JPH01279238A - Silver halide photographic sensitive material which is not degraded in covering power and has improved roller marking property - Google Patents
Silver halide photographic sensitive material which is not degraded in covering power and has improved roller marking propertyInfo
- Publication number
- JPH01279238A JPH01279238A JP10959188A JP10959188A JPH01279238A JP H01279238 A JPH01279238 A JP H01279238A JP 10959188 A JP10959188 A JP 10959188A JP 10959188 A JP10959188 A JP 10959188A JP H01279238 A JPH01279238 A JP H01279238A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- emulsion
- silver
- gelatin
- protective colloid
- 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 67
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 63
- 239000004332 silver Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 108
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 239000000084 colloidal system Substances 0.000 claims abstract description 29
- 230000001681 protective effect Effects 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000004816 latex Substances 0.000 claims abstract description 13
- 229920000126 latex Polymers 0.000 claims abstract description 13
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004820 halides Chemical class 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 7
- 230000004931 aggregating effect Effects 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 abstract description 37
- 229920000159 gelatin Polymers 0.000 abstract description 37
- 108010010803 Gelatin Proteins 0.000 abstract description 34
- 235000019322 gelatine Nutrition 0.000 abstract description 34
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 14
- 238000012545 processing Methods 0.000 abstract description 11
- 230000003311 flocculating effect Effects 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000006735 deficit Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 35
- 239000013078 crystal Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 13
- 229910021612 Silver iodide Inorganic materials 0.000 description 13
- 229940050521 gelatin agent Drugs 0.000 description 13
- 229940045105 silver iodide Drugs 0.000 description 13
- 238000011033 desalting Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000120 polyethyl acrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- WFNHDWNSTLRUOC-UHFFFAOYSA-M (2-nitrophenyl)-triphenylphosphanium;chloride Chemical compound [Cl-].[O-][N+](=O)C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WFNHDWNSTLRUOC-UHFFFAOYSA-M 0.000 description 1
- QKUGKZFASYQCGO-SREVYHEPSA-N (z)-4-oxo-4-phenylmethoxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1=CC=CC=C1 QKUGKZFASYQCGO-SREVYHEPSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- AXCGIKGRPLMUDF-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one;sodium Chemical compound [Na].OC1=NC(Cl)=NC(Cl)=N1 AXCGIKGRPLMUDF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LLOAINVMNYBDNR-UHFFFAOYSA-N 2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2NC(=S)NC2=C1 LLOAINVMNYBDNR-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 108010088751 Albumins Proteins 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- 238000012662 bulk polymerization Methods 0.000 description 1
- NBJVNLSDCVSQMV-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;methyl 2-methylprop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C(C)=C.CC(=C)C(=O)OCC1CO1 NBJVNLSDCVSQMV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000009193 crawling Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- PWHMFVALYNYYMZ-UHFFFAOYSA-N ethenyl phenylmethanesulfonate;sodium Chemical compound [Na].C=COS(=O)(=O)CC1=CC=CC=C1 PWHMFVALYNYYMZ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 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
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 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
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 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
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/015—Apparatus or processes for the preparation of emulsions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハロゲン化銀写真感光材料に関し、特に現像銀
の被覆力を低下させることなくローラーマーク性が改良
さ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, and particularly to a silver halide photographic material with improved roller mark properties without reducing the covering power of developed silver. .
近年、ハロゲン化銀写真感光材料に望まれる特性として
、迅速処理が可能であること、高画質であること、保存
安定性の良いこと、更に低コストであることなどがある
が、その中でも特に迅速に処理できるハロゲン化銀写真
感光材料が要請されている。In recent years, properties desired for silver halide photographic materials include rapid processing, high image quality, good storage stability, and low cost. There is a need for silver halide photographic materials that can be processed in a variety of ways.
迅速処理達成のために、現像処理の高ｐ１１化、高温化
（３０〜４０°Ｃ）が試みられているが、このような条
件下では写真性能の劣化を招くことが多かった。特に自
動現像機で処理を行う場合、感光材料の耐圧性が劣化し
、搬送ローラーの圧力により、いわゆるローラーマーク
が発生し著しく画質を損ねる傾向が強い。In order to achieve rapid processing, attempts have been made to increase the p11 and temperature (30 to 40°C) of the developing process, but such conditions often lead to deterioration of photographic performance. In particular, when processing is performed using an automatic processor, the pressure resistance of the photosensitive material deteriorates, and there is a strong tendency for so-called roller marks to occur due to the pressure of the conveying roller, significantly impairing image quality.
この問題を解決する手段として、従来数多くの報告があ
る。例えば、ハロゲン化銀乳剤にカブリ防止剤や安定剤
と称する化合物を含有させたり、写真感光材料のバイン
ダー（例えばゼラチン）を硬化させる硬膜剤を用いるこ
となどが知られている。There have been many reports on ways to solve this problem. For example, it is known to include a compound called an antifoggant or a stabilizer in a silver halide emulsion, or to use a hardening agent to harden the binder (eg, gelatin) of a photographic light-sensitive material.
しかし、上記いずれの方法でも写真性能を損なわずに十
分な画質を得るには至っていない。凝集高分子剤を用い
て得られたハロゲン化銀乳剤を使用することにより、写
真性能を殆ど損なわずに画質を改良することができるが
、この場合現像銀の被覆力（１ｍ”当りの現像された銀
のグラム数で、その光学濃度を割った値）が低下してし
まうことが判った。However, none of the above methods has been able to obtain sufficient image quality without impairing photographic performance. By using a silver halide emulsion obtained using an agglomerated polymer agent, image quality can be improved with almost no loss in photographic performance. It was found that the value obtained by dividing the optical density by the number of grams of silver decreased.
従って本発明の目的は、高ｐＨ１高温による迅速処理（
特に自動現像機による処理）での画質の劣化が少なく、
しかも写真性能を損なわないハロゲン化銀写真感光材料
を提供することにある。Therefore, the object of the present invention is to provide rapid treatment with high pH and high temperature (
There is little deterioration in image quality, especially during processing using automatic processing machines.
Moreover, it is an object of the present invention to provide a silver halide photographic material that does not impair photographic performance.
本発明の上記目的は、支持体の少なくとも一方の側に少
なくとも１ｍの感光性ハロゲン化銀乳剤層を有するハロ
ゲン化銀写真感光材料において、上記ハロゲン化銀乳剤
層が、保護コロイドを含む溶液中に水溶性銀塩溶液と水
溶性ハロゲン化物溶液を添加して生成したハロゲン化銀
粒子を凝集高分子剤により保護コロイドと共に凝集させ
、溶存物を除去して得たハロゲン化銀乳剤を含有し、か
つ、少なくとも１層のハロゲン化銀乳剤層がポリマーラ
テックスを含有するハロゲン化銀写真感光材料によって
達成された。The above-mentioned object of the present invention is to provide a silver halide photographic material having a light-sensitive silver halide emulsion layer of at least 1 m long on at least one side of a support, wherein the silver halide emulsion layer is in a solution containing a protective colloid. contains a silver halide emulsion obtained by agglomerating silver halide grains produced by adding a water-soluble silver salt solution and a water-soluble halide solution together with a protective colloid using an aggregating polymer agent, and removing dissolved substances, and was achieved by a silver halide photographic material in which at least one silver halide emulsion layer contains a polymer latex.
以下本発明について更に詳述する。The present invention will be explained in more detail below.
本発明のハロゲン化銀写真感光材料は、支持体の少なく
とも一方の側に少なくとも１層の感光性ハロゲン化銀乳
剤層を有する。The silver halide photographic material of the present invention has at least one light-sensitive silver halide emulsion layer on at least one side of the support.
即ち本発明においては、支持体の両側に少なくとも１層
の感光性ハロゲン化銀乳剤層を設けて両面感光材料とし
てもよく、また片側に設けて片面感光材料としてもよい
。That is, in the present invention, at least one photosensitive silver halide emulsion layer may be provided on both sides of the support to provide a double-sided photosensitive material, or it may be provided on one side to provide a single-sided photosensitive material.
本発明のハロゲン化銀写真感光材料は、保護コロイドを
含む溶液中に、水溶性銀塩溶液と、水溶性ハロゲン化物
溶液を添加して生成したハロゲン化銀粒子を、凝集高分
子剤により保護コロイドとともに凝集せしめ、溶存物を
除去して得たハロゲン化銀乳剤Ｃ以下、適宜ｒ本発明ｌ
コ係る乳剤」などと称する）を含有する。The silver halide photographic material of the present invention is produced by adding a water-soluble silver salt solution and a water-soluble halide solution to a solution containing a protective colloid. Silver halide emulsion C obtained by agglomerating and removing dissolved substances, as appropriate.
(referred to as "such emulsion").
本発明に係る乳剤は、本発明の感光材料のいずれか少な
くとも１層の乳剤層に含有されていればよいが、好まし
くは乳剤層の多く、より好ましくは乳剤層のすべてが本
発明に係る乳剤を含有していることである。The emulsion according to the present invention may be contained in at least one emulsion layer of the light-sensitive material of the present invention, but preferably many of the emulsion layers, more preferably all of the emulsion layers contain the emulsion according to the present invention. This means that it contains
本発明に係る乳剤は、例えば、保護コロイドを含む溶液
中に、水溶性銀塩溶液と、水溶性ハロゲン化物溶液を添
加して調製され、その後生成しｔ；ハロゲン化銀粒子を
、凝集高分子剤により保護コロイドとともに懸濁液より
凝集せしめ、懸濁液中の溶存物を除去することにより得
られる。The emulsion according to the present invention is prepared, for example, by adding a water-soluble silver salt solution and a water-soluble halide solution to a solution containing a protective colloid, and then produces silver halide grains with agglomerated polymers. It is obtained by coagulating the suspension together with a protective colloid using an agent and removing the dissolved matter in the suspension.
