JPH0348242A - Silver halide color photographic sensitive material - Google Patents
Silver halide color photographic sensitive materialInfo
- Publication number
- JPH0348242A JPH0348242A JP31370489A JP31370489A JPH0348242A JP H0348242 A JPH0348242 A JP H0348242A JP 31370489 A JP31370489 A JP 31370489A JP 31370489 A JP31370489 A JP 31370489A JP H0348242 A JPH0348242 A JP H0348242A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- general formula
- color
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 95
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 62
- 239000004332 silver Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 61
- 239000000839 emulsion Substances 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims abstract description 37
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 31
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 12
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 125000002252 acyl group Chemical group 0.000 claims abstract description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 25
- 238000000034 method Methods 0.000 description 41
- 239000002245 particle Substances 0.000 description 29
- 125000001424 substituent group Chemical group 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 20
- 125000003545 alkoxy group Chemical group 0.000 description 19
- 238000009835 boiling Methods 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 15
- 238000011161 development Methods 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 125000003342 alkenyl group Chemical group 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000005562 fading Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 125000004104 aryloxy group Chemical group 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 108010010803 Gelatin Proteins 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 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
- 238000009826 distribution Methods 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 3
- 102100033183 Epithelial membrane protein 1 Human genes 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 108010008594 epithelial membrane protein-1 Proteins 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 102100033176 Epithelial membrane protein 2 Human genes 0.000 description 2
- 108050009423 Epithelial membrane protein 2 Proteins 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ZJOJXRSMJNWWRN-UHFFFAOYSA-N 3-amino-6-[2-(4-aminophenyl)ethenyl]benzene-1,2-disulfonic acid Chemical class C1=CC(N)=CC=C1C=CC1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O ZJOJXRSMJNWWRN-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- MTOCKMVNXPZCJW-UHFFFAOYSA-N 4-n-dodecyl-4-n-ethyl-2-methylbenzene-1,4-diamine Chemical compound CCCCCCCCCCCCN(CC)C1=CC=C(N)C(C)=C1 MTOCKMVNXPZCJW-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102100030146 Epithelial membrane protein 3 Human genes 0.000 description 1
- 101710143764 Epithelial membrane protein 3 Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- MSRSSYQNDRSMQL-UHFFFAOYSA-N N.O.O.[Fe+2] Chemical group N.O.O.[Fe+2] MSRSSYQNDRSMQL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003593 chromogenic compound Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 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
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハロゲン化銀カラー写真感光材料に関し、詳し
くは製造面での安定性を低下することなく、シアン色素
画像の発色性、画像保存性及び色再現性が同時に改良さ
れたハロゲン化銀カラー写真感光材料に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a silver halide color photographic light-sensitive material. and a silver halide color photographic material having improved color reproducibility.
ハロゲン化銀写真感光材料を用いて色素画像を形或する
には、通常、芳香族第１級アミン系発色現像主薬が、露
光されたハロゲン化銀写真感光材料中のハロゲン化銀粒
子を還元する際に、自らが酸化され、この酸化体が、ハ
ロゲン化銀写真感光材料中に予め含有されたカプラーと
反応して色素を形戒することによって行なわれる。そし
て、通常はカプラーとしては、減色法による色再現を行
なうため、イエロー マゼンタ、シアンの３つの色素を
形或する３種のカプラーが用いられている。In order to form a dye image using a silver halide photographic light-sensitive material, an aromatic primary amine color developing agent is usually used to reduce the silver halide grains in the exposed silver halide photographic light-sensitive material. In this process, the dye itself is oxidized, and this oxidized product reacts with a coupler previously contained in the silver halide photographic light-sensitive material to form a dye. Generally, three types of couplers are used, each of which forms three pigments: yellow, magenta, and cyan, in order to perform color reproduction using the subtractive color method.
各カブラーは、通常、実質的に氷不溶性の高沸点有機溶
媒あるいはこの溶媒に必要に応じて補助溶剤を併用して
溶解してハロゲン化銀乳剤中に添加される。Each coupler is usually added to the silver halide emulsion by being dissolved in a substantially ice-insoluble high-boiling organic solvent or in this solvent, if necessary, in combination with an auxiliary solvent.
各カプラーに要求される基本的性質としては、先ず高沸
点有機溶媒等に対する溶解性が大きいこと、ハロゲン化
銀乳剤中における分散性および分散安定性が良好で容易
に析出しないこと、分光吸収特性に優れ、色調が良好で
広範な色再現域における鮮明な色素画像が形或されるこ
と、ならびに得られる色素画像が光、熱、湿気等に対し
て堅牢性を有することなどが挙げられる。とりわけ、カ
ラープリント材料に用いられるカプラーにおいては、写
真画像の記録保存という使命から、得られる色素画像の
光堅牢性および暗所保存性（暗退色性）の両方をできる
だけ高めることが望まれている。シアンカブラーとして
従来広く用いられている５位にメチル基を有するフェノ
ール系シアンカブラーを用いた場合には、形或されるシ
アン色素の色調や耐光性が良いものの、暗退色性が劣る
という問題点がある。暗退色性を改良するには、５位に
メチル基を有する７エノール系シアンカプラーに２．５
−ジアシルアミノフェノール系シア６ンカプラーを併用
する方法があるが暗退色性は改良されるものの、発色性
、耐光性、分散安定性および色調が劣化してしまう。The basic properties required of each coupler are firstly high solubility in high-boiling organic solvents, good dispersibility and dispersion stability in silver halide emulsions and not easy precipitation, and good spectral absorption characteristics. The dye image is excellent in color, has a good color tone, forms a clear dye image in a wide color reproduction gamut, and the dye image obtained has fastness to light, heat, moisture, etc. In particular, for couplers used in color print materials, it is desirable to improve both the light fastness and dark storage stability (dark fading resistance) of the resulting dye image as much as possible due to the mission of preserving photographic images. . When a phenolic cyan coupler having a methyl group at the 5-position, which has been widely used as a cyan coupler, is used, the color tone and light fastness of the cyan dye formed are good, but the problem is that dark fading resistance is poor. There is. To improve the dark fading property, add 2.5 to the 7 enol cyan coupler having a methyl group at the 5-position.
- There is a method of using diacylaminophenol-based cyan 6 couplers in combination, but although dark fading resistance is improved, color development, light resistance, dispersion stability, and color tone deteriorate.
更に５位にメチル基以外の炭素数２以上のアルキル基を
有するフェノール系２−アシルアミノシアンカプラーを
用いた場合には、５位がメチル基のフェノール系２−ア
シルアミノシアンカプラーと比較した場合、形或される
シアン色素の色調は良く、更に暗退色性も改良されるが
、耐光性及び発色性は更に劣化してしまうことがわかっ
た。Furthermore, when using a phenolic 2-acylaminocyan coupler having an alkyl group having 2 or more carbon atoms other than a methyl group at the 5th position, compared to a phenolic 2-acylaminocyan coupler having a methyl group at the 5th position. It has been found that, although the color tone of the cyan dye produced is good and the dark fading resistance is further improved, the light fastness and coloring property are further deteriorated.
耐光性を改良するには紫外線吸収剤や各種の色素画像安
定化剤を用いる方法が特公昭４８−３１２５６号、同４
８−３１６２５号、米国特許第３．０６９．２６２号、
同第３，４３２．３００号、同第３，５７４，６２７号
各明細書に記載されているが、その効果は不充分である
。増量すると効果は向上するが、発色性及び分散安定性
の劣化を伴ってしまう。To improve light resistance, methods using ultraviolet absorbers and various dye image stabilizers are described in Japanese Patent Publications No. 48-31256 and No. 4.
No. 8-31625, U.S. Patent No. 3.069.262;
Although it is described in the specifications of the same No. 3,432.300 and the same No. 3,574,627, the effect is insufficient. If the amount is increased, the effect will be improved, but this will be accompanied by deterioration in color development and dispersion stability.
発色性、分散安定性等に関しても改良技術が種々報告さ
れているが、いずれも他の写真性能に何かの影響を及ぼ
してしまうものであり、全てを同時に改良する手段が求
められている。Various techniques for improving color development, dispersion stability, etc. have been reported, but all of them have some kind of effect on other photographic performance, and there is a need for a means to improve them all at the same time.
本発明の目的は分散が安定で塗布故障などが起きないシ
アンカプラーを含有し、画像保存性、色再現性及び発色
性が改良されたハロゲン化銀カラー写真感光材料を提供
することにある。An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a cyan coupler which is stable in dispersion and does not cause coating failure, and which has improved image storage stability, color reproducibility and color development.
本発明の目的は下記構戊のハロゲン化銀カラー写真感光
材料により達戊される。The object of the present invention is achieved by a silver halide color photographic light-sensitive material having the following structure.
支持体上に下記一般式（Ｔ）で示される化合物、下記一
般式〔Ｃ−１〕で示されるシアンカプラー及び２．５−
ジアシルアミノフェノール系シアンカブラーを含有する
ハロゲン化銀乳剤層を少なくとも１層有することを特徴
とするハロゲン化銀カラー写真感光材料。A compound represented by the following general formula (T), a cyan coupler represented by the following general formula [C-1] and 2.5-
A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer containing a diacylaminophenol-based cyan coupler.
一般式〔Ｔ〕
式中、Ｒ．及びＲ２は水素原子又はアルキル基を、Ｒ３
．Ｒ．は水素原子、アルキル基、アリール基又はヘテロ
環基を、Ｒ Ｓ，Ｒ ＠は水素原子、アルキル基、アリ
ール基、アシル基又はアルコキシ力ルポニル基を、Ｘは
上記６員環の構戊原子としての炭素原子を有する２価基
を、ｎは０．１又は２を表す。General formula [T] In the formula, R. and R2 is a hydrogen atom or an alkyl group, R3
．． R. represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R S, R @ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxyl group, and X represents a constituent atom of the above 6-membered ring. n represents a divalent group having carbon atoms of 0.1 or 2.
一般式ＣＣ−１〕
式中、Ｒ，はバラスト基を表し、Ｒ，は炭素数２以上の
アルキル基を表す。２，は水素原子又は発色現像主薬の
酸化体との反応により離脱しうる原子又は基を表す。General Formula CC-1] In the formula, R represents a ballast group, and R represents an alkyl group having 2 or more carbon atoms. 2 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent.
以下、本発明をより具体的に説明する。The present invention will be explained in more detail below.
以下一般式（Ｔ）で示される化合物について詳しく説明
する。The compound represented by the general formula (T) will be explained in detail below.
Ｒ．又はＲ，で表されるアルキル基としてはメチル基が
好ましい。R. The alkyl group represented by R is preferably a methyl group.
Ｒ，〜Ｒ．で表されるアルキル基としては炭素数ｌ〜４
のものが、アリール基としては７エニル基が好ましい。R, ~R. The alkyl group represented by has 1 to 4 carbon atoms.
The preferred aryl group is a 7-enyl group.
