JPS6147409B2 - - Google Patents
Info
- Publication number
- JPS6147409B2 JPS6147409B2 JP8912879A JP8912879A JPS6147409B2 JP S6147409 B2 JPS6147409 B2 JP S6147409B2 JP 8912879 A JP8912879 A JP 8912879A JP 8912879 A JP8912879 A JP 8912879A JP S6147409 B2 JPS6147409 B2 JP S6147409B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- dye
- compound
- layer
- groups
- 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
- 150000001875 compounds Chemical class 0.000 claims description 62
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 48
- 239000000975 dye Substances 0.000 description 41
- -1 silver halide Chemical class 0.000 description 39
- 108010010803 Gelatin Proteins 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 229920000159 gelatin Polymers 0.000 description 18
- 235000019322 gelatine Nutrition 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229940124530 sulfonamide Drugs 0.000 description 5
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 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 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- CTVXXASFLKIDFS-UHFFFAOYSA-M sodium;3,6-dihydroxy-2-pentadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCC1=C(O)C=CC(O)=C1S([O-])(=O)=O CTVXXASFLKIDFS-UHFFFAOYSA-M 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 125000000565 sulfonamide group Chemical group 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 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 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical group O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- AXYOOMZMWSBTOK-UHFFFAOYSA-N 2-amino-5-tert-butyl-4-hexadecoxyphenol;hydrochloride Chemical compound Cl.CCCCCCCCCCCCCCCCOC1=CC(N)=C(O)C=C1C(C)(C)C AXYOOMZMWSBTOK-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- DQSHFKPKFISSNM-UHFFFAOYSA-N 2-methylbenzoxazole Chemical compound C1=CC=C2OC(C)=NC2=C1 DQSHFKPKFISSNM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- MRIBCCHYZOSDOM-UHFFFAOYSA-N 3-(1-phenyltetrazol-5-yl)sulfanylpropanenitrile Chemical compound N#CCCSC1=NN=NN1C1=CC=CC=C1 MRIBCCHYZOSDOM-UHFFFAOYSA-N 0.000 description 1
- UWOZQBARAREECT-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)C(C)(CO)C1 UWOZQBARAREECT-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- CJUFCZXDOQHQCT-UHFFFAOYSA-N 6-tert-butyl-2-methyl-1,3-benzoxazol-5-ol Chemical compound OC1=C(C(C)(C)C)C=C2OC(C)=NC2=C1 CJUFCZXDOQHQCT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000001013 indophenol dye Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 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
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/02—Photosensitive materials characterised by the image-forming section
- G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
- G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
本発明はカラー感光材料に関し、さらに詳しく
は、ハロゲン化銀の現像に関したレドツクス反応
によつて、拡散性色素を放出する化合物を含むカ
ラー感光材料に関するものである。
特開昭48−33826号にはこのような、色素放出
型レドツクス化合物を用いるカラー拡散転写色像
形成法が述べられている。ここで述べられている
色素放出レドツクス化合物とは、色素部と非拡散
性フエノール部またはナフトール部とがｐ―位で
スルフオンアミド基を介して結合しているｐ―ス
ルフオンアミドフエノール又はｐ―スルフオンア
ミドナフトール化合物である。感光性ハロゲン化
銀乳剤と共存下に露光すると、現像されたハロゲ
ン化銀量に応じて、色素放出レドツクス化合物が
酸化され、これがアルカリ処理液によつて、スル
フオンアミド基を有する色素部と非拡散性ベンゾ
キノン又は非拡散性ナフトキノンに分解し前者の
色素部が受像要素に転写されて転写像を与える。
前者、すなわちｐ―スルフオンアミドフエノー
ルの場合であるが、本発明者らの追試によれば充
分な転写濃度を与え難いし、又後者は色素放出後
にｐ―ナフトキノンが残存して黄色ステインを生
じるため、転写像は利用できても、感光層側ユニ
ツトは脱銀処理を行つたとしても、ネガ又はポジ
の画像として利用しがたい。
ｏ―スルホンアミドフエノールをレドツクス・
センターとする色素放出型レドツクス化合物を用
いる拡散転写色像形成法は特開昭51−113624号に
述べられている。ここには、色素放出型レドツク
ス化合物として具体的には、例えば２―スルフオ
ンアミド―４―ヘキサデシルオキシ―５―メチル
フエノール等を使用する事が述べられている。
ｏ―スルホンアミドフエノールをレドツクス・
センターとするレドツクス化合物は比較的高い転
写濃度を与える点で勝れているが、(1)未露光部に
於ける色素転写及び(2)レドツクス反応によつて酸
化されたレドツクス化合物の酸化体が色素を放出
する効率（即ち色素転写の効率）の点で更にいつ
そうの改良が望まれている。
本発明の目的は改良された色素放出型レドツク
ス化合物を含むハロゲン化銀写真感光材料を提供
することにある。具体的には第一に拡散転写法に
用いた場合さらに高い転写濃度を与える色素放出
型レドツクス化合物を含む感光材料を提供するこ
とにある。第二に色素放出後の残色（ステイン）
が少い残存色素像（感光要素中）を与える色素放
出型レドツクス化合物を含む感光材料を提供する
ことにある。第三に未露光部では色素転写を起こ
さない、いわゆるDminを低下させ色素放出型レ
ドツクス化合物を含む感光材料を提供することに
ある。
本発明者らは下記一般式で表わされる化合物を
含有する感光材料が上記の目的をよく満足するこ
とを見出した。
ここでＧは水酸基、又は加水分解により水酸基
を与える基を、Colは色退又は色素の与える基を
表わす。R1とR2は同じでも異つていてもよく、
アルキル基を表わし、又R1とR2は連結して環を
形成してもよい。R3はアルキル基又は水素原子
を表わす。R4はアルキル基又は芳香族基を表わ
す。Ｘ及びＹはそれぞれ水素原子、アルキル基、
アルキルオキシ基、ハロゲン原子、アシルアミノ
基、アルキルチオ基を表わし、ＸとＹは同一もし
くは異つていてもよく、さらにR4とＹもしくは
R4とR3とが連結して環を形成していてもよい。
上記のアルキル基又はアルキル残基は無置換及び
置換アルキル基並びに直鎖、分岐及び環状アルキ
ル基を含む。とくに上記一般式において、Ｇの具
体例としては水酸基の他に、アセトキシル基、プ
ロピオニルオキシ基のような、アシルオキシ基が
挙げられる。Ｇとしては、特に水酸基が好まし
い。Colの例としてはアゾ色素、アゾメチン色
素、インドアニリン色素、インドフエノール色
素、トリフエニルメタン系色素、アンスラキノン
色素、インジゴ系色素又はこれらの金属錯塩等々
の基が挙げられる。Colで表わされる色素を与え
る基としては、加水分解により色素を与えるもの
が代表的であり、例えば特開昭48−125818号、米
国特許3222196号および同3307947号等に記された
ように色素の助色団をアシル化したようなもの
（一時短波型色素）を挙げることができる。アシ
ル化により色素の吸収の露光の間一時的に短波化
させておくことによつて、これらの色像形成剤を
