JPH02296236A - Silver halid photographic sensitive material for lightroom requiring retouching - Google Patents
Silver halid photographic sensitive material for lightroom requiring retouchingInfo
- Publication number
- JPH02296236A JPH02296236A JP11785489A JP11785489A JPH02296236A JP H02296236 A JPH02296236 A JP H02296236A JP 11785489 A JP11785489 A JP 11785489A JP 11785489 A JP11785489 A JP 11785489A JP H02296236 A JPH02296236 A JP H02296236A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- sensitive material
- light
- matting agent
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- -1 silver halide Chemical class 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 239000006224 matting agent Substances 0.000 claims abstract description 15
- 229940090898 Desensitizer Drugs 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims description 10
- 239000000975 dye Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 6
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 125000001791 phenazinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 11
- 108010010803 Gelatin Proteins 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000005070 ripening Effects 0.000 description 5
- 229930182490 saponin Natural products 0.000 description 5
- 150000007949 saponins Chemical class 0.000 description 5
- 235000017709 saponins Nutrition 0.000 description 5
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 5
- 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 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- SAVMNSHHXUMFRQ-UHFFFAOYSA-N 1-[bis(ethenylsulfonyl)methoxy-ethenylsulfonylmethyl]sulfonylethene Chemical compound C=CS(=O)(=O)C(S(=O)(=O)C=C)OC(S(=O)(=O)C=C)S(=O)(=O)C=C SAVMNSHHXUMFRQ-UHFFFAOYSA-N 0.000 description 1
- WRNYEEDDKUIQSD-UHFFFAOYSA-N 1-methyl-3-[1-(5-sulfanylidene-2h-tetrazol-1-yl)cyclohexa-2,4-dien-1-yl]urea Chemical compound N1N=NC(=S)N1C1(NC(=O)NC)CC=CC=C1 WRNYEEDDKUIQSD-UHFFFAOYSA-N 0.000 description 1
- RSZXXBTXZJGELH-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)naphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=C(C(C)C)C(S(O)(=O)=O)=C21 RSZXXBTXZJGELH-UHFFFAOYSA-N 0.000 description 1
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical class C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical class C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CQJWSRCKSMDHFM-UHFFFAOYSA-N CCCCCCCCC1=CC=C(C=C1)OCCOCCOCCOC(C)S(=O)(=O)O Chemical compound CCCCCCCCC1=CC=C(C=C1)OCCOCCOCCOC(C)S(=O)(=O)O CQJWSRCKSMDHFM-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
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- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
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- 206010070834 Sensitisation Diseases 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
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- 150000001241 acetals Chemical class 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UGZVCHWAXABBHR-UHFFFAOYSA-O pyridin-1-ium-1-carboxamide Chemical class NC(=O)[N+]1=CC=CC=C1 UGZVCHWAXABBHR-UHFFFAOYSA-O 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- IZWPGJFSBABFGL-GMFCBQQYSA-M sodium;2-[methyl-[(z)-octadec-9-enoyl]amino]ethanesulfonate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CCS([O-])(=O)=O IZWPGJFSBABFGL-GMFCBQQYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 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
- 125000005323 thioketone group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は明室用ハロゲン化銀写真感光材料に関し、特に
オートポジ型乳剤をもちい、かつ加筆性を有する明室用
ハロゲン化銀写真感光材料に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic material for use in bright rooms, and more particularly to a silver halide photographic material for use in bright rooms that uses an autopositive emulsion and has addibility. .
（従来の技術）
従来より良く知られているように、機械や建築物の図面
や、図面からの複製などにマットフィルムが使用されて
いる。マットフィルムとは、膜中にマット剤を大量に添
加して、不透明化したフィルムのことをいう。マット剤
を膜中に大量に添加している理由として、マット化する
ことにより露光処理後、鉛筆やインク消しゴムで消去で
きるようにするためなとが挙げられ、これにより図面の
修正、書き込みが可能となる。従ってマットフィルムは
露光、処理後、上記の加筆消去による図面の修正、書き
込みを行うため使用され、又ジアゾ焼きを行いコピーを
とるなどのために使用されている。一般にマットフィル
ムは赤黄色照明下で取り扱われることが多い。しかし最
近では明るい環境下で作業する為、明室化の要求があり
、明室で作業できる感材が必要となった。この明室化の
技術に対応する為、ＵＶ光や可視光をカットする染料を
多量、膜中に添加しなければならず処理後の残色が問題
となり、この残色を良化し白色度をできるだけ上げる技
術が望まれたが解決しなかった。(Prior Art) As is well known in the past, matte films are used for drawings of machines and buildings, and reproductions from drawings. A matte film is a film made opaque by adding a large amount of matting agent into the film. The reason why a large amount of matting agent is added to the film is that by making it matte, it can be erased with a pencil or ink eraser after exposure processing, making it possible to correct and write on drawings. becomes. Therefore, after exposure and processing, matte films are used to correct and write on drawings by adding and erasing as described above, and are also used to perform diazo printing and make copies. Generally, matte films are often handled under red-yellow lighting. However, recently there has been a demand for brighter rooms to work in brighter environments, and a photosensitive material that can be used in brighter rooms has become necessary. In order to respond to this bright room technology, a large amount of dye that cuts UV light and visible light must be added to the film, resulting in a problem of residual color after processing. We hoped for a technology to improve the problem as much as possible, but we were unable to find a solution.