ここで保護コロイドを含む水溶液とは、ゼラチンその他
の親水性コロイドを構成し得る物質（バインダーとなり
得る物質など）により保護コロイドが水溶液中に形成さ
れているものをいい、好ましくはコロイド状の保護ゼラ
チンを含有する水溶液である。Here, the aqueous solution containing a protective colloid refers to an aqueous solution in which a protective colloid is formed from gelatin or other substances that can constitute a hydrophilic colloid (substances that can be a binder, etc.), and preferably a colloidal protective gelatin. It is an aqueous solution containing.
本発明を実施する際、上記保護コロイドとしてゼラチン
を用いる場合は、ゼラチンは石灰処理されたものでも、
酸を使用して処理されたものでもどちらでもよい。ゼラ
チンの製法の詳細はアーサー・ヴアイス著：ザ・マクロ
モレキュラー・ケミストリー・オブ・ゼラチン（アカデ
ミツク・プレス、１９６４年発行）に記載がある。When carrying out the present invention, if gelatin is used as the protective colloid, the gelatin may be lime-treated or
It may be treated with an acid. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin by Arthur Vuis (Academic Press, published in 1964).
保護コロイドとして用いることができるゼラチン以外の
親水性コロイドとしては、例えばゼラチン誘導体、ゼラ
チンと他の高分子とのグラフトポリマー、アルブミン、
カゼイン等の蛋白質；ヒドロキシエチルセルロース、カ
ルボキシメチルセルロース、セルロース硫酸エステル類
等の如きセルロース誘゛導体、アルギン酸ナトリウム、
澱粉誘導体などの糖誘導体：ポリビニルアルコール、ポ
リビニルアルコール部分アセタール、ポリビニルピロリ
ドン、ポリアクリル酸、ポリメタクリル酸、ポリアクリ
ルアミド、ポリビニルイミダゾール、ポリビニルピラゾ
ール等の単一あるいは共重合体の如き多種の合成親水性
高分子物質がある。Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin,
Proteins such as casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives: various synthetic highly hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. There are molecular substances.
ゼラチンの場合は、バギー法においてゼリー強度２００
以上のものを用いることが好ましい。In the case of gelatin, use the baggy method with a gel strength of 200.
It is preferable to use the above.
なお、本発明の感光材料において、必要に応じて形成さ
れる保護層、バッキング層、中間層等の写真構成層に用
いることのできる親水性コロイドとしては、ゼラチンを
用いるのが有利であるが、それ以外の上記親水性コロイ
ドも単独あるいはゼラチンと共に用いることができる。In the photographic material of the present invention, it is advantageous to use gelatin as a hydrophilic colloid that can be used in photographic constituent layers such as a protective layer, a backing layer, and an intermediate layer, which are formed as necessary. Other hydrophilic colloids mentioned above can also be used alone or together with gelatin.
水溶性銀塩溶液、水溶性ハロゲン化物溶液とは、所望の
ハロゲン化銀を得るために反応させるもので、適宜所望
のハロゲン化銀組成により選択され、組み合わせられる
。The water-soluble silver salt solution and the water-soluble halide solution are reacted to obtain the desired silver halide, and are appropriately selected and combined depending on the desired silver halide composition.
凝集高分子剤とは、ハロゲン化銀粒子を保護コロイドと
共に凝集せしめることができる高分子物質を言う。通常
、かかる凝集高分子剤により、保護コロイドであるゼラ
チン等を凝集させてゲル化し、液中の可溶性塩類などの
溶存物を除去する工程（いわゆる脱塩工程）を行う。The agglomerating polymeric agent refers to a polymeric substance capable of agglomerating silver halide grains together with a protective colloid. Usually, gelatin, which is a protective colloid, is agglomerated and gelled using such an aggregating polymer agent, and a step (so-called desalting step) is performed in which dissolved substances such as soluble salts in the liquid are removed.
本発明において、凝集高分子剤としては各種のものを用
いることができるが、この凝集高分子剤としては、ゼラ
チン分子のアミン基の少なくとも５０％以上がアシル、
カルバモイル、スルホニル、チオカルバモイル、アルキ
ル及び／又はアリールの各基で置換された凝集ゼラチン
剤であることが好ましい、又これと並んで好ましいもの
として、下記Ａ鎖及びＢ鎖からなる一般式ＣＩ）で表さ
れる高分子化合物を挙げることができる。In the present invention, various types of agglomerating polymeric agents can be used, but the aggregating polymeric agents include acyl groups in which at least 50% or more of the amine groups of gelatin molecules are acyl,
Preference is given to aggregated gelatin agents substituted with carbamoyl, sulfonyl, thiocarbamoyl, alkyl and/or aryl groups, and also preferred are those of the general formula CI) consisting of the following A and B chains: The polymer compounds represented can be mentioned.
一般式〔工〕
式中、Ｆ−ｒ、Ｒｘは脂肪族基を表し、互に異っていて
も同じでもよい。Ｒ１は水素原子、脂肪族基、アリール
基、またはアラルキル基を表す。Ｘは一〇−または−Ｎ
Ｈ−１Ｍ＋は陽イオンを表す。General Formula [Equation] In the formula, F-r and Rx represent aliphatic groups, and may be different or the same. R1 represents a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group. X is 10- or -N
H-1M+ represents a cation.
ｎはｌＯ〜１０１の数値をとる。なおり鎖の２つの連結
手は、Ａ鎖のＲ、、Ｒ、を配した第三級炭素に対し、い
ずれの側が結ばれてもよい。またＸが−ＮＨ−の場合に
は、Ｒ１と共に含窒素環を形成してもよい。n takes a value from lO to 101. The two linking hands of the naori chain may be connected on either side to the tertiary carbon on which R, , and R of the A chain are arranged. Further, when X is -NH-, it may form a nitrogen-containing ring together with R1.
本発明において、凝集高分子剤として凝集ゼラチン剤を
用いる場合には、ゼラチン分子のアミノ基の５０％以上
を置換した変性ゼラチンが好ましく用いられる。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２．５２５，
７５３号に記載がある。In the present invention, when an agglomerated gelatin agent is used as the agglomerated polymer agent, modified gelatin in which 50% or more of the amino groups of gelatin molecules are substituted is preferably used. Examples of substituents for amino groups in gelatin include U.S. Pat.
, No. 582, No. 2,614.928, No. 2.525,
It is described in No. 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、無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、アリールカル／くモイル等のカルバモ
イル基、
（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１分岐のアルキル基、（６
）置換、無置換のフェニル、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, and substituted or unsubstituted benzoyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcar/cumoyl; (3) alkylsulfonyl; Sulfonyl groups such as arylsulfonyl, (4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) linear monobranched alkyl groups having 1 to 18 carbon atoms, (6)
) Substituted and unsubstituted aryl groups such as phenyl, naphthyl, pyridyl, aromatic heterocycles such as furyl, and the like.
中でも、好ましい変性ゼラチンは、アシル基（−ＣＯＲ
’）またはカルバモイル基（−Ｃ０ＮＲＩ）によるもの
である。Among them, preferred modified gelatin has an acyl group (-COR
') or a carbamoyl group (-CONRI).
前記Ｒ＋は置換、無置換の脂肪族基（例えば炭素数１〜
１８個のアルキル基、アリル基）、アリール基またはア
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 (for example, a group having 1 to 1 carbon atoms)
18 alkyl groups, allyl groups), aryl 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 Ｒ１がアリール基、Ｒ２が水素原
子の場合である。Particularly preferred is the case where R1 is an aryl group and R2 is a hydrogen atom.
以下に本発明において凝集高分子剤として用いることが
できる凝集ゼラチン剤の具体例をアミン基置換基によっ
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 the flocculated gelatin agent that can be used as the flocculated polymer agent in the present invention are illustrated below using amine substituents, but the present invention is not limited thereto.
例示凝集ゼラチン剤（アミノ基置換基）−ＩＧ−２
ＣＯＣ４Ｈｓ（Ｌ） ＣＯＣＨｓＧ−７
Ｇ−８
Ｇ−１１Ｇ−１２
溶存物除去（脱塩）に際して凝集ゼラチン剤を使用する
場合、その添加量は特に制限はないが、除去時に保護コ
ロイドとして含まれている物質（好ましくはゼラチン）
の０．３〜１０倍量（重量）が適当であり、特に好まし
くは１〜５倍量（重量）である。Exemplary agglomerated gelatin agent (amino group substituent) -IG-2 COC4Hs (L) COCHsG-7
G-8 G-11G-12 When using an agglomerated gelatin agent for removing dissolved substances (desalting), the amount added is not particularly limited, but the substance (preferably gelatin) contained as a protective colloid during removal.
A suitable amount is 0.3 to 10 times (by weight), particularly preferably 1 to 5 times (by weight).
本発明においては、ハロゲン化銀粒子を、凝集高分子剤
により保護コロイドとともに凝集せしめるのであるが、
凝集高分子剤としては凝集ゼラチン剤を用いるときには
、該凝集ゼラチン剤を添加した後１）Ｈ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。In the present invention, silver halide grains are agglomerated together with a protective colloid by an aggregating polymer agent.
When an agglomerated gelatin agent is used as the agglomerated polymer agent, the silver halide emulsion can be coagulated by adjusting 1) H after adding the agglomerated gelatin agent.
凝析を行わせるｐＨとしては、５，５以下特に４６５〜
２が好ましい。The pH for coagulation is 5.5 or less, especially 465 to 465.