感光乳剤と混合して塗布する場合に、光吸収に基
づく減感を防ぐことができる。なお、この目的の
ためには、媒染剤上に転写した場合と、乳剤層中
に存在する場合とで、色相が異なるような色素を
利用することもできる。なお、Col部は例えばカ
ルボキシル基、スルホンアミド基のような水溶性
を与えるような基を有することができる。
R1，R2およびR3のアルキル基の好ましい例と
しては、それぞれメチル基、エチル基、プロピル
基、ブチル基、アミル基、ヘキシル基、オクチル
基、ドデシル基、ヘキサデシル基、オクタデシル
基等の如き直鎖アルキル基；シクロヘキシル基、
シクロペンチル基、シクロオクチル基等のシクロ
アルキル基；イソプロピル基、イソブチル基、
sec―ブチル基、イソアミル基、ｔ―オクチル基
等の分岐アルキル基や；ヒドロキシエチル基、ベ
ンジル基、フエネチル基、メトキシエチル基等の
置換アルキル基等が挙げられる。
R4の好ましい例としては、炭素数１〜30の直
鎖状あるいは分岐状のアルキル（例えばメチル
基、エチル基、プロピル基、ブチル基、ペンチル
基、ヘキシル基、オクチル基、ドデシル基、ペン
タデシル基、ヘキサデシル基、オクタデシル基、
イソプロピル基、イソブチル基、ｔ―ブチル基、
ｔ―アミル基、ネオペンチル基等）や；置換アル
キル基（例えばヒドロキシエチル基、ベンジル
基、メトキシエチル基など）や；フエニル基；置
換フエニル基（例えばｐ―アミルアミノフエニル
基、ｐ―ニトロフエニル基など）などが挙げられ
る。
Ｘ及びＹの好ましい例としては水素原子、メチ
ル基、エチル基、プロピル基、ブチル基、ペンチ
ル基、ヘキシル基、オクチル基、ドデシル基、ペ
ンタデシル基、ヘキサデシル基、オクタデシル
基、イソプロピル基、イソブチル基、ｔ―ブチル
基、ｔ―アミル基、ネオペンチル基、ｔ―オクチ
ル基等の直鎖又は分岐アルキル基；ヒドロキシエ
チル基、ベンジル基、フエニルエチル基、メトキ
シエチル基、エトキシエチル基等の置換アルキル
基；フエニル基；置換フエニル基；メトキシ基、
エトキシ基、プロピルオキシ基、イソプロピルオ
キシ基、オクチルオキシ基、ドデシルオキシ基、
テトラデシルオキシ基、ヘキサデシルオキシ基、
オクタデシルオキシ基等の直鎖又は分岐アルキル
オキシ基；フエニルオキシ基；置換フエニルオキ
シ基；置換アルキルオキシ基；塩素、臭素のよう
なハロゲン原子；アセチルアミノ基、ステアリル
アミノ基、ステアリルアミノ基のようなアシルア
ミノ基；メチルチオ基、エチルチオ基、オクチル
チオ基、ドデシルチオ基、ヘキサデシルチオ基の
ようなアルキルチオ基；等が挙げられ、かつR3
とR4もしくはＹとR4とは縮合環を形成していて
もよい。縮合環としては５〜６員の飽和環が好ま
しい。
これらの化合物は感光材料の現像時に使用され
るアルカリによつてそのままの形で拡散または流
出してしまうことを避けるために、実質的に拡散
もしくは流出しなくするようなバラスト基を必要
とする。バラスト基に要求される基のサイズ、も
しくは炭素数は、使用する条件、たとえば処理時
間やアルカリ濃度や、Col部に有する水溶性基の
数と種類により異るが、少くともR1〜R4の合計
で８以上は必要である。炭素数が必要以上に大き
くなると、溶解度や、吸光係数の点で不利となつ
てゆくが、原理的に炭素数の上限というものはな
い。一般にはR1〜R4の合計炭素数が13から40辺
りが最も好ましい範囲である。
リサーチ デイスローシヤー（Resarch
Disclosure）誌13024号（′75）にはｏ―スルフオ
ンアミドフエノール類が記載されておりその中で
５位にアルキル基を有する２―スルフオンアミド
フエノールは現像活性がほとんどなく、従つて色
素を離脱しないことが示されているが、本発明の
化合物において、フエノールの４位にOR基が結
合していることが重大な差異を生みだしているこ
とは明らかである。
さらに本発明の化合物において、５位に第二級
もしくは第三級のアルキル基を有していることが
性能上重要な差異を生み出している。この効果は
第二級もしくは第三級アルキル基の立体効果のた
めに、不都合な副反応を抑えているためと推定さ
れる。
さらに本化合物は現像時のレドツクス反応によ
つてｏ―キノンイミドを生成し、これが加水分解
をうけて、スルホンアミド部を離脱するのである
が、これにより生ずるｏ―ベンゾキノン体が既述
のナフトキノン類に比し浅色的な吸収しかもたな
いことが色素放出後の残色を少くしていると考ら
れる。
本発明に用いる最も好ましい化合物においてＧ
は水酸基；Ｘ及びＹは水素原子；R1＝R2＝R3＝
CH3もしくはR1＝R2＝CH3でR3＝Ｈ、もしくは
R1＝R2＝CH3で、
The present invention relates to a color photosensitive material, and more particularly to a color photosensitive material containing a compound that releases a diffusible dye through a redox reaction associated with development of silver halide. JP-A-48-33826 describes a color diffusion transfer color image forming method using such a dye-releasing redox compound. The dye-releasing redox compound described herein refers to p-sulfonamide phenol or p-sulfonamide phenol, in which a dye moiety and a non-diffusible phenol moiety or naphthol moiety are bonded at the p-position via a sulfonamide group. It is a sulfonamide naphthol compound. When exposed to light in the coexistence of a photosensitive silver halide emulsion, the dye-releasing redox compound is oxidized depending on the amount of developed silver halide, and the alkaline processing liquid oxidizes the dye part having a sulfonamide group and the non-dye part. It decomposes into diffusible benzoquinone or non-diffusible naphthoquinone, and the dye portion of the former is transferred to an image-receiving element to provide a transferred image. In the case of the former, that is, p-sulfonamidophenol, according to additional tests by the present inventors, it is difficult to provide sufficient transfer density, and in the latter, p-naphthoquinone remains after the dye is released, resulting in a yellow stain. Therefore, even if the transferred image can be used, it is difficult to use it as a negative or positive image even if the photosensitive layer side unit is desilvered. Redox o-sulfonamidophenol
A diffusion transfer color image forming method using a dye-releasing redox compound as a center is described in JP-A-51-113624. Specifically, the use of, for example, 2-sulfonamido-4-hexadecyloxy-5-methylphenol as the dye-releasing redox compound is described herein. Redox o-sulfonamidophenol
The redox compound used as the center is superior in that it provides relatively high transfer density, but (1) dye transfer in the unexposed area and (2) oxidized redox compound oxidized by redox reaction are Further improvements in dye release efficiency (ie, dye transfer efficiency) are desired. An object of the present invention is to provide a silver halide photographic material containing an improved dye-releasing redox compound. Specifically, the first objective is to provide a photosensitive material containing a dye-releasing redox compound that provides a higher transfer density when used in a diffusion transfer method. Second, residual color after pigment release (stain)
