JPH0554099B2 - - Google Patents
Info
- Publication number
- JPH0554099B2 JPH0554099B2 JP58086267A JP8626783A JPH0554099B2 JP H0554099 B2 JPH0554099 B2 JP H0554099B2 JP 58086267 A JP58086267 A JP 58086267A JP 8626783 A JP8626783 A JP 8626783A JP H0554099 B2 JPH0554099 B2 JP H0554099B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- dye
- dyes
- present
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 claims description 81
- 239000000463 material Substances 0.000 claims description 30
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 115
- 239000000839 emulsion Substances 0.000 description 43
- 239000010410 layer Substances 0.000 description 40
- 239000007864 aqueous solution Substances 0.000 description 37
- 239000000203 mixture Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 26
- 108010010803 Gelatin Proteins 0.000 description 25
- 239000008273 gelatin Substances 0.000 description 25
- 229920000159 gelatin Polymers 0.000 description 25
- 235000019322 gelatine Nutrition 0.000 description 25
- 235000011852 gelatine desserts Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229930182490 saponin Natural products 0.000 description 11
- 150000007949 saponins Chemical class 0.000 description 11
- 235000017709 saponins Nutrition 0.000 description 11
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000010186 staining Methods 0.000 description 6
- AXCGIKGRPLMUDF-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one;sodium Chemical compound [Na].OC1=NC(Cl)=NC(Cl)=N1 AXCGIKGRPLMUDF-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 5
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 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
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical class NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 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
- KCZRCYBAYWJVGD-UHFFFAOYSA-N 4-(diethylamino)-2-methylbenzaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(C)=C1 KCZRCYBAYWJVGD-UHFFFAOYSA-N 0.000 description 1
- HGDRXADJVGVGBC-UHFFFAOYSA-N 4-(dimethylamino)-2-methoxybenzaldehyde Chemical compound COC1=CC(N(C)C)=CC=C1C=O HGDRXADJVGVGBC-UHFFFAOYSA-N 0.000 description 1
- XZWMCPUAUNHGPF-UHFFFAOYSA-N 4-(dimethylamino)-2-methylbenzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C(C)=C1 XZWMCPUAUNHGPF-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- 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 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- LWVVNNZRDBXOQL-AATRIKPKSA-O [(e)-3-(dimethylamino)prop-2-enyl]-dimethylazanium Chemical compound CN(C)\C=C\C[NH+](C)C LWVVNNZRDBXOQL-AATRIKPKSA-O 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005354 acylalkyl group Chemical group 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 150000004983 alkyl aryl ketones Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 description 1
- 125000005154 alkyl sulfonyl amino alkyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004966 cyanoalkyl 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
- 229960003067 cystine Drugs 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- ZCRZCMUDOWDGOB-UHFFFAOYSA-N ethanesulfonimidic acid Chemical group CCS(N)(=O)=O ZCRZCMUDOWDGOB-UHFFFAOYSA-N 0.000 description 1
- YNTDWRYEWSWDON-UHFFFAOYSA-N ethene;2-hydroxyacetic acid Chemical compound C=C.OCC(O)=O.OCC(O)=O YNTDWRYEWSWDON-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000005359 phenoxyalkyl group Chemical group 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 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
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
産業上の利用分野
本発明は、写真技術、特に写真感光材料の製造
技術に利用することができる。
本発明は、ハロゲン化銀写真感光材料に関し、
更に詳しくは新規な光吸収染料により着色された
親水性コロイド層を有し、かつ処理後の残色汚染
が改良されたハロゲン化銀写真感光材料に関す
る。
従来技術
一般的にハロゲン化銀写真感光材料（以下、感
光材料と称す）においては、光吸収フイルター、
ハレーシヨン防止、イラジエーシヨン防止あるい
は感光性乳剤の感度調節の目的で、特定の波長の
光を吸収させるべく感光材料の構成層中に染料を
含有せしめることはよく知られているところであ
り、従つて上記染料によつて親水性コロイド層を
着色させることは従来から行なわれてきている。
上記感光材料の構成層のうち、フイルター層
は、通常感光性乳剤層の上層あるいは該乳剤層と
もう１つの乳剤層との間に位置し、乳剤層に到達
する入射光を好ましい分光組成の光に変える役割
を果すものである。またハレーシヨン防止層に関
して言えば、画像の鮮鋭度を改良する目的で、感
光性乳剤層と支持体との間に、あるいは支持体の
裏面にハレーシヨン防止層を設けて、乳剤層と支
持体との界面や支持体背面での有害な反射光を吸
収せしめて画像の鮮鋭性を向上させている。
またさらには、染料を用いて感光性乳剤層を着
色して、ハロゲン化銀粒子に対する有害な反射光
や散乱光等を吸収させ、イラジエーシヨンを防止
することによつて画像の鮮鋭性を改良させること
も屡々行なわれる。
このような種々の目的に用いられる染料として
は、その使用目的に応じて良好な吸収スペクトル
特性を有することは勿論、例えば現像処理中に完
全に脱色され、現像処理中に感光材料から容易に
溶出され、処理後には染料による残色汚染を生ぜ
しめることがなく、そのほか、感光性乳剤に対し
てカブリ、減感等の悪影響を及ぼすことがなく、
また着色された層から他層へ拡散することがな
く、さらには感光材料中においてあるいは水溶液
中において経時安定性にも優れていて変退色を起
さないこと等の諸条件を満足させるものでなけれ
ばならない。