（発明が解決しようとする課題）
前記問題点に対して、本発明の目的は明室で取り扱い可
能な残色の少ないハロゲン化銀写真感光材料を提供する
ことにある。(Problems to be Solved by the Invention) In order to solve the above problems, an object of the present invention is to provide a silver halide photographic material that can be handled in a bright room and has less residual color.
（課題を解決するための手段）
本発明の上記の目的は支持体上に少なくとも、一層のマ
ット剤を含有るす親水性コロイド層及びオートポジ型ハ
ロゲン化銀乳剤層を有する明室用ハロゲン化銀写真感光
材料において、該感光材料中に有機減感剤を含有し、か
つ現像処理後のヘイズ度が７０％以上であることを特徴
とする明室用ハロゲン化銀写真感光材料により達成され
た。(Means for Solving the Problems) The above-mentioned object of the present invention is to provide a bright room silver halide emulsion layer having at least one hydrophilic colloid layer containing a matting agent and an autopositive silver halide emulsion layer on a support. This was achieved by a silver halide photographic material for bright room use, which contains an organic desensitizer and has a haze degree of 70% or more after development.
本発明においてヘイズとは支持体又は塗布層の不透明度
を表、し、次のように定義される。すなわちヘイズは検
体への入射光、Ｉｏに対する透過光、■を測定し、（Ｉ
ｏ−１／■ｏ） Ｘ１００なる計算した結果の値である
。従ってこの値が大きいほど、検体の不透明度が高いこ
とになる。ヘイズは市販のヘイズメーター又はタービテ
ィメーターと呼ばれる測定機器で測定できる。本発明で
の値は市販品である「オートデジタルＴｕｖｂｉｄｉ
ｍｅｔｅｒ ＡＮＡ−１４７Ｊ（東京光電■製）で測定
した値を基準とする。In the present invention, haze refers to the opacity of a support or coating layer, and is defined as follows. In other words, haze is measured by measuring the incident light on the specimen, the transmitted light with respect to Io, and (I
This is the calculated value of o-1/■o)X100. Therefore, the larger this value, the higher the opacity of the specimen. Haze can be measured with a commercially available measuring device called a haze meter or turbiti meter. The values used in the present invention are based on the commercial product “Auto Digital Tuvbidi”.
The value measured with meter ANA-147J (manufactured by Tokyo Koden ■) is used as the standard.
本発明のハロゲン化銀写真感光材料は、親水性コイロド
層の少なくとも一層中に少なくとも一種のマット剤を少
なくとも１５０ｍｇ／ｎｆ含有する好ましくは１５０■
〜１５００ｍｇである。マット剤の含有量が１５Ｏｎ＋
ｇより少ないと充分な加筆性が得られにくく、より好ま
しくは３００■／ボ以上である。また２層以上に同種の
、または別種のマット剤を含有しても良く、その場合し
マット剤を添加する層は乳剤層、保護層、あるいは必要
に応じて設けられる下引層、中間層のいずれでも良い。The silver halide photographic light-sensitive material of the present invention preferably contains at least 150 mg/nf of at least one kind of matting agent in at least one of the hydrophilic colloid layers.
~1500mg. Matting agent content is 15On+
If it is less than g, it is difficult to obtain sufficient writability, and more preferably it is 300 .mu./bo or more. In addition, two or more layers may contain the same or different types of matting agents, in which case the layer to which the matting agent is added is an emulsion layer, a protective layer, or a subbing layer or intermediate layer provided as necessary. Either is fine.
マット剤の種類は任意であって、例えば公知のものを適
宜用いる事ができる。具体的には水不溶性の有機または
無機化合物の微粒子で、任・意の粒径のものを用いる事
が出来る。好ましくは０．３から５μｍまでの粒径のも
のを用いるのが良い。The type of matting agent is arbitrary, and for example, known ones can be used as appropriate. Specifically, fine particles of water-insoluble organic or inorganic compounds of any desired particle size can be used. Preferably, particles having a particle size of 0.3 to 5 μm are used.
有機化合物の例としては、水分散性ビニル重合体の例と
してポリメチルメタアクリレート、ポリアクリロニトリ
ル、アクリロニトリル−α−メチルスチレン共重合体、
ポリスチレン、スチレンジビニルベンゼン共重合体、ポ
リビニルアセテート、ポリエチレンカーボネート、ポリ
テトラフルオロエチレンなど、セルロース誘導体の例と
してメチルセルロース、エチルセルロース、セルロース
アセテート、セルロースアセテートプロピオネートなど
、澱粉誘導体の例としてカルボキシ澱粉、カルボキシニ
トロフェニル澱粉、尿素−ホルムアルデヒド−澱粉反応
物なと、公知の硬化剤で硬化したゼラチン及びコアセル
ベート硬化して縮小カプセル中空粒体とした硬化ゼラチ
ンをどを好ましく用いることができる。無機化合物の例
としては酸化珪素、二酸化チタン、二酸化マグネシウネ
、二酸化アルミニウム、硫酸バリウム、炭酸カルシウム
、公知の方法で減感した塩化銀、同じく臭化銀、ガラス
、ケイソウ土などを好ましく用いることができる。上記
のマット剤は必要に応じて異なる種類の物質を用いるこ
とができる。Examples of organic compounds include polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and water-dispersible vinyl polymers.
