JPH0445435A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH0445435A JPH0445435A JP15446490A JP15446490A JPH0445435A JP H0445435 A JPH0445435 A JP H0445435A JP 15446490 A JP15446490 A JP 15446490A JP 15446490 A JP15446490 A JP 15446490A JP H0445435 A JPH0445435 A JP H0445435A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- group
- gelatin
- emulsion layer
- halide emulsion
- 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
- -1 Silver halide Chemical class 0.000 title claims abstract description 118
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 75
- 239000004332 silver Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims description 41
- 239000000839 emulsion Substances 0.000 claims abstract description 84
- 239000000975 dye Substances 0.000 claims abstract description 65
- 229940050521 gelatin agent Drugs 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- 238000011161 development Methods 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 230000001235 sensitizing effect Effects 0.000 abstract description 17
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 238000011033 desalting Methods 0.000 abstract description 10
- 239000000298 carbocyanine Substances 0.000 abstract 2
- 230000032683 aging Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 72
- 239000000243 solution Substances 0.000 description 43
- 108010010803 Gelatin Proteins 0.000 description 36
- 229920000159 gelatin Polymers 0.000 description 36
- 239000008273 gelatin Substances 0.000 description 36
- 235000019322 gelatine Nutrition 0.000 description 36
- 235000011852 gelatine desserts Nutrition 0.000 description 36
- 235000013339 cereals Nutrition 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000018109 developmental process Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 15
- 239000011241 protective layer Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-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
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 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
- 239000003755 preservative agent Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 235000017709 saponins Nutrition 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- FTPPZZQMHSLCST-UHFFFAOYSA-N 1,2,3-tripropylnaphthalene Chemical compound C1=CC=C2C(CCC)=C(CCC)C(CCC)=CC2=C1 FTPPZZQMHSLCST-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical group C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- BJEWLOAZFAGNPE-UHFFFAOYSA-N 1-ethenylsulfonylethane Chemical compound CCS(=O)(=O)C=C BJEWLOAZFAGNPE-UHFFFAOYSA-N 0.000 description 1
- NXVHEHXRZVQDCR-UHFFFAOYSA-N 1-n,1-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1C NXVHEHXRZVQDCR-UHFFFAOYSA-N 0.000 description 1
- AHABMLPWPUZVOI-UHFFFAOYSA-N 1-n,1-n-diethylbenzene-1,2,4-triamine Chemical compound CCN(CC)C1=CC=C(N)C=C1N AHABMLPWPUZVOI-UHFFFAOYSA-N 0.000 description 1
- WFTSBMRVTWFBIF-UHFFFAOYSA-N 2-(4-aminophenyl)-3,4-dihydropyrazol-5-amine Chemical compound C1CC(N)=NN1C1=CC=C(N)C=C1 WFTSBMRVTWFBIF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XQHGAEQBYRZJIX-UHFFFAOYSA-N 2-amino-4-chloro-6-phenylphenol Chemical compound NC1=CC(Cl)=CC(C=2C=CC=CC=2)=C1O XQHGAEQBYRZJIX-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
- LTJMHCGDSFTOHA-UHFFFAOYSA-N 2-carbamoylbenzenesulfonic acid Chemical compound NC(=O)C1=CC=CC=C1S(O)(=O)=O LTJMHCGDSFTOHA-UHFFFAOYSA-N 0.000 description 1
- QWZOJDWOQYTACD-UHFFFAOYSA-N 2-ethenylsulfonyl-n-[2-[(2-ethenylsulfonylacetyl)amino]ethyl]acetamide Chemical compound C=CS(=O)(=O)CC(=O)NCCNC(=O)CS(=O)(=O)C=C QWZOJDWOQYTACD-UHFFFAOYSA-N 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
- OUIITAOCYATDMY-UHFFFAOYSA-N 4-amino-2-phenylphenol Chemical compound NC1=CC=C(O)C(C=2C=CC=CC=2)=C1 OUIITAOCYATDMY-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical class NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical group NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 241001553014 Myrsine salicina Species 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
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- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
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- 239000004571 lime Substances 0.000 description 1
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- 229910001425 magnesium ion Inorganic materials 0.000 description 1
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- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 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
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- 230000007935 neutral effect Effects 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 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
- 125000006678 phenoxycarbonyl group Chemical group 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
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoric acid amide group Chemical group P(N)(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
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- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は赤外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 material that is spectrally sensitized in the infrared region, and more specifically, it relates to a silver halide photographic material that has little residual color and has excellent storage stability over time. This invention relates to silver halide photographic materials.
写真感光材料の露光方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。この方法における記録用光源として
、半導体レーザが最も好ましく用いられる。この半導体
レーザーは、小型で安価、しかも変調が容易であり、他
のＨｅ−Ｎｅレーザー アルゴンレーザーなどよりも長
寿命で、かつ赤外域に発光するため、赤外域に感光性を
有する感光材料を用いると明るいセーフライトが使用で
きるため、取り扱い作業性が良くなるという利点を有し
ている。One of the exposure methods for photographic light-sensitive materials is a so-called scanner, which scans an original image and exposes the silver halide photographic light-sensitive material based on the image signal to form a negative or positive image corresponding to the image on the original image. One-way image forming methods are known. A semiconductor laser is most preferably used as the recording light source in this method. This semiconductor laser is small, inexpensive, easy to modulate, has a longer lifespan than other He-Ne lasers, argon lasers, etc., and emits light in the infrared region, so it uses a photosensitive material that is sensitive to the infrared region. It has the advantage of improving handling workability because a bright safelight can be used.
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.
写真乳剤層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 the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.
このような着色層はフィルター層と呼ばれる。重層カラ
ー感光材料の如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 a plurality of 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中に入射す
ることに基づく画像のボ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
間にハレーション防止層が置かれることもある。It is based on the fact that the light scattered during or after passing through the photographic emulsion layer 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. For the purpose of preventing image blurring, that is, halation, 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. Such a colored layer is called an antihalation layer. In the case of a multilayer color photosensitive material, an antihalation 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呼ばれている）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.
これ等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塔、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, in order to color them, a water-soluble dye is incorporated into the layer. This dye must satisfy the following conditions.
（１）使用目的に応じた適正な分光吸収を有すること。(1) Must have appropriate spectral absorption according to the purpose of use.
（２）写真化学的に不活性であること。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
えは感度の低下あるいはカブリを与えないこと。(2) Photochemically inert. In other words, it must not have an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity or fog.
（３）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。(3) No harmful coloration remains on the photographic material after processing by being bleached or dissolved and removed during the photographic processing process.
特に近年、処理の迅速化の要請が強く、このため残色に
ついてもも大きな問題となっている。Particularly in recent years, there has been a strong demand for faster processing, and as a result, residual color has also become a major problem.
このような条件を満足する赤外線吸収用の染料として、
例えば特開昭６２−１２３４５４号に記載の分子内に少
なくとも３個の酸基を有するトリカルボシアニン色素が
挙げられるが、これをハロゲン化銀写真感光材料に適用
すると、必ずしも経時保存性の面で充分安定でなく、感
度の低下または残色の劣化を引き起こすことが判った。As an infrared absorbing dye that satisfies these conditions,
For example, there is a tricarbocyanine dye having at least three acid groups in the molecule described in JP-A No. 62-123454, but when this is applied to a silver halide photographic light-sensitive material, it does not necessarily have good storage stability over time. It was found that it was not sufficiently stable and caused a decrease in sensitivity or deterioration of residual color.
従って本発明の第１の目的は、現像処理、特に迅速処理
においても残色が少なく、赤外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ｌこめる。本発明
の第２の目的は、良好ル′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
。Accordingly, a first object of the present invention is to provide a silver halide photographic material that has little residual color even during development processing, especially rapid processing, and is highly sensitive to infrared light. A second object of the present invention is to provide a silver halide photographic material which forms good color 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、該乳剤層がカチオン性のジおよびトリカルボシア
ニン色素からなる群から選ばれる少なくとも１つによっ
て分光増感され、がっ、下記一般式〔■〕で表される染
料を少なくとも１種含有し、かつ下記該ハロゲン化銀乳
剤層中のハロゲン化銀乳剤の脱塩処理が凝集ゼラチン剤
によっておこなわれたものであ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 object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the emulsion layer is at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. The desalting treatment of the silver halide emulsion in the silver halide emulsion layer is carried out by the agglomerated gelatin. This is achieved by a silver halide photographic material characterized in that it is produced using a silver halide agent.
また本発明の感光材料は、自動現像機を用いて処理され
、その現像、定着及び安定化までの処理時間が４５秒以
内であり、かつラインスピードが１０００■ｍ／ｍｉｎ
以上であることによりその効果を発揮する。Furthermore, the photosensitive material of the present invention is processed using an automatic processor, and the processing time for development, fixing, and stabilization is within 45 seconds, and the line speed is 1000 m/min.
By doing so, the effect is exhibited.
一般式〔Ｉ）
式中、Ｒはアリール基を表し、Ｘはカルボニルはベンゾ
縮合環又はナフト縮合環を形成するに必要な非金属原子
群を表す。General Formula [I] In the formula, R represents an aryl group, and X and carbonyl represent a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring.
Ｌｌは窒素原子又はメチン基を表し、Ｒ２及びり、はメ
チン基を表す。ｎは１〜６の整数を表す。Ll represents a nitrogen atom or a methine group, and R2 and R represent a methine group. n represents an integer of 1 to 6.
但し、Ｌ、が窒素原子を表す時、ｎは１を表すものとす
る。一般式（Ｉ）で表される化合物は分子内に少なくと
も１つの酸基を有するものとする。However, when L represents a nitrogen atom, n represents 1. The compound represented by general formula (I) shall have at least one acid group within the molecule.
蕎１目−−− 以下本発明について詳細に説明する。1st soba--- The present invention will be explained in detail below.
ハロゲン化銀乳剤は、一般的に物理熟成後、不要の塩類
を除去するため脱塩する。脱塩の方法としては、ゲル化
、透析による方法、あるいは水溶性硫酸塩等による塩析
法があり、さらに化学修飾ゼラチンすなわち本発明でい
うゼラチン誘導体を用いる方法が知られている。Silver halide emulsions are generally desalted to remove unnecessary salts after physical ripening. Desalting methods include gelation, dialysis, and salting out using water-soluble sulfates, and methods using chemically modified gelatin, ie, gelatin derivatives as referred to in the present invention, are also known.