今日まで上記の如き諸条件を満足させる染料を
開発することを目的として多数の研究が行なわ
れ、例えば米国特許第3540887号、同第3544325
号、同第3560214号、特公昭31−10578号および特
開昭51−3623号等にはベンジリデン染料が提案さ
れ、英国特許第506385号および特公昭39−22069
号にはオキソノール染料、米国特許第2493747号
にはメロシアニン染料、米国特許第1845404号に
はスチリル染料等がそれぞれ提案されている。
しかしながら今だに前記の如き諸条件を満足せ
しめる染料を見出すには至つていないのが現状で
ある。
発明の目的
そこで本発明の目的は、最適な吸収スペクトル
特性を有し、現像処理中において完全に脱色し、
処理後における残色汚染が極めて少なく、また他
層への拡散が少なく、かつ感光性乳剤中あるいは
水溶液中での経時安定性に優れた染料、ならびに
このような染料を含有するネガ型ハロゲン化銀写
真感光材料を提供することにある。
発明の構成
本発明者等は、種々検討を重ねた結果、上記の
目的は下記一般式〔〕で示される化合物が含有
されているネガ型ハロゲン化銀写真感光材料にお
いて達成し得ることを見出した。
一般式〔〕
式中、Ｇはメチル基、メトキシ基またはヒドロ
キシ基を表わし、R1はハメツトのσp値が−0.05
より小さい一価の基を表わし、R2は少くとも１
つのスルホ基を有するフエニル基を表わし、R3
は一価の基を表わし、ＸおよびＹは、それぞれ水
素原子、アルキル基または疎水性置換基定数πの
値の合計Σπが−4.70より大きい置換基を有するア
ルキル基を表わし、ＸとＹは互いに結合して５員
環または６員環を形成してもよい。Ｌはメチン基
を表わし、ｍは１、２、３または４の整数を表わ
し、ｎは１または２の整数を表わす。
以下、本発明を更に詳細に説明する。
本発明において、感光材料中に含有せしめられ
る染料は、前記一般式〔〕で示すことができる
が、該一般式〔〕においてR1で表わされるハ
メツトのσp値が−0.05より小さい一価の基として
は、好ましくは炭素原子数１〜４個の置換されて
いてもよい直鎖または分岐のアルキル基（例えば
メチル基、エチル基、ｎ−プロピル基、ｎ−ブチ
ル基、tert−ブチル基、カルボキシメチル基、２
−メトキシエチル基、２−ヒドロキシエチル基、
ベンジル基およびフエネチル基等）、シクロアル
キル基（例えばシクロヘキシル基）、ヒドロキシ
基、アルコキシ基（例えばメトキシ基、エトキシ
基、ｎ−ブトキシ基、２−メトキシエトキシ基、
エトキシメトキシ基、２−ヒドロキシエトキシ
基）、アミノ基（例えばアミノ基、メチルアミノ
基、ジメチルアミノ基、エチルアミノ基、ジエチ
ルアミノ基、アニリノ基）、ウレイド基（例えば
ウレイド基、メチルウレイド基、エチルウレイド
基）等を挙げることができる。上記ハメツトの
σp値については「薬物の構造活性相関」（南江
堂）第96頁、（1979年）に記載されており、この
表に基づいて置換基を選ぶことができる。さらに
は前記一般式〔〕において、R2が表わすスル
ホ基を有するフエニル基は、該スルホ基のほかに
他の置換基として、例えばハロゲン原子（フツ素
原子、塩素原子、臭素原子等）、ヒドロキシ基、
アルコキシ基（メトキシ基、エトキシ基、ｎ−プ
ロポキシ基等）、アリールオキシ基（フエノキシ
基等）、炭素原子数１〜４個のアルキル基（メチ
ル基、エチル基、ｎ−プロピル基、ｎ−ブチル基
等）、カルボキシル基、アルコキシカルボニル基
（メトキシカルボニル基、エトキシカルボニル基
等）、ニトロ基、アミノ基（例えばアミノ基、メ
チルアミノ基、ジエチルアミノ基、アニリノ基）、
シアノ基、アルキルスルホニル基（メチルスルホ
ニル基、エチルスルホニル基、ブチルスルホニル
基等）、アリールスルホニル基（フエニルスルホ
ニル基等）、カルバモイル基（カルバモイル基、
メチルカルバモイル基、エチルカルバモイル基
等）、スルフアモイル基（スルフアモイル基、メ
チルスルフアモイル基、エチルスルフアモイル基
等）、スルホンアミド基（メチルスルホンアミド
基、エチルスルホンアミド基等）、アシルアミノ
基（アセチルアミノ基、ベンゾイルアミノ基等）
を有していてもよい。これらの具体例としては例
えば３−スルホフエニル基、４−スルホフエニル
基、２−メチル−４−スルホフエニル基、２−ク
ロロ−４−スルホフエニル基、４−クロロ−３−
スルホフエニル基、２−クロロ−５−スルホフエ
ニル基、２−メトキシ−４−スルホフエニル基、
２−ヒドロキシ−４−スルホフエニル基、２，５
−ジクロロ−４−スルホフエニル基、２，６−ジ
メチル−４−スルホフエニル基、４−フエノキシ
−３−スルホフエニル基、２−クロロ−６−メチ
ル−４−スルホフエニル基、３−カルボキシ−２
−ヒドロキシ−５−スルホフエニル基、２，５−
ジスルホフエニル基、３，５−ジスルホフエニル
基等が挙げられる。
次にR3が表わす一価の基としては、炭素原子
数１〜４個のアルキル基（例えばメチル基、エチ
ル基、ｎ−ブチル基）、ハロゲン原子（例えばフ
ツ素原子、塩素原子、臭素原子）、ヒドロキシ基、
アルコキシ基（例えばメトキシ基、エトキシ基）、
ニトロ基、アミノ基（例えばアミノ基、エチルア
ミノ基、ジメチルアミノ基、アニリノ基）、アシ
ルアミノ基（アセチルアミノ基、ベンゾイルアミ
ノ基）、スルホンアミド基（例えばメチルスルホ
ンアミド）、カルボキシル基、シアノ基、スルホ
基、アルコキシカルボニル基（メトキシカルボニ
ル基、プロポキシカルボニル基等）、アルキルス
ルホニル基（メチルスルホニル基、エチルスルホ
ニル基等）、カルバモイル基（例えばカルバモイ
ル基、メチルカルバモイル基、エチルカルバモイ
ル基）、スルフアモイル基（例えばスルフアモイ
ル基、メチルスルフアモイル基、エチルスルフア
モイル基）、メルカプト基、アルキルチオ基（メ
チルチオ基、エチルチオ基等）を挙げることがで
きる。
またＸおよびＹがそれぞれ表わすアルキル基と
しては、炭素原子数１〜４個のアルキル基（例え
ばメチル基、エチル基、ｎ−プロピル基、ｎ−ブ
チル基、tert−ブチル基等）があり、また前記の
Σπが−4.70より大きい置換基を有するアルキル基
としては、例えばシアノアルキル基、ヒドロキシ
アルキル基、ハロゲン化アルキル基、カルボキシ
アルキル基、アルコキシカルボニルアルキル基、
アシルアルキル基、アシルオキシアルキル基、ア
ルコキシアルキル基、フエノキシアルキル基、ジ
アルキルアミノアルキル基、フエニルアミノアル
キル基、アセチルアミノアルキル基、アルキルス
ルホニルアミノアルキル基、アルキルスルホニル
アルキル基、アルキルチオアルキル基、アミノア
ルキル基、アラルキル基等を好ましく挙げること
ができる。そしてＸとＹは互いに同じでも異なつ
ていてもよく、さらにＸとＹが互いに結合して形
成する５員環または６員環としては、例えばピロ
リジノ環、ピペリジノ環、モルホリノ環等があ
る。
本発明においては、上記ＸおよびＹで表わされ
る置換基を有するアルキル基の置換基としては前
記のとおり、疎水性置換基定数πの値に合計Σπ
が−4.70より大きい置換基であることを特徴とす
る。すなわち、Ｘおよび／Ｙが、−Ｒ−X′およ
び／または−Ｒ−Y′（こゝでＲはアルキレン基
を、またX′、Y′はそれぞれ置換基を表わす）と
して表わされるとき、X′、Y′それぞれの疎水性
置換基定数πの和、Σπが−4.70より大きくなるよ
うに置換基X′、Y′が選択される。この疎水性置
換基定数πの値については、前述の刊行物の同上
頁に記載されていて、この表の記載に基づいて置
換基を選ぶことができる。
さらには前記一般式〔〕においてＬが表わす
メチン基は、炭素原子数１〜４個のアルキル基
（例えばメチル基、エチル基、ｎ−ブチル基等）
またはアリール基（例えばフエニル基）で置換さ
れていてもよい。
上記一般式〔〕で示される本発明に係わる染
料は、下記一般式〔〕で示されるアルデヒド化
合物と、下記一般式〔〕で示されるピラゾロン
化合物とを縮合させることにより合成することが
できる。
一般式〔〕
一般式〔〕
〔式中、R1、R2、R3、Ｘ、Ｙ、Ｇ、Ｌおよびｍ
は、前記一般式〔〕におけるものとそれぞれ同
義の基および数を表わす。ｐおよびｑは１または
２の整数を示す。但し前記一般式〔〕における
ｎとの間にはｎ＝ｐ＋ｑ−１なる関係にあるの
で、ｐとｑが同時に２であることはない。
上記の反応は塩基性縮合剤、例えば酢酸ソー
ダ、ピリジン、ピペリジン、トリエチルアミン等
の存在下に上記一般式〔〕と〔〕の混合物を
加熱させることにより行なわれる。また上記反応
は上記の塩基性縮合剤の存在下または非存在下
に、メタノール、エタノール、エチレングリコー
ル、メチルセルソルブ、アセトニトリル、ジメチ
ルスルホキシド、スルホラン、ジメチルホルムア
ミド、ジオキサン、酢酸、水の如き不活性溶媒中
においても行なうこともできる。
上記一般式〔〕で表わされるアルデヒド化合
物は、公知の方法で製造することができる。例え
ば一般式〔〕に於いてｐ＝１のアルデヒド化合
物は、ホルミル化剤としてジメチルホルムアミド
を用い、ビルスマイヤーとハツクの反応
（Berichte、第60巻119頁、1927年）によつて相当
する置換アニリンから作ることができる。一方、
ｐ＝２のアルデヒドは、Ｎ−メチルアニリノプロ
パン(1)−アル(3)及び適当なアニリンを用い、
Berichte、第91巻850頁（1958年）に記載されて
いる如く、ビルスマイヤー反応と同じ方法で作る
ことができる。またBerichte、第61巻2074頁
（1928年）に記載されている如く相当する置換ア
ミノベンズアルデヒドとパラアルデヒドとの反応
からも得られる。
一般式〔〕のｑ＝１で表わされるピラゾロン
化合物は、種々のスルホアリールヒドラジンを染
料化学で行われる既知の方法により適当な置換エ
ステル類と縮合させることによつて作ることがで
きる。一般式〔〕のｑ＝２で表わされる中間体
は、一般式〔〕のｑ＝１で表わされる生成物と
ジアルキルケトン、アルキルアリールケトンまた
は脂肪族アルデヒドの縮合によつて得ることがで
きる。
一般式〔〕で表わされるピラゾロン化合物
は、例えばOrganic Syntheses、第28巻87頁
（1948年）に記載の方法、J.Am.Chem.Soc. 第
66巻1849頁（1944年）記載の方法、J.Am.Chem.
Soc.、第65巻52頁（1943年）記載の方法、J.Am.
