはイエローカプラーの合成法に準じ、又、
アリールエステル基を導入する際の通常の有機合
成上の手法に従い、容易に合成することができ
る。
次に本発明におけるカプラーの合成例を示す。
合成例１ 〔例示カプラー（Ｍ―１）の合成〕
３―ニトロ―４―クロル安息香酸クロライド
220ｇ、２，４―ジターシヤリーアミルフエノー
ル257ｇとトリエチルアミン101ｇを１のトルエ
ンと共に加熱還流し、この加熱還流を３時間続け
たのち、析出したトリエチルアミン塩酸塩を水洗
して除去した。トルエン溶液を減圧濃縮し、残渣
をメタノール800mlで再結した。得られた融点97
〜８℃、淡黄色針状結晶352ｇをアルコール3.5
に溶解し、還元触媒としてパラジウムカーボン35
ｇを加え常圧水添を行ない、反応液を過してパ
ラジウムカーボンを除去し、液を減圧濃縮して
融点191〜192℃の白色針状結晶である、２―クロ
ル―５―（２，４―ジターシヤリーアミル）フエ
ノキシカルボニルアニリン234ｇを得た。このも
の40.7ｇを１―（２，４，６，トリクロロ）フエ
ニル―３―エトキシピラゾロン30.6ｇ、メタンス
ルホン酸1.2ｇ、トルエン45mlとともに20時間の
加熱還流を行つたのち、減圧濃縮し、残渣にメタ
ノール200ml加え結晶を集し、アセトニトリル
で再結晶して、融点142〜４℃の白色粉末の目的
物32.5ｇを得た。目的物の確認は元素分析によつ
て行つた。得られた結果を下記に示す。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 59.18 5.12 6.47 21.84
実測値 59.03 5.10 6.45 21.77
合成例２ 〔例示カプラー（Ｍ―２）の合成〕
２，４―ジターシヤリーアミルフエノールの代
りに３―ペンタデシルフエノール320ｇを用いて
合成例―１と同様の合成法にて、融点70〜72℃の
白色針状結晶である２―クロル―５―（３―ペン
タデシルフエノキシ）カルボニル―アニリン276
ｇを得た。
この中間体51.2ｇを２―クロル―５―（２，４
―ジターシヤリーアミルフエノキシ）カルボニル
アニリンの代りに用いた他は、合成例１と同様の
方法にて融点54〜８℃の白色粉末36.0ｇを得た。
このものを元素分析したところ下記に示される結
果を得、目的物であることが確認された。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 61.75 6.02 5.84 19.71
実測値 61.80 6.11 5.88 19.70
合成例３ 〔例示カプラー（Ｍ―３）の合成〕
２，４―ジターシヤリーアミルフエノールの代
りに以下の合成法で合成した、３―（２―メチル
―３―ドデシルスルホニルプロピオンアミド）フ
エノール432ｇを用い、合成例１と同様の合成法
で２―クロル―５―（２―メチル―３―ドデシル
スルホニルプロピオンアミド）フエノキシカルボ
ニルアニリン407ｇを得た。この中間体56.5ｇを、
２―クロル―（２，４―ジターシヤリアミル）フ
エノキシカルボニルアニリンの代りに用いて合成
例１と同様の合成法にて、融点137〜139℃の白色
粉末、41.3ｇを得た。このものは元素分析から目
的物であることが確認された。
なお、上記において、３―（２―メチル―３―
ドデシルスルホニルプロピオンアミド）フエノー
ルの合成は以下のようにして行つた。すなわち、
ｍ―アミノフエノール164ｇと２―メチル―３―
ドデシルスルホニルプロピオン酸クロライド470
ｇをアセトニトリル２と共に加熱還流を３時間
続けたのち、減圧濃縮乾固し、残渣をアセトニト
リルで再結晶して融点77〜９℃の白色粉末580ｇ
を得た。
合成例４ 〔例示カプラー（Ｍ―６）の合成〕
ｍ―アミノフエノール109ｇをアセトニトリル
600mlに溶解し、ドデシルベンゼンスルホニルク
ロライド304ｇを加え、撹拌しながら室温でトリ
エチルアミン110ｇを30分で滴下した。滴下終了
後加熱し、還流しながら撹拌を６時間続けた。冷
却後析出しているトリエチルアミン塩酸塩を過
して除去し、液を減圧濃縮して冷却し析出した
結晶を集して３―（４―ドデシルベンゼンスル
ホンアミド）フエノール285ｇを得た。このもの
を２，４―ジターシヤリーアミルフエノールの代
りに用い、３―ニトロ―４―クロル安息香酸クロ
ライド154ｇ、トリエチルアミン70ｇを用いて、
合成例１と同様の合成法にて２―クロル―５―
〔３―（４―ドデシルベンゼンスルホンアミド）
フエノキシ〕カルボニルアニリン325ｇを得た。
この中間体56ｇを２―クロル―５―（２，４―ジ
ターシヤリーアミルフエノキシ）カルボニルアニ
リンの代りに用い、合成例１と同様の合成法に
て、融点105〜107℃の目的物52.7ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl Ｓ
計算値 57.69 5.08 6.73 17.03 3.85
実測値 57.68 5.10 6.66 17.00 3.81
合成例５ 〔例示カプラー（Ｍ―10）の合成〕
２，４―ジターシヤリアミルフエノールの代り
に３―ドデシルオキシフエノール278ｇを用いて
合成例１と同様の合成法にて２―クロル―５―
（３―ドデシルオキシ）フエノキシカルボニルア
ニリン310ｇを得た。この中間体43.2ｇを２―ク
ロル―５―（２，４―ジターシヤリアミル）フエ
ノキシカルボニルアニリンの代りに用い、合成例
１と同様の合成法にて融点124〜126℃の目的物
50.3ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 58.88 5.38 6.06 20.45
実測値 59.00 5.41 6.06 20.43
合成例６ 〔例示カプラー（Ｍ―14〕の合成〕
カプリン酸384.5ｇとフエノール18.82ｇを撹拌
下、加温して融解させたのち放冷し、30℃で塩化
チオニール262ｇを滴下した。滴下終了後室温で
１時間撹拌、次いで80〜100℃で２時間撹拌した。
次いで、エチルアセテートで抽出し、水洗後、減
圧濃縮した。残渣を減圧蒸留し、bp164〜169
℃／5.5〜６mmHgの留分を留取した。得られた無
色透明液体のフエニルカプリネート397ｇを、無
水塩化アルミニウム212ｇを二硫化炭素420mlに溶
解した溶液中に、内温を20〜25℃に保持し、撹拌
しながら滴下した。滴下終了後内温50〜55℃で２
時間加熱撹拌して二硫化炭素を除去し、残渣を
135〜140℃で４時間加熱撹拌した。次に内温110
〜115℃で濃塩酸160mlを含む塩酸水溶液600mlを
少しづつ滴下し、滴下終了後内温120〜125℃で１
時間撹拌したのち氷水中に注入した。析出した結
晶をエチルアセテートで抽出し、水洗後減圧濃縮
乾固した。残渣を減圧蒸留し、２―デカノイルフ
エノールとして、bp160〜162℃／1.5mmHgの留分
を、130ｇ得た。残渣をリグロインで再結して融
点65〜66℃の４―デカノイルフエノール、164ｇ
を得た。得られた２―デカノイルフエノール124
ｇを２，４―ジターシヤリアミルフエノールの代
りに用いて、３―ニトロ―４―クロル安息香酸ク
ロライド110ｇ、とトリエチルアミン51ｇを反応
させ、合成例１と同様の合成法にて２―クロル―
５―（２―デカノイルフエノキシカルボニル）ア
ニリン147ｇを得た。このもの40.2ｇを、２―ク
ロル―５―（２，４―ジターシヤリーアミルフエ
ノキシ）カルボニルアニリンの代りに用いた他は
合成例１と同様の合成法にて融点96〜98℃の目的
物48.2ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 57.93 4.71 6.33 21.38
実測値 58.05 4.70 6.22 21.25
合成例７ 〔例示カプラー（Ｙ―１）の合成〕
合成例１で得られた中間体、２―クロル―５―
（２，４−ジターシヤリアミルフエノキシ）カル
ボニルアニリン194ｇをキシレンに溶解し加熱撹
拌しながらα―ピバロイルエチルアセテート103
ｇを滴下した。滴下終了後生成するアルコールを
留去しながら加熱を８時間続け、キシレンを留去
し残渣をメタノールで再結晶して融点107〜110℃
の白色針状晶、α―ピバロイル―２―クロル―５
―（２，４―ジターシヤリーアミルフエノキシ）
カルボニルアセトアニライド185ｇを得た。得ら
れた４当量カプラー185ｇをクロロホルム700mlに
溶解し、内温20〜30℃で撹拌しながらスルフリー
ルクロライド53.4ｇを含むクロロホルム溶液200
mlを滴下した。滴下終了後３時間撹拌したのち、
反応液を減圧濃縮乾固した。得られた淡黄色粘稠
液体α―ピバロイル―α―クロル―２―クロル―
５―（２，４―ジターシヤリーアミルフエノキ
シ）カルボニルアセトアニライドの54.9ｇを取り
エチルアセテートに溶解し、ベンジルヒダントイ
ンのカリウム塩27.4ｇを加え、加熱還流を４時間
続けた後、水洗して析出した塩化カリウムを除去
し、減圧濃縮乾固した。残渣をメタノールで再結
晶して、融点149〜151℃の目的物48.5ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 68.40 6.89 5.98 5.05
実測値 68.44 6.92 6.00 5.13
合成例８ 〔例示カプラー（Ｙ―２）の合成〕
合成例７で得られて中間体、α―ピバロイル―
α―クロル―５―（２，４―ジターシヤリーアミ
ルフエノキシ）カルボニルアセトアニライド54.9
ｇを用い、又ベンジルヒダントインカリウム塩の
代りに１―ベンジル―５―エトキシヒダントイン
カリウム塩32.9ｇを用いて合成例７と同様の合成
法にて融点98〜100℃の目的物61.5ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 67.59 7.02 5.63 4.75
実測値 67.48 7.00 5.53 4.62
合成例９ 〔例示カプラー（Ｙ―３）の合成〕
