JPH02153346A - Silver halide photographic sensitive material which is suppressed in generation of fogging - Google Patents
Silver halide photographic sensitive material which is suppressed in generation of foggingInfo
- Publication number
- JPH02153346A JPH02153346A JP30858888A JP30858888A JPH02153346A JP H02153346 A JPH02153346 A JP H02153346A JP 30858888 A JP30858888 A JP 30858888A JP 30858888 A JP30858888 A JP 30858888A JP H02153346 A JPH02153346 A JP H02153346A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- silver halide
- emulsion
- layer
- compd
- 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
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 55
- 239000004332 silver Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 36
- -1 Silver halide Chemical class 0.000 title claims abstract description 34
- 239000000839 emulsion Substances 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000035800 maturation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 230000035945 sensitivity Effects 0.000 description 14
- 230000001235 sensitizing effect Effects 0.000 description 14
- 238000012545 processing Methods 0.000 description 9
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 108010010803 Gelatin Proteins 0.000 description 7
- 229910021612 Silver iodide Inorganic materials 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229940045105 silver iodide Drugs 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical class OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- SVWJXSGDEUCSNL-UHFFFAOYSA-N P(=O)(OC1=CC=C(C=C1)C)(OC1=CC=C(C=C1)C)OC1=CC=C(C=C1)C.[Ag] Chemical compound P(=O)(OC1=CC=C(C=C1)C)(OC1=CC=C(C=C1)C)OC1=CC=C(C=C1)C.[Ag] SVWJXSGDEUCSNL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- WZTQWXKHLAJTRC-UHFFFAOYSA-N benzyl 2-amino-6,7-dihydro-4h-[1,3]thiazolo[5,4-c]pyridine-5-carboxylate Chemical compound C1C=2SC(N)=NC=2CCN1C(=O)OCC1=CC=CC=C1 WZTQWXKHLAJTRC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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〕
本発明はハロゲン化銀写真感光材料に関し、更に詳しく
はカブリの発生が防止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 light-sensitive material, and more particularly to a silver halide photographic light-sensitive material in which fogging is prevented.
感光性銀塩を含有する感光材料、特に化学的に増感され
たハロゲン化銀粒子を含む写真感光材料(以下、感光材
料という)は、露光されなくても現像され得る核の存在
によりカブリを生じることがよく知られている。Photosensitive materials containing photosensitive silver salts, particularly photographic materials containing chemically sensitized silver halide grains (hereinafter referred to as photosensitive materials), suffer from fog due to the presence of nuclei that can be developed without being exposed to light. is well known to occur.
この現象は、感光材料の長期に亘る保存(特に高温、高
湿の条件下での貯蔵)によって発生し易く、経時と共に
増大する傾向を有する。カブリの発生は同時に感度の低
下と階調の劣化という好ましくない結果を招く。This phenomenon tends to occur when photosensitive materials are stored for long periods of time (particularly when stored under conditions of high temperature and high humidity), and tends to increase over time. The occurrence of fog also brings about undesirable results such as a decrease in sensitivity and deterioration of gradation.
カブリを軽減する目的で、いわゆるカブリ防止剤あるい
は安定剤を感光材料の構成要素中に添加含有せいめるこ
とか古くから知られており、例えばメルカプト基を導入
した複素環化合物、イミノ基を配したアゾール、アザイ
ンデン類など極めて多くの技術が公開されている。It has been known for a long time to add so-called antifoggants or stabilizers to the constituent elements of photosensitive materials for the purpose of reducing fog. A large number of technologies have been published, including azoles and azaindenes.
また、近年、これら複素環化合物にカルボキシ基、スル
ホ基、ヒドロキシ基、アミン基、アシルアミノ元もしく
は、スルホンアミド基などの親水性置換基を導入し減感
性を緩和した型のカブリ防止剤が提案されており、代表
的なものとして例えば米国特許3,330,658号、
ベルギー国特許737.809号、同739,709号
、特公昭58−9939号、特開昭51102639号
等が挙げられる。In addition, in recent years, antifoggants have been proposed in which hydrophilic substituents such as carboxy groups, sulfo groups, hydroxy groups, amine groups, acylamino groups, or sulfonamide groups are introduced into these heterocyclic compounds to reduce desensitization. For example, US Patent No. 3,330,658,
Examples include Belgian Patent No. 737.809, Belgian Patent No. 739,709, Japanese Patent Publication No. 58-9939, and Japanese Patent Publication No. 51102639.
