JPH03223745A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH03223745A JPH03223745A JP1947090A JP1947090A JPH03223745A JP H03223745 A JPH03223745 A JP H03223745A JP 1947090 A JP1947090 A JP 1947090A JP 1947090 A JP1947090 A JP 1947090A JP H03223745 A JPH03223745 A JP H03223745A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- dyes
- alkyl group
- denote
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 36
- -1 Silver halide Chemical class 0.000 title claims description 153
- 229910052709 silver Inorganic materials 0.000 title claims description 57
- 239000004332 silver Substances 0.000 title claims description 57
- 239000000839 emulsion Substances 0.000 claims abstract description 63
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 75
- 230000001235 sensitizing effect Effects 0.000 abstract description 21
- 238000012545 processing Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 abstract description 3
- 231100000202 sensitizing Toxicity 0.000 abstract 3
- 239000003086 colorant Substances 0.000 abstract 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 1
- 150000002843 nonmetals Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- 239000000243 solution Substances 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 108010010803 Gelatin Proteins 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 125000000542 sulfonic acid group Chemical group 0.000 description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 206010070834 Sensitisation Diseases 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 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 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-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
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical group C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical group C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- CFSGUMFOSQULCJ-UHFFFAOYSA-N 1,3-bis(ethenylsulfonyl)-2,2-bis(ethenylsulfonylmethyl)propane Chemical compound C=CS(=O)(=O)CC(CS(=O)(=O)C=C)(CS(=O)(=O)C=C)CS(=O)(=O)C=C CFSGUMFOSQULCJ-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- DBCKMJVEAUXWJJ-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Cl)=C1Cl DBCKMJVEAUXWJJ-UHFFFAOYSA-N 0.000 description 1
- AYNPIRVEWMUJDE-UHFFFAOYSA-N 2,5-dichlorohydroquinone Chemical compound OC1=CC(Cl)=C(O)C=C1Cl AYNPIRVEWMUJDE-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- HIGSPBFIOSHWQG-UHFFFAOYSA-N 2-Isopropyl-1,4-benzenediol Chemical compound CC(C)C1=CC(O)=CC=C1O HIGSPBFIOSHWQG-UHFFFAOYSA-N 0.000 description 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-UHFFFAOYSA-N 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[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
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 1
- SOVXTYUYJRFSOG-UHFFFAOYSA-N 4-(2-hydroxyethylamino)phenol Chemical compound OCCNC1=CC=C(O)C=C1 SOVXTYUYJRFSOG-UHFFFAOYSA-N 0.000 description 1
- SRYYOKKLTBRLHT-UHFFFAOYSA-N 4-(benzylamino)phenol Chemical compound C1=CC(O)=CC=C1NCC1=CC=CC=C1 SRYYOKKLTBRLHT-UHFFFAOYSA-N 0.000 description 1
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JASONGFGOLHLGB-UHFFFAOYSA-N Atranol Chemical compound CC1=CC(O)=C(C=O)C(O)=C1 JASONGFGOLHLGB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 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
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 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
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005237 alkyleneamino group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000000987 azo dye 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
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical group C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007766 curtain coating Methods 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
- 238000004042 decolorization Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002473 indoazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CELWCAITJAEQNL-UHFFFAOYSA-N oxan-2-ol Chemical compound OC1CCCCO1 CELWCAITJAEQNL-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AMZPPWFHMNMIEI-UHFFFAOYSA-M sodium;2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C2NC(=S)NC2=C1 AMZPPWFHMNMIEI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は赤色域に分光増感されたハロゲン化銀写真感光
材料に関し、更に詳しくは、残色が少なく、かつ経時保
存性に優れたハロゲン化銀写真感光材料に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material spectrally sensitized in the red region, and more specifically to a silver halide photographic material that has little residual color and has excellent storage stability over time. This invention relates to silver oxide photographic materials.
写真感光材料の露光法の一つに原図を走査し、その画像
信号に基づいてハロゲン化銀写真感光材料上に露光を行
い、原図の画像に対応するネガ画像もしくはポジ画像を
形成する、いわゆるスキャナ一方式による画像形成方法
が知られているが、この方法における記録用光源として
、半導体レーザー、Ｈｅ−Ｎｅレーザー アルゴンレー
ザー ＬＥＤが用いられる。A so-called scanner is one of the exposure methods for photographic light-sensitive materials, in which an original image is scanned, and the silver halide photographic light-sensitive material is exposed to light based on the image signal to form a negative or positive image corresponding to the image on the original image. One type of image forming method is known, and a semiconductor laser, a He-Ne laser, an argon laser, or an LED is used as a recording light source in this method.
ハロゲン化銀写真感光材料において、特定の波長域の光
を吸収させる目的で、写真乳剤層またはその他の層を着
色することがしばしば行われる。In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.
写真に入射すべき光の分光組成を制御することが必要な
時、写真感光材料上の写真乳剤層よりも支持体から遠い
側に着色層が設けられる。When it is necessary to control the spectral composition of light incident on a photograph, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.
この様な着色層はフィルター層と呼ばれる。重層カラー
感光材料のごとく写真乳剤層が複数ある場合にはフィル
ター層がそれらの中間に位置することもある。Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.
写真乳剤層を通過する際、あるいは透過後に散乱された
光が、乳剤層と支持体の界面、あるいは乳剤層と反対側
の感光材料の表面で反射されて再び写真乳剤層に入射す
ることに基づく画像のポケすなわちハレーションを防止
することを目的として、写真乳剤層と支持体の間、ある
いは支持体の写真乳剤層とは反対の面に着色層を設ける
ことが行われる。このような着色層はハレーション防止
層と呼ばれる。重層カラー感光材料の場合には各層の中
間にハレーヨン防止層がおかれることもある。It is based on the fact that the light that is scattered when passing through the photographic emulsion layer or after being transmitted is reflected at the interface between the emulsion layer and the support or the surface of the light-sensitive material on the opposite side of the emulsion layer and enters the photographic emulsion layer again. A colored layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer, for the purpose of preventing pockmarking or halation of the image. Such a colored layer is called an antihalation layer. In the case of multilayer color light-sensitive materials, an anti-haleyon layer may be placed between each layer.
写真乳剤層中での光の散乱に基づく画像鮮鋭度の低下（
この現象は一般にイラジェーションとよばれえいる）を
防止するために、写真乳剤層を着色することも行われる
。Decreased image sharpness due to light scattering in the photographic emulsion layer (
In order to prevent this phenomenon (generally called irradiation), the photographic emulsion layer is also colored.
これらの着色すべき層は親水性コロイドからなる場合が
多く、従ってその着色のためには通常、水溶性染料を層
中に含有させる。この染料は下記のような条件を満足す
ることが必要である。These layers to be colored are often composed of hydrophilic colloids, and therefore, for the purpose of coloring them, water-soluble dyes are usually incorporated into the layers. This dye must satisfy the following conditions.
■使用目的に応じた適正な分光吸収を有すること。■Have appropriate spectral absorption according to the purpose of use.
■写真化学的に不活性であること。■It must be photochemically inert.
つまり、ハロゲン化銀写真乳剤層の性能に化学的な意味
での悪影響、例えば感度の低下あるいはカブリを与えな
いこと。In other words, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity or fog.
■写真処理過程において脱色されるか、溶解除去されて
処理後の写真感光材料上に有害な着色を残さないこと。- No harmful coloration remains on the photographic material after processing due to decolorization or dissolution removal during the photographic processing process.
今日までに、前記の条件を満足する染料をみいだすこと
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。例えば米国特許３２４７１２７号、特公昭
３９−２２０６９号、特開昭５０−９１６２７号、特開
昭５２−３４７１６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２４９３７４７号に代表されるメロシアニン
染料、米国特許２８４３４８６号に代表されるシアニン
染料等がある。しかし、前記の諸条件をすべて満足し、
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。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, oxonol dyes described in U.S. Pat. There are merocyanine dyes as typified by No. 1, cyanine dyes as typified by U.S. Pat. No. 2,843,486, and the like. However, if all the above conditions are satisfied,
The reality is that there are very few good dyes that can be used in silver halide photographic materials.
上記のごとき問題に対し、本発明の目的は、現像処理後
の残色が少ない赤色光に対して高感度のハロゲン化銀写
真感光材料を提供することにある。In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that is highly sensitive to red light and has little residual color after processing.
さらに本発明の他の目的は、良好な画像を形成し、経時
安定性に優れたハロゲン化銀写真感光材料を提供するこ
とにある。Still another object of the present invention is to provide a silver halide photographic material that forms good images and has excellent stability over time.
本発明の上記目的は、支持体上に少なくとも１層の感光
性ハロゲン化銀乳剤層を有するハロゲン化銀写真感光材
料において、該乳剤層が下記一般式〔Ｉ〕から選ばれる
少なくとも１種の増感色素により分光増感され、かつ下
記一般式（Ｉ［）で表される染料を少なくとも１種含有
した親水性コロイド層を少なくとも１層含有することを
特徴とするハロゲン化銀写真感光材料により達成される
。The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the emulsion layer has at least one compound selected from the following general formula [I]. Achieved by a silver halide photographic material characterized by containing at least one hydrophilic colloid layer that is spectrally sensitized with a sensitive dye and contains at least one dye represented by the following general formula (I[). be done.
一般式〔Ｉ〕
〔式中、Ｙｌ、及び Ｙ２は、各々ベンゾチアゾール環
、ベンゾセレナゾール環、ナフトチアゾール環、ナフト
セレナゾール環、またはキノリン環を形成するのに必要
な非金属原子団を表し、これらの複素環は低級アルキル
基、アルコキシ基、アリール基、ヒドロキシル基、アル
コキシカルボニル基、ハロゲン原子で置換されていても
良い。General formula [I] [In the formula, Yl and Y2 each represent a nonmetallic atomic group necessary to form a benzothiazole ring, benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, or quinoline ring. , these heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.
Ｒ，、Ｒ，は、それぞれ低級アルキル基、スルホ基を有
するアルキル基またはカルボキシル基を有するアルキル
基を表す。Ｒ８は、メチル基、エチル基、プロピル基を
表す。ｘｌはアニオンを表す。R, , R, each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R8 represents a methyl group, an ethyl group, or a propyl group. xl represents an anion.