2 is preferred.
ｐＨ調整に用いる酸には特に制限はないが、酢酸、くえ
ん酸、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。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。The acid used for pH 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. 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.
次に、本発明において凝集高分子剤として前記一般式（
Ｉ）で表される高分子化合物を用いる場合について説明
する。この高分子化合物は、分子量として好ましくはｉ
、ｏ’−ｉｏ’、より好ましくは３×１０３〜２ Ｘ
１０’であり、添加量は乳剤に含まれている保護コロイ
ド（好ましくはゼラチン）に対し重量比で好ましくは１
１５０〜１／４、より好ましくはｌ／４０〜１／ｌＯで
ある。使用方法は前記凝集ゼラチン剤に準する。Next, in the present invention, the agglomerating polymer agent has the general formula (
The case of using the polymer compound represented by I) will be explained. This polymer compound preferably has a molecular weight of i
, o'-io', more preferably 3x103~2X
10', and the amount added is preferably 1 in weight ratio to the protective colloid (preferably gelatin) contained in the emulsion.
150 to 1/4, more preferably 1/40 to 1/1O. The method of use is similar to that for the agglomerated gelatin agent.
以下一般式ＣＩ）で表される高分子化合物の具体例を掲
げるが、これに限定されない。Specific examples of the polymer compound represented by the general formula CI) are listed below, but the invention is not limited thereto.
一般式（１）で表される例示高分子化合物ニしｕＵｔｌ
Ｐ−９
Ｐ−１０
本発明に係る乳剤は、種晶を含有する乳剤を調製して、
種晶から粒子成長させて得るのでも、種晶を用いないで
得るのでもよい。種晶を用いたときは、種晶を含有する
乳剤自体が凝集高分子剤を用いた本発明に係る乳剤であ
る場合、これから得られる乳剤はすべて本発明に係る乳
剤に該当する。Exemplary polymer compound represented by general formula (1) Utl P-9 P-10 The emulsion according to the present invention is prepared by preparing an emulsion containing seed crystals.
It may be obtained by growing particles from seed crystals or without using seed crystals. When seed crystals are used, and if the emulsion containing the seed crystals itself is an emulsion according to the present invention using a coagulating polymer agent, all emulsions obtained therefrom fall under the emulsion according to the present invention.
但し本発明に係る乳剤を得るｔ；めの種晶乳剤は必ずし
も本発明に係る乳剤である必要はない。好ましくは種晶
として本発明に係る乳剤である種晶乳剤を用い、かつ、
それらからの粒子成長時にも本発明における凝集高分子
剤を使用して得た本発明に係る乳剤を用いることである
。However, the seed crystal emulsion used to obtain the emulsion according to the present invention does not necessarily have to be the emulsion according to the present invention. Preferably, a seed crystal emulsion which is an emulsion according to the present invention is used as a seed crystal, and
The emulsion according to the present invention obtained by using the coagulating polymer agent according to the present invention is also used during grain growth from them.
本発明に係る乳剤のハロゲン化銀組成は任意であり、例
えば使用できるハロゲン化銀には塩化銀、臭化銀、沃化
銀、塩臭化銀、沃臭化銀、塩沃化銀、塩沃臭化銀及びこ
れらの混合物等の任意のハロゲン化銀が包含されるが、
特に沃臭化銀が好ましく用いられる。沃臭化銀を用いる
場合、その沃化銀の含有量は特に限定されないが、ハロ
ゲン化銀粒子全体での平均沃化銀含有率は１０モル％以
下であることが好ましく、６モル％以下であることがよ
り好ましく、０．２〜６モル％であることが更に好まし
い。The silver halide composition of the emulsion according to the present invention is arbitrary. For example, silver halides that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloride Any silver halide is included, such as silver iodobromide and mixtures thereof, but
In particular, silver iodobromide is preferably used. When silver iodobromide is used, the silver iodide content is not particularly limited, but the average silver iodide content in the entire silver halide grains is preferably 10 mol% or less, and 6 mol% or less. It is more preferable that the amount is 0.2 to 6 mol %.
この場合沃化銀は内部に集中していることが望ましい。In this case, it is desirable that the silver iodide be concentrated inside.
また沃化銀を混晶として含むときも、その分布は任意で
あるが、沃化銀が内部に集中することが望ましい。Further, when silver iodide is included as a mixed crystal, its distribution is arbitrary, but it is desirable that the silver iodide be concentrated inside.
本発明に係る乳剤に含有される好ましいハロゲン化銀粒
子としては、多層構造を有するハロゲン化銀粒子、及び
平板状粒子を挙げることができる。Preferred silver halide grains contained in the emulsion of the present invention include silver halide grains having a multilayer structure and tabular grains.
平板状粒子は、粒子成長中にある種の薬剤、例えばチオ
エーテル類などを加えることにより得ることができる。Tabular grains can be obtained by adding certain agents, such as thioethers, during grain growth.
平板状粒子については、例えば特開昭５３−１１３９２
７号、同５８−１１３９２８号及び特開昭５９−１０５
６３６号の２５２〜２５３頁、同６０−１４７７２７号
等に開示がある。Regarding tabular grains, for example, JP-A-53-11392
No. 7, No. 58-113928 and JP-A-59-105
Disclosures are made in No. 636, pages 252-253, No. 60-147727, etc.
ここで多層構造を有する粒子とは、内部核の外側に任意
のハロゲン組成からなる被覆層を設けたものであり、い
わゆるコア／シェル型粒子を用いることができる。被覆
層は１層だけであってもよいし、２層以上、例えば３層
、４層と積層されていてもよい。好ましくは５層以下で
ある。Here, the particles having a multilayer structure are those in which a coating layer having an arbitrary halogen composition is provided on the outside of an inner core, and so-called core/shell type particles can be used. There may be only one covering layer, or two or more layers, for example three or four layers, may be stacked. Preferably the number of layers is 5 or less.
内部核及び被覆層のハロゲン化銀としては、臭化銀、沃
臭化銀、沃化銀が好ましく用いられるが、少量の塩化銀
との混合物（具体的には、好ましくは塩化銀を１００モ
ル％程以下、より好ましくは５モル％程度以下含有のも
の）であってもよい。As the silver halide for the inner core and coating layer, silver bromide, silver iodobromide, and silver iodide are preferably used, but a mixture with a small amount of silver chloride (specifically, preferably 100 mol of silver chloride) is used. % or less, more preferably 5 mol% or less).
好ましくは、沃化銀含有率が異なることにより層を形成
した沃臭化銀粒子を用いることである。Preferably, silver iodobromide grains having layers formed by different silver iodide contents are used.
また、最表層は実質的に臭化銀もしくは実質的に沃臭化
銀（沃化銀含有率１０％以下）であるのが好ましく、数
％未満の塩素原子を含んでいてもよい。Further, the outermost layer is preferably substantially silver bromide or substantially silver iodobromide (silver iodide content: 10% or less), and may contain less than several % of chlorine atoms.
本発明に係る乳剤は、保護コロイドを含む溶液中に、水
溶性銀塩溶液と、水溶性ハロゲン化物溶液を添加してハ
ロゲン化銀粒子を形成して調製するが、この場合の形成
手段としては、各種の技術を用いることかでさる。The emulsion according to the present invention is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a solution containing a protective colloid to form silver halide grains. , by using various techniques.
例えば同時混合法、ダブルジェット法、同時混合法の一
つの形式であるハロゲン化銀の生成される液相中のｐＡ
ｇを一定に保つ方法、即ち、いわゆるコンドロールド・
ダブルレジット法法、またダブルジェット法の別の形式
として異なる組成の可溶性ハロゲン塩を各々独立に添加
するトリプルダブルジェット法（例えば可溶性銀塩と可
溶性臭素塩と可溶性沃素塩）も用いることができる。For example, pA in the liquid phase produced by silver halide, which is one type of simultaneous mixing method, double jet method, and simultaneous mixing method.
A method of keeping g constant, that is, a so-called chondral
The double jet method and, as another form of the double jet method, a triple double jet method in which soluble halogen salts of different compositions are added independently (for example, a soluble silver salt, a soluble bromine salt, and a soluble iodine salt) can also be used.
順混合法を用いることもでき、また粒子を銀イオン過剰
の下において形成される方法（いわゆる逆混合法）を用
いることもできる。A forward mixing method can also be used, or a method in which particles are formed in an excess of silver ions (so-called back mixing method) can also be used.
コンドロールド・ダブルジェット法によると、結晶型が
規則的で粒子サイズが均一に近いハロゲン化銀乳剤を得
ることができる。According to the Chondrald double jet method, a silver halide emulsion having a regular crystal type and a nearly uniform grain size can be obtained.
このように規則正しいハロゲン化銀粒子を得るには、同
時混合法を用いてハロゲン化銀粒子を成長させる際の反
応条件を調節すればよいが、かかる同時混合法において
は、ハロゲン化銀粒子を、保護コロイドの水溶液中へ一
般に激しく撹拌しつつ、可溶性銀塩である例えば硝酸銀
溶液とハロゲン化物溶液とを略等量ずつ添加することに
より作る手段を用いることができる。In order to obtain regular silver halide grains in this way, it is sufficient to adjust the reaction conditions when growing silver halide grains using a simultaneous mixing method. A method can be used in which approximately equal amounts of a soluble silver salt, such as a silver nitrate solution and a halide solution, are added to an aqueous solution of a protective colloid, generally with vigorous stirring.