Examples of cellulose derivatives include methyl cellulose, ethyl cellulose, cellulose acetate, and cellulose acetate propionate; examples of starch derivatives include carboxy starch and carboxy nitro. Preferred examples include phenyl starch, urea-formaldehyde-starch reactants, gelatin hardened with a known hardening agent, and hardened gelatin hardened with coacervate to form reduced capsule hollow granules. As examples of inorganic compounds, silicon oxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth, etc. can be preferably used. . Different types of substances can be used as the above-mentioned matting agent as required.
本発明においては処理後のヘイズ度が７０％以上である
ことが必要であるが特に８０％以上、さらに９０％以上
であることが好ましい。In the present invention, it is necessary that the degree of haze after treatment is 70% or more, particularly 80% or more, and more preferably 90% or more.
本発明におけるヘイズ度は上記マット剤の添加量を調整
することにより調整しろる。The degree of haze in the present invention can be adjusted by adjusting the amount of the matting agent added.
本発明で述べる明室用ハロゲン化銀写真感光材料とは、
紫外光成分を含まない４００μｍ以上の波長をもつ光を
セーフライト光として用いることのてきる写真感光材料
のことである。The silver halide photographic material for bright room use described in the present invention is as follows:
This is a photographic light-sensitive material that can use light with a wavelength of 400 μm or more that does not contain an ultraviolet light component as safelight light.
本発明において添加するたとができる有機減感剤として
は、例えば、米国特許第２．６６９．５１５号記載のニ
ドロチチリル型化合物、ピナクリプトールイエロー、５
−にトロベンジアリデン）ローダニン等、特公昭４１３
−１５０５９号に記載のビス−ピリジニウム化合物、特
公昭４７−８７４６号に記載しのフェナジン系化合物、
特公昭４７−９３０７号、同４７−９３０５号、同４８
２４０４６号、同５８−１７６８号に記載の減感色素、
あるいは特開昭６３−７５７３８号、同６３−７５７３
９号に記載の有機減感剤をかげられる。Examples of organic desensitizers that can be added in the present invention include nidrotityryl type compounds described in U.S. Pat. No. 2,669,515, pinacryptol yellow,
-torobendiarydene) rhodanine, etc., Special Publication Showa 413
Bis-pyridinium compounds described in Japanese Patent Publication No. 15059, phenazine compounds described in Japanese Patent Publication No. 47-8746,
Special Publication No. 47-9307, No. 47-9305, No. 48
Desensitizing dyes described in No. 24046 and No. 58-1768,
Or JP-A No. 63-75738, No. 63-7573
The organic desensitizer described in No. 9 can be used.
有機減感剤として好ましくは、フェナジン系化合物であ
り、特に好ましくは下記一般式（１）、（ｉｔ）または
（Ｉ［［）で表わされる化合物である。Preferably, the organic desensitizer is a phenazine compound, and particularly preferably a compound represented by the following general formula (1), (it) or (I[[).
基（好ましくは０６〜Ｃ１゜のちの例えばフェニル、ナ
フチル、トルイルなど）、ハロゲン原子（クロル、ブロ
ム、ヨードなど）、アルコキシル基（好ましくは０１〜
Ｃ４のもの、例えばメトキシ、エトキシなど）、ヒドロ
キシル基、アシルアミノ基（好ましくは０１〜Ｃ４のも
の、例えばホルミルアミノ、アセトアミノなど）、カル
ボキシル基、ニトロ基またはベンゼン環に縮合した環状
炭化水式中Ｒ１〜Ｒ４は同一でも互いに異なっていても
よく、それぞれ水素原子、アルキル基（好ましくはＣ１
〜Ｃ４のもの、例えばメチル、エチル、プロピル、ブチ
ル、ｔ−ブチルなど）、アリールこれらの中でも水素原
子、アルキル基、ハロゲン原子、アルコキシル基、ニト
ロ基、ヒドロキシル基が好ましく、特に水素原子、アル
キル基又はアルコキシル基の場合が好ましい。group (preferably 06 to C1°, such as phenyl, naphthyl, tolyl, etc.), halogen atom (chloro, bromo, iodo, etc.), alkoxyl group (preferably 01 to
a cyclic hydrocarbon fused to a C4 group, such as methoxy, ethoxy, etc.), a hydroxyl group, an acylamino group (preferably a 01 to C4 group, such as formylamino, acetamino, etc.), a carboxyl group, a nitro group or a benzene ring; ~R4 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably C1
to C4 (e.g., methyl, ethyl, propyl, butyl, t-butyl, etc.), aryl Among these, hydrogen atoms, alkyl groups, halogen atoms, alkoxyl groups, nitro groups, and hydroxyl groups are preferred, particularly hydrogen atoms and alkyl groups. Or an alkoxyl group is preferred.
またｍ、ｎ、、ｐＸｑはそれぞれ１．２または３を表わ
す。Further, m, n, and pXq each represent 1.2 or 3.
以下に本発明に使用する前記一般式（Ｔ） （ＩＩ）
（１）で示される化合物で代表的具体例を上げるが、本
発明において使用する化合物がこれ等に限定されるもの
でないことは勿論である。The general formula (T) (II) used in the present invention is as follows:
Typical specific examples will be given of the compounds represented by (1), but it goes without saying that the compounds used in the present invention are not limited to these.