合成例７で得られた中間体α―ピバロイル―α
―クロル―２―クロル―５―（２，４―ジターシ
ヤリーアミルフエノキシ）カルボニルアセトアニ
ライド54.9ｇ、ベンジルヒダントインカリウム塩
の代りに、１―フエル―２―ベンジル―１，２，
４―トリアゾリジン―３，５―ジオンカリウム塩
33.6ｇを用い、合成例７と同様の合成法にて融点
162〜164℃の目的物53.0ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 69.91 6.87 6.94 4.39
実測値 69.91 6.77 6.91 4.40
合成例10 〔例示カプラー（Ｙ―４）の合成〕
合成例７で得られた中間体、α―ピバロイル―
α―クロル―２―クロル―５―（２，４―ジター
シヤリーアミルフエノキシ）カルボニルアセトア
ニライド54.9ｇ、ベンジルヒダントインカリウム
塩の代りに、１―（４メチルフエニル）―１，
２，３，４―テトラゾロンカリウム塩23.5ｇを用
い、合成例７と同様の合成法で融点167〜169℃の
目的物45.3ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 66.31 6.74 10.18 5.15
実測値 66.21 6.56 10.09 5.07
合成例11 〔例示カプラー（Ｙ―５）の合成〕
合成例２で得られた２―クロル―５―（３―ペ
ンタデシルフエノキシ）カルボニルアニリン45.8
ｇを２―クロル―５―（２，４―ジターシヤリー
アミルフエノキシ）カルボニルアニリンの代り
に、１―フエニル―２―ベンジル―１，２，４―
トリアゾリン―３，５ジオン、カリウム塩33.6ｇ
をベンジルヒダントインカリウム塩の代りに用
い、合成例７と同様の合成法にて融点75〜77℃の
目的物48.5ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 70.68 7.24 6.60 4.17
実測値 70.57 7.12 6.58 4.07
合成例12 〔例示カプラー（Ｙ―６）の合成〕
２，２―ジメチルオキサゾリジン―３，５―ジ
オンカリウム塩18.4ｇを１―フエニル―２―ベン
ジル―１，２，４―トリアゾリジン―３，５―ジ
オンカリウム塩の代りに用いた他は合成例11と同
様の合成法にて融点104〜106℃の目的物46.2ｇを
得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 67.53 7.79 3.94 4.98
実測値 67.50 7.81 4.00 4.07
合成例13 〔例示カプラー（Ｙ―８）の合成〕
合成例３で得られた中間体２―クロル―５―
（２―メチル―３―ドデシルスルホニルプロピオ
ンアミド）フエノキシカルボニルアニリン56.5ｇ
を２―クロル―５―（２，４―ジターシヤリーア
ミル）フエノキシカルボニルアニリンの代りに、
又α―ピバロイルエチルアセテート22.4ｇ、スル
フリールクロライド14.9ｇ、ベンジルヒダントイ
ンカリウム塩27.4ｇを用い、合成例７と同様の合
成法にて融点154〜156℃の目的物42.2ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl Ｓ
計算値 63.46 7.41 4.83 4.07 6.68
実測値 63.31 7.30 4.72 4.05 3.49
合成例14 〔例示カプラー（Ｙ―９）の合成〕
合成例４で得られた中間体２―クロル―５―
〔３―（４―ドデシルベンゼンスルホンアミド）
フエノキシ〕カルボニルアニリン56.1ｇを２―ク
ロル―５―（２―メチル―３―ドデシルスルホニ
ルプロピオンアミド）フエノキシカルボニルアニ
リンの代りに用い、合成例13と同様の合成法にて
融点118〜120℃の目的物46.4ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl Ｓ
計算値 64.73 7.02 6.29 3.98 3.60
実測値 64.70 7.00 6.30 4.00 3.53
合成例15 〔例示カプラー（Ｙ―14）の合成〕
合成例５の中間体として得られた２―クロル―
５―（３―ドデシルオキシ）フエノキシカルボニ
ルアニリン43.2ｇを２―クロル―５―（２―メチ
ル―３―ドデシルスルホニルプロピオンアミド）
フエノキシカルボニルアニリンの代りに用い、合
成例13と同様の合成法にて融点143〜145℃の目的
物46.3ｇを得た。
合成例16 〔例示カプラー（Ｙ―18）の合成〕
合成例６で得られた中間体、４―デカノイルフ
エノール124ｇを、２―デカノイルフエノールの
代りに用い合成例６と同様の合成法にて２―クロ
ロ―５―（４―デカノイルフエノキシ）カルボニ
ルアニリン143ｇを得た。
上記化合物80.4ｇ、α―ピバロイルエチルアセ
テート44.8ｇ、スルフリールクロライド27ｇ、と
ベンジルヒダントインカリウム塩45.6ｇを用い合
成例７と同様の合成法にて融点152〜４℃の目的
物71.6ｇを得た。
元素分析値（％）
Ｃ Ｈ Ｎ Cl
計算値 66.60 7.13 5.83 4.92
実測値 66.43 7.01 5.80 4.85
本発明におけるカプラーは、ハロゲン化銀写真
感光材料中の緑感性および／または青感性乳剤層
中に含有させられる。本発明におけるカプラーを
ハロゲン化銀写真感光材料に含有せしめる場合に
はハロゲン化銀１モル当り一般的に約0.07〜0.7
モル、好ましくは0.1モル〜0.4モルの範囲で用い
られるが、マスク方式の色補正に用いる場合、あ
るいは組合せて用いる他のカプラーの特性を向上
せしめる等の目的で使用する場合には概してハロ
ゲン化銀１モル当り約0.01〜0.1モル好ましくは
約0.03〜0.07モルの範囲で用いられる。乳剤層中
に含有させるには従来の公知の方法に従えばよ
い。
本発明におけるカプラーは目的に応じ種々の利
用ができ、それぞれの用途に於いて優れた特性を
示す。従つて、本発明のハロゲン化銀写真感光材
料は例えば拡散転写方式用ハロゲン化銀感光材
料、一般用ネガ感光材料、一般用リバーサル感光
材料、一般用ポジ感光材料、直接プジ型感光材料
等として用いられる。
これらの種々の型のハロゲン化銀写真感光材料
に用いられるハロゲン化銀は、塩化銀、沃化銀、
沃臭化銀、塩臭化銀、塩沃臭化銀等の任意のハロ
ゲン化銀であつて、これらのハロゲン化銀は感光
材料の種類に応じて、中性法、アンモニア法等の
種々の製法で製造される。そしてこれらハロゲン
化銀は活性ゼラチン、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）、セレ
ン増感剤、還元増感剤（例えば第１スズ塩、ポリ
アミン等）、貴金属増感剤（例えば金、ルテニウ
ム、ロジウム、イリジウム等の水溶性塩）等の単
独あるいは適宜併用（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）
によつて化学的に増感される。
更にこのハロゲン化銀は所望の波長域に光学的
に増感することができ、例えばゼロメチン色素、
モノメチン色素、ジメチン色素、トリメチン色素
等のシアニン色素あるいはメロシアニン色素等の
光学増感剤で単独にあるいは併用して（例えば超
色増感）光学的に増感することができる。
また感光材料の支持体としては、紙、ラミネー
ト紙（例えばポリエチレンと紙との積層体）、ガ
ラス、セルローズアセテート、セルローズナイト
レート、ポリエステル（例えばポリエチレンテレ
フタレート）、ポリカーボネート、ポリアミド、
ポリスチレン、ポリオレフイン等の基質からなる
フイルム状あるいはシート状のものが用いられ
る。
そして感光材料は、少なくとも支持体と、この
上に設けられた感光層とから構成されるが、目的
に応じて種々の位置に適当な層を有して、数層以
上から構成されるのが一般的である。
本発明におけるマゼンタカプラーおよび／また
はイエローカプラーはそれらを適宜組合せて用い
ることができるとともに、その他の２当量型カプ
ラーおよび４当量型カプラーと組合せて用いるこ
ともでき、それぞれ発色色素の色相の異なるカプ
ラーが適当な感光波長域の感光層に含有させられ
る。
また、本発明におけるハロゲン化銀カラー写真
感光材料において、或る感光波長域の感光層は２
層以上から構成されてもよく、更にこれらの感光
層は異なる感度の組合わせで用いることができ、
更にそれぞれの層に含有されるカプラーは、例え
ば２当量カプラーと４当量カプラーの如く、同色
の色素を形成するが異なる型に属するカプラーを
それぞれの層に含有させてもよく、このような態
様は一般に更に現像力を向上するあるいは感度を
向上する等の目的で行なわれる。
更に、本発明におけるカプラーは前記の如く、
他の２当量型カプラーあるいは４当量型カプラー
と併用することができるが、このとき２当量型の
カプラーとして所謂カラードカプラー（例えばカ
プラーの活性点に結合基としてアゾ基を有するス
プリツトオフ基が結合したカプラー）、あるいは
所謂DIRカプラー（発色現像時に現像抑制剤を放
出する型のカプラー、例えばカプラーの活性点に
結合基としてチオ基を有するスプリツトオフ基を
有するカプラー）等を用いることができる。
また写真感光材料は、感光層および／または他
の構成層（例えば中間層、下引層、フイルター
層、保護層、受像層等）に目的に応じて種々の写
真用添加剤を含むことができ、このような写真用
添加剤としては例えば安定剤（水銀化合物、トリ
アゾール類、アザインデン類、亜鉛あるいはカド
ミウム塩等）、増感剤（第４アンモニウム塩、ポ
リエチレングリコール等）、膜物性改良剤（例え
ばグリセリン、ジヒドロキシアルカン、エチレン
ビスグリコール酸のエステル、重合体の乳化分散
物等）、硬膜剤（例えばホルムアルデヒド、ハロ
ゲン置換脂肪酸、ジスルホン酸クロライド、ビス
アジリジン、ビニルスルホン酸、エチレンイミン
類等）、延展剤（例えばサポニン、ポリエチレン
グリコールのラウリルあるいはオレイルモノエー