ｎｌ、Ｒ２は、ｌまたは２を表す。ｍは、ｌまたは０を
表し、分子内塩の時はｍ＝０を表す。〕一般式（ＩＦ）
〔式中、Ｒ４，Ｒ，は各々少なくとも１つのスルホン酸
基又はカルボン酸基を有するアルキル基、アラルキル基
、アリール基又は複素環基を表し、スルホン酸基又はカ
ルボン酸基は２価の連結基を介してアルキル基、アラル
キル基、アリール基又は複素環基に結合してもよい。Ｒ
ｓ、Ｒｔは各々Ｃ０Ｒａ、 ５Ｏ２Ｒ８，５ＯＲａ又
は−３ＯｚＮＲＩＲ１゜を表しく但し、Ｒ，はアル キ
ル基、アラルキル基又はアリール基を表し、Ｒｓ、Ｒｔ
。は各々水素原子、アルキル基、アラル キル基又はア
リール基を表し、Ｒ９とＲｌｏは連結して５又は６員環
を形成していてもよい。）、 Ｌ ４． Ｌ ｓ、Ｌ
ａ、Ｌ ｒ及びり、は各々メチン基、 置換メチン基を
表し、Ｍは水素原子又はその他のカチオンを表す。〕
次に本発明の構成について、更に具体的に説明する。nl and R2 represent 1 or 2. m represents l or 0, and in the case of an inner salt, m=0. ] General formula (IF) [In the formula, R4, R, each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group having at least one sulfonic acid group or carboxylic acid group, and a sulfonic acid group or a carboxylic acid group may be bonded to an alkyl group, aralkyl group, aryl group or heterocyclic group via a divalent linking group. R
s and Rt each represent C0Ra, 5O2R8, 5ORa, or -3OzNRIR1°; however, R represents an alkyl group, an aralkyl group, or an aryl group, and Rs, Rt
. each represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R9 and Rlo may be connected to form a 5- or 6-membered ring. ), L 4. L s, L
a, L r and R each represent a methine group or a substituted methine group, and M represents a hydrogen atom or other cation. ] Next, the configuration of the present invention will be explained in more detail.
一般式（１）について説明する。General formula (1) will be explained.
上記一般式〔Ｉ〕中、Ｙ、及びＹ２は各々ベンゾチアゾ
ール環、ベンゾセレナゾール環、ナフトチアゾール環、
ナフトチアゾール環またはキノリン環を形成するのに必
要な非金属原子群を表し、これらの複素環は低級アルキ
ル基（例えばメチル基、エチル基等）、アルコキシ基（
例えばメトキシ基、エトキシ基等）、ヒドロキシル基、
アリール基（例えばフェニル基）、アルコキシカルボニ
ル基（例えばトメキシカルボニル基）、ハロゲン原子（
例えば塩素原子、臭素原子等）等で置換されていてもよ
い。Ｒ□、Ｒ３は、低級アルキル基（例えばメチル基、
エチル基、プロピル基、ブチル基等）、スルホ基を有す
るアルキル基（例工ばβ−スルホエチル基、γ−スルホ
プロピル基、γ−スルホブチル基、δ−スルホブチル基
、スルホアルコキシアルキル基（例えばスルホエトキシ
エチル基、スルホプロポキシエチル基）など） カルボ
キシル基を有するアルキル基（例えばβ−カルボキシル
エチル基、γ−カルボキシプロピル基、γカルボキシブ
チル基、δ−カルボキシブチル基等）を表す。Ｒ１は、
メチル基、エチル基、プロピル基を表す。Ｘｌは、シア
ニン色素に通常用いられるアニオン（例えばハロゲンイ
オン、ベンゼンスルホン酸イオン、ｐ−トルエンスルホ
ン酸イオン等）を表す。ｍは、１または０を表し、分子
内塩の時はｍ−０を表す。In the above general formula [I], Y and Y2 are each a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring,
Represents a group of nonmetallic atoms necessary to form a naphthothiazole ring or a quinoline ring, and these heterocycles include lower alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (
For example, methoxy group, ethoxy group, etc.), hydroxyl group,
Aryl groups (e.g. phenyl group), alkoxycarbonyl groups (e.g. tomexycarbonyl group), halogen atoms (
For example, chlorine atom, bromine atom, etc.) may be substituted. R□, R3 are lower alkyl groups (for example, methyl group,
ethyl group, propyl group, butyl group, etc.), alkyl groups having a sulfo group (e.g. β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (e.g. sulfoethoxy (ethyl group, sulfopropoxyethyl group), etc.) represents an alkyl group having a carboxyl group (for example, β-carboxylethyl group, γ-carboxypropyl group, γ-carboxybutyl group, δ-carboxybutyl group, etc.). R1 is
Represents a methyl group, an ethyl group, and a propyl group. Xl represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.). m represents 1 or 0, and represents m-0 when it is an inner salt.
次に、本発明で用いる上記一般式〔Ｉ〕で示される化合
物の具体的な例を示す。但し本発明で用いる化合物はこ
れらに限定されるものではない。Next, specific examples of the compound represented by the above general formula [I] used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.
上記一般式［１）で示される化合物の例示。Examples of compounds represented by the above general formula [1].
■
ｌ
■
■
■
■
■
■
■
■
■
１０
■
１１
■
３
■
１４
Ｈ３
■
１５
■
１６
■
１７
■
８
■
１９
■
２０
■
１
■
２
■
２３
■
４
ＣＣＨ，Ｊ３Ｓ○、′
■
２５
■
２６
■
７
■
＝２８
ｓｏ、ｅ
２９
■
３０
■
３１
■
３２
（ＣＨｚ ） ３ＣＯＯＨ
（ＣＨｚ）ｓＣ（Ｘ戸
■
−３３
■
３４
■
３５
■
３６
■
７
本発明の増感色素は、好ましくはハロゲン化銀１モル当
りｌ ｍｇ〜２ ｇ、更に好ましくは５ｍｇ−１ｇの範
囲でハロゲン化銀写真乳剤中に含有される。■ l ■ ■ ■ ■ ■ ■ ■ ■ ■ 10 ■ 11 ■ 3 ■ 14 H3 ■ 15 ■ 16 ■ 17 ■ 8 ■ 19 ■ 20 ■ 1 ■ 2 ■ 23 ■ 4 CCH, J3S○,' ■ 25 ■ 26 ■ 7 ■ =28 so, e 29 ■ 30 ■ 31 ■ 32 (CHz ) 3COOH (CHz) sC (X door ■ -33 ■ 34 ■ 35 ■ 36 ■ 7 The sensitizing dye of the present invention is preferably silver halide 1 It is contained in the silver halide photographic emulsion in a range of 1 mg to 2 g, more preferably 5 mg to 1 g per mole.
本発明の増感色素は、直接乳剤中へ分散することができ
る。まｌ；、これらはまず適当な溶媒、例えばメチルア
ルコール、エチルアルコール、メチルセロソルブ、アセ
トン、水、ピリジンあるいはこれらの混合溶媒などの中
に溶解され、溶液の形で乳剤へ添加することもできる。The sensitizing dyes of the present invention can be directly dispersed into emulsions. Alternatively, they can be first dissolved in a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.
本発明の増感色素は、単独で用いてもよく、２種類以上
併用してもよい。また、本発明以外の増感色素を組合せ
て用いることもできる。増感色素を併用する場合、総量
で上記含有量になることが好ましい。The sensitizing dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.
なお、本発明の増感色素は、米国特許２５０３７７６号
、英国特許７４２１１２号、仏間特許２０６５６６２号
、特公昭４０−２３４６号を参照して容易に合成するこ
とができる。The sensitizing dye of the present invention can be easily synthesized with reference to US Pat.
本発明の感光性ハロゲン化銀乳剤層は、下記−般式ＣＩ
［］で表される染料を含有した親水性コロイド層を少な
くとも１層有する。The photosensitive silver halide emulsion layer of the present invention has the following general formula CI
It has at least one hydrophilic colloid layer containing a dye represented by [ ].
一般式（１
式中、Ｒ６及びＲ６は各々、少なくとも１つのスルホン
酸基又はカルボン酸基を有するアルキル基、アラルキル
基、アリール基又は複素環基を表し、スルホン酸基又は
カルボン酸基は２価の連結基を介してアルキル基、アラ
ルキル基、アリール基又は複素環基に結合してもよい。General formula (1) In the formula, R6 and R6 each represent an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group having at least one sulfonic acid group or carboxylic acid group, and the sulfonic acid group or carboxylic acid group is a divalent group. may be bonded to an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group via a linking group.
２価の連結基としては、例えばアルキレンアミノ基（例
えば２−スルホエチルアミノ、３−スルホプロピルアミ
ノ、２−カルボキシエチルアミノ）、アルキレンオキシ
基（例えば２−カルボキシエトキシ、４−スルホブトキ
シ）、アルキレンアシルアミン基（例えばβ−カルボキ
シプロピオニルアミノ）、フェニレン基（例えば吋スル
ホフェニル）等が挙げられる。Examples of divalent linking groups include alkylene amino groups (e.g. 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino), alkyleneoxy groups (e.g. 2-carboxyethoxy, 4-sulfobutoxy), alkylene Examples thereof include acylamine groups (eg, β-carboxypropionylamino), phenylene groups (eg, sulfophenyl), and the like.
アリール基、アラルキル基、アルキル基又は複素環基は
、カルボン酸、スルホン酸以外の置換基（例えばフッ素
、塩素、臭素等の）・ロゲン原子、水酸基、シアノ基、
ニトロ基、炭素数１〜４のアルキル基（例えばメチル、
エチル、イソプロピル、ｎ−ブチル）、アリール基（例
えばフェニル、ナフチル）、炭素数１〜６のアルコキシ
基（例えばメトキシ、エトキシ、ｎ−ブトキシ、２−メ
トキシエトキシ、２−ヒドロキシエトキシ）、アリルオ
キシ基（例えばフェノキシ）、アミノ基（例えばジメチ
ルアミノ、ジエチルアミノ）、アシルアミノ基（例えば
アセチルアミノ）等）を有していても良い。Aryl groups, aralkyl groups, alkyl groups, or heterocyclic groups include substituents other than carboxylic acid and sulfonic acid (e.g., fluorine, chlorine, bromine, etc.), rogene atoms, hydroxyl groups, cyano groups,
Nitro group, alkyl group having 1 to 4 carbon atoms (e.g. methyl,
ethyl, isopropyl, n-butyl), aryl groups (e.g. phenyl, naphthyl), alkoxy groups having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-butoxy, 2-methoxyethoxy, 2-hydroxyethoxy), allyloxy groups ( (for example, phenoxy), an amino group (for example, dimethylamino, diethylamino), an acylamino group (for example, acetylamino), etc.).
