JPS6322571B2 - - Google Patents
Info
- Publication number
- JPS6322571B2 JPS6322571B2 JP57189538A JP18953882A JPS6322571B2 JP S6322571 B2 JPS6322571 B2 JP S6322571B2 JP 57189538 A JP57189538 A JP 57189538A JP 18953882 A JP18953882 A JP 18953882A JP S6322571 B2 JPS6322571 B2 JP S6322571B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- coupler
- couplers
- dyes
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 Silver halide Chemical class 0.000 claims description 81
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 8
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UDFSJHJKINSRFV-UHFFFAOYSA-N N1N=CN2N=CC=C21 Chemical compound N1N=CN2N=CC=C21 UDFSJHJKINSRFV-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 125000005462 imide group Chemical group 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 4
- 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 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
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical compound C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- 125000004173 1-benzimidazolyl group Chemical group [H]C1=NC2=C([H])C([H])=C([H])C([H])=C2N1* 0.000 description 1
- YGDWUQFZMXWDKE-UHFFFAOYSA-N 1-oxido-1,3-thiazole Chemical class [O-]S1=CN=C=C1 YGDWUQFZMXWDKE-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- KPVMVJXYXFUVLR-UHFFFAOYSA-N 12-ethyltetradecan-1-amine Chemical compound CCC(CC)CCCCCCCCCCCN KPVMVJXYXFUVLR-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- 150000001473 2,4-thiazolidinediones Chemical class 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- QTLHLXYADXCVCF-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C(C)=C1 QTLHLXYADXCVCF-UHFFFAOYSA-N 0.000 description 1
- WFXLRLQSHRNHCE-UHFFFAOYSA-N 2-(4-amino-n-ethylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C=C1 WFXLRLQSHRNHCE-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- SEEZWGFVHCMHJF-UHFFFAOYSA-N 2-nitrosophenol Chemical class OC1=CC=CC=C1N=O SEEZWGFVHCMHJF-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical class O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical class O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- GCABLKFGYPIVFC-UHFFFAOYSA-N 3-(1-benzofuran-2-yl)-3-oxopropanenitrile Chemical compound C1=CC=C2OC(C(CC#N)=O)=CC2=C1 GCABLKFGYPIVFC-UHFFFAOYSA-N 0.000 description 1
- PZSMZCQUKXCTFS-UHFFFAOYSA-N 3-[2,4-bis(2-methylbutan-2-yl)phenoxy]butanamide Chemical group CCC(C)(C)C1=CC=C(OC(C)CC(N)=O)C(C(C)(C)CC)=C1 PZSMZCQUKXCTFS-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- YLNKRLLYLJYWEN-UHFFFAOYSA-N 4-(2,2-dibutoxyethoxy)-4-oxobutanoic acid Chemical compound CCCCOC(OCCCC)COC(=O)CCC(O)=O YLNKRLLYLJYWEN-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- FFAJEKUNEVVYCW-UHFFFAOYSA-N 4-n-ethyl-4-n-(2-methoxyethyl)-2-methylbenzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(C)=C1 FFAJEKUNEVVYCW-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- UJUCBOIXAMPUQL-UHFFFAOYSA-N 7-aminothieno[2,3-b]pyrazine-6-carboxylic acid Chemical compound C1=CN=C2C(N)=C(C(O)=O)SC2=N1 UJUCBOIXAMPUQL-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FBKOEGMKQZSFLK-UHFFFAOYSA-N N-[2-[(4,4-diamino-3-methylcyclohexa-1,5-dien-1-yl)-ethylamino]ethyl]methanesulfonamide Chemical compound NC1(C(C=C(C=C1)N(CCNS(=O)(=O)C)CC)C)N FBKOEGMKQZSFLK-UHFFFAOYSA-N 0.000 description 1
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 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
- ZJRCIQAMTAINCB-UHFFFAOYSA-N benzoylacetonitrile Chemical compound N#CCC(=O)C1=CC=CC=C1 ZJRCIQAMTAINCB-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- COPHVUDURPSYBO-UHFFFAOYSA-N butyl dioctyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCC)OCCCCCCCC COPHVUDURPSYBO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 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
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 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 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 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
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical group OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- VUVFZUKPBAGTCQ-UHFFFAOYSA-M sodium;2,3-di(butan-2-yl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(C(C)CC)C(C(C)CC)=CC2=C1 VUVFZUKPBAGTCQ-UHFFFAOYSA-M 0.000 description 1
- UWSAIOMORQUEHN-UHFFFAOYSA-L sodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(5+) Chemical compound [Na+].[Fe+5].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O UWSAIOMORQUEHN-UHFFFAOYSA-L 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ARZGWBJFLJBOTR-UHFFFAOYSA-N tetradecanamide Chemical compound CCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCC(N)=O ARZGWBJFLJBOTR-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NJPOTNJJCSJJPJ-UHFFFAOYSA-N tributyl benzene-1,3,5-tricarboxylate Chemical compound CCCCOC(=O)C1=CC(C(=O)OCCCC)=CC(C(=O)OCCCC)=C1 NJPOTNJJCSJJPJ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30529—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site in rings of cyclic compounds
Description
本発明は新規な1H−ピラゾロ〔３，２−Ｃ〕−
Ｓ−トリアゾール誘導体を含有するハロゲン化銀
写真感光材料に関する。さらには、1H−ピラゾ
ロ〔３，２−Ｃ〕−Ｓ−トリアゾール型カプラー
で、カツプリング活性位に新規なカツプリング離
脱基を有する二当量マゼンタカプラーを含有する
ハロゲン化銀写真感光材料に関する。
ハロゲン化銀カラー写真材料を発色現像するこ
とにより、酸化された芳香族第１級アミン系カラ
ー現像主薬とカプラーが反応してインドフエノー
ル、インドアニリン、インダミン、アゾメチン、
フエノキサジン、フエナジン及びそれに類する色
素ができ、色画像が形成されることは良く知られ
ている。これらのうちマゼンタ色画像を形成する
ためには、５−ピラゾロン、シアノアセトフエノ
ン、インダゾロン、ピラゾロベンズイミダゾー
ル、ピラゾロトリアゾール系カプラーが使われ
る。
従来、マゼンタ色画像形成カプラーとして広く
実用に供され、研究が進められいたものはほとん
ど５−ピラゾロン類であつた。５−ピラゾロン系
カプラーから形成される色素は熱、光に対する堅
牢性が優れているが、430nm付近に黄色成分を有
する不要吸収が存在していて、色にごりの原因と
なつている事が知られていた。この黄色成分を減
少させるマゼンタ色画像形成カプラー骨核として
古くから英国特許1047612号に記載されるピラゾ
ロベンズイミダゾール骨核、米国特許3770447号
に記載されるインダゾロン骨核、また米国特許
3725067号に記載されるピラゾロトリアゾール骨
核が提案されている。
この中で米国特許3725067号、英国特許1252418
号、英国特許1334515号、英国特許139897号に記
載された1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリ
アゾール型カプラーから形成されるアゾメチン色
素は酢酸エチル等の溶媒中で430nm付近の不要吸
収が少なく、長波長側のシヤープカツト性も優れ
たものである。しかしながら上記特許の明細書に
記載されたカプラーは、実際の写真フイルム中に
導入する際に同業者間では周知の技術となつてい
るオイルプロテクト方式に用いる高沸点有機溶剤
（例えばトリクレジルホスフエート、ジブチルフ
タレート等）に対する溶解性が著しく低かつた
り、その上、かつ通常の発色現像処理浴に通して
も発色スピードが遅く、高い最大発色濃度を示さ
ない欠点を有していた。
本発明の発明者は、種々検討を加えた結果、こ
れらの欠点を改良する一連のカプラー群に到達し
た。したがつて本発明の目的は発色速度および最
大発色濃度が共に優れ、高沸点有機溶媒に対する
溶解性が改良された写真用の新規な２当量マゼン
タカプラーを含有するハロゲン化銀カラー感光材
料を提供することを目的とする。前記の目的は
1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾール
型カプラーで、現像主薬の酸化生成物とカツプリ
ングする位置に下記一般式がカツプリング離脱
基として置換している二当量マゼンタカプラーを
含有することによつて達成することができた。
（1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾ
ール骨核については前記米国特許3725067号で公
知なものである）
一般式
但し、A1とA2は同じでも異なつてもよく、そ
れぞれ水素原子、アルキル基、アリール基、ヘテ
ロ環基、アシル基、スルホニル基、カルバモイル
基、スルフアモイル基、アルコキシカルボニル
基、アリールオキシカルボニル基を表わし、A1
とA2が共に水素原子であることはない。またA1
とA2が互いに結合し、窒素原子と共に形成され
る５員もしくは６員環を形成してもよい。この５
員もしくは６員環はさらにベンゼン環・複素環と
縮合してもよい。
本発明のカプラーのうち好ましいものは一般式
であらわされるものである。
一般式
式中、A1、A2は同じでも異なつてもよく、そ
れぞれ、水素原子、アルキル基（好ましくは炭素
数１〜22のアルキル基で、例えば、メチル基、エ
チル基、ブチル基、オクチル基、２−エチルヘキ
シル基、及びハロゲン原子、水酸基、シアノ基、
アリール基、カルボキシ基、アルコキシ基、アリ
ールオキシ基、アシルアミノ基、スルホンアミド
基、イミド基、アルコキシカルボニル基、アリー
ルオキシカルボニル基、アルキルチオ基、アリー
ルチオ基、アルキルスルホニル基、アリールスル
ホニル基、カルバモイル基、スルフアモイル基、
アルキルオキシカルボニルアミノ基、アリールオ
キシカルボニルアミノ基、ウレイド基、アシル
基、アルキルアミノ基またはアリールアミノ基で
置換されたアルキル基等）、アリール基（好まし
くは、炭素数６〜32のアリール基で例えば、フエ
ニル基、ナフチル基及び上記アルキル基の所で述