Chem.Soc. 第64巻2136頁（1942年）記載の方法
等を用いることにより得ることができる。以下に
本発明に係わる染料の代表的具体例を記載する。
（例示化合物）
次に、本発明に係わる染料の合成法について合
成例を示し、具体的に説明する。
合成例 １
（例示染料(2)の合成）
メタノール40ml中に、2.54ｇの３−メチル−１
−（４−スルホフエニル）−２−ピラゾリン−５−
オンと2.1ｇの４−ジエチルアミノ−２−メチル
ベンズアルデヒドを加え、更にピリジン1.6ｇを
加えて加熱還流下２時間反応させた。その後、蒸
留水10mlに溶解した無水酢酸カリウム2.0ｇを加
えて５分間還流を続けた。反応液を冷却し、析出
した結晶を取し、メタノール250mlから再結晶
して2.4ｇの上記例示染料を得た。この染料の水
溶液のλmaxは513nｍであつた。
合成例 ２
（例示染料(4)の合成）
メタノール20ml中に、1.27ｇの３−メチル−１
−（４−スルホフエニル）−２−ピラゾリン−５−
オンと1.0ｇの４−ジメチルアミノ−２−メトキ
シベンズアルデヒドを加え、更にピリジン0.8ｇ
を加えて加熱還流下２時間反応させた。その後、
蒸留水５mlに溶解した無水酢酸ナトリウム0.82ｇ
を加えて５分間還流を続けた。反応液を冷却し、
析出した結晶を取し、これを水とメタノール混
合溶媒から酢酸ナトリウムで塩析を行ない精製し
た。1.1ｇの上記例示染料が得られ、この染料の
水溶液中のλmaxは498nｍであつた。
合成例 ３
（示例染料(13)の合成）
メタノール40ml中に、3.06ｇの３−エトキシ−
１−（４−スルホフエニル）−２−ピラゾリン−５
−オンナトリウム塩と1.71ｇの４−ジメチルアミ
ノ−２−メチルベンズアルデヒドを加え、更にピ
リジン1.6ｇを加えて加熱還流下３時間反応させ
た。その後、蒸留水５mlに溶解した無水酢酸ナト
リウム0.82ｇを加えて５分間還流を続けた。反応
液を冷却し、析出した結晶を取し、メタノール
で充分に洗浄後、乾燥して4.32ｇの上記例示染料
を得た。
この染料の水溶液のλmaxは482nｍであつた。
上記により製造される本発明に係わる染料は、
前記一般式〔〕において示される通り、ベンジ
リデン基をオルト位に置換基Ｇとしてメチル基、
メトキシ基またはヒドロキシ基を有し、かつピラ
ゾロン環の３位にR1としてハメツトのσp値が−
0.05よりも小さい一価の基を有することを構造上
の特徴とするものであり、このため従来公知の染
料に比較して水溶液（酸性水溶液）中での安定性
が著しく改良されたほか、疎水性置換基常数πの
値が特定された値を有する置換基を有するアルキ
ル基を前記ＸおよびＹに導入することにより染料
の拡散性が防止され、さらには処理工程における
流出、脱色性にも優れ、従つて残色汚染を生ずる
こともなく、またスペクトル吸収特性も良好で写
真特性に悪影響を与えることもなく、写真性能の
優れた染料である。
本発明に係わる染料は、本発明の感光材料の乳
剤層および／または非感光性親水性コロイド層中
に含有せしめられて用いられる。
本発明の感光材料において、前記一般式〔〕
で表わされるオキソノール染料は、ハロゲン化銀
乳剤中に含有させて、イラジエーシヨン防止染料
として用いることもできるし、また非感光性の親
水性コロイド層中に含有させて、フイルター染料
或はハレーシヨン防止染料として用いることもで
きる。また、使用目的により２種以上の染料を組
合わせて用いてもよいし、本発明の効果が損われ
ない範囲で他の染料と組合わせて用いてもよい。
本発明に係わる染料をハロゲン化銀乳剤層中或
は、その他の非感光性親水性コロイド層中に含有
させるためには、通常の方法により容易に行なう
ことができる。一般には、染料または、染料の有
機・無機アルカリ塩を水に溶解し、適当な濃度の
染料水溶液とし、塗布液に添加して、公知の方法
で塗布を行ない感光材料中に染料を含有させるこ
とができる。これらの染料の含有量としては、使
用目的によつて異なるが、一般には感光材料上の
面積１m2あたり１〜800mgになるように塗布して
用いる。
本発明の感光材料における支持体としては、酢
酸セルロース、硝酸セルロース、例えばポリエチ
レンテレフタレート等のポリエステルフイルム、
例えばポリエチレン等のポリオレフインフイル
ム、ポリスチレンフイルム、ポリアミドフイル
ム、ポリカーボネートフイルム、バライタ紙、ポ
リオレフイン被覆紙、ポリプロピレン合成紙、ガ
ラス板、金属等があり、これらの支持体は、それ
ぞれ写真材料の使用目的に応じて、適宜選択され
る。
本発明の感光材料における親水性コロイドとし
ては、ゼラチン、フタル化ゼラチンやベンゼンス
ルホニル化ゼラチン等の誘導体ゼラチン、寒天や
カゼイン或はアルギン酸等の水溶性天然高分子、
ポリビニルアルコールやポリビニルピロリドン等
の合成樹脂、カルボキシメチルセルロース等のセ
ルロース誘導体等が挙げられ、これらは単独もし
くは組合わせて用いることができる。
本発明の感光材料におけるハロゲン化銀乳剤と
しては、塩化銀、臭化銀、沃化銀、塩臭化銀、沃
臭化銀、塩沃臭化銀などの通常ハロゲン化銀乳剤
に用いられる任意のものが包含される。
本発明の感光材料に用いられるハロゲン化銀乳
剤は、通常行なわれる製法をはじめ種々の製法、
例えば特公昭46−7772号公報に記載されている如
き方法、或は米国特許第2592250号に記載されて
いる如き方法、すなわち、溶解度が臭化銀よりも
大きい、少なくとも一部の銀塩からなる銀塩粒子
の乳剤を形成し、次いでこの粒子の少なくとも一
部を臭化銀塩または沃臭化銀塩に変換する等の所
謂コンパージヨン乳剤の製法、あるいは0.1μ以下
の平均粒径を有する微粒子状ハロゲン化銀からな
るリツプマン乳剤の製法等あらゆる製法によつて
作成することができる。このハロゲン化銀乳剤
は、化学増感剤、例えば、チオ硫酸塩、アリルチ
オカルバミド、チオ尿素、アリルイソチオシアネ
ート、シスチン等の硫黄増感剤、活性或は不活性
のセレン増感剤、カリウムクロロオーレート、オ
ーリツクトリクロライド、カリウムオーリツクチ
オシアネート、２−オーロチアベンズチアゾール
メチルクロライドなどのような金化合物、アンモ
ニウムクロロパラデート、ナトリウムクロロパラ
ダイトなどのようなパラジウム化合物、カリウム
クロロプラチネートのようなプラチニウム化合
物、ルテニウム化合物などのような貴金属増感剤
またはこのような増感剤の組合わせを用いて増感
することができる。また、この乳剤は、化学増感
以外にも還元剤で還元増感することができ、トリ
アゾール類、イミダゾール類、アザインデン類、
ベンズチアゾリウム化合物、亜鉛化合物、カドミ
ウム化合物、メルカプタン類またはこれらの混合
物で安定化することができ、また、チオエーテル
型、第４級アンモニウム塩型または、ポリアルキ
レンオキサイド型の増感化合物を含有させること
ができる。
本発明の感光材料に用いられる写真乳剤は、必
要に応じて増感色素によつて分光増感されてよ
い。増感色素としては、シアニン色素、メロシア
ニン色素、コンプレツクスシアニン色素、オキソ
ノール色素、ヘミオキソノール色素、スチリル色
素、メロスチリル色素、ストレプトシアニン色素
等の種々のものを用いることができ、またそれぞ
れ、増感色素を１種或は２種以上組合わせて用い
ることができる。
本発明の感光材料において、ハロゲン化銀乳剤
層およびその他の非感光性親水性コロイド層中
に、グリセリン、１，５−ペンタンジオール等の
ジヒドロキシアルカン、エチレンビスグリコール
酸のエステル、ビスエトキシジエチレングリコー
ルサクシネート、乳化重合によつて得られる水分
散性の微粒子状高分子化合物等の湿潤剤、可塑
剤、膜物性改良剤等を含有させることができ、ま
た、アルデヒド化合物、Ｎ，N′−ジメチロール
尿素等のＮ−メチロール化合物、ムコハロゲン
酸、ジビニルスルホン類、２，４−ジクロル−６
−ヒドロキシ−Ｓ−トリアジン等の活性ハロゲン
化合物、ジオキサン誘導体、ジビニルケトン類、
イソシアネート類、カルボジイミド類等の硬膜剤
やサポニン、ポリアルキレングリコール、ポリア
ルキレングリコールエーテル、アルキルスルホン
酸塩、アルキルベンゼンスルホン酸塩、アルキル
ナフタレンスルホン酸塩等の界面活性剤、さら
に、蛍光増白剤、帯電防止剤、アンチステイン
剤、紫外線吸収剤、安定剤等の写真用添加剤を含
有させることができる。
本発明の感光材料において、ハロゲン化銀乳剤
層中に、カラーカプラーを含有してもよく、カプ
ラーとしては４当量もしくは２当量性のいずれで
もよく、マスキング用のカラードカプラーや現像
抑制剤を放出するカプラーであつてもよい。黄色
形成カプラーとしては、アシルアセトアミド系な
どの開鎖ケトメチレン系化合物、マゼンタ形成カ
プラーとしてはピラゾロン系化合物、シアン形成
カプラーとしてはフエノール系またはナフトール
系化合物が通常有利に用いられている。
また本発明の感光材料は通常の感光材料のとり
うるあらゆる層構成をとることができる。
次に、実施例により本発明を具体的に説明する
が、本発明がこれらによつて限定されるものでは
ない。
実施例 １
本発明に係わる例示染料(2)の2.0×10-5モル／
水溶液100mlに、氷酢酸0.5mlを加えて撹拌し、
分解速度測定液（PH2.8〜2.9）を調整した。分光
光度計により、この溶液の極大吸収波長での吸光
度の減少を時間経過（10分ごとに１時間）ととも
に測定し、初期分解速度を求めた。同様にして例
示染料(7)、(16)、(19)および（23）ならびに下記の比
較染料(A)、(B)、(C)、(D)および(E)についても測定を
行なつた。得られた結果を下記第１表に示す。
比較染料(A)
比較染料(B)
比較染料(C)
比較染料(D)
比較染料(E)
Industrial Application Field The present invention can be used in photographic technology, particularly in manufacturing technology for photographic light-sensitive materials. The present invention relates to a silver halide photographic material,
More specifically, the present invention relates to a silver halide photographic material having a hydrophilic colloid layer colored with a novel light-absorbing dye and having improved residual color staining after processing. Prior Art In general, silver halide photographic materials (hereinafter referred to as "photosensitive materials") use light absorption filters,
It is well known that for the purpose of preventing halation, preventing irradiation, or adjusting the sensitivity of a photosensitive emulsion, dyes are incorporated into the constituent layers of photosensitive materials in order to absorb light of a specific wavelength. Coloring of hydrophilic colloid layers has been conventionally carried out. Among the constituent layers of the above-mentioned light-sensitive material, the filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and converts incident light reaching the emulsion layer into light having a preferable spectral composition. It plays the role of changing the Regarding the antihalation layer, in order to improve the sharpness of images, an antihalation layer is provided between the light-sensitive emulsion layer and the support, or on the back side of the support, so that the emulsion layer and the support are separated. It improves image sharpness by absorbing harmful reflected light from the interface and the back surface of the support. Furthermore, the sharpness of images is improved by coloring the photosensitive emulsion layer using a dye to absorb harmful reflected light and scattered light to silver halide grains, thereby preventing irradiation. It is also often done. Dyes used for such various purposes need to have good absorption spectrum characteristics depending on the purpose of use, but also dyes that are completely decolorized during the development process and easily eluted from the photosensitive material during the development process. After processing, there is no residual color staining caused by dyes, and there are no other negative effects such as fogging or desensitization on photosensitive emulsions.