アリール基は少くとも１個のカルボン酸基又はスルホン
酸基を有するフェニル基（例えば４−スルホフェニル、
４−カルボキシフェニル、２−メチル−４−スルホフェ
ニル、３〜スルホフエニル、２．４−シスルホフェニル
、３．５−ジスルホフェニル、２−クロロ−４−スルホ
フェニル、２メトキシ−４−スルホ７エチル、４−クロ
ル−３−スルホ７エチル、２−メトキシ−５−スルホ７
エチル、２−ヒドロキシ４−スルホフェニル２．５−ジ
クロル−４−スルホフェニル、４−フェノキシ−３−ス
ルホフェニル、４−（３−スルホプロピルオキシ）フェ
ニル、４−（Ｎ−メチル−Ｎ−スルホエチルアミノ）フ
ェニル、３−カルボキシ−２−ヒドロキシ−５−スルホ
フェニル、２．６−ジエチル−４−スルホフェニル）又
はす７チル基（例えば３，６−ジスルホ−α−す７チル
、８−ヒトａキシ−３，６−ジスルホ−α−ナフチル、
５−ヒドロキシ＝７−スルホ−β−ナフチル、６．８−
ジスルホβ−す７チル）が好ましい。An aryl group is a phenyl group having at least one carboxylic or sulfonic acid group (e.g. 4-sulfophenyl,
4-carboxyphenyl, 2-methyl-4-sulfophenyl, 3-sulfophenyl, 2.4-cisulfophenyl, 3.5-disulfophenyl, 2-chloro-4-sulfophenyl, 2methoxy-4-sulfophenyl Ethyl, 4-chloro-3-sulfo7ethyl, 2-methoxy-5-sulfo7
Ethyl, 2-hydroxy 4-sulfophenyl 2.5-dichloro-4-sulfophenyl, 4-phenoxy-3-sulfophenyl, 4-(3-sulfopropyloxy)phenyl, 4-(N-methyl-N-sulfophenyl) ethylamino)phenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 2,6-diethyl-4-sulfophenyl) or 7-tyl groups (e.g. 3,6-disulfo-α-7-tyl, 8- human axy-3,6-disulfo-α-naphthyl,
5-hydroxy=7-sulfo-β-naphthyl, 6.8-
Disulfo β-su7tyl) is preferred.
アラルキル基は少くとも１個のカルボン酸基又はスルホ
ン酸基を有する炭素数７〜１５のアラルキル基（Ｍえハ
、４−スルホベンジル、２−スルホベンジル、２．４−
ジスルホベンジル、２−（４−スルホブチルオキシ）ベ
ンジル、４−メチル−２−スルホベンジル４−スルホ７
エネチル
４−シー（３−スルホプロピルオキシ）ベンジル、２−
ヒドロキシ−４−（２−スルホエトキシ）ベンジル）が
好ましい。The aralkyl group is a C7-15 aralkyl group having at least one carboxylic acid group or sulfonic acid group (Meha, 4-sulfobenzyl, 2-sulfobenzyl, 2.4-
Disulfobenzyl, 2-(4-sulfobutyloxy)benzyl, 4-methyl-2-sulfobenzyl 4-sulfo7
enethyl 4-c(3-sulfopropyloxy)benzyl, 2-
Hydroxy-4-(2-sulfoethoxy)benzyl) is preferred.
アルキル基は、少くとも１個のカルボン酸基又はスルホ
ン酸基を有する炭素数１〜６のアルキル基（例えば、ス
ルホメチル、カルボキシメチル、２スルホエチル、２−
カルボキシエチル、３−スルホブチル、３−スルホ−２
−メチルグロビル、３−スルホ−２，２−ジメチルプロ
ピル、４−スルホブチル、４〜カルポキシフチル、５−
スルホペンチルヘキシル、５−カルボキシペンチル、６
−カルボキシヘキシル）が好ましい。The alkyl group is an alkyl group having 1 to 6 carbon atoms and having at least one carboxylic acid group or sulfonic acid group (for example, sulfomethyl, carboxymethyl, 2-sulfoethyl, 2-
Carboxyethyl, 3-sulfobutyl, 3-sulfo-2
-Methylglobil, 3-sulfo-2,2-dimethylpropyl, 4-sulfobutyl, 4-carpoxyphthyl, 5-
Sulfopentylhexyl, 5-carboxypentyl, 6
-carboxyhexyl) is preferred.
複素環基は少くとも１個のカルボン酸基又はスルホン酸
基を有し、かつ少くとも１個の窒素原子を有する５又は
６員の含窒素複素環基（例えば５−スルホピリジン−２
−イル、５−カルボキシピリジン−２−イル、６−スル
ホキノリン−２−イル、６−スルホキノリン−４ーイル
、５−スルホベンゾチアゾール−２−イル、５〜カルボ
キシベンゾチアゾール−２−イル、６−スルホベンゾオ
キサゾール−２−イル、６〜カルボキシベンゾオキサゾ
ール−２−イル、６−スルホメチルビリジン−２−イル
、５−スルホピリミジン−２−イル）が好ましい。The heterocyclic group is a 5- or 6-membered nitrogen-containing heterocyclic group having at least one carboxylic acid group or sulfonic acid group and at least one nitrogen atom (for example, 5-sulfopyridine-2
-yl, 5-carboxypyridin-2-yl, 6-sulfoquinolin-2-yl, 6-sulfoquinolin-4-yl, 5-sulfobenzothiazol-2-yl, 5-carboxybenzothiazol-2-yl, 6 -sulfobenzoxazol-2-yl, 6-carboxybenzoxazol-2-yl, 6-sulfomethylpyridin-2-yl, 5-sulfopyrimidin-2-yl) are preferred.
但し、Ｒ４及びＲ．が少なくとも１個のスルホン酸基を
有するフェニル基、少くとも１個のスルホン酸基を有す
る炭素数１〜４のアルキル基、又は少くとも１個のスル
ホン酸基を有するベンジル基、もしくは７エネチル基で
あることが持に好ましい。However, R4 and R. a phenyl group having at least one sulfonic acid group, an alkyl group having 1 to 4 carbon atoms having at least one sulfonic acid group, a benzyl group having at least one sulfonic acid group, or a 7-enethyl group It is particularly preferable that
Ｒ，及びＲ，は各々−ＣＯＲ＊ 、 ＳＯｘＲａ
、 ＳＯＲｓ又はＳＯＪＲｅＲ＋ｏを表す。但し、
Ｒ．はアルキル基、アラルキル基又はアリール基を表し
、Ｒｔ，Ｒ１。は各々水素原子、アルキル基、アラルキ
ル基又はアリール基を表し、ＲｔとＲ，。は速結して５
又は６員環を形成していてもよい。Ｒ，、Ｒ，又はＲ１
．におけるアルキル基は置換基（例えばフッ素、塩素等
のハロゲン原子、水酸基、カルボン酸基、スルホン酸基
、炭素数１〜６のアルコキシ基（例えばメトキシ、エト
キシ、ｎ−ブトキシ）、シアノ基、アミノ基（例えばジ
メチルアミノ、ジエチルアミノ））を有していても良く
、炭素数１〜８のアルキル基（例えばメチル、エチル、
ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブ
チル、ｔ−ブチル、イソ７チル、ｎ−ペンチル、ｓｅｃ
−ペンチル、イソアミル、ｎ−ヘキシル、ｎ−へブチル
、ｎ−オクチル、２−エチルヘキシル、２−エチルブチ
ル、トリフルオロメチル、２−クロロエチル、２−ヒド
ロキシエチル、４−ヒドロキシブチル、５−ヒドロキシ
ペンチル、６−ヒドロキシヘキシル、７−ヒドロキシペ
ンチル、２−スルホエチル、２−カルボキシエチル、４
−スルホブチル、２−シアノエチル、４−ジメチルアミ
ノブチル）又は炭素数５〜７の脂肪式アルキル基（例え
ばシクロペンチル、シクロヘキシル）が好ましい。R, and R are respectively -COR* and SOxRa
, represents SORs or SOJReR+o. however,
R. represents an alkyl group, an aralkyl group, or an aryl group, and Rt, R1. each represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and Rt and R. is a quick connection of 5
Alternatively, it may form a 6-membered ring. R,, R, or R1
．． The alkyl group in is a substituent (e.g. halogen atom such as fluorine or chlorine, hydroxyl group, carboxylic acid group, sulfonic acid group, alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-butoxy), cyano group, amino group (e.g. dimethylamino, diethylamino)), and may have an alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, iso7tyl, n-pentyl, sec
-pentyl, isoamyl, n-hexyl, n-hebutyl, n-octyl, 2-ethylhexyl, 2-ethylbutyl, trifluoromethyl, 2-chloroethyl, 2-hydroxyethyl, 4-hydroxybutyl, 5-hydroxypentyl, 6 -Hydroxyhexyl, 7-hydroxypentyl, 2-sulfoethyl, 2-carboxyethyl, 4
-sulfobutyl, 2-cyanoethyl, 4-dimethylaminobutyl) or aliphatic alkyl groups having 5 to 7 carbon atoms (eg cyclopentyl, cyclohexyl).
Ｒ．、Ｒ，またはＲＩＤにおけるアラルキル基は置換基
（例えばフッ素、塩素等のハロゲン原子、水酸基、スル
ホン酸基、カルボン酸基、炭素数１〜４のアルキル基（
例えばメチル、エチル、ｎ〜プロヒル、ｎ−ブチル）、
炭素数１〜６のアルコキシ基（例えばメトキシ、エトキ
シ、ｎ−ブトキシ）、シアノ基、ニトロ基、アルコキシ
カルボニル基（例えばカルベトキシくメトキシカルボニ
ル）、アミン基（例えばジメチルアミノ、ジエチルアミ
ノ））を有していでも良く、炭素数７〜１５のアラルキ
ル基（例えばベンジル、フェネチル、４−メチルベンジ
ル、２−クロロベンジル、４−メトキシベンシル）カＪ
ｆＦ！しい。R. , R, or RID is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, an alkyl group having 1 to 4 carbon atoms (
For example, methyl, ethyl, n-proyl, n-butyl),
It has an alkoxy group (e.g. methoxy, ethoxy, n-butoxy), a cyano group, a nitro group, an alkoxycarbonyl group (e.g. carbethoxy, methoxycarbonyl), an amine group (e.g. dimethylamino, diethylamino)) having 1 to 6 carbon atoms. An aralkyl group having 7 to 15 carbon atoms (e.g. benzyl, phenethyl, 4-methylbenzyl, 2-chlorobenzyl, 4-methoxybenzyl) may also be used.
fF! Yes.