べた置換基が置換されてもよいアリール基等）、
ヘテロ環基（例えば２−ピリジル基、２−キノリ
ル基、２−ベンゾチアゾリル基、２−フリル基、
２−ピリミジニル基、等）、アシル基（例えばア
セチル基、ブタノイル基、ヘキサノイル基、トリ
フルオロアセチル基、ヘプタフルオロブタノイル
基、ベンゾイル基、ナフトイル基、ペンタフルオ
ロベンゾイル基、ペンタクロロフエニル基、２−
フランカルボニル基、２−キノリンカルボニル
基、等）、スルホニル基（例えば、メタンスルホ
ニル基、ヘキサンスルホニル基、ベンゼンスルホ
ニル基、ナフタレンスルホニル基、および前記ア
ルキル基の所で述べた置換基で置換されてもよい
アルカンスルホニル基、アリールスルホニル基
等）、カルバモイル基（例えばＮ−メチルカルバ
モイル基、Ｎ−ドデシルカルバモイル基、Ｎ，Ｎ
−ジエチルカルバモイル基、Ｎ−フエニルカルバ
モイル基、及び、前記アルキル基のところで述べ
た置換基で置換されてもよいＮ−アルキルカルバ
モイル基、Ｎ，Ｎ−ジアルキルカルバモイル基、
Ｎ−アリールカルバモイル基、Ｎ，Ｎ−ジアリー
ルカルバモイル基、等）、スルフアモイル基（例
えば、Ｎ−メチルスルフアモイル基、Ｎ−ｎ−オ
クチルスルフアモイル基、Ｎ−フエニルスルフア
モイル基、Ｎ，Ｎ−ジエチルスルフアモイル基、
及び前記アルキル基のところで述べた置換基で置
換されていてもよいＮ−アルキルスルフアモイル
基、Ｎ，Ｎ−ジアルキルスルフアモイル基、Ｎ−
アリールスルフアモイル基、Ｎ，Ｎ−ジアリール
スルフアモイル基、等）、アルコキシカルボニル
基（例えば、メトキシカルボニル基、ブチルオキ
シカルボニル基、ドデシルオキシカルボニル基、
２−エチルヘキシルオキシカルボニル基、及び前
記アルキル基のところで述べた置換基で置換され
てもよいアルコキシカルボニル基、等、アリール
オキシカルボニル基（例えば、フエノキシカルボ
ニル基、等）を表わし、A1とA2が共に水素原子
であることはない。
またA1とA2が互いに結合し、窒素原子と共に
形成される５員もしくは６員環については、例え
ば窒素原子を含み6πまたは10π電子系を構成する
芳香族ヘテロ環基（例えば、１−ピロリル基、１
−イミダゾリル基、１−ピラゾリル基、１−（１，
２，４−トリアゾリル基）、１−（１，２，３−ト
リアゾリル基）、１−（１，２，３，４−テトラゾ
リル基）、１−（１，２，３，５−テトラゾリル
基）、１−インドリル基、２−イソインドリル基、
１−ベンゾイミダゾリル基、１−ベンゾトリアゾ
リル基、及び上記芳香族ヘテロ環基に、ハロゲン
原子、シアノ原子、ニトロ基、アルキル基、アリ
ール基、カルボキシル基、アルコキシ基、アリー
ルオキシ基、アシルアミノ基、スルホンアミド
基、イミド基、アルコキシカルボニル基、アリー
ルオキシカルボニル基、アルキルチオ基、アリー
ルチオ基、アルカンスルホニル基、アリールスル
ホニル基、カルバモイル基、スルフアモイル基、
アルコキシカルボニルアミノ基、アリールオキシ
カルボニルアミノ基、ウレイド基、アシル基、ア
ルキルアミノ基、アリールアミノ基で置換されて
いてもよい芳香族ヘテロ環基、等）、窒素原子を
含む芳香環を形成しない飽和または不飽和ヘテロ
環基（例えば、１−ピロリジニル基、１−ピペリ
ジニル基、Ｎ−モルホリニル基、Ｎ−（１，２，
３，４−テトラヒドロキノリル基、１−ピロリニ
ル基、１−イミダゾリニル基、１−ピラゾリジニ
ル基、２−イソインドリニル基、１−インドリニ
ル基、及び上記飽和または不飽和ヘテロ環基に、
前記芳香族ヘテロ環基のところで述べた置換基が
置換していてもよいヘテロ環基、等）、環状イミ
ド基（例えば、Ｎ−コハク酸イミド基、Ｎ−フタ
ルイミド基、１−Ｎ−ヒダントイニル基、３−Ｎ
−２，４−ジオキソーオキサゾリジニル基、４−
Ｎ−ウラゾリル基等、及び上記イミド基に、前記
芳香族ヘテロ環基のところで述べた置換基が置換
してもよいイミド基等）、２−Ｎ−１，１−ジオ
キソ−３（2H）−オキソ−１，２−ベンズイソチ
アゾリル基（サツカリン）、前記芳香族ヘテロ環
基のところで述べた置換基を有してもよい２−Ｎ
−１，１−ジオキシ−３−（2H）−オキソ−１，
２−ベンズイソチアゾリル基、
The present invention provides novel 1H-pyrazolo[3,2-C]-
The present invention relates to a silver halide photographic material containing an S-triazole derivative. The present invention further relates to a silver halide photographic light-sensitive material containing a two-equivalent magenta coupler which is a 1H-pyrazolo[3,2-C]-S-triazole coupler and has a novel coupling-off group at the coupling active position. By color-developing silver halide color photographic materials, the oxidized aromatic primary amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, etc.
It is well known that phenoxazine, phenazine and similar dyes are produced to form color images. Among these, 5-pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used to form a magenta color image. Hitherto, most of the magenta image-forming couplers that have been put into practical use and have been studied are mostly 5-pyrazolones. Although dyes formed from 5-pyrazolone couplers have excellent fastness to heat and light, it is known that unnecessary absorption with a yellow component exists around 430 nm, causing color turbidity. was. The magenta image-forming coupler bone core that reduces this yellow component has long been used as a pyrazolobenzimidazole bone core described in British Patent No. 1047612, an indazolone bone core described in US Patent No. 3770447, and a U.S. patent
A pyrazolotriazole bone core described in No. 3725067 has been proposed. Among them, US Patent No. 3725067, British Patent No. 1252418
Azomethine dyes formed from 1H-pyrazolo[3,2-C]-S-triazole type couplers described in British Patent No. 1334515 and British Patent No. 139897 exhibit unnecessary absorption near 430 nm in solvents such as ethyl acetate. It also has excellent sharp cut properties on the long wavelength side. However, the couplers described in the specifications of the above-mentioned patents are incorporated into actual photographic films using high-boiling organic solvents (e.g. tricresyl phosphate) used in the oil protection system, which is a well-known technique among those skilled in the art. , dibutyl phthalate, etc.), and furthermore, the speed of color development is slow even when passed through a normal color development bath, and the color development speed is slow and the maximum color density is not high. As a result of various studies, the inventors of the present invention have arrived at a series of couplers that improve these drawbacks. Therefore, an object of the present invention is to provide a silver halide color photosensitive material containing a novel two-equivalent magenta coupler for photography, which is excellent in both color development speed and maximum color development density, and has improved solubility in high-boiling organic solvents. The purpose is to The purpose of the above is
A 1H-pyrazolo[3,2-C]-S-triazole coupler containing a two-equivalent magenta coupler in which the following general formula is substituted as a coupling-off group at the position where it couples with the oxidation product of the developing agent. I was able to achieve this. (The 1H-pyrazolo[3,2-C]-S-triazole bone core is known from the above-mentioned US Pat. No. 3,725,067) General formula However, A 1 and A 2 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Representation, A 1
and A 2 cannot both be hydrogen atoms. Also A 1
and A 2 may be bonded to each other to form a 5- or 6-membered ring formed with a nitrogen atom. This 5
The membered or 6-membered ring may further be fused with a benzene ring/heterocycle. Among the couplers of the present invention, preferred are those represented by the general formula. general formula In the formula, A 1 and A 2 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an octyl group, 2-ethylhexyl group, and halogen atom, hydroxyl group, cyano group,
Aryl group, carboxy group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, imide group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl basis,
an alkyl group substituted with an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a ureido group, an acyl group, an alkylamino group or an arylamino group), an aryl group (preferably an aryl group having 6 to 32 carbon atoms, e.g. , phenyl group, naphthyl group, aryl group which may be substituted with the substituent mentioned above for the alkyl group, etc.),
Heterocyclic groups (e.g. 2-pyridyl group, 2-quinolyl group, 2-benzothiazolyl group, 2-furyl group,
2-pyrimidinyl group, etc.), acyl group (e.g. acetyl group, butanoyl group, hexanoyl group, trifluoroacetyl group, heptafluorobutanoyl group, benzoyl group, naphthoyl group, pentafluorobenzoyl group, pentachlorophenyl group, 2-
(furancarbonyl group, 2-quinolinecarbonyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, hexanesulfonyl group, benzenesulfonyl group, naphthalenesulfonyl group, and even if substituted with the substituents mentioned above for the alkyl group) Good alkanesulfonyl group, arylsulfonyl group, etc.), carbamoyl group (e.g. N-methylcarbamoyl group, N-dodecylcarbamoyl group, N,N
-diethylcarbamoyl group, N-phenylcarbamoyl group, N-alkylcarbamoyl group optionally substituted with the substituents mentioned above for the alkyl group, N,N-dialkylcarbamoyl group,
N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc.), sulfamoyl group (e.g., N-methylsulfamoyl group, N-n-octylsulfamoyl group, N-phenylsulfamoyl group, N-phenylsulfamoyl group, , N-diethylsulfamoyl group,