ゼラチンに二塩基酸無水物を反応させると、ゼラチンの
アミノ基と反応し、Ｇｅ１−ＮＨ−Ｃｏ−Ｒ−ＣＯＯＨ
の形となり、アミノ基が消え、酸基が１個増す。このよ
うなゼラチンは酸基のＰＫ値以下にｐＨを下げると酸基
は非解離形になり、アミン基は反応して大部分がなくな
り、水溶性が減少し、ゼラチンを凝集することができる
のである。When dibasic acid anhydride is reacted with gelatin, it reacts with the amino group of gelatin and forms Ge1-NH-Co-R-COOH.
The amino group disappears and one acid group increases. When the pH of such gelatin is lowered to below the PK value of the acid group, the acid group becomes non-dissociated, and the amine group reacts and most of it disappears, reducing its water solubility and allowing the gelatin to aggregate. be.
本発明においては、ゼラチン分子のアミン基の少なくと
も５０％以上を置換したゼラチン誘導体を使用する。In the present invention, a gelatin derivative in which at least 50% or more of the amine groups of the gelatin molecule are substituted is used.
ゼラチンのアミノ基に対する置換基例は、米国特許２，
６９１，５８２号、同２，６１４，９２８号、同２，５
２５，７５３号に記載がある。Examples of substituents for amino groups in gelatin are U.S. Pat.
No. 691,582, No. 2,614,928, No. 2,5
It is described in No. 25,753.
有用な置換基としては、
（１）アルキルアシル、アリールアシル、アセチル及び
置換、非置換のベンゾイル等のアシル基、（２）アルキ
ルカルバモイル
（３）アルキルスルホニル、アリールスルホニル等のス
ルホニル基、
（４）アルキルチオカルバモイル、アリールチオカルバ
モイル等のチオカルバモイル基、
（５）炭素数１〜１８の直鎖，分岐のアルキル基、（６
）置換．非置換のフェニル、ナフチル及びピリジル、フ
リル等の芳香族複素環等のアリール基が挙げられる。Useful substituents include (1) acyl groups such as alkylacyl, arylacyl, acetyl, substituted and unsubstituted benzoyl, (2) alkylcarbamoyl, (3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl, (4) Thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) straight chain, branched alkyl groups having 1 to 18 carbon atoms, (6
) substitution. Examples include aryl groups such as unsubstituted phenyl, naphthyl, and aromatic heterocycles such as pyridyl and furyl.
中でも、好ましい変性ゼラチンは、アンル基（−ＣＯＲ
，）またはカルバモイル基（ − ＣＯＮＲ，）による
ものである。Among them, preferred modified gelatin has anlu group (-COR
, ) or a carbamoyl group (-CONR,).
前記Ｒ，は置換、非置換の脂肪族基（例えば炭素数１−
１８個のアルキル基、アリル基）、アリル基またはアラ
ルキル基（例えばフェネチル基）であり、Ｒ２は水素原
子、脂肪族基、アリール基、またはアラルキル基である
。The above R is a substituted or unsubstituted aliphatic group (e.g., a carbon number 1-
18 alkyl groups, allyl groups), allyl groups, or aralkyl groups (for example, phenethyl groups), and R2 is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.
特に好ましいものは、Ｒ，がアリール基、Ｒ２が水素原
子の場合である。Particularly preferred is the case where R is an aryl group and R2 is a hydrogen atom.
以下に本発明において用いることができる凝集用ゼラチ
ン誘導体（以下、凝集ゼラチン剤という）の具体例をア
ミノ基置換基によって例示するが、本発明はこれに限定
されるものではない。Specific examples of gelatin derivatives for flocculating (hereinafter referred to as flocculating gelatin agents) that can be used in the present invention are illustrated below using amino group substituents, but the present invention is not limited thereto.
例示凝集ゼラチン剤（アミン基置換基）一ＣＯＣ，Ｈ，
ｔＪ） −ＣＯＣＨ。Exemplary agglomerated gelatin agent (amine group substituent) - COC, H,
tJ) -COCH.
ＣＯＯＨ
Ｇ−１１
Ｇ−１２
凝集ゼラチン剤はハロゲン化銀写真乳剤製造中の脱塩工
程以前で用いることが出来るが、好ましくは脱塩工程時
である。また凝集ゼラチン剤の添加量は特に制限は無い
が脱塩に際して使用する場合、脱塩後、保護コロイドと
して含まれている物質（好ましくはゼラチン）の０．１
〜ＩＯ倍量（重量）が適当であり、特に好ましくは０．
２〜５倍量（重量）である。COOH G-11 G-12 The agglomerated gelatin agent can be used before the desalting step during the production of silver halide photographic emulsions, but is preferably used during the desalting step. The amount of flocculated gelatin agent added is not particularly limited, but when used for desalting, 0.1 of the substance (preferably gelatin) contained as a protective colloid after desalting.
~IO times (weight) is appropriate, particularly preferably 0.
It is 2 to 5 times the amount (weight).
凝集ゼラチン剤はハロゲン化銀粒子を保護コロイドと共
に凝集せしめるものであるが、該凝集ゼラチン剤を添加
した後、ｐＨを調整してハロゲン化銀乳剤を凝析せしめ
るようにすることができる。The flocculating gelatin agent coagulates silver halide grains together with a protective colloid, and after adding the flocculating gelatin agent, the pH can be adjusted to coagulate the silver halide emulsion.
凝析を行わせるｐｏとしては、５．５以下特に４．８〜
２が好ましい。Ｉ）Ｈ調整に用いる酸には特に制限はな
いが、酢酸、クエン酸、サリチル酸等の有機酸や、塩酸
、硝酸、硫酸、燐酸等の無機酸が好ましく用いられる。The po for coagulation should be 5.5 or less, especially 4.8 to 4.8.
2 is preferred. I) The acid used for H adjustment is not particularly limited, but organic acids such as acetic acid, citric acid, and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are preferably used.
凝集ゼラチン剤に併用して重金属イオン例えばマグネシ
ウムイオン、カドミウムイオン、鉛イオン、ジルコニウ
ムイオン等を添加してもよい。Heavy metal ions such as magnesium ions, cadmium ions, lead ions, zirconium ions, etc. may also be added to the aggregated gelatin agent.
溶存物除去（脱塩）は１回でも数回繰返してもかまわな
い。数回繰返す場合、除去の度に凝集ゼラチン剤を添加
してもよいが、最初に凝集ゼラチン剤を添加しただけで
もよい。Removal of dissolved substances (desalting) may be repeated once or several times. When repeating several times, the flocculated gelatin agent may be added each time the removal is performed, or the flocculated gelatin agent may be added only at the beginning.
また、本発明の現像、定着、水洗又は／及び安定化液で
の処理時間が４５秒以内とはフィルムの先端が現像液に
入ってから、定着液、水洗液又は／及び安定化液から出
てくるまでの時間が４５秒以内であり、現像液から定着
液への渡りの時間及び定着液から水洗液への渡りの時間
が含まれる。Furthermore, the processing time in the developing, fixing, washing and/or stabilizing solution of the present invention is within 45 seconds after the leading edge of the film enters the developing solution and comes out of the fixing solution, washing solution and/or stabilizing solution. The time it takes for the liquid to dry is within 45 seconds, which includes the time from the developer to the fixer and the time from the fixer to the washing liquid.
本発明において処理ラインの長さを短くぜずに処理ライ
ン速度を上げることにより本発明のコ的を達成し得るこ
とをみいだした。In the present invention, it has been found that the object of the present invention can be achieved by increasing the speed of the processing line without shortening the length of the processing line.
次に本発明の一般式〔■〕で表される染料は、分子中に
酸基（スルホ基、カルボキシル基、ホスホン酸基、ホス
フィン酸基、燐酸エステル基、燐酸アミド基等）を有す
る。Next, the dye represented by the general formula [■] of the present invention has an acid group (sulfo group, carboxyl group, phosphonic acid group, phosphinic acid group, phosphoric ester group, phosphoric acid amide group, etc.) in the molecule.
これらの酸基は各々、その塩を包含する。塩としては、
ナトリウム、カリウム等のアルカリ金属塩、アンモニウ
ム、トリエチルアミン、ピリジン等の有機アンモニウム
塩を挙げることができる。Each of these acid groups includes its salts. As salt,
Examples include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.
Ｌ、〜Ｌ、で表されるメチン基には、炭素数１〜３のア
ルキル基（例えばメチル、エチルなど）、フェニル基、
ベンジル基、フェネチル基、ヒドロキンル基、アシルオ
キシ基、ハロゲン原子等が置換されていてもよい。The methine group represented by L, ~L, includes an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, etc.), a phenyl group,
It may be substituted with a benzyl group, phenethyl group, hydroquine group, acyloxy group, halogen atom, etc.
又、メチン基の置換基が環（例えば５．５−ジメチル−
１−フクロヘキセン−１−イル−３−イリデンなど）を
形成してもよい。In addition, the substituent of the methine group is a ring (for example, 5,5-dimethyl-
1-fuclohexen-1-yl-3-ylidene, etc.).
Ｒで表されるアリール基としては、例えばフェニル、ナ
フチル等が挙げられるが、好ましくは次Ｒ、、Ｒ、は各
々、水素原子、アルキル基を表し、Ｒ、、Ｒ、は同じで
も異なっていてもよく、又互いに結合して環を形成して
もよい。Examples of the aryl group represented by R include phenyl, naphthyl, etc., but preferably the following R and R each represent a hydrogen atom and an alkyl group, and R and R may be the same or different. They may also be combined with each other to form a ring.