Ｒ，又はＲ．で表されるヘテロ環基としてはチェニル基
が好ましい。R, or R. The heterocyclic group represented by is preferably a chenyl group.
Ｒｓ．Ｒａで表されるアルコキシ力ルボニル基としては
炭素数２〜ｌ９のものが、アシル基としてはアセチル基
、ベンゾイル基が好ましい。Rs. The alkoxycarbonyl group represented by Ra is preferably one having 2 to 19 carbon atoms, and the acyl group is preferably an acetyl group or a benzoyl group.
Ｒ，〜Ｒ．で表される各基は置′換基を有するものを含
み、ＲＳ，Ｒ，がフェニルの場合、好ましい置換基とし
てはハロゲン原子、炭素数１〜８個のアルキル基、７エ
ニル基、シクロヘキシル基、炭素数１〜１８のアルコキ
シ基、炭素数７〜９の７エニルアルキル基、ヒドロキシ
ル基が挙げられ、Ｒ．，Ｒ．がアルキル基の場合、好ま
しい置換基としてはヒドロキシル基、フェニル基、炭素
数１〜ｌ２のアルコキシ基、ペンゾイルオキシ基、炭素
数２〜ｌ８のアルキル力ルポニルオキシ基が挙げられる
。R, ~R. Each group represented by includes those having a substituent, and when RS, R, is phenyl, preferred substituents include a halogen atom, an alkyl group having 1 to 8 carbon atoms, a 7-enyl group, and a cyclohexyl group. , an alkoxy group having 1 to 18 carbon atoms, a 7-enylalkyl group having 7 to 9 carbon atoms, and a hydroxyl group; ,R. When is an alkyl group, preferred substituents include a hydroxyl group, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, a penzoyloxy group, and an alkyloxy group having 2 to 18 carbon atoms.
Ｘで表される２価基としては好ましいものと）Ｃ−ＮＮ
Ｈ−アシルが挙げられる。Preferred divalent groups represented by X) C-NN
Examples include H-acyl.
ここにＲ，は水素原子、炭素数１〜４のアルキを、Ｒ．
は水素原子、メチル基、７エニル基、Ｐ （Ｏ ＸＯア
ルキル），（アルキルの炭素数は１〜４）、アリルオキ
シ基、ベンジルオキシ基、炭素数１〜ｌ２のアルコキシ
基を、Ｒ，は水素原子、ＯＨ，アリルオキシ基、ペンジ
ルオキシ基、炭素数１−１２のアルコキシ基、アシルオ
キシ基、アシルアミノ基を、Ｒ１。は水素原子、アシル
基を、Ｒ．は水素原子、炭素数ｌ〜４のアルキル基、−
Ｃ｝１，ＯＲ．，を、Ｒｌ２は水素原子、炭素数１〜４
のアルキル基を、Ｒ．は水素原子、アシル基を表す。Here, R represents a hydrogen atom, alkyl having 1 to 4 carbon atoms, R.
represents a hydrogen atom, a methyl group, a 7-enyl group, P (O R1 is an atom, OH, an allyloxy group, a penzyloxy group, an alkoxy group having 1 to 12 carbon atoms, an acyloxy group, an acylamino group. represents a hydrogen atom, an acyl group, R. is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -
C}1, OR. , Rl2 is a hydrogen atom and has 1 to 4 carbon atoms
The alkyl group of R. represents a hydrogen atom or an acyl group.
Ｒ，で表されるアシルオキシ基、アシルアミノ基におけ
るアシル基、Ｒ ｌＯ．Ｒ １４で表されるアシ＼
ル基及びＸで表されるＣ＝ＮＮＨ−アシル基におけ／
けるアシル基はべ冫ゾイル基、炭素数２〜ｌ８ノアルキ
ルカルポニル基の他、好ましいものとして、Ｋ４
が挙げられる。Acyloxy group represented by R, acyl group in acylamino group, R lO. In the acyl group represented by R14 and the C═NNH-acyl group represented by K4 is an example.
ここにＲ１〜Ｒ ａ ＋ ｎは前述のものと同義であり
、Ｑ，ｍは０又はｌであり、ｍ ．２：Ｑであり、Ｒ１
，は単なる結合手、２価の結合基（例えば炭素数１ −
１４アルキレン＝（ｐは０又はｌ）基を％Ｒｌ，は水素
原子、アルキル基（好ましくは炭素数１〜８のアルキル
基）、アシル基、アルコキシオキサリル基、スルホニル
基、カルバモイル基を、Ｒ ｒａ．Ｒ ＋ｙハ水素厚子
、
アルキル基、
ア
リール基を、
Ｒ１８は水
Ｒｌ７は前述のものと同義であり、
Ｒ
．は−〇一
Ｒ！Ｉ
原子、
アルキル基１
を表す。Here, R1 to R a + n have the same meanings as above, Q and m are 0 or l, and m . 2: Q and R1
, is a simple bond, a divalent bonding group (e.g. carbon number 1 -
14 Alkylene = (p is 0 or l) group, % Rl, hydrogen atom, alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), acyl group, alkoxyoxalyl group, sulfonyl group, carbamoyl group, R ra ．． R +y represents a hydrogen atom, an alkyl group, an aryl group; R18 is water; Rl7 has the same meaning as above; R. Ha-〇1R! I represents an atom and an alkyl group.
） を表す。) represents.
以下に一般式
（Ｔ）
で示される化合物の具体例
Ｔ−１３
Ｔ−１４
Ｔ−３０
Ｔ−３１
一般式（Ｔ）で示される化合物は公知の方法により合戊
できる。例えば４−ヒドロキシテトラヒドロチオビラン
系化合物を酸クロライドでアシル化する方法、４−ケト
テトラヒドロチオピラン系化合物とジオールと反応させ
て１．５−ジオキサ−９−チアースピロ［５．５１−ウ
ンデヵン系化合物、１．４−ジオキサ−８−チアースピ
ロ［４．５１一デヵン系化合物を得る方法等を用いるこ
とができる。Specific examples of compounds represented by the general formula (T) below: T-13 T-14 T-30 T-31 The compounds represented by the general formula (T) can be synthesized by known methods. For example, a method of acylating a 4-hydroxytetrahydrothiopyran compound with an acid chloride, a method of reacting a 4-ketotetrahydrothiopyran compound with a diol to produce a 1,5-dioxa-9-thiaspiro[5.51-undecane compound, A method for obtaining a 1,4-dioxa-8-thiaspiro[4.51-decane compound, etc. can be used.
一般式（Ｔ）で示される化合物は感光材料中、シアンカ
プラーと共にハロゲン化銀乳剤層に添加されるが、その
添加方法は米国特許第２．３２２．０２７号、同２，８
０１．１７０号、同２，８０１．１７１号、同２，２７
２．１９１号及び同２，３０４．９４０号に記載の方法
に従って高沸点溶媒に、必要に応じて低沸点溶媒を併用
して溶解し、分散して親水性コロイド溶液に添加するの
が好ましく、このとき必要に応じてカブラー、ハイドロ
キノン誘導体、紫外線吸収剤或いは公知の色素画像褪色
防止剤等を併用しても何ら差し支えなく、例えば、公知
の色素画像褪色防止剤としては、特開昭６１−１４３７
５４号等に記載されている化合物を挙げることができる
。このとき本発明の化合物を２種以上混合しても何ら差
し支えない。The compound represented by the general formula (T) is added to the silver halide emulsion layer together with a cyan coupler in a light-sensitive material, and the method of addition is described in U.S. Pat.
No. 01.170, No. 2,801.171, No. 2,27
2.191 and 2,304.940, it is preferable to dissolve it in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse it, and add it to the hydrophilic colloid solution. At this time, if necessary, there is no problem in using a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor.
Examples include compounds described in No. 54 and the like. At this time, there is no problem even if two or more kinds of compounds of the present invention are mixed.
一般式（Ｔ）で示される化合物の添加量は１１当り１．
５ｇ４下が好ましく、特に０．旧〜０．６ｇが好ましい
。The amount of the compound represented by the general formula (T) added is 1/11.
5g4 or less is preferable, especially 0. Old to 0.6g is preferable.
・前記一般式〔Ｃ−１〕で示されるシアンカプラーにお
いて、Ｒ！で表されるアルキル基は直鎖でも分岐でもよ
く、置換基を有するものも包含する。- In the cyan coupler represented by the general formula [C-1], R! The alkyl group represented by may be linear or branched, and includes those having a substituent.
Ｒ，は好ましくは炭素原子数２〜６のアルキル基である
。R is preferably an alkyl group having 2 to 6 carbon atoms.
Ｒ，で表されるバラスト基は、カブラーが適用される層
からカプラーを実質的に他層は拡散できないようにする
のに十分な嵩ばりをカプラー分子に与えるところの大き
さと形状を有する有機基である。A ballast group, represented by R, is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to render the coupler substantially unable to diffuse from the layer to which it is applied to other layers. It is.
該バラスト基として好ましいものは下記一般式で表され
るものである。Preferred ballast groups are those represented by the following general formula.
［：Ｃ−１−Ａ）
？■は炭素原子数１−１２のアルキル基を表し、Ａｒは
、フェニル基等のアリール基を表し、このアリール基は
置換基を有するものを包含する。[:C-1-A)? (2) represents an alkyl group having 1 to 12 carbon atoms, and Ar represents an aryl group such as a phenyl group, and this aryl group includes those having a substituent.
次に一般式〔Ｃ−１〕で表されるカブラーの具体例を示
すが、これらに限定されるものではない。Next, specific examples of the coupler represented by the general formula [C-1] will be shown, but the invention is not limited thereto.
ＯＨ
これらを含め、本発明において用いることのできるシア
ンカプラーの具体例は特公昭４０−１１５７２号、特開
昭６１−３１４２号、同６１−９６５２号、同６１−９
６５３号、同６１−３９０４５号、同６１−５０１３６
号、同６ｌ・９９１４１号、同６１−１０５５４５号な
どに記載されている。OH Including these, specific examples of cyan couplers that can be used in the present invention include Japanese Patent Publication Nos. 40-11572, 61-3142, 61-9652, and 61-9.
No. 653, No. 61-39045, No. 61-50136
No. 61-99141, No. 61-105545, etc.
本発明の前記一般式〔Ｃ−１〕で示されるシアン色素形
戊カプラーは、通常ハロゲン化銀１モル当たりｌｘｌＯ
−３モル〜ｌモル、好ましくはＩＸＩＯ−２モル〜８
Ｘ １０−’モルの範囲で用いることができる。The cyan dye-form coupler of the present invention represented by the general formula [C-1] is usually lxlO per mole of silver halide.
-3 mol to 1 mol, preferably IXIO-2 mol to 8 mol
It can be used in the range of X 10-' moles.
２．５・ジアシルアミノフェノール系シアンカプラーと
しては、下記一般式〔Ｃ−２）で示されるものが好まし
い。2.5. As the diacylaminophenol cyan coupler, those represented by the following general formula [C-2] are preferred.