The object of the present invention is to provide a photosensitive material containing a dye-releasing redox compound that provides a residual dye image (in a photosensitive element) with less residual dye. The third object is to provide a photosensitive material containing a dye-releasing redox compound that does not cause dye transfer in unexposed areas and has a lower so-called Dmin. The present inventors have discovered that a photosensitive material containing a compound represented by the following general formula satisfies the above objectives. Here, G represents a hydroxyl group or a group that provides a hydroxyl group upon hydrolysis, and Col represents a group that provides color fading or pigmentation. R 1 and R 2 may be the same or different,
It represents an alkyl group, and R 1 and R 2 may be connected to form a ring. R 3 represents an alkyl group or a hydrogen atom. R 4 represents an alkyl group or an aromatic group. X and Y are each a hydrogen atom, an alkyl group,
represents an alkyloxy group, a halogen atom, an acylamino group, an alkylthio group, X and Y may be the same or different, and R 4 and Y or
R 4 and R 3 may be connected to form a ring.
The alkyl groups or alkyl residues mentioned above include unsubstituted and substituted alkyl groups as well as straight chain, branched and cyclic alkyl groups. In particular, in the above general formula, specific examples of G include acyloxy groups such as acetoxyl group and propionyloxy group in addition to hydroxyl group. As G, a hydroxyl group is particularly preferable. Examples of Col include groups such as azo dyes, azomethine dyes, indoaniline dyes, indophenol dyes, triphenylmethane dyes, anthraquinone dyes, indigo dyes, and metal complex salts thereof. Typical examples of the dye-giving group represented by Col include those that give a dye by hydrolysis, such as those described in JP-A-48-125818, U.S. Pat. No. 3,222,196 and U.S. Pat. Examples include acylated auxochromes (transient short-wave dyes). To prevent desensitization due to light absorption when these color image forming agents are mixed with a light-sensitive emulsion and coated by temporarily shortening the wavelength during exposure of dye absorption through acylation. I can do it. Note that for this purpose, it is also possible to use a dye that has different hues when transferred onto the mordant and when present in the emulsion layer. Note that the Col moiety can have a group that imparts water solubility, such as a carboxyl group or a sulfonamide group. Preferred examples of alkyl groups for R 1 , R 2 and R 3 include methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, etc. Straight chain alkyl group; cyclohexyl group,
Cycloalkyl groups such as cyclopentyl group and cyclooctyl group; isopropyl group, isobutyl group,
Branched alkyl groups such as a sec-butyl group, isoamyl group, and t-octyl group; and substituted alkyl groups such as a hydroxyethyl group, benzyl group, phenethyl group, and methoxyethyl group. Preferred examples of R4 include linear or branched alkyl groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, pentadecyl group). , hexadecyl group, octadecyl group,
Isopropyl group, isobutyl group, t-butyl group,
t-amyl group, neopentyl group, etc.), substituted alkyl groups (e.g. hydroxyethyl group, benzyl group, methoxyethyl group, etc.); phenyl group; substituted phenyl group (e.g. p-amylaminophenyl group, p-nitrophenyl group) etc.). Preferred examples of X and Y include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, pentadecyl group, hexadecyl group, octadecyl group, isopropyl group, isobutyl group, Linear or branched alkyl groups such as t-butyl group, t-amyl group, neopentyl group, t-octyl group; Substituted alkyl groups such as hydroxyethyl group, benzyl group, phenylethyl group, methoxyethyl group, ethoxyethyl group; phenyl group; substituted phenyl group; methoxy group,
Ethoxy group, propyloxy group, isopropyloxy group, octyloxy group, dodecyloxy group,
Tetradecyloxy group, hexadecyloxy group,
Straight chain or branched alkyloxy groups such as octadecyloxy groups; phenyloxy groups; substituted phenyloxy groups; substituted alkyloxy groups; halogen atoms such as chlorine and bromine; acylamino groups such as acetylamino groups, stearyl amino groups, and stearyl amino groups ; alkylthio groups such as methylthio group, ethylthio group, octylthio group, dodecylthio group, hexadecylthio group; and R 3