In addition, it must not diffuse from the colored layer to other layers, and it must also have excellent stability over time in photosensitive materials or aqueous solutions, and must meet various conditions such as not causing discoloration or fading. Must be. To date, many studies have been carried out with the aim of developing dyes that satisfy the above conditions, such as US Pat. No. 3,540,887, US Pat.
Benzylidene dyes were proposed in British Patent No. 506385 and Japanese Patent Publication No. 39-22069.
No. 2493747 proposes oxonol dyes, US Patent No. 2493747 proposes merocyanine dyes, and US Patent No. 1845404 proposes styryl dyes. However, the present situation is that a dye that satisfies the above conditions has not yet been found. Purpose of the Invention Therefore, the purpose of the present invention is to have optimal absorption spectrum characteristics, completely decolorize during development processing,
Dyes with extremely little residual color staining after processing, little diffusion to other layers, and excellent stability over time in photosensitive emulsions or aqueous solutions, as well as negative-working silver halide containing such dyes. Our objective is to provide photographic materials. Structure of the Invention As a result of various studies, the present inventors have found that the above object can be achieved in a negative-working silver halide photographic material containing a compound represented by the following general formula []. . General formula [] In the formula, G represents a methyl group, a methoxy group, or a hydroxy group, and R 1 is a sigma whose σp value is −0.05.
represents a smaller monovalent group, R 2 is at least 1
represents a phenyl group having two sulfo groups, R 3
represents a monovalent group, X and Y each represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent for which the sum of the values of hydrophobic substituent constant π is larger than -4.70, They may be combined to form a 5- or 6-membered ring. L represents a methine group, m represents an integer of 1, 2, 3 or 4, and n represents an integer of 1 or 2. The present invention will be explained in more detail below. In the present invention, the dye contained in the photosensitive material can be represented by the above general formula [], and in the general formula [], the monovalent group represented by R 1 has a σp value of less than -0.05. is preferably an optionally substituted linear or branched alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, carboxy Methyl group, 2
-methoxyethyl group, 2-hydroxyethyl group,
benzyl group, phenethyl group, etc.), cycloalkyl group (e.g. cyclohexyl group), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, n-butoxy group, 2-methoxyethoxy group,
ethoxymethoxy group, 2-hydroxyethoxy group), amino group (e.g. amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, anilino group), ureido group (e.g. ureido group, methylureido group, ethylureido group) (Group) etc. The above Hammett's σp value is described in "Structure-Activity Relationship of Drugs" (Nankodo), p. 96 (1979), and substituents can be selected based on this table. Furthermore, in the above general formula [], the phenyl group having a sulfo group represented by R 2 may have other substituents in addition to the sulfo group, such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.), hydroxy basis,
Alkoxy groups (methoxy, ethoxy, n-propoxy, etc.), aryloxy groups (phenoxy, etc.), alkyl groups with 1 to 4 carbon atoms (methyl, ethyl, n-propyl, n-butyl) groups), carboxyl groups, alkoxycarbonyl groups (methoxycarbonyl groups, ethoxycarbonyl groups, etc.), nitro groups, amino groups (e.g. amino groups, methylamino groups, diethylamino groups, anilino groups),
Cyano group, alkylsulfonyl group (methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, etc.), carbamoyl group (carbamoyl group,
methylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, etc.), sulfonamide group (methylsulfonamide group, ethylsulfonamide group, etc.), acylamino group (acetyl amino group, benzoylamino group, etc.)
It may have. Specific examples of these include 3-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4-sulfophenyl group, 4-chloro-3-
Sulfophenyl group, 2-chloro-5-sulfophenyl group, 2-methoxy-4-sulfophenyl group,
2-hydroxy-4-sulfophenyl group, 2,5
-dichloro-4-sulfophenyl group, 2,6-dimethyl-4-sulfophenyl group, 4-phenoxy-3-sulfophenyl group, 2-chloro-6-methyl-4-sulfophenyl group, 3-carboxy-2
-hydroxy-5-sulfophenyl group, 2,5-
Examples include disulfophenyl group and 3,5-disulfophenyl group. Next, monovalent groups represented by R3 include alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-butyl group), halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom). ), hydroxy group,
alkoxy group (e.g. methoxy group, ethoxy group),
Nitro group, amino group (e.g. amino group, ethylamino group, dimethylamino group, anilino group), acylamino group (acetylamino group, benzoylamino group), sulfonamide group (e.g. methylsulfonamide), carboxyl group, cyano group, Sulfo group, alkoxycarbonyl group (methoxycarbonyl group, propoxycarbonyl group, etc.), alkylsulfonyl group (methylsulfonyl group, ethylsulfonyl group, etc.), carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group), sulfamoyl group ( Examples include sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group), mercapto group, and alkylthio group (methylthio group, ethylthio group, etc.). The alkyl groups represented by X and Y include alkyl groups having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, etc.), and Examples of the alkyl group having a substituent with a Σπ larger than −4.70 include a cyanoalkyl group, a hydroxyalkyl group, a halogenated alkyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group,
Acylalkyl group, acyloxyalkyl group, alkoxyalkyl group, phenoxyalkyl group, dialkylaminoalkyl group, phenylaminoalkyl group, acetylaminoalkyl group, alkylsulfonylaminoalkyl group, alkylsulfonylalkyl group, alkylthioalkyl group, amino Preferred examples include alkyl groups and aralkyl groups. Further, X and Y may be the same or different from each other, and examples of the 5- or 6-membered ring formed by combining X and Y with each other include a pyrrolidino ring, a piperidino ring, and a morpholino ring. In the present invention, as described above, the substituents of the alkyl group having the substituents represented by X and Y are added to the value of the hydrophobic substituent constant π.
is a substituent that is larger than −4.70. That is, when X and /Y are represented as -R-X' and/or -R-Y' (where R represents an alkylene group, and X' and Y' each represent a substituent), Substituents X′ and Y′ are selected such that the sum of the hydrophobic substituent constants π of each of ′ and Y′, Σπ, is greater than −4.70. The value of this hydrophobic substituent constant π is described on the same page of the above-mentioned publication, and the substituent can be selected based on the description in this table. Furthermore, the methine group represented by L in the above general formula [] is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, etc.)