Ｒｓ、Ｒ４，Ｒｓの表すアルキル基としては、例えばメ
チル、エチル、ブチル、ヒドロキンアルキル（例えばヒ
ドロキノエチなど）、アルフキ／アルキル（例えば、β
−エトキ／エチルなど）、カルボキノアルキル（例えば
、β−カルポキ／エチルなど）アルフキ／カルボニルア
ルキル（例えば、β−エトキンカルボニルエチルなど）
、シアノアルキル
アルキル（例えば、β−スルホエチル、γースルホプロ
ピルなど）等の各基が挙げられる。Examples of the alkyl group represented by Rs, R4, and Rs include methyl, ethyl, butyl, hydroquine alkyl (e.g., hydroquinoethyl, etc.), alfkyl/alkyl (e.g., β
-ethoxy/ethyl, etc.), carboquinoalkyl (e.g., β-carpoki/ethyl, etc.), alfky/carbonylalkyl (e.g., β-ethkynecarbonylethyl, etc.)
, cyanoalkylalkyl (eg, β-sulfoethyl, γ-sulfopropyl, etc.).
Ｒ４とＲ，は互いに結合して５員〜６員環を形成しても
よく、具体例としてはモルホリノ、ピペリジノ、ピロリ
ジノ基等が挙げられる。R4 and R may be combined with each other to form a 5- to 6-membered ring, and specific examples include morpholino, piperidino, and pyrrolidino groups.
Ｒ２は水素原子、アルキル基、ハロゲン原子、アシルア
ミノ基、ヒドロキシル基、アルコキシ基、スルホ基、カ
ルボキシル基を表すが、アルキル基としては、例えばメ
チル、エチル等が挙げられ、ハロゲン原子としては、例
えば塩素原子が挙げられ、アシルアミノ基としては、例
えばアセチルアミノが挙げられ、アルコキシ基としては
、例えばメトキシ、エトキシ等が挙げられる。又、Ｒ１
とＲ８で環を形成してもよい。ｍは１〜４の整数を表す
。R2 represents a hydrogen atom, an alkyl group, a halogen atom, an acylamino group, a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group; examples of the alkyl group include methyl and ethyl; examples of the halogen atom include chlorine, Examples of the acylamino group include acetylamino, and examples of the alkoxy group include methoxy, ethoxy, and the like. Also, R1
and R8 may form a ring. m represents an integer of 1 to 4.
Ｚで表されるベンゾ縮合環又はナフト縮合環は種々の置
換基を有することができ、置換基として、例えばスルホ
、カルボキンル、ヒドロキシル、シアノ、ハロゲン（例
えば弗素、塩素など）、アルキル（例えばメチル、イソ
プロピル、トリフルオロメチル、ｔ−ブチル、エトキシ
カルボニルメチル、スルホメチルなど）、アミン（例え
ばアミノ、ジメチルアミノ、スルホエチルアミノ、ピペ
リジノ、モルホリノなど）、アルコキシ（例えばメトキ
シ、エトキシ、スルホプロポキシなど）、スルホニル（
例エバ、メタンスルホニル、エタンスルホニルなど）、
スルファモイル（例えばスルファモイル、ジメチルスル
ファモイルなど）、アシルアミノ（例えば、アセトアミ
ド、ベンズアミド、スルホベンズアミドなど）、カルバ
モイル（例えばカルバモイル、フェニルカルバモイル、
スルホ７エ二ルカルバモイルなど）、スルホンアミド（
例えばメタンスルホンアミド、ベンゼンスルホンアミド
など）、アルコキシカルボニル（例えばエトキシカルボ
ニル、ヒドロキシエトキシカルボニル、ベンジルオキシ
カルボニルなど）、アリールオキシカルボニル（例えば
フェノキシカルボニル、ニトロフェノキシカルボニルな
ど）、などの基を挙げることができる。The benzo-fused ring or naphtho-fused ring represented by Z can have various substituents, such as sulfo, carboxyl, hydroxyl, cyano, halogen (e.g. fluorine, chlorine, etc.), alkyl (e.g. methyl, isopropyl, trifluoromethyl, t-butyl, ethoxycarbonylmethyl, sulfomethyl, etc.), amines (e.g. amino, dimethylamino, sulfoethylamino, piperidino, morpholino, etc.), alkoxy (e.g. methoxy, ethoxy, sulfopropoxy, etc.), sulfonyl (e.g.
(e.g. Eva, methanesulfonyl, ethanesulfonyl, etc.),
Sulfamoyl (e.g. sulfamoyl, dimethylsulfamoyl, etc.), acylamino (e.g. acetamide, benzamide, sulfobenzamide, etc.), carbamoyl (e.g. carbamoyl, phenylcarbamoyl, etc.)
sulfo-7enylcarbamoyl, etc.), sulfonamides (
For example, groups such as methanesulfonamide, benzenesulfonamide, etc.), alkoxycarbonyl (e.g., ethoxycarbonyl, hydroxyethoxycarbonyl, benzyloxycarbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl, nitrophenoxycarbonyl, etc.), and the like can be mentioned. .
本発明に用いられる前記一般式１”Ｉ）で表される染料
（以下、本発明の染料と称す）の具体例を以下に示すが
、本発明はこれ等に限定されるものではない。Specific examples of the dye represented by the general formula 1''I) used in the present invention (hereinafter referred to as the dye of the present invention) are shown below, but the present invention is not limited thereto.
本発明の感光材料において、旧記一般式（１）で表され
る染料は、ハロゲン化銀乳剤中に含有させて、イラジェ
ーンヨン防止染料として用いることもできるし、また非
感光性の親水性コロイド層中に含有させて、フィルター
染料あるいは ハレーンヨン防止染料として用いること
もでざる。また、使用目的により２種以上の染料を組合
わせて用いてもよいし、他の染料と組合わせて用いても
よい。本発明の染料をハロゲン化銀乳剤層中あるいは、
その他の親水性コロイド層中に含有させるためには、通
常の方法により容易に行なうことができる。一般には、
染料または、染料の有機・無機アルカリ塩を水に溶解し
、適当な濃度の染料水溶液とし、塗布液に添加して、公
知の方法で塗布を行ない感光材料中に染料を含有させる
ことができる。これらの染料の含有量としては、使用目
的によって異なるが、一般には写真材料上の面積１厘２
当り１〜８００ｒａｉになるように塗布して用いる。In the light-sensitive material of the present invention, the dye represented by formula (1) can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or can be used as a non-photosensitive hydrophilic colloid. It cannot be incorporated into a layer and used as a filter dye or halayone preventive dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye of the present invention is contained in a silver halide emulsion layer or
Incorporation into other hydrophilic colloid layers can be easily carried out by conventional methods. In general,
The dye or the organic/inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, which is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. The content of these dyes varies depending on the purpose of use, but in general, the content of these dyes is 1 cm2 per area on the photographic material.
It is applied and used in an amount of 1 to 800 rai per coat.
本発明が適用される感光材料としては、黒白写真感光材
料の他、カラー写真感光材料も挙げることができる。前
者の例としては印刷用感光材料などを挙げることができ
る。The light-sensitive materials to which the present invention is applied include not only black-and-white photographic materials but also color photographic materials. Examples of the former include photosensitive materials for printing.
上記染料は適当な溶媒（例えば、水、アルコール、メチ
ルセロソルブ等）に溶解して親水性コロイド層用塗布液
中に添加される。これ等の染料は２種以上組合わせて用
いることもできる。The above dye is dissolved in a suitable solvent (eg, water, alcohol, methyl cellosolve, etc.) and added to the coating solution for the hydrophilic colloid layer. These dyes can also be used in combination of two or more.
染料の添加量は、その目的に応じて異なるが一般に１０
１〜Ｉｇ／閣２、好ましくはＩＯ弓〜０．５ｇ／ｍ”の
範囲で用いられる。The amount of dye added varies depending on the purpose, but generally 10
It is used in the range of 1 to Ig/m2, preferably IO to 0.5 g/m''.
本発明の染料は特にイラジェーション防止の目的に有効
であり、この目的で用いる場合は主として乳剤層に添加
される。The dye of the present invention is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer.
本発明の染料は、またハレーション防止のための染料と
しても特に有用であり、この場合は支持体裏面あるいは
支持体と乳剤層の間に添加される。The dyes of this invention are also particularly useful as antihalation dyes, in which case they are added to the back of the support or between the support and the emulsion layer.
本発明の染料はセーフライト安全性を付与するための染
料としても使用することができ、この場合は必要に応じ
て他の波長の光を吸収する染料と組合わせて乳剤層の上
部に位置する層（保護層等）に添加される。The dyes of the invention can also be used as dyes to impart safelight safety, in which case they are placed on top of the emulsion layer, optionally in combination with dyes that absorb light at other wavelengths. added to layers (protective layers, etc.).
その他、本発明の染料はフィルター染料としても有利に
用いることができる。Additionally, the dyes of the present invention can be advantageously used as filter dyes.
本発明の染料は、通常の方法によって目的の写真構成層
中に導入できる。すなわち、写真構成層のバインダーで
ある親水性コロイドの水溶液に染料の適当な濃度の溶液
を加え、この液を支持体上に、あるいは他の構成層上に
塗布すればよい。The dye of the present invention can be introduced into the desired photographic constituent layer by a conventional method. That is, a solution of a dye at an appropriate concentration may be added to an aqueous solution of a hydrophilic colloid, which is a binder for a photographic constituent layer, and this solution may be coated on the support or other constituent layers.
本発明において染料はハロゲン化銀写真感光材料を構成
する親水性コロイド層のいずれに添加してもよく、例え
ば保護層、ハロゲン化銀乳剤層、アンチハレーション層
、パック層などである。In the present invention, the dye may be added to any of the hydrophilic colloid layers constituting the silver halide photographic material, such as the protective layer, silver halide emulsion layer, antihalation layer, and pack layer.
本発明において染料を実質的に非感光性の親水性コロイ
ド層のみに含有させる場合には、染料が非感光性の親水
性コロイド層から乳剤層へ拡散していくのを防止してや
ればよい。例えばハロゲン化銀乳剤層を塗布し、完全に
セットさせｔ；後、この乳剤層上に非拡散性染料を添加
した非感光性親水性コロイド層を塗布する方法が用いら
れる。また、多層同時塗布法により乳剤層や非感光性の
親水性コロイド層を同時に塗布する場合には、非感光性
の親水性コロイド層中に非拡散性染料、あるいは染料と
共にポリマー媒染剤を添加するのが最も好ましい。In the present invention, when the dye is contained substantially only in the non-photosensitive hydrophilic colloid layer, it is sufficient to prevent the dye from diffusing from the non-photosensitive hydrophilic colloid layer to the emulsion layer. For example, a method is used in which a silver halide emulsion layer is coated and, after it is completely set, a non-photosensitive hydrophilic colloid layer containing a non-diffusible dye is coated on this emulsion layer. In addition, when coating an emulsion layer and a non-photosensitive hydrophilic colloid layer at the same time using a multilayer simultaneous coating method, it is necessary to add a non-diffusible dye or a polymer mordant together with the dye to the non-photosensitive hydrophilic colloid layer. is most preferred.