テル、硫酸化およびアルキル化したポリエチレン
グリコール塩類等）、有機溶媒（例えばカプラー
溶媒すなわち高沸点有機溶媒および／または低沸
点有機溶媒、具体的にはジブチルフタレート、ト
リクレジルホスフエート、アセトン、メタノー
ル、エタノール、エチルセロソルブ等）、発色現
像時に現像抑制剤を放出すると共に実質的に無色
の化合物を生成するような所謂DIR化合物、その
他帯電防止剤、消泡剤、紫外線吸収剤、螢光増白
剤、スベリ防止剤、マツト剤、ハレーシヨン防止
剤あるいはイラジエーシヨン防止剤等があり、こ
れらの種々の写真用添加剤はそれぞれ単独でまた
は併用して用いられる。
また感光材料と別体であつて感光材料と組合わ
せて拡散転写方式に用いられる受像材料は、写真
用支持体上に少なくとも受像層を有し、必要に応
じて保護層、下引層、PH調節層を有しており、こ
れら各構成層は保護コロイドを層構成成分とし、
これらに前記各種写真用添加剤を目的に応じて含
有させることができる。例えば受像層は発色現像
処理した際に感光層から拡散してくる拡散性色素
の再拡散を防止するためあるいは色滲みを防止す
るために、色素を捕獲する性質の化合物あるいは
色素の拡散性を消失せしめる化合物等を含有する
ことが望ましく、またはこれらの化合物を受像層
に隣接する層中に含有せしめることもできる。例
えばモルダント、具体的には米国特許第2882156
号明細書に記載されているようなビニルメチルケ
トンのアミノグアニジン誘導体ポリマー、あるい
は米国特許第3271148号明細書、米国特許第
3271147号明細書に記載されているようなモルダ
ント類、またはPH調節剤、例えば無機、有機の酸
類等が代表的なものである。
一方本発明のハロゲン化銀写真感光材料は、露
光後公知の方法に従い画像形成処理を施される。
その際発色現像するために用いられる発色現像液
は、発色現像主薬を主成分とするものであるが、
本発明のハロゲン化銀写真感光材料に対して用い
る発色現像主薬は芳香族第１級アミンであり、と
くにｐ―フエニレンジアミン系のものが代表的で
あつて、具体的には例えばジエチル―ｐ―フエニ
レンジアミン塩酸塩、モノメチル―ｐ―フエニレ
ンジアミン塩酸塩、ジメチル―ｐ―フエニレンジ
アミン塩酸塩、２―アミノ―５―ジエチルアミノ
トルエン塩酸塩、２―アミノ―５―（Ｎ―エチル
―Ｎ―ドデシルアミノ）―トルエン、Ｎ―エチル
―Ｎ―β―メタンスルホンアミドエチル―３―メ
チル―４―アミノアニリン硫酸塩、Ｎ―エチル―
Ｎ―β―メタンスルホンアミドエチル―４―アミ
ノアニリン、４―Ｎ―エチル―Ｎ―β―ヒドロキ
シエチルアミノアニリン等が挙げられる。
そして、これらの発色現像主薬は単独であるい
は２種以上併用して、また所望により白黒現像主
薬、例えばハイドロキノン等と併用して用いら
れ、更に発色現像液は一般的にアルカリ剤例えば
水酸化ナトリウム、水酸化アンモニウム、炭酸ナ
トリウム、硫酸ナトリウム、亜硫酸ナトリウム等
を含み、更に種々の添加剤例えばハロゲン化アル
カリ金属例えば臭化カリウム、あるいは現像調節
剤例えばシトラジン酸等を含有してもよい。この
発色現像液は例えば或る種の拡散転写方法等に於
いては受像材料中に予め含有せしめることが行な
われるが、このような技術に於いては発色現像主
薬とアルカリ剤とを別にし、アルカリ剤のみを含
有せしめるかあるいは発色現像主薬を含有せしめ
る方法を用い、現像時に他方の液で処理すること
もできる。
本発明におけるカプラーはこのような発色現像
液でハロゲン化銀を現像した際に生成する発色現
像主薬の酸化生成物と反応し、色素を形成すると
共に、カプラーの種類によつては他の色素を形成
する。
発色現像の処理後に、感光材料中のハロゲン化
銀あるいは現像銀を系外に除去する場合には、一
般に定着液と漂白液の組合わせあるいは漂白定着
液等が用いられ、これらは各種の処理例えば水
洗、停止処理、安定液処理等と組合わせて用いら
れるが、定着成分としてはチオ硫酸ナトリウム、
チオ硫酸アンモニウム等のハロゲン化銀溶剤が用
いられ、漂白成分としては赤血塩、エチレンジア
ミンテトラ酢酸第２鉄アンモニウムあるいはナト
リウム塩等が用いられる。
以下本発明を実施例により更に具体的に説明す
るが、これにより本発明の実施の態様が限定され
るものではない。
実施例 １
第１表に示す如き本発明のカプラー（前記例示
カプラーの番号で示す）および下記比較カプラー
の1.5×10-1モル（ハロゲン化銀１モルあたり）
をそれぞれ同一重量グラムに相当するジブチルフ
タレート２倍量のエチルアセテートに加温溶解
し、５％のドデシルベンゼンスルホン酸ソーダ
120mlを含む５％ゼラチン溶液1000mlを加えコロ
イドミルで乳化分散した。この分散液をゼラチン
沃臭化銀乳剤（沃化銀６モル％臭化銀94モル％）
1000mlに加えフイルムベース上に塗布乾燥してハ
ロゲン化銀カラー感光材料の試料を作成した（塗
布膜厚6μ、塗布銀料3.5ｇ／m2）。
この場合、用いた比較カプラーは、下記(A)〜(E)
であり、比較カプラー(A)および(E)は前記特開昭48
−66834号公報記載のものと同種のイエローカプ
ラー、比較カプラー(C)および(D)は前記特開昭48−
66835号公報記載のものと同種のイエローカプラ
ー、又比較カプラー(E)は米国特許第2600788号明
細書記載のものと同種のマゼンタカプラーであ
り、これらは拡散阻止基中の親油性基としてアリ
ールオキシアルキルアミド基またはアルキルモノ
エステル基を有するものである。
比較カプラー
次いでこれらの試料を通常の方法でウエツジ露
光し下記の処理を行なつた。
処理工程（38℃） 処理時間
発色現像 ３分15秒
漂 白 ６分30秒
水 洗 ３分15分
定 着 ６分30秒
水 洗 ３分15秒
安定浴 １分30秒
各処理工程において使用した処理液組成は下記
のとおりである。
〔発色現像液組成〕
４―アミノ―３―メチル―Ｎ―エチル―Ｎ―
（β―ヒドロキシエチル）―アニリン硫酸塩
4.75ｇ
無水亜硫酸ナトリウム 4.25ｇ
ヒドロキシアミン1/2硫酸塩 2.0ｇ
無水炭酸カリウム 37.5ｇ
臭化ナトリウム 1.3ｇ
ニトリロトリ酢酸・３ナトリウム塩（１水
塩） 2.5ｇ
水酸化カリウム 1.0ｇ
水を加えて１として水酸化カリウムを用い
てPH10.0に調整する。
〔漂白液組成〕
エチレンジアミンテトラ酢酸鉄アンモニウム塩
100.0ｇ
エチレンジアミンテトラ酢酸２アンモニウム
塩 10.0ｇ
臭化アンモニウム 150.0ｇ
氷酢酸 10.0ml
水を加えて１としアンモニア水を用いてPH
6.0に調整する。
〔定着液組成〕
チオ硫酸アンモニウム（50％水溶液） 162ml
無水亜硫酸ナトリウム 12.4ｇ
水を加えて１として酢酸を用いてPH6.5に
調整する。
〔安定化液組成〕
ホルマリン（37％水溶液） 5.0ml
コニダツクス（小西六写真工業株式会社製）
7.5ml
水を加えて１とする。
上記の条件で現像処理を行なつた。
得られた色画像の各濃度をPD―7R濃度計（小
西六写真工業社製）を用いて測定した結果を第１
表に示す。
又、得られた色画像の耐光性、耐湿性を調べる
為に、キセノンフエードメーターで100時間瀑射
後の又60℃80％の恒温相対湿度の恒湿槽に入れ、
２週間後の初濃度1.0に於けるテスト後の濃度を
色素残存率として各カプラーの安定性を調べたと
ころ、第１表に示される結果を得た。
The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide color photographic material that has improved color development and image storage stability by incorporating a coupler having a specific group. Formation of color photographic images based on the subtractive color method is generally carried out by color-developing a silver halide color photographic light-sensitive material using an aromatic primary amine developing agent in the presence of a cyan coupler, a magenta coupler, and a yellow coupler. At this time, the exposed silver halide grains of the silver halide color photographic light-sensitive material are reduced by the developing agent, and the oxidized products of the developing agent produced at the same time undergo a coupling reaction with each coupler to form a cyan dye. , forming a color photographic image consisting of magenta and yellow dyes. Incidentally, in recent years, the amount of image forming processing of silver halide color photographic light-sensitive materials has greatly increased, and there is an extremely strong demand for rapid processing. As one means for achieving this rapid