JPH0554098B2 - - Google Patents
Info
- Publication number
- JPH0554098B2 JPH0554098B2 JP58082210A JP8221083A JPH0554098B2 JP H0554098 B2 JPH0554098 B2 JP H0554098B2 JP 58082210 A JP58082210 A JP 58082210A JP 8221083 A JP8221083 A JP 8221083A JP H0554098 B2 JPH0554098 B2 JP H0554098B2
- 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 83
- 239000000463 material Substances 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 102
- 239000000839 emulsion Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 14
- 239000008273 gelatin Substances 0.000 description 14
- 229920000159 gelatin Polymers 0.000 description 14
- 235000019322 gelatine Nutrition 0.000 description 14
- 235000011852 gelatine desserts Nutrition 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229930182490 saponin Natural products 0.000 description 7
- 150000007949 saponins Chemical class 0.000 description 7
- 235000017709 saponins Nutrition 0.000 description 7
- 238000010186 staining Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000013078 crystal Substances 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
- 239000011241 protective layer Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- XSQFAWMDRFSIMY-UHFFFAOYSA-N 2-chloro-4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C(Cl)=C1 XSQFAWMDRFSIMY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910021607 Silver chloride 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
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 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 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- 229940081735 acetylcellulose Drugs 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
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000470 constituent Substances 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
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid 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
- 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000000126 substance Substances 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
- 238000005406 washing Methods 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
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- 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
- RANPNKFNOWAPSO-UHFFFAOYSA-N 4-(3-oxo-1h-pyrazol-2-yl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1N1C(=O)C=CN1 RANPNKFNOWAPSO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 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
- 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
- 206010070834 Sensitisation Diseases 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
- 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
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy 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
- 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
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 1
- 125000004414 alkyl thio 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
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000009792 diffusion process Methods 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
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 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
- AEOQMMHATQYSLZ-UHFFFAOYSA-N ethenyl ethenesulfonate Chemical compound C=COS(=O)(=O)C=C AEOQMMHATQYSLZ-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens 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
- 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
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000000962 organic group Chemical group 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
- 239000002245 particle Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 150000003058 platinum compounds Chemical class 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- 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 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 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
- 238000005556 structure-activity relationship Methods 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
- 125000000565 sulfonamide group Chemical group 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
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 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褪色を起さ
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、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はハロゲン原子を表わし、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は少なくとも１つのスルホ基を有するア
リール基を表わし、R3は一価の基を表わす。た
だし、R3は
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 dyes are incorporated into constituent layers of photosensitive materials to absorb light of specific wavelengths for the purpose of preventing halation, preventing irradiation, or adjusting the sensitivity of photosensitive emulsions. Coloring of hydrophilic colloid layers with dyes has been practiced for some time. Among the constituent layers of the above-mentioned light-sensitive material, a filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and converts incident light that reaches the emulsion layer into light with a preferable spectral composition. It plays a role in changing things. 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 can be improved by coloring the photosensitive emulsion layer using dyes to absorb harmful reflected light and scattered light to silver halide grains and prevent irradiation. It is 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 the dye, no other negative effects such as fogging or desensitization on the photosensitive emulsion, and no diffusion from the colored layer to other layers. Without,
Furthermore, it must satisfy various conditions such as being excellent in stability over time in photosensitive materials or in aqueous solutions and not causing discoloration or fading. To date, numerous studies have been conducted with the aim of developing dyes that satisfy the above conditions.
For example, US Pat. No. 3,540,887, US Pat. No. 3,544,325, US Pat.