Alternatively, it may be substituted with an aryl group (for example, a phenyl group). The dye according to the present invention represented by the above general formula [] can be synthesized by condensing an aldehyde compound represented by the following general formula [] and a pyrazolone compound represented by the following general formula []. General formula [] General formula [] [In the formula, R 1 , R 2 , R 3 , X, Y, G, L and m
represent the same groups and numbers as in the above general formula []. p and q represent an integer of 1 or 2. However, since the relationship with n in the general formula [] is n=p+q-1, p and q cannot be 2 at the same time. The above reaction is carried out by heating a mixture of the above general formulas [] and [] in the presence of a basic condensing agent such as sodium acetate, pyridine, piperidine, triethylamine, etc. The above reaction may be carried out in an inert solvent such as methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane, acetic acid, or water in the presence or absence of the above basic condensing agent. It can also be done inside. The aldehyde compound represented by the above general formula [] can be produced by a known method. For example, an aldehyde compound with p=1 in the general formula [] can be prepared by using dimethylformamide as a formylating agent and using the reaction of Vilsmeier and Hack (Berichte, Vol. 60, p. 119, 1927) to produce the corresponding substituted aniline. It can be made from. on the other hand,
The aldehyde with p=2 is prepared using N-methylanilinopropane(1)-al(3) and the appropriate aniline,
It can be produced in the same manner as the Vilsmeier reaction, as described in Berichte, Vol. 91, p. 850 (1958). It can also be obtained from the reaction of the corresponding substituted aminobenzaldehyde with paraldehyde as described in Berichte, Vol. 61, p. 2074 (1928). Pyrazolone compounds represented by the general formula [] where q=1 can be prepared by condensing various sulfoarylhydrazines with appropriate substituted esters by known methods practiced in dye chemistry. The intermediate represented by q=2 in the general formula [] can be obtained by condensation of the product represented by the general formula [] with q=1 and a dialkyl ketone, alkylaryl ketone or aliphatic aldehyde. The pyrazolone compound represented by the general formula [] can be prepared, for example, by the method described in Organic Syntheses, Vol. 28, p. 87 (1948), J.Am.Chem.Soc.
66, p. 1849 (1944), J.Am.Chem.
Soc., Vol. 65, p. 52 (1943), J.Am.
It can be obtained by using the method described in Chem.Soc., Vol. 64, p. 2136 (1942). Typical specific examples of the dyes according to the present invention are described below. (Exemplary compound) Next, a method for synthesizing a dye according to the present invention will be specifically explained by showing a synthesis example. Synthesis Example 1 (Synthesis of Exemplary Dye (2)) 2.54g of 3-methyl-1 in 40ml of methanol
-(4-sulfophenyl)-2-pyrazoline-5-
2.1 g of 4-diethylamino-2-methylbenzaldehyde were added to the mixture, followed by 1.6 g of pyridine, and the mixture was reacted under heating under reflux for 2 hours. Thereafter, 2.0 g of anhydrous potassium acetate dissolved in 10 ml of distilled water was added, and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected and recrystallized from 250 ml of methanol to obtain 2.4 g of the above exemplary dye. The λmax of the aqueous solution of this dye was 513 nm. Synthesis Example 2 (Synthesis of Exemplary Dye (4)) 1.27g of 3-methyl-1 in 20ml of methanol
-(4-sulfophenyl)-2-pyrazoline-5-
Add 1.0g of 4-dimethylamino-2-methoxybenzaldehyde and 0.8g of pyridine.
was added and reacted for 2 hours under heating under reflux. after that,
0.82 g of anhydrous sodium acetate dissolved in 5 ml of distilled water
was added and reflux was continued for 5 minutes. Cool the reaction solution,
The precipitated crystals were collected and purified by salting out with sodium acetate from a mixed solvent of water and methanol. 1.1 g of the above exemplary dye was obtained, and the λmax of this dye in aqueous solution was 498 nm. Synthesis Example 3 (Synthesis of Exemplary Dye (13)) In 40 ml of methanol, 3.06 g of 3-ethoxy-
1-(4-sulfophenyl)-2-pyrazoline-5
-one sodium salt and 1.71 g of 4-dimethylamino-2-methylbenzaldehyde were added, followed by 1.6 g of pyridine, and the mixture was reacted under heating under reflux for 3 hours. Thereafter, 0.82 g of anhydrous sodium acetate dissolved in 5 ml of distilled water was added, and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected, thoroughly washed with methanol, and then dried to obtain 4.32 g of the above exemplary dye. The λmax of the aqueous solution of this dye was 482 nm. The dye according to the present invention produced by the above method is
As shown in the above general formula [], a methyl group as a substituent G at the ortho position of a benzylidene group,
It has a methoxy group or a hydroxy group, and R1 is set at the 3-position of the pyrazolone ring, and the σp value of the
It has a structural feature of having a monovalent group smaller than 0.05, and because of this, it has significantly improved stability in aqueous solutions (acidic aqueous solutions) compared to conventionally known dyes, and has a hydrophobic property. By introducing an alkyl group having a substituent having a specified value of the sex substituent constant π into the above X and Y, the diffusibility of the dye is prevented, and furthermore, it has excellent run-off and decolorization properties in the treatment process. Therefore, it is a dye with excellent photographic performance, without causing residual color staining, and with good spectral absorption characteristics and without adversely affecting photographic properties. The dye according to the present invention is used by being contained in the emulsion layer and/or the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention. In the photosensitive material of the present invention, the general formula []
The oxonol dye represented by can be used as an anti-irradiation dye by being included in a silver halide emulsion, or can be used as a filter dye or an anti-halation dye by being included in a non-photosensitive hydrophilic colloid layer. It can also be used. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes as long as the effects of the present invention are not impaired.
The dye according to the present invention can be easily incorporated into a silver halide emulsion layer or other non-photosensitive hydrophilic colloid layer by a conventional method. In general, a dye or an organic or inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. I can do it. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1 to 800 mg per square meter of area on the photosensitive material. Supports in the photosensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate,
Examples include polyolefin film such as polyethylene, polystyrene film, polyamide film, polycarbonate film, baryta paper, polyolefin coated paper, polypropylene synthetic paper, glass plate, metal, etc. These supports are used depending on the intended use of the photographic material. , is selected as appropriate. Hydrophilic colloids in the photosensitive material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid;
Examples include synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose derivatives such as carboxymethyl cellulose, and these can be used alone or in combination. The silver halide emulsion in the light-sensitive material of the present invention may be any of the silver halide emulsions normally used for silver halide emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. are included. The silver halide emulsion used in the light-sensitive material of the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, the method described in Japanese Patent Publication No. 46-7772 or the method described in U.S. Pat. A method for producing a so-called compound emulsion, such as forming an emulsion of silver salt grains and then converting at least a part of the grains into silver bromide salt or silver iodobromide salt, or fine grains having an average grain size of 0.1μ or less It can be produced by any production method such as the production method of Lippmann emulsion made of silver halide. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloride sensitizers, etc. Gold compounds such as aurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc., palladium compounds such as ammonium chloroparadate, sodium chloropalladite, etc., potassium chloroplatinate, etc. Noble metal sensitizers such as platinium compounds, ruthenium compounds, etc. or combinations of such sensitizers can be used for sensitization. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes,
It can be stabilized with a benzthiazolium compound, a zinc compound, a cadmium compound, a mercaptan, or a mixture thereof, and also contains a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound. be able to. The photographic emulsion used in the light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. Various sensitizing dyes can be used, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, and streptocyanine dyes. One type of dye or a combination of two or more types can be used. In the light-sensitive material of the present invention, glycerin, dihydroxyalkane such as 1,5-pentanediol, ester of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate is contained in the silver halide emulsion layer and other non-photosensitive hydrophilic colloid layers. , a wetting agent such as a water-dispersible particulate polymer compound obtained by emulsion polymerization, a plasticizer, a film property improver, etc., and an aldehyde compound, N,N'-dimethylol urea, etc. N-methylol compounds, mucohalogenic acids, divinyl sulfones, 2,4-dichloro-6
Active halogen compounds such as -hydroxy-S-triazine, dioxane derivatives, divinyl ketones,
Hardening agents such as isocyanates and carbodiimides, surfactants such as saponins, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates, and optical brighteners, Photographic additives such as antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers can be included. In the light-sensitive material of the present invention, a color coupler may be contained in the silver halide emulsion layer, and the coupler may be either 4-equivalent or 2-equivalent, and may release a colored coupler for masking or a development inhibitor. It may also be a coupler. As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenolic or naphthol-based compounds are usually advantageously used. Furthermore, the photosensitive material of the present invention can have any layer structure that can be used in conventional photosensitive materials. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 2.0×10 -5 mol/of exemplary dye (2) according to the present invention
Add 0.5ml of glacial acetic acid to 100ml of aqueous solution and stir.
