JPH0345815B2 - - Google Patents
Info
- Publication number
- JPH0345815B2 JPH0345815B2 JP57149498A JP14949882A JPH0345815B2 JP H0345815 B2 JPH0345815 B2 JP H0345815B2 JP 57149498 A JP57149498 A JP 57149498A JP 14949882 A JP14949882 A JP 14949882A JP H0345815 B2 JPH0345815 B2 JP H0345815B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- dye
- dyes
- silver halide
- 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 32
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000009931 harmful effect Effects 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000005504 styryl group Chemical group 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
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-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
- 229920001817 Agar Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 150000001298 alcohols 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
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 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
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- XXTISPYPIAPDGY-UHFFFAOYSA-N n,n-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1N(C=N)C1=CC=CC=C1 XXTISPYPIAPDGY-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
本発明は、染料を含有するハロゲン化銀写真感
光材料に関し、特に光吸収染料として有用な染料
によつて着色された親水性コロイド層を含有する
ハロゲン化銀写真感光材料に関するものである。
ハロゲン化銀写真感光材料において、フイルタ
ー、ハレーシヨン防止あるいはイラジエーシヨン
防止のため、特定の波長の光を吸収させる目的
で、ハロゲン化銀写真感光材料に染料を含有させ
ることはよく知られており、これらの染料によつ
て、親水性コロイド層を着色させている。
フイルター層は、通常感光性乳剤層の上層ある
いは乳剤層と乳剤層の間に位置し、乳剤層に到達
する入射光を好ましい分光組成の光とする役割を
はたす。また、写真画像の鮮鋭度を向上させる目
的で、乳剤層と支持体との間あるいは支持体裏面
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、支持体背面等での有害な反射光を吸
収させて、ハレーシヨン防止をしたり、乳剤層を
着色してハロゲン化銀粒子等による有害な反射光
や散乱光等を吸収させて、イラジエーシヨン防止
をすることがよく行なわれている。
このような目的で用いられる染料は、使用目的
に応じた良好な吸収スペクトル特性を有するこ
と、写真現像処理中に完全に脱色させるかまたは
ハロゲン化銀写真感光材料中から容易に溶出して
現像処理後に染料による残色汚染がないこと、写
真乳剤に対してカブリ、減感等の悪影響を及ぼさ
ないこと、着色された層から他の層へ拡散しない
こと、さらに溶液中あるいはハロゲン化銀写真感
光材料中での経時安定性に優れ、変褪色しないこ
と等の諸条件を満足しなければならない。
今日までに前記の条件を満足する染料を見出す
ことを目的として、多くの努力がなされ多数の染
料が提案されてきた。たとえば、英国特許第
506385号、米国特許第3247127号および特公昭39
−22069号等に記載されたオキソノール染料、米
国特許1845404号に代表されるスチリル染料、米
国特許第2493747号に代表されるメロシアニン染
料、米国特許第2843486号に代表されるシアニン
染料等がある。しかし、前記の諸条件を全て満足
し、ハロゲン化銀写真感光材料に使用し得る良好
な染料が非常に少ないのが実情である。
したがつて、本発明の目的は、前記の染料とし
ての諸条件を充分に満たし、特に良好な分光吸収
特性を有し写真現像処理中に、完全に脱色され
て、処理後の残色染料が極めて少なく、写真乳剤
に対して不活性である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。
前記本発明の目的は、下記一般式〔〕で示さ
れる新規なオキソノール染料（以下、「本発明に
係るオキソノール染料」という。）をハロゲン化
銀写真感光材料中に含有させることによつて達成
された。
一般式〔〕
式中、Z1およびZ2は、それぞれ５員もしくは６
員環を形成するのに必要な非金属原子群を表わ
し、同一でも異なつていてもよく、Y1およびY2
は、それぞれSO2基、Ｃ＝Ｏ基を表わし、同
一でも異なつていてもよく、Ｒは少なくとも１個
のスルホ基を有するアリール基を表わし、Ｌはメ
チン基を表わし、m1およびm2は、それぞれ０又
は１であり、同一でも異なつていてもよく、ｎは
０、１又は２である。
Z1およびZ2で表わされる５員もしくは６員を形
成するのに必要な非金属原子群としては、具体的
には、アルキレン基（例えばエチレン基又はトリ
メチレン基等）、アリーレン基（例えば１，２−
フエニレン基、２，３−ナフチレン基又は１，８
−ナフチレン基等）、ビニレン基、ヒドラゾ基等