一般式〔Ｃ−２）
ｔ
〔式中、Ｒｌはアルキル基またはアリール基を表す。Ｒ
，はアルキル基、シクロアルキル基、アリール基または
複素環基を表す。Ｒ，は水素原子、ハロゲン原子、アル
キル基またはアルコキシ基を表す。また、Ｒ３はＲ１と
共同して環を形或してもよい。２は水素原子または芳香
族第１級アミン系発色現像主薬の酸化体との反応により
離脱可能な原子又は基を表す。〕
前記一般式〔Ｃ−２）で表されるシアンカプラーにおい
て、ＲＩで表されるアルキル基としては、炭素数１〜３
２のものが好ましく、これらは直鎖でも分岐でもよく、
置換基を有するものも含む。General formula [C-2) t [In the formula, Rl represents an alkyl group or an aryl group. R
, represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Furthermore, R3 and R1 may form a ring. 2 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] In the cyan coupler represented by the general formula [C-2), the alkyl group represented by RI has 1 to 3 carbon atoms.
2 are preferred, and these may be linear or branched,
It also includes those with substituents.
Ｒ１で表されるアリール基としてはフェニル基が好まし
く、置換基を有するものも含む。The aryl group represented by R1 is preferably a phenyl group, including those having substituents.
Ｒ！で表されるアルキル基としては炭素数ｌ〜？２のも
のが好ましく、これらのアルキル基は直鎖でも分岐でも
よく、又、置換基を有するものも含む。R! The alkyl group represented by has a carbon number l~? 2 is preferred, and these alkyl groups may be linear or branched, and also include those having substituents.
Ｒ，で表されるシクロアルキル基としては炭素数３〜ｌ
２のものが好ましく、これらのシクロアルキル基は置換
基を有するものも含む。The cycloalkyl group represented by R has 3 to 1 carbon atoms.
2 is preferred, and these cycloalkyl groups also include those having substituents.
Ｒ■で表されるアリール基としてはフェニル基が好まし
く、置換基を有するものも含む。The aryl group represented by R■ is preferably a phenyl group, including those having substituents.
Ｒ，で表される複素環基としては５〜７員のものが好ま
しく、置換基を有するものを含み、又、縮合していても
よい。The heterocyclic group represented by R is preferably a 5- to 7-membered one, may have a substituent, and may be fused.
Ｒ３は水素原子、ハロゲン原子、アルキル基又はアルコ
キシ基を表し、該アルキル基及び該アルコキシ基は置換
基を有するものを含むが、Ｒ，は好ましくは水素原子で
ある。R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, but R is preferably a hydrogen atom.
又、ＲｌとＲ３が共同して形或する環としては５〜６員
環が好ましく、その例としては、Ｈ
１
一般式（１〕において２で表される発色現像主薬の酸化
体との反応により離脱可能な原子又は基としては、ハロ
ゲン原子、アルコキシ基、アリールオキシ基、アシルオ
キシ基、スルホニルオキシ基、アシルアミノ基、スルホ
ニルアミノ基、アルコキシ力ルポニルオキシ基、アリー
ルオキシカルポニルオキシ基及びイミド基など（それぞ
れ置換基を有するものを含む）が挙げられるが、好まし
くは、ハロゲン原子、アリールオキシ基、アルコキシ基
である。Furthermore, the ring formed by Rl and R3 together is preferably a 5- to 6-membered ring, such as H
1 In general formula (1), atoms or groups that can be separated by reaction with the oxidized product of the color developing agent represented by 2 include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, and acylamino groups. , a sulfonylamino group, an alkoxylponyloxy group, an aryloxycarponyloxy group, and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, or an alkoxy group.
上述のシアンカプラーのうち特に好ましいものは、下記
一般式〔Ｃ−２Ａ）で示されるものである。Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula [C-2A].
一般式〔Ｃ−２Ａ）
Ｚｏ
式中、ＲＧＩは少なくとも１個のハロゲン原子で置換さ
れたフェニル基を表し、これらのフェニル基は更にハロ
ゲン原子以外の置換基を有するものを含む。Ｒ０，は前
記一般式ＣＣ−２）のＲｌと同義である。ｚ６はハロゲ
ン原子、アリールオキシ基またはアルコキシ基を表し、
置換基を有するものを含む。General Formula [C-2A) Zo In the formula, RGI represents a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom. R0 has the same meaning as Rl in the general formula CC-2). z6 represents a halogen atom, an aryloxy group or an alkoxy group,
Including those with substituents.
以下に一般式〔Ｃ−２１で表されるシアンヵプラーの代
表的具体例を示す。Typical specific examples of the cyan coupler represented by the general formula [C-21] are shown below.
ン
上述のシアンカプラーの具体例としては更に例えば、特
願昭６１・２１８５３号明細書第２６頁〜３５頁、特開
昭６０−２２５１５５号公報第７頁左下の欄〜ｌＯ頁右
下の欄、特開昭６０−２２２８５３号公報第６頁左上の
欄〜８頁右下の欄及び特開昭５９−１８５３３５号公報
第６頁左下の欄〜９頁左上の欄に記載された２．５−ジ
アシルアミノ系シアンカプラーを含み、これらの明細書
及び公報に記載されている方法に従って合戊することが
できる。Specific examples of the above-mentioned cyan couplers include Japanese Patent Application No. 61/21853, pages 26 to 35, and JP-A-60-225155, lower left column on page 7 to lower right column on page 10. , 2.5 described in JP-A-60-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, upper left column. - diacylamino cyan couplers, and can be combined according to the methods described in these specifications and publications.
本発明の前記一般式（ｃ−２）で示されるシアン色素形
式カプラーは、通常ハロゲン化銀１モル当りＩＸＩＧ−
”〜ｌモル、好ましくはＩＸＩＯ−”モル〜８Ｘ １０
−”モルの範囲で用いることができる。The cyan dye type coupler of the present invention represented by the above general formula (c-2) usually contains IXIG-
"~1 mol, preferably IXIO-" mol ~8X 10
-" can be used in the molar range.
カプラー等の分散に用いる高沸点有機溶媒とは沸点１５
０℃以上の有機溶媒をいい、その種類は特に制限される
ものではなく、例えばフタル酸エステル、燐酸エステル
、安息香酸エステル等のエステル類、有機酸アミド類、
ケトン類、炭化水素化合物等が挙げられる。The high boiling point organic solvent used for dispersing couplers etc. has a boiling point of 15
Refers to an organic solvent having a temperature of 0°C or higher, and its type is not particularly limited, such as esters such as phthalate esters, phosphate esters, and benzoate esters, organic acid amides,
Examples include ketones and hydrocarbon compounds.
高沸点有機溶媒の中では３０℃における誘電率が６．０
以下のものが好ましく、誘電率６．０以下１．９以上で
、１００℃における蒸気圧が０．５ｍｍＨｇ以下のもの
７）｛更に好ましく、特にフタル酸エステル類又は燐酸
エステル類が好ましい。Among high boiling point organic solvents, the dielectric constant at 30℃ is 6.0.
The following are preferable, and those having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mmHg or less at 100°C7) are more preferable, and phthalate esters or phosphate esters are particularly preferable.
又、高沸点有機溶媒は２種以上混合して用いてもよい。Further, two or more types of high boiling point organic solvents may be used in combination.
本発明において有利に用いられる７タル酸エステルとし
ては、下記一般式（Ｓ−１〕で示されるものが挙げられ
る。Examples of the heptatarate esters advantageously used in the present invention include those represented by the following general formula (S-1).
一般式（ｓ−１〕
式中、Ｒ′及びＲ２はそれぞれアルキル基、アルケニル
基又はアリール基を表す。但し、ＲＩ及びＲ３で表され
る基の炭素数の総和はｌ２ないし３２である。より好ま
しくは炭素数の総和はｌ６ないし２４であり、更に好ま
しくはｌ８ないし２４である。General formula (s-1) In the formula, R' and R2 each represent an alkyl group, an alkenyl group, or an aryl group.However, the total number of carbon atoms in the groups represented by RI and R3 is 12 to 32. Preferably, the total number of carbon atoms is 16 to 24, more preferably 18 to 24.
本発明において、前記一般式（Ｓ−１〕のＲｌ及びＲ１
で表されるアルキル基は、直鎖でも分岐のものでもよく
、例えばブチル基、ペンチル基、ヘキシル基、２−エチ
ルヘキシル基、３．５．５−トリメチルヘキシル基、オ
クチル基、ノニル基、デシル基、ドデシル基、テトラデ
シル基、ヘキサデシル基、オクタデシル基等である。Ｒ
１及びＲ２で表されるアリール基は、例えばフエニル基
、ナフチル基等であり、アルケニル基は、例えばヘキセ
ニル基、ヘプテニル基、オクタデセニル基等である。In the present invention, Rl and R1 of the general formula (S-1)
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, 2-ethylhexyl group, 3.5.5-trimethylhexyl group, octyl group, nonyl group, decyl group. , dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. R
The aryl group represented by 1 and R2 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc.
これらのアルキル基、アルケニル基及びアリール基は、
単一もしくは複数の置換基を有するものも含み、アルキ
ル基及びアルケニル基の置換基としては、例えばハロゲ
ン原子、アルコキシ基、アリール基、アリールオキシ基
、アルケニル基、アルコキシ力ルボニル基等が挙げられ
、アリール基の置換基としては、例えばハロゲン原子、
アルキル基、アルコキシ基、アリール基、アリールオキ
シ基、アルケニル基、アルコキシ力ルポニル基等を挙げ
ることができる。These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents, and examples of substituents for alkyl and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents for the aryl group include halogen atoms,
Examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, an alkoxyl group, and the like.
上記において Ｒｌ及びＲ！は好ましくはアルキル基で
あり、例えば２−エチルヘキシル基、３，５．５−トリ
メチルヘキシル基、ｎ−オクチル基、ｎ一ノニル基等で
ある。In the above, Rl and R! is preferably an alkyl group, such as a 2-ethylhexyl group, a 3,5.5-trimethylhexyl group, an n-octyl group, or an n-nonyl group.
本発明において有利に用いられる燐酸エステルとしては
、下記一般式（Ｓ−２）で示されるものが挙げられる。Phosphoric esters advantageously used in the present invention include those represented by the following general formula (S-2).
一般式（Ｓ−２）
式中，Ｒ３，Ｒ’及びＲ１はそれぞれアルキル基、アル
ケニル基又はアリール基を表す。但し ＲＩＲ４及びＲ
ゝで表される基の炭素数の総和は２４ないし５４であり
、好ましくは２７ないし３６である。General Formula (S-2) In the formula, R3, R' and R1 each represent an alkyl group, an alkenyl group or an aryl group. However, RIR4 and R
The total number of carbon atoms in the group represented by ゝ is 24 to 54, preferably 27 to 36.