and N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-
arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group,
It represents an aryloxycarbonyl group (e.g., a phenoxycarbonyl group, etc.) such as a 2-ethylhexyloxycarbonyl group and an alkoxycarbonyl group which may be substituted with the substituent mentioned above for the alkyl group, and A 1 and A 2 cannot both be hydrogen atoms. In addition, for the 5- or 6-membered ring formed by A 1 and A 2 bonding with each other and a nitrogen atom, for example, an aromatic heterocyclic group containing a nitrogen atom and constituting a 6π or 10π electron system (for example, 1-pyrrolyl base, 1
-imidazolyl group, 1-pyrazolyl group, 1-(1,
2,4-triazolyl group), 1-(1,2,3-triazolyl group), 1-(1,2,3,4-tetrazolyl group), 1-(1,2,3,5-tetrazolyl group) , 1-indolyl group, 2-isoindolyl group,
1-benzimidazolyl group, 1-benzotriazolyl group, and the above aromatic heterocyclic group, a halogen atom, a cyano atom, a nitro group, an alkyl group, an aryl group, a carboxyl group, an alkoxy group, an aryloxy group, an acylamino group, Sulfonamide group, imide group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, alkanesulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group,
alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, acyl group, alkylamino group, aromatic heterocyclic group optionally substituted with an arylamino group, etc.), saturated that does not form an aromatic ring containing a nitrogen atom or unsaturated heterocyclic groups (e.g., 1-pyrrolidinyl group, 1-piperidinyl group, N-morpholinyl group, N-(1,2,
3,4-tetrahydroquinolyl group, 1-pyrrolinyl group, 1-imidazolinyl group, 1-pyrazolidinyl group, 2-isoindolinyl group, 1-indolinyl group, and the above saturated or unsaturated heterocyclic group,
a heterocyclic group which may be substituted with the substituent mentioned above for the aromatic heterocyclic group, etc.), a cyclic imide group (for example, an N-succinimide group, an N-phthalimide group, a 1-N-hydantoinyl group) , 3-N
-2,4-dioxooxazolidinyl group, 4-
N-urazolyl group, etc., and an imide group which may be substituted with the substituent mentioned above for the aromatic heterocyclic group on the imide group, etc.), 2-N-1,1-dioxo-3(2H)- Oxo-1,2-benzisothiazolyl group (saccharin), 2-N which may have a substituent as mentioned above for the aromatic heterocyclic group
-1,1-dioxy-3-(2H)-oxo-1,
2-benzisothiazolyl group,
【式】
であらわされる基（Ｘは−CH＝、または−Ｎ＝
を表わし、R3、R4は水素原子または前記芳香族
ヘテロ環基のところで述べた置換基を有してもよ
い。またR3、R4で縮合環を形成してもよい例え
ば好ましい基として２（1H）−ピリドン基、フタ
ラジオン基、等）および[Formula] A group represented by (X is -CH= or -N=
and R 3 and R 4 may have a hydrogen atom or a substituent as described above for the aromatic heterocyclic group. In addition, R 3 and R 4 may form a fused ring (for example, preferred groups include a 2(1H)-pyridone group, a phthaladione group, etc.) and
【式】であら
わされる基（ｎ＝１、または２で、R3、R4は水
素原子または前記芳香族ヘテロ環基のところで述
べた置換基を有してもよい。またR3、R4で縮合
環を形成してもよい。例えば好ましい基として、
２−オキソ−１−ピロリジニル基、２−オキソ−
１−ピペリジニル基、等）が挙げられる。
R1とR2は同じでも異なつていてもよく、それ
ぞれ水素原子、アルキル基（例えばメチル基、プ
ロピル基、ｔ−ブチル基、ヘキサデシル基、２−
（２，４，６−トリクロロフエニル）エチル基、
３−（３−ペンタデシルフエノキシ）プロピル基、
３−（２，４−ジ−tert−アミルフエノキシ）プ
ロピル基、２−〔α−（３−tert−ブチル−４−ヒ
ドロキシフエノキシ）テトラデカンアミド〕エチ
ル基、等）、アリール基（例えば、フエニル基、
α−またはβ−ナフチル基、４−メチルフエニル
基、２，４，６−トリクロロフエニル基、４−
〔α−（２，４−ジ−tert−アミルフエノキシ）ブ
チルアミド〕フエニル基、４−〔α−（３−tert−
ブチル−４−ヒドロキシフエノキシ）テトラデカ
ンアミド〕−２，６−ジクロロフエニル基、等）、
ヘテロ環基（例えば、ピリジル基、チエニル基、
キノリル基、等）、アシルアミノ基（例えば、ア
セチルアミノ基、ベンズアミド基、３−（２，４
−ジ−tert−アミルフエノキシ）ブチルアミド
基、３−（３−ペンタデシルフエノキシ）ブチル
アミド基、等）、アルキルアミノ基（例えば、メ
チルアミノ基、ジエチルアミノ基、ｎ−ドデシル
アミノ基、等）、アニリノ基（例えば、フエニル
アミノ基、２−クロロ−５−テトラデカンアミド
フエニルアミノ基、４−〔α−（３−ｔ−ブチル−
４−ヒドロキシフエノキシ）テトラデカンアミ
ド〕アニリノ基、等）アルコキシカルボニル基
（例えば、メトキシカルボニル基、テトラデシル
オキシカルボニル基、等）、アルキルチオ基（例
えば、ヘキシルチオ基、ドデシルチオ基、等）を
表わし、R1とR2が同時に水素原子であることは
ない。
以下に本発明にかかる代表的なマゼンタカプラ
ーの具体例を示すが、これらによつて限定される
ものではない。
一般式であらわされるカプラーのうち特に好
ましいものは離脱基A group represented by [Formula] (n=1 or 2, R 3 and R 4 may have a hydrogen atom or a substituent as described above for the aromatic heterocyclic group. Also, R 3 and R 4 may form a fused ring.For example, as a preferable group,
2-oxo-1-pyrrolidinyl group, 2-oxo-
1-piperidinyl group, etc.). R 1 and R 2 may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g. methyl group, propyl group, t-butyl group, hexadecyl group, 2-
(2,4,6-trichlorophenyl)ethyl group,
3-(3-pentadecylphenoxy)propyl group,
3-(2,4-di-tert-amylphenoxy)propyl group, 2-[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamide]ethyl group, etc.), aryl group (e.g., phenyl basis,
α- or β-naphthyl group, 4-methylphenyl group, 2,4,6-trichlorophenyl group, 4-
[α-(2,4-di-tert-amylphenoxy)butyramide] phenyl group, 4-[α-(3-tert-
butyl-4-hydroxyphenoxy)tetradecanamide]-2,6-dichlorophenyl group, etc.),
Heterocyclic groups (e.g. pyridyl group, thienyl group,
quinolyl group, etc.), acylamino group (e.g. acetylamino group, benzamide group, 3-(2,4
-di-tert-amylphenoxy)butyramide group, 3-(3-pentadecylphenoxy)butyramide group, etc.), alkylamino group (e.g., methylamino group, diethylamino group, n-dodecylamino group, etc.), anilino group groups (e.g., phenylamino group, 2-chloro-5-tetradecanamide phenylamino group, 4-[α-(3-t-butyl-
4-hydroxyphenoxy)tetradecanamide]anilino group, etc.) represents an alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), an alkylthio group (e.g., hexylthio group, dodecylthio group, etc.), R 1 and R 2 are never hydrogen atoms at the same time. Specific examples of typical magenta couplers according to the present invention are shown below, but the invention is not limited thereto. Among couplers represented by the general formula, particularly preferred are
【式】のA1A2が環を作
り、５員・６員環もしくはこの環とベンゼン環と
で縮合した複素環となつている場合で、本発明の
目的の点で特に性能がよい。本発明のカプラーの
添加量は銀１モルあたり２×10-3〜５×10-1モル
好ましくは１×10-2〜５×10-1モルである。
次にこれらのカプラーの一般的合成法について
記す。
1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾー
ル骨核およびバラスト基の連結は、英国特許
1252418号、米国特許3705896号明細書記載の方法
で合成することができる。
(1) カツプリング活性位にアミノ基を導入して、
そのアミノ基を修飾する方法：
カツプリング活性位へのアミノ基の導入は米国
特許3419391号に示されている方法、すなわち適
当なニトロソ化剤、例えば亜硝酸ナトリウム、イ
ソアミル亜硝酸（iso amylnitrite）等で、カツ
プリング活性位をニトロソ化し、それを適当な方
法で還元（例えば、パラジウムカーボン等を触媒
とした水素ガスによる水素添加法、塩化第一スズ
等を使用した化学還元法）して容易に得ることが
出来る。
このアミノ基を修飾して得る事の出来る本発明
の範囲の二当量カプラーとしての離脱基は、上記
式(1)でA1またはA2がアシル基、スルホニル基、
カルバモイル基、スルフアモイル基、アルコキシ
カルボニル基、アリールオキシカルボニル基であ
り、A1−halまたはA2−hal
（R1、R2については前記記載の意味と同一の
意味を表わし、halは塩素原子、臭素原子等のハ
ロゲン原子を表わす。）
と、前記アミノ体を、０℃から100℃の温度範囲
で、A1−halに対し、不活性な溶媒（例えば、酢
酸、塩化メチレン、クロロホルム、ベンゼン、ピ
リジン、ジメチルホルムアミド、ジメチルスルホ
キシド、アセトニトリル、等）で反応させること
ができる。また反応に際しては、適当な脱ハロゲ
ン化水素剤（例えば、トリエチルアミン、ジアザ
ビシクロ〔２・２・２・〕オクタン、酢酸ナトリ
ウム等）を使用することが好ましい。
この方法で合成できたカプラーは、Cp−３、
４、５、６、７、８、９である。
(2) カツプリング活性位にハロゲン原子を導入し
て、そのハロゲン原子をIn the case where A 1 A 2 of the formula forms a ring and is a 5- or 6-membered ring or a heterocyclic ring fused with this ring and a benzene ring, performance is particularly good for the purpose of the present invention. The amount of the coupler of the present invention added is 2.times.10.sup. - 3 to 5.times.10.sup. - 1 mol, preferably 1.times.10.sup.-2 to 5.times.10.sup. - 1 mol per mol of silver. Next, general synthetic methods for these couplers will be described. The linkage of the 1H-pyrazolo[3,2-C]-S-triazole core and the ballast group is described in the British patent.