次に本発明に用いられるカチオン性のジ又はトリカルボ
シアニン赤外増感色素としては、下記−般式（ＩＩ−ａ
）および〔■−ｂ）で表される化合物が好ましい。Next, the cationic di- or tricarbocyanine infrared sensitizing dye used in the present invention has the following general formula (II-a
) and [■-b) are preferred.
一般式ＣＩ −ａ）
１ｉ
Ｒ＋２
ｌｌ
一般式〔■
ｂ〕
式中、Ｙ、、、Ｙ、□、Ｙ２．およびＹｆｆｉ２は、各
々５員または６員の含窒素複素環を完成するに必要な非
金属原子群を表し、例えばベンゾチアゾール環、ナフト
チアゾール環、ベンゾセレナゾール環、ナフトセレナゾ
ール環、ベンゾオキサゾール環、ナフトオキサゾール環
、キノリン環、３．３−ジアルキルインドレニン環、ベ
ンツイミタソール核、ヒリジン環等を挙げることができ
る。General formula CI-a) 1i R+2 ll General formula [■ b] In the formula, Y, , Y, □, Y2. and Yffi2 each represent a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring , a naphthoxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, a benzimitasol nucleus, a hyridine ring, and the like.
これらの複素環は、低級アルキル基、アルコキノ基、ヒ
ドロキンル基、アリール基、アルコキンカルボニル基、
ハロゲン原子で置換されていてもよい。These heterocycles include lower alkyl groups, alkokino groups, hydroquine groups, aryl groups, alkoxycarbonyl groups,
It may be substituted with a halogen atom.
Ｒ，、、Ｒ，□、Ｒ２１およびＲ１は、各々、置換もし
くは無置換のアルキル基、アリール基またはアラルキル
基を表す。R, , R, □, R21 and R1 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.
Ｒ，、、Ｒ，、、Ｒ，、、Ｒ，、、Ｒ２，、Ｒ１，およ
びＲｏは各々、水素原子、置換もしくは無置換のアルキ
ル基、アルコキ７基、フェニル基、ベンジル基、しくは
無置換のアルキル基（アルキル部分の炭素原子数１−１
訳好ましくは１〜４、）、アリール基を表し、ＷｌとＷ
２とは互いに連結して５員または６員の含窒素複素環を
形成することもできる。R,,,R,,,R,,,R,,,R2,,R1,and Ro are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, or an unsubstituted alkyl group, Substituted alkyl group (number of carbon atoms in alkyl moiety: 1-1)
preferably 1 to 4), represents an aryl group, and Wl and W
2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.
また、Ｒ１３とＲＩｌｌおよびＲ１３とＲ１，は互いに
連結して５員環または６員環を形成することができる。Further, R13 and RIll and R13 and R1 can be linked to each other to form a 5-membered ring or a 6-membered ring.
ｘ、ＩおよびＸ、１はアニオンを表す。＋１１１＋ ｎ
Ｉ２＋ｎ、１およびｎＢは０またはｌを表す。x, I and X, 1 represent anions. +111+n
I2+n, 1 and nB represent 0 or l.
次に、本発明に用いられる増感色素（以下、本発明の増
感色素という）の具体例を示すが、本発明はこれらに限
定されるものではない。なオ、■−１−１３は前記一般
式（Ｉ［−ｂ）でＩ［−１４〜２１は一般式（Ｉ［−ａ
）で表される化合物である。Next, specific examples of the sensitizing dye used in the present invention (hereinafter referred to as the sensitizing dye of the present invention) will be shown, but the present invention is not limited thereto. E, ■-1-13 is the general formula (I[-b) and I[-14 to 21 are the general formula (I[-a
) is a compound represented by
Ｃ，Ｈ。C,H.
にｓｔｌ。ni stl.
ド ■ ２Ｈ６ ｅ １゜ ２Ｈ５ ■ｅ １［−６ ［−７ Ｃ，Ｈ。de ■ 2H6 e 1゜ 2H5 ■e 1[-6 [-7 C,H.
ｓＨｓ ！ｅ ｅ ｃＩ２ｏ 、ｅ ■ ■ ■ ■ ＣＨ、ＣＨ２０Ｈ ｅ ｅ Ｉθ ＣＨ，ＣＨ２０Ｈ ｎ−１４ ■ Ｉ［−１６ １［−１７ Ｑ Ｃ，Ｈ。sHs ! e e cI2o, e ■ ■ ■ ■ CH, CH20H e e Iθ CH, CH20H n-14 ■ I[-16 1[-17 Q C,H.
ｅ ｔＨｉ ■ｅ Ｃ，Ｈ。e tHi ■e C,H.
ｅ ■ Ｉ［−１９ ■ ■ Ｃ，Ｈ。e ■ I[-19 ■ ■ C,H.
Ｉθ
ＣＨｚＧＨｚＯＨ
ｅ
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ｌＢ−２ｇ、更に好ましくは５ ｍｇ−１ｇの範囲で
ハロゲン化銀写真乳剤中に含有される。Iθ CHzGHzOH e The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of 1B-2 g, more preferably 5 mg-1 g per mole of silver halide.
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。また、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、仏国特許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. No. 2,503,776, British Patent No. 742,112, French Patent No. 2,065,662, and Japanese Patent Publication No. 40-2346.
本発明のハロゲン化銀乳剤には、ハロゲン化銀として臭
化銀、沃臭化銀、沃塩化銀、塩臭化銀、塩沃臭化銀およ
び塩化銀等の通常のハロゲン化銀乳剤に使用される任意
のものを用いることかでさる。In the silver halide emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. are used as silver halide in ordinary silver halide emulsions. You can use any of the following.
ハロゲン化銀乳剤に用いられる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。該粒子は一時に成長させてもよいし、種粒子
をつくった後成長させてもよい。種粒子をつくる方法と
成長させる方法は同じであっても、異なってもよい。The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.
ハロゲン化銀乳剤はハロゲン化物イオンと銀イオンを同
時に混合しても、いずれか一方が存在する液中に、他方
を混合してもよい。また、ハロゲン化銀結晶の臨界成長
速度を考慮しつつ、ハロゲン化物イオンと銀イオンを混
合釜内のｐＨ及び／又はｐＡｇをコントロールしつつ逐
次同時に添加することにより生成させてもよい。この方
法により、結晶形が規則的で粒子サイズが均一に近いハ
ロゲン化銀粒子が得られる。成長後にコンバージョン法
を用いて、粒子のハロゲン組成を変化させてもよい。In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and/or pAg in the mixing tank. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a conversion method may be used to change the halogen composition of the particles.
ハロゲン化銀乳剤は、その製造時に、必要に応じてハロ
ゲン化銀溶剤を用いて、ハロゲン化銀粒子の粒子サイズ
、粒子の形状、粒子サイズ分布及び粒子の成長速度をコ
ントロールすることができる。When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.
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（錯塩を含む）、ロジウム塩（錯塩
を含む）及び鉄塩（錯塩を含む）から選ばれる少なくと
も１種を用いて金属イオンを添加し、粒子内部に及び／
又は粒子表面にこれらの金属元素を含有させることがで
き、また適当な還元的雰囲気におくことにより、粒子内
部及び／又は粒子表面に還元増感核を付与できる。During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.
ハロゲン化銀乳剤は、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よいし、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（Ｒｅｓｅａｒｃｈ Ｄ １ｓ
ｃｌｏｓｕｒｅ 以下ＲＤと略す）１７６４３号■項
に記載の方法に基づいて行うことができる。Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17643, Section (2) may be used.
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
よい。The 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 of the grain and the surface layer.
ハロゲン化銀粒子は、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よく、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。The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.
ハロゲン化銀粒子は、立方体、八面体、十四面体のよう
な規則的な結晶形を持つものでもよいし、球状や板状の
ような変則的な結晶形を持つものでもよい。これらの粒
子において、（１００１面と（１１１１面の比率は任意
のものが使用できる。又、これら結晶形の複合形を持つ
ものでもよく、様々な結晶形の粒子が混合されてもよい
。The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of (1001 planes to (1111 planes) can be used. Also, they may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.
ハロゲン化銀粒子の平均粒子サイズ（粒子サイズは投影
面積と等しい面積の円の直径を表す）は、２μ■以下が
好ましいが、特に好ましいのは０．７μ■以下である。The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 2 μm or less, and particularly preferably 0.7 μm or less.
ハロゲン化銀乳剤は、いかなる粒子サイズ分布を持つも
のを用いても構わない。粒子サイズ分布の広い乳剤（多
分散乳剤と称する）を用いでもよいし、粒子サイズ分布
の狭い乳剤（単分散乳剤と称する。ここでいう単分散乳
剤とは、粒径の分布の標準偏差を平均粒径で割ったとき
に、その値が０．２０以下のものをいう。ここで粒径は
球状のハロゲン化銀の場合はその直径を、球状以外の形
状の粒子の場合は、その投影像を同面積の円像に換算し
たときの直径を示す。）を単独又は数種類混合してもよ
い。又、多分散乳剤と単分散乳剤を混合して用いてもよ
い。Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle whose value is 0.20 or less when divided by the grain size.The grain size is the diameter in the case of spherical silver halide, and the projected image in the case of grains with a shape other than spherical. ) may be used alone or in combination. Further, 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.
本発明の感光材料には、目的に応じて種々の添加剤を用
いることができる。Various additives can be used in the photosensitive material of the present invention depending on the purpose.
これ等の添加剤は、詳しくはＲＤ１７６４３号（１９７
１１１年１２月）および同１８７１６号（１９７９年１
１月）に記載されており、その該当箇所を後掲の表にま
とめて示した。These additives are detailed in RD17643 (197
December 111) and No. 18716 (January 1979)
(January), and the relevant sections are summarized in the table below.