一般式（Ｓ−２）のＲ３．Ｒ４及びＲ３で表されるアル
キル基は、例えばブチル基、ぺ冫チル基、ヘキシル基、
２−エチルヘキシル基、ヘプチル基、ノニル基、デシル
基、ドデシル基、テトラデシル基、ヘキサデシル基、オ
クタデシル基、ノナデシル基等であり、アリール基とし
ては、例えば７エニル基、ナフチル基等であり、又アル
ケニル基としては、例えばヘキセニル基、ヘプテニル基
、オクタデセニル基等である。R3 in general formula (S-2). The alkyl group represented by R4 and R3 is, for example, a butyl group, a pethyl group, a hexyl group,
Examples of aryl groups include 2-ethylhexyl group, heptyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, and examples of aryl groups include 7enyl group and naphthyl group, and alkenyl group. Examples of the group include hexenyl group, heptenyl group, and octadecenyl group.
これらのアルキル基、アルケニル基及びアリール基は、
単一もしくは複数の置換基を有するものも含む。好まし
くはＲ３Ｒ４及びＲｌはアルキル基であり、例えば２−
エチルヘキシル基、ｎ−オクチル基、３．５．５−トリ
メチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、ｓｅ
ｃ−デシル基、ｓｅｃ−ドデシル基、ｔーオクチル基等
が挙げられる。These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents. Preferably R3R4 and Rl are alkyl groups, for example 2-
Ethylhexyl group, n-octyl group, 3.5.5-trimethylhexyl group, n-nonyl group, n-decyl group, se
Examples include c-decyl group, sec-dodecyl group, and t-octyl group.
以下に、本発明に好ましく用いられる高沸点有機溶媒の
代表的具体例を示すが、本発明はこれらに限定されるも
のではない。Typical specific examples of high boiling point organic solvents preferably used in the present invention are shown below, but the present invention is not limited thereto.
Ｓ−１
Ｓ−２
Ｃ，Ｈ，
じ鵞Ｈ＄
Ｓ−３
Ｓ−４
Ｓ−５
ｓ−６
Ｓ−７
Ｓ〜８
Ｓ−９
Ｓ −１０
一
〇，Ｈ．
Ｓ−１３
Ｓ−１５
Ｓ−１７
Ｓ−１９
Ｓ −２１
Ｓ−１４
Ｓ−１６
Ｓ−１８
Ｓ−２０
Ｓ−２２
高沸点有機溶媒の使用量としては、カプラー１ｇに対し
、０−１＝ＩＯ＋ｍｌ２が好ましく、特に０．１〜５ｍ
１２が好ましい。10,H. S-13 S-15 S-17 S-19 S-21 S-14 S-16 S-18 S-20 S-22 The amount of high boiling point organic solvent used is 0-1 = IO + ml2 for 1 g of coupler. is preferable, especially 0.1 to 5 m
12 is preferred.
上述の高沸点有機溶媒と併用してもよい高沸点有機溶媒
としては現像主薬の酸化体と反応しない７エノール誘導
体、フタル酸エステル、燐酸エステル、クエン酸エステ
ル、安息香酸エステル、アルキルアミド、脂肪酸エステ
ル、トリメシン酸エステル等の沸点１５０℃以上の有機
溶媒が用いられる。Examples of high-boiling organic solvents that may be used in combination with the above-mentioned high-boiling organic solvents include 7-enol derivatives, phthalate esters, phosphoric esters, citric esters, benzoic esters, alkylamides, and fatty acid esters that do not react with the oxidized product of the developing agent. An organic solvent having a boiling point of 150° C. or higher, such as trimesic acid ester or the like, is used.
前述のシアンカプラーを含有する分散物中には更に下記
一般式（Ｎ−１〕で示される非発色性化合物を含有せし
めることが好ましい。It is preferable that the dispersion containing the cyan coupler described above further contains a non-color-forming compound represented by the following general formula (N-1).
一般式（Ｎ−１〕
〔式中、Ｒ１，及びＲ．は各々、水素原子、アルキル基
、アリール基又は複素環基を表し、Ｒ．はアルキル基、
アリール基、シアノ基又は複素環基を表す。ＪはーＳＪ
Ｓｏ ＣＯＯ ＣＯ−、原子、ア
ルキル基、アリール基又は複素環基を表す。ａは０又は
ｌを表す。ＲｌＦ及びＲ．のいずれか一方はＲ．と結合
して環を形威してもよい。〕次に前記一般式（Ｎ−１〕
で示される非発色性化合物（以下、本発明の非発色性化
合物という。）について説明する。General formula (N-1) [In the formula, R1 and R. each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R. is an alkyl group,
Represents an aryl group, a cyano group, or a heterocyclic group. J-SJ
So COO CO- represents an atom, an alkyl group, an aryl group or a heterocyclic group. a represents 0 or l. RlF and R.F. Either one of R. It may be combined with to form a ring. ] Next, the general formula (N-1)
The non-color-forming compound represented by (hereinafter referred to as the non-color-forming compound of the present invention) will be explained.
前記一般式（Ｎ−１〕において、Ｒｌ７、Ｒ．及びＲ．
で表されるアルキル基としては炭素厚子数１〜３２のも
のが好ましく、直鎖でも分岐でもよく、置換基を有する
ものも含む。In the general formula (N-1), Rl7, R. and R.
The alkyl group represented by is preferably one having 1 to 32 carbon atoms, and may be linear or branched, including those having a substituent.
Ｒｌ７、ＲＩＩ及びＲ．で表されるアリール基としては
フェニル基が好ましく、該基は置換基を有するものも含
む。Rl7, RII and R. The aryl group represented by is preferably a phenyl group, and this group also includes those having substituents.
Ｒ１？、Ｒｌｌ及びＲ．で表される複素環としては５〜
７員環のものが好ましく、縮合していてもよく、又これ
らの基は置換基を有するものも含む。R1? , Rll and R. The heterocycle represented by is 5~
A seven-membered ring is preferred, and it may be fused, and these groups also include those having substituents.
Ｒａｙ及びＲ１．のいずれか一方がＲｌｌと結合して形
或する環としては、
例えば
Ｈ
これらの環は置換基を有するものも含む。Ray and R1. A ring in which either one of these is bonded to Rll is, for example, H. These rings also include those having a substituent.
表されるアルキル基としては、炭素原子数１〜３のもの
が好ましい。The alkyl group represented is preferably one having 1 to 3 carbon atoms.
Ｒ２。で表されるアリール基としては、フェニル基が好
ましく、該７エニル基は置換基を有するものも含む。R2. The aryl group represented by is preferably a phenyl group, and the 7-enyl group also includes those having a substituent.
Ｒ，。で表される複素環基としては、例えばフリル基、
ピリジル基、ピペリジル基などが挙げられ、これらの基
は置換基を有するものも含む。R. Examples of the heterocyclic group represented by include furyl group,
Examples include pyridyl group and piperidyl group, and these groups also include those having substituents.
キル基が好ましい。Kill groups are preferred.
本発明の非発色性化合物の中でより好ましいものは、下
記一般式（Ｎ−２）で示される化合物である。More preferred among the non-color-forming compounds of the present invention are compounds represented by the following general formula (N-2).
一般式（Ｎ−２）
Ｒ ’ ＩＦ ＮＨＳＯ！ Ｒ ’ ＋ｓ式中、Ｒ′
１７及びＲ′１，はそれぞれ水素原子、アルキル基、シ
クロアルキル基、アルケニル基、シクロアルケニル基、
アルキニル基、アリール基、複素環基、アルコキシ基、
アリールオキシ基、複Ｒａ
／
Ｒａ及びＲｈは各々水素厚子、アルキル基又はアリール
基を表す。ＲａとＲｈは同じであっても異なっていても
よい。General formula (N-2) R' IF NHSO! R'+sIn the formula, R'
17 and R′1 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Alkynyl group, aryl group, heterocyclic group, alkoxy group,
The aryloxy group, Ra/Ra and Rh each represent a hydrogen atom, an alkyl group or an aryl group. Ra and Rh may be the same or different.
本発明の非発色性化合物の中で特に好ましいものは下記
一般式（Ｎ−３）で示される化合物である。Particularly preferred among the non-color-forming compounds of the present invention are compounds represented by the following general formula (N-3).
一般式（Ｎ−３）
Ｒ ＃ｌｔ ＮＨＳＯ！ Ｒ“１，式中、Ｒ“，７
及びＲ“１，は各々アルキル基又はアリール基であり、
これらの基は置換されているものも含む。更に好ましく
は、Ｒ＃，，とＲ＃，，の少なくとも一方がアリール基
である。最も好ましくはＲ“，，とＲ“１，が共にアリ
ール基であり、特に好ましくはフェニル基である。ここ
で、Ｒ”１７が７エニル基の時、スルホンアミド基のパ
ラ位の置換基のハメットのδｐ値が−０．４以上である
ことが特に好ましい。General formula (N-3) R #lt NHSO! R"1, in the formula, R",7
and R"1, are each an alkyl group or an aryl group,
These groups also include substituted groups. More preferably, at least one of R#, , and R#, is an aryl group. Most preferably R", , and R"1 are both aryl groups, particularly preferably phenyl groups. Here, when R''17 is a 7-enyl group, it is particularly preferable that the Hammett's δp value of the substituent at the para position of the sulfonamide group is -0.4 or more.
Ｒ“，７又はＲ“．で表されるアルキル基及びアリール
基は、前記一般式（Ｎ−２）のＲ′，７又はＲ ’ Ｉ
Ｓで表されるアルキル基、アリール基と同義である。R", 7 or R". The alkyl group and aryl group represented by R', 7 or R' I of the general formula (N-2) are
It has the same meaning as the alkyl group and aryl group represented by S.
以下に一般式（Ｎ−１〕で示される化合物の代表的な具
体例を挙げるが、これに限定されない。Typical specific examples of the compound represented by the general formula (N-1) are listed below, but the invention is not limited thereto.
化合物Ｎｏ．
Ｒ Ａ−ＮＨＳＯ，−Ｒ．
ＲＡ ＲＢ
化合物Ｎｏ．
ＲＡ−ＮＨＳＯ！″−Ｒ．
ＲＡ ＲＢ
化合物Ｎｏ．
Ｒ Ａ Ｎ Ｈ Ｃ Ｏ Ｒ ｍＲＡ
ＲＢ
Ｎ
２６
本発明の非発色性化合物は例えば、特願昭６１−２０５
８９号記載の方法等、従来公知の方法で合或することが
できる。Compound no. R A-NHSO, -R. RA RB Compound No. RA-NHSO! ″-R. RA RB Compound No. RA NH C O R mRA
RB N 26 The non-chromogenic compound of the present invention is disclosed in Japanese Patent Application No. 61-205, for example.
The combination can be performed by a conventionally known method such as the method described in No. 89.
本発明の非発色性化合物の使用量は、本発明のシアンカ
プラーに対して５〜５００モル％が好ましく、より好ま
しくはｌＯ〜３００モル％である。又、一般式（Ｎ−１
〕で示される化合物は高沸点有機溶媒としても使える。The amount of the non-color-forming compound of the present invention to be used is preferably 5 to 500 mol%, more preferably 10 to 300 mol%, based on the cyan coupler of the present invention. Also, the general formula (N-1
] The compounds shown can also be used as high boiling point organic solvents.