It can be synthesized by the method described in No. 1252418 and US Pat. No. 3,705,896. (1) Introducing an amino group into the coupling active position,
How to modify its amino group: The introduction of an amino group into the coupling active position is carried out by the method shown in U.S. Pat. It can be easily obtained by reducing it by an appropriate method (for example, a hydrogenation method using hydrogen gas using palladium carbon as a catalyst, a chemical reduction method using stannous chloride, etc.). The leaving group as a two-equivalent coupler within the scope of the present invention that can be obtained by modifying this amino group is the above formula (1) where A 1 or A 2 is an acyl group, a sulfonyl group,
A carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, A 1 -hal or A 2 -hal (R 1 and R 2 have the same meaning as described above, hal is a chlorine atom, represents a halogen atom such as a bromine atom) and the amino compound in a solvent inert to A 1 -hal (for example, acetic acid, methylene chloride, chloroform, benzene, (pyridine, dimethylformamide, dimethylsulfoxide, acetonitrile, etc.). Further, during the reaction, it is preferable to use a suitable dehydrohalogenating agent (eg, triethylamine, diazabicyclo[2.2.2.]octane, sodium acetate, etc.). The couplers synthesized by this method are Cp-3,
4, 5, 6, 7, 8, 9. (2) Introducing a halogen atom into the coupling active position and
【式】基で置換す
る方法：
1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾー
ル骨核のカツプリング活性位、７位にhal（halは
例えば塩基原子、臭素原子）を導入する方法は米
国特許3725067号に記載の方法、すなわち適当な
ハロゲン化剤、例えば塩化スルフリル、塩素ガ
ス、臭素、Ｎ−クロロコハク酸イミド、Ｎ−ブロ
モコハク酸イミド等によつて行なうことができ
る。
このハロゲン原子を置換して得ることの出来る
本発明の範囲の二当量カプラーとしての離脱基は
上記式(2)で、A1またはA2がアルキル基、アリー
ル基、ヘテロ環基、およびA1とA2が互いに結合
し、窒素原子と共に５員もしくは６員環を形成し
うる窒素ヘテロ環基であり、[Formula] Method for substituting with group: The method for introducing hal (hal is, for example, a base atom, a bromine atom) into the coupling active position, the 7-position, of the 1H-pyrazolo[3,2-C]-S-triazole bone core is the method described in U.S. Pat. No. 3,725,067, i.e. This can be carried out using a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide and the like. The leaving group as a two-equivalent coupler within the scope of the present invention that can be obtained by substituting this halogen atom is represented by the above formula (2), where A 1 or A 2 is an alkyl group, an aryl group, a heterocyclic group, and A 1 and A 2 are a nitrogen heterocyclic group that can be bonded to each other and form a 5- or 6-membered ring with a nitrogen atom,
【式】と前記
ハロゲン置換体とを、0゜〜100℃の温度範囲でア
ルコール系溶媒（例えばエタノール、イソプロピ
ルアルコール、等）、非プロトン性極性溶媒（例
えば、ジメチルホルムアミド、スルホラン、ヘキ
サメチルホストリアミド、等）ハロゲン化炭化水
素溶媒（例えば、塩化メチレン、クロロホルム、
等）に溶解し適当な塩基（例えば、トリエチルア
ミン、水酸化ナトリウム、水酸化カリウム、ジア
ザビシクロ〔２・２・２〕オクタン、無水炭酸カ
リウム、等）存在下で反応させることができる。
（特公昭56−45135参照）
この方法で合成できたカプラーは、Cp1、２、
10、11、12、13、14、15、16、17、18、19、20、
21、22、23である。
また、6πまたは10π電子系芳香族窒素ヘテロ環
を導入する場合には、特公昭57−36577号に記載
の方法、すなわち前記ハロゲン置換体と本発明に
記載されている6πまたは10π電子系芳香族窒素ヘ
テロ環化合物をハロゲン置換体に対し、２倍モル
以上添加し、無溶媒で50゜〜150℃に加熱または非
プロトン性極性溶媒（例えば、ジメチルホルムア
ミド、スルホラン、ヘキサメチルホスホトリアミ
ド、等）中で30℃〜150℃に加熱し、反応させる
ことができる。
合成例 １
３−｛３−（２，４−ジ−tert−アミルフエノキ
シ）プロピル｝−７−ヘプタフルオロブチルアミ
ド−６−プロピル−1H−ピラゾロ〔３，２−Ｃ〕
−Ｓ−トリアゾールの合成（例示カプラー３）
8.49ｇの３−｛３−（２，４−ジ−tert−アミル
フエノキシ）プロピル｝−６−プロピル−1H−ピ
ラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾールを80ml
の氷酢酸中に加え、室温で撹拌した。これに亜硝
酸イソアミル2.34ｇの氷酢酸溶液（20ml）を15分
間で滴下し、さらに１時間撹拌を続けた。この反
応混合物を水1.5にゆつくり注ぎ込み、１時間
撹拌した。析出した沈澱を取し、水800mlで沈
澱を洗浄した。塩化カルシウムをいれた真空デシ
ケーター中で乾燥し、8.98ｇ（99％）の３−｛３
−（２，４−ジ−tert−アミルフエノキシ）プロ
ピル｝−７−ニトロソ−６−プロピル−1H−ピラ
ゾロ〔３，２−Ｃ〕−Ｓ−トリアゾールを得た。
これを、160mlのエタノールに溶解し、窒素気
流下に加熱撹拌して還流状態にした。これに塩化
第一スズ19.0ｇの濃塩酸溶液（40ml）を15分間で
滴下した。滴下終了後、水で冷却したのち水800
mlにゆつくり注ぎ、酢酸エチルで抽出した。有機
層を無水硫酸マグネシウム上で乾燥したのち濃縮
乾固し、７−アミノ−３−｛３−２，４−ジ−
tert−アミルフエノキシ）プロピル｝−６−プロ
ピル−1H−ピラゾロ〔３，２−Ｃ〕−Ｓ−トリア
ゾールを得た。これをピリジン100mlに加え、窒
素気流下に水で冷却しながら撹拌した。これに、
無水ヘプタフルオロ酪酸8.20ｇを滴下し、さらに
30分間撹拌した。この反応混合物を水１に注
ぎ、酢酸エチルで抽出した。有機層を無水硫酸マ
グネシウム上で乾燥したのち濃縮し、シリカゲル
カラムクロマトグライー（シリカゲル300ｇ、溶
出液クロロホルム：メタノール＝100：１）で分
取し、溶出液を濃縮乾固して10.6ｇ（83％）の白
色粉末の目的物（カプラー３）を得た。
元素分析
理論値
Ｈ（6.34％）Ｃ（56.69％）Ｎ（11.02％）
実験値
Ｈ（6.45％）Ｃ（56.52％）Ｎ（10.98％）
合成例 ２
３−｛１−（２−エトキシエトキシ）トリデシ
ル｝−６−メチル−７−（１−ピラゾリル）−1H−
ピラゾロ〔３，２−Ｃ〕−Ｓ−トリアゾールの合
成（例示カプラー21）
7.85ｇの３−｛１−（２−エトキシエトキシ）ト
リデシル｝−６−メチル−1H−ピラゾロ〔３，２
−Ｃ〕−Ｓ−トリアゾールを80mlのジクロロメタ
ンに加え、室温で撹拌した。これに、Ｎ−ブロモ
コハク酸イミド3.56ｇを加え、20分間撹拌した。
このジクロロメタン溶液を水で洗浄し（100ml×
３）、無水硫酸マグネシウム上で乾燥した。この
ジクロロメタン溶液を濃縮して、完全に除媒し
た。これに、ピラゾール13.6ｇを加え、窒素雰囲
気下に120℃の油浴上で１時間、さらに140℃の油
浴上で３時間撹拌した。冷却後、反応混合物を酢
酸エチル200mlに溶かし、水洗した（150ml×３）。
有機層を無水硫酸マグネシウム上で乾燥したの
ち、濃縮した。これをシリカゲルカラムクロマト
グラフイー（シリカゲル250ｇ、溶出液ベンゼ
ン：酢酸エチル＝10：１）で分取し、溶出液を濃
縮乾固して1.83ｇ（20％）の白色粉末のカプラー
21を得た。
元素分析
理論値
Ｈ（9.23％）Ｃ（65.47％）Ｎ（18.32％）
実験値
Ｈ（9.09％）Ｃ（65.35％）Ｎ（18.29％）
この方法で合成できたカプラーはCp−15、16、
17、18、19、20であつた。
本発明において本発明のカプラーの他に用いる
ことのできるカプラー類としては以下の如き色素
形成カプラー、即ち、発色現像処理において芳香
族１級アミン現像薬（例えば、フエニレンジアミ
ン誘導体や、アミノフエノール誘導体など）との
酸化カツプリングによつて発色しうる化合物を、
例えばマゼンタカプラーとして、５−ピラゾロン
カプラー、ピラゾロベンツイミダゾールカプラ
ー、シアノアセチルクマロンカプラー、開鎖アシ
ルアセトニトリルカプラー等があり、イエローカ
プラーとして、アシルアセトアミドカプラー（例
えばベンゾイルアセトアニリド類、ピバロイルア
セトアニリド類）、等があり、シアンカプラーと
して、ナフトールカプラー、及びフエノールカプ
ラー等がある。これらのカプラーは分子中にバラ
スト基とよばれる疏水基を有する非拡散性のも
の、またはポリマー化されたものが望ましい。カ
プラーは、銀イオンに対し４当量性あるいは２当
量性のどちらでもよい。又、色補正の効果をもつ
カラードカプラー、あるいは現像にともなつて現
像抑制剤を放出するカプラー（いわゆるDIRカプ
ラー）であつてもよい。
又、DIRカプラー以外にも、カツプリング反応
の生成物が無色であつて、現像抑制剤を放出する
無呈色DIRカツプリング化合物を含んでもよい。
上記カプラー等は、感光材料に求められる特性