また、本発明の感光材料の露光、現像処理条件に関して
は特に制限はなく、例えば前記Ｒ０１７６４３号の２８
〜３０頁の記載を参考にすることができる。Furthermore, there are no particular limitations on the exposure and development conditions for the photosensitive material of the present invention; for example, 28 of R017643,
You can refer to the description on pages 30 to 30.
ハロゲン化銀乳剤を用いた感光材料の写真乳剤層その他
の親水性コロイド層にはす度安定性の改良などを目的と
して、水不溶性または難溶性合成ポリマーの分散物（ラ
テックス）を含有させることができる。A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using a silver halide emulsion for the purpose of improving stability. can.
本発明の感光材料の支持体としては、例えばバライタ紙
、ポリエチレン被覆紙、ポリプロピレン合成紙、ガラス
板、セルロースアセテート、セルロースナイトレート、
例えばポリエチレンテレフタレート等のポリエステルフ
ィルム、ポリアミドフィルム、ポリプロピレンフィルム
、ポリカーボネートフィルム、ポリスチレンフィルム等
が、それぞれ使用目的に応じて用いられる。Examples of the support for the photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc. are used depending on the purpose of use.
本発明により得られた写真乳剤をバライタ紙、レジンコ
ート紙、合成樹脂フィルム、ガラス等に塗布することに
より感光材料を得ることができる。A photosensitive material can be obtained by applying the photographic emulsion obtained according to the present invention to baryta paper, resin coated paper, synthetic resin film, glass, etc.
本発明のハロゲン化銀写真感光材料を現像する場合に用
いられる現像主薬としては具体的に製造された感光材料
に応じて種々の任意のものを挙げることができる。例え
ば次のものが挙げられる。As the developing agent used in developing the silver halide photographic light-sensitive material of the present invention, various arbitrary ones can be mentioned depending on the specifically produced light-sensitive material. Examples include:
ＨＯ−（（Ｊｌ −ＣＨ） 、−０ＦＩ型現像主薬の代
表的なものとしては、ハイドロキノンがあり、その他に
カテコール、ピロガロール及びその誘導体ならびにアス
コルビン酸、クロロハイドロキノン、ブロモハイドロキ
ノン、イングロビルハイドロキノン、トルハイドロキノ
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−ジメチルハイドロキノン、２．３−ジ
ブロモハイドロキノン等がある。 また、ＨＯ−（ＣＨ
−ＣＨ）、−ＮＨ２型現像現像剤ては、オルト及びパラ
のアミノフェノールまたはアミノピラゾロンが代表的な
もので、４−アミノフェノール、２−アミノ−６−７二
二ルフエノール、２−アミノ−４−クロロ−６−フェニ
ルフェノール、４−アミノ−２−フェニルフェノール等
がある。Representative examples of HO-((Jl-CH), -0FI type developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, inglobil hydroquinone, and toluhydroquinone). , methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3-dibromohydroquinone, etc. Also, HO-(CH
-CH), -NH2 type developers are typically ortho- and para-aminophenols or aminopyrazolones, such as 4-aminophenol, 2-amino-6-7 dynylphenol, 2-amino-4 -chloro-6-phenylphenol, 4-amino-2-phenylphenol, etc.
更に、ＨｚＮ−（ＣＨ−Ｃｔｌ）、−ＮＨｘ型現像現像
剤ては、例えば４−アミノ−２−メチル−Ｎ、Ｎ−ジエ
チルアニリン、２，４−ジアミノ−Ｎ、Ｎ−ジエチルア
ニリン、Ｎ−（４−アミノ−３−メチルフェニル）−七
ルホリン、ｐ・フェニレンジアミン、４−アミノ−Ｎ、
Ｎ−ジメチル−３−ヒドロキシアニリン等がある。Furthermore, HzN-(CH-Ctl), -NHx type developing agents include, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N- (4-amino-3-methylphenyl)-7ruforine, p-phenylenediamine, 4-amino-N,
Examples include N-dimethyl-3-hydroxyaniline.
ヘテロ環型現像剤としては、１−７二二ルー３−ピラゾ
リドン、■−フェニルー４．４−ジメチルー３−ピラゾ
リドン、ｌ−フェニル−４−メチル−４−ヒドロキンメ
チル−３−ピラゾリドン、１−フェニル−４−メチル−
４−ヒドロキンメチル−３−ピラゾリドンのような３−
ピラゾリドン類、ｌ−７エニルー４−アミノ−５−ピラ
ゾロン、１−（ｐ−アミノフェニル）−３−アミノ−２
−ピラゾリン、ｌ−フェニル−３−メチル−４−アミノ
−５−ピラゾロン、５−アミノウランル等を挙げること
ができる。Examples of the heterocyclic developer include 1-722-3-pyrazolidone, ■-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroquinemethyl-3-pyrazolidone, and 1-phenyl-4-dimethyl-3-pyrazolidone. phenyl-4-methyl-
3- such as 4-hydroquinemethyl-3-pyrazolidone
Pyrazolidones, l-7enyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
-pyrazoline, l-phenyl-3-methyl-4-amino-5-pyrazolone, 5-aminouranyl, and the like.
その他、Ｔ、Ｈ，ジェームス著ザ・セオリイ・オブ・ザ
・ホトグラフィック・プロセス第４版（Ｔｈｅ Ｔｈｅ
ｏｒｙ ｏｆ ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐ
ｒｏｃｅｓｓ、 Ｆｏｕｒｔｈ Ｅｄｉｔ １ｏｎ）第
２９１〜３３４頁及びジャナール・オブ・ザ・アメリカ
ン・ケミカル・ソサエティ（Ｊｏｕｒｎａｌｏｆ ｔｈ
ｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ ５ｏｃｉｅ
ｔｙ）第７３巻、第３，１００頁（１９５１）に記載さ
れている如き現像剤が本発明に有効に使用し得るもので
ある。これらの現像剤は単独で使用しても２種以上を組
合せてもよいが、２種以上を組み合わせて用いる方が好
ましい。また本発明の感光材料の現像に使用する現像液
には保恒剤として、例えば亜硫酸ソーダ、亜硫酸カリ、
等の亜硫酸塩を用いても、本発明の効果が損なわれるこ
とはない。また保恒剤としてヒドロキシルアミン、ヒド
ラジド化合物を用いてもよい。その他一般白黒現像液で
用いられるような苛性アルカリ、炭酸アルカリまたはア
ミンなどにょるｐＨの調整とパン７ア一機能をもたせる
こと、及びブロムカリなど無機現像抑制剤及びベンゾト
リアゾールなどの有機現像抑制剤、エチレンジアミン四
酢酸等の金属イオン捕捉剤、メタノール、エタノール、
ベンジルアルコール、ポリアルキレンオキシド等の現像
促進剤、アルキルアリールスルポン酸ナトリウム、天然
のサポニン、糖類または前記化合物のアルキルエステル
物等の界面活性剤、グルタルアルデヒド、ホルマリン、
グリオキザール等の硬膜剤、硫酸ナトリウム等のイオン
強度調整剤等の添加を行なうことは任意である。Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess, Fourth Edit 1on) pp. 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society).
e American Chemical 5ocie
ty) Vol. 73, p. 3,100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. The developer used for developing the photosensitive material of the present invention may contain preservatives such as sodium sulfite, potassium sulfite, etc.
Even if sulfites such as sulfites are used, the effects of the present invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH using caustic alkali, alkali carbonate, or amines used in general black and white developers, and providing a pan-7a function, as well as inorganic development inhibitors such as bromkali and organic development inhibitors such as benzotriazole; Metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol,
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin,
It is optional to add a hardening agent such as glyoxal, an ionic strength adjusting agent such as sodium sulfate, etc.
本発明において使用される現像液には、有機溶媒として
アルカノールアミン類やグリコール類を含有させてもよ
い。The developer used in the present invention may contain alkanolamines or glycols as an organic solvent.
上記の組成になる現像液のｐＨ値は９〜１２がよいが、
保恒性及び写真特性上からはｐＨ値は１０〜１１の範囲
が好ましい。The pH value of the developer having the above composition is preferably 9 to 12, but
From the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.
本発明のハロゲン化銀写真感光材料は、種々の条件で処
理することができる。処理温度は、例えば現像温度は５
０℃以下が好ましく、特に３０°Ｃ〜４０℃の範囲が好
ましく、また現像時間は３分以内に終了することが一般
的であるが、特に好ましくは１分以内が好結果をもたら
すことが多い。また現像以外の処理工程、例えば水洗、
停止、安定、定着、更に必要に応じて前硬膜、中和等の
工程を採用することは任意であり、これらは適宜省略す
ることもできる。更にまた、これらの処理は皿現像、粋
現像などいわゆる手現像処理でも、ローラー現像、ハン
ガー現像など機械現像であってもよい。The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably in the range of 30°C to 40°C, and the development time is generally completed within 3 minutes, but particularly preferably within 1 minute, which often brings good results. . Processing steps other than development, such as washing with water,
It is optional to adopt steps such as stopping, stabilizing, fixing, and if necessary, preduration and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development treatments such as dish development and suki development, or mechanical development such as roller development and hanger development.