７゜
８゜
１７゜
”Ｃｌ２）１２５
ＣＨ３Ｓｏ４ｅ
Ｃｌ５
２８゜
２９゜
ｊυ３■
２Ｃｊ２
３５゜
本発明において、前記一般式（１） （ＩＩ） （
ＩＩＩ）で示される化合物はハロゲン化銀１モルあたり
１×ｌ０−６モル−５Ｘ １０−’モル含有されるのが
好ましく、特にｌＸｌ０−’モル−２Ｘ １０−２モル
の範囲が好ましい添加量である。7゜8゜17゜"Cl2)125 CH3So4e Cl5 28゜29゜jυ3■ 2Cj2 35゜In the present invention, the general formula (1) (II) (
The compound represented by III) is preferably contained in an amount of 1 x 10-6 mol - 5 be.
写真感光材料中に含有させるときは、水溶性の場合は水
溶液として、水不溶性の場合はアルコール類（例えばメ
タノール、エタノール）、エステル類（例えば酢酸エチ
ル）、ケトン類（例えばアセトン）などの水に混和しう
る有機溶媒の溶液としてハロゲン化銀乳剤溶液またはそ
の隣接層用親水性コロイド溶液に添加すればよい。ハロ
ゲン化銀乳剤溶液に添加する場合は、その添加は化学熟
成の開始から塗布までの任意の時間に行うことができる
が、化学熟成終了後に行うのが好ましく、特に塗布のた
めに用意された塗布液中に添加するのが好ましい。When incorporated into a photographic light-sensitive material, water-soluble substances may be added as an aqueous solution; water-insoluble substances may be contained in water such as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketones (e.g. acetone), etc. It may be added as a solution in a miscible organic solvent to the silver halide emulsion solution or the hydrophilic colloid solution for its adjacent layer. When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferably done after chemical ripening, especially in the coating prepared for coating. It is preferable to add it to the liquid.
本発明のハロゲン化銀乳剤層に含まれるハロゲン化銀粒
子は０〜８０％の塩化銀を含む塩臭化銀もしくは臭化銀
である必要がある。好ましくは純臭化銀が望ましい。The silver halide grains contained in the silver halide emulsion layer of the present invention must be silver chlorobromide or silver bromide containing 0 to 80% silver chloride. Preferably, pure silver bromide is used.
本発明に用いられるオートポジ型ハロゲン化銀乳剤は写
真業界で公知の方法を用いることが出来る。The autopositive silver halide emulsion used in the present invention can be prepared by methods known in the photographic industry.
たとえば特開昭６３−７５７３８号、同６３７５７３９
号、同６２−２３４１５６号、同６２２３２６４４号、
同６２−９１９４６号、同６１−１２９６４３号、同６
０−１７０８４２号、同５！１１−２２８２４８号、同
５９−１１６７４２号等の記載を参考にすることができ
る。For example, JP-A-63-75738, JP-A No. 6375739
No. 62-234156, No. 62232644,
No. 62-91946, No. 61-129643, No. 6
Reference may be made to the descriptions in No. 0-170842, No. 511-228248, No. 59-116742, etc.
ハロゲン化銀粒子形成または物理熟成の過程において、
イリジウム、ロジウム等の８族金属の塩化物をハロゲン
化銀粒子モル当たり１０−７〜１０−３好ましくは１０
−５〜１０−３モル量をハロゲン化銀粒子の調製時に水
溶液として添加すればよい。In the process of silver halide grain formation or physical ripening,
The chloride of Group 8 metal such as iridium and rhodium is contained in an amount of 10-7 to 10-3, preferably 10 per mole of silver halide grains.
-5 to 10-3 molar amount may be added as an aqueous solution during preparation of silver halide grains.
本発明に用いられる写真乳剤には、感光材料の製造工程
、保存中あるいは写真処理中のカブリを防止し、あるい
は写真性能を安定化させる目的で、種々の化合物を含有
させることができる。すなわちアゾール類（例えばベン
ゾチアゾリウム塩、ニトロイミダゾール類、ニトロヘン
ズイミダゾール類、クロロベンズイミダゾール類、ブロ
モベンズイミダゾール類、ニトロインダゾール類、ベン
ゾトリアゾール類、アミノトリアゾール類など）メルカ
プト化合物類（例えばメルカプトチアシル類、メルカプ
トベンゾチアゾール類、メルカプトベンズイミダゾール
類、メルカプトチアジアゾール類、メルカプトテトラゾ
ール類（特に１−フェニル−５−メルカプトテトラゾー
ル）、メルカプトピリミジン類、メルカプトトリアジン
類など）例えばオキサドリンチオンのようなチオケト化
合物；アザインデン類（例えばトリアザインデン類、テ
トラアザインデン類（特に４−ヒドロキシ置換（１，３
，３ａ、７）テトラアザインデン類）、ペンタアザイン
デン類など） ；ベンゼンチオスルホン酸、ベンゼンス
ルフィン酸、ベンゼンスルホン酸アミドのようなカブリ
防止剤または安定剤として知られた、多くの化合物を加
えることができる。The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrohenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.), mercapto compounds (e.g., mercaptothiazoles, etc.) Thioketo compounds such as oxadorinthione ; azaindenes (e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3
, 3a, 7) tetraazaindenes), pentaazaindenes, etc.); add a number of compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide. be able to.
本発明の感光性ハロゲン化銀乳剤は、増感色素によって
比較的長波長の青色光、緑色光、赤色光または赤外光に
分光増感されてもよい。増感色素として、シアニン色素
、メロシアニン色素、コンプレックスシアニン色素、コ
ンプレックスメロシアニン色素、ホロホーラージアニン
色素、スチリク色素、ヘミシアニン色素、オキソノール
色素、ヘミオキソノール色素等を用いることができる。The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopholarianine dyes, styric dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.