-3623, etc., benzylidene dyes were proposed, British Patent No. 506385 and Japanese Patent Publication No. 39-22069 proposed oxonol dyes, U.S. Patent No. 2493747 proposed merocyanine dyes, and U.S. Patent No. 1845404 proposed styryl dyes. Each is proposed. 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,
It is an object of the present invention to provide a dye that has extremely little residual color staining after processing and has excellent stability over time in a light-sensitive emulsion or an aqueous solution, and a silver halide photographic light-sensitive material containing such a dye. Structure of the Invention As a result of various studies, the present inventors have found that the above object can be achieved in a silver halide photographic material containing a compound represented by the following general formula []. General formula [] In the formula, G represents a halogen atom, R 1 represents a monovalent group having a σ p value of less than −0.05, R 2 represents an aryl group having at least one sulfo group, and R 3 represents a monovalent group. represents the group of However, R 3 is
【式】に対しメタ位にあることは
ない。ＸおよびＹは、それぞれ水素原子またはア
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を表わし、ｎ
は１または２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、ハロゲン化銀乳剤層および／
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Ｇで表わされる
ハロゲン原子としては、フツ素原子、塩素原子、
臭素原子およびヨウ素原子等がある。また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、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−ブチル基等を表わし、
置換基を有していてもよく、例えばカルボキシメ
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であ
る。）、シクロアルキル基（例えばシクロペンチル
基、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
トキシ基等を表わし、置換基を有してもよく、例
えば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等である。）、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）等が
好ましく挙げられる。前記ハメツトのσp値は「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アリール基は、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）、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）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、３，６−ジスルホ−２−ナフチル基、８−ヒ
ドロキシ−３，６−ジスルホ−２−ナフチル基、
５−ヒドロキシ−７−スルホ−β−ナフチル基、
６，８−ジスルホ−β−ナフチル基等を挙げるこ
とができる。
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）、
ニトロ基等を好ましく挙げることができる。
ただし、R3はIt is never in the meta position with respect to [formula]. X and Y each represent a hydrogen atom or an alkyl group, and X and Y may be bonded to each other to form a 5-membered ring or a 6-membered ring. L represents a methine group, m represents 1, 2, 3 or 4, n
represents 1 or 2. The present invention will be explained in more detail below. In the present invention, a silver halide emulsion layer and/or
Alternatively, the dye contained in the non-photosensitive hydrophilic colloid layer can be represented by the above general formula [], and the halogen atom represented by G in the general formula [] is a fluorine atom, a chlorine atom,
Examples include bromine atoms and iodine atoms. The monovalent group represented by R 1 with a σ p value of less than -0.05 is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group). , represents a tert-butyl group, etc.
It may have a substituent, such as a carboxymethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, benzyl group, and phenethyl group. ), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, n-butoxy group, etc.), which may have a substituent, e.g. 2-methoxyethoxy group , ethoxymethoxy group, 2-hydroxyethoxy group, etc.), amino group (e.g. amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, anilino group), ureido group (e.g. ureido group, methyl Preferred examples include ureido group, ethylureido group), and the like. Hammett's σ p value is from "Structure-Activity Relationship of Drugs" (Nankodo), p. 96 (1979).
Substituents can be selected based on this table. Furthermore, in the above general formula [], the aryl group having a sulfo group represented by R 2 may have other substituents in addition to the sulfo group, such as a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl atom, etc. group, alkoxy group (methoxy group, ethoxy group,