本発明の感光材料を多色用に用いる場合、イエローカプ
ラーとしては例えばペンゾイルアセトアニリド系、ピバ
ロイルアセトアニリド系のものを、マゼンタカプラーと
しては例えばピラゾロン系のものを用いることができる
。When the light-sensitive material of the present invention is used for multiple colors, the yellow coupler can be, for example, a penzoylacetanilide or pivaloylacetanilide type, and the magenta coupler can be, for example, a pyrazolone type.
各ハロゲン化銀乳剤層の配置としては、支持体側から順
にイエローカプラーを含む青感光性ハロゲン化銀乳剤層
、マゼンタカプラーを含む緑感光性ハロゲン化銀乳剤層
、シアンカプラーを含む赤感光性ハロゲン化銀乳剤層で
あることが好ましく、感光材料全体としては支持体上に
必須層として該支持体側から順にイエローカプラーを含
む青感光性ハロゲン化銀乳剤層、マゼンタカプラーを含
む緑感光性ハロゲン化銀乳剤層、紫外線吸収剤を含む非
感光性中間層、シアンカプラー及び本発明の化合物を含
む赤感光性″ハロゲン化銀乳剤層、紫外線吸収剤を含む
非感光性層、保護層を配置したものが好ましい。The arrangement of each silver halide emulsion layer is, in order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. Preferably, it is a silver emulsion layer, and in the light-sensitive material as a whole, essential layers on the support include, in order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a green-sensitive silver halide emulsion containing a magenta coupler. A non-photosensitive intermediate layer containing an ultraviolet absorber, a red-sensitive silver halide emulsion layer containing a cyan coupler and the compound of the present invention, a non-photosensitive layer containing an ultraviolet absorber, and a protective layer are preferably arranged. .
支持体としてはレジンコートした紙支持体、白色顔料を
含有するポリエチレンテレフタレート支持体が好ましく
用いられる。As the support, a resin-coated paper support or a polyethylene terephthalate support containing a white pigment is preferably used.
紫外線吸収剤としては下記一般式（Ｕ−１〕で示される
ものが好ましい。As the ultraviolet absorber, those represented by the following general formula (U-1) are preferred.
一般式（Ｕ）
Ｋ！
（上記一般式（Ｕ）において、Ｒ，、Ｒ８及びＲ，はそ
れぞれ水素原子、ハロゲン原子、アルキル基、アリール
基、アルコキシ基、アリールオキシ基、アルケニル基、
ニトロ基又は水酸基を表す。）Ｒ ， − Ｒ ，で表
される各基は置換基を有するものを含む。General formula (U) K! (In the above general formula (U), R, R8 and R are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group,
Represents a nitro group or a hydroxyl group. ) Each group represented by R, -R, includes one having a substituent.
Ｒ．及びＲ，で表される基のうち、水素原子、アルキル
基、アルコキシ基及びアリール基が好ましく、特に水素
原子、アルキル基及びアルコキシ基が好ましい。R. Among the groups represented by and R, a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group are preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are particularly preferred.
Ｒ，で表される基のうち、特に水素原子、ハロゲン原子
、アルキル基、アルコキシ基が好ましい。Among the groups represented by R, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.
Ｒ１〜Ｒ１のうち、少なくとも１つはアルキル基である
ことが好ましく、更に少なくとも２つがアルキル基であ
ることが好ましい。又、Ｒ１〜Ｒ，の少なくとも１つは
分岐アルキル基であることが好ましい。It is preferable that at least one of R1 to R1 is an alkyl group, and it is further preferable that at least two of them are an alkyl group. Moreover, it is preferable that at least one of R1 to R is a branched alkyl group.
代表的具体例を示す。A typical example is shown below.
一般式（Ｕ）で示される化合物の添加量は、該化合物を
添加する層のバインダーに対して０．１〜３００重量％
が好ましく、更に１〜２００重量％が好ましい。The amount of the compound represented by the general formula (U) added is 0.1 to 300% by weight based on the binder of the layer to which the compound is added.
is preferred, and more preferably 1 to 200% by weight.
本発明のハロゲン化銀写真感光材料に用いられるハロゲ
ン化銀乳剤には、ハロゲン化銀として臭化銀、沃臭化銀
、沃塩化銀、塩臭化銀及び塩化銀等の通常のハロゲン化
銀乳剤に使用される任意のものを用いることが出来るが
、特に塩化銀含有率が９０モル％以上のものが好ましく
、臭化銀含有率はｌＯモル％以下、沃化銀含有率は０．
５モル％以下であることが好ましい。更に好ましくは、
臭化銀含有率が０．１〜２モル％の塩臭化銀である。The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any material used in emulsions can be used, but those with a silver chloride content of 90 mol % or more are particularly preferred, a silver bromide content of 10 mol % or less, and a silver iodide content of 0.
It is preferably 5 mol% or less. More preferably,
It is silver chlorobromide with a silver bromide content of 0.1 to 2 mol%.
本発明のハロゲン化銀粒子は、単独で用いてもよいし、
組或の異なる他のハロゲン化銀粒子と混合して用いても
よい。又塩化銀含有率がｌＯモル％以下のハロゲン化銀
粒子と混合して用いてもよい。The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains of a different set. It may also be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.
又、本発明の９０モル％以上の塩化銀含有率を有するハ
ロゲン化銀粒子が含有されるハロゲン化銀乳剤層におい
ては、該乳剤層に含有される全ハロゲン化銀粒子に占め
る塩化銀含有率９０モル％以上のハロゲン化銀粒子の割
合は６０重量％以上、好ましくは８０重量％以上である
。Furthermore, in the silver halide emulsion layer of the present invention containing silver halide grains having a silver chloride content of 90 mol % or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.
本発明のハロゲン化銀粒子の組或は、粒子内部から外部
に至るまで均一なものであってもよいし、粒子内部と外
部の組戊が異なってもよい。又粒子内部と外部の組戊が
異なる場合、連続的に組戊が変化してもよいし、不連続
であってもよい。The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.
本発明のハロゲン化銀粒子の粒子径は特に制限はないが
、迅速処理性及び感度等、他の写真性能等を考慮すると
、好ましくは０．２〜１．６μ重、更に好ましくは０．
２５〜１．２μ會の範囲である。尚、上記粒字径は、当
該技術分野において一般に用いられる各種の方法によっ
て測定することができる。代表的な方法としては、ラブ
ランドの「粒子径分析法」（Ａ．Ｓ．Ｔ．Ｍ．シンポジ
ウム・オン・ライト・マイクロスコピー． １９５５午
．９４〜１２２頁）又は「写真プロセスの理論」 （ミ
ース及びジェームズ共著、第３版、マクミラン社発行（
１９６６午）の第２章）に記載されている。There is no particular restriction on the particle size of the silver halide grains of the present invention, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6 microns, more preferably 0.2 to 1.6 microns.
It is in the range of 25 to 1.2 μm. The particle size can be measured by various methods commonly used in the technical field. Typical methods include Loveland's "Particle Size Analysis" (A.S.T.M. Symposium on Light Microscopy, 1955, p. 94-122) or "Theory of Photographic Processes" ( Co-authored by Mies and James, 3rd edition, published by Macmillan (
1966), Chapter 2).
この粒子径は、粒子の投影面積か直径近似値を使ってこ
れを測定することができる。粒子が実質的に均一形状で
ある場合は、粒径分布は直径か投影面積としてかなり正
確にこれを表すことができる。The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.
本発明のハロゲン化銀粒子の粒子径の分布は、多分散で
あってもよいし、単分散であってもよい。The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
好ましくはハロゲン化銀粒子の粒径分布において、その
変動係数が０．２２以下、更に好ましくは０．１５以下
の単分散ハロゲン化銀粒子である。ここで変動係数は、
粒径分布の広さを示す係数であり、次式によって定義さ
れる。Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is
This is a coefficient indicating the breadth of particle size distribution, and is defined by the following formula.
平均粒径（７）一 Σｎｉ ここでｒｉは粒子個々の粒径、ｎｉはその数を表す。Average particle size (7) - Σni Here, ri represents the particle diameter of each particle, and ni represents the number thereof.
ここで言う粒径とは、球状のハロゲン化銀粒子の場合は
その直径、又立方体や球状以外の形状の粒子の場合は、
その投影像を周面積の円像に換算した時の直径を表す。The grain size here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than cubic or spherical.
It represents the diameter when the projected image is converted into a circular image of the circumferential area.
本発明の乳剤に用いられるハロゲン化銀粒子は酸性法、
中性法、アンモニア法のいずれで得られたものでもよい
。該粒子は一時に戊長させてもよいし、種粒子をつくっ
た後、或長させてもよい。The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be elongated all at once, or may be elongated to a certain extent after forming seed particles.
種粒子をつくる方法と戊長させる方法は同じであっても
、異なってもよい。The method for creating seed particles and the method for elongating them may be the same or different.
又、可溶性銀塩と可溶性ハロゲン塩を反応させる形式と
しては、順混合法、逆混合法、同時混合法、それらの組
合せなどいずれでもよいが、同時混合法で得られたもの
が好ましい。更に同時混合法の一形式として特開昭５４
−４８５２１号等に記載されいてい６ ｐＡｇ−コント
ローノレドーダブノレジェット法を用いることもできる
。The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the 6 pAg control method described in No. 48521 and the like.
更に必要であればチオエーテル等のハロゲン化銀溶剤を
用いてもよい。又、メルカプト基含有化合物、含窒素へ
テロ環化合物又は増感色素のような化合物をハロゲン化
銀粒子の形或時、又は粒子形戊終了の後に添加して用い
てもよい。Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added either in the form of silver halide grains or after the grain formation is completed.
本発明に係るハロゲン化銀粒子の形状は任意のものを用
いることができる。好ましい１つの例は、｛ １００｝
面を結晶表面として有する立方体である。Any shape of the silver halide grains according to the present invention can be used. One preferred example is {100}
It is a cube with planes as crystal surfaces.
又、米国特許４，１８３．７５６号、同４，２２５，６
６６号、特開昭５５−２６５８９号、特公昭５５−４２
７３７号や、ザ・ジャーナル・オブ・フォトグラフィッ
ク・サイエンス（ Ｊ．Ｐｈｏｔｇｒ．Ｓｃｉ．）＋
２１．３９ （ １９７３）等の文献に記載された方法
により、８面体、１４面体、１２面体等の形状を有する
粒子をつくり、これを用いることもできる。更に、双晶
面を有する粒子を用いてもよい。本発明に係るハロゲン
化銀粒、子は、単一の形状からなる粒子を用いてもよい
し、種々の形状の粒子が混合されたものでもよい。Also, U.S. Patent Nos. 4,183.756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
No. 737 and The Journal of Photographic Science (J.Photogr.Sci.) +
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 21.39 (1973) and used. Furthermore, particles having twin planes may be used. The silver halide grains and particles according to the present invention may be of a single shape or may be a mixture of grains of various shapes.