しかしながら、これら多くの従来技術も最近における感
光材料の高感度化、高活性化に十分対応することは難し
く、殊に高温下(約45°C以上)に放置されたり、あ
るいは高温、高湿下(約50〜80℃、相対湿度約60
〜90%)で貯蔵されたりする苛酷な条件下でのカブリ
防止性および写真特性安定性には、欠けるのが実状であ
る。However, it is difficult for many of these conventional techniques to sufficiently respond to the recent high sensitivity and high activation of photosensitive materials, especially those that are left at high temperatures (approximately 45°C or higher) or exposed to high temperatures and high humidity. (Approximately 50-80℃, relative humidity approximately 60
The actual situation is that they lack antifogging properties and stability of photographic properties under severe conditions such as storage at temperatures of up to 90%.
従って高温下あるし゛は高温、高湿下のいずれの場合に
もカブリ防止性能が充分発揮され、かつ写真特性(感度
、階調等)に悪影響を与えることのないカブリ抑制技術
が強く要望されている。Therefore, there is a strong demand for fog suppression technology that exhibits sufficient antifogging performance under both high temperature and high humidity conditions and does not adversely affect photographic characteristics (sensitivity, gradation, etc.). .
本発明は上記の実状に濫みてなされたものであり、その
第1の目的は、感光材料を高温下あるいは高温・高湿下
で経時保存した場合にも安定した写真特性を維持し、カ
ブリの発生を防止した感光材料を提供することにある。The present invention was made in view of the above-mentioned circumstances, and its first purpose is to maintain stable photographic properties even when a photosensitive material is stored at high temperatures or at high temperatures and high humidity over time, and to prevent fogging. The object of the present invention is to provide a photosensitive material that prevents this from occurring.
本発明の第2の目的は、現像抑制に基づく感度の低下や
階調の劣化を招く恐れのない感光材料を提供することに
ある。A second object of the present invention is to provide a photosensitive material that does not cause a decrease in sensitivity or deterioration of gradation due to suppression of development.
更に第3の目的は、高温迅速処理、特に30°C以上で
現像した時のカブリ発生を著しく軽減した感光材料を提
供することにある。A third object of the present invention is to provide a photosensitive material in which the occurrence of fog is significantly reduced during high-temperature rapid processing, particularly when developing at 30° C. or higher.
本発明の上記目的は、ハロゲン化銀乳剤層および/また
は隣接する親水性コロイド層中に、下記−形式〔I〕で
表される化合物の少なくとも1つを含有せしめた感光材
料によって達成される。The above object of the present invention is achieved by a light-sensitive material containing at least one compound represented by the following format [I] in the silver halide emulsion layer and/or the adjacent hydrophilic colloid layer.
−形式(1)
〔式中 R+はアルキル基、アリール基、アルコ表し
R)、 R4はそれぞれ水素原子、アルキル基、アリー
ル基を表し、R2は水素原子、ハロゲン原子を表す。〕
以下、本発明をより具体的に説明する。-Format (1) [In the formula, R+ represents an alkyl group, an aryl group, or an alkyl group.
R) and R4 each represent a hydrogen atom, an alkyl group, or an aryl group, and R2 represents a hydrogen atom or a halogen atom. ] Hereinafter, the present invention will be explained in more detail.
本発明において用いられる前記−形式(I)で表される
カブリ防止剤は、m−ニトロフェノール誘導体である。The antifoggant represented by the above-mentioned form (I) used in the present invention is an m-nitrophenol derivative.
R1で表されるアルキル基、アリール基、アルコキシ基
、アリールオキシ基としては、炭素数1〜25(好まし
くは1〜18)の基があげられ、これらの基は置換基を
有するものも含み、好ましい置換基とじ−Cはハロゲン
原子、アリールオキシ基、ニトロ基等があげられる。Examples of the alkyl group, aryl group, alkoxy group, and aryloxy group represented by R1 include groups having 1 to 25 carbon atoms (preferably 1 to 18 carbon atoms), and these groups include those having substituents, Preferred substituents -C include a halogen atom, an aryloxy group, a nitro group, and the like.
また R2で表されるハロゲン原子としては、フッ基、
塩素、臭素、沃素があげられる。Further, the halogen atom represented by R2 includes a fluoro group,
Examples include chlorine, bromine, and iodine.