Ｒ，、Ｒ，またはＲ□。におけるアリール基は置換基（
例えばフッ素、塩素等のハロゲン原子、水酸基、カルボ
ン酸基、スルホン酸基、炭素数１〜４のアルキル基（例
えばメチル、エチル、イソプロピル、ｎ−プロピル、ｎ
−ブチル）、炭素数１〜６のアルコキシ基（例えばメト
キシ、エトキシ、ｎ−ブトキシ）、シアノ基、ニトロ基
、アルコキシカルボニル基（例えばカルベトキシ、メト
キシカルボニル）、アミノ基（例えばジメチルアミノ、
ジエチルアミノ））を有していても良く、フェニル基（
例、ｔ ｉｆ 非ｆ Ｗｋのフェニル基、３−スルホフ
ェニル、４−スルホフェニル、４−力ルポキシフェニル
、４−ヒドロキシフェニル、２−ヒドロキシフェニル、
２−スルホフェニル、４−シアノフェニル、 ３．４−
ジクロルフェニル、４−メトキシフェニル、４−（３−
スルホプロポキシ）フェニル、４−ニトロフェニル、４
−カルベトキシフェニル、４−メチルフェニル、２−メ
チルフェニル、４−フルオロフェニル）又はす７チル基
が好ましい。R,, R, or R□. The aryl group in is a substituent (
For example, halogen atoms such as fluorine and chlorine, hydroxyl groups, carboxylic acid groups, sulfonic acid groups, alkyl groups having 1 to 4 carbon atoms (e.g. methyl, ethyl, isopropyl, n-propyl, n
-butyl), alkoxy groups having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-butoxy), cyano groups, nitro groups, alkoxycarbonyl groups (e.g. carbetoxy, methoxycarbonyl), amino groups (e.g. dimethylamino,
diethylamino)), and may have a phenyl group (
Examples, t if non-f Wk phenyl group, 3-sulfophenyl, 4-sulfophenyl, 4-rupoxyphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl,
2-sulfophenyl, 4-cyanophenyl, 3.4-
Dichlorophenyl, 4-methoxyphenyl, 4-(3-
sulfopropoxy)phenyl, 4-nitrophenyl, 4
-carbetoxyphenyl, 4-methylphenyl, 2-methylphenyl, 4-fluorophenyl) or 7-tyl group are preferred.
Ｌ４− Ｌｓ、Ｌｍ、 Ｌｙ、及びＬ８は各々メチン基
、置換メチン基を表し、置換基としては例えばメチル基
、エチル基、スルホエチル基、塩素原子、シアノ基等が
挙げられる。L4-Ls, Lm, Ly, and L8 each represent a methine group or a substituted methine group, and examples of the substituent include a methyl group, an ethyl group, a sulfoethyl group, a chlorine atom, and a cyano group.
Ｍは水素原子又はその他のカチオンを表し、カチオンと
しては、金属イオン（例えばＮａ、 Ｋ）又は無機もし
くは有機アンモニウムイオン（例えばＮＨ，、（ＣｚＨ
ｓ）ｓＮＨい ピリジニウム）が好ましい。M represents a hydrogen atom or other cation, and the cation may be a metal ion (e.g. Na, K) or an inorganic or organic ammonium ion (e.g. NH, (CzH)
s) sNH (pyridinium) is preferred.
次に上記一般式（ｎ）で示される化合物の具体例を示す
が、本発明はこれによって限定されるも一般式（ＩＦ）
で表される染料は特公昭４３−３５０４号、特開昭４９
−９９６２０号、特開昭４９−５１２５号、米国特許第
２，２７４．７８２号、特開昭６２−２７３５２７号に
、また中間体の２−ピラゾリン−５−オンは特開昭６２
−２７３５２７号あるいはアール・エッチ・ウィリ（Ｒ
，Ｈ，Ｗｉｌｅｙ）、ピー・ウィリー（ｐ、Ｗｉ １ｅ
ｙ）著、ヘテロサイクリック・コンパウンド：ピラゾロ
ン、ビプゾリドン・アンドプリバチイブ（Ｈｅｔｅｒｏ
ｃｙｃｌｉｃ Ｃｏｍｐｏｎｄｓ ：Ｐｙｒａｚｏｒｏ
ｎｅｓ、 Ｐｙｒａｚｏｒｉｄｅｎｅｓ ａｎｄ Ｄｅ
ｒｉｖａｔｉｖｅｓ）（インターサイエンス バプリシ
ャー ジョン・ウイリーアンドサンズニューヨーク １
９６４年）等に記載された方法で合成することができる
。Next, specific examples of the compound represented by the above general formula (n) will be shown, but although the present invention is limited thereto, the general formula (IF)
The dye represented by is disclosed in Japanese Patent Publication No. 43-3504,
-99620, JP-A No. 49-5125, U.S. Pat.
-273527 or R H Willi (R
, H, Wiley), Pee Wiley (p, Wiley)
Y), Heterocyclic Compounds: Pyrazolone, Bipzolidone and Privatib (Hetero
cyclic compounds: Pyrazoro
nes, Pyrazoridenes and De
rivatives) (Interscience Vaprisher John Wiley and Sons New York 1)
964) and others.
本発明のハロゲン化銀写真感光材料において、前記一般
式（ｎ）で示される染料は、ハロゲン化銀写真感光乳剤
中に含有させてイラジェーショ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
含有させてフィルター染料あるいはハレーション防止染
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
合せ用いてもよい。本発明に係る染料をハロゲン化銀写
真感光乳剤中あるいは、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ｌこ行うと
ができる。一般には、染料または染料の有機・無機アル
カリ塩の水溶液を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、使用目的によって異な
るが、一般には感光材料上の面積１ｍ２あたり１．０−
１０００ｍｇにするように塗布して用いる。In the silver halide photographic light-sensitive material of the present invention, the dye represented by the general formula (n) can be incorporated into the silver halide photographic emulsion and used as an irradiation-preventing dye, or it can be used as an anti-irradiation dye. It can also be used as a filter dye or antihalation dye by incorporating it into a hydrophilic colloid layer. Also, depending on the purpose of use, 2
More than one type of dye 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 or other hydrophilic colloid layer by a conventional method. Generally, an aqueous solution of a dye or an organic or inorganic alkali salt of a dye is added to a coating solution for coating, thereby making it possible to incorporate the dye into the silver halide photographic light-sensitive material. The content of these dyes varies depending on the purpose of use, but is generally 1.0-1 m2 of area on the photosensitive material.
It is applied and used to give a total amount of 1000 mg.
本発明の感光材料に用いるハロゲン化銀乳剤には、ハロ
ゲン化銀として、臭化銀、塩化銀、沃臭化銀、塩臭化銀
、塩沃臭化銀等の通常のハロゲン化銀乳剤に使用される
任意のものを用いる事ができるが、塩化銀を５０モル％
以上含むことが好ましく、粒径は０．２μｍ以上、０．
５μｍ以下が好ましい。また乳剤層側のゼラチン量は２
．８ｇ／ｍ”以下、好ましくは２−５ｇ／ｍ”以下であ
る。The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used material can be used, but 50 mol% silver chloride
The particle size is preferably 0.2 μm or more, and 0.2 μm or more.
The thickness is preferably 5 μm or less. Also, the amount of gelatin on the emulsion layer side is 2
．． 8 g/m" or less, preferably 2-5 g/m" or less.
ハロゲン化銀粒子は、酸性法、中性法及びアンモニア法
のいずれで得られたものでもよい。The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.
ハロゲン化銀粒子は、粒子内において均一なハロゲン化
銀組成分布を有するものでも、粒子の内部と表面層とで
ハロゲン化銀組成が異なるコア／シェル粒子であっても
よく、潜像が主として表面に形成されるような粒子であ
っても、また主として粒子内部に形成されるような粒子
でもよい。Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.
本発明に係るハロゲン化銀粒子の形状は任意のものを用
いることができる。好ましい１つの例は、（１００）面
を結晶表面として有する立方体である。Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.
又、米国特許４．１８３．７５６号、同４，２２５．６
６６号、特開昭５５−２６５８９号、特公昭５５−４２
７３７号等の明細書や、ザ・ジャーナル・オブ・フォト
グラフィック・サイエンス（Ｊ、Ｐｈｏｔｇｒ、５ｃｉ
） 、 ２１．３９ （１９７３）等の文献に記載され
た方法により、８面体、１４面体、１２面体等の形状を
有する粒子をつくり、これを用いることもできる。更に
、双晶面を有する粒子を用いてもよい。Also, U.S. Patent Nos. 4.183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
Specifications such as No. 737, The Journal of Photographic Science (J, Photogr, 5ci
), 21.39 (1973), etc., particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared and used. Furthermore, particles having twin planes may be used.
本発明に係るハロゲン化銀粒子は、単一の形状からなる
粒子を用いてもよいし、種々の形状の粒子が混合された
ものでもよい。The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.
又、いかなる粒子サイズ分布を持つものを用いてもよく
、粒子サイズ分布の広い乳剤（多分散乳剤と称する）を
用いてもよいし、粒子サイズ分布の狭い乳剤（単分散乳
剤と称する。）を単独又は数種類混合してもよい。又、
多分散乳剤上単分散乳剤を混合して用いてもよい。Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A mixture of a polydisperse emulsion and a monodisperse emulsion may be used.
ハロゲン化銀乳剤は、別々に形成した２種以上のハロゲ
ン化銀乳剤を混合して用いてもよい。The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.
本発明において、単分散乳剤が好ましい。単分散乳剤中
の単分散のハロゲン化銀粒子としては、平均粒径７を中
心に１２０％の粒径範囲内に含まれるハロゲン化銀重量
が、全ハロゲン化銀粒子重量の６０％以上であるものが
好ましく、特に好ましくは７０％以上、更に好ましくは
８０％以上である。In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within a grain size range of 120% around an average grain size of 7 is 60% or more of the weight of all silver halide grains. It is particularly preferably 70% or more, and even more preferably 80% or more.
ここに平均粒径Ｔは、粒径ｒｉを有する粒子の頻度ｎｉ
とｒｉ３との積ｎｉＸ ｒｉ’が最大となるときの粒径
ｒｉを定義する。Here, the average particle size T is the frequency ni of particles having particle size ri
The grain size ri when the product niX ri' of ri3 and ri3 is maximum is defined.
（有効数字３桁、最小桁数字は四捨五入する。）ここで
言う粒径とは、球状のハロゲン化銀粒子の場合は、その
直径、又球状以外の形状の粒子の場合は、その投影像を
周面積の円像に換算した時の直径である。(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.