を満足するために同一層に二種類以上を併用する
こともできるし、同一の化合物を異なつた２層以
上の添加することも、もちろん差支えない。
カプラーをハロゲン化銀乳剤層に導入するには
公知の方法、例えば米国特許2322027号に記載の
方法などが用いられる。例えばフタール酸アルキ
ルエステル（ジブチルフタレート、ジオクチルフ
タレートなど）、リン酸エステル（ジフエニルフ
オスフエート、トリフエニルフオスフエート、ト
リクレジルフオスフエート、ジオクチルブチルフ
オスフエート）、クエン酸エステル（例えばアセ
チルクエン酸トリブチル）、安息香酸エステル
（例えば安息香酸オクチル）、アルキルアミド（例
えばジエチルラウリルアミド）、脂肪酸エステル
類（例えばジブトキシエチルサクシネート、ジエ
チルアゼレート）、トリメシン酸エステル類（例
えばトリメシン酸トリブチル）など、又は沸点約
30℃ないし150℃の有機溶媒、例えば酢酸エチル、
酢酸ブチルの如き低級アルキルアセテート、プロ
ピオン酸エチル、２級ブチルアルコール、メチル
イソブチルケトン、β−エトキシエチルアセテー
ト、メチルセロソルブアセテート等に溶解したの
ち、親水性コロイドに分散される。上記の高沸点
有機溶媒と低沸点有機溶媒とは混合して用いても
よい。
又、特公昭51−39853号、特開昭51−59943号に
記載されている重合物による分散法も使用するこ
とができる。
カプラーがカルボン酸、スルフホン酸の如き酸
基を有する場合には、アルカリ性水溶液として親
水性コロイド中に導入される。
使用する写真用カラー発色剤は、中間スケール
画像をあたえるように選ぶと都合がよい。シアン
発色剤から形成されるシアン染料の最大吸収帯は
約600から720nmの間であり、マゼンタ発色剤か
ら形成されるマゼンタ染料の最大吸収帯は約500
から580nmの間であり、黄色発色剤から形成され
る黄色染料の最大吸収帯は約400から480nmの間
であることが好ましい。
本発明を実施するに際して、下記の公知の退色
防止剤を併用することもでき、また本発明に用い
る色像安定剤は単独または２種以上併用すること
もできる。公知の退色防止剤としては、たとえ
ば、米国特許2360290号、同2418613号、同
2675314号、同2701197号、同2704713号、同
2728659号、同2732300号、同2735765号、同
2710801号、同2816028号、英国特許1363921号等
に記載されたハイドロキノン誘導体、米国特許
3457079号、同3069262号等に記載された没食子酸
誘導体、米国特許2735765号、同3698909号、特公
昭49−20977号、同52−6623号に記載されたｐ−
アルコキシフエノール類、米国特許3432300号、
同3573050号、同3574627号、同3764337号、特開
昭52−35633号、同52−147434号、同52−152225
号に記載されたｐ−オキシフエノール誘導体、米
国特許3700455号に記載のビスフエノール類等が
ある。
本発明を用いて作られる感光材料は、色カブリ
防止剤として、ハイドロキノン誘導体、アミノフ
エノール誘導体、没食子酸誘導体、アスコルビン
酸誘導体などを含有してもよく、その具体例は、
米国特許2360290号、同2336327号、同2403721号、
同2418613号、同2675314号、同2701197号、同
2704713号、同2728659号、同2732300号、同
2735765号、特開昭50−92988号、同50−92989号、
同50−93928号、同50−110337号、同52−146235
号、特公昭50−23813号等に記載されている。
本発明を用いて作られた感光材料には、親水性
コロイド層にフイルター染料として、あるいはイ
ラジエーシヨン防止その他種々の目的で水溶性染
料を含有していてもよい。このような染料には、
オキソノール染料、ヘミオキソノール染料、スチ
リル染料、メロシアニン染料、シアニン染料及び
アゾ染料が包含される。なかでもオキソノール染
料；ヘミオキソノール染料及びメロシアニン染料
が有用である。用い得る染料の具体例は、英国特
許584609号、同1177429号、特開昭48−85130号、
同49−99620号、同49−114420号、同52−108115
号、米国特許2274782号、同2533472号、同
2956879号、同3148187号、同3177078号、同
3247127号、同3540887号、同3575704号、同
3653905号、同3718472号、同4071312号、同
4070352号に記載されたものである。
本発明の写真感光材料の写真乳剤層には感度上
昇、コントラスト上昇、または現像促進の目的
で、たとえばポリアルキレンオキシドまたはその
エーテル、エステル、アミンなどの誘導体、チオ
エーテル化合物、チオモルフオリン類、四級アミ
モニウム塩化合物、ウレタン誘導体、尿素誘導
体、イミダゾール誘導体、３−ピラゾリドン類等
を含んでもよい。たとえば米国特許2400532号、
同2423549号、同2716062号、同3617280号、同
3772021号、同3808003号、英国特許1488991号等
に記載されたものを用いることができる。
本発明を用いて作られる感光材料には、親水性
コロイド層に柴外線吸収剤を含んでもよい。例え
ば、アリール基で置換されたベンゾトリアゾール
化合物（例えば米国特許3533794号に記載のも
の）、４−チアゾリドン化合物（例えば米国特許
3314794号、同3352681号に記載のもの）、ベンゾ
フエノン化合物（例えば特開昭46−2784号に記載
のもの）、ケイヒ酸エステル化合物（例えば米国
特許3705805号、同3707375号に記載のもの）、ブ
タジエン化合物（例えば米国特許4045229号に記
載のもの）、あるいは、ベンゾオキシドール化合
物（例えば米国特許3700455号に記載のもの）を
用いることができる。さらに、米国特許3499762
号、特開昭54−48535号に記載のものも用いるこ
とができる。紫外線吸収性のカプラー（例えばα
−ナフトール系のシアン色素形成カプラー）や、
紫外線吸収性のポリマーなどを用いてもよい。こ
れらの紫外線吸収剤は特定の層に媒染されていて
もよい。
本発明に用いられる写真乳剤は、メチン色素類
その他によつて分光増感されてもよい。用いられ
る色素には、シアニン色素、メロシアニン色素、
複合シアニン色素、複合メロシアニン色素、ホロ
ポーラーシアニン色素、ヘミシアニン色素、スチ
リル色素およびヘミオキソノール色素が包含され
る。特に有用な色素は、シアニン色素、メロシア
ニン色素、および複合メロシアニン色素に属する
色素である。これらの色素類には、塩基性異節環
核としてシアニン色素類に通常利用される核のい
ずれをも適用できる。すなわち、ピロリン核、オ
キサゾリン核、チアゾリン核、ピロール核、オキ
サゾール核、チアゾール核、セレナゾール核、イ
ミダゾール核、テトラゾール核、ピリジン核な
ど；これらの核に脂環式炭化水素環が融合した
核；及びこれらの核に芳香族炭化水素環が融合し
た核、即ち、インドレニン核、ベンズインドレニ
ン核、インドール核、ベンズオキサドール核、ナ
フトオキサゾール核、ベンゾチアゾール核、ナフ
ナチアゾール核、ベンゾセレナゾール核、ベンズ
イミダゾール核、キノリン核などが適用できる。
これらの核は炭素原子上に置換されていてもよ
い。
メロシアニン色素または複合メロシアニン色素
にはケトメチレン構造を有する核として、ピラゾ
リン−５−オン核、チオヒダントイン核、２−チ
オオキサゾリジン−２，４−ジオン核、チアゾリ
ジン−２，４−ジオン核、ローダニン核、チオバ
ルビツール酸核などの５〜６員異節環核を適用す
ることができる。
有用な増感色素としては例えば、ドイツ特許
929080号、米国特許2231658号、同2493748号、同
2503776号、同2519001号、同2912329号、同
3656959号、同3672897号、同3694217号、同
4025349号、同4046572号、英国特許1242588号、
特公昭44−14030号、同52−24844号に記載された
ものを挙げることが出来る。
これらの増感色素は単独に用いてもよいが、そ
れらの組合せを用いてもよく、増感色素の組合せ
は特に、強色増感の目的でしばしば用いられる。
その代表例は米国特許2688545号、同2977229号、
同3397060号、同3522052号、同3527641号、同
3617293号、同3628964号、同3666480号、同
3672898号、同3679428号、同3703377号、同
3769301号、同3814609号、同3837862号、同
4026707号、英国特許1344281号、同1507803号、
特公昭43−4936号、同53−12375号、特開昭52−
110618号、同52−109925号に記載されている。
増感色素とともに、それ自身分光増感作用をも
たない色素あるいは可視光を実質的に吸収しない
物質であつて、強色増感を示す物質を乳剤中に含
んでもよい。例えば、含窒素異節環基で置換され
たアミノスチル化合物（たとえば米国特許
2933390号、同3635721号に記載のもの）、芳香族
有機酸ホルムアルデヒド縮合物（たとえば米国特
許3743510号に記載のもの）、カドミウム塩、アザ
インデン化合物などを含んでもよい。米国特許
3615613号、同3615641号、同3617295号、同
3635721号に記載の組合せは特に有用である。
本発明の感光材料の写真処理には、公知の方法
のいずれをも用いることができるし処理液には公
知のものを用いることができる。又、処理温度は
通常、18℃から50℃の間に選ばれるが、18℃より
低い温度または50℃をこえる温度としてもよい。
目的に応じ、銀画像を形成する現像処理（黒白写
真処理）、或いは、色素像を形成すべき現像処理
から成るカラー写真処理のいずれをも適用するこ
とが出来る。
カラー現像液は、一般に、発色現像主薬を含む
アルカリ性水溶液から成る。発色現像主薬は公知
の一級芳香族アミン現像剤、例えばフエニルレン
ジアミン類（例えば４−アミノ−Ｎ，Ｎ−ジエチ
ルアニリン、３−メチル−４−アミノ−Ｎ，Ｎ−
ジエチルアニリン、４−アミノ−Ｎ−エチル−Ｎ
−β−ヒドロキシエチルアニリン、３−メチル−
４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエ
チルアニリン、３−メチル−４−アミノ−Ｎ−エ
チル−Ｎ−β−メタンスルホアミドエチルアニリ
ン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
β−メトキシエチルアニリンなど）を用いること
ができる。
この他L.F.A.Mason著Photo−graphic
Processing Chemistry（Focal Press刊、1966年）
のP226〜229、米国特許2193015号、同2592364
号、特開昭48−64933号などに記載のものを用い
てもよい。
カラー現像液はその他、アルカリ金属の亜硫酸
塩、炭酸塩、ホウ酸塩、及びリン酸塩の如きPH緩
衝剤、臭化物、沃化物、及び有機カプリ防止剤の
如き現像抑制剤ないし、カプリ防止剤などを含む
ことができる。又必要に応じて、硬水軟化剤、ヒ
ドロキシルアミンの如き保恒剤、ベンジルアルコ
ール、ジエチレングリコールの如き有機溶剤、ポ
リエチレングリコール、四級アンモニウム塩、ア
ミン類の如き現像促進剤、色素形成カプラー、競
争カプラー、ナトリウムボロンハイドライドの如
きかぶらせ剤、１−フエニル−３−ピラゾリドン
の如き補助現像薬、粘性付与剤、米国特許
4083723号に記載のポリカルボン酸系キレート剤、
西独公開（OLS）2622950号に記載の酸化防止剤
などを含んでもよい。
発色現像後の写真乳剤層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、個別に行われてもよい。漂白剤としては、
例えば鉄（）、コバルト（）、クロム（）、
銅（）などの多価金属の化合物、過酸類、キノ