ここで増感色素は写真乳剤の製造工程のいかなる工程に
存在させて用いることもできるし、製造後塗布直前まで
のいかなる段階に存在させることもできる。前者の例と
しては、ハロゲン化銀粒子形成工程、物理熟成工程、化
学熟成工程などである。The sensitizing dye can be used at any stage of the photographic emulsion manufacturing process, or at any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.
本発明の感光材料の写真乳剤層または他の親水性コロイ
ド層には塗布助剤、帯電防止、スベリ性改良、乳化分散
、接着防止及び写真特性改良（例えば、現像促進、硬調
化、増感）等種々の目的で、種々の界面活性剤を含んで
もよい。The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes.
例えばサポニン（ステロイド系）、アルキレンオキサイ
ド誘導体（例えばポリエチレングリコ−ル、ポリエチレ
ングリコール／ポリプロピレングリコール縮合物、ポリ
エチレングリコールアルキルエーテル類又はポリエチレ
ングリコールアルキルアリールエーテル類、シリコーン
のポリエチレンオキサイド付加物類）、糖のアルキルエ
ステル類などの非イオン性界面活性剤；アルキルスルフ
ォン酸塩、アルキルベンゼンスルフォン酸塩、アルキル
ナフタレンスルフォン酸塩、アルキル硫酸エステル類、
Ｎ−アシル−Ｎ−アルキルタウリン類、スルホコハク酸
エステル類、スルホアルキルポリオキシエチレンアルキ
ルフェニルエーテル類、などのアニオン界面活性剤；ア
ルキルベタイン類、アルキルスルホベタイン類などの両
性界面活性剤；脂肪族あるいは芳香族第４級アンモニウ
ム塩類、ピリジニウム塩類、イミダゾリウム塩類などの
カチオン界面活性剤を用いることができる。この内、サ
ポニン、ドデシルベンゼンスルホン酸Ｎａ塩、ジ・２・
エチルへキシルα−スルホコハク酸Ｎａ塩、ｐ−オクチ
ルフェノキシエトキシエトキシエタンスルホン酸Ｎａ塩
、ドデシル硫酸Ｎａ塩、トリイソプロピルナフタレンス
ルホン酸Ｎａ塩、Ｎメチル−オレオイルタウリンＮａ塩
、等のアニオン、ドデシルトリメチルアンモニウムクロ
ライド、Ｎ−オレオイル−Ｎ’ 、Ｎ’ 、Ｎ’ −ト
リメチルアンモニオジアミノプロパンブロマイド、ドデ
シルピリジウムクロライドなどのカチオン、Ｎドデシル
−Ｎ、Ｎ−ジメチルカルボキシベタイン、Ｎ−オレイル
−Ｎ、Ｎ−ジメチルスルホブチルベタインなどのベタイ
ン、ポリ（平均重合度ｎ＝１０）オキシエチレンセチル
エーテル、ポリ（ｎ＝２５）オキシエチレン−ｐ−ノニ
ルフェノールエーテル１．ビス（１−ポリ（ｎ＝１５）
オキシエチレン−オキシ−２４−ジ−ｔ−ペンチルフェ
ニル）エタンなどのノニオンを特に好ましく用いること
ができる。For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), sugar alkyl Nonionic surfactants such as esters; alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates,
Anionic surfactants such as N-acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; aliphatic or Cationic surfactants such as aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts can be used. Among these, saponin, dodecylbenzenesulfonic acid Na salt, di-2-
Anions such as ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalene sulfonic acid Na salt, N-methyl-oleoyl taurine Na salt, etc., dodecyltrimethyl Cations such as ammonium chloride, N-oleoyl-N', N', N'-trimethylammoniodiaminopropane bromide, dodecylpyridium chloride, N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-N,N - Betaines such as dimethylsulfobutyl betaine, poly(average degree of polymerization n=10) oxyethylene cetyl ether, poly(n=25) oxyethylene-p-nonylphenol ether1. Bis(1-poly(n=15)
Nonions such as oxyethylene-oxy-24-di-t-pentylphenyl)ethane can be particularly preferably used.
帯電防止剤としてはパーフルオロオクタンスルホン酸に
塩、Ｎ−プロピル−Ｎ−パーフルオロオクタンスルホニ
ルグリシンＮａ塩、Ｎ−プロピルあることが好ましい。The antistatic agent is preferably perfluorooctanesulfonic acid salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, or N-propyl.
本発明の写真感光材料の表面層には滑り剤として米国特
許第３，４８９，５７６号、同４，０４７．９５８号等
に記載のシリコーン化合物、特公昭５６−２３１３９号
公報に記載のコロイダルシリカの他に、パラフィンワツ
クス、高級脂肪酸エステル、デン粉誘導体等を用いるこ
とができる。The surface layer of the photographic light-sensitive material of the present invention contains silicone compounds described in U.S. Pat. No. 3,489,576 and U.S. Pat. In addition, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.