粒径は例えば該粒子を電子顕微鏡で１万倍から５万倍に
拡大して撮影し、そのプリント上の粒子直径又は投影時
の面積を実測することＩこよって得られることができる
。（測定粒子個数は無差別に１０００個以上ある事とす
る。）
本発明の特に好ましい高度の単分散乳剤はによって定義
しｔ；単分散度が２０以下のものであり、更に好ましく
は１５以下のものである。The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on a print. (The number of grains to be measured is indiscriminately 1,000 or more.) Particularly preferred highly monodisperse emulsions of the present invention are those with a degree of monodispersity of 20 or less, more preferably 15 or less. It is something.
ここに平均粒径及び粒径標準偏差は前記定義のｒｉから
求めるものとする。単分散乳剤は特開昭５４４８５２１
号、同５８−４９９３８号及び同６０−１２２９３５号
等を参考にして得ることができる。Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. The monodispersed emulsion is disclosed in Japanese Patent Application Laid-Open No. 5448521.
No. 58-49938 and No. 60-122935.
感光性ハロゲン化銀乳剤は、化学増感を行わないで、い
わゆる未後熱（ｐｒｉｍｉｔｉｖｅ）乳剤のまま用いる
こともできるが、通常は化学増感される。Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized.
化学増感のためには、前記Ｇｌａｆｋｉｄｅｓ又は、Ｚ
ｅｌｉｋｍａｎらの著書、或いはＨ，Ｆｒ １ｅｓｅｒ
編デ・グルンドラーゲン・デル・フォトグラフィジエン
・プロツェセ・ミド・ジルベルハロゲニーデン（Ｄｉｅ
Ｇｒｕｎｄｌａｇｅｎ ｄｅｒ Ｐｈｏｔｏｇｒａｐ
ｈｉｓｃｈｅｎ Ｐｒｏｚｅｓｓｅ ｍｉｔ Ｓｉｌｂ
ｅｒｈａｌｏｇｅｎｉｄｅｎ、 Ａｋａｄａｍｉｃｃｈ
ｅ Ｖｅｒｌａｇｓｇｅｓｅｌｌｓｃｈａｆｔ１１９６
８）に記載の方法を用いることができる。For chemical sensitization, the Glafkides or Z
elikman et al. or H.Fr.
Die Grundlagen der Fotografisien Prozesse Mid Zilber Halogennieden (Die
Grundlagen der Photograp
hischen Prozesse mit Silb
Erhalogeniden, Akadamich
e Verlagsgesellschaft1196
The method described in 8) can be used.
即ち、銀イオンと反応し得る硫黄を含む化合物や活性ゼ
ラチンを用いる硫黄増感法、還元性物質を用いる還元増
感法、金その他の貴金属化合物を用いることができる。That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.
又、化学増感時のｐＨ，Ｉ）Ａｇ、温度等の条件は特に
制限はないが、ｐＨ値としては４〜９、特に５〜８が好
ましく、ｐＡｇ値としては５〜１１、特に７〜９に保つ
のが好ましい。又温度としては、４０〜９０℃、特に４
５〜７５℃が好ましい。In addition, there are no particular restrictions on the conditions such as pH, I)Ag, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11, particularly 7 to 8. It is preferable to keep it at 9. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.
本発明で用いる写真乳剤は、前述した硫黄増感、金・硫
黄増感の他、還元性物質を用いる還元増感法：貴金属化
合物を用いる貴金属増感法などを併用することもできる
。In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.
感光性乳剤としては、前記乳剤を単独で用いてもよく、
二種以上の乳剤を混合してもよい。As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.
本発明の実施に際しては、上記のような化学増感の終了
後に、例えば、４−ヒドロキシ−６−メチル−１，３，
３ａ、７−チトラザインデン、５−メルカプト−１−フ
ェニルテトラゾール、２−メルカプトベンゾチアゾール
等を始め、種々の安定剤も使用できる。When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.
更に必要であればチオエーテル等のハロゲン化銀溶剤、
又はメルカプト基含有化合物や増感色素のような晶癖コ
ントロール剤を用いてもよい。Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.
本発明の乳剤に用いられるハロゲン化銀粒子は、粒子を
形成する過程及び／又は成長させる過程で、カドミウム
塩、亜鉛塩、鉛塩、タリウム塩、イリジウム塩又は錯塩
、ロジウム塩又は錯塩、鉄塩又は錯塩を用いて金属イオ
ンを添加し、粒子内部に及び／又は粒子表面に包含させ
る事ができる。The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.
本発明の乳剤は、ハロゲン化銀粒子の成長の終了後に不
要な可溶性塩類を除去しても良いし、あるいは含有させ
たままでもよい。該塩類を除去する場合には、リサーチ
・ディスクロジャー１７６４３号記載の方法に基づいて
行うことができる。In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.
本発明に係るハロゲン化銀写真感光材料においては、更
に増感色素を添加して併用してもよい。In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.
用いられる色素には、シアニン色素、メロシアニン色素
、複合シアニン色素、複合メロシアニン色素、ホロポー
ラ−シアニン色素、ヘミシアニン色素、スチリル色素及
びヘミオキサノール色素等が包含される。The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.
本発明で用いる増感色素は、通常のネガ型ハロゲン化銀
に用いられると同等の濃度で用いられる。The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver halide.
特に、ハロゲン化銀乳剤の固有感度を実質的に落とさな
い程度の色素濃度で用いるのが有利である。In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.
ハロゲン化＃！Ｉモル当り増感色素の約１．ＯＸ １０
−’〜約５ Ｘ １０−’モルが好ましく、特にハロゲ
ン化銀１モル当り増感色素の約４ Ｘ １０−’〜２
Ｘ １０−’モルの濃度で用いることが好ましい。Halogenated #! Approximately 1.0 mol of sensitizing dye per mole. OX10
-' to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 moles of sensitizing dye per mole of silver halide.
It is preferred to use a concentration of X 10-' molar.
本発明の増感色素を１種又は２種以上組合せて用いるこ
とができる。増感色素は単独で用いてもよく、又これら
を組合せて用いてもよい。増感色素の組合せは特に強色
増感の目的でしばしば用いられる。The sensitizing dyes of the present invention can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.
本発明Ｉこ係るハロゲン化銀写真感光材料には、親水性
コロイド層にフィルター染料として、あるいはイラジェ
ーシコン防止、ハレーション防止その他種々の目的で水
溶性染料を含有してよい。このような染料には、オキソ
ノール染料、ヘミオキソノール染料、スチリル染料、メ
ロシアニン染料、シアニン染料及びアゾ染料等が包含さ
れる。中でもオキサノール染料：ヘミオキサノール染料
及びメロシアニン染料が有用である。The silver halide photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful.
本発明に係るハロゲン化銀写真感光材料において、親水
性コロイド層に染料や紫外線吸収剤等が包含される場合
に、それらはカチオン性ポリマー等によって媒染されて
もよい。In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.
上記の写真乳剤には、ハロゲン化銀写真感光材料の製造
工程、保存中或いは処理中の感度低下やカブリの発生を
防ぐために種々の化合物を添加することができる。Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material.
又、本発明のハロゲン化銀写真感光材料は、写真構成層
中に米国特許３，４１１．９１１号、同３，４１１．９
１２号、特公昭４５−５３３１号等に記載のアルキルア
クリレート系ラテックスを含むことができる。Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411.911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.
本発明の感光材料には、更に目的に応じて種々の添加剤
を用いることができる。これらの添加剤は、より詳しく
は、リサーチディスクロージャー第１７６巻１ ｔｅｍ
１７６４３ （１９７８年１２月）及び同１８７巻■ｔ
ｅｍ１８７１６ （１９７９年１１月）に記載されてお
り、その添加剤種類
ＲＤ １７６４３
ＲＤ １８７１６
１、化学増感剤
２３頁
６４８頁右欄
２、感度上昇剤
同上
４、増白剤
２４頁
７、スティン防止剤 ２５頁右欄 ６５０
頁左〜右欄８、色素画像安定剤 ２５頁９、
硬 膜 剤 ２６頁 ６５１頁左
欄ｌＯ，バインダー ２６頁
同上１１、可塑剤・潤滑剤 ２７頁
６５０右欄１２、塗布助剤・表面活性剤 ２６〜２７
頁 同上１３、スタチック防止剤 ２７
頁 同上本発明のハロゲン化銀写真感光材料の
実施において、例えば乳剤層その他の層は写真感光材料
に通常用いられている可撓性支持体の片面又は両面に塗
布して構成することができる。可撓性支持体として有用
なものは、硝酸セルロース、酢酸セルロース、酢酸酪酸
セルロース、ホリスチレン、ポリ塩化ビニル、ポリエチ
レンテレフタレート、ポリカーボネート等の半合成又は
合成高分子からなるフィルム、バライタ層又はσ−オレ
フィンポリマー（例えばポリエチレン、ポリプロピレン
、エチレン／ブテン共重合体）等を塗布又はラミネート
した紙などである。支持体は、染料や顔料を用いて者色
されてもよい。遮光の目的で黒色にしてもよい。これら
の支持体の表面は一般に、乳剤層等との接着をよくする
ために下塗処理される。下！＆処理は、特開昭５２−１
（１４９１３号、同５９−１８９４９号、同５９−１９
９４０号、同５９−１８９４９号各公報に記載されてい
る処理が好ましい。The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the additive types are RD 17643 RD 18716 1, chemical sensitizers, page 23, page 648, right column 2, sensitivity increasing agents, same as above 4, brighteners, page 24, 7, stain prevention. Agent page 25 right column 650
Page left to right column 8, Dye image stabilizer 25 page 9,
Hardener page 26, page 651 left column lO, binder page 26
Same as above 11, plasticizer/lubricant page 27
650 right column 12, coating aid/surfactant 26-27
Page same as above 13, anti-static agent 27
Page Same as above In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers, or σ-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. under! & Processing is JP-A-52-1
(No. 14913, No. 59-18949, No. 59-19
The treatments described in Publications No. 940 and No. 59-18949 are preferred.
支持体表面は、下塗処理の前又は後にコロナ放電、紫外
線照射、火焔処理等を施してもよい。The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.
本発明に係るハロゲン化銀写真感光材料において、写真
乳剤層その他の親水性コロイド層は種々の塗布法により
支持体上又は他の層の上に塗布できる。塗布には、デイ
ツプ塗布法、ローラー塗布法、カーテン塗布法、押出し
塗布法等を用いることができる。In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.
本発明における現像時間が２０秒以内好ましくは、１５
秒以内で処理される現像・定漕・水洗・乾燥工程につい
て記す。The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describes the development, constant tank, water washing, and drying processes that are completed within seconds.