を挙げることができ、これらＺで形成される５員
もしくは６員環は、さらにヒドロキシ基、ハロゲ
ン原子（例えばフツ素原子、塩素原子又は臭素原
子等）、シアノ基、ニトロ基、炭素原子数１〜４
個のアルキル基（例えばメチル基、エチル基又は
トリフルオロメチル基等）、アルコキシ基（例え
ばメトキシ基、エトキシ基等）、カルボキシ基又
は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）等の置換
基によつて任意に置換してもよい。
Ｒで表わされる少なくとも１個のスルホ基を有
するアリール基としては、例えば４−スルホフエ
ニル基、３，５−ジスルホフエニル基、６，８−
ジスルホ−２−ナフチル基、２−クロロ−４−ス
ルホフエニル基、２−メチル−４−スルホフエニ
ル基又は２，５−ジクロロ−４−スルホフエニル
基等を挙げることができる。
Ｌで表わされるメチン基はアルキル基又はアリ
ール基で置換されていてもよく、アルキル基とし
ては、例えばメチル基又はエチル基等を挙げるこ
とができ、アリール基としてはフエニル基等を挙
げることができる。
以下に、本発明に係るオキソノール染料の代表
的な具体例を示すが、これらによつて限定される
ものではない。
本発明に係るオキソノール染料は、下記一般式
〔〕で示されるピラゾロン体と下記一般式〔
ａ〕、〔ｂ〕、〔ｃ〕又は〔α〕で示されるメ
チン鎖供給体とを塩基性縮合剤（例えばピリジ
ン、α−ピコリン、β−ピコリン、γ−ピコリ
ン、２，４，６−コリジン、トリエチルアミン又
はＮ−エチルピペリジン等）の存在下に反応させ
て合成することができる。酸無水物と３−アミノ
ピラゾロン体とを酸（例えば、氷酢酸、塩酸又は
硫酸等）の存在下で反応させることにより得られ
る下記一般式〔〕で示されるピラゾロン体とピ
ラゾロン体に対して等モルのメチン鎖供給体とを
塩基性縮合剤の存在下に反応させた後、さらに下
記一般式〔）で示されるピラゾロン体とを反応
させることにより、前記一般式〔〕で示される
モノ−、トリ−、又はペンタ−メチンオキソノー
ルを合成することができる。また、メチン鎖供給
体に対して下記一般式〔〕のピラゾロン体を２
倍モル以上用いて反応させることにより、前記一
般式〔〕で示されるモノ−、トリ−、又はペン
タメチンオキソノールを合成することができる。
一般式〔〕
一般式〔ａ〕
HC（OC2H5）3
一般式〔〕
（式中、Ｚ、Ｙ、R1、R2、ｍ及びｎは前記一
般式〔〕で定義されたものとそれぞれ同義であ
り、Ｘはアニオン（例えばクロライド、ブロマイ
ド、ヨーダイド、パークロレート、メチルスルフ
エート又はｐ−トリエンスルフオネート等）を表
わす。）
次に、本発明に係るオキソノール染料の代表的
な合成例を下記に示す。
合成例 １
例示化合物(1)の合成
３−アミノ−１−（ｐ−スルホフエニル）−５−
ピラゾロン10.2ｇと無水コハク酸4.0ｇを氷酢酸
100ml中に入れ加熱還流させた。還流開始後、ま
もなく均一溶液となり、数分後に結晶が析出し
た。８時間還流させた後室温に戻し結晶を取
し、アセトニトリルで十分洗浄し、目的の２−ス
クシンイミド−１−（ｐ−スルホフエニル）−５−
ピラゾロン10.8ｇを得た。
３−スクシンイミド−１−（ｐ−スルホフエニ
ル）−５−ピラゾロン3.4ｇと、ジフエニルホルム
アミジン1.0ｇとをメタノール40ml中に入れ、こ
れにトリエチルアミン3.0ｇを加えて５時間加熱
還流した。次に酢酸カリウム1.5ｇを加え20分間
還流した。析出した染料を取し、メタノールで
十分洗浄後、乾燥し、1.8ｇの目的物を得た。こ
の染料の水溶液のλmaxは405nmであつた。
合成例 ２
例示化合物(6)の合成
３−アミノ−１−（ｐ−スルホフエニル）−５−
ピラゾロン及び無水フタル酸を用いて合成例１と
同様の方法により３−フタルイミド−１−（ｐ−
スルホフエニル）−５−ピラゾロンを得た。
このピラゾロン体3.85ｇと、ペロペンジアニル
1.11ｇをメタノール30ml中に溶かし、これにトリ
エチルアミン3.04ｇを加えて、２時間加熱還流し
た。次に、メタノール10ml中に溶解した酢酸カリ
ウム1.5ｇを加え15分間還流した。析出した染料
を取し、メタノールで十分洗浄後、乾燥し、
2.2ｇの目的物を得た。この染料の水溶液のλmax
は531nmであつた。
合成例 ３
例示化合物（15）の合成
３−フタルイミド−１−（ｐ−スルホフエニル）
−５−ピラゾロン1.75ｇと１，３−ペンタジエン
ジアニル塩酸塩0.65ｇをメタノール20ml中に溶か
し、水冷下、トリエチルアミン1.4ｇをゆつくり
滴下し、そのまま15時間反応させた。反応液を
200mlエーテル中に注ぎ、析出した結晶を取し
た後、シリカゲルクロマトグラフイーにより精製
を行ない、0.3ｇの目的物を得た。この染料の水
溶液のλmaxは629nmであつた。
合成例 ４
例示化合物（16）の合成
３−スクシンイミド−１−（ｐ−スルホフエニ
ル）−５−ピラゾロン3.5ｇと、１，３−ペンタジ
エンジアニル塩酸塩1.5ｇをメタノール35ml中に
溶かし、水冷下、トリエチルアミン3.15ｇをゆつ
くり滴下し、そのまま１時間反応させた。次に酢
酸カリウム1.53ｇを加え15分間反応させた。析出
した染料を取し、メタノールで十分洗浄後、乾
燥し、1.6ｇの目的物を得た。この染料の水溶液
のλmaxは622nmであつた。
本発明に係るオキソノール染料は、ハロゲン化
銀写真感光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
ー染料ある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
の染料を組合せて用いてもよいし、他の染料と組
合せて用いてもよい。本発明による染料をハロゲ
ン化銀写真感光乳剤層中あるいは、その他の親水
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溶液
あるいは有機溶媒（例えば、アルコール類、グリ
コール類、セロソルブ類、ジメチルホルムアルデ
ヒド、ジブチルフタレート、トリタレジルフオス
フエート等）に溶解し、必要であれば乳化分散
し、塗布液に添加して塗布を行ないハロゲン化銀
写真感光材料中に染料を含有させることができ
る。これら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1.0〜1000mgになるように塗布して用いる。