本発明の乳剤に用いられるハロゲン化銀粒子は、粒子を
形或する過程及び／又は成長させる過程で、カドミウム
塩、亜鉛塩、鉛塩、タリウム塩、イリジウム塩又は錯塩
、ロジウム塩又は錯塩、鉄塩又は錯塩を用いて金属イオ
ンを添加し、粒子内部に及び／又は粒子表面に包含させ
ることができ、又、適当な還元的雰囲気におくことによ
り、粒子内部及び／又は粒子表面に還元増感核を付与で
きる。The silver halide grains used in the emulsion of the present invention may be formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron Metal ions can be added to the inside of the particles and/or on the surface of the particles by using salts or complex salts, and reduction sensitization can be performed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can give a nucleus.
本発明のハロゲン化銀粒子を含有する乳剤（以下、本発
明の乳剤という）は、ハロゲン化銀粒子の戊長の終了後
に不要な可溶性塩類を除去してもよいし、あるいは含有
させたままでもよい。該塩類を除去する場合には、リサ
ーチ・ディスクロージャー１７６４３号記載の方法に基
づいて行うことができる。In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the elongation of the silver halide grains or they may be left in the emulsion. good. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.
本発明の乳剤に用いられるハロゲン化銀粒子は、潜像が
主として表面に形戊される粒子であってもよく、又主と
して粒子内部に形或される粒子でもよい。好ましくは潜
像が主として表面に形戊される粒子である。The silver halide grains used in the emulsion of the present invention may be grains in which the latent image is formed mainly on the surface, or may be grains in which the latent image is formed mainly inside the grain. Preferably the particles are particles on which the latent image is primarily formed.
本発明の乳剤は、常法により化学増感される。The emulsion of the present invention is chemically sensitized by conventional methods.
本発明の感光材料は露光後、発色現像工程、脱銀処理工
程を少なくとも含む処理を施すことにより、色素画像を
与えることができるが、好ましくは露光後、発色現像処
理し、次に漂白定着処理した後、水洗処理又は安定化処
理する方法である。After exposure, the light-sensitive material of the present invention can be subjected to a process including at least a color development process and a desilvering process to give a dye image, but preferably, after exposure, a color development process is performed, and then a bleach-fixing process is performed. After that, it is washed with water or stabilized.
発色現像処理工程においては、通常、発色現像液中に発
色現像主薬を含有させるが、カラー写真感光材料中に発
色現像主薬の一部又は全てを内蔵させ、発色現像主薬を
含有する又は含有しない発色現像液で処理することも含
まれる。In the color development process, a color developing agent is usually contained in a color developing solution, but some or all of the color developing agent is incorporated into a color photographic light-sensitive material, and color development with or without a color developing agent is carried out. It also includes processing with a developer.
発色現像液に含まれる発色現像主薬は芳香族第１級アミ
ン発色現像主薬であり、アミノフェノール系及びｐ−フ
二二レンジアミン系誘導体が含まれるが、特にｐ−フェ
ニレンジアミン系誘導体が好ましい。これらの発色現像
主薬は有機酸及び無機酸の塩として用いることができ、
例えば塩酸塩、硫ｊｌ 塩、ｐ− トルエンスルホン酸
塩、亜硫酸塩、蓚酸塩、ベンゼンスルホン酸塩等を用い
ることができる。The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylene diamine derivatives, with p-phenylene diamine derivatives being particularly preferred. These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used.
これらの化合物は一般に発色現像液ＩＱについて約０．
１〜約３０ｇの濃度、更に好ましくは、発色現像液ｌＩ
２について約１ｇ〜約１５ｇの濃度で使用する。These compounds generally have a color developer IQ of about 0.
1 to about 30 g, more preferably a color developer lI
2 is used at a concentration of about 1 g to about 15 g.
特に有用な第１級芳香族アミン系発色現像剤はＮ，Ｎ−
ジアルキルーｐ−フェニレンジアミン系化合物であり、
アルキル基及びフェニル基は置換されていても、あるい
は置換されていなくてもよい。その中でも特に有用な化
合物例としてはＮ，Ｎ−ジエチルーｐ−フェニレンジア
ミン塩酸塩、Ｎ−メチルーｐ−７エニレンジアミン塩酸
塩、Ｎ，Ｎ−ジメチルーｐ−７ェニレンジアミン塩酸塩
、２−アミノー５−（Ｎ一エチルーＮ−ドデシルアミノ
）一トルエン、Ｎ一エチルーＮ一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ｉ［［、
Ｎ一エチルーＮ一β−ヒドロキシエチルアミノアリニン
、４−アミノー３−メチノレーＮ，Ｎ−ジエチルアニリ
ン、４−アミノーＮ−（２一メトキシエチル）一Ｎエチ
ル−３−メチルアニリンーＰ−｝ルエンスノレホネート
等を挙げることができる。A particularly useful primary aromatic amine color developer is N,N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful examples include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-7-phenylenediamine hydrochloride, N,N-dimethyl-p-7-phenylenediamine hydrochloride, and 2-amino-5- (N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline i [[,
N-ethyl-N-β-hydroxyethylaminoalinine, 4-amino-3-methynole-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-P-}ruenesnolefo Nate et al.
又、上記発色現像主薬は単独であるいは２種以上併用し
て用いてもよい。又、発色現像液は通常用いられるアル
カリ剤、例えば水酸化ナトリウム、水酸化カリウム、水
酸化アンモニウム、炭酸ナトリウム、炭酸カリウム、燐
酸ナトリウム、メタ硼酸ナトリウム又は硼砂等を含むこ
とができ、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又は塩化カリウム等、ある
いは現像調節剤として例えばシトラジン酸等、保恒剤と
してヒドロキシルアミン、ポリエチレンイミン、ブドウ
糖又は亜硫酸塩例えばナトリウム塩、カリウム塩等を含
有してもよい。更に各種消泡剤や界面活性剤を、又、メ
タノール、Ｎ，Ｎ−ジメチルホルムアミト、エチレング
リコーノレ、ジエチレングリコーノレ又はジメチノレス
ノレホキシド、べ冫ジノレアルコール等を含有せしめる
ことができるが、本発明においては実質的にべ冫ジルア
ルコールヲ含まず、かつ２ Ｘ １０−”モル／Ｑ以下
の亜硫酸塩を含む発色現像液で処理することが好ましい
。亜硫酸塩濃度はｌ Ｘ １０−４〜１．７Ｘ １０−
”モル／ Ｑが更に好ましく、特に５ Ｘ １０−”
− １ ｘ １０−”モル／ Ｑが好ましい。又、実質
的にベンジルアルコールを含まないとは濃度がＱ．５ｍ
ｆｆ／４未満のことをいい、全く含有しないことが好ま
しい。Further, the above color developing agents may be used alone or in combination of two or more. Further, the color developing solution may contain commonly used alkaline agents such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metaborate, or borax, and may further contain various additives. agents, such as alkali metal halides, such as potassium bromide or potassium chloride, or development regulators, such as citradinic acid, and preservatives, such as hydroxylamine, polyethyleneimine, glucose or sulfites, such as sodium salts, potassium salts, etc. You may. Furthermore, various antifoaming agents and surfactants can be contained, such as methanol, N,N-dimethylformamide, ethylene glycol, diethylene glycol, dimethylene glycol, dimethyl alcohol, etc. However, in the present invention, it is preferable to process with a color developing solution that does not substantially contain baseyl alcohol and contains sulfite in an amount of 2 x 10-" mol/Q or less. The sulfite concentration is 1 x 10-" mol/Q or less. 4~1.7X 10-
"Mole/Q is more preferable, especially 5 x 10-"
- 1 x 10-" mole/Q is preferred. Also, "substantially free of benzyl alcohol" means that the concentration is Q.5m
It means less than ff/4, and it is preferable that it is not contained at all.
発色現像液のｐｉは通常７以上であり、好ましくは約９
〜ｌ３である。The pi of the color developer is usually 7 or more, preferably about 9.
~l3.
又、発色現像槽の処理液温度は好ましくはＩＯ”０〜６
５℃、より好まし＜２５℃〜４５℃で処理される。Further, the temperature of the processing solution in the color developing tank is preferably IO"0 to 6.
Processing is carried out at 5°C, more preferably <25°C to 45°C.
現像時間は２分３０秒以内が好ましく、２分以内が更に
好ましい。The developing time is preferably within 2 minutes and 30 seconds, more preferably within 2 minutes.
カラー現像後のハロゲン化銀カラー感光材料は通常、漂
白処理される。漂白処理は、定着処理と同時に行われて
もよいし（漂白定着）、個別に行われてもよいが、漂白
と定着を一浴で処理する漂白定着浴であることが好まし
い。漂白定着液のｐＨは４．５〜６．８が好ましく、特
に４．５〜６．０が好ましい。After color development, silver halide color photosensitive materials are usually bleached. The bleaching treatment may be performed simultaneously with the fixing treatment (bleach-fixing) or separately, but a bleach-fixing bath that processes bleaching and fixing in one bath is preferred. The pH of the bleach-fix solution is preferably 4.5 to 6.8, particularly preferably 4.5 to 6.0.
該漂白定着液に使用することができる漂白剤としては有
機酸の金属錯塩が好ましく、特にアミノポリカルボン酸
又は蓚酸、クエン酸等の有機酸で鉄、コバルト、銅等の
金属イオンを配位したものが好ましい。The bleaching agent that can be used in the bleach-fix solution is preferably a metal complex salt of an organic acid, particularly a complex salt of an organic acid such as aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt or copper. Preferably.
漂白定着液に添加される添加剤としては、特にアルカリ
ハライド又はアンモニウムハライド、例えば、臭化カリ
ウム、臭化ナトリウム、塩化ナトリウム、臭化アンモニ
ウム等の再ハロゲン化剤、金属塩、キレート剤などが挙
げられる。Additives added to the bleach-fix solution include, in particular, alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, etc. It will be done.
又、硼酸塩、蓚酸塩、酢酸塩、炭酸塩、燐酸塩等のｐＨ
緩衝剤、アルキルアミン類、ポリエチレンオキサイド類
等の通常漂白液に添加することが知られているものを適
宜添加することができる。Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.
更に、漂白゛定着液は、亜硫酸アンモニウム、亜硫酸カ
リウム、重亜硫酸アンモニウム、重亜硫酸カリウム、重
亜硫酸ナトリウム、メタ重亜硫酸アンモニウム、メタ重
亜硫酸カリウム、メタ重亜硫酸ナトリウム等の亜硫酸塩
や硼酸、硼砂、水酸化ナトリウム、水酸化カリウム、炭
酸ナトリウム、炭酸カリウム、重亜硫酸ナトリウム、重
炭酸ナトリウム、重炭酸カリウム、酢酸、酢酸ナトリウ
ム、水酸化アンモニウム等の各種の塩から戊るｐＨ緩衝
剤を単独あるいは２種以上含むことができる。Furthermore, the bleach/fix solution contains sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, and water. One or more pH buffers selected from various salts such as sodium oxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. can be included.