processing, conventionally, benzyl alcohols are added to the color developing solution to improve the permeability of the developing agent and increase the coloring efficiency of the coupler. However, the addition of benzyl alcohols is undesirable in terms of environmental pollution, such as increasing the BOD (biochemical oxygen demand) value in the developer waste solution, and it is desirable to reduce the amount of benzyl alcohol added or eliminate this addition. ing. On the other hand, as the cyan, magenta and yellow couplers, so-called internal couplers are mainly used, in which each coupler is incorporated into the red, green and blue light-sensitive emulsion layers of a silver halide color photographic light-sensitive material. These internal couplers contain so-called diffusion-blocking groups to prevent diffusion between the emulsion layers. For example, magenta couplers generally have a pyrazolone or pyrazolinobenzimidazole type core structure, and have a lipophilic group on the aryl group bonded to the carbon atom adjacent to the active site via an imino group, amide group, etc. The aryl group and the lipophilic group form a diffusion inhibiting group. In addition, yellow couplers generally have an acylacetanilide type core structure,
This acylacetanilide has a structure in which a lipophilic group is bonded to the benzene ring. The lipophilic group of the diffusion inhibiting group in such a magenta or yellow coupler has conventionally been described in British Patent No. 1040710, British Patent No. 1077874, U.S. Patent No. 3408194, U.S. Patent No. 3519429, Aryloxyalkyl acylamide groups such as the tertiary phenoxybutyroamide group as described in JP-A-48-66834 and JP-A-50-13229 are widely used.
However, when the benzyl alcohol in the color developing solution is removed or reduced, magenta or yellow couplers having such diffusion-blocking groups exhibit reactivity with oxidation products of the developing agent (coupling property).
This results in extremely poor color development, and photographic properties are greatly affected by slight changes in the amount of the high-boiling organic solvent normally used to incorporate it into the light-sensitive emulsion layer. Become. On the other hand, the lipophilic group of the diffusion inhibiting group of magenta or yellow couplers is
Publication No. 5582, Publication No. 48-16374, Japanese Unexamined Patent Publication No. 1973-
It is known that monoalkyl ester groups such as tetradecyloxycarbonyl groups and hexadecyloxycarbonyl groups, as described in Publications No. 123034 and 49-74028, improve the coloring efficiency of couplers. . However, even with this monoalkyl ester type lipophilic group, if the benzyl alcohol in the color developer is reduced or removed, the coupling property deteriorates and the color development efficiency is insufficient.
The maximum density of the image obtained is not sufficient, and in addition,
Compared to the above-mentioned aryloxyalkylacylamide type lipophilic group, it has the disadvantage of extremely poor image storage stability, particularly light resistance. The present invention was made in view of the drawbacks of conventional magenta or yellow couplers, and has good color development properties and is sufficient even when processed with a color developer containing a reduced amount of benzyl alcohol. The main object of the present invention is to provide a silver halide photographic material containing a novel magenta or yellow coupler, which provides a dye image with a high quality and has good image storage stability. The present inventors have completed the present invention as a result of various studies for this purpose. That is, the present invention provides a coupler that forms a magenta or yellow dye by coupling with an oxidation product of an aromatic primary amine developing agent represented by the following general formula [] in a silver halide photographic light-sensitive material. A silver halide photographic light-sensitive material comprising a coupler having one active methylene group or one active methine group. General formula [1] (In the formula, R 1 is a hydrogen atom or a halogen atom,
R 2 is an alkyl group, an alkylcarbonylamino group, an arylsulfonamide group, an alkoxy group,
Alkylcarbonyl group or succinimide
Coup represents a 1-yl group, and Coup represents a coupler residue.