本発明のハロゲン化銀写真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、ポリエチレンテレフタレートのようなポリエ
ステル、ポリエチレンのようなポリオレフイン、
ポリスチレン、バライタ紙、ポリオレフインを塗
布した紙、ガラス又は金属等が用いられる。
本発明のハロゲン化銀写真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のようなゼ
ラチン誘導体、寒天やカゼインあるいはアルギン
酸のような水溶性の天然高分子、ポリビニルアル
コールやポリビニルピロリドンのような合成樹脂
及び／又はカルボキシメチルセルロースのような
セルロース誘導体等が挙げられ、これらは単独も
しくは組合せて用いることができる。
本発明のハロゲン化銀写真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、沃臭化銀又は塩沃臭化銀などの乳
剤が用いられ、これら乳剤は硫黄化合物、貴金属
増感剤あるいはポリアルキレンオキサイド誘導体
などにより公知の方法で増感してもよい。また、
これら乳剤は、さらにシアニン色素、ヘミシアニ
ン色素、メロシアニン色素、オキソノール色素、
スチリル色素などの分光増感剤を含有してもよ
い。
本発明のハロゲン化銀写真感光材料において、
媒染剤としてアミノ基またはアンモニウム基を有
するポリマー、含窒素複素環を有するポリマー等
を含有してもよく、また硬膜剤、塗布助剤、安定
剤、紫外線吸収剤、螢光増白剤、帯電防止剤等の
写真材料に通常使用される添加剤を含有してもよ
い。また、カラーカプラーやその分散剤及び現像
抑制化合物等を含有してもよい。
本発明に係るオキソノール染料は、ピラゾロン
の３位に
The present invention relates to a silver halide photographic material containing a dye, and more particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. It is well known that silver halide photographic materials contain dyes for the purpose of absorbing light of specific wavelengths to prevent filters, halation, or irradiation. The hydrophilic colloid layer is colored with a dye. A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and serves to convert the incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back side of the support to prevent harmful effects at the interface between the emulsion layer and the support, or on the back side of the support. It is common practice to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light or scattered light from silver halide grains, etc. . Dyes used for this purpose must have good absorption spectrum characteristics depending on the purpose of use, and must be completely decolorized during photographic processing or easily eluted from the silver halide photographic light-sensitive material and processed during development. There should be no residual color contamination caused by dyes afterwards, there should be no adverse effects such as fogging or desensitization on the photographic emulsion, there should be no diffusion from the colored layer to other layers, and there should be no residual color contamination caused by dyes, and there should be no discoloration in solution or silver halide photographic light-sensitive materials. It must satisfy various conditions such as excellent stability over time and no discoloration. To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, UK patent no.
No. 506385, U.S. Patent No. 3247127 and Special Publication No. 39 Sho.