and R 4 or Y and R 4 may form a fused ring. The fused ring is preferably a 5- to 6-membered saturated ring. In order to prevent these compounds from being diffused or washed out as they are by the alkali used during the development of the light-sensitive material, they require a ballast group that substantially prevents them from being diffused or washed out. The size of the group or the number of carbon atoms required for the ballast group varies depending on the conditions used, such as treatment time and alkali concentration, and the number and type of water-soluble groups in the Col part, but at least R 1 to R 4 A total of 8 or more is required. If the number of carbon atoms becomes larger than necessary, it becomes disadvantageous in terms of solubility and extinction coefficient, but in principle there is no upper limit to the number of carbon atoms. Generally, the most preferable range is for the total carbon number of R 1 to R 4 to be around 13 to 40. Research
Disclosure) magazine No. 13024 ('75) describes o-sulfonamide phenols, and among them, 2-sulfonamide phenol, which has an alkyl group at the 5-position, has almost no developing activity and is therefore difficult to use for dyes. Although shown not to be eliminated, it is clear that the attachment of the OR group at the 4-position of the phenol in the compounds of the invention makes a significant difference. Furthermore, in the compound of the present invention, having a secondary or tertiary alkyl group at the 5-position produces an important difference in performance. This effect is presumed to be due to the steric effect of the secondary or tertiary alkyl group, which suppresses undesirable side reactions. Furthermore, this compound generates o-quinone imide through a redox reaction during development, which undergoes hydrolysis and leaves the sulfonamide moiety, and the resulting o-benzoquinone forms into the aforementioned naphthoquinones. It is thought that the fact that it only has a relatively hypsochromic absorption reduces the residual color after the dye is released. In the most preferred compound used in the present invention, G
is a hydroxyl group; X and Y are hydrogen atoms; R 1 = R 2 = R 3 =
CH 3 or R 1 = R 2 = CH 3 and R 3 = H, or
R 1 = R 2 = CH 3 ,
【式】もし くは[Expression] If Kuha
【式】が[Formula] is
【式】である場合であ
り；R4はドデシル基、テトラデシル基、ヘキサ
デシル基もしくはオクタデシル基である。
本発明に使用される色素放出レドツクス化合物
を以下に例示する。
化合物例 １
化合物例 ２
化合物例 ３
化合物例 ４
化合物例 ５
化合物例 ６
化合物例 ７
化合物例 ８
化合物例 ９
化合物例 10
化合物例 11
本発明の感光材料の処理に当つては、レドツク
ス反応を円滑にするため、補助現像薬の存在下で
処理が行なわれることが望ましい。用いられる補
助現像薬として次のものを例示することができ
る。
１―フエニル―３―ピラゾリドン
１―フエニル―４，４―ジメチル―３―ピラゾ
リドン
１―フエニル―４―メチル―３―ピラゾリドン
ｐ―アミノ―フエノール
Ｎ―メチル―ｐ―アミノフエノール
Ｎ，Ｎ―ジエチルアミノ―フエノール
ｐ―トリルハイドロキノン
Ｎ，Ｎ―ジエチル―ｐ―フエニレンジアミン
６―ヒドロキシ―１，２，３，４―テトラヒド
ロキノリン
本発明の色素放出レドツクス化合物は担体であ
る親水性コロイド中に通常の方法で分散される。
本発明に於て、特に青感性ハロゲン化銀乳剤と
黄色色素放出レドツクス化合物との組合せ、緑感
性乳剤とマゼンタ色素放出レドツクス化合物との
組合せ並びに赤感性乳剤とシアン色素放出レドツ
クス化合物との組合せからなる感光材料は有用で
ある。これら乳剤と色素放出レドツクス化合物と
の組合せ単位は感光材料中で面対面の関係で層状
に重ねて塗布されてもよいし、或いは乳剤中にレ
ドツクス化合物を粒子状の形で混合して一層とし
て塗布されてもよい。好ましい重層構成では、露
光側から青感性乳剤、緑感性乳剤、赤感性乳剤が
順次に配置される。
本発明の色素放出レドツクス化合物は、それと
組合せられるハロゲン化銀乳剤の銀と色素放出レ
ドツクス化合物のモル比が約50〜0.5、好ましく
は約10〜２の範囲となる量で使用される。
本発明の感光材料に使用するハロゲン化銀乳剤
は、転写ポジ色像を得るために、カブらせ剤との
組合せによつて直接ポジ銀像のできる内部潜像型
乳剤が好ましい。
また本発明の感光材料は感光要素（レドツクス
化合物と感光層を含む）、受像要素（媒染層を含
む）及び処理要素（処理液含有容器）が一体とな
つたフイルム・ユニツトである事が好ましい。こ
のようなフイルム・ユニツトの詳細は米国特許
4055428等多数の文献に述べられている。
本発明のレドツクス化合物は一般にアゾ色素の
スルホニルクロリドと種々の有機バラスト基を有
するｏ―アミノフエノール誘導体と反応させるこ
とによつて合成することができる。また色素部お
よびそれらのスルホニルクロリドの合成法は、特
開昭48−12581号、同48−33826号、同49−114424
号、同49−126332号に記載されている。
次に本発明に関する化合物例の中からいくつか
の具体的な合成例と実施例とを以下に記す。
化合物例７の合成
ａ ２，５―ジヒドロキシ―４―ｔ―ブチルアセ
トフエノンの合成
ｔ―ブチルヒドロキシノン83gを酢酸400mlに
溶解させ80〜90℃に加熱しながら三フツ化ホウ素
（BF3）を約３時間導入した。反応終了後１の氷
水中に注ぎ析出した粘調な固体を取した。この
固体を2N―NaOH600mlに溶解させ不溶部を去
した。液を希塩酸により酸性とし、析出した結
晶を取して水洗した後、含水メタノールより再
結晶した。
収量 68g（65％）
ｂ ２，５―ジヒドロキシ―４―ｔ―ブチルアセ
トフエノン、オキシムの合成
上記ａ）で得られたケトン21gをエタノール70
ml、酢酸ナトリウム24gとともに加熱溶解させ、
撹拌しながら塩酸ヒドロキシルアミン12gを水70
mlに溶解させた液を加え約１時間還流した。反応
終了後500mlの氷水に注ぎ析出結晶を取しベン
ゼン―ヘキサンより再結晶した。
収量 17g（76％）
ｃ ６―ｔ―ブチル―５―ヒドロキシ―２―メチ
ルベンズオキサゾールの合成
上記ｂ）で得たオキシム14gを酢酸100ml中に
溶解させ加熱しながら乾燥塩酸ガスを導入し、
1.5時間還流した。反応終了後500mlの氷水中に注
ぎ析出結晶を取し水洗した。
収量 9g（70％）
ｄ ６―ｔ―ブチル―５―ヘキサデシルオキシ―
２―メチルベンズオキサゾールの合成
上記ｃ）で得たベンズオキサゾール6.9gをジメ
チルホルムアミド50mlに溶解させ、無水炭酸カリ
ウム8gとヘキサデシルブロミド11gと共に80〜90
℃にて６時間撹拌した。反応終了後、無機物を
去して液にメタノール150ml加え氷冷すると結
晶が析出した。これを取することにより標記化
合物を得た。
収量 8.8g（62％）
ｅ ２―アミノ―５―ｔ―ブチル―４―ヘキサデ
シルオキシフエノール塩酸塩の合成
上記ｄ）で得たベンズオキサゾール化合物7.3g
をエタノール30ml、濃塩酸20mlと共に３時間滑流
した。反応終了後、放冷し析出した結晶を取し
水洗した後アセトンで洗浄した。
収量 6.9g（92％）
ｆ 化合物例７の合成
上記ｅ）で得た塩酸塩6gと下記構造式の色素
のスルホニルクロリド8.8gをジメチルアセトアミ
ド50mlに溶解させ、ピリジン４mlを加えて室温で
１時間撹拌した。反応終了後、希塩酸中に注ぎ析
出した結晶を取し、水洗した。乾燥後シリカゲ
ルクロマトグラフイーにて精製し実質的に１成分
の標記化合物を2.2g得た。
色素スルホニルクロリド：
実施例 １
透明なポリエステル支持体上に順次、以下の層
を塗布した感光シートを作製した。
(1) 下記のマゼンタDRR化合物（0.99g／m2）、
トリシクロヘキシルホスフエート（0.19g／
m2）およびゼラチン（2.0g／m2）を含有する
層。
(2) 緑感性の内部潜像型直接反転臭化銀乳剤（銀
の量で1.75g／m2）、ゼラチン（1.8g／m2）、下
記の造核剤（0.06mg／m2）およびペンタデシル
ハイドロキノンスルホン酸ナトリウム
（0.11g／m2）を含有する層。
(3) ゼラチン（1.1g／m2）を含有する層。
下記組成の処理液を0.8g破裂可能な容器に充
填した。
処理液
１―フエニル―４―ヒドロキシメチル―４―メ
チル―３―ピラゾリジノン 13g
メチルハイドロキノン 0.3g
５―メチルベンツトリアゾール 3.5g
亜硫酸ナトリウム（無水） 0.2g
カルボキシメチルセルロース・Na塩 58g
水酸化カリウム（28％水溶液） 200c.c.