ン類、ニトロソ化合物等が用いられる。例えば、
フエリシアン化物、重クロム酸塩、鉄（）また
はコバルト（）の有機錯塩、例えばエチレンジ
アミン四酢酸、ニトリロトリ酢酸、１，３−ジア
ミノ−２−プロパノール四酢酸などのアミノポリ
カルボン酸類あるいはクエン酸、酒石酸、リンゴ
酸などの有機酸の錯塩；過硫酸塩、過マンガン酸
塩；ニトロソフエノールなどを用いることができ
る。これらのうちフエリシアン化カリ、エチレン
ジアミン四酢酸鉄（）ナトリウム及びエチレン
ジアミン四酢酸鉄（）アンモニウムは特に有用
である。エチレンジアミン四酢酸鉄（）錯塩は
独立の漂白液においても、一浴漂白定着液におい
ても有用である。
漂白または漂白定着液には、米国特許3042520
号、銅3241966号、特公昭45−8506号、特公昭45
−8836号などに記載の漂白促進剤、特開昭53−
65732号に記載のチオール化合物の他、種々の添
加剤を加えることもできる。
実施例 １
フイルム Ａ；
本発明のカプラー22の10ｇに、トリオクチルホ
スフエート10c.c.、酢酸エチル20c.c.を加えて溶解
し、この溶液をドデシルベンゼンスルホン酸ナト
リウムを含む10％ゼラチン100ｇに加え、ホモジ
ナイザー乳化機を用いて撹拌乳化した。得られた
乳化物を三酢酸セルロース支持体上に塗布、乾燥
して試料フイルムを得た。この試料フイルムは透
明性良好であり、表面も滑らかであつた。
フイルム Ｂ；
下記に示す比較カプラーＡを上記と同様の操作
で試料フイルムを作製した所透明性悪く、表面が
ザラザラしていた。カプラーＡが析出しており明
らかに本発明の化合物の方が溶解性、乳化物安定
性に優れていることを示す。
実施例 ２
実施例１のフイルムＡと同様にして本発明のカ
プラー３，８，９，16，17，18の溶解性、乳化物
安定性を調べた。
これらの試料は透明性良好で表面も滑らかであ
つた。
また乳化物を10日間冷蔵庫に放置した後にこれ
を用いてフイルムを作つたが、これらも透明性良
好で表面も滑らかであつた。
実施例 ３
フイルム Ｃ；
下記に示す比較カプラーB8.2ｇにトリオクチ
ルホスフエート10c.c.トリクレジルホスフエート５
c.c.、酢酸エチル10c.c.を加えて溶解し、この溶液を
ジ−sec−ブチルナフタレンスルホン酸ナトリウ
ムを含む10％ゼラチン水溶液100ｇに加え、ホモ
ジナイザー乳化機を用いて撹拌乳化し、乳化物を
得た。この乳化物を緑感性塩臭化銀乳剤（Br45
モル％、Cl55モル％）300ｇ（銀13.5ｇ含有）と
混合し、塗布用助剤；ドデシルベンゼンスルホン
酸ナトリウム、硬膜剤；２−ヒドロキシ−４，６
−ジクロロ−Ｓ−トリアジンを加え三酢酸セルロ
ース支持体上に塗布した。さらにこの層の上に保
護層としてゼラチン塗布液を塗布し（ゼラチン１
ｇ／m2）乾燥した。
フイルム Ｄ；
本発明のカプラー21を9.3ｇ、緑感性乳剤200ｇ
を用いた以外は上記フイルムＣと同じフイルム。
Ｃ、Ｄフイルム試料を感光計で1.000ルツクス
１秒で露光し、次の処理液で処理した。
現像液
ベンジルアルコール 15ml
Na2SO3 ５ｇ
KBr 0.4ｇ
ヒドロキシルアミン硫酸塩 ２ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
〔β−（メタンスルホンアミド）エチル〕−ｐ−
フエニレンジアミン ６ｇ
Na3CO3（１水塩） 30ｇ
水を加えて１にする （PH10.1）
漂白定着液
チオ硫酸アンモニウム（70wt％） 150ml
Na2SO3 15ｇ
Na〔Fe（EDTA）〕 40ｇ
EDTA ４ｇ
水を加えて１にする （PH6.9）
処理工程
温度 時間
現像液 33℃ ３分
漂白定着液 33℃ １分30秒
水洗 28〜35℃ ３分
乾 燥
処理した後の色素現像濃度をマクベス濃度計ス
テースAAフイルターにて測定した。[Formula] and the halogen-substituted product are mixed in an alcoholic solvent (e.g., ethanol, isopropyl alcohol, etc.) or an aprotic polar solvent (e.g., dimethylformamide, sulfolane, hexamethylhost) at a temperature range of 0° to 100°C. amide, etc.) halogenated hydrocarbon solvents (e.g. methylene chloride, chloroform, etc.)
etc.) and reacted in the presence of an appropriate base (eg, triethylamine, sodium hydroxide, potassium hydroxide, diazabicyclo[2.2.2]octane, anhydrous potassium carbonate, etc.).
(Refer to Japanese Patent Publication No. 56-45135) The couplers synthesized by this method are Cp1, 2,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,
21, 22, 23. In addition, when introducing a 6π or 10π electron system aromatic nitrogen heterocycle, the method described in Japanese Patent Publication No. 57-36577, that is, the halogen-substituted product and the 6π or 10π electron system aromatic ring described in the present invention, can be used. Add a nitrogen heterocyclic compound at least twice the mole of the halogen-substituted compound and heat to 50° to 150°C without a solvent or with an aprotic polar solvent (e.g. dimethylformamide, sulfolane, hexamethylphosphotriamide, etc.) The mixture can be heated to 30°C to 150°C to react. Synthesis Example 1 3-{3-(2,4-di-tert-amylphenoxy)propyl}-7-heptafluorobutyramide-6-propyl-1H-pyrazolo[3,2-C]
Synthesis of -S-Triazole (Exemplary Coupler 3) 8.49 g of 3-{3-(2,4-di-tert-amylphenoxy)propyl}-6-propyl-1H-pyrazolo[3,2-C]-S- 80ml of triazole
of glacial acetic acid and stirred at room temperature. A solution of 2.34 g of isoamyl nitrite in glacial acetic acid (20 ml) was added dropwise to this over 15 minutes, and stirring was continued for an additional hour. This reaction mixture was slowly poured into 1.5 liters of water and stirred for 1 hour. The deposited precipitate was collected and washed with 800 ml of water. Dry in a vacuum dessicator containing calcium chloride to remove 8.98 g (99%) of 3-{3
-(2,4-di-tert-amylphenoxy)propyl}-7-nitroso-6-propyl-1H-pyrazolo[3,2-C]-S-triazole was obtained. This was dissolved in 160 ml of ethanol, heated and stirred under a nitrogen stream to bring it to a reflux state. A concentrated hydrochloric acid solution (40 ml) containing 19.0 g of stannous chloride was added dropwise to this over 15 minutes. After dropping, cool with water and add 800 ml of water.
ml and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated to dryness to give 7-amino-3-{3-2,4-di-
tert-amylphenoxy)propyl}-6-propyl-1H-pyrazolo[3,2-C]-S-triazole was obtained. This was added to 100 ml of pyridine, and the mixture was stirred while cooling with water under a nitrogen stream. to this,
Drop 8.20 g of anhydrous heptafluorobutyric acid, and
Stir for 30 minutes. The reaction mixture was poured into water 1 and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated, fractionated using silica gel column chromatography (300 g of silica gel, eluent chloroform:methanol = 100:1), and the eluate was concentrated to dryness to give 10.6 g (83%). ) was obtained as a white powder (Coupler 3). Elemental analysis Theoretical value H (6.34%) C (56.69%) N (11.02%) Experimental value H (6.45%) C (56.52%) N (10.98%) Synthesis example 2 3-{1-(2-ethoxyethoxy) tridecyl}-6-methyl-7-(1-pyrazolyl)-1H-
Synthesis of pyrazolo[3,2-C]-S-triazole (Exemplary coupler 21) 7.85 g of 3-{1-(2-ethoxyethoxy)tridecyl}-6-methyl-1H-pyrazolo[3,2
-C]-S-triazole was added to 80 ml of dichloromethane and stirred at room temperature. To this, 3.56 g of N-bromosuccinimide was added and stirred for 20 minutes.