l represents 0 or l, and m represents 1 or 2. ) The magenta or yellow coupler used in the present invention has a faster dye formation rate and excellent color development than conventional couplers, and the dye formed from the coupler has excellent durability against light, heat, humidity, etc. shows. Therefore, the silver halide photographic material of the present invention containing this coupler has extremely high sensitivity and maximum density even when processed with a color developing solution containing a reduced amount of benzyl alcohol, and also has excellent light resistance, moisture resistance, and heat resistance. The image storage properties such as quality are also very good. The superiority of the silver halide photographic material of the present invention is due to the aryloxyalkylamide group, which has conventionally been widely used as a lipophilic group for a diffusion-blocking group, as shown in the examples below, and the ester structure as in the present invention. This will be clarified by comparative experiments with couplers having lipophilic groups in the diffusion blocking group, which are particularly comprised of alkyl esters. In addition to these, the coupler in the present invention is
It has excellent solubility and dispersibility, and its photographic properties are not significantly affected by changes in the amount of high-boiling organic solvent used when protecting and dispersing it, and it exhibits stable color development. Furthermore, the magenta or yellow dye obtained from the coupler of the present invention by color development processing exhibits excellent spectral absorption characteristics, and together with the excellent color forming property of the coupler, it is possible to form a photosensitive emulsion layer containing the coupler. The silver halide photographic material of the present invention can be made into a thinner film, and therefore exhibits excellent image sharpness, resolution, and developability. Furthermore, although color development is improved, color staining does not occur and fog density does not increase. The silver halide photographic material of the present invention will be explained in more detail below. The coupler in the present invention is characterized by being represented by the general formula [], and the coupler residue represented by Coup in the general formula [] couples with the oxidation product of an aromatic primary amine developing agent to form a magenta or yellow dye. Any group may be used as long as it can produce . The R 2 group in the general formula [] is a lipophilic group, The group functions as a diffusion-blocking group, and the coupler residue represented by the Coup- group functions as a coupler core. The coupler residue Coup constituting the coupler core may be one that can produce a magenta or yellow dye through a coupling reaction as described above, but generally pyrazolone-type magenta couplers, pyrazolinobenzimidazole Preferably, the residue is a coupler selected from the coupler group consisting of magenta couplers and yellow acylacetanilide couplers, except for the diffusion-blocking group. In the present invention, the preferred coupler residue Coup when bonded to the group represented by the above general formula [] is represented by the following general formula [], [] or []. General formula [] General formula [] General formula [] In the above general formulas [] to [], n represents an integer from 1 to 5, and X is a hydrogen atom, a halogen atom, an alkyl group (such as a methyl group), an alkoxy group (such as a methoxy group), or an aryloxy group (such as a phenoxy group). , sulfonamide group (phenylsulfonamide group, etc.),
It represents an alkoxycarbonyl group (dodecyloxycarbonyl group, etc.), an aryloxycarbonyl group (phenoxycarbonyl group, etc.), and Y 1 and
Y2 represents a hydrogen atom or an active point substituent, and W represents a substituted or unsubstituted benzoyl group or pivaloyl group. In this case, substituents include a halogen atom, an alkyl group (such as a methyl group), an alkoxy group ( These substituents are generally selected from aryloxy groups (such as methoxy groups), sulfonyl groups (such as methylsulfonyl groups, isopropylsulfonyl groups, phenylsulfonyl groups, and benzylsulfonyl groups). Furthermore, it may be substituted with other similar substituents. However, in the general formula [], when the group represented by W is a substituted or unsubstituted pivaloyl group, Y 2 is not hydrogen. Representative examples of active site substituents that can be taken by Y 1 and Y 2 in the general formulas [], [] and [] are listed below. In the present invention, the coupler having a group having the structure of the general formula [] and forming a magenta or yellow dye by coupling with an oxidation product of an aromatic primary amine developing agent includes This includes both 4-equivalent couplers having a hydrogen atom at the active site in the coupler mother nucleus and 2-equivalent couplers having a so-called split-off group at this active site, which is a group that is easily separated in the reaction system with a color developing agent. . Also, a coupler that inhibits development when the split-off group is released, a so-called phenomenon inhibitor-releasing coupler (DIR coupler), or a dye moiety contained in the split-off group and the released dye forms a dye image on the image-receiving layer. Diffusible dye-releasing couplers (DDR couplers)
Also included in the couplers in the present invention. Next, typical examples of couplers in the present invention will be listed, but the present invention is not limited thereto. The coupler in the present invention has a diffusion inhibiting group on the normal coupler core. Since it is formed by bonding groups, it can be synthesized according to known synthesis methods for magenta or yellow couplers, and
It can be easily synthesized by following conventional organic synthesis techniques for introducing an aryl ester group. Next, a synthesis example of the coupler in the present invention will be shown. Synthesis Example 1 [Synthesis of exemplary coupler (M-1)] 3-nitro-4-chlorobenzoic acid chloride
220 g of 2,4-ditertiary amylphenol, 257 g of triethylamine, and 101 g of triethylamine were heated under reflux with 1 part of toluene, and after this heating and reflux was continued for 3 hours, the precipitated triethylamine hydrochloride was removed by washing with water. The toluene solution was concentrated under reduced pressure, and the residue was reconsolidated with 800 ml of methanol. Obtained melting point 97
~8℃, 352g of pale yellow needle crystals with 3.5g of alcohol
Palladium on carbon 35 as a reduction catalyst dissolved in
The reaction solution was filtered to remove palladium carbon, and the solution was concentrated under reduced pressure to obtain 2-chloro-5-(2, 234 g of 4-ditertiary amyl) phenoxycarbonylaniline was obtained. 40.7 g of this material was heated under reflux for 20 hours with 30.6 g of 1-(2,4,6,trichloro)phenyl-3-ethoxypyrazolone, 1.2 g of methanesulfonic acid, and 45 ml of toluene, and then concentrated under reduced pressure to form a residue. 200 ml of methanol was added to collect the crystals and recrystallized with acetonitrile to obtain 32.5 g of the desired product as a white powder with a melting point of 142-4°C. The target product was confirmed by elemental analysis. The results obtained are shown below. Elemental analysis value (%) C H N Cl Calculated value 59.18 5.12 6.47 21.84 Actual value 59.03 5.10 6.45 21.77 Synthesis example 2 [Synthesis of exemplary coupler (M-2)] 3- instead of 2,4-ditertiary amylphenol 2-chloro-5-(3-pentadecylphenoxy)carbonyl-aniline 276, which is a white needle-like crystal with a melting point of 70-72°C, was synthesized using the same method as in Synthesis Example-1 using 320 g of pentadecylphenol.
I got g. 51.2 g of this intermediate was added to 2-chloro-5-(2,4
36.0 g of a white powder with a melting point of 54 to 8° C. was obtained in the same manner as in Synthesis Example 1, except that tertiary amylphenoxy)carbonylaniline was used instead.
When this product was subjected to elemental analysis, the results shown below were obtained, and it was confirmed that it was the desired product. Elemental analysis value (%) C H N Cl Calculated value 61.75 6.02 5.84 19.71 Actual value 61.80 6.11 5.88 19.70 Synthesis example 3 [Synthesis of exemplified coupler (M-3)] The following was used instead of 2,4-ditertiary amylphenol Using 432 g of 3-(2-methyl-3-dodecylsulfonylpropionamide)phenol synthesized by the synthesis method, 2-chloro-5-(2-methyl-3-dodecylsulfonylpropionamide) was synthesized by the same synthesis method as in Synthesis Example 1. 407 g of amide) phenoxycarbonylaniline was obtained. 56.5g of this intermediate,
41.3 g of a white powder with a melting point of 137 to 139°C was obtained by the same synthesis method as in Synthesis Example 1 using 2-chloro-(2,4-ditertyalyamyl)phenoxycarbonylaniline instead. This product was confirmed to be the target product through elemental analysis. In addition, in the above, 3-(2-methyl-3-
Synthesis of dodecylsulfonylpropionamide) phenol was carried out as follows. That is,
164g of m-aminophenol and 2-methyl-3-
Dodecylsulfonylpropionic acid chloride 470
After heating and refluxing g with acetonitrile 2 for 3 hours, it was concentrated to dryness under reduced pressure, and the residue was recrystallized with acetonitrile to obtain 580 g of white powder with a melting point of 77-9°C.
I got it. Synthesis Example 4 [Synthesis of exemplified coupler (M-6)] 109 g of m-aminophenol was dissolved in acetonitrile.
The solution was dissolved in 600 ml, 304 g of dodecylbenzenesulfonyl chloride was added, and 110 g of triethylamine was added dropwise over 30 minutes at room temperature while stirring. After the dropwise addition was completed, the mixture was heated and stirred for 6 hours while refluxing. After cooling, the precipitated triethylamine hydrochloride was removed by filtration, and the liquid was concentrated under reduced pressure, cooled, and the precipitated crystals were collected to obtain 285 g of 3-(4-dodecylbenzenesulfonamido)phenol. Using this product in place of 2,4-ditertiary amylphenol, using 154 g of 3-nitro-4-chlorobenzoic acid chloride and 70 g of triethylamine,
2-chloro-5- by the same synthesis method as Synthesis Example 1
[3-(4-dodecylbenzenesulfonamide)
325 g of phenoxy]carbonylaniline was obtained.
Using 56 g of this intermediate in place of 2-chloro-5-(2,4-di-tertiaryamylphenoxy)carbonylaniline, the same synthesis method as in Synthesis Example 1 was carried out to obtain the desired product with a melting point of 105 to 107°C (52.7 g). I got g. Elemental analysis value (%) C H N Cl S Calculated value 57.69 5.08 6.73 17.03 3.85 Actual value 57.68 5.10 6.66 17.00 3.81 Synthesis example 5 [Synthesis of exemplified coupler (M-10)] Substitute for 2,4-diterthyalyamylphenol Using 278 g of 3-dodecyloxyphenol, 2-chloro-5-
310 g of (3-dodecyloxy)phenoxycarbonylaniline was obtained. Using 43.2 g of this intermediate in place of 2-chloro-5-(2,4-ditasharyamyl)phenoxycarbonylaniline, the same synthesis method as in Synthesis Example 1 was carried out to obtain the desired product with a melting point of 124-126°C.