本発明の写真感光材料の親水性コロイド層には、トリメ
チロールプロパン、ベンタンジオール、ブタンジオール
、エチレングリコール、グリセリン等のポリオール類を
可塑剤として用いることができる。さらに、本発明の写
真感光材料の親水性コロイド層には、耐圧力性改良の目
的でポリマーラテックスを含有せしめることが好ましい
。ポリマーとしてはアクリル酸のアルキルエステルのホ
モポリマー又はアクリル酸とのコポリマー、スチレン−
ブタジェンコポリマー、活性メチレン基を有するモノマ
ーからなるポリマー又はコポリマーを好ましく用いるこ
とができる。Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Polymers include homopolymers of alkyl esters of acrylic acid or copolymers with acrylic acid, styrene-
Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.
本発明の写真乳剖及び非感光性の親水性コロイドには無
機または有機の硬膜剤を含有してよい。The photographic mammography and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardening agents.
例えばクロム塩、アルデヒド類（ホルムアルデヒド、ク
リクールアルデヒドなど）、Ｎ−メチロール化合物（ジ
メチロール尿素など）、活性ビニル化合物（１，３，５
−１−リアクリロイル−へキサヒドロ−ｓ −１−ＩＪ
アジン、ビス（ビニルスルホニル）メチルエーテル、Ｎ
、 Ｎ’ −メチレンビス〔β〜（ビニルスルホニル）
プロピオンアミド〕など）、活性ハロゲン化合物（２，
４−ジクロル６−ヒドロキシ−５−）リアジンなど）、
ムコハロケン酸１１ｆ（ムコクロル酸など）、Ｎ−カル
バモイルピリジニウム塩類（（１−モルホリノカルボニ
ル−３−ピリジニオ）メタンスルホナートなど）、ハロ
アミジニウム塩類（１−（１−クロロ１−ピリジノメチ
レン）ピロリジニウム、２ナフタレンスルホナートなど
）を単独または組合せて用いることができる。なかでも
、特開昭５３４１２２０号、同５３−５７２５７号、同
５９１６２５４６号、同６０−８０８４６号に記載の活
性ビニル化合物および米国特許３，３２５゜２８７号に
記載の活性ハロゲン化物が好ましい。For example, chromium salts, aldehydes (formaldehyde, cricoaldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), activated vinyl compounds (1,3,5
-1-lyacryloyl-hexahydro-s -1-IJ
Azine, bis(vinylsulfonyl)methyl ether, N
, N'-methylenebis[β~(vinylsulfonyl)
propionamide], active halogen compounds (2,
4-dichloro6-hydroxy-5-)riazine, etc.),
Mucohalokenic acid 11f (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(1-chloro1-pyridinomethylene)pyrrolidinium, 2-naphthalene) sulfonates, etc.) can be used alone or in combination. Among these, active vinyl compounds described in JP-A-5341220, JP-A-53-57257, JP-A-59162-546, and JP-A-60-80846 and active halides described in US Pat. No. 3,325.287 are preferred.
本発明の感光材料の乳剤層や中間層に用いることのでき
る結合剤または保護コロイドとしては、ゼラチンを用い
るのが有利であるが、それ以外の親水性コロイドも用い
ることができる。As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.
例えばデキストラン、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−Ｎ−ビニルピロリ
ドン、ポリアクリル酸、ポリアクリルアミド、ポリビニ
ルイミダゾール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を用いることができる。A variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of dextran, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and polyvinylimidazole.
本発明に用いられる染料等、種々の添加剤に関しては前
記特開昭６３−７５７３８号、同６３７５７３９号、同
６２−２３２６４４号、同６２９１９４６号、同６１−
１２９６４３号などの記載を参考にすることができる。Regarding various additives such as dyes used in the present invention, please refer to the above-mentioned JP-A Nos. 63-75738, 6375739, 62-232644, 6291946, 61-
129643 etc. can be referred to.
本発明の感光材料に用いられる支持体は、任意の適当な
写真用支持体、例えばガラス、フィルムベース、例えば
セルロースアセテート、セルロースアセテートブチレー
ト、ポリエステル（例えばポリ（エチレンテレフタレー
ト）〕等が用いられる。The support used in the photographic material of the present invention may be any suitable photographic support, such as glass, film base, such as cellulose acetate, cellulose acetate butyrate, polyester (for example, poly(ethylene terephthalate)), and the like.
本発明の感光材料の現像処理には公知のいずれをも用い
る事が出来る。この現像処理は目的に応じて銀画像を形
成する処理（黒白現像処理）あるいは色画像を形成する
現像処理のいずれであっても良い。Any known method can be used for developing the photosensitive material of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose.
黒白現像処理としては、現像処理工程、定着処理工程が
なされる。現像処理工程後、停止処理工程を行ったり定
着処理工程後、安定化処理工程を施す場合は、水洗処理
工程が省略される場合がある。また現像主薬またはその
プレカーサーを感材中に内蔵し現像処理をアルカリ液の
みで行ってもよい。現像液、としてリス現像液を用いた
現像処理工程を行ってもよい。The black and white development process includes a development process and a fixing process. When a stopping process is performed after the development process or a stabilizing process is performed after the fixing process, the washing process may be omitted. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material and development may be carried out using only an alkaline solution. A development process may be performed using a Lith developer as the developer.
以下に実施例を挙げ、本発明をさらに説明する。The present invention will be further explained with reference to Examples below.