ベンジルアルコール 1.5c.c.
H2O 685c.c.
透明なポリエステル支持体上に、下記の媒染剤
（3.0g／m2）およびゼラチン（3.0g／m2）を含有
する媒染層シートを作製した。
上記感光シートの層(1)のマゼンタDRR化合物
を含む試料を(A)とし、マゼンタDRR化合物を前
記の化合物例７に（1.04g／m2）に置き換えた試
料(B)を作製した。
試料(A)、(B)を露光後、上記処理液を含む容器お
よび媒染層シートと共に一体化させて、15℃およ
び25℃の条件で押圧部材により処理液を80μｍの
厚みに展開した。５分後、媒染層シートを剥離し
て酢酸の２％溶液に浸漬し、その後水洗、乾燥し
て転写色画像を得た。その結果を表−１に示し
た。[Formula]; R 4 is a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group. The dye-releasing redox compounds used in the present invention are illustrated below. Compound example 1 Compound example 2 Compound example 3 Compound example 4 Compound example 5 Compound example 6 Compound example 7 Compound example 8 Compound example 9 Compound example 10 Compound example 11 When processing the light-sensitive material of the present invention, it is desirable to carry out the processing in the presence of an auxiliary developer in order to facilitate the redox reaction. The following can be exemplified as the auxiliary developer that can be used. 1-Phenyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-4-methyl-3-pyrazolidone p-amino-phenol N-methyl-p-aminophenol N,N-diethylamino- Phenol p-Tolylhydroquinone N,N-diethyl-p-phenylenediamine 6-Hydroxy-1,2,3,4-tetrahydroquinoline The dye-releasing redox compound of the present invention is prepared in a hydrophilic colloid as a carrier by a conventional method. distributed. In the present invention, in particular, a combination of a blue-sensitive silver halide emulsion and a yellow dye-releasing redox compound, a combination of a green-sensitive emulsion and a magenta dye-releasing redox compound, and a combination of a red-sensitive emulsion and a cyan dye-releasing redox compound. Photosensitive materials are useful. The combined units of these emulsions and dye-releasing redox compounds may be coated in layers in a face-to-face relationship in the light-sensitive material, or the redox compound may be mixed in the emulsion in the form of particles and coated as a single layer. may be done. In a preferred multilayer structure, a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion are sequentially arranged from the exposure side. The dye-releasing redox compound of this invention is used in an amount such that the molar ratio of silver to dye-releasing redox compound in the silver halide emulsion with which it is combined ranges from about 50 to 0.5, preferably from about 10 to 2. The silver halide emulsion used in the light-sensitive material of the present invention is preferably an internal latent image type emulsion that can directly form a positive silver image when combined with a fogging agent in order to obtain a transferred positive color image. The photosensitive material of the present invention is preferably a film unit in which a photosensitive element (containing a redox compound and a photosensitive layer), an image receiving element (containing a mordant layer) and a processing element (containing a processing liquid) are integrated. Details of such film units can be found in US patents.
It is described in many documents such as 4055428. The redox compound of the present invention can generally be synthesized by reacting an azo dye sulfonyl chloride with an o-aminophenol derivative having various organic ballast groups. Furthermore, methods for synthesizing dye moieties and their sulfonyl chlorides are disclosed in JP-A-48-12581, JP-A No. 48-33826, and JP-A No. 49-114429.
No. 49-126332. Next, some specific synthesis examples and examples from among the compound examples related to the present invention will be described below. Synthesis of Compound Example 7 a Synthesis of 2,5-dihydroxy-4-t-butylacetophenone 83 g of t-butyl hydroxylone was dissolved in 400 ml of acetic acid and boron trifluoride (BF 3 ) was dissolved while heating to 80-90°C. was introduced for about 3 hours. After the reaction was completed, the mixture was poured into ice water in Step 1 to collect the precipitated viscous solid. This solid was dissolved in 600 ml of 2N-NaOH and the insoluble portion was removed. The solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were collected, washed with water, and then recrystallized from aqueous methanol. Yield 68g (65%) b Synthesis of 2,5-dihydroxy-4-t-butylacetophenone, oxime Add 21g of the ketone obtained in a) above to 70% ethanol
ml, heat and dissolve with 24g of sodium acetate,
While stirring, add 12 g of hydroxylamine hydrochloride to 70 g of water.
ml of the solution was added and refluxed for about 1 hour. After the reaction was completed, the mixture was poured into 500 ml of ice water, and the precipitated crystals were collected and recrystallized from benzene-hexane. Yield 17g (76%) c Synthesis of 6-t-butyl-5-hydroxy-2-methylbenzoxazole 14g of the oxime obtained in b) above was dissolved in 100ml of acetic acid, and while heating, dry hydrochloric acid gas was introduced.