n-propoxy group, etc.), aryloxy group (phenoxy group, etc.), alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, n-butyl group, etc.), carboxyl group, alkoxycarbonyl group groups (methoxycarbonyl group, ethoxycarbonyl group, etc.), nitro group, alkylsulfonyl group (methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, etc.), carbamoyl group (carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group It may have a group (sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, etc.), a sulfonamide group (methylsulfonamide group, ethylsulfonamide group, etc.), and the like. 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-
Disulfophenyl group, 3,5-disulfophenyl group, 3,6-disulfo-2-naphthyl group, 8-hydroxy-3,6-disulfo-2-naphthyl group,
5-hydroxy-7-sulfo-β-naphthyl group,
Examples include 6,8-disulfo-β-naphthyl 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),
Preferred examples include nitro group. However, R 3 is
【式】に対しメタ位にあるこ
とはない。
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）が好ましく、これ
らのアルキル基には更に置換基として、例えばシ
アノ基、ハロゲン原子（例えばフツ素原子、塩素
原子、臭素原子等）、ヒドロキシ基、アルコキシ
基（例えばメトキシ基、エトキシ基、ｎ−プロボ
キシ基等）、カルボキシ基、アルコキシカルボニ
ル基（例えばメトキシカルボニル基、エトキシカ
ルボニル基等）、アシル基（例えばアセチル基、
プロピオニル基等）、アシルオキシ基（例えばア
セチルオキシ基、プロピオニルオキシ基等）、ア
リールオキシ基（例えばフエノキシ基）、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、ジエチルアミノ基、アニリノ基等）、
アルキルチオ基（例えばメチルチオ基、エチルチ
オ基等）、アルキルスルホニル基（例えばメチル
スルホニル基、エチルスルホニル基等）、アシル
アミノ基（例えばアセチルアミノ基）、アルキル
スルホニルアミノ基（例えばメチルスルホニルア
ミノ基、エチルスルホニルアミノ基等）、アリー
ル基（例えばフエニル基）、スルホ基等が挙げら
れる。
さらに上記ＸとＹと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
基、ピペリジノ基、モルホリノ基等を挙げること
ができる。
さらには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)およ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りう
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る得ることが
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）
蒸留水35ml中に5.09ｇの３−メチル−１−
（4′−スルホフエニル）ピラゾリン−５−オンを
入れ、さらに無水炭酸ナトリウム1.17ｇを加えて
溶解する。次に3.67ｇの２−クロロ−４−ジメチ
ルアミノベンズアルデヒドと35mlのメタノールを
加え、加熱還流下1.5時間反応させた。反応後、
メタノール50mlを加え、一夜放置後析出した結晶
を取し、メタノールで充分に洗浄後、乾燥して
6.80ｇの上記例示染料を得た。この染料の水溶液
のλmaxは、488nｍであつた。
合成例 ２
（例示染料(12)の合成）
メタノール80ml中に5.12ｇの３−ヒドロキシ−
１−（4′−スルホフエニル）ピラゾリン−５−オ
ンと4.04ｇの２−クロロ−４−ジメチルアミノベ
ンズアルデヒドを加え、さらにピリジン3.16ｇを
加えて、加熱還流下2.5時間反応させた。その後
蒸留水20mlに溶解した無水酢酸ナトリウム3.28ｇ
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5.80ｇの上記例示染料を得た。この
染料の水溶液のλmaxは、489nｍであつた。
合成例 ３
（例示染料(15)の合成）
メタノール80ml中に6.12ｇの３−エトキシ−１
−（4′−スルホフエニル）ピラゾリン−５−オン
と3.86ｇの２−クロロ−４−ジメチルアミノベン
ズアルデヒドを加え、さらにピリジン3.16ｇを加
えて、加熱還流下３時間反応させた。その後反応
液を冷却し、析出した結晶を取した。この結晶
を蒸留水とメタノールの１：１混合溶媒に溶解
し、酢酸ナトリウムを加えて、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4.00ｇ
の上記例示染料を得た。この染料の水溶液の
λmaxは、460nｍ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としてハロゲン原
子を有し、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）中での安定性が著るしく改良されたほか、
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、或い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、或い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、或い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、或いは米国特許第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
謂コンバ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、或いは不活
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、或いは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
ニルスルホン酸、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、さらに螢光増白
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を与えて撹拌し、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る。同様にして例示
染料(5)、(12)、(15)および(18)ならびに下記の比較染
料
(A)、(B)、(C)、(D)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)
It is never in the meta position with respect to [formula]. 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,
butyl group, tert-butyl group, etc.), and these alkyl groups may further have substituents such as cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, n-proboxy group, etc.), carboxy group, alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), acyl group (e.g. acetyl group,