A solution for measuring decomposition rate (PH2.8-2.9) was prepared. Using a spectrophotometer, the decrease in absorbance at the maximum absorption wavelength of this solution was measured over time (every 10 minutes for 1 hour) to determine the initial decomposition rate. Measurements were also made in the same manner for exemplified dyes (7), (16), (19) and (23) and the following comparative dyes (A), (B), (C), (D) and (E). Ta. The results obtained are shown in Table 1 below. Comparative dye (A) Comparative dye (B) Comparative dye (C) Comparative dye (D) Comparative dye (E)
【表】
上記第１表の結果から、本発明に係わる染料
は、水溶液（酸性水溶液）中での分解が改良さ
れ、著るしく安定性が優れていることがわかる。
これに対して前記一般式〔〕の構造を満足せし
めない本発明外の比較染料では水溶液中での分解
が著るしいことも示された。また比較染料(E)のよ
うに、ベンジリデン基のオルト位にメチル基を有
していてもピラゾロン環の１位がアルキル基で置
換されたものは同様に保存安定性に劣つているこ
とも明らかにされた。
実施例 ２
蒸留水35mlにゼラチン3.5ｇを加えて溶解し、
これに、本発明に係る例示染料(1)、(4)および(19)を
それぞれ2.0×10-4モル含む５mlの水溶液を加え、
さらに10％のサポニン水溶液1.25mlと１％ホルマ
リン溶液0.75mlを添加し、水を加えて全量を50ml
とした。この染料溶液をアセチルセルロースフイ
ルム支持体上に塗布し、乾燥して、試料〔１〕
〔２〕および〔３〕とした。また、本発明に係る
染料にかえて、下記の比較染料(F)および(G)を用い
て、同様の方法で比較試料〔４〕および〔５〕を
作成した。
比較染料(F)
比較染料(G)
これらの各試料を下記組成の現像液に25℃で１
分間浸漬し、20秒間水洗した後、乾燥した。
（現像液の組成）
メトール 3.0ｇ
亜硫酸ナトリウム（無水） 45.0ｇ
ハイドロキノン 12.0ｇ
炭酸ナトリウム（１水塩） 80.0ｇ
臭化カリウム 2.0ｇ
水を加えて１とする。
現像液浸漬前、浸漬後の各試料の可視スペクト
ルを測定し、吸収極大波長における吸光度の差か
ら脱色率を求めた。その結果を下記第２表に示
す。
脱色率＝E1−E2／E1×100（％）
（E1は、現像液浸漬前の吸光度であり、E2は現
像液浸漬後の吸光度を表わす。）[Table] From the results in Table 1 above, it can be seen that the dye according to the present invention has improved decomposition in an aqueous solution (acidic aqueous solution) and has significantly excellent stability.
On the other hand, it was also shown that comparative dyes other than the present invention which do not satisfy the structure of the general formula [] are significantly decomposed in aqueous solutions. It is also clear that even if the comparative dye (E) has a methyl group at the ortho position of the benzylidene group, the 1st position of the pyrazolone ring is substituted with an alkyl group, which similarly has poor storage stability. was made into Example 2 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
To this, 5 ml of an aqueous solution containing 2.0 x 10 -4 mol each of exemplary dyes (1), (4) and (19) according to the present invention was added,
Add 1.25 ml of 10% saponin solution and 0.75 ml of 1% formalin solution, and add water to bring the total volume to 50 ml.
And so. This dye solution was applied onto an acetyl cellulose film support, dried, and sample [1]
[2] and [3]. Comparative samples [4] and [5] were also prepared in the same manner using the following comparative dyes (F) and (G) instead of the dye according to the present invention. Comparative dye (F) Comparative dye (G) Each of these samples was added to a developer with the following composition at 25°C.
After soaking for 20 minutes, washing with water for 20 seconds, and drying. (Composition of developer) Metol 3.0g Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 80.0g Potassium bromide 2.0g Add water to make 1. The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 2 below. Decolorization rate = E 1 - E 2 / E 1 × 100 (%) (E 1 is the absorbance before immersion in the developer, and E 2 is the absorbance after immersion in the developer.)
【表】
第２表から明らかなように、本発明に係わる染
料は比較染料に比較して優れた脱色性を示すこと
がわかつた。本発明外の試料５の比較染料(G)は、
前記一般式〔〕においてベンジリデン基のオル
ト位にペンチルオキシ基を有する染料であり、ベ
ンジリデン基のオルト位にメトキシ基を有する本
発明に係わる染料とは区別され、脱色性において
劣つていることがわかる。
実施例 ３
塩化銀80モル％と臭化銀19.5モル％および沃化
銀0.5モル％から成り、粒子の平均粒径が0.32μの
塩沃臭化銀ゼラチン乳剤を調整した。このゼラチ
ン乳剤１Kg（銀48ｇ、ゼラチン75ｇを含む。）当
り、２，４−ジクロロ−６−ヒドロキシ−１，
３，５−トリアジンナトリウム塩（１％水溶液）
35mlとサポニン（10％水溶液）50mlを添加した
後、下引き処理されたポリエチレンテレフタレー
トフイルム支持体上に、100cm2当り銀が50mg含ま
れるように塗布し乾燥した。
さらにこの乳剤層の上に本発明に係わる例示染
料(2)を含む下記の組成の保護層を乾燥膜厚が2μ
ｍになるように塗布した。（試料６とする）
（保護層組成）
ゼラチン 40ｇ
水 850ml
本発明に係わる例示染料(2)
（２％水溶液） 100ml
２，４−ジクロロ−６−ヒドロキシ−１，３，
５−トリアジンナトリウム塩（１％水溶液）
20ml
サポニン（10％水溶液） 30ml
同様にして本発明に係わる例示染料(2)に代え
て、本発明に係わる例示染料(5)および(10)ならびに
実施例２で用いた比較染料(F)および(G)をそれぞれ
含む試料を作成し、それぞれ試料７、８、９およ
び10とした。
これらの各試料を小片に断裁し、写真光楔を介
して露光し、下記組成の現像液および定着液を用
いて、処理した。現像は20℃で1.5分間行ない、
定着は20℃で２分間行ない、水洗は20℃で５分間
行なつた後乾燥した。
（現像液の組成）
ハイドロキノン 15ｇ
ホルムアルデヒド亜硫酸水素ナトリウム付加物
55ｇ
無水亜硫酸ナトリウム ３ｇ
炭酸ナトリウム（一水塩） 80ｇ
硼 酸 ５ｇ
臭化カリウム 2.5ｇ
エチレンジアミン四酢酸二ナトリウム ２ｇ
水を加えて 1000ml
（定着液の組成）
チオ硫酸ナトリウム 160ｇ
無水亜硫酸ナトリウム 14ｇ
氷酢酸 12ml
ホウ砂 12ｇ
カリ明ばん ５ｇ
水を加えて 1000ml
現像処理した各試料をそれぞれ10枚ずつ重ねあ
わせ、試料上の着色汚染の有無を調べた。得られ
た結果を下記第３表に示す。[Table] As is clear from Table 2, it was found that the dyes according to the present invention exhibited superior decolorizing properties compared to the comparative dyes. The comparative dye (G) of sample 5 outside the present invention is:
It is a dye having a pentyloxy group at the ortho position of the benzylidene group in the general formula [], and is distinguished from the dye according to the present invention having a methoxy group at the ortho position of the benzylidene group, and is found to be inferior in decolorizing property. . Example 3 A silver chloroiodobromide gelatin emulsion containing 80 mol % of silver chloride, 19.5 mol % of silver bromide and 0.5 mol % of silver iodide and having an average grain size of 0.32 μm was prepared. 2,4-dichloro-6-hydroxy-1, 2,4-dichloro-6-hydroxy-1,
3,5-triazine sodium salt (1% aqueous solution)
After adding 35 ml and 50 ml of saponin (10% aqueous solution), it was coated on a subbed-treated polyethylene terephthalate film support so that 50 mg of silver was contained per 100 cm 2 and dried. Further, on this emulsion layer, a protective layer containing the exemplary dye (2) according to the present invention and having the following composition was applied to a dry film thickness of 2 μm.
It was applied so that the thickness was m. (Protective layer composition) Gelatin 40g Water 850ml Exemplary dye (2) according to the present invention (2% aqueous solution) 100ml 2,4-dichloro-6-hydroxy-1,3,
5-triazine sodium salt (1% aqueous solution)
20ml Saponin (10% aqueous solution) 30ml Similarly, instead of the exemplary dye (2) according to the present invention, exemplary dyes (5) and (10) according to the present invention and the comparative dye (F) used in Example 2 and Samples containing (G) were prepared and designated as samples 7, 8, 9, and 10, respectively. Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using a developer and fixer having the following compositions. Development was performed at 20℃ for 1.5 minutes.
Fixing was carried out at 20°C for 2 minutes, water washing was carried out at 20°C for 5 minutes, and then dried. (Developer composition) Hydroquinone 15g Formaldehyde sodium bisulfite adduct
55g Anhydrous sodium sulfite 3g Sodium carbonate (monohydrate) 80g Boric acid 5g Potassium bromide 2.5g Disodium ethylenediaminetetraacetate 2g Add water 1000ml (Fixer composition) Sodium thiosulfate 160g Anhydrous sodium sulfite 14g Glacial acetic acid 12ml Add 12 g of sand, 5 g of potash alum, and 1000 ml of water. Ten sheets of each developed sample were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 3 below.