本発明に使用する黒白現像液に用いる現像主薬には良好
な性能を得やすい点で、ジヒドロキシベンゼン鋼と１−
フェニル−３−ピラゾリドン類の組合せが最も好ましい
。勿論この他にｐ−アミノフェノール系現像主薬を含ん
でもよい。The developing agent used in the black and white developer used in the present invention is dihydroxybenzene steel and 1-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.
本発明に用いるジヒドロキシベンゼン現像主薬としては
ハイドロキノン、クロロハイドロキノン、ブロムハイド
ロキノン、イソプロピルハイドロキノン、メチルハイド
ロキノン、２．３−ジクロロハイドロキノン、２．５−
ジクロロハイドロキノン１．２．３−ジブロムハイドロ
キノン、２．５−ジメチルハイドロキノンなどがあるが
特にハイドロキノンが好ましい。The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Dichlorohydroquinone, 1,2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred.
本発明に用いるｌ−）二ニルー３−ピラゾリドン又はそ
の誘導体の現像主薬としては１−フェニル＝４．４−ジ
メチル−３−ピラゾリドン、ｌ−フェニル−４−メチル
−４−ヒドロキシメチル−３−ピラゾリドン、ｌ−フェ
ニル−４，４−ジヒドロキシメチル−３−ピラゾリドン
などがある。As the developing agent for l-)dynyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl=4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone , l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, and the like.
本発明に用いるｐ−アミノフェノール系現像主薬として
はＮ−メチル−ｐ−アミノフェノール、ｐ−アミノフェ
ノール、Ｎ−（β−ヒドロキシエチル）−ｐ−アミノフ
ェノール、Ｎ−（４−ヒドロキシフェニル）クリジン、
２−メチル−ｐ−アミノフェノール、ｐ−ベンジルアミ
ノフェノール等があるが、なかでもＮ−メチル−ｐ−ア
ミノフェノールが好ましい。Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)cridine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.
現像主薬は通常００吋モル／（１−１，２モル／ａの量
で用いられるのが好ましい。The developing agent is preferably used in an amount of 00 mmol/(1-1.2 mol/a).
本発明に用いる亜硫酸塩の保恒剤としては亜硫酸ナトリ
ウム、亜硫酸カリウム、亜硫酸リチウム、亜硫酸アンモ
ニウム、重亜硫酸ナトリウム、メタ重亜硫酸カリウム、
ホルムアルデヒド重亜硫酸ナトリウムなどがある。亜硫
酸塩は０．２モル／ａ以上特に０．４モルフ１２以上が
好ましい。また、上限は２．５モル／ａまでとするのが
好ましい。Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The sulfite is preferably 0.2 mol/a or more, particularly 0.4 mol/a or more. Further, the upper limit is preferably up to 2.5 mol/a.
本発明に用いる現像液のｐＨは９から１３までの範囲の
ものが好ましい。更に好ましくはｐＨ１０から１２まで
の範囲である。The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12.
ｐＨの設定のために用いるアルカリ剤には水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム
、第三リン酸ナトリウム、第三リン酸カリウムの如きｐ
Ｈ調節剤を含む。Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.
特開昭δｌ−２８７０８号（ホウ酸塩）、特開昭６０−
９３４３９号（例えば、サッカロース、アセトオキシム
、５−スルホサルチル酸）、リン酸塩、炭酸塩などの緩
衡剤を用いてもよい。JP-A No. 81-28708 (Borate), JP-A No. 60-
Buffers such as No. 93439 (e.g., sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.
上記成分以外に用いられる添加剤としては、臭化ナトリ
ウム、臭化カリウム、沃化カリウムの如き現像抑制剤：
エチレングリコール、ジエチレングリコール、トリエチ
レングリコール、ジメチルホルムアミド、メチルセロソ
ルブ、ヘキシレングリコール、ニチノール、メタノール
の如き有機溶剤：１−フェニル−５−メルカプトテトラ
ゾール、２メルカプトベンツイミダゾール−５−スルホ
ン酸ナトリウム塩等のメルカプト系化合物、５−ニトロ
インダゾール等のインダゾール系化合物、５−メチルベ
ンツトリアゾール等のペンツトリアゾール系化合物など
のカブリ防止剤を含んでもよく、更に必要に応じて色調
剤、界面活性剤、消泡剤、硬水軟化剤、特開昭５６−１
０６２４４号記載のアミン化合物などを含んでもよい。Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, nitinol, methanol; mercapto such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt; It may also contain antifoggants such as indazole compounds such as 5-nitroindazole, penztriazole compounds such as 5-methylbenztriazole, and, if necessary, color toners, surfactants, antifoaming agents, etc. Hard water softener, JP-A-56-1
The amine compound described in No. 06244 may also be included.
本発明においては現像液に銀汚れ防止剤、例えば特開昭
５６−２４３４７号に記載の化合物を用いることができ
る。In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.
本発明の現像液には、特開昭５６−１０６２４４号に記
載のアルカノールアミンなどのアミノ化合物を用いるこ
とができる。In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.
この他り、Ｆ、Ａ、メソン著「フォトグラフィック・プ
ロセシン・ケミストリー」、７オーカル・プレス刊り、
Ｆ、Ａ、ＭＡＳＯＮ、Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒ
ｏｃｅｒｓｉｎｇＣｈｅｍｉｓｔｒｙ、Ｆｏｃａｌ Ｐ
ｒｅｓｓ、Ｌｏｎｄｏｎ （１９６６年）の２２６〜２
２９頁、米国特許第２．１９３，０１５号、同２，５９
２，３６４号、特開昭４８−６４９３３号などに記載の
ものを用いてもよい。In addition, "Photographic Processing Chemistry" by F. A. Meson, published by 7 Orcal Press,
F, A, MASON, Photographic Pr.
occeringChemistry, Focal P
ress, London (1966), 226-2.
p. 29, U.S. Patent No. 2,193,015, 2,59
2,364, JP-A No. 48-64933, etc. may be used.
以下、本発明を実施例により説明するが、本発明はこれ
により限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
ゼラチン６０ｇを水で溶解し、その中に表１で示す染料
を２．０ｇそれぞれ添加した。更に延展剤として１−デ
シル−２−（３−インペンチル）サクシネート−２−ス
ルホン酸ナトリウム塩１％水溶液を４０ｍＱ、硬膜剤と
してグリオキザールの４％水溶液４５ｍ１２加えて全量
ＩＩ２とした。このゼラチン含有水溶液をポリエチレン
テレフタレートフィルム支持体上ｌこゼラチン付量が３
−２ｇ７ｍ”になるように塗布した。Example 1 60 g of gelatin was dissolved in water, and 2.0 g of each of the dyes shown in Table 1 was added thereto. Further, 40 mQ of a 1% aqueous solution of 1-decyl-2-(3-inpentyl)succinate-2-sulfonic acid sodium salt as a spreading agent and 45 m12 of a 4% aqueous solution of glyoxal as a hardening agent were added to make the total amount II2. This gelatin-containing aqueous solution was coated on a polyethylene terephthalate film support so that the amount of gelatin applied was 3.
-2 g and 7 m''.
方、下記処方により、塩臭化銀乳剤を調製した。Meanwhile, a silver chlorobromide emulsion was prepared according to the following recipe.
（乳剤層用塗布液の調製）
溶液Ａ
水
９８０ｍρ塩化ナトリウム ２
．０ｇゼラチン ２０ｇへキ
サクロロイリジウム酸
カリウム塩の０．１０％水溶液 ２．１３ｍＱ
ヘキサブロモロジウム酸
カリウム塩の０．００１％水溶液 ２ 、５ｍＱ
溶液Ｂ
水
３８０＋＋１２塩化ナトリウム
３８ｇ臭化カリウム
４２ｇ溶液溶
液
３８０ｍ１２硝酸銀
１７０ｇ４０°Ｃに保温された上記溶液中に、ｐＨ
を３、ｐ／１ｇを７．７に保ちながら上記溶液Ｂ及び溶
液Ｃを同時に関数的に８０分間に互って加え、更に５分
間攪拌し続けた後、炭酸ナトリウム水溶液でｐＨを５．
６に調整し、通常の脱塩、水洗工程を経て、５００ｍ＜
＋の水と３０ｇのゼラチンを加えて、５０°Ｃで３０分
間分散させる。(Preparation of coating solution for emulsion layer) Solution A Water
980 mρ Sodium chloride 2
．． 0g gelatin 20g 0.10% aqueous solution of hexachloroiridate potassium salt 2.13mQ
0.001% aqueous solution of potassium hexabromorodate salt 2, 5 mQ
Solution B water
380++12 Sodium Chloride
38g potassium bromide
42g solution solution
380m12 silver nitrate
Into the above solution kept at 40°C, 170g was added with pH
3. While maintaining p/1g at 7.7, the solutions B and C were added functionally one after the other for 80 minutes at the same time, and after continued stirring for an additional 5 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
6 and went through the usual desalination and water washing processes to reach
Add water and 30g of gelatin and disperse at 50°C for 30 minutes.
これによって塩化銀６２モル％、臭化銀３８モル％、平
均粒径０．３６μｍ１立方晶粒子の乳剤を得た。この乳
剤にクエン酸と臭化カリウムを加えｐＨ５，４゜ｐＡｇ
７．６に調整し５５℃で金増感及びイオウ増感したのち
、ハロゲン化銀１モル当り４−ヒドロキシ−６−メチル
−１，３，３ａ、７−チトラザインデンを１．５ｇ１−
フェニル−５−メルカプトテトラゾールを０．２ｇ添加
し分割し、５０°Ｃに温度を下げ表１に示す増感色素の
０．１％メタノール溶液をハロゲン化銀１モル当り５０
Ｉ！ｌａ加え、６０分間停滞させたのち３６℃にしてカ
プリ防止剤としてハイドロキノンの１０％メタノール溶
液を５０ｍｆｆ、延展剤として２０％サポニン水溶液を
１９ｍ１２．増粘剤としてスチレン−マレイン酸共重合
体の４％水溶液を５０ｍ１２、アクリル酸エチルの高分
子ポリマーラテックスを３０ｇ添加し、硬膜剤として１
−ヒドロキシ−３，５−ジクロロトリアジンナトリウム
塩１％水溶液２０ｍ１２とホルマリン４％水溶液１０ｒ
ｔｒＱを加えて撹拌し、前記フィルム上のゼラチン塗布
面とは反対の面に塗設した。更にその上に保護層として
、ゼラチンと１−デシル−２−（３−イソペンチル）サ
クシネート−２−スルホン酸ナトリウム塩を含む水溶液
を塗布した。As a result, an emulsion containing 62 mol % of silver chloride, 38 mol % of silver bromide, and 1 cubic grain with an average grain size of 0.36 μm was obtained. Add citric acid and potassium bromide to this emulsion and adjust the pH to 5.4°pAg.