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
（乳剤層用塗布液の調製）
溶液Ａ
水
９８０ｍｆｆ塩化ナトリウム
２．０ｇオセインゼラチン ２０ｇへ
キサクロロイリジウム酸
カリウム塩の０．１θ％水溶液 ２．８ｍ（１
ヘキサブロモロジウム酸
カリウム塩の０．００１％水溶液 ２．５ｍ１２
溶液Ｂ
水
３８０ｖａｎ塩化ナトリウム
３８ｇ臭化カリウム ４２ｇ
溶液溶
液
３８０ｔｒｒｌ硝酸銀
１７０ｇ溶液り
凝集ゼラチン剤
（Ｇ−８、変性率９０％）３６ｇ
水
３００ｃｃ４０℃に保温された上記溶液中に、ｐ
Ｈを３ 、 ｐＡｇ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分間に亙って加え、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、溶液りを加え、５分間撹拌し、酢酸（
２０％）でｐＨ４，７に下げ、ゼラチンを凝集、沈澱さ
せて上澄駅を排水し、１回目同様に酢酸（２０％）ｄｅ
ｐＨ４，７に下げ、２回目の脱塩を行った。この操作
をもう１度繰り返して、３度目の脱塩を行い、乳剤（Ａ
）を得た。この間液温は４０℃に保持し、５００ｍＱの
水と３０ｇのゼラチンを加えて、５０℃で３０分間分散
させる。これによって臭化銀３５モル％、塩化銀６５モ
ル％、平均粒径０，２７μ重の立方体粒子が得られる。Example-1 (Preparation of coating solution for emulsion layer) Solution A Water
980mff sodium chloride
2.0g ossein gelatin 20g 0.1θ% aqueous solution of hexachloroiridate potassium salt 2.8m (1
0.001% aqueous solution of potassium hexabromorodate salt 2.5m12
Solution B water
380van sodium chloride
38g potassium bromide 42g
solution solution
380trrl silver nitrate
170g solution flocculated gelatin agent (G-8, denaturation rate 90%) 36g water
In 300 cc of the above solution kept at 40°C, p
The above solution B and solution C were added functionally simultaneously over 80 minutes while maintaining H3 and pAg at 7.7, and after continued stirring for an additional 5 minutes, the pH was adjusted to 5.6 with an aqueous sodium carbonate solution. Adjust, add solution, stir for 5 minutes, add acetic acid (
20%) to lower the pH to 4.7, coagulate and precipitate the gelatin, drain the supernatant, and add acetic acid (20%) as before.
The pH was lowered to 4.7 and desalting was performed for the second time. This operation is repeated once again to perform the third desalination, and the emulsion (A
) was obtained. During this time, the liquid temperature was maintained at 40°C, 500 mQ of water and 30g of gelatin were added, and the mixture was dispersed at 50°C for 30 minutes. As a result, cubic grains having 35 mol % of silver bromide, 65 mol % of silver chloride, and an average grain size of 0.27 μl are obtained.
（乳剤Ｂの調製）
乳剤Ａにおいて、脱塩工程で凝集ゼラチン剤を使用せず
に、デモール（花王話製）及び硫酸マグ、序シウムを用
いて脱塩を行い、これを乳剤Ｂとしｔこ。(Preparation of Emulsion B) In the desalting step, emulsion A was desalted using Demol (manufactured by Kaowa), sulfuric acid mag, and Shisium, and this was used as emulsion B. .
このようにして得られｔ；乳剤Ａ、Ｂに対して、クエン
酸１％の水溶液を１０１１ＩＱ、塩化ナトリウム５％の
水溶液を１０ｍｆ２加えて、ｐＨ５，５，ｐＡｇ７に調
整した乳剤に、チオ硫酸ナトリウム０．１％の水溶液を
１０＋ｏ１２及び０．２％の塩化金酸水溶液７ｍ１２を
加えて５７°Ｃで熟成して最高感度にする。To emulsions A and B, 1011IQ of 1% citric acid aqueous solution and 10mf2 of 5% sodium chloride aqueous solution were added to the emulsion, which was adjusted to pH 5.5 and pAg 7. Add 10+o12 of 0.1% aqueous solution and 7ml2 of 0.2% chloroauric acid aqueous solution and ripen at 57°C to achieve maximum sensitivity.
上記乳剤Ａ、Ｂを分割して、それぞれに表１に示す本発
明および比較の赤外増感色素の０．１％メタノール溶液
をハロゲン化銀１モル当り５０ｍ１２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２５ａ＋Ｑ、安定剤として４−
ヒドロキシ−６−メチル１．３，３ａ。The above emulsions A and B were divided, and 50 mL of a 0.1% methanol solution of infrared sensitizing dyes of the present invention and comparative infrared sensitizing dyes shown in Table 1 were added to each of them per mole of silver halide, and 1 l of each was added as an antifoggant. - 0.5% solution of phenyl-5 mercaptotetrazole in 25a+Q, 4- as stabilizer
Hydroxy-6-methyl 1.3,3a.
７−チトラザインデンの１％溶液１８０ｍ（２，及びゼ
ラチンの１０％水溶液３００ｍΩを加え熟成を停止させ
た。Ripening was stopped by adding 180 m of a 1% solution of 7-chitrazaindene (2) and 300 mΩ of a 10% aqueous solution of gelatin.
これらに塗布助剤として、１０％のトリー１−プロピル
ナフタレンスルホン酸ナトリウム塩水溶液を１５ｍ（１
，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５９ｍｆ２．アクリル酸ブチルの高分子ポリマー
ラテンクスを３０ｇ１安定剤としてハイドロキノンの２
０％水溶液を２０＋ｅＬ臭化カリウムの１０％水溶液を
２０ｗ＋Ｉ２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ｌ：ｏ、２５モル反応生成物をゼラチン１ｇ当り５０
＋＋＋ｇ添加し、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、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
。As a coating aid, 15 m (1
, a 4% aqueous solution of styrene-maleic acid copolymer was used as a thickener at 59mf2. 30g of polymeric polymer Latinx of butyl acrylate 1stabilizer and 2 parts of hydroquinone
Add 20 eL of 0% aqueous solution + 20 eL of 10% aqueous solution of potassium bromide + I2, stir, and use Tetrakis as a hardening agent.
50 l:o, 25 mol reaction product of (vinylsulfonylmethyl)methane and taurine potassium salt per gram of gelatin.
+++g was added, and the emulsified dispersion shown below was added so that the optical brightener amount was 15 mg/m'', and the pH was adjusted to 5.6 with citric acid to prepare a coating solution for the 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１記載の染料を付量が２００ａ＋ｇ／
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１５＋ａｇ／■１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１５ｍ１２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 amount of the dye listed in Table 1 was added to an aqueous solution of 200a+g/
Furthermore, the emulsified dispersion shown below was added to give a fluorescent brightener loading of 15+ag/■1, and 4% of styrene-maleic acid copolymer was added as a thickener.
A coating solution for an antihalation layer was prepared by adding 15ml of an aqueous solution.
（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１ＯＯＩ１１０と酢酸エチル１００ｍ１２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
１５００ｍΩ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ＩＯｇ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 ml of talesyl phenyl phosphate and 100 ml of ethyl acetate, and add the entire amount of this solution to tripropylnaphthalene. Mix with 1500 mΩ of a 12% gelatin aqueous solution containing 3 g of sodium sulfonate salt, emulsify and disperse by ultrasonic dispersion, and then add IOg of butyl acrylate polymer latex as a solid content to prepare an emulsified dispersion of an oil-soluble optical brightener. did.
蛍光増白剤（Ｆ）
（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
３（ｌａｇ／■２、マット剤として平均粒径４μｌのポ
リメチルメタクリレートを４０ｍｇ／■２、含弗素界面
活性剤として下記（Ｓ）の化合’ｋｌ ヲ３０ｍｇ／■
２、硬膜剤としてホルマリンをゼラチンＩｇ当りｌＯ履
ｇ添加し、保護層用塗布液を調製した。Fluorescent brightener (F) (Preparation of coating solution for protective layer) Add 3 (lag/■2) of 2-sulfosuccinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid to an aqueous gelatin solution, on average as a matting agent. 40 mg/■2 of polymethyl methacrylate with a particle size of 4 μl, and 30 mg/■ of the following compound (S) as a fluorine-containing surfactant.
2. A coating solution for a protective layer was prepared by adding 10 g of formalin per Ig of gelatin as a hardening agent.
含弗素界面活性剤（Ｓ）
ＣＨｚＣＯＯＣＲ２（ＣＦ２ ）ａＨ
ＮａＯ，Ｓ −ＣＨＣＯＯＣＨ，（ＣＦ２）８８（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
ｖｔ％含有する厚さ１１０μｍのポリエチレンフート紙
上に同時３層塗布した。得られｔユ試料の塗布銀量は１
．４ｇ／ｉ＋”、ゼラチン塗布量はハレーション防止層
が１．４ｇ／ｍ２、乳剤層カ月、４ｇ／ｍ”、保護層が
０．９ｇ／ｍ”であった。Fluorine-containing surfactant (S) CHzCOOCR2(CF2)aH NaO,S -CHCOOCH, (CF2)88 (Sample preparation and evaluation) Coating liquid for antihalation layer, coating liquid for emulsion layer prepared in this way, and a coating solution for a protective layer, which has a hydrophilic colloid backing layer and an undercoat layer, and contains 15% titanium dioxide.
Three layers were simultaneously coated on a 110 μm thick polyethylene foot paper containing vt%. The coated silver amount of the obtained sample was 1
．． The coating amount of gelatin was 1.4 g/m2 for the antihalation layer, 4 g/m'' for the emulsion layer, and 0.9 g/m'' for the protective layer.
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。 即日および経時
劣化試料を光学クサビ及びコダックラッテンフィルター
Ｎｏ 、 ８８Ａを通してキセノンフラッンユで１０−
’秒の閃光露光した後、自動現像機としてサクラオート
マチックブロセッサーＧＲ−１４（コニカ株式会社製）
、現像液として下記に示す処方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。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. Same-day and aged samples were filtered through an optical wedge and a Kodak Wratten filter No. 88A with a xenon flannel for 10-10 minutes.
After 'second flash exposure, Sakura Automatic Processor GR-14 (manufactured by Konica Corporation) is used as an automatic processor.
A developing solution and a fixing solution having the following formulations were used as the developing solution to carry out development and evaluation. In addition, unexposed samples were also processed in the same manner for evaluation of residual color.
なお処理条件は、現像が３８°ｃ２０秒、定着が約３８
°Ｃ２０秒、水洗は常温で２０秒、乾燥温度が約４０″
Ｃであった。The processing conditions are: development at 38°C for 20 seconds, and fixing at approximately 38°C.
°C 20 seconds, washing with water for 20 seconds at room temperature, drying temperature approximately 40''
It was C.
得られた結果を表１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 1. 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.
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、「ｌ
」は強い青色系の残色を示した。In addition, for samples processed without exposure to light, residual color was visually evaluated and evaluated on a five-point scale, with "5" being colorless and "l"
” showed a strong blue residual color.