propionyl group, etc.), acyloxy group (e.g. acetyloxy group, propionyloxy group, etc.), aryloxy group (e.g. phenoxy group), amino group (e.g. amino group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.) ,
Alkylthio groups (e.g. methylthio group, ethylthio group, etc.), alkylsulfonyl groups (e.g. methylsulfonyl group, ethylsulfonyl group, etc.), acylamino groups (e.g. acetylamino group), alkylsulfonylamino groups (e.g. methylsulfonylamino group, ethylsulfonylamino group) group, etc.), an aryl group (for example, a phenyl group), a sulfo group, and the like. Furthermore, examples of the 5-membered ring or 6-membered ring formed by combining X and Y with each other include a pyrrolidino group, a piperidino group, and a morpholino group. Furthermore, the methine group represented by L has 1 carbon atom
It may be substituted with ~4 alkyl groups (eg, methyl, ethyl, n-butyl, etc.) or aryl groups (eg, phenyl). 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 are 1 or 2
indicates an integer. However, n in the general formula []
Since there is a relationship n=p+q-1 between
p and q cannot be 2 at the same time. The above reaction is performed using a basic condensing agent, such as pyridine,
This is carried out by heating a mixture of the above general formulas [] and [] in the presence of piperidine, triethylamine, etc. The above reaction can be carried out in the presence or absence of the above basic condensing agent using methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane,
It can also be carried out in an inert solvent such as acetic acid or water. 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 corresponding substituted aniline by the reaction of Vilsmeyer and Hack (Berichte, Vol. 60, p. 119, 1927). 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.
Volume 66, page 1849 (1944) Method described, J.Am.
Chem.Soc., Vol. 65, p. 52 (1943), J.Am.Chem.Soc., Vol. 64, p. 2136 (1942)
It can be obtained by using the method described in 2010). Typical specific examples of the dyes according to the present invention are described below. (Exemplary compound) Next, the method for synthesizing the dye according to the present invention will be specifically explained by showing synthesis examples. Synthesis Example 1 (Synthesis of Exemplary Dye (2)) 5.09 g of 3-methyl-1- in 35 ml of distilled water
Add (4'-sulfophenyl)pyrazolin-5-one and 1.17 g of anhydrous sodium carbonate to dissolve. Next, 3.67 g of 2-chloro-4-dimethylaminobenzaldehyde and 35 ml of methanol were added, and the mixture was reacted under heating under reflux for 1.5 hours. After the reaction,
Add 50ml of methanol, leave it overnight, collect the precipitated crystals, wash thoroughly with methanol, and dry.
6.80 g of the above exemplary dye was obtained. The λmax of the aqueous solution of this dye was 488 nm. Synthesis Example 2 (Synthesis of Exemplary Dye (12)) 5.12g of 3-hydroxy- in 80ml of methanol
1-(4'-sulfophenyl)pyrazolin-5-one and 4.04 g of 2-chloro-4-dimethylaminobenzaldehyde were added, followed by 3.16 g of pyridine, and the mixture was reacted under heating under reflux for 2.5 hours. 3.28 g anhydrous sodium acetate then dissolved in 20 ml distilled water
was added and reflux was continued for 5 minutes. Cool the reaction solution,
The precipitated crystals were collected, thoroughly washed with methanol, and then dried to obtain 5.80 g of the above exemplary dye. The λmax of the aqueous solution of this dye was 489 nm. Synthesis Example 3 (Synthesis of Exemplary Dye (15)) 6.12g of 3-ethoxy-1 in 80ml of methanol
-(4'-sulfophenyl)pyrazolin-5-one and 3.86 g of 2-chloro-4-dimethylaminobenzaldehyde were added, followed by 3.16 g of pyridine, and the mixture was reacted under heating under reflux for 3 hours. Thereafter, the reaction solution was cooled and the precipitated crystals were collected. Dissolve the crystals in a 1:1 mixed solvent of distilled water and methanol, add sodium acetate, collect the precipitated crystals, wash thoroughly with methanol, and dry to give 4.0g.