R3及びR′で表されるアルキル基としては炭素数、1
〜8(好ましくは1〜4)のアルギル基があげられ、ア
リール基としてはフェニル基、ナフチル基があげられ、
これらのアルキル基、アリール基は置換基を有するもの
も含み、好ましい置換基としてはハロゲン原子、シアノ
基、アルキルスルホニル基等があげられる。The alkyl group represented by R3 and R' has a carbon number of 1
~8 (preferably 1 to 4) argyl groups, examples of aryl groups include phenyl groups, naphthyl groups,
These alkyl groups and aryl groups include those having substituents, and preferred substituents include halogen atoms, cyano groups, and alkylsulfonyl groups.
以下に本発明に用いられる一形式〔I〕で表される化合
物(以下本発明の化合物という)の代表的具体例を示す
が、これらに限定されない。Typical specific examples of the compound represented by one type [I] (hereinafter referred to as the compound of the present invention) used in the present invention are shown below, but the compounds are not limited thereto.
化合物 I−7 化合物 C,F。Compound I-7 Compound C,F.
−N)lc、H,、(n)
化合物
ニー10
− (CFよ)4H
−(CFり4H
−(CFx)*)l
■−14
−CsH+x(n)
Ca
叶eCH,CH,OhC,H9(n)
H
■−19
−OC,Fl
H
■−20
−OC,H,ア
CQ
これらの化合物は特開昭57−204545、同59−
31953、同61−72245号公報に記載の方法、
またはそれに準じた方法により合成することができる。-N) lc, H,, (n) Compound 10 - (CFyo) 4H - (CFri 4H - (CFx)*)l ■-14 -CsH+x(n) Ca KanaeCH,CH,OhC,H9( n) H ■-19 -OC,Fl H ■-20 -OC,H, ACQ These compounds are described in JP-A-57-204545 and JP-A-57-204545, JP-A-59-
31953, the method described in Publication No. 61-72245,
Alternatively, it can be synthesized by a similar method.
本発明の化合物は、感光材料のハロゲン化銀乳剤層およ
び/または隣接する親水性コロイド層(中間層、フィル
ター層、ハレーション防止層、保護層、下塗り層等)の
少なくとも1層に含有される。The compound of the present invention is contained in at least one of the silver halide emulsion layer and/or the adjacent hydrophilic colloid layer (intermediate layer, filter layer, antihalation layer, protective layer, undercoat layer, etc.) of the light-sensitive material.
特に好ましい層としてはハロゲン化銀乳剤層である。A particularly preferred layer is a silver halide emulsion layer.
本発明の化合物の添加量は、ハロゲン化銀乳剤層の場合
、ハロゲン化銀1モル当りIn+g〜2gの範囲で用い
られるのが好ましく、より好ましくは10mg−1gで
ある。非感光性層に添加する場合も乳剤層添加に準じて
用いられる。In the case of a silver halide emulsion layer, the amount of the compound of the present invention added is preferably in the range of In+g to 2g, more preferably 10mg-1g, per mole of silver halide. When it is added to a non-photosensitive layer, it is used in the same manner as when it is added to an emulsion layer.
また、その添加時期はハロゲン化銀乳剤の場合、化学熟
成中、化学熟成終了後、及び/又は乳剤塗布直前に添加
されるが、より好ましいのはハロゲン化銀乳剤の化学熟
成終了時である。Further, in the case of a silver halide emulsion, it is added during chemical ripening, after chemical ripening, and/or immediately before coating the emulsion, but it is more preferably added at the end of chemical ripening of the silver halide emulsion.
本発明に用いられるハロゲン化銀乳剤は、ハロゲン化銀
として臭化銀、沃臭化銀、沃塩化銀、塩臭化銀、および
塩化銀等の通常のハロゲン化銀乳剤に使用される任意の
ものを用いることができる。The silver halide emulsion used in the present invention includes any silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.
ハロゲン化銀乳剤に用いられるハロゲン化銀粒子は、粒
子内において均一なハロゲン化銀組成分布を有するもの
でも、粒子の内部と表面層とでハロゲン化銀組成が異な
るコア/シェル粒子であってもよい。The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.
ハロゲン化銀粒子は、潜像が主として表面に形成される
ような粒子であってもよく、また主として粒子内部に形
成されるような粒子でもよい。The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.
ハロゲン化銀乳剤は、いかなる粒子サイズ分布を持つも
のを用いても構わない。粒子サイズ分布の広い乳剤(多
分散乳剤と称する)を用いてもよいし、粒子サイズ分布
の狭い乳剤(単分散乳剤と称する)を単独又は数種類混
合してもよい。また、多分散乳剤と単分散乳剤を混合し
て用いてもよい。Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.