ハロゲン化銀粒子の粒子サイズは、特に制限はないが、
平均粒径が０．１〜３μｍのものが好ましい。The grain size of silver halide grains is not particularly limited, but
Those having an average particle size of 0.1 to 3 μm are preferable.
更に好ましくは０．３〜２μｍである。More preferably, it is 0.3 to 2 μm.
本発明に係る乳剤は、単分散乳剤でも多分散乳剤であっ
ても、本発明の効果を有効に発揮し得る。The emulsion according to the present invention can effectively exhibit the effects of the present invention whether it is a monodisperse emulsion or a polydisperse emulsion.
本発明に係る乳剤は、化学増感することができる。The emulsion according to the invention can be chemically sensitized.
本発明に用いられるポリマーラテックスの分子量は、７
，０００〜２００，０００が好ましく、より好ましくは
１５，０００〜７０，０００である。The molecular weight of the polymer latex used in the present invention is 7
,000 to 200,000 is preferable, and more preferably 15,000 to 70,000.
ポリマーラテックスを得るために用いられる七ツマ−と
しては、重合可能なエチレン仕上ツマ−であれば特に制
限されないが、好ましくは疎水性ビニルモノマーである
。このような疎水性ビニル七ツマ−としては、アクリル
酸エステル、メタクリル酸エステル、アクリロニトリル
、アクリルアミド、メタクリルアミド、酢酸ビニル、エ
チレン、プロピレン、スチレン、塩化ビニル、塩化ビニ
リデン、ブタジェン等が好ましく用いられる。The polymer used to obtain the polymer latex is not particularly limited as long as it is a polymerizable ethylene-finished polymer, but hydrophobic vinyl monomers are preferred. As such hydrophobic vinyl salts, acrylic esters, methacrylic esters, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, ethylene, propylene, styrene, vinyl chloride, vinylidene chloride, butadiene, and the like are preferably used.
ポリマーラテックスは公知の乳化重合法、溶液重合法ま
たは塊状重合法で得たポリマーを再分散することにより
容易に製造できる。これらの重合法の内、乳化重合法が
好ましい。Polymer latex can be easily produced by redispersing a polymer obtained by a known emulsion polymerization method, solution polymerization method, or bulk polymerization method. Among these polymerization methods, emulsion polymerization method is preferred.
乳化重合法においては、反応温度が２０〜１８０°Ｃ１
より好ましくは４０〜１００°Ｃで、水と、水に対して
１０〜５０重量％の疎水性ビニルモノマーと、該七ツマ
−に対して０．０５〜５重量％の重合開始剤と０．１〜
２０重量％の乳化剤を用いて行うことができる。In the emulsion polymerization method, the reaction temperature is 20 to 180°C1
More preferably, at 40 to 100°C, water, 10 to 50% by weight of a hydrophobic vinyl monomer based on the water, 0.05 to 5% by weight of a polymerization initiator based on the monomer, and 0.05% by weight of a polymerization initiator based on the seven polymers. 1~
This can be done using 20% by weight of emulsifier.
乳化剤は一般に使用しなくても合成できるが、得られる
ポリマーラテックスの経時安定性、親木性コロイドとの
相溶性等から用いることが好ましい・アニオン性、カチ
オン性、両性、ノニオン性の界面活性剤や水溶性ポリマ
ー等の乳化剤を用いることができる。Emulsifiers can generally be synthesized without the use of emulsifiers, but it is preferable to use them in view of the stability of the resulting polymer latex over time, compatibility with wood-philic colloids, etc. Anionic, cationic, amphoteric, nonionic surfactants Emulsifiers such as water-soluble polymers and water-soluble polymers can be used.
ポリマーラテックスの乳化重合法に用いられる重合開始
剤としては、例えば過硫酸カリウム、過硫酸アンモニウ
ム、過硫酸ナトリウム等の過硫酸塩類； ４，４’−ア
ゾビス−４−シアノ吉草酸ナトリウム、２．２′−アゾ
ビス＝（２−アミジノプロパン）塩酸塩等の水溶性アゾ
化合物；過酸化水素などを用いることができる。Polymerization initiators used in the emulsion polymerization method for polymer latex include, for example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; sodium 4,4'-azobis-4-cyanovalerate, 2.2' Water-soluble azo compounds such as -azobis=(2-amidinopropane) hydrochloride; hydrogen peroxide, etc. can be used.
ポリマーラテックスの中でも、特に下記一般式〔ｌｌ）
で表される繰り返し単位を含む重合体からなるものが好
ましい。Among polymer latexes, especially the following general formula [ll]
It is preferable to use a polymer containing a repeating unit represented by:
式中、Ｒ１は水素原子または炭素原子数１〜６のアルキ
ル基を、Ｒ２およびＲ１は各々、水素原子、炭素原子数
１−１０の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し、同じであっても異なって
もよい。また、Ｒ２とＲ１が互いに結合し、窒素原子と
共に含窒素複素環を形成してもよい。Ｌは２価の連結基
を表し、ｎは０またはｌを、ｍは１または２を表す。In the formula, R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R2 and R1 each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. , may be the same or different. Furthermore, R2 and R1 may be bonded to each other to form a nitrogen-containing heterocycle together with the nitrogen atom. L represents a divalent linking group, n represents 0 or l, and m represents 1 or 2.
一般式ＣＩ＋）において、Ｒ３で表される置換基は水素
原子およびメチル基が好ましい。In the general formula CI+), the substituent represented by R3 is preferably a hydrogen atom or a methyl group.
Ｒ２およびＲ１が有してもよい置換基としては、ハロゲ
ン原子、ヒドロキシル基、低級アルコキシ基、アミド基
、シアノ基、スルホ基およびその塩、カルボキシル基お
よびその塩等が挙げられる。Examples of the substituents that R2 and R1 may have include a halogen atom, a hydroxyl group, a lower alkoxy group, an amide group, a cyano group, a sulfo group and its salt, a carboxyl group and its salt, and the like.
Ｒ、、Ｒ、で表される置換基は水素原子、メチル基およ
びフェニル基が好ましく、その中でも水素原子が最も好
ましい。The substituents represented by R and R are preferably a hydrogen atom, a methyl group, or a phenyl group, and among these, a hydrogen atom is most preferred.
して表される２価の連結基としては、炭素原子数１−１
０のアルキレン基、アリーレン基あるいは、それらとエ
ーテル結合、エステル結合、アミド結合などを組み合せ
て得られる２価基が挙げられる。The divalent linking group represented by has 1-1 carbon atoms.
0 alkylene group, arylene group, or a divalent group obtained by combining them with an ether bond, ester bond, amide bond, etc.
ｎ＝０、ｍ＝ ｌであるのが好ましい。It is preferable that n=0 and m=l.
一般式（ＩＩ）で表される繰り返し単位を構成するエチ
レン性不飽和七ツマ−の好ましい具体例を挙げる。Preferred specific examples of the ethylenically unsaturated heptamer constituting the repeating unit represented by general formula (II) are given below.
１ｌ−Ｉｌｌ−２ ｎ−３１１−４ ｎ −１，１９，。1l-Ill-2 n-311-4 n-1, 19,.
Ｉ［−１２ｌｌ−１３
Ｉｔ−１４ｎ−１５
一般式［１１）で表される繰り返し単位は、重合体とし
て複合機能を発揮させるために２種類以上の七ツマー単
位を含んでもよい。I[-12ll-13 It-14n-15 The repeating unit represented by the general formula [11] may contain two or more types of heptamer units in order to exhibit a composite function as a polymer.
本発明に用いられるポリマーラテックスのポリマー成分
は、一般式〔■〕で表される繰り返し単位を、ポリマー
構成単位として７０モル％以上、好ましくは８０モル％
以上、更に好ましくは９０モル％以上含む下記一般式（
ＩＩＩ）で表される化合物である。The polymer component of the polymer latex used in the present invention contains repeating units represented by the general formula [■] in an amount of 70 mol% or more, preferably 80 mol% as polymer constitutional units.
The following general formula (
This is a compound represented by III).
一般式〔■〕
式中、Ｒｌ ＋ Ｒ２＋ Ｒ３＋ Ｌ ＋ ’およびｎ
は一般式（ＩＩ）におけるものと、それぞれ同義である
。Ａは共重合可能なエチレン性不飽和七ツマー単位を表
し、Ｘはモル％を表す。General formula [■] In the formula, Rl + R2+ R3+ L + ' and n
have the same meanings as those in general formula (II). A represents a copolymerizable ethylenically unsaturated heptamer unit, and X represents mol%.
Ｘは７０〜１００が好ましく、Ａとしては例えば、エチ
レン、フロピレン、１−ブテン、スチレン、クロロメチ
ルスチレン、ビニルベンゼンスルホン酸ナトリウム、ビ
ニルベンジルスルホン酸ナトリウム、Ｎ、Ｎ−ジメチル
−Ｎ−ベンジル−Ｎ−ビニルベンジルアンモニウムクロ
リド、２−ビニルピリジン、ベンジルビニルビリジウム
クロリド、Ｎ−ビニルアセトアミド、Ｎ−ヒニルビロリ
ドン、■−ビニル−２−メチルイミダゾール、アクリル
酸、メタクリル酸、イタコン酸、マレイン酸、アクリル
酸ナトリウム、メタクリル酸カリウム、ブチルアクリレ
ート、ヒドロキシエチルアクリレート、ベンジルメタク
リレート、メトキシエチルメタクリレート、Ｎ、Ｎ−ジ
エチルアミノエチルメタクリレート、Ｎ、Ｎ、Ｎ−トリ
エチル−Ｎ−メタクリロイルオキシエチルアンモニウム
−
チル、マレイン酸モノベンジルエステル等が挙ケられる
。X is preferably 70 to 100, and examples of A include ethylene, phlopylene, 1-butene, styrene, chloromethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N,N-dimethyl-N-benzyl-N -Vinylbenzylammonium chloride, 2-vinylpyridine, benzylvinylpyridium chloride, N-vinylacetamide, N-hinylpyrrolidone, ■-vinyl-2-methylimidazole, acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate , potassium methacrylate, butyl acrylate, hydroxyethyl acrylate, benzyl methacrylate, methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-N-methacryloyloxyethylammonium-thyl, maleic acid monobenzyl ester, etc. can be mentioned.