【表】
比較染料を用いた試料では、試料に着色汚染が
みられたが、本発明に係わる染料では、流出、脱
色性に優れまつたく着色汚染がなかつた。
実施例 ４
塩化銀70モル％と臭化銀30モル％から成り、粒
子の平均粒径が0.3μｍの塩臭化銀ゼラチン乳剤を
調整した。このゼラチン乳剤１Kg（銀48ｇ、ゼラ
チン75ｇを含む）当り、ホルマリン（１％水溶
液）20mlとサポニン（10％水溶液）50mlを添加し
た後、下引き処理したポリエチレンテレフタレー
トフイルム支持体上に塗布し、さらにこの乳剤層
の上に下記の組成の保護層を塗布した。
（保護層組成）
ゼラチン 40ｇ
水 960ml
ホルマリン（１％水溶液）12ml 12ml
サポニン（10％水溶液） 30ml
次に、乳剤層および保護層を塗布した支持体の
裏面に下記の組成の染料を含有するゼラチン層を
乾燥膜厚が3μｍになるように塗布した。（試料11
とする）
（セラチン層組成）
ゼラチン 50ｇ
水 835ml
発明に係わる例示染料(3)（２％水溶液） 100ml
ホルマリン（１％水溶液） 15ml
サポニン（10％水溶液） 50ml
同様にして、本発明に係わる例示染料(3)にかえ
て、本発明に係わる例示染料（25）および下記の
比較染料(H)を用いて、試料を作成し、試料(12)およ
び(13)とした。
比較染料(H)
前記実施例３と同様の方法で現像処理をし、各
試料10枚ずつを重ねあわせて着色汚染の評価をし
た。得られた結果を下記第４表に示す。[Table] In the samples using comparative dyes, colored stains were observed in the samples, but with the dyes according to the present invention, there was no colored staining due to excellent run-off and decoloring properties. Example 4 A silver chlorobromide gelatin emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having grains having an average particle size of 0.3 μm was prepared. After adding 20 ml of formalin (1% aqueous solution) and 50 ml of saponin (10% aqueous solution) per 1 kg of this gelatin emulsion (containing 48 g of silver and 75 g of gelatin), it was coated on a subbed-treated polyethylene terephthalate film support, and then A protective layer having the following composition was coated on this emulsion layer. (Protective layer composition) Gelatin 40 g Water 960 ml Formalin (1% aqueous solution) 12 ml Saponin (10% aqueous solution) 30 ml Next, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye with the following composition is applied. was applied to a dry film thickness of 3 μm. (Sample 11
) (Seratin layer composition) Gelatin 50g Water 835ml Exemplary dye according to the invention (3) (2% aqueous solution) 100ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml Similarly, exemplary dye according to the invention Instead of (3), samples were prepared using the exemplary dye (25) according to the present invention and the following comparative dye (H), and designated as samples (12) and (13). Comparative dye (H) Development was performed in the same manner as in Example 3, and 10 sheets of each sample were stacked one on top of the other to evaluate color staining. The results obtained are shown in Table 4 below.
【表】
上記表が示すように比較染料を用いた試料で
は、試料に着色汚染がみられたが、本発明に係わ
る染料ではまつたく着色汚染がみられなかつた。
また、本発明に係わる染料は写真乳剤に対してカ
ブリ、減感等の悪影響を及ぼすことなく、優れた
ハレーシヨン防止効果を有する感光材料を得るこ
とができることがわかつた。
実施例 ５
ポリエチレンテレフタレートフイルム支持体上
に、第１層として下記染料を含有する下記組成の
ゼラチン液を乾燥膜厚2μｍとなるように塗布し
た。
（ゼラチン液組成）
ゼラチン 40ｇ
水 900ml
ポリ−（２−ジエチルアミノエチルアクリレー
ト）（５％水溶液） 120ml
本発明に係わる例示染料(3) （２％水溶液）
80ml
２，４−ジクロロ−６−ヒドロキシ−１，３，
５−トリアジンナトリウム塩（１％水溶液）
20ml
サポニン（10％水溶液） 30ml
次に、臭化銀96モル％と沃化銀４モル％から
なり、粒子の平均粒径が0.8μｍの沃臭化銀ゼラ
チン乳剤に、ゼラチン乳剤１Kg当り、２，４−
ジクロロ−６−ヒドロキシ−１，３，５−トリ
アジンナトリウム塩（１％水溶液）20mlとドデ
シルベンゼンスルホン酸ナトリウム（１％水溶
液）20mlとを添加し、乾燥膜厚が5μｍとなる
ように第２層を塗布した。
さらにこの乳剤層の上に保護層として下記の
組成のゼラチン液を乾燥膜厚が2μｍとなるよ
うに塗布し、試料(14)を調製した。
（ゼラチン液組成）
ゼラチン 20ｇ
水 940ml
２，４−ジクロロ−６−ヒドロキシ−１，３，
５−トリアジンナトリウム塩（１％水溶液）
10ml
ドデシルベンゼンスルホン酸ナトリウム（１％
水溶液） 50ml
同様にして、第１層における前記例示染料(3)に
かえて、本発明に係わる例示染料(10)および(16)なら
びに下記の比較染料(I)、(J)および(K)を用いて試料
を作成した。また同時に染料を含まない試料をも
作成し、これらの試料をそれぞれ順に試料(15)、
(16)、(17)、(18)、(19)および(20)とした。
比較染料(I)
比較染料(J)
比較染料(K)
上記の各試料を小片に断裁し、写真光楔を介し
て露光し、下記組成の現像液および実施例３で使
用した定着液を用いて処理した。現像は25℃で２
分間行ない、定着は25℃で２分間行ない、また水
洗は25℃で５分間行なつた後、乾燥した。
（現像液組成）
フエニドン 0.5ｇ
無水亜硫酸ナトリウム 50ｇ
ハイドロキノン 12ｇ
無水炭酸ナトリウム 60ｇ
臭化カリウム ２ｇ
ベンゾトリアゾール 0.2ｇ
水を加えて 1000ml
現像処理後、センシトメトリーを行ない特性曲
線を求め、染料を含まない試料(20)の感度を100と
して相対感度を求めた。得られた結果を下記第５
表に示す。[Table] As shown in the above table, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes according to the present invention.
Furthermore, it has been found that the dye according to the present invention can provide a photographic material having an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on the photographic emulsion. Example 5 On a polyethylene terephthalate film support, a gelatin solution containing the following dye and having the composition shown below was coated as a first layer to a dry film thickness of 2 μm. (Gelatin liquid composition) Gelatin 40g Water 900ml Poly-(2-diethylaminoethyl acrylate) (5% aqueous solution) 120ml Exemplary dye according to the present invention (3) (2% aqueous solution)
80ml 2,4-dichloro-6-hydroxy-1,3,
5-triazine sodium salt (1% aqueous solution)
20 ml saponin (10% aqueous solution) 30 ml Next, add 20 ml of saponin per 1 kg of gelatin emulsion to a silver iodobromide gelatin emulsion consisting of 96 mol% silver bromide and 4 mol% silver iodide with an average grain size of 0.8 μm. ,4-
Add 20 ml of dichloro-6-hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) and 20 ml of sodium dodecylbenzenesulfonate (1% aqueous solution) to form a second layer with a dry film thickness of 5 μm. was applied. Furthermore, a gelatin solution having the composition shown below was coated as a protective layer on this emulsion layer so that the dry film thickness was 2 μm, thereby preparing sample (14). (Gelatin liquid composition) Gelatin 20g Water 940ml 2,4-dichloro-6-hydroxy-1,3,
5-triazine sodium salt (1% aqueous solution)
10ml Sodium dodecylbenzenesulfonate (1%
Aqueous solution) 50ml Similarly, in place of the above-mentioned exemplary dye (3) in the first layer, exemplary dyes (10) and (16) according to the present invention and the following comparative dyes (I), (J) and (K) are used. A sample was created using At the same time, samples containing no dye were also prepared, and these samples were sequentially treated as sample (15),
(16), (17), (18), (19) and (20). Comparative dye (I) Comparative dye (J) Comparative dye (K) Each of the above samples was cut into small pieces, exposed through a photographic light wedge, and processed using the developer and fixer used in Example 3 having the following composition. Develop at 25℃ 2
Fixing was carried out at 25°C for 2 minutes, and washing with water was carried out at 25°C for 5 minutes, followed by drying. (Developer composition) Phenidone 0.5g Anhydrous sodium sulfite 50g Hydroquinone 12g Anhydrous sodium carbonate 60g Potassium bromide 2g Benzotriazole 0.2g Add water to 1000ml After development, perform sensitometry to obtain a characteristic curve, and select a sample containing no dye. The relative sensitivity was determined by setting the sensitivity of (20) as 100. The obtained results are shown in Section 5 below.
Shown in the table.