Examples include oxonol dyes such as those described in US Pat. No. 22069, styryl dyes as represented by US Pat. No. 1,845,404, merocyanine dyes as represented by US Pat. No. 2,493,747, and cyanine dyes as represented by US Pat. No. 2,843,486. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in silver halide photographic materials. Therefore, an object of the present invention is to fully satisfy the above-mentioned conditions as a dye, to have especially good spectral absorption characteristics, and to be completely decolorized during photographic processing so that no residual color remains after processing. The object of the present invention is to provide a silver halide photographic material containing a very small amount of dye which is inert to photographic emulsions. The above object of the present invention can be achieved by incorporating a novel oxonol dye represented by the following general formula [] (hereinafter referred to as "the oxonol dye according to the present invention") into a silver halide photographic light-sensitive material. Ta. General formula [] In the formula, Z 1 and Z 2 are each 5-membered or 6-membered
Represents a group of nonmetallic atoms necessary to form a membered ring, which may be the same or different, and Y 1 and Y 2
represent an SO 2 group and a C═O group, respectively, and may be the same or different, R represents an aryl group having at least one sulfo group, L represents a methine group, m 1 and m 2 are respectively 0 or 1 and may be the same or different, and n is 0, 1 or 2. Specifically, the nonmetallic atomic groups necessary to form the 5- or 6-membered group represented by Z 1 and Z 2 include alkylene groups (e.g., ethylene or trimethylene groups), arylene groups (e.g., 1, 2-
Phenylene group, 2,3-naphthylene group or 1,8
-naphthylene group, etc.), vinylene group, hydrazo group, etc. The 5- or 6-membered ring formed by these Z may further contain a hydroxy group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, etc.). ), cyano group, nitro group, carbon number 1-4
Alkyl groups (e.g. methyl, ethyl, trifluoromethyl, etc.), alkoxy groups (e.g. methoxy, ethoxy), carboxyl or alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, etc.), etc. It may be optionally substituted with a substituent. The aryl group having at least one sulfo group represented by R includes, for example, 4-sulfophenyl group, 3,5-disulfophenyl group, 6,8-
Examples include a disulfo-2-naphthyl group, a 2-chloro-4-sulfophenyl group, a 2-methyl-4-sulfophenyl group, and a 2,5-dichloro-4-sulfophenyl group. The methine group represented by L may be substituted with an alkyl group or an aryl group; examples of the alkyl group include a methyl group or an ethyl group, and examples of the aryl group include a phenyl group. . Typical specific examples of the oxonol dye according to the present invention are shown below, but the present invention is not limited thereto. The oxonol dye according to the present invention comprises a pyrazolone compound represented by the following general formula [] and a pyrazolone compound represented by the following general formula [].