また重合体は複合機能を発揮させるために、Ａとして２
種以上のモノマー単位を含んでもよい。In addition, in order for the polymer to exhibit multiple functions, A is 2
It may contain more than one type of monomer unit.
本発明に用いられるポリマーラテックスの重合体の代表
的具体例を以下に示すが、これらに限定されるものでは
ない。Typical specific examples of the polymer latex used in the present invention are shown below, but the invention is not limited thereto.
ｍ−１ ＣＯＮ）Ｉ２ １ｌ−２ ＣＨ。m-1 CON)I2 1l-2 CH.
０ＮＨ２ ♀Ｈ・ １１［−５ １１１−６ＣＨ３ Ｃ０ＮＨ，Ｃ００ＣＨ，にＨ２υし２Ｈ５ｌｌ−７ ■−８ＣＩ。0NH2 ♀H・ 11[-5 111-6CH3 H2υ to C0NH, C00CH, 2H5ll-7 ■-8CI.
Ｉ［［−９ Ｓｏ、Ｋ ［１−１０ Ｉ［１−１１Ｃ０゜ ＯＮＨ２ ＩＩＩ−１４０，。I[[-9 So, K [1-10 I[1-11C0゜ ONH2 III-140,.
これら重合体からなるポリマーラテックスは、写真構成
層の全バインダーの５〜５４１％が好ましく、２０〜４
０重量％がより好ましい。The polymer latex made of these polymers preferably accounts for 5 to 541% of the total binder in the photographic constituent layer, and preferably 20 to 4% of the total binder in the photographic constituent layer.
0% by weight is more preferred.
ポリマーラテックスを含有させる写真乳剤層はどの層で
もよいが、全部の写真乳剤層に含有させることが好まし
い。The polymer latex may be contained in any photographic emulsion layer, but it is preferably contained in all photographic emulsion layers.
その他、本発明に係る乳剤や、そのほか必要に応じて本
発明の感光材料を構成するために用いる乳剤には、適宜
添加剤を含有させることができる。In addition, the emulsion according to the present invention and other emulsions used to constitute the light-sensitive material of the present invention may contain appropriate additives, if necessary.
即ち、本発明を具体化した感光材料には、任意の添加剤
が含有されていてよく、これらはリサーチ・ディスクロ
ージャー （Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ
。That is, the photosensitive material embodying the present invention may contain arbitrary additives, and these additives are subject to Research Disclosure.
.
以下ＲＤと略す）１７６巻、 Ｎｏ、１７６４３ （１
９７８年１２月）および同１８７巻、 Ｎｏ、１．８７
１６ （１９７６年１１月）に記載されており、その該
当箇所を次の表に纏めた。Hereinafter abbreviated as RD) Volume 176, No. 17643 (1
December 978) and Volume 187, No. 1.87
16 (November 1976), and the relevant parts are summarized in the table below.
また、上記本発明の実施に際して、乳剤調製に使用でき
る写真用添加剤も上記の２つのリサーチ・ディスクロー
ジャーに記載されており、次の表に本発明のハロゲン化
銀写真感光材料を構成するために用いるゼラチン量は任
意であるが、迅速処理という点でゼラチン量が少ない方
が望ましい。In addition, the photographic additives that can be used for emulsion preparation in carrying out the present invention are also described in the above two Research Disclosures, and the following table shows the additives that can be used to form the silver halide photographic light-sensitive material of the present invention. The amount of gelatin used is arbitrary, but from the viewpoint of rapid processing, it is desirable to use a smaller amount of gelatin.
例えば、感光性乳剤層を有する側の片側当りのゼラチン
量（両面感光材料では片面だけのゼラチン量）を２、θ
〜３．５ｇ／ｍ”とするのが好ましい。For example, the amount of gelatin per side on the side with the photosensitive emulsion layer (the amount of gelatin on only one side in a double-sided photosensitive material) is 2, θ
It is preferable to set it as 3.5 g/m''.
本発明は特に、ゼラチン量を少なくした場合でも顕著に
効果を発揮できるので、迅速処理用に適したものである
。The present invention is particularly suitable for rapid processing because it can exhibit remarkable effects even when the amount of gelatin is reduced.
感光材料の支持体は任意である。The support for the photosensitive material is arbitrary.
感光材料を現像処理する現像剤としては、ジヒドロキシ
ベンゼン類（例えばハイドロキノン）、３−ピラゾリド
ン類（例えばｌ−ブエニルー３−ピラゾリドン）、アミ
ノフェノール類（例えばＮ−メチル−ｐ−アミンフェノ
ール）等の現像主薬を単独あるいは組み合わせて用いる
ことができる。Examples of developing agents for developing photosensitive materials include dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., l-buenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminephenol), and the like. The main drugs can be used alone or in combination.
詳細はメースン著「フォトグラフィック・プロセシング
・ケミス］・リー」フォーカルプレス社刊（Ｌ、Ｆ、Ａ
、Ｍａｓｏｎ、Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅ
ｓｓｉｎｇ Ｃｈｅｍｉｓｔｒｙ、Ｆｏｃａｌ Ｐｒｅ
ｓｓ、１９７５）やＲＤ、１８８巻、 Ｎｏ、１８８７
３（１９７９年１２月）および同２０４巻、 Ｎｏ、２
０４０５ （１９８１年４月）に記載されている。For details, see "Photographic Processing Chemistry" by Mason, published by Focal Press (L, F, A
, Mason, Photographic Process
ssing Chemistry, Focal Pre
ss, 1975) and RD, vol. 188, No. 1887
3 (December 1979) and Volume 204, No. 2
0405 (April 1981).
以下、本発明の実施例を詳細に説明するが、本発明はこ
れらに限定されるものではない。Examples of the present invention will be described in detail below, but the present invention is not limited thereto.
実施例−１
下記に示すように２種の種晶Ｔ−１，Ｔ−２を調製し、
種晶Ｔ−１（比較種晶乳剤）からυ子成長させて得た乳
剤１−１（比較乳剤）、乳剤１−２（本発明に係る乳剤
）、及び種晶Ｔ−２（本発明に係る種晶乳剤）から粒子
成長させて得た乳剤１−３（本発明に係る乳剤）、乳剤
１−４（本発明に係る乳剤）を調製した。更に、種晶を
用いない単分散の乳剤１−５（比較乳剤）、乳剤１−６
（本発明に係る乳剤）を得た。また、多分散の乳剤１−
７（比較乳剤）、乳剤１−８（本発明に係る乳剤）を得
、更に、平板状粒子を含有する乳剤１−９（比較乳剤）
、乳剤１−１０（本発明に係る乳剤）を得た。Example-1 Two types of seed crystals T-1 and T-2 were prepared as shown below,
Emulsion 1-1 (comparative emulsion), emulsion 1-2 (emulsion according to the present invention), and seed crystal T-2 (emulsion according to the present invention) obtained by υ child growth from seed crystal T-1 (comparative seed crystal emulsion). Emulsions 1-3 (emulsion according to the present invention) and Emulsion 1-4 (emulsion according to the present invention) obtained by grain growth from such a seed crystal emulsion were prepared. Furthermore, monodispersed emulsion 1-5 (comparative emulsion), emulsion 1-6 without using seed crystals
(Emulsion according to the present invention) was obtained. In addition, polydisperse emulsion 1-
7 (comparative emulsion), emulsion 1-8 (emulsion according to the present invention) and emulsion 1-9 (comparative emulsion) containing tabular grains were obtained.
, Emulsion 1-10 (emulsion according to the present invention) was obtained.
尚、本実施例における化合物の添加量は、特に記載がな
い限り、ハロゲン化銀１モル当りのものを示す。Incidentally, the amount of the compound added in this example is per mole of silver halide unless otherwise specified.
（乳剤の調製）
（１）種晶Ｔ−１，Ｔ−２の調製
６０°ｃ、ｐＡｇ＝３、ｐＨ−２，０にコントロールし
つつ、ダブルジェット法で、平均粒径０．３μＩの沃化
銀２モル％を含む沃臭化銀の単分散立方晶粒子を調製し
た。得られた粒子を含む反応液を２分割し、それぞれ下
記に示すような脱塩を行い、２種類の種晶（Ｔ−１，Ｔ
−２）を得た。(Preparation of emulsion) (1) Preparation of seed crystals T-1 and T-2 At 60°C, pAg=3, pH-2. Monodisperse cubic grains of silver iodobromide containing 2 mol % of silver oxide were prepared. The reaction solution containing the obtained particles was divided into two parts, each was desalted as shown below, and two types of seed crystals (T-1, T
-2) was obtained.