50.3g was obtained. Elemental analysis value (%) C H N Cl Calculated value 58.88 5.38 6.06 20.45 Actual value 59.00 5.41 6.06 20.43 Synthesis example 6 [Synthesis of exemplary coupler (M-14)] 384.5 g of capric acid and 18.82 g of phenol were heated while stirring. The mixture was allowed to cool, and 262 g of thionyl chloride was added dropwise at 30° C. After the addition was completed, the mixture was stirred at room temperature for 1 hour, and then at 80 to 100° C. for 2 hours.
Next, it was extracted with ethyl acetate, washed with water, and concentrated under reduced pressure. Distill the residue under reduced pressure, bp164-169
A fraction of 5.5 to 6 mmHg was collected. 397 g of the resulting colorless transparent liquid phenyl caprinate was added dropwise to a solution of 212 g of anhydrous aluminum chloride dissolved in 420 ml of carbon disulfide while stirring while maintaining the internal temperature at 20 to 25°C. After the completion of dripping, the internal temperature is 50-55℃.
Heat and stir for hours to remove carbon disulfide and remove the residue.
The mixture was heated and stirred at 135-140°C for 4 hours. Then internal temperature 110
At ~115℃, add 600ml of hydrochloric acid aqueous solution containing 160ml of concentrated hydrochloric acid little by little, and after the dropwise addition is complete, reduce the internal temperature to 120~125℃.
After stirring for an hour, the mixture was poured into ice water. The precipitated crystals were extracted with ethyl acetate, washed with water, and then concentrated to dryness under reduced pressure. The residue was distilled under reduced pressure to obtain 130 g of a fraction with a bp of 160 to 162°C/1.5 mmHg as 2-decanoylphenol. Reconcile the residue with ligroin to obtain 164 g of 4-decanoylphenol with a melting point of 65-66°C.
I got it. Obtained 2-decanoylphenol 124
2-chloro-
147 g of 5-(2-decanoylphenoxycarbonyl)aniline was obtained. The objective was to obtain a melting point of 96 to 98°C using the same synthesis method as in Synthesis Example 1, except that 40.2 g of this product was used in place of 2-chloro-5-(2,4-di-tertiaryamylphenoxy)carbonylaniline. 48.2g of product was obtained. Elemental analysis value (%) C H N Cl Calculated value 57.93 4.71 6.33 21.38 Actual value 58.05 4.70 6.22 21.25 Synthesis example 7 [Synthesis of exemplary coupler (Y-1)] Intermediate obtained in Synthesis example 1, 2-chloro- 5-
Dissolve 194 g of (2,4-ditercyariamylphenoxy) carbonylaniline in xylene and heat and stir to obtain 103 α-pivaloyl ethyl acetate.
g was added dropwise. After the dropwise addition, heating was continued for 8 hours while distilling off the alcohol produced, xylene was distilled off, and the residue was recrystallized with methanol to give a melting point of 107-110℃.
white needle-like crystals of α-pivaloyl-2-chlor-5
-(2,4-ditercyamylphenoxy)
185 g of carbonylacetanilide was obtained. Dissolve 185 g of the obtained 4-equivalent coupler in 700 ml of chloroform, and add 200 g of a chloroform solution containing 53.4 g of sulfuryl chloride while stirring at an internal temperature of 20 to 30°C.
ml was added dropwise. After stirring for 3 hours after the completion of dropping,
The reaction solution was concentrated to dryness under reduced pressure. The obtained pale yellow viscous liquid α-pivaloyl-α-chlor-2-chlor-
Take 54.9g of 5-(2,4-ditertiaryamylphenoxy)carbonylacetanilide, dissolve it in ethyl acetate, add 27.4g of potassium salt of benzylhydantoin, continue heating under reflux for 4 hours, and then wash with water. The precipitated potassium chloride was removed, and the mixture was concentrated to dryness under reduced pressure. The residue was recrystallized from methanol to obtain 48.5 g of the desired product having a melting point of 149-151°C. Elemental analysis value (%) C H N Cl Calculated value 68.40 6.89 5.98 5.05 Actual value 68.44 6.92 6.00 5.13 Synthesis example 8 [Synthesis of exemplary coupler (Y-2)] Intermediate obtained in Synthesis example 7, α-pivaloyl-
α-Chlor-5-(2,4-ditertiaryamylphenoxy)carbonylacetanilide 54.9
61.5 g of the target product with a melting point of 98 to 100°C was obtained by the same synthesis method as in Synthesis Example 7 using 32.9 g of 1-benzyl-5-ethoxyhydantoin potassium salt instead of benzylhydantoin potassium salt. . Elemental analysis value (%) C H N Cl Calculated value 67.59 7.02 5.63 4.75 Actual value 67.48 7.00 5.53 4.62 Synthesis example 9 [Synthesis of exemplary coupler (Y-3)] Intermediate α-pivaloyl-α obtained in Synthesis example 7
-Chlor-2-chloro-5-(2,4-ditertiaryamylphenoxy)carbonylacetanilide 54.9 g, 1-fer-2-benzyl-1,2, instead of benzylhydantoin potassium salt
4-triazolidine-3,5-dione potassium salt
Using 33.6g, the melting point was determined by the same synthesis method as in Synthesis Example 7.
53.0 g of the target product was obtained at 162-164°C. Elemental analysis value (%) C H N Cl Calculated value 69.91 6.87 6.94 4.39 Actual value 69.91 6.77 6.91 4.40 Synthesis example 10 [Synthesis of exemplary coupler (Y-4)] Intermediate obtained in Synthesis example 7, α-pivaloyl-
54.9 g of α-chloro-2-chloro-5-(2,4-ditertiaryamylphenoxy)carbonylacetanilide, 1-(4methylphenyl)-1,
Using 23.5 g of 2,3,4-tetrazolone potassium salt, 45.3 g of the desired product having a melting point of 167-169°C was obtained by the same synthesis method as in Synthesis Example 7. Elemental analysis value (%) C H N Cl Calculated value 66.31 6.74 10.18 5.15 Actual value 66.21 6.56 10.09 5.07 Synthesis example 11 [Synthesis of exemplary coupler (Y-5)] 2-Chlor-5-( obtained in Synthesis example 2) 3-pentadecylphenoxy)carbonylaniline 45.8
1-phenyl-2-benzyl-1,2,4- in place of 2-chloro-5-(2,4-ditertiaryamylphenoxy)carbonylaniline
Triazoline-3,5 dione, potassium salt 33.6g
48.5 g of the target product having a melting point of 75 to 77° C. was obtained by the same synthesis method as in Synthesis Example 7, using the benzylhydantoin potassium salt instead of the benzylhydantoin potassium salt. Elemental analysis value (%) C H N Cl Calculated value 70.68 7.24 6.60 4.17 Actual value 70.57 7.12 6.58 4.07 Synthesis example 12 [Synthesis of exemplary coupler (Y-6)] 2,2-dimethyloxazolidine-3,5-dione potassium salt The objective was to obtain a melting point of 104 to 106°C using the same synthesis method as in Synthesis Example 11, except that 18.4 g of 1-phenyl-2-benzyl-1,2,4-triazolidine-3,5-dione potassium salt was used. 46.2g of product was obtained. Elemental analysis value (%) C H N Cl Calculated value 67.53 7.79 3.94 4.98 Actual value 67.50 7.81 4.00 4.07 Synthesis example 13 [Synthesis of exemplary coupler (Y-8)] Intermediate 2-chloro-5 obtained in Synthesis example 3 ―
(2-Methyl-3-dodecylsulfonylpropionamide) phenoxycarbonylaniline 56.5g
in place of 2-chloro-5-(2,4-ditertiaryamyl)phenoxycarbonylaniline,
In addition, 42.2 g of the target product with a melting point of 154 to 156°C was obtained using the same synthesis method as Synthesis Example 7 using 22.4 g of α-pivaloylethyl acetate, 14.9 g of sulfuryl chloride, and 27.4 g of benzylhydantoin potassium salt. . Elemental analysis value (%) C H N Cl S Calculated value 63.46 7.41 4.83 4.07 6.68 Actual value 63.31 7.30 4.72 4.05 3.49 Synthesis example 14 [Synthesis of exemplary coupler (Y-9)] Intermediate 2 obtained in synthesis example 4 Kroll-5-
[3-(4-dodecylbenzenesulfonamide)
Using 56.1 g of phenoxy]carbonylaniline instead of 2-chloro-5-(2-methyl-3-dodecylsulfonylpropionamide) phenoxycarbonylaniline, the melting point was 118 to 120°C using the same synthesis method as Synthesis Example 13. 46.4 g of the target product was obtained. Elemental analysis value (%) C H N Cl S Calculated value 64.73 7.02 6.29 3.98 3.60 Actual value 64.70 7.00 6.30 4.00 3.53 Synthesis example 15 [Synthesis of exemplified coupler (Y-14)] 2 obtained as an intermediate in Synthesis example 5 -Kroll-
43.2g of 5-(3-dodecyloxy)phenoxycarbonylaniline was converted into 2-chloro-5-(2-methyl-3-dodecylsulfonylpropionamide)
Using this instead of phenoxycarbonylaniline, 46.3 g of the target product having a melting point of 143 to 145°C was obtained by the same synthesis method as in Synthesis Example 13. Synthesis Example 16 [Synthesis of Exemplary Coupler (Y-18)] The same synthesis method as in Synthesis Example 6 was carried out using 124 g of 4-decanoylphenol, the intermediate obtained in Synthesis Example 6, instead of 2-decanoylphenol. 143 g of 2-chloro-5-(4-decanoylphenoxy)carbonylaniline was obtained. Using 80.4 g of the above compound, 44.8 g of α-pivaloylethyl acetate, 27 g of sulfuryl chloride, and 45.6 g of benzylhydantoin potassium salt, 71.6 g of the target product with a melting point of 152 to 4°C was synthesized in the same manner as in Synthesis Example 7. I got it. Elemental analysis value (%) C H N Cl Calculated value 66.60 7.13 5.83 4.92 Actual value 66.43 7.01 5.80 4.85 The coupler in the present invention is contained in the green-sensitive and/or blue-sensitive emulsion layer of the silver halide photographic light-sensitive material. . When the coupler of the present invention is incorporated into a silver halide photographic light-sensitive material, it is generally about 0.07 to 0.7 per mole of silver halide.