a], [b], [c] or [α] with a basic condensing agent (e.g. pyridine, α-picoline, β-picoline, γ-picoline, 2,4,6-collidine). , triethylamine, N-ethylpiperidine, etc.). For pyrazolone bodies and pyrazolone bodies represented by the following general formula [] obtained by reacting an acid anhydride and a 3-aminopyrazolone body in the presence of an acid (for example, glacial acetic acid, hydrochloric acid, or sulfuric acid), etc. By reacting molar amount of methine chain donor in the presence of a basic condensing agent and further reacting with a pyrazolone compound represented by the following general formula [), the mono-, represented by the general formula [], Tri- or pentamethine oxonol can be synthesized. In addition, the pyrazolone compound of the following general formula [] was added to the methine chain donor.
Mono-, tri-, or pentamethine oxonol represented by the above general formula [] can be synthesized by reacting with twice the molar amount or more. General formula [] General formula [a] HC (OC 2 H 5 ) 3 General formula [] (In the formula, Z, Y, R 1 , R 2 , m and n have the same meanings as defined in the above general formula [], and X is an anion (for example, chloride, bromide, iodide, perchlorate, methyl sulfate) phate or p-trienesulfonate, etc.) Next, a typical synthesis example of the oxonol dye according to the present invention is shown below. Synthesis Example 1 Synthesis of Exemplified Compound (1) 3-amino-1-(p-sulfophenyl)-5-
Add 10.2g of pyrazolone and 4.0g of succinic anhydride to glacial acetic acid.
The mixture was poured into a 100ml volume and heated to reflux. Shortly after refluxing started, the solution became homogeneous, and crystals precipitated several minutes later. After refluxing for 8 hours, the crystals were recovered to room temperature, washed thoroughly with acetonitrile, and the desired 2-succinimide-1-(p-sulfophenyl)-5-
10.8 g of pyrazolone was obtained. 3.4 g of 3-succinimide-1-(p-sulfophenyl)-5-pyrazolone and 1.0 g of diphenylformamidine were placed in 40 ml of methanol, and 3.0 g of triethylamine was added thereto, followed by heating under reflux for 5 hours. Next, 1.5 g of potassium acetate was added and the mixture was refluxed for 20 minutes. The precipitated dye was collected, thoroughly washed with methanol, and then dried to obtain 1.8 g of the desired product. The λmax of the aqueous solution of this dye was 405 nm. Synthesis Example 2 Synthesis of Exemplified Compound (6) 3-amino-1-(p-sulfophenyl)-5-
3-phthalimide-1-(p-
Sulfophenyl)-5-pyrazolone was obtained. 3.85g of this pyrazolone and peropendianil
1.11 g was dissolved in 30 ml of methanol, 3.04 g of triethylamine was added thereto, and the mixture was heated under reflux for 2 hours. Next, 1.5 g of potassium acetate dissolved in 10 ml of methanol was added and refluxed for 15 minutes. Remove the precipitated dye, wash thoroughly with methanol, and dry.