The above exemplified dye was obtained. The λmax of the aqueous solution of this dye was 460 nm. The dye according to the present invention produced by the above method is
As shown in the above general formula [], a monovalent compound having a halogen atom as a substituent G at the ortho position of a benzylidene group and R 1 at the 3-position of the pyrazolone ring has a Hammett's σ p value of less than -0.05. It has a structural feature of having a group, and as a result, it has significantly improved stability in aqueous solutions (acidic aqueous solutions) compared to conventionally known dyes.
It is a dye with excellent photographic performance as it has excellent run-off and decolorization properties in processing steps, and therefore does not cause residual color staining, and also has good spectral absorption characteristics and does not adversely affect photographic properties. The dye according to the present invention is used by being contained in the emulsion layer and/or 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 contained in a silver halide emulsion, or can be used as a filter dye or an anti-halation dye by being contained 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. Generally, a dye or an organic or inorganic alkali salt of a 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 a photosensitive material. 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, agar, casein, water-soluble natural polymers such as alginic acid, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. , cellulose derivatives such as carboxymethyl cellulose, etc., 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. Includes: 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 process for producing a so-called conversion emulsion, such as forming an emulsion of grains and then converting at least a portion of the grains into silver bromide salt or silver iodobromide salt, or fine-grained halogen having an average grain size of 0.1μ or less. It can be produced by any method such as the method of producing a Lippmann emulsion made of silver oxide. 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. rate,
Gold compounds such as orithic trichloride, potassium orithic thiocyanate, 2-orothiabenzthiazole methyl chloride, etc., palladium compounds such as ammonium chloroparadate, sodium chloropalladite, etc., platinum compounds such as potassium chloroplatinate, etc. , ruthenium compounds, etc., or a combination of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It can be stabilized, and a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be included. 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, It can contain wetting agents such as water-dispersible particulate polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc., and aldehyde compounds, N,N'-dimethylol urea, etc. Active halogen compounds such as N-methylol compounds, mucohalogenic acid, divinylsulfonic acid, 2,4-dichloro-6-hydroxy-S-triazine,
Hardening agents such as dioxane derivatives, divinyl ketones, isocyanates, carbodiimides, etc.; surfactants such as saponins, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates; Furthermore, photographic additives such as fluorescent brighteners, 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 be a colored coupler for masking or a coupler that releases a development inhibitor. It may be. 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. Further, the photosensitive material of the present invention can have any layer structure that can be used in conventional photosensitive materials. EXAMPLES 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
0.5 ml of glacial acetic acid was added to 100 ml of the aqueous solution and stirred to prepare a solution for measuring decomposition rate (PH 2.8 to 2.9). Using a spectrophotometer, the decrease in absorbance at the maximum absorption wavelength of this solution is measured over time (every 10 minutes for 1 hour) to determine the initial decomposition rate. Similarly, exemplified dyes (5), (12), (15) and (18) and the following comparative dyes
Measurements were also made for (A), (B), (C), and (D). The results obtained are shown in Table 1 below. Comparative dye (A) Comparative dye (B) Comparative dye (C) Comparative dye (D)
【表】【table】
【表】【table】
【表】
第１表から明らかなように、本発明に係わる染
料は、比較染料と比べて溶液（酸性水溶液）中で
の分解が改良され、安定性が著るしく向上してい
ることがわかる。また、比較染料のように、該染
料の構造式においてベンジリデン基のオルト位
（本発明による染料の一般式〔〕中のＧの位置）
にハロゲン原子がない染料あるいは該染料の構造
式においてピラゾロン環の３位（本発明による染
料の一般式〔〕中のR1の位置）にハメツトの
σp値が−0.05より大きな有機基を有する染料で
は、溶液中での分解が著しいことがわかつた。
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)、(11)および(15)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(E)、(F)、(G)および
(H)を用いて同様の方法で比較試料〔４〕、〔５〕、
〔６〕および〔７〕を作成した。
比較染料(E)
比較染料(F)
比較染料(G)
比較染料(H)
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] As is clear from Table 1, the dye according to the present invention has improved decomposition in a solution (acidic aqueous solution) and significantly improved stability compared to the comparative dye. . Also, like the comparative dyes, the ortho position of the benzylidene group in the structural formula of the dye (the position of G in the general formula [ ] of the dye according to the present invention)