mol, preferably in the range of 0.1 mol to 0.4 mol, but when used for mask-based color correction or for the purpose of improving the properties of other couplers used in combination, silver halide is generally used. The amount used is about 0.01 to 0.1 mol, preferably about 0.03 to 0.07 mol per mol. In order to incorporate it into the emulsion layer, conventionally known methods may be followed. The coupler of the present invention can be used in various ways depending on the purpose, and exhibits excellent characteristics in each use. Therefore, the silver halide photographic light-sensitive material of the present invention can be used as, for example, a silver halide light-sensitive material for diffusion transfer method, a negative light-sensitive material for general use, a reversal light-sensitive material for general use, a positive light-sensitive material for general use, a direct positive light-sensitive material, etc. used. The silver halides used in these various types of silver halide photographic materials include silver chloride, silver iodide,
Any silver halide such as silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. These silver halides can be processed by various methods such as neutral method and ammonia method depending on the type of light-sensitive material. Manufactured using a manufacturing method. These silver halides include active gelatin, sulfur sensitizers (for example, allylthiocarbamide, thiourea, cystine, etc.), selenium sensitizers, reduction sensitizers (for example, stannous salts, polyamines, etc.), and noble metal sensitizers. (for example, water-soluble salts of gold, ruthenium, rhodium, iridium, etc.) alone or in combination as appropriate (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.)
chemically sensitized by Furthermore, this silver halide can be optically sensitized to a desired wavelength range, such as a zeromethine dye,
Optical sensitization can be carried out using optical sensitizers such as cyanine dyes such as monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes alone or in combination (for example, supercolor sensitization). Supports for photosensitive materials include paper, laminated paper (for example, a laminate of polyethylene and paper), glass, cellulose acetate, cellulose nitrate, polyester (for example, polyethylene terephthalate), polycarbonate, polyamide,
A film or sheet made of a substrate such as polystyrene or polyolefin is used. A photosensitive material is composed of at least a support and a photosensitive layer provided thereon, but it may be composed of several layers or more, with appropriate layers at various positions depending on the purpose. Common. The magenta coupler and/or yellow coupler in the present invention can be used in appropriate combinations, and can also be used in combination with other 2-equivalent type couplers and 4-equivalent type couplers. It is contained in a photosensitive layer in an appropriate photosensitive wavelength range. In addition, in the silver halide color photographic light-sensitive material of the present invention, the photosensitive layer for a certain photosensitive wavelength range is 2
It may be composed of more than one layer, and furthermore, these photosensitive layers can be used in combinations of different sensitivities,
Furthermore, the couplers contained in each layer may include couplers that form dyes of the same color but belong to different types, such as a 2-equivalent coupler and a 4-equivalent coupler. Generally, this is carried out for the purpose of further improving developing power or sensitivity. Furthermore, the coupler in the present invention is as described above,
It can be used in combination with other 2-equivalent type couplers or 4-equivalent type couplers, but in this case, the 2-equivalent type coupler is a so-called colored coupler (for example, a coupler in which a split-off group having an azo group as a bonding group is bonded to the active site of the coupler). ), or a so-called DIR coupler (a type of coupler that releases a development inhibitor during color development, for example, a coupler having a split-off group having a thio group as a bonding group at the active site of the coupler), etc. can be used. In addition, photographic materials can contain various photographic additives in the photosensitive layer and/or other constituent layers (for example, intermediate layer, subbing layer, filter layer, protective layer, image-receiving layer, etc.) depending on the purpose. Examples of such photographic additives include stabilizers (mercury compounds, triazoles, azaindenes, zinc or cadmium salts, etc.), sensitizers (quaternary ammonium salts, polyethylene glycol, etc.), and film property improvers (e.g. Glycerin, dihydroxyalkanes, esters of ethylene bisglycolic acid, emulsified dispersions of polymers, etc.), hardening agents (e.g. formaldehyde, halogen-substituted fatty acids, disulfonic acid chloride, bisaziridine, vinylsulfonic acid, ethyleneimines, etc.), spreading agents. agents (e.g. saponins, lauryl or oleyl monoethers of polyethylene glycol, sulfated and alkylated polyethylene glycol salts, etc.), organic solvents (e.g. coupler solvents i.e. high boiling organic solvents and/or low boiling organic solvents, in particular dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol, ethyl cellosolve, etc.), so-called DIR compounds that release development inhibitors and produce virtually colorless compounds during color development, other antistatic agents, and quenchers. There are foaming agents, ultraviolet absorbers, fluorescent whitening agents, anti-slip agents, matting agents, antihalation agents, anti-irradiation agents, and the like, and these various photographic additives can be used alone or in combination. In addition, an image-receiving material that is separate from the photosensitive material and used in combination with the photosensitive material in a diffusion transfer method has at least an image-receiving layer on a photographic support, and if necessary, a protective layer, an undercoat layer, a PH It has an adjustment layer, and each of these constituent layers has a protective colloid as a layer constituent component,
These may contain the various photographic additives described above depending on the purpose. For example, in order to prevent the re-diffusion of diffusible dyes that diffuse from the photosensitive layer during color development processing, or to prevent color bleeding, the image-receiving layer contains a compound that captures the dye or eliminates the diffusibility of the dye. It is desirable to contain compounds that make the image-receiving layer or the like, or these compounds can be contained in a layer adjacent to the image-receiving layer. For example mordant, specifically US Patent No. 2882156
Aminoguanidine derivative polymers of vinyl methyl ketone as described in US Pat. No. 3,271,148, US Pat.
Typical examples include mordants as described in No. 3271147, or PH regulators such as inorganic and organic acids. On the other hand, after exposure, the silver halide photographic material of the present invention is subjected to an image forming process according to a known method.
The color developing solution used for color development in this case has a color developing agent as its main component.
The color developing agent used in the silver halide photographic light-sensitive material of the present invention is an aromatic primary amine, and p-phenylenediamine-based ones are particularly representative, and specifically, for example, diethyl-p -Phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N -dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-
Examples include N-β-methanesulfonamidoethyl-4-aminoaniline and 4-N-ethyl-N-β-hydroxyethylaminoaniline. These color developing agents can be used alone or in combination of two or more, and if desired, can be used in combination with a black and white developing agent such as hydroquinone.Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, It contains ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and may further contain various additives such as alkali metal halides such as potassium bromide, or development regulators such as citradinic acid. For example, in some types of diffusion transfer methods, this color developing solution is pre-contained in the image-receiving material, but in such techniques, the color developing agent and the alkaline agent are separated; It is also possible to use a method of containing only an alkaline agent or a color developing agent, and processing with the other solution at the time of development. The coupler in the present invention reacts with the oxidation product of the color developing agent produced when silver halide is developed with such a color developer to form a dye, and depending on the type of coupler, may also react with other dyes. Form. When silver halide or developed silver in a light-sensitive material is removed from the system after color development processing, a combination of a fixer and a bleach solution or a bleach-fix solution is generally used, and these can be processed by various treatments, such as It is used in combination with water washing, stop treatment, stabilizer treatment, etc., but the fixing components include sodium thiosulfate,
A silver halide solvent such as ammonium thiosulfate is used, and as a bleaching component, red blood salt, ferric ammonium or sodium salt of ethylenediaminetetraacetate, etc. are used. The present invention will be explained in more detail below with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 1.5 x 10 -1 mole (per mole of silver halide) of the couplers of the invention as shown in Table 1 (indicated by the numbers of the exemplary couplers above) and the comparative couplers below.
were heated and dissolved in ethyl acetate of twice the amount of dibutyl phthalate corresponding to the same weight of grams, and 5% sodium dodecylbenzenesulfonate was added.