ハロゲン化銀乳剤は、別々に形成した2種以上のハロゲ
ン化銀乳剤を混合して用いてもよい。The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.
本発明のハロゲン化銀写真乳剤には公知の写真用添加剤
を使用することができる。Known photographic additives can be used in the silver halide photographic emulsion of the present invention.
公知の写真用添加剤としては例えば下表に示したリサー
チ・ディスクロヂャーのRD−176438よびRD−
18716に記載の化合物が挙げられる。Examples of known photographic additives include Research Disclosure's RD-176438 and RD- shown in the table below.
Examples include compounds described in 18716.
添 加 剤 RD−17643RD−
18716頁 分類 頁 分類
化学増感剤 23 III 648−右上増感
色素 23 IV 648右−右上現像促進剤
29 1n 648−右上刃ブリ防止剤 24
Vl 649−右下安 定 剤
// 11色汚染防止
剤 25 ■ 650 左−右画像安定
剤 25 ■
紫外線吸収剤 25〜26 ■ 649右〜6
50左フイルター染料 //〃
増 白 剤 24 V硬
化 剤 26 X
651右塗布助剤 26〜27ri650右
界面活性剤 26〜27XI650右
可 塑 剤 27 n
ttス ペ リ 剤
〃スタチック防止剤 27 XI[ttマ
ッ ト 剤 28 1VI
650右バインダー 26 XI
651右本発明をカラー感光材料に適用する場合には、
カプラーが用いられる。更に色補正の効果を有している
競合カプラーおよび現像主薬の酸化体とのカップリング
によって現像促進剤、漂白促進剤、現像剤、ハロゲン化
銀溶剤、調色剤、硬膜剤、カブリ剤、カブリ防止剤、化
学増感剤、分光増感剤および減感剤のような写真的に有
用なフラグメントを放出する化合物を用いることができ
る。Additive RD-17643RD-
18716 pages Classification Page Classification Chemical sensitizers 23 III 648-Upper right sensitizing dye 23 IV 648 Right-Upper right development accelerator
29 1n 648-Right upper blade anti-blur agent 24
Vl 649-Lower right stabilizer
// 11 Color anti-staining agent 25 ■ 650 Left-right image stabilizer 25 ■ Ultraviolet absorber 25-26 ■ 649 Right-6
50 left filter dye //〃 brightening agent 24 V hard
Curing agent 26 X
651 Right coating aid 26-27ri650 Right surfactant 26-27XI650 Right plasticizer 27 n
tt super agent
〃Static prevention agent 27 XI [tt Matting agent 28 1VI
650 right binder 26 XI
651 Right When applying the present invention to color photosensitive materials,
A coupler is used. Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, Compounds that release photographically useful fragments such as antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.
イエロー色素形成カプラーとしては、公知のアンルアセ
トアニリド系カプラーを好ましく用いることができる。As the yellow dye-forming coupler, known anruacetanilide couplers can be preferably used.
これらのうち、ベンゾイルアセトアニリド系及びピバロ
イルアセトアニリド系化合物は有利である。Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.
マゼンタ色素形成カプラーとしては、5−ピラゾロン系
カプラー ピラゾロアゾール系カプラーピラゾロペンツ
イミダゾール系カプラー 開鎖アシルアセトニトリル系
カプラー インダシロン系カプラー等を用いることがで
きる。As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolopenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.
シアン色素形成カプラーとしては、フェノールまたはナ
フトール系カプラーが一般的に用いられる。Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.
本発明の感光材料に用いることのできる支持体としては
、例えば前述RD−17643の28頁、およびRD−
18716の647頁左欄に記載されているものが挙げ
られる。適当な支持体としてはポリマーフィルム、紙な
どで、これらは接着性、帯電防止性などを高めるための
処理がなされていてもよい。Examples of the support that can be used in the photosensitive material of the present invention include the above-mentioned RD-17643, page 28, and RD-
18716, page 647, left column. Suitable supports include polymer films, paper, etc., which may be treated to enhance adhesiveness, antistatic properties, etc.
本発明による感光材料は、前述のRD−17643の2
8〜29頁、およびRD−18716の651頁左欄〜
右欄に記載された通常の方法によって現像処理すること
ができる。The photosensitive material according to the present invention is the above-mentioned RD-17643-2.
Pages 8 to 29, and page 651 left column of RD-18716 ~
Development processing can be carried out by the usual methods described in the right column.