Wash this dichloromethane solution with water (100ml x
3), dried over anhydrous magnesium sulfate. This dichloromethane solution was concentrated to completely remove the solvent. To this, 13.6 g of pyrazole was added, and the mixture was stirred for 1 hour on a 120°C oil bath under a nitrogen atmosphere, and then for 3 hours on a 140°C oil bath. After cooling, the reaction mixture was dissolved in 200 ml of ethyl acetate and washed with water (150 ml x 3).
The organic layer was dried over anhydrous magnesium sulfate and then concentrated. This was fractionated using silica gel column chromatography (250 g of silica gel, eluent: benzene: ethyl acetate = 10:1), and the eluate was concentrated to dryness to yield 1.83 g (20%) of white powder coupler.
Got 21. Elemental analysis Theoretical values H (9.23%) C (65.47%) N (18.32%) Experimental values H (9.09%) C (65.35%) N (18.29%) The couplers synthesized by this method are Cp-15, 16,
It was 17, 18, 19, 20. Examples of couplers that can be used in the present invention in addition to the couplers of the present invention include the following dye-forming couplers: aromatic primary amine developers (e.g., phenylene diamine derivatives, aminophenol derivatives) in color development processing; compounds that can develop color through oxidative coupling with
For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. Two or more types of the above-mentioned couplers and the like can be used together in the same layer in order to satisfy the characteristics required of a photosensitive material, and it is of course possible to add the same compound to two or more different layers. A coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or boiling point approx.
Organic solvent at 30°C to 150°C, such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. The photographic color formers used are conveniently selected to provide intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan color former is between about 600 and 720 nm, and the maximum absorption band of the magenta dye formed from the magenta color former is about 500 nm.
and 580 nm, and the maximum absorption band of the yellow dye formed from the yellow color former is preferably between about 400 and 480 nm. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
No. 2675314, No. 2701197, No. 2704713, No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
Hydroquinone derivatives described in No. 2710801, No. 2816028, British Patent No. 1363921, etc., US patent
Gallic acid derivatives described in US Pat. No. 3457079 and US Pat. No. 3069262, etc.;
Alkoxyphenols, US Pat. No. 3,432,300,
3573050, 3574627, 3764337, JP 52-35633, 52-147434, 52-152225
p-oxyphenol derivatives described in US Pat. No. 3,700,455, and bisphenols described in US Pat. No. 3,700,455. The photosensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include:
U.S. Patent No. 2360290, U.S. Patent No. 2336327, U.S. Patent No. 2403721,
Same No. 2418613, No. 2675314, No. 2701197, Same No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, No. 52-146235
No., Special Publication No. 50-23813, etc. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609, British Patent No. 1177429, Japanese Patent Application Laid-Open No. 1985-85130,
No. 49-99620, No. 49-114420, No. 52-108115
No., U.S. Patent No. 2274782, U.S. Patent No. 2533472, U.S. Patent No.
No. 2956879, No. 3148187, No. 3177078, No.
No. 3247127, No. 3540887, No. 3575704, No.
No. 3653905, No. 3718472, No. 4071312, No. 3653905, No. 3718472, No. 4071312, No.
It is described in No. 4070352. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532,
Same No. 2423549, No. 2716062, No. 3617280, Same No.
Those described in No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. The photosensitive material produced using the present invention may contain a ray absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. Additionally, U.S. Patent 3499762
The material described in JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes include, for example, the German patent
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No.
No. 2503776, No. 2519001, No. 2912329, No. 2519001, No. 2912329, No.
No. 3656959, No. 3672897, No. 3694217, No.
No. 4025349, No. 4046572, British Patent No. 1242588,
Examples include those described in Japanese Patent Publication Nos. 44-14030 and 52-24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C.
Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer such as phenyl diamines (e.g. 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-
Diethylaniline, 4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N-ethyl- N-
β-methoxyethylaniline, etc.) can be used. OthersPhoto-graphic by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US patents
The polycarboxylic acid chelating agent described in No. 4083723,
It may also contain antioxidants such as those described in OLS 2622950. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No., Copper No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. Example 1 Film A: To 10 g of coupler 22 of the present invention, 10 c.c. of trioctyl phosphate and 20 c.c. of ethyl acetate were added and dissolved, and this solution was mixed with 100 g of 10% gelatin containing sodium dodecylbenzenesulfonate. In addition, the mixture was stirred and emulsified using a homogenizer emulsifier. The obtained emulsion was coated on a cellulose triacetate support and dried to obtain a sample film. This sample film had good transparency and a smooth surface. Film B: A sample film was prepared using comparative coupler A shown below in the same manner as above, but the transparency was poor and the surface was rough. Coupler A was precipitated, clearly indicating that the compound of the present invention is superior in solubility and emulsion stability. Example 2 In the same manner as in Film A of Example 1, the solubility and emulsion stability of couplers 3, 8, 9, 16, 17, and 18 of the present invention were investigated. These samples had good transparency and smooth surfaces. The emulsion was left in the refrigerator for 10 days and then used to make films, which also had good transparency and smooth surfaces. Example 3 Film C; 10 c.c. of trioctyl phosphate and 5 tricresyl phosphate to 8.2 g of comparative coupler B shown below.
cc, and 10 c.c. of ethyl acetate to dissolve, add this solution to 100 g of a 10% aqueous gelatin solution containing sodium di-sec-butylnaphthalene sulfonate, and stir and emulsify using a homogenizer emulsifier to obtain an emulsion. Ta. This emulsion was converted into a green-sensitive silver chlorobromide emulsion (Br45
mol%, Cl55 mol%) 300 g (contains 13.5 g of silver), coating aid: sodium dodecylbenzenesulfonate, hardener: 2-hydroxy-4,6
-Dichloro-S-triazine was added and coated onto a cellulose triacetate support. Furthermore, a gelatin coating solution is applied as a protective layer on top of this layer (gelatin 1
g/m 2 ) dried. Film D: 9.3g of coupler 21 of the present invention, 200g of green-sensitive emulsion
Same film as above film C except that . C and D film samples were exposed to light at 1.000 lux for 1 second using a sensitometer and treated with the following processing solution. Developer Benzyl alcohol 15ml Na 2 SO 3 5g KBr 0.4g Hydroxylamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-
[β-(methanesulfonamido)ethyl]-p-
Phenylenediamine 6g Na 3 CO 3 (monohydrate) 30g Add water to make 1 (PH10.1) Bleach-fix ammonium thiosulfate (70wt%) 150ml Na 2 SO 3 15g Na [Fe (EDTA)] 40g EDTA Add 4g water to make it 1 (PH6.9) Processing process Temperature Time Developer 33℃ 3 minutes Bleach-fix solution 33℃ 1 minute 30 seconds Washing 28-35℃ Dry 3 minutes Macbeth Measured using a densitometer station AA filter.
【表】
本発明のカプラーを用いたＤフイルムは塗布銀
量少ないにもかかわらず発色濃度が高いことが判
つた。
実施例 ４
実施例３のフイルムＤにおいて、乳剤として緑
感性沃臭化銀乳剤（Ｉ…６モル％、Br…94モル
％）200ｇ（銀９ｇ含有）を用い、カプラーとし
て表２に記載したものを用いる以外は実施例３と
同様して試料Ｅ〜Ｎを作り、同様の処理をして最
大濃度を測定した。銀とカプラーのモル比
（Ag／Cp）はいずれも４になるように調製した。
表 ２
フイルム カプラー 最大濃度
Ｅ ２ 2.20
Ｆ ３ 2.45
Ｇ ７ 2.40
Ｈ ９ 2.25
Ｉ 12 2.60
Ｊ 14 2.65
Ｋ 16 2.65
Ｌ 17 2.65
Ｍ 19 2.60
Ｎ 21 2.65
本発明のカプラーは、高い発色性を示すことが
表２より明らかである。
また実施例１，２より良好な溶解性をもつてい
ることも明らかである。[Table] It was found that the D film using the coupler of the present invention had a high color density even though the amount of coated silver was small. Example 4 In Film D of Example 3, 200 g of green-sensitive silver iodobromide emulsion (I...6 mol%, Br...94 mol%) (containing 9 g of silver) was used as the emulsion, and the couplers listed in Table 2 were used. Samples E to N were prepared in the same manner as in Example 3, except for using . The molar ratio of silver to coupler (Ag/Cp) was adjusted to 4 in both cases. Table 2 Film coupler maximum density E 2 2.20 F 3 2.45 G 7 2.40 H 9 2.25 I 12 2.60 J 14 2.65 K 16 2.65 L 17 2.65 M 19 2.60 N 21 2.65 The coupler of the present invention shows high color development. This is clearer than 2. It is also clear that it has better solubility than Examples 1 and 2.