A dye that does not have a halogen atom, or has an organic group with a Hammett's σ p value of greater than -0.05 at the 3-position of the pyrazolone ring (the R 1 position in the general formula [] of the dye according to the present invention) in the structural formula of the dye. It was found that dyes decompose significantly in solution. Example 2 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
To this was added 5 ml of an aqueous solution containing 2.0 x 10 -4 mol each of exemplary dyes (1), (11) and (15) according to the present invention,
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 coated on an acetyl cellulose film support and dried to produce samples [1],
[2] and [3]. In addition, instead of the dye according to the present invention, the following comparative dyes (E), (F), (G) and
Comparative samples [4], [5],
[6] and [7] were created. Comparative dye (E) Comparative dye (F) Comparative dye (G) Comparative dye (H) 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, E 2 is
It represents the absorbance after immersion in 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。また、比較染料（Ｅ、Ｆ、Ｇおよび
Ｈ）を含有する試料では、溶出した染料により処
理液がわずかに着色し汚染したが、本発明に係わ
る染料では、このような着色汚染はまつたくみら
れなかつた。
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)を含む下記組成の保護層を乾燥膜厚が2μｍ
になるよえに塗布した。（試料８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(13)ならびに
実施例２で用いた比較染料(E)および(F)をそれぞれ
含む試料を作成し、それぞれ試料９、10、11およ
び12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。その後乾燥した。
（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（１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枚ずつ重ね合
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. In addition, in the samples containing comparative dyes (E, F, G, and H), the processing solution was slightly colored and contaminated by the eluted dye, but with the dye according to the present invention, such color staining was not observed at all. Nakatsuta. 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,
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 having the following composition containing the exemplary dye (2) according to the present invention was applied to a dry film thickness of 2 μm.
I applied it to prevent it from becoming a problem. (Same as sample 8) (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 (13) according to the present invention and the comparative dye (E) used in Example 2 and Samples containing (F) were prepared and designated as samples 9, 10, 11 and 12, respectively. Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using developer and fixer solutions having the following compositions. Development was performed at 20°C for 1.5 minutes, fixing was performed at 20°C for 2 minutes, and washing was performed at 20°C for 5 minutes. It was then dried. (Composition of developer) 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 to 1000ml (of fixer) Composition) Sodium thiosulfate 160 g Anhydrous sodium sulfite 14 g Glacial acetic acid 12 ml Borax 12 g Potassium alum 5 g Add water to 1000 ml 10 sheets of each developed sample were stacked together to examine the presence or absence of colored contamination on the sample. 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
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13と
する）
（ゼラチン層組成）
ゼラチン 50ｇ
水 835ml
本発明に係わる例示染料(2)（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(2)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〔Ｉ〕を用いて試料を作成し、試料(14)お
よび(15)とした。
比較染料〔Ｉ〕
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 the comparative dyes, colored stains were observed in the samples, but the dyes according to the present invention had excellent run-off and decoloring properties, and were completely free of colored stains. 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 40g Water 960ml Formalin (1% aqueous solution) 12ml Saponin (10% aqueous solution) 30ml Next, dry a gelatin layer containing a dye with the following composition on the back side of the support coated with the emulsion layer and protective layer. The coating was applied to a film thickness of 3 μm. (Same as sample 13) (Gelatin layer composition) Gelatin 50g Water 835ml Exemplary dye (2) according to the present invention (2% aqueous solution)
100ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml Similarly, in place of the exemplary dye (2) according to the present invention, exemplary dye (25) according to the present invention and the following comparative dye [I] were used. Samples were prepared using this method and designated as samples (14) and (15). Comparative dye [I] 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。
発明の効果
本発明に係わる染料は、酸性水溶液中において
分解することなく安定で、処理浴中での流出性に
も優れ、かつ写真特性も良好であるところから、
これを含有する感光材料は色汚染が防止され、写
真特性、特に画像の鮮鋭度が改良された性能を有
するに至る。[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. Effects of the Invention The dye according to the present invention is stable in an acidic aqueous solution without decomposing, has excellent flowability in a processing bath, and has good photographic properties.