〈実施例〉
■ 乳剤層用塗布液の調製
１％ゼラチン溶液１２中に塩化ロジウム２０■を含む溶
液に０． ５モルの臭化カリウムと０．５モルの硝酸銀
を６０°Ｃで１分間混合した。これは電子捕獲する欠損
部をもつ臭化銀コアをなすものである。次に硝酸銀０．
５モルと臭化カリウム０゜５モルを６０°Ｃで約６０分
要して加え、臭化銀の外殻を作った。続いて常法のフロ
キュレーション法で洗浄しゼラチンを加えた。次に銀１
モル当り（ホルムアミジスルフィン酸）３０ｎ＋ｇを加
えｐＨ−６，５、ＰＡｇ６．５に保ちながら露光せずと
も最大濃度にまで現像せられる様６５°Ｃで１００分間
加熱して化学増感でカブらせた。<Example> ■ Preparation of coating solution for emulsion layer A solution containing 20 μm of rhodium chloride in 12 μm of 1% gelatin solution was added with 0.00 μm of rhodium chloride. 5 moles of potassium bromide and 0.5 moles of silver nitrate were mixed at 60°C for 1 minute. This forms a silver bromide core with a defect that captures electrons. Next, silver nitrate 0.
5 moles of potassium bromide and 0.5 moles of potassium bromide were added over about 60 minutes at 60°C to form a silver bromide shell. Subsequently, it was washed by a conventional flocculation method and gelatin was added. Next, silver 1
Add 30n+g of formamidisulfinic acid per mole, maintain the pH at -6.5 and PAg6.5, and heat at 65°C for 100 minutes so that it can be developed to the maximum density without exposure to light. I set it.
この乳剤に安定剤として１− ［１（３−メチルウレイ
ド）フェニル］−５−メルカプトテトラゾールを２００
ｍｇ、減感剤として下記化合物（ａ）を１００■添加し
増粘剤としてスチレン−無水マレイン酸共重合体を１ｇ
、硬膜剤として２．４−ジクロロ−６−ヒトロキシート
リアジンナトリムウを０．５ｇ添加し乳剤用塗布液を調
製した。200% of 1-[1(3-methylureido)phenyl]-5-mercaptotetrazole was added to this emulsion as a stabilizer.
mg, 100 μg of the following compound (a) was added as a desensitizer, and 1 g of styrene-maleic anhydride copolymer was added as a thickener.
A coating solution for emulsion was prepared by adding 0.5 g of 2,4-dichloro-6-hydroxytriazine sodium as a hardening agent.
■ 保護層用塗布液の調製
ゼラチン１００ｇに水を１５００ｄ添加し、溶解した後
染料として下記化合物（ｂ）を２０ｇ、（Ｃ）を６ｇ、
（ｄ）を５ｇ、マット剤として平均粒径３．５μのシリ
カ粉末を表−１に示す量、界面活性剤としてサポニンを
５ｇ、増粘剤としてスチレン−無水マレイン酸を１ｇ、
ラテックスポリマーとしてメチルメタアクリレート３．
０ｇ、硬膜剤として１．３−ビニルスルフォニル−２−
プロパツールを５ｇ添加して保護層用塗布液を調製した
。■ Preparation of coating solution for protective layer Add 1500 d of water to 100 g of gelatin and dissolve, then add 20 g of the following compound (b) and 6 g of (C) as dyes.
5 g of (d), silica powder with an average particle size of 3.5 μ as a matting agent in the amount shown in Table 1, 5 g of saponin as a surfactant, 1 g of styrene-maleic anhydride as a thickener,
Methyl methacrylate as latex polymer3.
0g, 1,3-vinylsulfonyl-2- as hardener
A protective layer coating solution was prepared by adding 5 g of propatool.
（ｃ）
（ｄ）
■ バッキング下層用塗布液の調製
ゼラチン１００’ｇ中に水を１０００ ｍｌ添加し溶解
した後、染料として下記化合物（ｅ）を５ｇ、（ｆ）を
２ｇ、（（２）を３ｇ、（ｈ）を１０ｇ、マット剤とし
て平均粒径３．５μのシリカ粉末を４０ｇ、界面活性剤
としてサポニンを３ｇ、増粘剤としてスチレン無水マレ
イン酸１ｇ、ラテックスポリマーとしてメチルメタアク
リレートを５０ｇ１硬膜剤として１３−ビニルスルフォ
ニル−２−プロパツールを１０ｇ添加し、バッキング下
層用塗布液を調製した。(c) (d) ■ Preparation of coating solution for backing lower layer Add 1000 ml of water to 100 g of gelatin and dissolve, then add 5 g of the following compounds (e) and 2 g of (f) as dyes, ((2) 3g of (h), 10g of (h), 40g of silica powder with an average particle size of 3.5μ as a matting agent, 3g of saponin as a surfactant, 1g of styrene maleic anhydride as a thickener, and 50g of methyl methacrylate as a latex polymer. A coating solution for the lower backing layer was prepared by adding 10 g of 13-vinylsulfonyl-2-propanol as a hardening agent.
（ｇ）
ＳＯ，Ｋ
０３Ｋ
ＳＯｓＫ ５ＯｓＫ
ＳＯ，Ｎａ
■ バッキング上層用塗布液の調製
ゼラチン５０ｇ中に水を１００〇−添加し、溶解した後
界面活性剤としてサポニン３ｇ、増粘剤としてスチレン
−無水マレイン酸１ｇを添加しバッキング上層用塗布液
を調製した。(g) SO,K 03K SOsK 5OsK SO,Na ■ Preparation of coating solution for backing upper layer Add 1000ml of water to 50g of gelatin and dissolve, then add 3g of saponin as a surfactant and styrene-maleic anhydride as a thickener. A coating solution for the upper backing layer was prepared by adding 1 g of acid.