「３」を下回る残色は、一般的な使用に耐えないレベル
である。Residual color below "3" is at a level that cannot withstand general use.
現像液処方
純水（イオン交換水） 約 ８０ｏｌＩｆｆ
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 ２ｇ水酸化カリウム
１０−５ｇ５−メチルベンゾ
トリアゾール
ジエチレングリコール
１−フェニル−４，４−ジメチル−
３−ピラゾリジノン ３００膳ｇｌ−フェニル
−５〜メルカプトテトラ
ゾール ６０ｍｇ臭化カリウム
ハイドロキノン
炭酸カリウム
純水（イオン交換水）
げろ。Developer prescription Pure water (ion exchange water) Approximately 80olIff
Potassium sulfite 60g Ethylenediaminetetraacetic acid disodium salt 2g Potassium hydroxide 10-5g 5-methylbenzotriazole diethylene glycol 1-phenyl-4,4-dimethyl-3-pyrazolidinone 300 servings gl-phenyl-5-mercaptotetrazole 60mg Potassium bromide hydroquinone carbonate Potassium pure water (ion exchange water) Gero.
現像液のｐＨは約ｌ００８であった。The pH of the developer was approximately 1008.
定着液処方
（組成Ａ）
チオ硫酸アンモニウム（７２，５％Ｗ／Ｖ３．５ｇ
０ｇ
５ｇ
を加えて１，０００−ａに仕上
亜硫酸ナトリウム
酢酸ナトリウム・３水塩
硼 酸
クエン酸ナトリウム・２水塩
３００１１ｇ
５ｇ
水溶液）
４０ｍＱ
７ｇ
６．５ｇ
６ｇ
６ｇ
酢 ＃（９０％ｗ／ｗ水溶液）
（組成り）
純 水（イオン交換水）
酢 酸（５０％ｖ／ｖ水溶液）
硫酸アルミニウム
（Ａら０．換算含量が８．１％ｖ／ｖの水溶液）１３．
６＊Ｉ２
７ｒａＱ
４．７ｇ
２６．５ｇ
使用時に水５００ｍｆｆ中に上記組成Ａ、組成りの順Ｉ
こ溶かし、１βに仕上げて用いた。この定着比較赤外増
感色素
（Ｃ）Ｉｓ）ａｓＯ３＠
ＣＩＨ。Fixer formulation (composition A) Add ammonium thiosulfate (72.5% W/V 3.5g 0g 5g to make 1,000-a) Sodium sulfite Sodium acetate trihydrate Boric acid Sodium citrate dihydrate 30011g 5g Aqueous solution) 40mQ 7g 6.5g 6g 6g Vinegar # (90% w/w aqueous solution) (Composition) Pure water (ion-exchanged water) Acetic acid (50% v/v aqueous solution) Aluminum sulfate (A et al.0. conversion content 8.1% v/v aqueous solution)13.
6*I2 7raQ 4.7g 26.5g In 500mff of water when using, the above composition A, composition order I
It was dissolved and used after finishing to 1β. This fixed comparison infrared sensitizing dye (C)Is)asO3@CIH.
比較染料
（しＩ′Ｉ２ハｂす、″
（ＣＨｘ）＊ＳＯｓＫ
表１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。Comparative dye (CHx)*SOsK As is clear from the results in Table 1, the samples belonging to the present invention had good sensitivity and residual color, and did not deteriorate in performance over time. It turns out that there are few.
実施例２
ゼラチン６０ｇを水で溶解し、その中に表２で示す染料
を２．Ｏｇ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４０１１Ｉｆｆ、硬
膜剤としてグリオキザールの４％水溶液４５ｍ（２加え
て全量１ａ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にゼラチン付量が
３．２ｇ／ｍ”になるように塗布した。一方、実施例１
と同様にして塩臭化銀（塩化銀６２モル％、臭化銀３８
モル％、平均粒径０．２６μｍ１立方晶粒子）乳剤を得
た。この乳剤を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テトラザインデンを１．５ｇｌ −７ｘニル
−５−メルカプトテトラゾールを０．２９添加し分割し
、表２に示す赤外増感色素の０．１％メタノール溶液ヲ
ハロゲン化銀１モル当り５０鴎α加え、カブリ防止剤と
してハイドロキノンの１０％メタノール溶液を５９ｍ（
２，延展剤として２０％サポニン水溶液を１９ｍＬ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
５０ｍｆｆ、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２０
ｔｒｒＱとホルマリン４％水溶液１０■ａ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−インペンチル）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。Example 2 60 g of gelatin was dissolved in water, and 2.0 g of the dye shown in Table 2 was added thereto. Og was added respectively. Furthermore, 4011Iff of a 1% aqueous solution of 1-decyl-2-(3-impentyl)succinate-2-sulfonic acid sodium salt was added as a spreading agent, and 45ml of a 4% aqueous solution of glyoxal was added as a hardening agent to make the total amount 1a. A gelatin-containing aqueous solution was applied onto a polyethylene terephthalate film support so that the amount of gelatin applied was 3.2 g/m''.On the other hand, Example 1
Silver chlorobromide (62 mol% silver chloride, 38 mol% silver bromide)
An emulsion (mol%, average grain size: 0.26 μm, 1 cubic grain) was obtained. After gold sensitization and sulfur sensitization of this emulsion, 4-hydroxy-6-methyl-1,3
, 3a, 7-tetrazaindene (1.5 g) -7x Nyl-5-mercaptotetrazole (0.29 g) was added and divided into 0.1% methanol solutions of infrared sensitizing dyes shown in Table 2 per mole of silver halide. Add 50 ml of 10% methanol solution of hydroquinone as an antifoggant.
2. Added 19 mL of 20% saponin aqueous solution as a spreading agent, 50 mff of 4% aqueous solution of styrene-maleic acid copolymer as a thickener, and 30 g of ethyl acrylate polymer latex, and added 1-hydroxy- as a hardening agent. 3
,5-dichlorotriazine sodium salt 1% aqueous solution 20
trrQ and 10 μa of a 4% formalin aqueous solution were 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-inpentyl)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、実施例１と同様の処理
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２
３℃相対湿度４８％で調湿後、ポリ酢酸ビニル （厚さ
１００μ嘗）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。結果を表２に示す。The film thus produced was subjected to the same processing as in Example 1, and its photographic properties were evaluated. However, the evaluation of stability over time was performed using the following method. In other words, divide one and a half into two
After controlling the humidity at 3°C and a relative humidity of 48%, it was sealed and packaged with a moisture-proof material laminated with polyvinyl acetate (thickness: 100 μm), and heat-treated in a thermostat at 55°C and a relative humidity of 50% for 72 hours. The results are shown in Table 2.
ただし写真感度は実施例１
と同様に試料１
を１００
表２に示すように、本発明の試料は感度、残色ともに長
杆で、かつ経時での性能の劣化が少ないことがわかる。However, the photographic sensitivity of Sample 1 was 100 as in Example 1. As shown in Table 2, the samples of the present invention have long sensitivity and residual color, and show little deterioration in performance over time.
実施例３
ＫＢｒ １３０ｇ、 Ｋｌ ２．５ｇ、 ｌ−７ｚ ニ
ール−５−メルカプトテトラゾール ３０鳳ｇ及びゼラ
チン１５ｇを含む溶液ｌＱを４０℃にて撹拌する中に０
．５モルのアンモニア性硝酸銀を含む液５００ｔＱを１
分間で添加し、添加後２分で酢酸を添加してｐｏを６．
０にした。さらに１分後に硝酸銀０．５モルを含む液５
００ｔＱを１分間で添加し、１５分間撹拌後、ナフタレ
ンスルホン酸ナトリウムのホルマリン縮合物と硫酸マグ
ネシウムの水溶液を加えて乳剤を凝縮させた。上澄液を
除去後、４０℃の温水２Ｑを加え、ＩＯ分間撹拌後再び
硫酸マグネシウムの水溶液を加えて乳剤を凝集させ、上
澄液除去後５％のゼラチン溶液３００１１＋＜＋を加え
て５５℃にて３０分間撹拌し乳剤を作った。Example 3 A solution lQ containing 130 g of KBr, 2.5 g of Kl, 30 g of l-7z Neal-5-mercaptotetrazole and 15 g of gelatin was stirred at 40°C.
．． 500 tQ of a solution containing 5 mol of ammoniacal silver nitrate
2 minutes after addition, acetic acid was added to raise the po to 6.5 minutes.
I set it to 0. After another minute, solution 5 containing 0.5 mol of silver nitrate
00tQ was added over 1 minute, and after stirring for 15 minutes, an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to condense the emulsion. After removing the supernatant, 2Q of 40°C warm water was added, and after stirring for IO minutes, an aqueous solution of magnesium sulfate was added again to coagulate the emulsion. After removing the supernatant, 5% gelatin solution 30011+<+ was added and the emulsion was heated at 55°C. An emulsion was prepared by stirring for 30 minutes.
この乳剤は平均粒径が０．４０μｍで、０．２〜０．７
μ■に全粒子個数の９０％が含まれていた。This emulsion has an average grain size of 0.40 μm, 0.2 to 0.7
μ■ contained 90% of the total number of particles.
次にこの乳剤にチオシアン酸アンモニウムと塩化金酸及
びチオ硫酸ナトリウムを加え、金−′ｆＩＬ′ｉＬ増感
を行った。得られた乳剤に下記に示す増感色素を加え、
さらに４−ヒドロキシ−６−メチル−１−３−３ａ−７
−チトラザインデンをハロゲン化銀１モル当たり１．Ｏ
ｇ加えた。Next, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to this emulsion to carry out gold-'fIL'iL sensitization. Add the sensitizing dye shown below to the obtained emulsion,
Furthermore, 4-hydroxy-6-methyl-1-3-3a-7
- Citrazaindene at 1.0% per mole of silver halide. O
g added.