7.6 and sensitized with gold and sulfur at 55°C, 1.5 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide.
0.2 g of phenyl-5-mercaptotetrazole was added and divided, the temperature was lowered to 50°C, and a 0.1% methanol solution of the sensitizing dye shown in Table 1 was added at 50% methanol per mole of silver halide.
I! After stagnation for 60 minutes, the temperature was raised to 36°C, and 50 mff of a 10% methanol solution of hydroquinone was added as an anti-capri agent, and 19 m12. Added 50ml of a 4% aqueous solution of styrene-maleic acid copolymer as a thickener, 30g of ethyl acrylate polymer latex, and 1ml as a hardening agent.
-Hydroxy-3,5-dichlorotriazine sodium salt 1% aqueous solution 20ml 12 and formalin 4% aqueous solution 10r
trQ was added, stirred, and coated on the opposite side of the film from the gelatin coated side. Furthermore, an aqueous solution containing gelatin and 1-decyl-2-(3-isopentyl)succinate-2-sulfonic acid sodium salt was applied thereon as a protective layer.
このように作製したフィルムは、下記の処理を行った。The film thus produced was subjected to the following treatments.
現像液処方
純水（イオン交換水） 約 ８００ｍｆｆ亜硫
酸カリウム ６０ｇエチレンジア
ミン四酢酸二ナトリウム塩 ２水酸化カリウム
ｉｏ、５ｇ５−メチルベンゾトリアゾー
ル ３００ｍｇジエチレングリコール
２５ｇ１−７二二ルー４．４−ジメチル−
３−ピラゾリジノン ３００＋ｎｇ
ｌ−フェニルー５−メルカプトテトラ
ゾール ６０ｍｇ臭化カ
リウム ３．５ｇハイドロキノ
ン ２０ｇ炭酸カリウム
１５ｇ純水（イオン交換水）を加えて
１，０００ｍ１２に仕上げる。現像液のｐＨは約１Ｏ１
８であった。Developer formulation Pure water (ion exchange water) Approximately 800mff Potassium sulfite 60g Ethylenediaminetetraacetic acid disodium salt Potassium dihydroxide
io, 5g 5-methylbenzotriazole 300mg diethylene glycol
25g1-722-4,4-dimethyl-3-pyrazolidinone 300+ng
l-Phenyl-5-mercaptotetrazole 60mg Potassium bromide 3.5g Hydroquinone 20g Potassium carbonate
Add 15g of pure water (ion-exchanged water) to make a total volume of 1,000m12. The pH of the developer is approximately 1O1
It was 8.
定着液処方
（組成Ａ）
チオ硫酸アンモニウム（７２，５％Ｗ／Ｖ水溶液）４０
ｍ１２
亜硫酸ナトリウム
７ｇ
酢酸ナトリウム・３水塩 ６．５ｇ硼
酸
６ｇクエン酸ナトリウム・２水塩 ２ｇ酢
酸（９０％ｗ／ｗ水溶液） １３．６＋ｏｆ
ｆ（組成り）
純 水（イオン交換水） １７ｍ＜１酢
酸（５０％ｗ／ｖ水溶液） ４．７ｇ硫酸
アルミニウム
（ｉ、ｏ、換算含量が８．１％Ｗ／ｗの水溶液）２６．
５ｇ
使用時に水５００＋＋＋Ｑ中に上記組成Ａ１組成りの順
に溶かし、ＩＱに仕上げて用いた。この定着液のｐ）（
は約４．３であった。Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 40
m12 Sodium sulfite 7g Sodium acetate trihydrate 6.5g
acid
6g sodium citrate dihydrate 2g vinegar
Acid (90% w/w aqueous solution) 13.6+of
f (composition) Pure water (ion exchange water) 17m<1 vinegar
Acid (50% w/v aqueous solution) 4.7 g aluminum sulfate (i, o, aqueous solution with a converted content of 8.1% w/w) 26.
5g When used, they were dissolved in 500+++Q water in the order of the above compositions A1 and finished to IQ. This fixer p)(
was approximately 4.3.
比較色素
比較染料
上記処理を行ない写真特性を評価した。ただし、経時安
定性の評価は以下の方法によった。すなわち、二分した
一半を２３°Ｃ相対湿度４８％で調湿後、ポリ酢酸ビニ
ル（厚さ１００μｍ）でラミネート加工した防湿材で密
封包装し、５５℃相対湿度５０％の恒温器で７２時間加
熱処理した。即日および経時劣化試料を光学クサビ及び
６８０ｎｍの干渉フィルターを通してキセノンフラッシ
ュで１Ｏ−ｓ秒の閃光露光した後、自動現像機としてコ
ニカオートマチックプロセッサーＧＲ−２６（コニカ株
式会社製）、現像液として前記の現像液と定着液を用い
て現像処理を行い、評価した。また、残色評価用として
、未露光の試料も同様に処理した。なお処理条件は、現
像が３８°０２０秒、定着が約３８℃２０秒、水洗は常
温で２０秒、乾燥温度が約４０℃であった。Comparative Dye Comparative Dye The above treatment was carried out and the photographic properties were evaluated. However, the evaluation of stability over time was performed using the following method. That is, one half of the halves was conditioned at 23°C and 48% relative humidity, then sealed and packaged with a moisture-proof material laminated with polyvinyl acetate (thickness 100 μm), and heated in a thermostat at 55°C and 50% relative humidity for 72 hours. Processed. After exposing the same-day and aged samples to 10-s seconds of xenon flash through an optical wedge and a 680 nm interference filter, we used a Konica Automatic Processor GR-26 (manufactured by Konica Corporation) as an automatic developer and the above-mentioned developer as a developer. A developing process was performed using a solution and a fixer, and evaluation was made. In addition, unexposed samples were also processed in the same manner for evaluation of residual color. The processing conditions were: development at 38°C for 20 seconds, fixing at about 38°C for 20 seconds, washing with water at room temperature for 20 seconds, and drying temperature at about 40°C.
結果を表１に示す。ただし写真感度は試料ｌを１００と
した時の相対感度で示した。また、露光をかけずに処理
をした試料については、残色を目視評価し、５段階評価
を行い「５」は無色、ＮＪは強い青色系の残色を示した
。「３」を下回る残表１に示すように、本発明の試料は
感度、残色ともに良好で、かつ経時での性能の劣化が少
ないことがわかる。The results are shown in Table 1. However, the photographic sensitivity is expressed as a relative sensitivity when sample 1 is taken as 100. For samples processed without exposure, residual color was visually evaluated and evaluated on a 5-point scale, with "5" being colorless and NJ having a strong blue residual color. As shown in Table 1 below, the sample of the present invention has good sensitivity and residual color, and shows little deterioration in performance over time.
実施例２
実施例１と同様にして、塩臭化銀乳剤（臭化銀３５モル
％、塩化銀６５モル％、平均粒径０．２７μｍの立方体
粒子）を得た。Example 2 In the same manner as in Example 1, a silver chlorobromide emulsion (35 mol % of silver bromide, 65 mol % of silver chloride, cubic grains with an average grain size of 0.27 μm) was obtained.
クエン酸１％の水溶液をｌＯｍＱ、塩化ナトリウム５％
の水溶液を１０ｍＱ加えて、ｐＨ５，５、ｐＡｇ ７に
調整した乳剤に、チオ硫酸ナトリウム０．１％の水溶液
をｌＯｍＱ及び０．２％の塩化金酸水溶液７ｒｔｒＱを
加えて５７℃で熟成して最高感度にする。10mQ aqueous solution of 1% citric acid, 5% sodium chloride
To the emulsion, which was adjusted to pH 5.5 and pAg 7 by adding 10 mQ of an aqueous solution of Set to maximum sensitivity.
上記乳剤を分割して、それぞれに表２に示す本発明およ
び比較の増感色素の０．１％メタノール溶液をハロゲン
化銀１モル当り５０ｍＱ加え、それぞれにカブリ防止剤
としてｌ−フェニル−５−メルカプトテトラゾールの０
．５％溶液を２５＋＋＋Ｑ、安定剤として４−ヒドロキ
シ−６−メチル１，３，３ａ、７−チトラザインデンの
１％溶液１８０ｎ＋Ｑ、及びゼラチンの１０％水溶液３
００ＩＩＩＱを加え熟成を停止させた。これらに塗布助
剤として、１０％のトリーｉ−グロビルナフタレンスル
ホン酸ナトリウム塩水溶液をｌ ５ｍｆｆ、増粘剤とし
てスチレン−マレイン酸共重合体の４％水溶液を５Ｑｍ
Ｑ、アクリル酸ブチルの高分子ポリマーラテックスを３
０ｇ１安定剤としてハイドロキノンの２０％水溶液を２
０ｍ１２、臭化カリウムの１０％水溶液を２０ｍＱ添加
攪拌し、硬膜剤としてテトラキス（ビニルスルホニルメ
チル）メタンとタウリンカリウム塩の１ ： ０．２５
モル反応生成物をゼラチンＩｇ当り５０ｍｇ添加し、表
２に示す乳化分散物を蛍光増白剤付量として１５ｎ＋ｇ
／ｍ”になるように添加し、クエン酸でｐＨ＝５．６に
調整して、乳剤層用塗布液を調整した。The above emulsion was divided, and 50 mQ of 0.1% methanol solutions of the sensitizing dyes of the present invention and comparative sensitizing dyes shown in Table 2 were added per mole of silver halide to each of the emulsions as an antifoggant. Mercaptotetrazole 0
．． 25+++Q 5% solution, 180n+Q 1% solution of 4-hydroxy-6-methyl 1,3,3a, 7-titrazaindene as stabilizer, and 3 10% aqueous solution of gelatin.
Aging was stopped by adding 00IIIQ. To these, 5 mff of 10% aqueous solution of tri-i-globylnaphthalenesulfonic acid sodium salt was added as a coating aid, and 5 Qm of a 4% aqueous solution of styrene-maleic acid copolymer was added as a thickener.
Q. Butyl acrylate polymer latex 3
0g1 20% aqueous solution of hydroquinone as a stabilizer
0m12, 20mQ of 10% aqueous solution of potassium bromide was added and stirred, and as a hardening agent, tetrakis(vinylsulfonylmethyl)methane and taurine potassium salt were mixed in a ratio of 1:0.25.
50 mg of molar reaction product was added per Ig of gelatin, and the emulsified dispersion shown in Table 2 was added as an optical brightener amount of 15n+g.
/m'' and the pH was adjusted to 5.6 with citric acid to prepare a coating solution for an emulsion layer.