この写真処理方法は銀画像を得るための黒白写真処理で
あっても色画像を得るためのカラー写真処理であっても
よい。写真地理に適用される処理温度は通常18°C〜
50°Cであるが、18°Cより低い温度でも50℃以
上の温度であっても処理は可能である。This photographic processing method may be a black and white photographic processing to obtain a silver image or a color photographic processing to obtain a color image. The processing temperature applied to photogeography is usually 18°C ~
Although the temperature is 50°C, the treatment can be performed at a temperature lower than 18°C or higher than 50°C.
本発明の写真乳剤が適用できる写真感光材料としては、
種々のカラー及び白黒感光材料を挙げることができる。Photographic materials to which the photographic emulsion of the present invention can be applied include:
Mention may be made of various color and black-and-white photosensitive materials.
例えば撮影用カラーネガフィルム(一般用、映画用等)
、カラー反転フィルム(スライド用、映画用、またはカ
プラーを含有しない場合も含有する場合もある)、カラ
ー印画紙、カラーポジフィルム(映画用等)、カラー反
転印画紙、熱現像用カラー感光材料、製版用写真感光材
料(リスフィルム、スキャナーフィルム等)、Xレイ写
真感光材料(直接・間接医療用、工業用)、撮影用白黒
ネガフィルム、白黒印画紙、マイクロ用感光材料(00
M用、マイクロフィルム等)カラー拡散転写感光材料(
DTR) 、銀塩拡散転写感光材料、プリントアウト感
光材料などを挙げることができる。For example, color negative film for photography (general use, movie use, etc.)
, color reversal film (for slides, movies, or with or without couplers), color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, color photosensitive materials for heat development, plate making photographic materials (lithographic film, scanner film, etc.), X-ray photographic materials (direct/indirect medical use, industrial use), black and white negative film for photography, black and white photographic paper, microphotosensitive materials (00
M, micro film, etc.) color diffusion transfer photosensitive materials (
Examples include DTR), silver salt diffusion transfer photosensitive materials, and printout photosensitive materials.
以下に実施例を挙げて本発明を更に詳細に説明する。 The present invention will be explained in more detail with reference to Examples below.
実施例−1
沃化銀3.0モル%を含む高感度ネガ用沃臭化銀乳剤を
金および硫黄増感法により最高感度まで化学熟成したの
ち、ハロゲン化銀1モル当り4−ヒドロキシ−6−メチ
ル−1,3,3a、7−チトラザインデンを1.0g添
加して熟成を停止させた。Example 1 A high-sensitivity negative silver iodobromide emulsion containing 3.0 mol% of silver iodide was chemically ripened to the highest sensitivity by gold and sulfur sensitization, and then 4-hydroxy-6 was added per mol of silver halide. -1.0 g of methyl-1,3,3a,7-chitrazaindene was added to stop the ripening.
得られた乳剤を15分割して1部をそのままブランク試
料とし、他に下記表−1の如く本発明に係る化合物およ
び比較化合物を添加し、充分に吸着せしめたのち、塗布
助剤としてサポニンの適量および硬膜剤としてホルマリ
ンの適量を添加して塗布用乳剤を調製した。The obtained emulsion was divided into 15 parts, one part was used as a blank sample, and the compounds according to the present invention and comparative compounds as shown in Table 1 below were added to the emulsion, and after sufficient adsorption, saponin was added as a coating aid. An emulsion for coating was prepared by adding an appropriate amount of formalin and a suitable amount of formalin as a hardening agent.
塗布用乳剤を下引済みのポリエステルベース上に銀量が
3g/m”になるように均一塗布してから乾燥して15
種の試料を作成した(No、 l ” 15)。The coating emulsion was uniformly coated on the undercoated polyester base to a silver content of 3 g/m'' and then dried for 15 minutes.
Seed samples were prepared (No. l”15).
以上のように作成した写真材料をフレッシュ試料として
室温下で3日間放置したもの、及び温度65°C下に3
日間のものと、温度50°C相対湿度80%下に3日間
それぞれ放置した強制劣化経時試料を作成した。The photographic materials prepared as described above were used as fresh samples, and were left at room temperature for 3 days, and at 65°C for 3 days.
One sample was prepared for one day, and the other sample was subjected to forced deterioration after being left at a temperature of 50° C. and a relative humidity of 80% for three days.