【表】
上記表からも明らかなように、本発明に係わる
染料を含有する試料では、比較染料を含有する試
料に比べて感度の低下が少ない。このことはすな
わち本発明に係わる染料では媒染された層から他
の近接層への染料の拡散が少ないことを意味して
いる。一方、比較染料(I)、(J)および(K)のようにピ
ラゾロン環の４位に置換されている置換アルキル
アミノベンジリデン基における置換アルキル基の
置換基の疎水性置換基定数πの値が−4.70より小
さいもの（SO- 3のπ値は−4.76）では、これら染
料を含有する試料の感度低下が大きくなる。
実施例 ６
平均粒子径0.2μｍの（ネガ型）臭化銀ゼラチン
乳剤を調整し、このゼラチン乳剤１Kg当たり、ホ
ルマリン（１％水溶援）20mlとサポニン（10％水
溶液）50mlを添加した後、下引き処理されたポリ
エチレンテレフタレートフイルム支持体上に、
100cm2当たり銀が50mg含まれるように塗布した。
更にこの乳剤層の上に本発明に係わる例示染料(1)
を含む下記の組成の保護層を乾燥膜厚が2μｍと
なるように塗布し、試料21を調製した。
ゼラチン 40ｇ
水 900ml
本発明に係わる例示染料(1)（２％水溶液） 80ml
ホルマリン（１％水溶液） 15ml
サポニン（10％水溶液） 50ml
一方、上記試料のうち乳剤層のみを、かぶらせ
剤としてヒドラジンを加えてかぶりを付与した平
均粒子径0.2μｍの直接反転臭化銀ゼラチン乳剤に
変えてその他は同様に塗布した試料22を調製し
た。
これらの各試料を60℃、50％相対湿度の条件下
３日間保存後、小片に断裁し、写真光楔を介して
露光し、下記組成の現像液および定着液を用いて
処理した。現像は25℃で２分間行い、定着は25℃
で２分間行い、また水洗は25℃で５分間行つた後
乾燥した。
（現像液の組成）
メトール 3.0ｇ
無水亜硫酸ナトリウム 45.0ｇ
ハイドロキノン 12.0ｇ
炭酸ナトリウム（１水塩） 80.0ｇ
臭化カリウム 2.0ｇ
水を加えて１とする。
（定着液の組成）
チオ硫酸ナトリウム 160ｇ
無水亜硫酸ナトリウム 14ｇ
氷酢酸 12ml
ホウ砂 12ｇ
カリ明ばん ５ｇ
水を加えて１とする。
現像処理した各試料をそれぞれ10枚ずつ重ねあ
わせ、試料上の着色汚染の有無を調べた。試料21
は着色汚染がなかつたが、試料22は淡い橙色の汚
染が認められた。
この結果から本発明の（ネガ型）ハロゲン化銀
乳剤と染料の組み合せは、比較の直接反転ハロゲ
ン化銀乳剤と染料の組み合せに対し、感光材料生
試料の経時保存後の処理において、着色汚染が少
ないことがわかる。
発明の効果
本発明に係わる染料は、酸性水溶液中における
分解が改良され著るしく優れた安定性を有し、ま
た処理液中での流出が良好で、残色汚染を生ずる
こともなく、かつ層中における拡散が少なく、感
度を低下させることもない。[Table] As is clear from the above table, the sensitivity decreases less in the samples containing the dye according to the present invention than in the samples containing the comparative dye. This means that the dye according to the invention has less diffusion of the dye from the mordanted layer to other adjacent layers. On the other hand, the value of the hydrophobic substituent constant π of the substituent of the substituted alkyl group in the substituted alkylaminobenzylidene group substituted at the 4-position of the pyrazolone ring as in comparative dyes (I), (J), and (K) is If it is smaller than -4.70 (the π value of SO - 3 is -4.76), the sensitivity of samples containing these dyes will be greatly reduced. Example 6 A (negative type) silver bromide gelatin emulsion with an average particle size of 0.2 μm was prepared, and 20 ml of formalin (1% water-assisted) and 50 ml of saponin (10% aqueous solution) were added per 1 kg of this gelatin emulsion. on a pull-treated polyethylene terephthalate film support.
It was applied so that 50mg of silver was contained per 100cm2 .
Further, on this emulsion layer, an exemplary dye (1) according to the present invention is applied.
Sample 21 was prepared by applying a protective layer containing the following composition to a dry film thickness of 2 μm. Gelatin 40g Water 900ml Exemplary dye (1) according to the present invention (2% aqueous solution) 80ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml On the other hand, only the emulsion layer of the above sample was treated with hydrazine as a fogging agent. In addition, sample 22 was prepared in which the emulsion was coated in the same manner except that a direct inversion silver bromide gelatin emulsion with an average grain size of 0.2 .mu.m was coated with a fog. Each of these samples was stored for 3 days at 60° C. and 50% relative humidity, then cut into small pieces, exposed through a photographic light wedge, and processed using a developer and fixer having the following compositions. Developing at 25℃ for 2 minutes, fixing at 25℃
The sample was washed with water for 5 minutes at 25°C, and then dried. (Composition of developer) Metol 3.0g Anhydrous sodium sulfite 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 80.0g Potassium bromide 2.0g Add water to make 1. (Fixer composition) Sodium thiosulfate 160g Anhydrous sodium sulfite 14g Glacial acetic acid 12ml Borax 12g Potassium alum 5g Add water to make 1. Ten sheets of each developed sample were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. Sample 21
Sample 22 had no colored stain, but sample 22 had pale orange stain. These results show that the combination of the (negative-working) silver halide emulsion and dye of the present invention has less color contamination in the processing of photosensitive material raw samples after storage over time, compared to the comparative direct reversal silver halide emulsion and dye combination. It turns out that there are few. Effects of the Invention The dye according to the present invention has improved decomposition in an acidic aqueous solution, has significantly excellent stability, has good flow out in a processing solution, does not cause residual color contamination, and Diffusion in the layer is small and sensitivity does not decrease.
Claims (1)
れていることを特徴とするネガ型ハロゲン化銀写
真感光材料。 一般式〔〕 〔式中、Ｇはメチル基、メトキシ基またはヒドロ
キシ基を表わし、R1はハメツトのσp値が−0.05
より小さい一価の基を表わし、R2は少くとも１
つのスルホ基を有するフエニル基を表わし、R3
は一価の基を表わし、ＸおよびＹは、それぞれ水
素原子、アルキル基または疎水性置換基定数πの
値の合計Σπが−4.70より大きい置換基を有するア
ルキル基を表わし、ＸとＹは互いに結合して５員
環または６員環を形成してもよい。Ｌはメチン基
を表わし、ｍは１、２、３または４の整数を表わ
し、ｎは１または２の整数を表わす。〕 ２ ハメツトのσp値が−0.05より小さい一価の基
が、アルキル基、シクロアルキル基、ヒドロキシ
基、アルコキシ基、ウレイド基またはアミノ基で
あることを特徴とする特許請求の範囲第１項記載
のハロゲン化銀写真感光材料。[Scope of Claims] 1. A negative-working silver halide photographic material characterized by containing a compound represented by the following general formula []. General formula [] [In the formula, G represents a methyl group, a methoxy group, or a hydroxy group, and R 1 has a σp value of -0.05.
represents a smaller monovalent group, R 2 is at least 1
represents a phenyl group having two sulfo groups, R 3
represents a monovalent group, X and Y each represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent for which the sum of the values of hydrophobic substituent constant π is larger than -4.70, They may be combined to form a 5- or 6-membered ring. L represents a methine group, m represents an integer of 1, 2, 3 or 4, and n represents an integer of 1 or 2. 2. Claim 1, wherein the monovalent group having a σp value of less than -0.05 is an alkyl group, a cycloalkyl group, a hydroxy group, an alkoxy group, a ureido group, or an amino group. silver halide photographic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58086267A JPS59211041A (en) | 1983-05-16 | 1983-05-16 | Photosensitive silver halide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58086267A JPS59211041A (en) | 1983-05-16 | 1983-05-16 | Photosensitive silver halide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59211041A JPS59211041A (en) | 1984-11-29 |
| JPH0554099B2 true JPH0554099B2 (en) | 1993-08-11 |
Family
ID=13882039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58086267A Granted JPS59211041A (en) | 1983-05-16 | 1983-05-16 | Photosensitive silver halide material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59211041A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2601297B2 (en) * | 1988-01-27 | 1997-04-16 | 富士写真フイルム株式会社 | Silver halide photographic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS513623A (en) * | 1974-06-28 | 1976-01-13 | Fuji Photo Film Co Ltd | Senryoofukumu harogenkaginshashinkankozairyo |
| JPS5883841A (en) * | 1981-11-12 | 1983-05-19 | Konishiroku Photo Ind Co Ltd | Silver halide photographic material |
| JPS59154439A (en) * | 1983-02-21 | 1984-09-03 | Fuji Photo Film Co Ltd | Direct reversal silver halide photosensitive material |
-
1983
- 1983-05-16 JP JP58086267A patent/JPS59211041A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS513623A (en) * | 1974-06-28 | 1976-01-13 | Fuji Photo Film Co Ltd | Senryoofukumu harogenkaginshashinkankozairyo |
| JPS5883841A (en) * | 1981-11-12 | 1983-05-19 | Konishiroku Photo Ind Co Ltd | Silver halide photographic material |
| JPS59154439A (en) * | 1983-02-21 | 1984-09-03 | Fuji Photo Film Co Ltd | Direct reversal silver halide photosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59211041A (en) | 1984-11-29 |
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