以下、本発明を実施例により具体的に説明するが本発明
の実施の態様はこれらに限定されない。Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.
実施例ｌ
シアンカプラー〔Ｃ − １ ） ６０ｇを高沸点有機
溶媒（Ｄ Ｂ Ｐ ）４０−と酢酸エチルｌ００ｍＱに
溶解した溶液を分散添加剤（ドデシルベンゼンスルホン
酸ンーダ）５ｇを含む５％ゼラチン水溶液に添加し超音
波ホモジナイザーで分散し、得られた分散液を１５００
ｍＱに仕上げた。この分散液を塗布用３％ゼラチン水溶
液ｌ０００ｌＩ１２に加え、更に赤感性塩臭化銀乳剤４
００ｇを添加し赤感光性乳剤層塗布液を調整した。Example 1 A solution of 60 g of cyan coupler [C-1] dissolved in 40-40 of a high boiling point organic solvent (D B P ) and 100 mQ of ethyl acetate was added to a 5% aqueous gelatin solution containing 5 g of a dispersing additive (dodecylbenzenesulfonate). and dispersed with an ultrasonic homogenizer, and the resulting dispersion was heated to 1500
Finished in mQ. This dispersion was added to a 3% aqueous gelatin solution for coating 1000lI12, and then red-sensitive silver chlorobromide emulsion 4
00g was added to prepare a red-sensitive emulsion layer coating solution.
同様にして各層の塗布液を調整し、ポリエチレン被覆紙
支持体上に表−１の構成となるよう支持体側から順次塗
設した。Coating solutions for each layer were prepared in the same manner, and coated sequentially from the support side onto a polyethylene-coated paper support so as to have the structure shown in Table 1.
使用したハロゲン化銀乳剤は以下のごとく調整した。The silver halide emulsion used was prepared as follows.
【青感性ハロゲン化銀乳剤の調製方法］４０℃に保温し
た２％ゼラチン水溶液１０００＋ｓａ中に下記（Ａ液）
及び（Ｂ液）をｐＡｇ− ６．５、ｐＨ−３．０に制御
しつつ３０分かけて同時添加し、更に下記〔Ｃ液）及び
（Ｄ液）をｐＡｇ＝ ７．３、ｐＨ−５．５に制御しつ
つ１８０分かけて同時添加した。[Preparation method of blue-sensitive silver halide emulsion] The following (liquid A) is added to a 2% gelatin aqueous solution 1000+sa kept at 40°C.
and (Solution B) were simultaneously added over 30 minutes while controlling the pAg to 6.5 and pH to 3.0, and then added the following [Solution C] and (Solution D) to pAg = 7.3 and pH-5. They were simultaneously added over 180 minutes while controlling the temperature to be .5.
このとき、Ｉ）Ａｇの制御は特開昭５９−４５４３７号
記載の方法により行い、ｐ｝Ｉの制御は硫酸又は水酸化
ナトリウムの水溶液を用いて行った。At this time, I) Ag was controlled by the method described in JP-A-59-45437, and p}I was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.
（Ａ液）
Ｎ ａ Ｃ Ｑ ３．４
２ｇＫ Ｂ ｒ ０．
０３ｇＨ，Ｏを加えｆ ２０
０ｍｆｆ（Ｂ液）
ＡｇＮＯｓ ｌＯｇＨ，
０を加えて ２００ｆｉＩＱ〔
Ｃ液）
Ｎ ａ Ｃ Ｑ ｌ０２
．７ｇＫ Ｂ ｒ
１．ＯｇＨ，０を加えて ６０
０ｗ（１（Ｄ液）
Ａ ｇ Ｎ Ｏ ｓ ３
００ｇＨ２０を加えテ６００ｍ（ｔ
添加終了後、花王アトラスト社製デモールＮの５％水溶
液と硫酸マグネシウムの２０％水溶液を用いて脱塩を行
った後、ゼラチン水溶液と混合して平均粒径０．８５μ
―、変動係数（Ｓ／ｒ）＝０．０７、塩化銀含有率９９
．５モル％の単分散立方体乳剤ＥＭＰ一１を得た。(Liquid A) N a C Q 3.4
2gK B r 0.
Add 03gH and O and f 20
0mff (Liquid B) AgNOs lOgH,
Add 0 to 200fiIQ [
C liquid) N a C Q l02
．． 7gK B r
1. Add OgH,0 60
0w (1 (D liquid) A g N O s 3
After adding 00 g H20 and 600 m (t) of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85μ.
-, coefficient of variation (S/r) = 0.07, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-1 was obtained.
上記乳剤ＥＭＰ−１に対し、下記化合物を用い、５０℃
にて９０分化学熟戊を行い、青感性ハロゲン化銀乳剤（
ＥｍＡ）を得た。The following compound was used for the above emulsion EMP-1 at 50°C.
A blue-sensitive silver halide emulsion (
EmA) was obtained.
チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ
塩化金酸 ０．５ｍｇ／モルＡｇＸ
安定剤 Ｓ Ｂ − ５ ６ Ｘ １０−’モル
／モルＡｇＸ増感色素 Ｄ−１５Ｘ１０−’モル／モル
ＡｇＸ［緑感性ハロゲン化銀乳剤の調製方法］（Ａ液）
と（Ｂ液）の添加時間及び〔Ｃ液）と（Ｄ液）の添加時
間を変更する以外はＥＭＰ−１と同様にして、平均粒径
０．４３μｍ１変動係数（Ｓ／ｒ）＝ Ｏ．Ｏａ、塩化
銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−２
を得た。Sodium thiosulfate 0.8mg/mol AgX
Chloroauric acid 0.5mg/mol AgX
Stabilizer S B-5 6 X 10-' mol/mol AgX Sensitizing dye D-15X 10-' mol/mol AgX [Preparation method of green-sensitive silver halide emulsion] (Liquid A)
The procedure was the same as EMP-1, except that the addition time of [Liquid B] and the addition time of [Liquid C] and (Liquid D) were changed, and the average particle size was 0.43 μm 1 Coefficient of variation (S/r) = O. Oa, monodisperse cubic emulsion EMP-2 with silver chloride content of 99.5 mol%
I got it.
ＥＭＰ−２に対し、下記化合物を用いて５５゜Ｃで１２
０分化学熟或を行い、緑感性ハロゲン化銀乳剤（Ｅ ｍ
Ｂ ）を得ｔ；。For EMP-2, the following compound was used at 55°C for 12
A green-sensitive silver halide emulsion (E m
B) obtained t;.
チオ硫酸ナトリウム １．５＋ａｇ／モルＡｇ
Ｘ塩化金酸 １．０ｍｇ／ モルＡ
ｇＸ安定剤 ＳＢ−５６×ｌＯ−６モル／モルＡｇｘ増
感色素 Ｄ−２ ４．ＯＸｌＯ−’−ｖ−ル／モル
ＡｇＸ［赤感性ハロゲン化銀乳剤の調製方法］（Ａ液）
と＜Ｂ液）の添加時間及び〔Ｃ液）と（Ｄ液）の添加時
間を変更する以外はＥＭＰ−１と同様にして、平均粒径
０，５０μ鵬、変動係数（Ｓ／−ｒ）− ０．０８、塩
化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−
３を得た。Sodium thiosulfate 1.5+ag/mol Ag
X Chloroauric acid 1.0 mg/mol A
gX stabilizer SB-56×lO-6 mol/mol Agx sensitizing dye D-2 4. OXlO-'-vol/mol AgX [Preparation method of red-sensitive silver halide emulsion] (Liquid A)
The average particle size was 0.50μ, the coefficient of variation (S/-r) - 0.08, monodispersed cubic emulsion EMP- with a silver chloride content of 99.5 mol%
I got 3.
ＥＭＰ−３に対し、下記化合物を用いて６０℃で９０分
化学熟成を行い、赤感性ハロゲン化銀乳剤（ＥｍＣ）を
得た。EMP-3 was chemically ripened at 60° C. for 90 minutes using the following compound to obtain a red-sensitive silver halide emulsion (EmC).
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０鵬ｇ／モルＡｇＸ
安定剤 Ｓ Ｂ − ５ ６ｘ ｌｏ−’％
ル／ モルＡｇＸ増感色素 Ｄ − ３ ８．Ｏ
Ｘ １０−’−ｔ− ル／ モルＡｇｘＤ−１
Ｄ−３
ＳＢ−５
表−１
（１〕
表−１
（２）
ｙ”Ｌｌ
ｐＶＰ （ポリビニルピロリ
ドン）
ＤＢＰ
（ジブチルフタレート）
ＩＱ−１
ＳＴ−３
ＳＴ−４
Ａ
■
ｌ
Ａ
！−２
この試料を常法に従って赤色光楔露光後下記の処理工程
に従って処理を・行った。Sodium thiosulfate 1.8mg/mol AgX
Chloroauric acid 2.0g/mol AgX
Stabilizer SB-5 6x lo-'%
l/mol AgX sensitizing dye D-3 8. O
X 10-'-t- Le/Mole AgxD-1 D-3 SB-5 Table-1 (1) Table-1 (2) y”Ll pVP (Polyvinylpyrrolidone) DBP (Dibutyl phthalate) IQ-1 ST-3 ST-4 A ■ l A !-2 This sample was exposed to red light wedge according to a conventional method and then processed according to the following processing steps.
［処理工程］ 温 度
発色現像 ３５．０±０．３℃
漂白定着 ３５．０±０．５℃
安定化 ３０〜３４℃
乾 燥 ６０〜８０°Ｃ
時 間
４５秒
４５秒
９０秒
６０秒
【発色現像液］
純水
トリエタノールアミン
Ｎ，Ｎ−ジエチルヒドロキシルアミン
臭化カリウム
塩化カリウム
亜硫酸カリウム
■−ヒドロキシエチリデン−１．１−
ジホスホン酸
エチレンジアミン四酢酸
カテコールー３．５−ジスルホン酸
二ナトリウム塩
Ｎ一エチルー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
蛍光増白剤（４．４’−ジアミノスチルベンジスルホン
酸誘導体）
炭酸カリウム
水を加えて全量をｌＱとし、
る。[Processing process] Temperature color development 35.0±0.3℃ Bleach-fixing 35.0±0.5℃ Stabilization 30-34℃ Drying 60-80℃ Time 45 seconds 45 seconds 90 seconds 60 seconds [ Color developer] Pure water triethanolamine N,N-diethylhydroxylamine Potassium bromide Potassium chloride Potassium sulfite ■-Hydroxyethylidene-1.1-Diphosphonate Ethylenediamine Tetraacetic acid catechol-3.5-Disulfonic acid disodium salt N-ethyl N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Add potassium carbonate water to bring the total volume to 1Q.