Claims (1)
ール型カプラーで、現像主薬の酸化生成物とカツ
プリングする位置に下記一般式がカツプリング離
脱基として置換している二当量マゼンタカプラー
を含有することを特徴とするハロゲン化銀写真感
光材料 一般式 但しA1とA2は同じでも異なつてもよく、それ
ぞれ水素原子、アルキル基、アリール基、ヘテロ
環基、アシル基、スルホニル基、カルバモイル
基、スルフアモイル基、アルコキシカルボニル
基、アリールオキシカルボニル基を表わし、A1
とA2が共に水素原子であることはない。またA1
とA2が互いに結合し、窒素原子と共に５員もし
くは６員環を形成してもよい。この５員もしくは
６員環はさらにベンゼン環・複素環と縮合してい
てもよい。[Scope of Claims] 1 H-pyrazolo[3,2-C]-S-triazole coupler, two equivalents in which the following general formula is substituted as a coupling-off group at the position where it couples with the oxidation product of the developing agent. Silver halide photographic material characterized by containing a magenta coupler General formula However, A 1 and A 2 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. , A 1
and A 2 cannot both be hydrogen atoms. Also A 1
and A 2 may be bonded to each other to form a 5- or 6-membered ring with the nitrogen atom. This 5- or 6-membered ring may be further fused with a benzene ring or a heterocycle.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18953882A JPS5999437A (en) | 1982-10-28 | 1982-10-28 | Color photosensitive silver halide material |
| GB08328716A GB2132783A (en) | 1982-10-28 | 1983-10-27 | Color photographic silver halide material containing a two-equivalent magenta coupler |
| DE19833339201 DE3339201A1 (en) | 1982-10-28 | 1983-10-28 | COLOR PHOTOGRAPHIC LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18953882A JPS5999437A (en) | 1982-10-28 | 1982-10-28 | Color photosensitive silver halide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5999437A JPS5999437A (en) | 1984-06-08 |
| JPS6322571B2 true JPS6322571B2 (en) | 1988-05-12 |
Family
ID=16242980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18953882A Granted JPS5999437A (en) | 1982-10-28 | 1982-10-28 | Color photosensitive silver halide material |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5999437A (en) |
| DE (1) | DE3339201A1 (en) |
| GB (1) | GB2132783A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453174U (en) * | 1990-09-12 | 1992-05-07 |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60158448A (en) * | 1984-01-26 | 1985-08-19 | Konishiroku Photo Ind Co Ltd | Method for processing color photographic sensitive silver halide material |
| JPS60229029A (en) * | 1984-04-26 | 1985-11-14 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JPS6147957A (en) * | 1984-08-14 | 1986-03-08 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material |
| JPS6150145A (en) * | 1984-08-18 | 1986-03-12 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
| US4695533A (en) * | 1984-09-14 | 1987-09-22 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic light-sensitive material |
| JPS61120154A (en) * | 1984-11-15 | 1986-06-07 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| AU4743985A (en) * | 1984-09-14 | 1986-04-10 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic material with magenta coupler |
| JPS61141446A (en) * | 1984-12-14 | 1986-06-28 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| AU4744085A (en) * | 1984-09-14 | 1986-03-27 | Konishiroku Photo Industry Co., Ltd. | Pyrazolo-triazole magenta couplers and their use in silver halide colour photography |
| JPS61120147A (en) * | 1984-11-15 | 1986-06-07 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| US4639415A (en) * | 1984-09-17 | 1987-01-27 | Konishiroku Photo Industry Co., Ltd. | Silver halide color photographic material containing a magenta color image-forming coupler |
| US4675280A (en) * | 1984-10-09 | 1987-06-23 | Konishiroku Photo Industry Co., Ltd. | Silver halide color photographic material containing a 1H-pyrazolo [3,2-C]-S |
| JPS6199141A (en) * | 1984-10-22 | 1986-05-17 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| JPS61165756A (en) * | 1985-01-17 | 1986-07-26 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JPS61167952A (en) * | 1985-01-21 | 1986-07-29 | Fuji Photo Film Co Ltd | Multi-layered silver halide color photosensitive material |
| JPS61189536A (en) * | 1985-02-19 | 1986-08-23 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| JPS61189537A (en) * | 1985-02-19 | 1986-08-23 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| US5278038A (en) * | 1985-04-22 | 1994-01-11 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide color photographic material |
| JPH0812388B2 (en) * | 1985-04-22 | 1996-02-07 | コニカ株式会社 | Silver halide color photographic light-sensitive material |
| JPH0614174B2 (en) * | 1985-04-23 | 1994-02-23 | コニカ株式会社 | Silver halide photographic light-sensitive material |
| JPS61251852A (en) | 1985-04-30 | 1986-11-08 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
| JPS61250645A (en) | 1985-04-30 | 1986-11-07 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| JPS61252554A (en) * | 1985-05-01 | 1986-11-10 | Konishiroku Photo Ind Co Ltd | Method for fastening magenta dyestuff to light |
| US4752561A (en) * | 1985-05-17 | 1988-06-21 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material incorporating metal complex with high quenching constant and an oil soluble dye |
| JPS6210650A (en) * | 1985-07-09 | 1987-01-19 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| JPH0795190B2 (en) * | 1985-10-18 | 1995-10-11 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JPS62159144A (en) * | 1985-12-31 | 1987-07-15 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| JPH07117730B2 (en) * | 1986-01-11 | 1995-12-18 | コニカ株式会社 | Silver halide photographic light-sensitive material |
| JPH0715568B2 (en) | 1986-01-20 | 1995-02-22 | コニカ株式会社 | Silver halide color photographic light-sensitive material |
| DE3624544C2 (en) * | 1986-07-19 | 1996-02-01 | Agfa Gevaert Ag | Color photographic recording material with a color coupler of the pyrazoloazole type |
| DE3633364C3 (en) * | 1986-10-01 | 1995-07-13 | Agfa Gevaert Ag | Color photographic recording material with a color coupler of the pyrazoloazole type |
| US4992361A (en) * | 1987-03-09 | 1991-02-12 | Eastman Kodak Company | Photographic silver halide materials and process comprising a pyrazolotriazole coupler |
| JPH0259584A (en) * | 1988-08-25 | 1990-02-28 | Fuji Photo Film Co Ltd | Production of 7-azolyl-1h-pyrazolo(1,5-b)-1,2,4-triazoles |
| EP0435334B1 (en) | 1989-12-29 | 1997-11-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing yellow colored cyan coupler |
| JP2772877B2 (en) * | 1991-09-06 | 1998-07-09 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| FR2746391B1 (en) | 1996-03-22 | 1998-04-17 | Oreal | COSMETIC COMPOSITIONS BASED ON PYRAZOLIN-4,5-DIONES, NEW PYRAZOLIN-4,5 DIONES, METHODS OF PREPARATION AND USES |
| FR2746310B1 (en) | 1996-03-22 | 1998-06-12 | Oreal | KERATINIC FIBER DYEING COMPOSITIONS CONTAINING PYRAZOLIN-3,5-DIONE; THEIR USE FOR DYEING AS COUPLERS, DYEING METHOD |
| FR2746306B1 (en) | 1996-03-22 | 1998-04-30 | Oreal | KERATINIC FIBER DYEING COMPOSITIONS CONTAINING PYRAZOLO-AZOLES; THEIR USE FOR DYEING AS COUPLERS, DYEING METHOD |
| FR2746308B1 (en) * | 1996-03-22 | 1998-04-30 | Oreal | KERATINIC FIBER DYEING COMPOSITIONS CONTAINING IMIDAZOLO-AZOLES; THEIR USE IN DYEING AS COUPLERS; DYEING PROCESS |
| FR2746307B1 (en) | 1996-03-22 | 1998-04-30 | Oreal | KERATINIC FIBER DYEING COMPOSITIONS CONTAINING PYRROLO-AZOLES; USE AS COUPLERS; DYEING PROCESS |
| FR2746309B1 (en) | 1996-03-22 | 1998-04-17 | Oreal | COMPOSITION FOR DYEING KERATIN FIBERS CONTAINING PYRAZOLOPYRIMIDINEOXO; THEIR USE FOR DYEING AS COUPLER, DYEING PROCESSES |
| FR2772379B1 (en) | 1997-12-16 | 2000-02-11 | Oreal | DYE COMPOSITIONS OF KERATINIC FIBERS CONTAINING PYRAZOLO-AZOLES; THEIR USE FOR DYING AS AN OXIDIZING BASE, DYING PROCESS; NEW PYRAZOLO-AZOLES |
| FR2786092B1 (en) | 1998-11-20 | 2002-11-29 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME |
| FR2786094B1 (en) | 1998-11-20 | 2001-01-12 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME |
| DE60029783T2 (en) | 1999-06-22 | 2007-10-31 | Lion Corp. | HAIR COLORING AGENT INDOLIN AND / OR AN INDOLIN COMPOUND AND LACCASE CONTAINING |
| FR2805737B1 (en) | 2000-03-06 | 2003-01-03 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME |
| FR2806299B1 (en) | 2000-03-14 | 2002-12-20 | Oreal | COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING PYRROLIDINYL GROUPED PARAPHENYLENEDIAMINE DERIVATIVES |
| US10407964B2 (en) | 2017-04-19 | 2019-09-10 | Nissan North America, Inc. | Door striker assembly |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58115437A (en) * | 1981-12-28 | 1983-07-09 | Konishiroku Photo Ind Co Ltd | Blocked magenta dye forming coupler |
-
1982
- 1982-10-28 JP JP18953882A patent/JPS5999437A/en active Granted
-
1983
- 1983-10-27 GB GB08328716A patent/GB2132783A/en not_active Withdrawn
- 1983-10-28 DE DE19833339201 patent/DE3339201A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58115437A (en) * | 1981-12-28 | 1983-07-09 | Konishiroku Photo Ind Co Ltd | Blocked magenta dye forming coupler |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0453174U (en) * | 1990-09-12 | 1992-05-07 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3339201A1 (en) | 1984-05-03 |
| GB8328716D0 (en) | 1983-11-30 |
| GB2132783A (en) | 1984-07-11 |
| JPS5999437A (en) | 1984-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6322571B2 (en) | ||
| US4585732A (en) | Silver halide photographic light-sensitive material | |
| US4931382A (en) | Silver halide color photographic light-sensitive material | |
| US4588679A (en) | Color photographic silver halide light-sensitive material | |
| JPH037101B2 (en) | ||
| JPH0365529B2 (en) | ||
| JPH0244051B2 (en) | ||
| JPH0365530B2 (en) | ||
| JPH0413699B2 (en) | ||
| EP0178789A1 (en) | Silver halide color photograhic material | |
| US4822730A (en) | Silver halide color photographic light-sensitive materials containing a pyrazoloazole magenta coupler | |
| JPH0365531B2 (en) | ||
| US4501898A (en) | Photographic development inhibitor (1H- or 2H-) indazolyl hydroquinone derivatives | |
| JPH0365532B2 (en) | ||
| JPH043860B2 (en) | ||
| EP0183445B1 (en) | Silver halide color photo-sensitive material | |
| US4594313A (en) | Color image forming process comprising blocked magenta dye forming coupler | |
| JPH0562729B2 (en) | ||
| EP0133503B1 (en) | Color photographic light-sensitive material | |
| JPH0417413B2 (en) | ||
| JPH0380296B2 (en) | ||
| JP2711710B2 (en) | New cyan coupler | |
| JPH0413700B2 (en) | ||
| JPH0562972B2 (en) | ||
| JPS6232780B2 (en) |