2.2g of the target product was obtained. λmax of the aqueous solution of this dye
was 531 nm. Synthesis Example 3 Synthesis of Exemplified Compound (15) 3-phthalimido-1-(p-sulfophenyl)
1.75 g of -5-pyrazolone and 0.65 g of 1,3-pentadienedianil hydrochloride were dissolved in 20 ml of methanol, and 1.4 g of triethylamine was slowly added dropwise under water cooling, followed by reaction for 15 hours. reaction solution
After pouring into 200 ml of ether and collecting the precipitated crystals, the mixture was purified by silica gel chromatography to obtain 0.3 g of the desired product. The λmax of the aqueous solution of this dye was 629 nm. Synthesis Example 4 Synthesis of Exemplified Compound (16) 3.5 g of 3-succinimide-1-(p-sulfophenyl)-5-pyrazolone and 1.5 g of 1,3-pentadienedianyl hydrochloride were dissolved in 35 ml of methanol, and under water cooling, 3.15 g of triethylamine was slowly added dropwise, and the reaction was continued for 1 hour. Next, 1.53 g of potassium acetate was added and reacted for 15 minutes. The precipitated dye was collected, thoroughly washed with methanol, and then dried to obtain 1.6 g of the desired product. The λmax of the aqueous solution of this dye was 622 nm. The oxonol dye according to the present invention can be used as an anti-irradiation dye by being included in a silver halide photographic 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. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method. In general,
Dissolve the dye or organic/inorganic alkali salt of the dye in an aqueous solution or organic solvent (e.g., alcohols, glycols, cellosolves, dimethyl formaldehyde, dibutyl phthalate, tritalesyl phosphate, etc.) and emulsify and disperse if necessary. However, the dye can be incorporated into the silver halide photographic material by adding it to the coating solution and coating it. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1.0 to 1000 mg per square meter of area on the photosensitive material. Supports in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene,
Polystyrene, baryta paper, paper coated with polyolefin, glass, metal, etc. are used. Hydrophilic colloids in the silver halide photographic material of the present invention include gelatin, gelatin derivatives such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid, polyvinyl alcohol, and Examples include synthetic resins such as polyvinylpyrrolidone and/or cellulose derivatives such as carboxymethylcellulose, and these may be used alone or in combination. As the silver halide emulsion in the silver halide photographic light-sensitive material of the present invention, an emulsion of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide is used, These emulsions may be sensitized using known methods such as sulfur compounds, noble metal sensitizers, or polyalkylene oxide derivatives. Also,
These emulsions further contain cyanine dyes, hemicyanine dyes, merocyanine dyes, oxonol dyes,
It may also contain a spectral sensitizer such as styryl dye. In the silver halide photographic material of the present invention,
It may contain a polymer having an amino group or an ammonium group, a polymer having a nitrogen-containing heterocycle, etc. as a mordant, and may also contain a hardening agent, a coating aid, a stabilizer, an ultraviolet absorber, a fluorescent whitening agent, and an antistatic agent. It may also contain additives commonly used in photographic materials such as additives. It may also contain color couplers, their dispersants, development inhibiting compounds, and the like. The oxonol dye according to the present invention is located at the 3rd position of pyrazolone.
メトール 3.0ｇ 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） 30.0ｇ 臭化カリウム 2.0ｇ 水を加えて１とする。 Metol 3.0g Sodium sulfite 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 30.0g Potassium bromide 2.0g Add water to make 1.
【表】
第１表から明らかなように、本発明に係る染料
は公知染料ＡおよびＢに比較して優れた脱色性を
示すことがわかつた。
実施例 ２
例示化合物（15）、そして比較試料として下記
の公知染料Ｃ及びＤを用いて、実施例１と同様の
方法で試料（）、（）及び（）を作成し、そ
の脱色率を求めた。その結果及びゼラチン中にお
ける吸収極大波長を第２表に示す。
[Table] As is clear from Table 1, the dye according to the present invention was found to exhibit superior decolorizing properties compared to known dyes A and B. Example 2 Using the exemplified compound (15) and the following known dyes C and D as comparative samples, samples (), () and () were prepared in the same manner as in Example 1, and their decolorization rates were determined. Ta. The results and the maximum absorption wavelength in gelatin are shown in Table 2.