この後、通常のセンシトメトリー用ウェッジを用いて露
光を行い、次いで下記処理液[A]にて35°Cで30
秒の現像を行い定着したのち、水洗乾燥して感度測定を
した。After this, exposure was performed using a regular sensitometric wedge, and then the following treatment solution [A] was used for 30 minutes at 35°C.
After developing for a few seconds and fixing, the film was washed with water and dried, and the sensitivity was measured.
処理液[A](黒白写真感光材料用現像液)l−フェニ
ル−3−ピラゾリドン 1.5gハイドロキノ
ン 30g5−二トロインダゾ
ール 0.25g臭化カリウム
5g無水亜硫酸ナトリウム
55g水酸化カリウム
30g硼 酸
]、 Ogグルタルアルデヒド
(25%) 5g水を加えて全量を1(
2とする。Processing liquid [A] (Developer for black and white photographic materials) l-phenyl-3-pyrazolidone 1.5g Hydroquinone 30g 5-nitroindazole 0.25g Potassium bromide
5g anhydrous sodium sulfite
55g potassium hydroxide
30g boric acid
], Ogglutaraldehyde
(25%) Add 5g water and reduce the total amount to 1(
Set it to 2.
得られた結果を下記表−1に示す。The results obtained are shown in Table 1 below.
但し、カブリ値はベース濃度を差し引いた値を示し、感
度値はカブリ値+0.5の位置の感度から、本発明の乳
剤のブランク試料(No、 l )の自然放置3日のも
のを100として表した相対感度で表し、ガンマは特性
曲線上における直線部の傾斜で示し上記表−1からも明
らかな如く、本発明に係る試料は、いずれも苛酷な保存
条件下にも拘らず、カブリの発生が抑えられ、フィルム
保存下での安定性が改良されていることが判る。However, the fog value shows the value after subtracting the base density, and the sensitivity value is calculated from the sensitivity at the fog value + 0.5 position, with the blank sample (No. 1) of the emulsion of the present invention left for 3 days as 100. Gamma is expressed as the slope of the straight line on the characteristic curve.As is clear from Table 1 above, all the samples of the present invention showed no fog despite being stored under severe storage conditions. It can be seen that the occurrence is suppressed and the stability of the film during storage is improved.
実施例−2
セルローズトリアセテートフィルム支持体上に下記に示
す組成の各層を順に設けて多層カラー感光材料試料(比
較)を作製した。Example 2 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.
第1層、ハレーション防止剤
黒色コロイド銀を含むゼラチン層
第2層;中間層
ゼラチン層
第3層:赤感性低感度乳剤層
沃臭化銀乳剤 沃化銀:5モル%
平均粒径0.5μm
銀塗布量・・・1.79g/m”
増感色素I・・・・・・銀1モルに対して6 X 10
−’モル
増感色素■・・・・・・銀1モルに対して3 X 10
−’モル
カプラーA・・・・・・銀1モルに対して0.06モル
カプラーB・・・・・・銀1モルに対して0.003モ
ルカプラーD・・・・・銀1モルに対して0.003モ
ルトリ・クレジルホスフェート塗布量
0.3mff/m2
第4層:赤感性高感度乳剤層
沃臭化銀乳剤 沃化銀=4モル%
平均粒径0.7μm
銀塗布量・・・・・・1.4g/m2
増感色素I・・・・・・銀1モルに対して3 X 10
−’モル
増感色素■・・・・・・銀1モルに対して1.2X 1
0−’モル
カプラーF・・・・・銀1モルに対して0.0125モ
ル
カプラーC・・・・・・銀1モルに対して0.0016
モル
トリクレジルホスフェート塗布量
0.2m4/m”
第5層:中間層
第2層と同じ
第6層:緑感性低感度乳剤層
沃臭化銀乳剤 沃化銀=44モル
%平均径0.5μm
銀塗布量・・・・・・1.0g/m”
増感色素■・・・・・・銀1モルに対して3 X 10
−’モル
増感色素■・・・・・・銀1モルに対してI X 10
−5モル
カプラーB・・・・・・銀1モルに対して0.08モル
カプラーM・・・・・・銀1モルに対してo、ooaモ
ル
カプラーD・・・・・・銀1モルに対して0.0015
モル
トリクレジルホスフェート塗布量
1.4mQ/m”
第7層:緑感性高感度乳剤層
沃臭化銀乳剤 沃化銀:5モル%
平均粒径0.75μm
銀塗布量・・・・・・1.6g/m”
増感色素■・・・・・・銀1モルに対して2.5X 1
0−’モル
増感色素■・・・・・・銀1モルに対して0.8X 1
0−’モル
カプラーB・・・・・・銀1モルに対して0.02モル
カプラーM・・・・・・銀1モルに対して0.003モ
ル
トリクレジルホスフェート塗布量
0.8m(2/a+2
第8層:イエローフィルター層