Ｔ−１の脱塩方法：
混合終了した反応液に、４０ ’Ｏのまま、ナフタレン
スルホン酸ナトリウムとホルマリンの縮合物（化合物Ｉ
）と硫酸マグネシウム（ＭｇＳＯ＋）をそれぞれ、１５
ｇ、 ６０ｇ加え、３分撹拌した。その後静置し、デカ
ンテーションにより過剰な塩を除去する。その後、４０
°Ｃの純水２．ＩＱを加え、分散させた後、Ｍｇ５Ｏ１
を３０ｇ加え、３分撹拌した後、静置し、デカンテーシ
ョンを行った。その後、後ゼラチンを添加し、５５°Ｃ
に保ち、２０分撹拌し再分散させ、Ｔ−■を得た。Desalting method for T-1: A condensate of sodium naphthalene sulfonate and formalin (compound I
) and magnesium sulfate (MgSO+), respectively.
g and 60 g were added, and the mixture was stirred for 3 minutes. After that, it is left to stand and excess salt is removed by decantation. After that, 40
Pure water at °C2. After adding and dispersing IQ, Mg5O1
After adding 30 g of and stirring for 3 minutes, the mixture was left to stand and decanted. After that, add post-gelatin and heat at 55°C.
The mixture was stirred for 20 minutes and redispersed to obtain T-■.
Ｔ−２の脱塩方法（本発明に係る乳剤を得る溶存物除去
手段に該当）：
混合終了した反応液に、４０°Ｃのまま凝集高分子剤と
して前記例示の例示凝集ゼラチン剤Ｇ−８を３８ｇ添加
し、３分撹拌した。その後、水酸化カリウム（Ｋｏｏ）
０．１３ｇを添加し、ｐＨを４．０にし、静置、デカ
ンテーションを行う。その後、４０°Ｃの純水２，１ａ
を加えた後、ＫＯＨを０．２５ｇ加え、ｐＨを５．８に
し、５分撹拌する。その後、硝酸ＨＮＯ，（１，７規定
）を１ 、５ｍＱ加え、ｐＨを４．３にし、静置、デカ
ンテーションする。その後、後ゼラチンとＫＯＨＯ，２
ｇを加え、ｐＨ５４８にし、再分散を行い、Ｔ−２を得
た。Desalting method of T-2 (corresponds to the means for removing dissolved substances to obtain an emulsion according to the present invention): Add the above-mentioned exemplary flocculated gelatin agent G-8 as an agglomerated polymer agent to the mixed reaction solution at 40°C. 38g of was added and stirred for 3 minutes. Then potassium hydroxide (Koo)
Add 0.13 g, adjust the pH to 4.0, let stand, and decant. After that, pure water 2,1a at 40°C
After adding 0.25 g of KOH, the pH was adjusted to 5.8, and the mixture was stirred for 5 minutes. Thereafter, 1.5 mQ of nitric acid HNO (1.7 normal) was added to adjust the pH to 4.3, and the mixture was allowed to stand still and decanted. After that, gelatin and KOHO, 2
g was added thereto, the pH was adjusted to 548, and redispersion was performed to obtain T-2.
この種晶乳剤Ｔ−２は本発明に係る乳剤であるので、こ
れから得られる乳剤は本発明に係るものである。Since this seed crystal emulsion T-2 is an emulsion according to the present invention, the emulsion obtained from it is according to the present invention.
（ｉｆ）種晶からの成長
上述のＴ−１，Ｔ−２の種晶を用い、次のように粒子を
成長させた。まず、４０°Ｃに保たれた保護ゼラチンお
よび、必要に応じたアンモニアを含む溶液８．５ｉ２
（保護コロイドを含む溶液に該当）に、この種晶Ｔ−１
溶解させ、更に酢酸によりｐＨを調製した。この液を母
液として、水溶性銀塩溶液として、３．２規定のアンモ
ニア性銀イオン水溶液をダブルジェット法で添加した。(if) Growth from seed crystals Using the above seed crystals T-1 and T-2, particles were grown as follows. First, a solution of 8.5i2 containing protected gelatin kept at 40°C and ammonia as needed.
(corresponding to a solution containing a protective colloid), this seed crystal T-1
The solution was dissolved and the pH was adjusted with acetic acid. Using this solution as a mother liquid, a 3.2N aqueous ammoniacal silver ion solution was added as a water-soluble silver salt solution by a double jet method.
この場合、ｐ１］とｐＡｇは、沃化銀含有率及び晶癖に
より随時変化させた。つまり、ｐＡｇを７．３． ｐＨ
を９．７に制御し、沃化銀含有率３５モル％の層を形成
させた。次に粒径の９５％までｐ）Ｉを９〜８に変化さ
せ、ｐＡｇは９．０に保ち成長させた。その後、水溶性
ノ＼ロゲン化物溶液として臭化カリウム溶液をノズルで
８分かけ添加し、１）Ａｇを１１．０に上げ、その臭化
カリウム添加終了３分後に混合終了させた。次に酢酸で
ｐＨを６．０に落とした。この乳剤は、平均粒径０．５
３μｍ１沃化銀含有率は約２モル％の単分散粒子であっ
た。次にこの反応液を２分割し、それぞれ、下記に示す
ような脱塩方法（イ）、（ロ）の２種の方法で過剰な可
溶塩の除去（溶存物の除去に該当）を行つｌ：。In this case, p1] and pAg were changed as needed depending on the silver iodide content and crystal habit. That is, pAg is 7.3. pH
was controlled to 9.7 to form a layer with a silver iodide content of 35 mol%. Next, p)I was changed from 9 to 8 until 95% of the particle size, and pAg was kept at 9.0 for growth. Thereafter, a potassium bromide solution was added as a water-soluble halogenide solution using a nozzle over a period of 8 minutes, 1) Ag was increased to 11.0, and the mixing was completed 3 minutes after the end of the potassium bromide addition. The pH was then lowered to 6.0 with acetic acid. This emulsion has an average grain size of 0.5
The 3 μm 1 silver iodide content was about 2 mol % of monodisperse grains. Next, this reaction solution was divided into two parts, and excess soluble salts were removed (corresponding to the removal of dissolved substances) using the two desalting methods (a) and (b) shown below. Tsul:.
脱塩方法（イ）
１、混合終了した反応液に、４０°Ｃのまま、前記化合
物工（本発明に用いる凝集高分子剤に対する比較化合物
に当る）を５．５ｇ％Ｍｇ５Ｏ，を８．５ｇ加え、３分
撹拌した後、静置し、デカンテーションを行う。Desalting method (a) 1. Add 5.5 g% Mg5O of the above compound (corresponding to the comparative compound for the flocculating polymer agent used in the present invention) to the mixed reaction solution at 40°C. After adding and stirring for 3 minutes, let stand and decant.
２．４０°Ｃの純水１．８ｆ２を加え、分散させた後、
Ｍｇ５Ｏ，を２０ｇ加え、３分撹拌した後、静置、デカ
ンテーションを行う。After adding 1.8 f2 of 2.40°C pure water and dispersing it,
Add 20g of Mg5O, stir for 3 minutes, then let stand and decant.
３、上記２の工程をもう１回繰り返す。3. Repeat step 2 above one more time.
４、後ゼラチン１５ｇと水を加え、４５０ｍ（２に仕上
げた後、５５°Ｃで２０分間撹拌し、分散させる。4. Add 15 g of post-gelatin and water, and after finishing to 450 m (2), stir at 55°C for 20 minutes to disperse.
このようにして、乳剤１−１を得た。In this way, emulsion 1-1 was obtained.
脱塩方法（ロ）
１、混合終了した反応液に、４０°Ｃのまま、凝集高分
子剤として前記例示の例示凝集ゼラチン剤Ｇ−８を５０
ｇ加え、その後、５５ｖｔ％酢酸を１１０ｍＱ加えてｐ
ｔｉを５．０に落とし、静置、デカンテーションを行う
。Desalting method (b) 1. Add 50% of the above-exemplified flocculated gelatin agent G-8 as a flocculating polymer agent to the mixed reaction solution at 40°C.
g, then add 110 mQ of 55vt% acetic acid and p
Lower the ti to 5.0, let stand, and decant.
２．４０°Ｃの純水１．８ｆ２を加えた後、ＫＯＨ６，
８ｇ加え、ｐＨを６．０にし、分散させる。よく分散さ
せた後、５５ｗｔ％酢酸を７０ｒｎＱ加えてｐＨを４，
５にし、静置し、デカンテーションを行う。2. After adding 1.8 f2 of pure water at 40°C, KOH6,
Add 8g, adjust the pH to 6.0, and disperse. After being well dispersed, 70rnQ of 55wt% acetic acid was added to adjust the pH to 4.
5, let stand, and decant.
３、上記２の工程をもう１回繰り返す。3. Repeat step 2 above one more time.
４、その後、後ゼラチン１５ｇ、 ＫＯＨｌ、ｇと水を
加え、４５０ｍＱに仕上げる。4. Then, add 15 g of post-gelatin, 1 g of KOH, and water to make a final volume of 450 mQ.
このようにして、乳剤１−２を得た。上記脱塩方法（ロ
）は、本発明に係る乳剤を得る溶存物除去手段に該当す
る。In this way, emulsion 1-2 was obtained. The desalting method (b) above corresponds to a means for removing dissolved substances to obtain an emulsion according to the present invention.
また、同様にして、種晶Ｔ−２を用いて粒子を成長させ
、前述の２種の脱塩方法により乳剤１−３．１−４を得
た。In the same manner, grains were grown using seed crystal T-2, and emulsion 1-3.1-4 was obtained by the two desalting methods described above.
（ｉｉｉ）種晶を用いない単分散粒子の調製による乳剤
１−５．１−６の調製
種晶と同様の調製方法、つまり、６０℃でｐＡｇが８、
ｐＨが２．０の条件下にコンドロールド・ダブルジエ・
ント法で、ハロゲン塩水溶液と、銀塩水溶液を添加し、
平均粒径０．５３μｍで平均沃化銀含有率が２モル％の
粒子を得た。かかる粒子含有の乳剤を、種晶と同様に２
種の方法で脱塩し、乳剤１−５（比較乳剤）および乳剤
１−６（本発明に係る乳剤）を得ｔ；。(iii) Preparation of emulsion 1-5.1-6 by preparation of monodisperse grains without using seed crystals.