Refluxed for 1.5 hours. After the reaction was completed, the mixture was poured into 500 ml of ice water, and the precipitated crystals were collected and washed with water. Yield 9g (70%) d 6-t-butyl-5-hexadecyloxy
Synthesis of 2-methylbenzoxazole 6.9 g of benzoxazole obtained in c) above was dissolved in 50 ml of dimethylformamide, and 80 to 90 g of anhydrous potassium carbonate and 11 g of hexadecyl bromide were dissolved.
The mixture was stirred at ℃ for 6 hours. After the reaction was completed, inorganic substances were removed and 150 ml of methanol was added to the solution, which was then cooled on ice to precipitate crystals. By taking this, the title compound was obtained. Yield 8.8g (62%) e Synthesis of 2-amino-5-t-butyl-4-hexadecyloxyphenol hydrochloride 7.3g of the benzoxazole compound obtained in d) above
was rinsed with 30 ml of ethanol and 20 ml of concentrated hydrochloric acid for 3 hours. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were collected, washed with water, and then washed with acetone. Yield 6.9g (92%) f Synthesis of Compound Example 7 6g of the hydrochloride obtained in e) above and 8.8g of the sulfonyl chloride of the dye having the structural formula below were dissolved in 50ml of dimethylacetamide, 4ml of pyridine was added, and the mixture was heated at room temperature for 1 hour. Stirred. After the reaction was completed, the precipitated crystals were poured into dilute hydrochloric acid and washed with water. After drying, the residue was purified by silica gel chromatography to obtain 2.2 g of the title compound, which was essentially one component. Dye sulfonyl chloride: Example 1 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support. (1) The following magenta DRR compound (0.99g/m 2 ),
Tricyclohexyl phosphate (0.19g/
m 2 ) and a layer containing gelatin (2.0 g/m 2 ). (2) Green-sensitive internal latent image direct reversal silver bromide emulsion (silver content 1.75 g/m 2 ), gelatin (1.8 g/m 2 ), the following nucleating agent (0.06 mg/m 2 ) and Layer containing sodium pentadecylhydroquinone sulfonate (0.11 g/m 2 ). (3) Layer containing gelatin (1.1g/m 2 ). A rupturable container was filled with 0.8 g of a treatment solution having the following composition. Treatment liquid 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidinone 13g Methylhydroquinone 0.3g 5-methylbenztriazole 3.5g Sodium sulfite (anhydrous) 0.2g Carboxymethylcellulose Na salt 58g Potassium hydroxide (28% aqueous solution) ) 200c.c. Benzyl alcohol 1.5cc H 2 O 685c.c. A mordant layer sheet containing the following mordant (3.0g/m 2 ) and gelatin (3.0g/m 2 ) was placed on a transparent polyester support. Created. A sample containing the magenta DRR compound in layer (1) of the photosensitive sheet was designated as (A), and a sample (B) was prepared in which the magenta DRR compound was replaced with Compound Example 7 (1.04 g/m 2 ). After exposing samples (A) and (B), they were integrated with a container containing the treatment liquid and a mordant layer sheet, and the treatment liquid was spread to a thickness of 80 μm using a pressing member at 15°C and 25°C. After 5 minutes, the mordant layer sheet was peeled off and immersed in a 2% acetic acid solution, then washed with water and dried to obtain a transferred color image. The results are shown in Table-1.
【表】
表−１より明らかなように、試料(A)に比較し
て、試料(B)は最大透過濃度が高く、しかも最小透
過濃度が低く、かつ足部階調の切れの良好な特性
値を与えた。また試料(B)は最大透過濃度近くでの
変換率（転写色画像濃度／現像銀量）が大きく利
用率（転写色画像濃度／DRR化合物の塗布量）
も大きかつた。
実施例 ２
実施例１の試料(A)および(B)について、処理液の
組成のうち、現像主薬を１―ｐ―トリル―４―ヒ
ドロキシメチル―４―メチル―３―ピラゾリジノ
ン（6.9g）に変えた他は実施例１と同様の処理液
で処理した。25℃条件での結果を表−２に示し
た。[Table] As is clear from Table 1, compared to sample (A), sample (B) has a higher maximum transmittance density, a lower minimum transmittance density, and better sharpness of the toe gradation. given the value. In addition, sample (B) has a high conversion rate (transfer color image density/developed silver amount) near the maximum transmission density and utilization rate (transfer color image density/coating amount of DRR compound).
It was also big. Example 2 Regarding samples (A) and (B) of Example 1, the developing agent was changed to 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidinone (6.9 g) in the composition of the processing solution. The treatment was performed using the same treatment solution as in Example 1 except for the following changes. The results under 25°C conditions are shown in Table 2.
【表】
表−２より明らかなように試料(A)に比較して、
試料(B)は最大透過濃度が高く、最小透過濃度が低
く、かつ足部階調の切れの良好な特性値を与え
た。また試料(B)は最大透過濃度近くでの変換率が
大きく利用率も大きかつた。
実施例 ３
透明なポリエステル支持体上に順次、以下の層
を塗布した感光シートを作製した。
(1) 実施例１の媒染剤（3.0g／m2）とゼラチン
（3.0g／m2）を含有する媒染層。
(2) 二酸化チタン（20g／m2）およびゼラチン
（2.0g／m2）を含有する白色反射層。
(3) カーボンブラツク（2.70g／m2）およびゼラ
チン（2.70g／m2）を含有する遮光層。
(4) 実施例１の層(1)と同じ層。
(5) 実施例１の層(2)と同じ層。
(6) 実施例１の層(3)と同じ層。
カーボンブラツクを150g加える他は実施例１
と同一組成の処理液を0.8g破裂可能な容器に充填
した。
透明なポリエステル支持体上に順次、以下の層
を塗布したカバーシートを作製した。
(1) アクリル酸とアクリル酸ブチルの80対20（重
量比の共重合体（22g／m2）および１，４―ビ
ス（２，３―エポキシプロポキシ）―ブタン
（0.44g／m2）を含有する層。
(2) アセチルセルロース（100gのアセチルセル
ロースを加水分解して、39.4gのアセチル基を
生成する。（3.8g／m2）およびスチレンと無水