ゼラチン水溶液中に黄色コロイド銀を含むゼラチン層。1st layer, antihalation agent black gelatin layer containing colloidal silver 2nd layer; intermediate gelatin layer 3rd layer: red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.5 μm Silver coating amount: 1.79 g/m" Sensitizing dye I: 6 x 10 per mole of silver
-'molar sensitizing dye ■...3 x 10 per mole of silver
-'Molar coupler A: 0.06 mol per mol of silver Coupler B: 0.003 mol per mol of silver Coupler D: 0 per mol of silver .003 Moltri-cresyl phosphate coating amount 0.3 mff/m2 4th layer: red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 4 mol% Average grain size 0.7 μm Silver coating amount...・1.4g/m2 Sensitizing dye I...3 x 10 per mole of silver
-'molar sensitizing dye■...1.2X 1 per mole of silver
0-' mole coupler F...0.0125 mole per mole of silver Coupler C...0.0016 per mole of silver
Coating amount of mol tricresyl phosphate 0.2 m4/m" 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green sensitive low sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 44 mol% Average diameter 0. 5 μm Silver coating amount: 1.0 g/m” Sensitizing dye ■: 3 x 10 per mole of silver
-'molar sensitizing dye ■...I x 10 per mole of silver
-5 mole coupler B: 0.08 mole per mole of silver Coupler M: o, ooa mole per mole of silver Coupler D: per mole of silver 0.0015
Moltricresyl phosphate coating amount: 1.4 mQ/m'' 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size: 0.75 μm Silver coating amount... 1.6g/m" Sensitizing dye■...2.5X 1 per mole of silver
0-'Mole sensitizing dye■...0.8X per mole of silver 1
0-' mole coupler B...0.02 moles per mole of silver Coupler M...0.003 moles per mole of silver Tricresyl phosphate coating amount 0.8 m (2/ a+2 8th layer: Yellow filter layer A gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.
第9層:青感性低感度乳剤層
沃臭化銀乳剤 沃化銀:6モル%
平均粒径0.7μm
銀塗布量・・・・・・0.5g/m”
カプラーY・・・・・・銀1モルに対して0.125モ
ル
トリクレジルホスフェート塗布量
0.3n+12/m2
第1θ層:青感性高感度乳剤層
沃臭化銀乳剤 沃化銀:6モル%
平均粒径0,8μm
銀塗布量・・・・・・0.6g/m”
カプラーY:・・・・・銀1モルに対して0.04モル
トリクレジルホスフェート塗布量
0.1v2/m”
第11層:保護層
トルメチルメタアクリレート粒子(直径1.5μm)を
含むゼラチン層を塗布。9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.7 μm Silver coating amount: 0.5 g/m" Coupler Y...・0.125 mole tricresyl phosphate coating amount per 1 mole of silver 0.3n+12/m2 1st theta layer: Blue sensitive high sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.8 μm Coating amount of silver: 0.6 g/m" Coupler Y: 0.04 mol of tricresyl phosphate per mole of silver 0.1 v2/m" 11th layer: Protection Apply a layer of gelatin containing tolumethyl methacrylate particles (1.5 μm in diameter).
各層のカプラーはトリクレジルホスフェートと酢酸エチ
ルの溶液にカプラーを添加し、乳化剤としてp−ドデシ
ルベンゼンスルホン
を加えて加熱溶解後、加熱した10%ゼラチン溶液と混
合し、コロイドミルで乳化したもの使用した各層には上
記組成物の他にゼラチン硬化剤や界面活性剤を添加した
。The couplers for each layer were prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding p-dodecylbenzenesulfone as an emulsifier, dissolving it by heating, mixing it with a heated 10% gelatin solution, and emulsifying it in a colloid mill. In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.