４−アミノ−３−メチル−Ｎ−エチル Ｎ−
（β−ヒドロキシエチル）−アニリン硫酸塩
4.8ｇ
無水亜硫酸ナトリウム 4.0ｇ
ヒドロキシルアミン・1/2硫酸塩 2.0ｇ
無水炭酸カリウム 28.0ｇ
臭化カリウム 1.5ｇ
水酸化カリウム 1.0ｇ
水を加えて１とする。
〔漂白定着液の組成〕
エチレンジアミンテトラ酢酸鉄塩 65.0ｇ
エチレンジアミンテトラ酢酸−２ナトリウム塩
3.0ｇ
無水亜硫酸ナトリウム 9.5ｇ
チオ硫酸アンモニウム 77.5ｇ
無水炭酸ナトリウム 4.0ｇ
水を加えて１とする。
〔安定液の組成〕
氷酢酸 ９ml
酢酸ナトリウム ３ｇ
水を加えて１とする。
処理後の各試料の未露光部の濃度を第３表に示
す。
4-amino-3-methyl-N-ethyl N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 4.0g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 28.0g Potassium bromide 1.5g Potassium hydroxide 1.0g Add water to make 1. [Composition of bleach-fix solution] Ethylenediaminetetraacetic acid iron salt 65.0g Ethylenediaminetetraacetic acid-disodium salt
3.0g Anhydrous sodium sulfite 9.5g Ammonium thiosulfate 77.5g Anhydrous sodium carbonate 4.0g Add water to make 1. [Composition of stable solution] Glacial acetic acid 9ml Sodium acetate 3g Add water to make 1. Table 3 shows the density of the unexposed area of each sample after treatment.
【表】
また、染料を含まない試料（）の青感度、緑
感度、赤感度をそれぞれ100として、各試料の感
度を第４表に示す。[Table] Furthermore, the sensitivity of each sample is shown in Table 4, assuming that the blue sensitivity, green sensitivity, and red sensitivity of the sample (2) containing no dye are each 100.
【表】
第３表及び第４表から明らかなように本発明に
係る染料を含有する試料では、公知染料を含有す
る試料が示すような染料の残色による着色汚染が
認められなかつた。また、乳剤に対する悪影響が
極めて少ないことがわかつた。[Table] As is clear from Tables 3 and 4, in the samples containing the dye according to the present invention, color staining due to residual color of the dye was not observed, as was the case with the samples containing the known dye. It was also found that there was very little adverse effect on the emulsion.
Claims (1)
料を含有することを特徴とするハロゲン化銀写真
感光材料。 一般式〔〕 （式中、Z1およびZ2は、それぞれ５員もしくは
６員環を形成するのに必要な非金属原子群を表わ
し、同一でも異なつていてもよく、Y1およびY2
は、それぞれSO2基、Ｃ＝Ｏ基を表わし、同
一でも異なつていてもよく、Ｒは少なくとも１個
のスルホ基を有するアリール基を表わし、Ｌはメ
チン基を表わし、m1およびm2は、それぞれ０又
は１であり、同一でも異なつていてもよく、ｎは
０、１又は２である。）[Scope of Claims] 1. A silver halide photographic material containing an oxonol dye represented by the following general formula []. General formula [] (In the formula, Z 1 and Z 2 each represent a group of nonmetallic atoms necessary to form a 5- or 6-membered ring, and may be the same or different, and Y 1 and Y 2
represent an SO 2 group and a C═O group, respectively, and may be the same or different, R represents an aryl group having at least one sulfo group, L represents a methine group, m 1 and m 2 are respectively 0 or 1 and may be the same or different, and n is 0, 1 or 2. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57149498A JPS5938742A (en) | 1982-08-27 | 1982-08-27 | Photosensitive silver halide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57149498A JPS5938742A (en) | 1982-08-27 | 1982-08-27 | Photosensitive silver halide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5938742A JPS5938742A (en) | 1984-03-02 |
| JPH0345815B2 true JPH0345815B2 (en) | 1991-07-12 |
Family
ID=15476459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57149498A Granted JPS5938742A (en) | 1982-08-27 | 1982-08-27 | Photosensitive silver halide material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5938742A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04296747A (en) * | 1991-03-26 | 1992-10-21 | Konica Corp | Silver halide photographic sensitive material |
| JP3449406B2 (en) * | 1999-04-07 | 2003-09-22 | Ｈｏｙａヘルスケア株式会社 | Novel pyrazolone compound and ophthalmic plastic lens using the same |
-
1982
- 1982-08-27 JP JP57149498A patent/JPS5938742A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5938742A (en) | 1984-03-02 |
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