マレイン酸の60対40（重量比）の共重合体（分
子量約５万）（0.2g／m2）および５―（β―シ
アノエチルチオ）―１―フエニルテトラゾール
（0.115g／m2）を含有する層。
(3) 塩化ビニリデンとメチルアクリレートとアク
リル酸の85対12対12対３（重量比）の共重合体
ラテツクス（2.5g／m2）およびポリメチルメタ
アクリレートラテツクス（粒径１〜３μｍ）
（0.05g／m2）を含有する層。
上記感光シートの層(4)のマゼンタDRR化合物
を含む試料を(C)とし、マゼンタDRR化合物を前
記化合物例７におき換えた試料(D)を作製した。
試料(C)および(D)を露光後、実施例１の処理液お
よびカバーシートと共に一体化させて、15℃およ
び25℃の条件で押圧部材により処理液を80μｍの
厚みに展開して転写色画像を得た。その結果、実
施例１と同様に、試料(C)に比較して、試料(D)が良
好な写真性を示した。
実施例 ４
透明なポリエステル支持体上に順次、以下の層
を塗布した感光シートを作製した。
(1) 実施例３の層(1)と同じ媒染層。
(2) 実施例３の層(2)と同じ白色反射層。
(3) 実施例３の層(3)と同じ遮光層。
(4) 前記の化合物例９〔シアンDRR化合物〕
（0.44g／m2）、トリシクロヘキシルホスフエー
ト（0.09g／m2）、２，５―ジ―ｔ―ペンタデシ
ルハイドロキノン（0.008g／m2）およびゼラチ
ン（0.8g／m2）を含有する層。
(5) 赤感性の内部潜像型直接反転臭化銀乳剤（銀
の量で1.03g／m2）、ゼラチン（1.2g／m2）、下
記の造核剤（0.05mg／m2）およびペンタデシル
ハイドロキノンスルホン酸ナトリウム
（0.13g／m2）を含有する層。
(6) ２，５―ジ―ｔ―ペンタデシルハイドロキノ
ン（0.71g／m2）、ビニルピロリドンと酢酸ビニ
ルの共重合体（モル比７：３）（0.24g／m2）お
よびゼラチン（0.6g／m2）を含有する層。
(7) ２種のマゼンタDRR化合物、即ち前記の化
合物例７（0.29ｇ／mm2）と化合物例10
（0.15g／m2）、トリシクロヘキシルホスフエー
ト（0.08g／m2）、２，５―ジ―ｔペンタデシル
ナイドロキノン（0.009g／m2）およびゼラチン
（0.9g／m2）を含有する層。
(8) 緑感性の内部潜像型直接反転臭化銀乳剤（銀
の量で（0.82g／m2）、ゼラチン（0.9g／m2）、
層(5)と同じ造核剤（0.03mg／m2）およびペンタ
デシルハイドロキノンスルホン酸ナトリウム
（0.08g／m2）を含有する層。
(9) ２，５―ジ―ｔ―ペンタデシルハイドロキノ
ン（0.71g／m2）、ビニルピロリドンと酢酸ビニ
ルの共重合体（モル比７：３）（0.24g／m2）お
よびゼラチン（0.6g／m2）を含有する層。
(10) 前記の化合物例11〔イエローDRR化合物〕
（0.53g／m2）、トリシクロヘキシルホスフエー
ト（0.13g／m2）、２，５―ジ―ｔ―ペンタデシ
ルハイドロキノン（0.014g／m2）およびゼラチ
ン（0.7g／m2）を含有する層。
(11) 青感性の内部潜像型直接反転臭化銀乳剤（銀
の量で1.09g／m2）、ゼラチン（1.1g／m2）、層
(5)と同じ造核剤（0.04mg／m2）およびペンタデ
シルハイドロキノンスルホン酸ナトリウム
（0.07g／m2）を含有する層。
(12) ゼラチン（1.0g／m2）を含有する層。
上記の感光シートを露光後、実施例３の処理液
および実施例３のカバーシートと一体化させて、
25℃の条件で押圧部材により処理液を80μｍの厚
みに展開して転写色画像を得た。その結果、満足
な最大反射濃度、満足な最小反射濃度および良好
な階調を有する転写色画像を示した。
実施例 ５
透明なポリエステル支持体上に順次、以下の層
を塗布した感光シートを作製した。
(1) 下記のマゼンタDRR化合物、トリシクロヘ
キシルホスフエート（0.19g／m2）およびゼラ
チン（2.0g／m2）を含有する層。
(2) 実施例１の第(2)層と同じ層
(3) ゼラチン（1.1g／m2）を含有する層。
次に実施例１と同じ処理液容器と媒染層シート
と前記の感光シートとを一体化させ、25℃で押圧
部材により処理液を80μｍの厚みに展開した。５
分後、媒染層シートを剥離して酢酸の２％溶液に
浸漬し、その後水洗、乾燥して転写色画像を得
た。その結果を表−３に示した。[Table] As is clear from Table 2, compared to sample (A),
Sample (B) had a high maximum transmission density, a low minimum transmission density, and gave characteristic values with good toe gradation sharpness. In addition, sample (B) had a high conversion rate near the maximum permeation concentration and a high utilization rate. Example 3 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support. (1) A mordant layer containing the mordant of Example 1 (3.0 g/m 2 ) and gelatin (3.0 g/m 2 ). (2) White reflective layer containing titanium dioxide (20g/m 2 ) and gelatin (2.0g/m 2 ). (3) A light shielding layer containing carbon black (2.70g/m 2 ) and gelatin (2.70g/m 2 ). (4) Same layer as layer (1) of Example 1. (5) Same layer as layer (2) of Example 1. (6) Same layer as layer (3) of Example 1. Example 1 except adding 150g of carbon black
A rupturable container was filled with 0.8 g of a treatment solution having the same composition as . A cover sheet was prepared with the following layers applied sequentially onto a transparent polyester support. (1) A copolymer of acrylic acid and butyl acrylate in a weight ratio of 80:20 (22 g/m 2 ) and 1,4-bis(2,3-epoxypropoxy)-butane (0.44 g/m 2 ). (2) Acetylcellulose (100g of acetylcellulose is hydrolyzed to produce 39.4g of acetyl groups (3.8g/m 2 ) and 60:40 (weight ratio) of styrene and maleic anhydride. (molecular weight approximately 50,000) (0.2 g/m 2 ) and 5-(β-cyanoethylthio)-1-phenyltetrazole (0.115 g/m 2 ). (3) Vinylidene chloride and 85:12:12:3 (weight ratio) copolymer latex of methyl acrylate and acrylic acid (2.5 g/m 2 ) and polymethyl methacrylate latex (particle size 1-3 μm)
(0.05g/m 2 ). A sample containing the magenta DRR compound in layer (4) of the photosensitive sheet was designated as (C), and a sample (D) was prepared in which the magenta DRR compound was replaced with Compound Example 7. After exposing samples (C) and (D), they were integrated with the processing solution of Example 1 and the cover sheet, and the processing solution was spread to a thickness of 80 μm using a pressing member at 15°C and 25°C to obtain the transfer color. Got the image. As a result, as in Example 1, sample (D) showed better photographic properties than sample (C). Example 4 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support. (1) Same mordant layer as layer (1) of Example 3. (2) White reflective layer same as layer (2) of Example 3. (3) The same light-shielding layer as layer (3) of Example 3. (4) The above compound example 9 [cyan DRR compound]
(0.44g/m 2 ), tricyclohexyl phosphate (0.09g/m 2 ), 2,5-di-t-pentadecylhydroquinone (0.008g/m 2 ) and gelatin (0.8g/m 2 ). layer. (5) Red-sensitive internal latent image direct reversal silver bromide emulsion (silver content 1.03g/m 2 ), gelatin (1.2g/m 2 ), the following nucleating agent (0.05mg/m 2 ) and Layer containing sodium pentadecylhydroquinone sulfonate (0.13g/m 2 ). (6) 2,5-di-t-pentadecylhydroquinone (0.71g/m 2 ), copolymer of vinylpyrrolidone and vinyl acetate (molar ratio 7:3) (0.24g/m 2 ), and gelatin (0.6g) /m 2 ). (7) Two magenta DRR compounds, namely Compound Example 7 (0.29 g/mm 2 ) and Compound Example 10 above.