Chondrale double jelly under the condition of pH 2.0.
Add a halogen salt aqueous solution and a silver salt aqueous solution using the
Grains having an average grain size of 0.53 μm and an average silver iodide content of 2 mol % were obtained. The emulsion containing such grains was prepared in the same manner as the seed crystal.
Desalting was carried out by a different method to obtain emulsion 1-5 (comparative emulsion) and emulsion 1-6 (emulsion according to the present invention).
（ｉｖ）多分散乳剤の調製
順混合法により、下記の４種の溶液により調製し ｊこ
。(iv) Preparation of polydisperse emulsion The following four types of solutions were prepared using the mixing method.
硝酸銀 １００ｇ
Ａ液 アンモニア水（２８％） ７８ｍ（２水を
加えて ２４０ｍＣ
オセインゼラチン ８ｇ
水を加えて ５５０ｍ＋２アンモニア水
６ｍ（２
Ｃ液 氷酢酸 ］ＯｍＱ水
３４ｍｆ２氷酢酸
２２６ｍ（２Ｄ液
水を加えて ４００ｍ１２溶液Ｂと溶液Ｃ
を乳剤調製用の反応釜に注入し、回転１３００回転／分
のプロペラ型撹拌器で撹拌し、反応温度を５５°Ｃに保
った。Silver nitrate 100g Part A Ammonia water (28%) 78m (Add 2 water and add 240mC Ossein gelatin 8g Add water 550m + 2 ammonia water
6m (2C liquid glacial acetic acid) OmQ water
34mf2 glacial acetic acid
226 m (add 2D liquid water, 400 m12 solution B and solution C
was poured into a reaction vessel for emulsion preparation, and stirred with a propeller type stirrer at 1300 revolutions/minute, and the reaction temperature was maintained at 55°C.
次に、Ａ液をｌ：２（容量比）の割合に分割し、その内
の１００＋ｎｆ２を１分間かけて投入した。１０分間撹
拌を続けた後、Ａ液の残余の２００ｍ（２を１０分間か
けて投入した。更に３０分間撹拌を継続した。そしてＤ
液を加えて、反応釜中の溶液のｐＨを６．０に調整し、
反応を停止させた。Next, solution A was divided into 1:2 (volume ratio) ratio, and 100+nf2 of the divided solution was added over 1 minute. After continuing stirring for 10 minutes, the remaining 200 m of solution A (2) was added over 10 minutes. Stirring was continued for an additional 30 minutes.
and adjust the pH of the solution in the reaction vessel to 6.0.
The reaction was stopped.
その後、脱塩方法（イ）、（ロ）の２種で脱塩を行い、
それぞれ乳剤１−７（比較乳剤）および乳剤１−８（本
発明に係る乳剤）を得た。After that, desalination is performed using two desalination methods (a) and (b),
Emulsion 1-7 (comparative emulsion) and Emulsion 1-8 (emulsion according to the present invention) were obtained, respectively.
（ｖ）平板粒子の調製
水ＩＱ中に臭化カリウム１０．５９、チオエーテル（Ｈ
Ｏ（ＣＨ２）２ｓ（ＣＨｔ）２ｓ（ＣＨｔ）２Ｓ（ＣＨ
２）ｚＯＨ）０．５ｗｔ％水溶液ｌ０ＩＩＩＱおよびゼ
ラチン３０ｇを加えて溶解し、７０°Ｃに保った。この
溶液中に、撹拌しながら、硝酸銀水溶液０．８８モル溶
液３０ｒｎＱと、沃化カリウムと臭化カリウム（モル比
３．５ ： ９６．５）の０．８８モル溶液３０ｍＱと
をダブルジェット法により添加した。該混合溶液の添加
終了後４０°Ｃまで降温した。その後２分割し、一方は
、化合物（Ｉ）およびＭｇ５Ｏ，を、それぞれ２４．６
ｇ添加し、ｐＨ４−０に降下させ脱塩を行い、その後、
後ゼラチン１５ｇを添加して、乳剤１−９（比較乳剤）
を調製した。また、一方は、脱塩方法（ロ）の工程１お
よび４により脱塩を行い、乳剤１−１０（本発明に係る
乳剤）を得た。(v) Preparation of tabular grains Potassium bromide 10.59, thioether (H
O(CH2)2s(CHt)2s(CHt)2S(CH
2) zOH) 0.5 wt% aqueous solution 10IIIQ and 30 g of gelatin were added and dissolved, and kept at 70°C. Into this solution, while stirring, 30 rnQ of a 0.88 molar silver nitrate aqueous solution and 30 mQ of a 0.88 molar solution of potassium iodide and potassium bromide (molar ratio 3.5:96.5) were added by a double jet method. Added. After the addition of the mixed solution was completed, the temperature was lowered to 40°C. Thereafter, it was divided into two parts, and one part contained 24.6% of compound (I) and Mg5O, respectively.
g was added, the pH was lowered to 4-0 and desalted, and then,
After adding 15 g of gelatin, emulsion 1-9 (comparative emulsion)
was prepared. Further, one was desalted by steps 1 and 4 of the desalting method (b) to obtain emulsion 1-10 (emulsion according to the present invention).
以上により乳剤１−１〜１−１０を得たが、（１）〜（
ｖ）の粒子について、いずれの場合も、本発明に係る乳
剤を得るだめの手段により脱塩したものの方が、再分散
性が良好であった。As described above, emulsions 1-1 to 1-10 were obtained, including (1) to (
Regarding the particles of v), in all cases, the redispersibility was better in those desalted by the means used to obtain the emulsion according to the present invention.
（試料の作成および評価）
上記で得られた１０種の乳剤について、チオシアン酸ア
ンモニウムと塩化金酸とチオ硫酸ナトリウムを加え、金
−硫黄増感を行った。(Preparation and Evaluation of Samples) The ten emulsions obtained above were subjected to gold-sulfur sensitization by adding ammonium thiocyanate, chloroauric acid, and sodium thiosulfate.
この化学増感終了後、４−ヒドロキシ−６−メチル−１
，３，３ａ、７−チトラザインデンを加えた。その後、
沃化カリウム１５０ｍｇと、下記分光増感色素１．２を
、それぞれ３００＋＋＋ｇ 、 １５ｍｇ添加して、分
光増感を行った。After this chemical sensitization, 4-hydroxy-6-methyl-1
,3,3a,7-chitrazaindene was added. after that,
Spectral sensitization was carried out by adding 150 mg of potassium iodide and 300+++ g and 15 mg of the following spectral sensitizing dye 1.2, respectively.
分光増感色素 １
分光増感色素 ２
このようにして得られた塗布用乳剤と、保護層用塗布液
とを、下引流のポリエステルフィルム支持体の両面に、
支持体側からハロゲン化銀乳剤層、保護層の順に、２層
同時に重層塗布した。その後、乾燥して、ハロゲン化銀
写真フィルムを作製した。Spectral sensitizing dye 1 Spectral sensitizing dye 2 The coating emulsion thus obtained and the coating liquid for protective layer are applied to both sides of the underflow polyester film support.
Two layers were coated at the same time in the order of the silver halide emulsion layer and the protective layer from the support side. Thereafter, it was dried to produce a silver halide photographic film.
乳剤添加剤（ハロゲン化銀１モル当り）表−１記載の化
合物（重合体） 表−１記載量【−ブチルカテコール
４００ｍｇポリビニルピロリドン（分
子３１１００００） １．０ｇスチレン−無水マレイ
ン酸共重合体 ２．５ｇトリメチロールプロパン
１０ｇジエチレングリコール
５ｇニトロフェニル・トリフェニル
ホスホニウムクロライド ５０ｍｇ１．
３−ジヒドロキシベンゼン−４−
スルホン酸アンモニウム ４ｇ２−メル
カプトベンゾイミダゾール−５−スルホン酸ナトリウム
１５ｇＣ４Ｈｅ０Ｃ）１ｚＣ［（Ｃ
ＨｚＮ（Ｃ１（ｚｃＯＯＨ）ｚ Ｉｇ
Ｈ
１，１−ジメチロール−１−ブロム−１−二トロメタン
］、Ｏｍ ｇ保護層添加剤（
ゼラチンＩｇ当り）
Ｓｏ、Ｎａ
Ｃ５Ｆ＋ ＊０（ＣＩ２ＣＨｚＯ） ＋ ｏｃＨ２ｃＨ
２０Ｈ２ｔｎｇＣ，Ｆｌ ｙｓｏｘｘ
３ｍｇ平均粒径
５μｍのポリメチルメタクリレート（マット剤）
７ｍｇコロイダル
シリカ（平均粒径０．０１３μｍ） ７０ｍｇグリ
オキザール （４０％水溶液） １．５ｍＱホ
ルムアルデヒド（３５％水溶液） ２ｍ（２
２，４−ジクロロ−６−ヒドロキシ−１，３，５−トリ
アジンナトリウム塩（２％水溶液） １０ｍｆ２下
引液としては、下記のものを用いた。Emulsion additive (per mole of silver halide) Compound (polymer) listed in Table 1 Amount listed in Table 1 [-Butylcatechol
400mg polyvinylpyrrolidone (3110000 molecules) 1.0g styrene-maleic anhydride copolymer 2.5g trimethylolpropane
10g diethylene glycol
5g nitrophenyl triphenylphosphonium chloride 50mg1.