1000 ml of a 5% gelatin solution containing 120 ml was added and emulsified and dispersed using a colloid mill. This dispersion was mixed into a gelatin silver iodobromide emulsion (silver iodide 6 mol% silver bromide 94 mol%).
A sample of a silver halide color light-sensitive material was prepared by adding 1000 ml of the solution and coating it on a film base and drying it (coating film thickness: 6 μm, coated silver material: 3.5 g/m 2 ). In this case, the comparison couplers used are (A) to (E) below.
Comparative couplers (A) and (E) are disclosed in the above-mentioned Japanese Patent Application Laid-open No. 1973
- Yellow couplers of the same type as those described in Publication No. 66834, comparative couplers (C) and (D) are
The yellow coupler is the same type as that described in US Pat. No. 66835, and the comparative coupler (E) is a magenta coupler of the same type as described in US Pat. No. 2,600,788. It has an alkylamide group or an alkyl monoester group. comparison coupler These samples were then wedge exposed in a conventional manner and subjected to the following treatments. Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 minutes Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds Used in each processing step The composition of the treatment liquid is as follows. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 Adjust the pH to 10.0 using potassium hydroxide. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to 1 and pH using ammonia water
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water and adjust to PH6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Development processing was carried out under the above conditions. The results of measuring each density of the obtained color image using a PD-7R densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) are
Shown in the table. In addition, in order to check the light resistance and humidity resistance of the obtained color image, after 100 hours of irradiation using a xenon fade meter, the image was placed in a constant temperature and humidity chamber at 60°C and 80% relative humidity.
The stability of each coupler was investigated using the density after the test at an initial density of 1.0 two weeks later as the dye residual rate, and the results shown in Table 1 were obtained.
【表】【table】
ベンジルアルコール 1.0ml
ヘキサメタリン酸ナトリウム 3.00ｇ
無水亜硫酸ナトリウム 1.85ｇ
臭化ナトリウム 1.40ｇ
臭化カリウム 0.50ｇ
ホウ酸（Na2B4O7・10H2O） 39.10ｇ
Ｎ―エチル―Ｎ―〔２―（メタンスルホンア
ミドエチル）〕―３―メチル―４―アミ ノア
ニリン硫酸塩 450ｇ
水を加えて１に仕上げ、水酸化ナトリウム
でPH10.3に調整した。
〔漂白定着液〕
エチレンジアミンテトラ酢酸鉄アンモニウム
61.0ｇ
エチレンジアミンテトラ酢酸―２―アンモニ
ウム 5.0ｇ
チオ硫酸アンモニウム 124.5ｇ
メタ重亜硫酸ナトリウム 13.3ｇ
亜硫酸ナトリウム 2.7ｇ
水を加えて１に仕上げ、PHを6.5に調整し
た。
〔安定化液〕
氷酢酸（３水塩） 20ml
純水800mlを加え、酢酸ナトリウム３水塩を
用いてPH3.5〜4.0に調整した後１に仕上げ
た。
上記の条件で現像処理を行なつて感度、カブリ
および最高濃度を測定した。又、得らた色素画像
の耐光性を調べるためにキセノンフエードメータ
ーで100時間曝射後、初濃度1.0に於ける曝射後の
濃度を色素残存率として各カプラーの安定性を調
べた。結果を第２表に示す。
Benzyl alcohol 1.0ml Sodium hexametaphosphate 3.00g Anhydrous sodium sulfite 1.85g Sodium bromide 1.40g Potassium bromide 0.50g Boric acid (Na 2 B 4 O 7・10H 2 O) 39.10 g N-Ethyl-N-[2-( Methanesulfonamidoethyl)]-3-methyl-4-aminoaniline sulfate 450g Water was added to make the solution 1, and the pH was adjusted to 10.3 with sodium hydroxide. [Bleach-fix solution] Ethylenediaminetetraacetate iron ammonium
61.0g Ethylenediaminetetraacetate-2-ammonium 5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Sodium sulfite 2.7g Water was added to bring the mixture to 1, and the pH was adjusted to 6.5. [Stabilizing solution] 20 ml of glacial acetic acid (trihydrate) 800 ml of pure water was added, and the pH was adjusted to 3.5 to 4.0 using sodium acetate trihydrate. Development was performed under the above conditions, and sensitivity, fog, and maximum density were measured. Further, in order to examine the light resistance of the obtained dye image, the stability of each coupler was examined after exposure for 100 hours using a xenon fade meter, using the density after exposure at an initial density of 1.0 as the dye residual rate. The results are shown in Table 2.
【表】
第２表から明らかなように、本発明におけるイ
エローカプラーを含有する試料18〜23はアシルア
ミド型親油性基を有するイエローカプラーを含有
する比較試料16より発色性が、アルキルモノエス
テル型親油性バラスト基を有する比較試料17より
発色性、耐光性が非常に優れていることがよく判
る。又本発明におけるマゼンタカプラーも比較試
料と比し、発色性、耐光性が優れていることがよ
く判る。
尚第２表中、感度はイエローカプラーは試料16
を、マゼンタカプラーは、試料24をそれぞれ100
％とし相対感度で示した。[Table] As is clear from Table 2, Samples 18 to 23 containing yellow couplers in the present invention have better coloring properties than Comparative Sample 16 containing yellow couplers having an acylamide type lipophilic group. It is clearly seen that color development and light resistance are much better than Comparative Sample 17, which has an oil-based ballast group. It is also clearly seen that the magenta coupler of the present invention has excellent color development and light resistance compared to the comparative sample. In Table 2, the sensitivity is for yellow coupler sample 16.
, the magenta coupler is 100 each for 24 samples.
% and expressed as relative sensitivity.
Claims (1)
アミン現像主薬の酸化生成物とカツプリングして
マゼンタまたは、イエロー色素を生成するカプラ
ーであつて、活性メチレン基または活性メチン基
を一つ有するカプラーを含有することを特徴とす
るハロゲン化銀写真感光材料。 一般式〔１〕 （式中R1は水素原子またはハロゲン原子を、
R2は、アルキル基、アルキルカルボニルアミノ
基、アリールスルホンアミド基、アルコキシ基、
アルキルカルボニル基、またはコハク酸イミド―
１―イル基を表わし、Coupはカプラー残基を、
ｌは０または１、ｍは１または２を表わす。）[Scope of Claims] 1 A coupler represented by the following general formula [1] that produces a magenta or yellow dye by coupling with an oxidation product of an aromatic primary amine developing agent, which has an active methylene group or A silver halide photographic material comprising a coupler having one active methine group. General formula [1] (In the formula, R 1 is a hydrogen atom or a halogen atom,
R 2 is an alkyl group, an alkylcarbonylamino group, an arylsulfonamide group, an alkoxy group,
Alkylcarbonyl group or succinimide
Coup represents a 1-yl group, and Coup represents a coupler residue.
l represents 0 or 1, and m represents 1 or 2. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10640179A JPS5630126A (en) | 1979-08-20 | 1979-08-20 | Silver halide photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10640179A JPS5630126A (en) | 1979-08-20 | 1979-08-20 | Silver halide photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5630126A JPS5630126A (en) | 1981-03-26 |
| JPH0140340B2 true JPH0140340B2 (en) | 1989-08-28 |
Family
ID=14432657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10640179A Granted JPS5630126A (en) | 1979-08-20 | 1979-08-20 | Silver halide photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5630126A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01140153A (en) | 1987-11-27 | 1989-06-01 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| US5834167A (en) * | 1995-11-30 | 1998-11-10 | Eastman Kodak Company | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process |
| DE69608648T2 (en) * | 1995-11-30 | 2001-02-08 | Eastman Kodak Co | Photographic element comprising a yellow dye-forming coupler having a ballast group that improves the lightfastness of the dye, and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5382332A (en) * | 1976-12-24 | 1978-07-20 | Ciba Geigy Ag | Materials for color photograph |
-
1979
- 1979-08-20 JP JP10640179A patent/JPS5630126A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5382332A (en) * | 1976-12-24 | 1978-07-20 | Ciba Geigy Ag | Materials for color photograph |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630126A (en) | 1981-03-26 |
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