〈試料の作成〉
両面に下引き加工を施した厚さ１００μｍのポリエチレ
ンテレフタレート支持体上に上記バッキング下層用塗布
液とバッキング上層用塗布液と同時重層塗布し、続いて
バッキング層と反対側に前記乳剤用塗布液と保護用塗布
液を同時に重層塗布して試料を作成した。<Preparation of sample> On a polyethylene terephthalate support with a thickness of 100 μm that has been undercoated on both sides, the above coating solution for the lower backing layer and the coating solution for the upper backing layer are simultaneously coated in a multilayer manner, and then the above coating solution is applied on the side opposite to the backing layer. A sample was prepared by simultaneously coating an emulsion coating liquid and a protective coating liquid in multiple layers.
塗布銀量は２．５ｇ／ｒｒｆ、ゼラチン付量はバッキン
グ下層が２．５ｇ／ｎｆ、バッキング上層が０゜５ｇ／
ボ、乳剤層が２ｇ／ボ、保護層が１．３ｇ／ｎｆであっ
た。The amount of coated silver is 2.5g/rrf, the amount of gelatin applied is 2.5g/nf for the lower backing layer, and 0°5g/nf for the upper backing layer.
The weight of the emulsion layer was 2 g/nf, and the weight of the protective layer was 1.3 g/nf.
十分露光した試料を下記現像液と定着液を入れた自動現
像機で処理し、島津分光光度計を用いて分光濃度を測定
し評価した。The sufficiently exposed sample was processed in an automatic processor containing the following developer and fixer, and the spectral density was measured and evaluated using a Shimadzu spectrophotometer.
処理条件：ＦＣ；２５Ｌ自動現像機（富士写真フィルム
■製）
処理現像：フジリス液体現像剤（富士写真フィルム■製
）Ｈ３−１，２７°Ｃ１１分
４０秒
処理定着：フジリス定着剤（富士写真フィルム■製）Ｌ
Ｆ−３０８，２５°Ｃ１５５
〔加筆性の評価］
十分露光した試料を残色の評価と同様に現像処理した後
、製図用鉛筆と製図用ロン１−リングペンを用いて加筆
性を評価した。評価は１０倍のルーペを使い線の濃度、
濃度の均一性、線巾の安定性を重点において目視評価し
た。Processing conditions: FC; 25L automatic processor (manufactured by Fuji Photo Film ■) Processing and development: Fujiris liquid developer (manufactured by Fuji Photo Film ■) H3-1, 27°C 11 minutes 40 seconds Processing fixing: Fujiris fixing agent (Fuji Photo Film ■) ■Made in)L
F-308, 25° C. 155 [Evaluation of retouchability] After the sufficiently exposed sample was developed in the same manner as in the evaluation of residual color, the retouchability was evaluated using a drafting pencil and a drafting Ron 1-ring pen. For evaluation, use a 10x magnifying glass to check the density of the line,
Visual evaluation was performed with emphasis on uniformity of density and stability of line width.
ＵＶ光をカット（フジホワイトライトチューブにて）し
た東芝製退色防止用蛍光灯を使用して１３ＱＬｕｘの照
度にて露光した後、残色の評価と同様に現像処理し、未
露光部の濃度との差が出始める時間で評価した。After exposure at an illuminance of 13QLux using a Toshiba anti-fading fluorescent lamp with UV light cut (using a Fuji White Light Tube), development was performed in the same manner as in the evaluation of residual color, and the density of the unexposed area was determined. The evaluation was made based on the time at which a difference begins to appear.
３４〜
〔発明の効果〕
本発明により、明室で取り扱い可能で加筆性を有し、か
つ白色度の良いハロゲン化銀写真感光材料を提供するこ
とができた。34~ [Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic light-sensitive material that can be handled in a bright room, has addibility, and has good whiteness.
事件の表示 平成 年特願第１ ／ ７１１１４Ｉ号Display of incidents Heisei Patent Application No. 1/71114I
Claims (1)
性コロイド層及びオートポジ型ハロゲン化銀乳剤層を有
する明室用ハロゲン化銀写真感光材料において、該感光
材料中に有機減感剤を含有し、かつ現像処理後のヘイズ
度が７０％以上であることを特徴とする明室用ハロゲン
化銀写真感光材料。A silver halide photographic light-sensitive material for bright room use, which has at least one hydrophilic colloid layer containing a matting agent and an autopositive silver halide emulsion layer on a support, wherein the light-sensitive material contains an organic desensitizer. 1. A silver halide photographic material for bright room use, which has a haze degree of 70% or more after development.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11785489A JPH02296236A (en) | 1989-05-11 | 1989-05-11 | Silver halid photographic sensitive material for lightroom requiring retouching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11785489A JPH02296236A (en) | 1989-05-11 | 1989-05-11 | Silver halid photographic sensitive material for lightroom requiring retouching |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02296236A true JPH02296236A (en) | 1990-12-06 |
Family
ID=14721935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11785489A Pending JPH02296236A (en) | 1989-05-11 | 1989-05-11 | Silver halid photographic sensitive material for lightroom requiring retouching |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02296236A (en) |
-
1989
- 1989-05-11 JP JP11785489A patent/JPH02296236A/en active Pending
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