Ammonium 3-dihydroxybenzene-4-sulfonate 4gSodium 2-mercaptobenzimidazole-5-sulfonate 15gC4He0C)1zC[(C
HzN(C1(zcOOH)z Ig
H 1,1-dimethylol-1-bromo-1-nitromethane], Omg protective layer additive (
per gelatin Ig) So, Na C5F+ *0 (CI2CHzO) + ocH2cH
20H2tngC,Flysoxx
3mg Polymethyl methacrylate (matting agent) with an average particle size of 5μm
7mg colloidal silica (average particle size 0.013μm) 70mg glyoxal (40% aqueous solution) 1.5mQ formaldehyde (35% aqueous solution) 2m (2
2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt (2% aqueous solution) The following was used as the 10mf2 subtraction liquid.
（下引液）
グリシジルメタクリレート−メチルメタクリレート−ブ
チルメタクリレ−） （５０：１０：４０）共重合体を
、その濃度がｌＱｗｔ％になるように希釈して、共重合
体水性分散液を得、これを下引液とした。(Subbing liquid) Glycidyl methacrylate - methyl methacrylate - butyl methacrylate - (50:10:40) The copolymer was diluted to a concentration of 1Qwt% to obtain an aqueous copolymer dispersion, This was used as the subtraction liquid.
また、フィルムの全バインダー量は、片面当り３、ｌＯ
ｇ／ｍ”であった（全バインダー量とは、ゼラチンおよ
び本発明に係る凝集高分子剤および一般式（１）で表さ
れる繰返し単位を含む重合体（化合物例）の合計量であ
る。）。このようにして、試料１〜３９を得ｔ；。In addition, the total amount of binder in the film was 3.1 O per side.
g/m'' (the total binder amount is the total amount of gelatin, the agglomerated polymer agent according to the present invention, and the polymer (example compound) containing the repeating unit represented by the general formula (1)). ).In this way, samples 1 to 39 were obtained.
上記の各試料について、次のような測定・評価を行つｊ
；。Perform the following measurements and evaluations for each sample above.
;.
センシトメトリー測定
【新編・照明のデータブックｊ （社団法人照明学会編
纂１版第２刷）第３９頁に記載の標準の光Ｂを光源とし
、試料を露光時間０．１秒で、３ 、２ＣＭＳでノンフ
ィルターで露光する、いわゆる白色露光を施した。ここ
で、この露光は、フィルムの両面に同一の光量となるよ
うにフィルムの両側から露光した。上記試料は、コニカ
株式会社製Ｋ Ｘ −５００自動現像機を用い、３５°
Ｃの現像液Ｘ Ｄ −９０（同社製）で現像、定着液Ｘ
Ｆ（同社製）で定着し、水洗、乾燥までを９０秒で処理
し、各試料の感度を求め ｌこ 。Sensitometric measurement [New Edition/Illumination Data Book J (Compiled by Illuminating Society of Japan, 1st Edition, 2nd Printing) Using the standard light B described on page 39 as the light source, the sample was exposed for 0.1 seconds, 3, So-called white exposure was performed using 2CMS without a filter. Here, this exposure was performed from both sides of the film so that both sides of the film received the same amount of light. The above sample was processed at 35° using a KX-500 automatic processor manufactured by Konica Corporation.
Developed with C developer X D-90 (manufactured by the same company), fixer X
The sample was fixed with F (manufactured by the same company), washed with water, and dried in 90 seconds, and the sensitivity of each sample was determined.
感度は露光によって、黒化濃度が１，０だけ増加するの
に必要な光量の逆数を求めて得た。但し感度は、試料ｌ
の感度を１００とした相対感度で表した。The sensitivity was obtained by calculating the reciprocal of the amount of light required for the blackening density to increase by 1.0 due to exposure. However, the sensitivity is
It is expressed as a relative sensitivity with the sensitivity of 100 as 100.
カバーリングパワーの測定
試料に最大濃度となるような露光を与えた後、コダック
Ｄ−９０現像液を用いて２０°Ｃで５分間現像し、続い
てエース・フィックス定着液（コニカ（株）製）で定着
５分、毎分２Ｑの流水で水洗１０分、自然乾燥を行い、
現像済試料を得た。得られた試料を蛍光Ｘ線分析法によ
り銀量（ａ＋ｇ／ｄｉ”）を測定し、濃度を銀量で割っ
てカバーリングパワーを求メタ。After exposing the sample for measurement of covering power to maximum density, it was developed at 20°C for 5 minutes using Kodak D-90 developer, followed by Ace Fix fixer (manufactured by Konica Corporation). ) for 5 minutes, rinse with running water at 2 Q/min for 10 minutes, and dry naturally.
A developed sample was obtained. The amount of silver (a+g/di'') of the obtained sample was measured using fluorescent X-ray analysis, and the covering power was calculated by dividing the concentration by the amount of silver.
ローラマークの評価
現像時の耐圧力性（自動現像機のローラーによる圧力マ
ーク、即ちローラマーク）は以下のようにして評価した
。即ち、試料を露光しないで、対向式ローラーを有する
凹凸の強い特別のローラーを持つＸレイ自動現像機で処
理した。Evaluation of Roller Marks Pressure resistance during development (pressure marks caused by the roller of an automatic processor, ie, roller marks) was evaluated as follows. That is, the samples were processed without exposure to light using an X-ray automatic processor equipped with a special roller with opposing rollers and highly uneven surfaces.
その時発生したローラーマークを、その程度により５段
階に分類して評価した。The roller marks generated at that time were classified into five grades according to their severity and evaluated.
Ａ：ローラーマークの発生なし Ｂ：ごく僅か発生あり Ｃ：やや発生あり（実用許容内） Ｄ二発生が多い（実用許容外） Ｅ：発生が非常に多い 結果を併せて表−１に示す。A: No roller marks. B: Very slight occurrence C: Slight occurrence (within practical tolerance) Frequently occurs D2 (outside practical tolerance) E: Occurrence is very common. The results are also shown in Table-1.
男−＋ ＯｐＭき） ＊・全バインダー鼠にヌ１する■這んでボ■。Male - + OpM) ＊・Nu1 to all the binder mice ■Crawling Bo■.
試料１７〜２４に用いたラテックスは、以下の通り（い
ずれも平均粒径０．０５μｍ）。The latexes used for samples 17 to 24 are as follows (all have an average particle size of 0.05 μm).
ＰＥＡ：ポリエチルアクリレート
ＰＨＭＡ：ポリエチルメタクリレート
ＰＢｚＡ：ポリベンジルアクリレート
ＭＡＡ−ＢｕＡ：メタクリル酸−ブチルアゲリレート共
重合体
表−１から明らかなように、本発明の試料はローラーマ
ーク性が大幅に改良され、しかも被覆力の低下が少ない
。PEA: polyethyl acrylate PHMA: polyethyl methacrylate PBzA: polybenzyl acrylate MAA-BuA: methacrylic acid-butyl agellylate copolymer As is clear from Table 1, the roller mark properties of the samples of the present invention were significantly improved. , and there is little decrease in covering power.
実施例−２
実施例−１の試料を特開昭６３−２３１５４号の実施例
１に記載の現像液、定着液および自動現像機を用いて３
５°Ｃ１４５秒処理を行った所、本発明の効果を得 ｌ
こ 。Example 2 The sample of Example 1 was processed using the developer, fixer and automatic processor described in Example 1 of JP-A No. 63-23154.
When treated at 5°C for 145 seconds, the effect of the present invention was obtained.
child .
Claims (1)
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、上記ハロゲン化銀乳剤層が、保護コロイドを
含む溶液中に水溶性銀塩溶液と水溶性ハロゲン化物溶液
を添加して生成したハロゲン化銀粒子を凝集高分子剤に
より保護コロイドと共に凝集させ、溶存物を除去して得
たハロゲン化銀乳剤を含有し、かつ、少なくとも１層の
ハロゲン化銀乳剤層がポリマーラテックスを含有するこ
とを特徴とするハロゲン化銀写真感光材料。In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of a support, the silver halide emulsion layer is mixed with a water-soluble silver salt solution in a solution containing a protective colloid. It contains a silver halide emulsion obtained by aggregating silver halide grains produced by adding an aqueous halide solution with a protective colloid using an aggregating polymer agent and removing dissolved substances, and at least one layer of halogen A silver halide photographic material characterized in that the silver emulsion layer contains a polymer latex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10959188A JPH01279238A (en) | 1988-04-30 | 1988-04-30 | Silver halide photographic sensitive material which is not degraded in covering power and has improved roller marking property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10959188A JPH01279238A (en) | 1988-04-30 | 1988-04-30 | Silver halide photographic sensitive material which is not degraded in covering power and has improved roller marking property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01279238A true JPH01279238A (en) | 1989-11-09 |
Family
ID=14514147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10959188A Pending JPH01279238A (en) | 1988-04-30 | 1988-04-30 | Silver halide photographic sensitive material which is not degraded in covering power and has improved roller marking property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01279238A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428557A (en) * | 1977-08-05 | 1979-03-03 | Pioneer Electronic Corp | Frequency synthesizer |
| JPS6076812A (en) * | 1983-10-04 | 1985-05-01 | Nec Corp | Phase locked loop circuit |
-
1988
- 1988-04-30 JP JP10959188A patent/JPH01279238A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428557A (en) * | 1977-08-05 | 1979-03-03 | Pioneer Electronic Corp | Frequency synthesizer |
| JPS6076812A (en) * | 1983-10-04 | 1985-05-01 | Nec Corp | Phase locked loop circuit |
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