増感色素
裏引層として、ゼラチン４００ｇ、ポリメチルメタクリ
レート２ｇ１ ドデシルベンゼンスルホン酸ナトリウム
６ｇ、下記ハレーション防止染料２０ｇ、及びＮ、Ｎ’
−エチレンビス−（ビニルスルホニルアセトアミド）、
ポリエチレンスルホン酸ソーダ、グリシジルメタクリレ
ート５０ｖ％、メチルアクリレート１０Ｗ％、ブチルメ
タクリレート４０１％の３種のモノマーからなる共重合
体を、その濃度が１０１％になるように希釈して得た共
重合体水性分散液を下引液として塗設したポリエチレン
テレフタレートベースの片側の面にゼラチン、マッ
ト剤（ポリ
メ
チルメタクリレート：平均粒子サイズ３．５μｍ）及
び下記構造式の混合物。As a sensitizing dye backing layer, 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and N, N'
-ethylene bis-(vinylsulfonylacetamide),
An aqueous copolymer dispersion obtained by diluting a copolymer consisting of three monomers: sodium polyethylene sulfonate, 50% glycidyl methacrylate, 10% methyl acrylate, and 401% butyl methacrylate to a concentration of 101%. A mixture of gelatin, a matting agent (polymethyl methacrylate: average particle size 3.5 μm), and the following structural formula was applied to one side of a polyethylene terephthalate base coated with the liquid as a subbing liquid.
ＣＩＦ１７３Ｏ□Ｎ（Ｃ，！（、）ＣＨ，Ｃ００Ｋ
の混合物ＣａＦ＋ ｒｓＯｚＮｃｃｓＨｒ）ＣＣＨｘＣ
ＨｘＯ）ｉ ｓＨの混合物からなる保護層液と共に塗布
して得られた裏引きずみの支持体を用意した。塗布量は
裏引き層、保護層をそれぞれゼラチン付き量として２．
５９／１１”、２．０ｇ／ｍ２である。CIF173O□N(C,!(,)CH,C00K
mixture of CaF+ rsOzNccsHr)CCHxC
A drag-back support was prepared by coating with a protective layer solution consisting of a mixture of HxO)i sH. The amount of coating is based on the amount of gelatin applied to the backing layer and protective layer.2.
59/11", 2.0 g/m2.
（ハレーション防止染料） （塗布試料の作成） ハロゲン化銀１モル当たり ト リメチロールプロ パン １０ｇ１ニトロフエニル ト リフェニルホスホ ニウムクロライ ド５０ＩＩ１ｇ、 １．３−ジヒドロキンベンゼ スルホン酸アンモニウム １ ｇ、 ２−メルカプト ベンツイミダゾール ス ルホン リウム１０ ｇ Ｈ １、１ ジメチロ ブロム １−ニ トロ メ タ ０ｍｇ 等を加えて乳剤層としｔ：。(Antihalation dye) (Preparation of coating sample) per mole of silver halide to limethylol pro Bread 10g 1 Nitrophenyl to Riphenylphospho Nium Chlorai Do50II1g, 1.3-dihydroquinebenze Ammonium sulfonate 1 g, 2-Mercapto Benzimidazole vinegar Lehon Rium 10 g H 1, 1 dimethylo Blom 1-2 Toro Mail Ta 0mg etc. to form an emulsion layer.
保護層液は、 次のように調製した。The protective layer liquid is Prepared as follows.
（保護層液） 添加量は塗布液Ｋｌ当たりの量で示す。(Protective layer liquid) The amount added is expressed per Kl of coating liquid.
石灰処理イナートゼラチン
６８ｇ
酸処理ゼラチン
ポリメチルメタクリレート
面積平均粒径３．５μｍのマット剤
二酸化ケイ素粒子
面積平均粒子１．２μ■のマット剤
ルドックスＡＭ（デュポン社製）
（コロイドシリカ）
２−４−ジクロロ−６−ヒドロキシ−１，３，５−トナ
トリウム塩の水溶液２％（硬膜剤）
ホルマリン３５％（硬膜剤）
グリオキザール水溶液４０％（硬膜剤）０．３ｇ
１．１ｇ
０．５ｇ
０ｇ
リアジン
０ｔＱ
２園ａ
１．５鳳Ｑ
ＣＨ，Ｃ００（ＣＯ，）、ＣＨ。Lime-treated inert gelatin 68 g Acid-treated gelatin Polymethyl methacrylate Matting agent with area average particle size of 3.5 μm Silicon dioxide particles Matting agent with area average particle size of 1.2 μm Ludox AM (manufactured by DuPont) (Colloidal silica) 2-4-dichloro 2% aqueous solution of -6-hydroxy-1,3,5-tosodium salt (hardener) Formalin 35% (hardener) 40% glyoxal aqueous solution (hardener) 0.3g 1.1g 0.5g 0g Reazin 0tQ 2 Garden a 1.5 Otori Q CH, C00 (CO,), CH.
ＣＨ，Ｃ００ＣＨ，（Ｃ，Ｆ、）ｓＨｏ、 ５ 。CH, C00CH, (C, F,)sHo, 5.
Ｆ＋ｓＣｓ ０ｆＣＨｚＣ［（２０’ｒＴ；璽ＣＨｚ
ＣＨｚ−０１（３ｍｇＣ，Ｆ、ＳＯ，Ｋ
２Ｂ上記裏引き済
みベースに各層をスライドホッパー法により支持体から
順次ハロゲン化銀乳剤層、保護層を塗布速度６０ｍ／ｍ
ｉｎで２層同時に重層塗布し、試料を得た。銀量は２．
５９／■３、ゼラチン量は乳剤層３ｇ／■２、保護層１
．３９／■２であった。F+sCs 0fCHzC[(20'rT; Seal CHz
CHz-01 (3mgC,F,SO,K
2B Each layer was coated on the above-mentioned backed base using the slide hopper method, and the silver halide emulsion layer and protective layer were sequentially applied from the support at a coating speed of 60 m/m.
A sample was obtained by applying two layers at the same time. The amount of silver is 2.
59/■3, gelatin amount is emulsion layer 3g/■2, protective layer 1
．． It was 39/■2.
上記試料を実施例２と同様に評価したところ感度、残色
ともに良好で経時性の優れたものが得られた。When the above sample was evaluated in the same manner as in Example 2, it was found that both the sensitivity and residual color were good, and the aging properties were excellent.
実施例４ 実施例１と同様の試料を、下記処理条件で処理しｊ二。Example 4 The same sample as in Example 1 was treated under the following treatment conditions.
尚、処理液は実施例１と同じである。Note that the treatment liquid is the same as in Example 1.
工程 温度（°Ｃ） 時間（秒）現像
３４１５
定着 ３４ 約１５水洗 常
温 約１２
乾燥 ５０１０
表３の結果から本発明によれば、超迅速処理によっても
高感度で、残色が抑えられていることがわかる。Process Temperature (°C) Time (seconds) Development
3415 Fixing 34 Approximately 15 Washing Room temperature Approximately 12 Drying 5010 From the results in Table 3, it can be seen that according to the present invention, even with ultra-rapid processing, high sensitivity and residual color were suppressed.
本発明により、高感度で残色が少なく、シかも保存期間
中における性能の劣化が極めて少ない赤外増感されたハ
ロゲン化銀写真感光材料を提供することが出来た。According to the present invention, it was possible to provide an infrared sensitized silver halide photographic material with high sensitivity, little residual color, and very little deterioration in performance during storage.
Claims (2)
を有するハロゲン化銀写真感光材料において、該乳剤層
がカチオン性のジおよびトリカルボシアニン色素からな
る群から選ばれる少なくとも１つによって分光増感され
、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、かつ下記該ハロゲン化銀乳剤層中のハロ
ゲン化銀乳剤の脱塩処理が凝集ゼラチン剤によっておこ
なわれたものであることを特徴とするハロゲン化銀写真
感光材料。(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer is spectroscopically treated by at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. The silver halide emulsion in the silver halide emulsion layer is sensitized and contains at least one dye represented by the following general formula [I], and the silver halide emulsion in the silver halide emulsion layer described below is desalted using an agglomerated gelatin agent. A silver halide photographic material characterized by being
び安定化までの処理時間が４５秒以内であり、かつライ
ンスピードが１０００ｍｍ／ｍｉｎ以上であることを特
徴とする請求項１記載の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、Ｒはアリール基を表し、Ｘはカルボニル基、ス
ルホニル基、又は▲数式、化学式、表等があります▼基
を表し、Ｚはベンゾ縮合環又はナフト縮合環を形成する
に必要な非金属原子群を表す。 Ｌ＿１は窒素原子又はメチン基を表し、Ｌ＿２及びＬ＿
３はメチン基を表す。ｎは１〜６の整数を表す。 但し、Ｌ＿１が窒素原子を表す時、ｎは１を表すものと
する。一般式〔 I 〕で表される化合物は分子内に少な
くとも１つの酸基を有するものとする。〕(2) Processed using an automatic developing machine, the processing time for development, fixing and stabilization is within 45 seconds, and the line speed is 1000 mm/min or more. Silver halide photographic material. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents an aryl group, X represents a carbonyl group, sulfonyl group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. represents a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring. L_1 represents a nitrogen atom or a methine group, L_2 and L_
3 represents a methine group. n represents an integer of 1 to 6. However, when L_1 represents a nitrogen atom, n shall represent 1. The compound represented by the general formula [I] has at least one acid group in the molecule. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15446490A JPH0445435A (en) | 1990-06-13 | 1990-06-13 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15446490A JPH0445435A (en) | 1990-06-13 | 1990-06-13 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0445435A true JPH0445435A (en) | 1992-02-14 |
Family
ID=15584818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15446490A Pending JPH0445435A (en) | 1990-06-13 | 1990-06-13 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0445435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019238121A1 (en) * | 2018-06-15 | 2019-12-19 | The Hong Kong University Of Science And Technology | Nir-ii emissive luminogens |
-
1990
- 1990-06-13 JP JP15446490A patent/JPH0445435A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019238121A1 (en) * | 2018-06-15 | 2019-12-19 | The Hong Kong University Of Science And Technology | Nir-ii emissive luminogens |
| CN112218855A (en) * | 2018-06-15 | 2021-01-12 | 香港科技大学 | NIR-II-emitting luminophores |
| CN112218855B (en) * | 2018-06-15 | 2024-01-05 | 香港科技大学 | NIR-II emissive luminophores |
| US12023387B2 (en) | 2018-06-15 | 2024-07-02 | The Hong Kong University Of Science And Technology | NIR-II emissive luminogens |
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