(0.15g/m 2 ), tricyclohexyl phosphate (0.08g/m 2 ), 2,5-di-tpentadecylnidroquinone (0.009g/m 2 ) and gelatin (0.9g/m 2 ). layer to do. (8) Green-sensitive internal latent image type direct reversal silver bromide emulsion (silver content (0.82 g/m 2 ), gelatin (0.9 g/m 2 ),
Layer containing the same nucleating agent (0.03 mg/m 2 ) and sodium pentadecylhydroquinone sulfonate (0.08 g/m 2 ) as layer (5). (9) 2,5-di-t-pentadecylhydroquinone (0.71g/m 2 ), copolymer of vinylpyrrolidone and vinyl acetate (molar ratio 7:3) (0.24g/m 2 ), and gelatin (0.6g) /m 2 ). (10) Compound Example 11 [Yellow DRR compound]
(0.53g/m 2 ), tricyclohexyl phosphate (0.13g/m 2 ), 2,5-di-t-pentadecylhydroquinone (0.014g/m 2 ) and gelatin (0.7g/m 2 ). layer. (11) Blue-sensitive internal latent image direct reversal silver bromide emulsion (silver content 1.09 g/m 2 ), gelatin (1.1 g/m 2 ), layer
A layer containing the same nucleating agent (0.04 mg/m 2 ) and sodium pentadecylhydroquinone sulfonate (0.07 g/m 2 ) as in (5). (12) Layer containing gelatin (1.0g/m 2 ). After exposing the above photosensitive sheet, it is integrated with the processing solution of Example 3 and the cover sheet of Example 3,
The processing liquid was spread to a thickness of 80 μm using a pressing member at 25° C. to obtain a transferred color image. The results showed a transferred color image having satisfactory maximum reflection density, satisfactory minimum reflection density, and good gradation. Example 5 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support. (1) A layer containing the following magenta DRR compounds, tricyclohexyl phosphate (0.19 g/m 2 ) and gelatin (2.0 g/m 2 ). (2) The same layer as the layer (2) of Example 1. (3) A layer containing gelatin (1.1 g/m 2 ). Next, the same processing liquid container as in Example 1, the mordant layer sheet, and the photosensitive sheet were integrated, and the processing liquid was spread to a thickness of 80 μm at 25° C. using a pressing member. 5
After a few minutes, the mordant layer sheet was peeled off and immersed in a 2% acetic acid solution, then washed with water and dried to obtain a transferred color image. The results are shown in Table 3.
【表】
表−３より明らかなように、試料(E)や(F)に比較
して本発明による試料(B)は最大透過度が顕著に高
く、しかも最小透過濃度が低いという優れた写真
性をもつ事がわかる。又試料(B)は試料(E)や(F)に比
べて変換率や利用率も高かつた。[Table] As is clear from Table 3, sample (B) according to the present invention is an excellent photograph with a significantly higher maximum transmittance and lower minimum transmittance density than samples (E) and (F). I understand that it has sex. Sample (B) also had higher conversion and utilization rates than samples (E) and (F).
Claims (1)
化合物を含有するカラー写真感光材料。 ここでＧは水素基又は加水分解により水酸基を
与える基を、Colは色素又は色素を与える基を表
わす、R1及びR2は同じでも異つていてもよく、
それぞれアルキル基であるか、又はR1とR2が連
結して環を形成してもよい。R3は水素原子又は
アルキル基を、R4はアルキル基又は芳香族基を
表わす。Ｘ及びＹは同じでも異つてもよく、それ
ぞれ水素原子、アルキル基、アルキルオキシ基、
ハロゲン原子、アシルアミノ基又はアルキルチオ
基を表わし、さらにR4とＹ又はR4とR3とが連結
して環を形成してもよい。[Scope of Claims] 1. A color photographic material containing a dye-releasing redox compound represented by the following general formula. Here, G represents a hydrogen group or a group that provides a hydroxyl group by hydrolysis, Col represents a dye or a group that provides a dye, R 1 and R 2 may be the same or different,
Each may be an alkyl group, or R 1 and R 2 may be linked to form a ring. R 3 represents a hydrogen atom or an alkyl group, and R 4 represents an alkyl group or an aromatic group. X and Y may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkyloxy group,
It represents a halogen atom, an acylamino group, or an alkylthio group, and R 4 and Y or R 4 and R 3 may be linked to form a ring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8912879A JPS5612642A (en) | 1979-07-13 | 1979-07-13 | Color photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8912879A JPS5612642A (en) | 1979-07-13 | 1979-07-13 | Color photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5612642A JPS5612642A (en) | 1981-02-07 |
| JPS6147409B2 true JPS6147409B2 (en) | 1986-10-18 |
Family
ID=13962239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8912879A Granted JPS5612642A (en) | 1979-07-13 | 1979-07-13 | Color photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5612642A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3482606D1 (en) | 1983-11-25 | 1990-08-02 | Fuji Photo Film Co Ltd | HEAT-DEVELOPABLE LIGHT-SENSITIVE MATERIAL. |
| JP2597908B2 (en) | 1989-04-25 | 1997-04-09 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
-
1979
- 1979-07-13 JP JP8912879A patent/JPS5612642A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5612642A (en) | 1981-02-07 |
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