A light-sensitive material containing it is prevented from color staining and has improved photographic properties, particularly image sharpness.
Claims (1)
れていることを特徴とするハロゲン化銀写真感光
材料。 一般式〔〕 〔式中、Ｇはハロゲン原子を表わし、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は少なくとも１つのスルホ基を有するア
リール基を表わし、R3は一価の基を表わす。た
だし、R3は【式】に対してメタ位にあること はない。 ＸおよびＹは、それぞれ水素原子またはアルキ
ル基を表わす。また、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を表わし、
ｎは１または２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、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 silver halide photographic material containing a compound represented by the following general formula []. General formula [] [In the formula, G represents a halogen atom, R 1 represents a monovalent group with a σ P value of less than −0.05, R 2 represents an aryl group having at least one sulfo group, and R 3 represents a monovalent group having a sulfo group of less than −0.05. Represents a valence group. However, R 3 is never in the meta position with respect to [formula]. X and Y each represent a hydrogen atom or an alkyl group. Also, X and Y are combined with each other to form 5
A membered ring or a 6-membered ring may be formed. L represents a methine group, m represents 1, 2, 3 or 4,
n represents 1 or 2. ] 2 The monovalent group with a σ P value of less than −0.05 is an alkyl group, a hydroxy group, an alkoxy group,
2. The silver halide photographic material according to claim 1, which is a ureido group or an amino group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58082210A JPS59206829A (en) | 1983-05-10 | 1983-05-10 | Photosensitive silver halide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58082210A JPS59206829A (en) | 1983-05-10 | 1983-05-10 | Photosensitive silver halide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59206829A JPS59206829A (en) | 1984-11-22 |
| JPH0554098B2 true JPH0554098B2 (en) | 1993-08-11 |
Family
ID=13768055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58082210A Granted JPS59206829A (en) | 1983-05-10 | 1983-05-10 | Photosensitive silver halide material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59206829A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0215124B1 (en) * | 1985-02-06 | 1991-09-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic photo-sensitive material |
| JPH0833610B2 (en) * | 1987-08-10 | 1996-03-29 | 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
- 1983-05-10 JP JP58082210A patent/JPS59206829A/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 |
|---|---|
| JPS59206829A (en) | 1984-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0128938B2 (en) | ||
| JPH06194784A (en) | Filter dye for quick processing | |
| JPH01291247A (en) | Silver halide photographic sensitive material | |
| JP2557252B2 (en) | Silver halide photographic material | |
| JPH0562323B2 (en) | ||
| JPS59111641A (en) | Silver halide photosensitive material | |
| JPS6053304B2 (en) | Silver halide photographic material | |
| JP2632397B2 (en) | Silver halide photographic material | |
| JP2676212B2 (en) | Silver halide photographic material | |
| JPH0554098B2 (en) | ||
| JPH01293343A (en) | Silver halide photographic sensitive material | |
| JPH0559419B2 (en) | ||
| JPH0554099B2 (en) | ||
| JP2867372B2 (en) | Silver halide photographic material | |
| JPH04223457A (en) | Silver halide photographic sensitive material | |
| JPH0554654B2 (en) | ||
| US5370980A (en) | Silver halide photographic light-sensitive material | |
| JPS6241262B2 (en) | ||
| JP2632398B2 (en) | Silver halide photographic material | |
| JPH04130429A (en) | Silver halide photographic sensitive material | |
| JPH01234844A (en) | Silver halide photographic sensitive material | |
| JPS6241263B2 (en) | ||
| JPH0693095B2 (en) | Silver halide photographic light-sensitive material | |
| JPS6241265B2 (en) | ||
| JPH0345815B2 (en) |