（ハレーション防止層用塗布液の調製）ゼラチン４０ｇ
の水溶液に、表２記載の染料を付量が２００ｍｇ／ｍ’
になるように加え、更に下記に示す乳化分散物を蛍光増
白剤付量として１５ｍｇ／ｍ”になるように添加し、増
粘剤としてスチレン−マレイン酸共重合体の４％水溶液
を１５ｍ４加えて、ハレーション防止層用塗布液を調製
した。(Preparation of coating solution for antihalation layer) 40 g of gelatin
The dye listed in Table 2 was applied in an amount of 200 mg/m' to an aqueous solution of
Furthermore, the following emulsified dispersion was added as a fluorescent brightener amount to 15 mg/m'', and 15 m4 of a 4% aqueous solution of styrene-maleic acid copolymer was added as a thickener. A coating solution for an antihalation layer was prepared.
（保護層用塗布液の調製）
ゼラチン水溶液中に、塗布助剤として２−スルホコハク
酸ビス（２−エチルヘキシル）エステルナトリウム塩を
３０ｍｇ／ｍ”、マット剤として平均粒径４μｍのポリ
メチルメタクリレートを４０ｍｇ／ｍ’、含弗素界面活
性剤として下記（Ｓ）の化合物を３０ｍｇ／ｍ”。(Preparation of coating solution for protective layer) In an aqueous gelatin solution, add 30 mg/m'' of 2-sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid and 40 mg of polymethyl methacrylate with an average particle size of 4 μm as a matting agent. /m', 30mg/m'' of the following compound (S) as a fluorine-containing surfactant.
硬膜剤としてホルマリンをゼラチン１ｇ当り１０ｎ＋ｇ
添加し、保護層用塗布液を調製した。10n+g of formalin per 1g of gelatin as a hardening agent
A coating solution for a protective layer was prepared.
含弗素界面活性剤（Ｓ）
ＣＨｚＣＯＯＣＨｚ（ＣＦ２）ｉＨ
Ｎａ０３Ｓ ＣＨＣＯＯＣ）ｌｘ（ＣＦＪａＨ（試料の
調製及び評価）
このようにして調製されたハレーション防止層用塗布液
、乳剤層用塗布液、及び保護層用塗布液を、親水性コロ
イドバッキング層と下塗層を有し、二酸化チタンを１５
ｗｔ％含有する厚さ１１０μｍのポリエチレンコート紙
上に同時３層塗布した。得られた試料の塗布銀量は１．
４ｇ／ｍ”、ゼラチン塗布量はハレーション防止層が１
．４ｇ／＋”、乳剤層が１．４ｇ／ｍ２、保護層が０．
９ｇ／ｍ’であった。Fluorine-containing surfactant (S) CHzCOOCHz(CF2)iH Na03S CHCOOC)lx(CFJaH (Sample preparation and evaluation) Antihalation layer coating solution, emulsion layer coating solution, and protective layer coating solution prepared in this way The coating solution has a hydrophilic colloid backing layer and a subbing layer, and contains 15% titanium dioxide.
Three layers were simultaneously coated on a polyethylene coated paper having a thickness of 110 μm and containing % wt. The coated silver amount of the obtained sample was 1.
4g/m”, gelatin coating amount is 1 for antihalation layer
．． 4g/+”, emulsion layer 1.4g/m2, protective layer 0.
It was 9 g/m'.
得られた試料を、それぞれ二分し、−半はそのまま、他
の一半は経時安定性をみるため、ポリエチレン製の袋に
入れ、更に紙製の袋で包装した後、５５℃相対湿度５０
％の恒温器で７２時間加熱処理した。Each of the obtained samples was divided into two parts, one half was left as is, and the other half was placed in a polyethylene bag and then wrapped in a paper bag to check its stability over time.
% in a thermostat for 72 hours.
残色は、実施例１と同様にして評価した。The remaining color was evaluated in the same manner as in Example 1.
得られた結果を表２に示す。なお感度は、濃度１．０を
与えるのに必要な露光量の逆数で、試料１を１００とし
た相対値である。The results obtained are shown in Table 2. Note that the sensitivity is the reciprocal of the exposure amount required to give a density of 1.0, and is a relative value with Sample 1 set as 100.
以下余白
表２の結果より明らかなように、本発明に属する試料は
感度、残色とも良好で、かつ経時での性能の劣化が少な
いことがわかる。As is clear from the results in Margin Table 2 below, the samples belonging to the present invention have good sensitivity and residual color, and show little deterioration in performance over time.
（油溶性蛍光増白剤乳化分散物の調製）下記油溶性蛍光
増白剤（Ｆ）５．０ｇをタレジルフェニルホスフェート
ｌＯＯｍＱと酢酸エチル１００ｍＱの混合溶液に溶解し
、この溶液全量をトリプロピルナフタレンスルホン酸ナ
トリウム塩を３ｇ含む１２％ゼラチン水溶液１５００ｍ
１２と混合し、超音波分散により乳化分散した後、アク
リル酸ブチルポリマーラテックスを固型分として１０ｇ
加えて油溶性蛍光増白剤の乳化分散物を調製した。(Preparation of emulsified dispersion of oil-soluble optical brightener) Dissolve 5.0 g of the following oil-soluble optical brightener (F) in a mixed solution of 100 mQ of talesyl phenyl phosphate and 100 mQ of ethyl acetate. 1500ml of 12% gelatin aqueous solution containing 3g of sodium sulfonate
After mixing with 12 and emulsifying and dispersing by ultrasonic dispersion, 10g of butyl acrylate polymer latex as a solid content
In addition, an emulsified dispersion of an oil-soluble optical brightener was prepared.
蛍光増白剤（Ｆ）
〔発明の効果〕
上記実施例により詳細に説明した通り、本発明により、
高感度で残色が少なく、しかも保存期間中における性能
の劣化が極めて少ない赤色増感されたハロゲン化銀写真
感光材料を提供することカ（出来た。Fluorescent brightener (F) [Effects of the invention] As explained in detail in the above examples, according to the present invention,
To provide a red-sensitized silver halide photographic material with high sensitivity, little residual color, and extremely little deterioration of performance during storage.
Claims (1)
層を有するハロゲン化銀写真感光材料において、該乳剤
層が下記一般式〔 I 〕から選ばれる少なくとも１種の
増感色素により分光増感され、かつ下記一般式〔II〕で
表される染料を少なくとも１種含有した親水性コロイド
層を少なくとも１層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〔 I 〕 ▲数式、化学式、表等があります▼ 〔式中、Ｙ＿１、及び Ｙ＿２は、各々ベンゾチアゾー
ル環、ベンゾセレナゾール環、ナフトチアゾール環、ナ
フトセレナゾール環、またはキノリン環を形成するのに
必要な非金属原子団を表し、これらの複素環は低級アル
キル基、アルコキシ基、アリール基、ヒドロキシル基、
アルコキシカルボニル基、ハロゲン原子で置換されてい
ても良い。 Ｒ＿１、Ｒ＿２は、それぞれ低級アルキル基、スルホ基
を有するアルキル基またはカルボキシル基を有するアル
キル基を表す。Ｒ＿３は、メチル基、エチル基、プロピ
ル基を表す。Ｘ＿１はアニオンを表す。 ｎ＿１、ｎ＿２は、１または２を表す。ｍは、１または
０を表し、分子内塩の時はｍ＝０を表す。〕一般式〔I
I〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿４、Ｒ＿５は各々少なくとも１つのスルホ
ン酸基又はカルボン酸基を有するアルキル基、アラルキ
ル基、アリール基又は複素環基を表し、スルホン酸基又
はカルボン酸基は２価の連結基を介してアルキル基、ア
ラルキル基、アリール基又は複素環基に結合してもよい
。Ｒ＿６、Ｒ＿７は各々−ＣＯＲ＿８、−ＳＯ＿２Ｒ＿
８、−ＳＯＲ＿８又は−ＳＯ＿２ＮＲ＿９Ｒ＿１＿０を
表し（但し、Ｒ＿８はアルキル基、アラルキル基又はア
リール基を表し、Ｒ＿９、Ｒ＿１＿０は各々水素原子、
アルキル基、アラルキル基又はアリール基を表し、Ｒ＿
９とＲ＿１＿０は連結して５又は６員環を形成していて
もよい。）、Ｌ＿４、Ｌ＿５、Ｌ＿６、Ｌ＿７及びＬ＿
８は各々メチン基、置換メチン基を表し、Ｍ＾■は水素
原子又はその他のカチオンを表す。〕 次に本発明の構成について、更に具体的に説明する。[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer contains at least one additive selected from the following general formula [I]. 1. A silver halide photographic material comprising at least one hydrophilic colloid layer that is spectrally sensitized with a sensitive dye and contains at least one dye represented by the following general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. These heterocycles represent lower alkyl groups, alkoxy groups, aryl groups, hydroxyl groups,
It may be substituted with an alkoxycarbonyl group or a halogen atom. R_1 and R_2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X_1 represents an anion. n_1 and n_2 represent 1 or 2. m represents 1 or 0, and when it is an inner salt, m=0. ] General formula [I
I] ▲ Numerical formulas, chemical formulas, tables, etc. The group or carboxylic acid group may be bonded to an alkyl group, an aralkyl group, an aryl group or a heterocyclic group via a divalent linking group. R_6 and R_7 are respectively -COR_8 and -SO_2R_
8, -SOR_8 or -SO_2NR_9R_1_0 (wherein, R_8 represents an alkyl group, an aralkyl group, or an aryl group, and R_9 and R_1_0 each represent a hydrogen atom,
Represents an alkyl group, aralkyl group or aryl group, R_
9 and R_1_0 may be connected to form a 5- or 6-membered ring. ), L_4, L_5, L_6, L_7 and L_
8 represents a methine group or a substituted methine group, respectively, and M^■ represents a hydrogen atom or other cation. ] Next, the configuration of the present invention will be explained in more detail.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1947090A JPH03223745A (en) | 1990-01-29 | 1990-01-29 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1947090A JPH03223745A (en) | 1990-01-29 | 1990-01-29 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03223745A true JPH03223745A (en) | 1991-10-02 |
Family
ID=12000209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1947090A Pending JPH03223745A (en) | 1990-01-29 | 1990-01-29 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03223745A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05188516A (en) * | 1992-01-14 | 1993-07-30 | Fuji Photo Film Co Ltd | Silver halide photographic |
-
1990
- 1990-01-29 JP JP1947090A patent/JPH03223745A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05188516A (en) * | 1992-01-14 | 1993-07-30 | Fuji Photo Film Co Ltd | Silver halide photographic |
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