ｐＨ＝ １０．１０に調整す
８００ｍｌ２
Ｌｏｇ
５ｇ
０．０２ｇ
２ｇ
０．３ｇ
１．０ｇ
１．０ｇ
１．０ｇ
４．５ｇ
１．０ｇ
２７ｇ
［漂白定着液］
漂白定着液１１２中、
エチレンジアミン四酢酸第二鉄
アンモニウム２水塩 ６０ｇエチレン
ジアミン四酢酸 ３ｇチオ硫酸アンモニ
ウム（７０％水溶液） １００ｍ！亜硫酸アンモニウ
ム（４０％水Ｗｌ 液） ２７．５ｓＩ２を含有。Adjust to pH = 10.10 800ml2 Log 5g 0.02g 2g 0.3g 1.0g 1.0g 1.0g 4.5g 1.0g 27g [Bleach-fix solution] In bleach-fix solution 112, ethylenediaminetetraacetic acid secondary Iron ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100m! Contains ammonium sulfite (40% water Wl solution) 27.5sI2.
炭酸カリウム又は氷酢酸でｐＨ−５．７に調整する。Adjust pH to -5.7 with potassium carbonate or glacial acetic acid.
［安定化液］
安定化液１１２中、
５−クロロ−２−メチル−４−インチアゾリン−３−オ
ン １．０ｇエチ
レングリコール ｌ．Ｏｇｌ−ヒドロ
キシェチリデン−１．１−
ジホスホン酸 ２．０ｇエチレ
ンジアミン四酢酸 １．０ｇ水酸化アンモ
ニウム（２０％水溶液） ３．０ｇ亜硫酸アンモニ
ウム ３．０ｇ蛍光増白剤（４．４’
−ジアミノスチルベンジホスホン酸誘導体）
１．５ｇを含有。硫酸又は水酸化カリウムでｐＨ＝
７．０に調整する。[Stabilizing liquid] In the stabilizing liquid 112, 5-chloro-2-methyl-4-thiazolin-3-one 1.0 g ethylene glycol l. Ogl-hydroxyethylidene-1.1-diphosphonic acid 2.0g ethylenediaminetetraacetic acid 1.0g ammonium hydroxide (20% aqueous solution) 3.0g ammonium sulfite 3.0g optical brightener (4.4'
-diaminostilbene diphosphonic acid derivative)
Contains 1.5g. pH = with sulfuric acid or potassium hydroxide
Adjust to 7.0.
以上の試料を試料ｌとし、次に試料ｌの第５層のシアン
カプラー 添加剤及び高沸点有機溶媒を表−２に示す如
く代えた他は同様にして試料を作り、試料ｌと同様に露
光、処理を行った。The above sample was designated as Sample 1. Next, a sample was made in the same manner except that the cyan coupler additive and high boiling point organic solvent in the fifth layer of Sample 1 were changed as shown in Table 2, and exposed in the same manner as Sample 1. , processed.
全試料について下記の評価を行った。All samples were evaluated as follows.
〔発色性〕 ：試料の最大反射濃度を測定した。[Color development]: The maximum reflection density of the sample was measured.
〔光堅牢性試験〕 ：アンダーグラス屋外日光＠露台を
用いて、３０日間太陽光を照射したときの初濃度１．０
の残存率で示した。[Lightfastness test]: Initial concentration 1.0 when exposed to sunlight for 30 days using an underglass outdoor sunlight @ exposure stand
It was expressed as the residual rate.
残存率＝（退色後の濃度）ＸＩＯＯ
〔暗退色性試験〕 二暗所にて７０゜０，４０％ＲＨに
て２週間保存した後の退色性を上記光堅牢性と同様に残
存率として求めた。Residual rate = (density after fading) Ta.
〔発色色素の分光吸収特性〕 ：シアン色素画像の最大
濃度が１．０のときの５５０ｎｍの濃度（Ｄ０）を測定
した。値が小さい程、色素純度が高いことを示す。[Spectral absorption characteristics of coloring dye]: The density (D0) at 550 nm when the maximum density of the cyan dye image was 1.0 was measured. The smaller the value, the higher the dye purity.
〔カプラー分散液安定性試験〕 ：前述のカプラー分散
液の分散直後及び１０時間停滞後の濁度（値が小さいほ
ど分散粒子の粒径が小さく好ましい。）及び表面の粒子
析出性（析出開始時間）を測定した。保存条件は無撹拌
で４０℃で１０時間まで測定しｔこ 。[Coupler dispersion stability test]: Turbidity immediately after dispersion of the above-mentioned coupler dispersion and after stagnation for 10 hours (the smaller the value, the smaller the particle size of the dispersed particles is) and the particle precipitation property on the surface (precipitation start time) ) was measured. The storage conditions were 40°C without stirring for up to 10 hours.
結果を表−２に示す。The results are shown in Table-2.
表−２から明らかなように試料ｌでは暗退色性が非常に
悪く、又、ＤＣ．も高い値を示している。As is clear from Table 2, Sample 1 had very poor dark fading properties, and DC. also shows high values.
これに一般式〔Ｃ−２）で示されるカプラーを併用した
試料２では暗退色性に非常に有効であるが、反面、分光
吸収特性が大きく劣化し、発色性、光堅牢性も若干低下
し、更には分散安定性も劣化してしまう。これに一般式
〔Ｃ−１〕で示されるカプラー及び比較の添加剤を用い
た試料３．４では暗退色性、分光吸収特性の改良は見ら
れるものの光堅牢性の劣化が大きく、添加剤を増量した
試料５では発色性、分散安定性を更に劣化してしまう。Sample 2, in which a coupler represented by the general formula [C-2] was used in combination, was very effective in preventing dark fading, but on the other hand, the spectral absorption characteristics were greatly deteriorated, and the color development and light fastness were also slightly reduced. Furthermore, dispersion stability also deteriorates. In addition, sample 3.4 using the coupler represented by the general formula [C-1] and a comparative additive showed improvement in dark fading and spectral absorption characteristics, but a large deterioration in light fastness. Sample 5, which had an increased amount, further deteriorated color development and dispersion stability.
これらの比較試料に対し、本発明の試料は全ての点で良
好な特性を示している。又、高沸点有機溶媒を低誘電率
のものに代えた場合、更に本発明の効果が向上しており
、一般式（Ｎ−１〕で示される化合物を用いると分光吸
収特性が著しく向上することがわかる。Compared to these comparative samples, the samples of the present invention exhibit better characteristics in all respects. Furthermore, when the high boiling point organic solvent is replaced with one having a low dielectric constant, the effects of the present invention are further improved, and when the compound represented by the general formula (N-1) is used, the spectral absorption characteristics are significantly improved. I understand.
尚、試料７のシアンカプラーＣ−１−４の代わりにＣ
− １ −１０， Ｃ − １ −１４． Ｃ − １
−１８を、Ｃ一２−２の代わりにＣ−２−１８． Ｃ−
２ −２４， Ｃ−２−２７を、又、試料８のＮ−１９
の代わりにＮ一２． Ｎ−２４． Ｎ−２６， Ｎ−２
７を、試料６のＴ − １１の代わりにＴ− １ ，
Ｔ−１４， Ｔ− ７ ， Ｔ−１６， Ｔ−１７を、
試料１１のＴ−２４の代わりにＴ−２０，Ｔ−２９，Ｔ
−３１を用いた各試料についても本発明の効果が認めら
れた。Furthermore, instead of cyan coupler C-1-4 of sample 7, C
- 1 -10, C - 1 -14. C-1
-18 instead of C-2-18. C-
2-24, C-2-27, and N-19 of sample 8
Instead of N-2. N-24. N-26, N-2
7, T-1 instead of T-11 of sample 6,
T-14, T-7, T-16, T-17,
T-20, T-29, T instead of T-24 of sample 11
The effects of the present invention were also observed for each sample using -31.
Claims (1)
般式〔Ｃ−１〕で示されるシアンカプラー及び２，５−
ジアシルアミノフェノール系シアンカプラーを含有する
ハロゲン化銀乳剤層を少なくとも１層有することを特徴
とするハロゲン化銀カラー写真感光材料。 一般式〔Ｔ〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１及びＲ＿２は水素原子又はアルキル基を
、Ｒ＿３、Ｒ＿４は水素原子、アルキル基、アリール基
又はヘテロ環基を、Ｒ＿５、Ｒ＿６は水素原子、アルキ
ル基、アリール基、アシル基又はアルコキシカルボニル
基を、Ｘは上記６員環の構成原子としての炭素原子を有
する２価基を、ｎは０、１又は２を表す。〕 一般式〔Ｃ−１〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１はバラスト基を表し、Ｒ＿２は炭素数２
以上のアルキル基を表す。Ｚ＿１は水素原子又は発色現
像主薬の酸化体との反応により離脱しうる原子又は基を
表す。〕[Scope of Claims] A compound represented by the following general formula [T], a cyan coupler represented by the following general formula [C-1], and a 2,5-
A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer containing a diacylaminophenol cyan coupler. General formula [T] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms or alkyl groups, R_3 and R_4 are hydrogen atoms, alkyl groups, aryl groups, or heterocyclic groups, R_5, R_6 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, X represents a divalent group having a carbon atom as a constituent atom of the 6-membered ring, and n represents 0, 1 or 2. ] General formula [C-1] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a ballast group, R_2 represents a carbon number of 2
It represents the above alkyl group. Z_1 represents a hydrogen atom or an atom or group that can be separated by reaction with an oxidized product of a color developing agent. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31370489A JPH0348242A (en) | 1989-04-18 | 1989-12-01 | Silver halide color photographic sensitive material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9935289 | 1989-04-18 | ||
| JP1-99352 | 1989-04-18 | ||
| JP31370489A JPH0348242A (en) | 1989-04-18 | 1989-12-01 | Silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0348242A true JPH0348242A (en) | 1991-03-01 |
Family
ID=26440493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31370489A Pending JPH0348242A (en) | 1989-04-18 | 1989-12-01 | Silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0348242A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006022405A1 (en) | 2004-08-24 | 2006-03-02 | Fujifilm Corporation | Silver halide color photographic photosensitive material and method of image forming |
| WO2009123141A1 (en) | 2008-03-31 | 2009-10-08 | 富士フイルム株式会社 | Ultraviolet absorbent compositions |
| WO2010024441A1 (en) | 2008-09-01 | 2010-03-04 | 富士フイルム株式会社 | Ultraviolet absorbing agent composition |
-
1989
- 1989-12-01 JP JP31370489A patent/JPH0348242A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006022405A1 (en) | 2004-08-24 | 2006-03-02 | Fujifilm Corporation | Silver halide color photographic photosensitive material and method of image forming |
| WO2009123141A1 (en) | 2008-03-31 | 2009-10-08 | 富士フイルム株式会社 | Ultraviolet absorbent compositions |
| WO2010024441A1 (en) | 2008-09-01 | 2010-03-04 | 富士フイルム株式会社 | Ultraviolet absorbing agent composition |
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