く試料を作るのに用いた化合物〉
増感色素I:アンヒドロー5,5′−ジクロロ−3.3
’−ジー(γースルホプロピル)−9−エチル−チアカ
ルボシアニンヒドロキシド・ピリジウム塩
増感色素■:アンヒドロ−9−エチル−3.3′−ジ(
Tスルホプロピル)−4.5.4 ’,5 ’ージアン
ゾチア力ルポシアニンヒドロキシド・トリエチルアミン
塩増感色素■:アンヒドロ−9−エチル−5.5′−ジ
クロロ−3.3′−ジー(γースルホプロピル)オキサ
カルボシアニンヒドロキシド・ナトリウム塩増感色素■
:アンヒドロ−5.6.5 ’,6 ’ーテトラクロロ
ー1,1′−ジエチル−3.3′−ジ(β−〔β−(γ
ースルホプロポキシ)エトキシ〕エチルイミダゾロカル
ボシアニンヒドロキシド・ナトリウム塩カプラーA
カプラーB
カプラーF
CH。Compounds used to prepare samples> Sensitizing dye I: Anhydro 5,5'-dichloro-3.3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye ■: anhydro-9-ethyl-3.3'-di(
T-sulfopropyl)-4.5.4',5'-dianzothiatric lupocyanine hydroxide triethylamine salt sensitizing dye ) Oxacarbocyanine hydroxide/sodium salt sensitizing dye■
:anhydro-5.6.5',6'-tetrachloro1,1'-diethyl-3.3'-di(β-[β-(γ
-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler A coupler B coupler F CH.
カプラーC
しα
カプラーY
L;μ
前記のハロゲン化銀乳剤層である第3層および第4層の
赤感層と第6層および第7層の緑感性層と第9層および
M2O層に青感性層には、いずれも増感色素を添加して
後に比較化合物および本発明の化合物を表−2の如く添
加してから調整し重層塗布したものである。(試料16
〜36)得られた多層カラー感光材料を実施例−1と同
様に保存性試験のための高温高湿下処理を施してから、
通常のウェッジ露光をして後、下記のカラー処理を行っ
た。Coupler C and α Coupler Y L; μ Blue in the red-sensitive layers of the third and fourth layers, the green-sensitive layers of the sixth and seventh layers, the ninth layer and the M2O layer, which are the silver halide emulsion layers. In each case, a sensitizing dye was added to the sensitive layer, and then a comparative compound and a compound of the present invention were added as shown in Table 2, and the layers were adjusted and coated in a multilayer manner. (Sample 16
~36) The obtained multilayer color photosensitive material was subjected to high temperature and high humidity treatment for storage test in the same manner as in Example-1, and then
After normal wedge exposure, the following color processing was performed.
処理工程〔処理温度38°C〕 処理時間発色現象
3分15秒漂 白
6 分30秒水 洗
3分15秒定 着
6分30秒水
洗 3分15秒安定化
1分30秒
乾 燥
各処理工程において使用した処理液組成は下記の如くで
ある。Treatment process [Processing temperature 38°C] Processing time Color development phenomenon
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
6 minutes 30 seconds water
Washing: Stabilization for 3 minutes and 15 seconds; Drying for 1 minute and 30 seconds. The composition of the treatment liquid used in each treatment step is as follows.
4−アミノ−3−メチル−N−エチル−Nロキシエチル
)アニリン硫酸塩
無水亜硫酸ナトリウム
ヒドロキシアミンl/2硫酸塩
無水炭酸カリウム
臭化すi・リウム
ニトリロ三酢酸・3す
(β−ヒ ド
4.75g
4.25g
2.0g
37.5g
1.3g
トリウム塩(I水塩)
2.5g
1.0g
水酸化ナトリウムを用い
水酸化カリウム
水を加えてIQとし、
てpH10,6に調整する。4-Amino-3-methyl-N-ethyl-N-oxyethyl)aniline sulfate Anhydrous sodium sulfite Hydroxyamine l/2 sulfate Anhydrous potassium carbonate I-lium nitrilotriacetic acid 3-s(β-hydride 4.75 g 4.25g 2.0g 37.5g 1.3g Thorium salt (I hydrate) 2.5g 1.0g Using sodium hydroxide, add potassium hydroxide water to make IQ, and adjust to pH 10.6.
エチレンジアミ
ン四酢酸鉄アンモニウム塩
100.0g
エチレンジアミン四酢酸2アンモニウム塩10.0g
臭化アンモニウム 150.0g氷酢酸
10.0g水を加えてIQ
とし、アンモニア水を用いてpH6.0に調整する。IQ
and adjust the pH to 6.0 using aqueous ammonia.
チオ硫酸アンモニウム 175.0g無水亜
硫酸ナトリウム 8.6gメタ亜硫酸ナト
リウム 2.3g水を加えてlQとし、酢
酸を用いてpH6、0に調整する。Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make up to 1Q, and adjust to pH 6.0 using acetic acid.
ホリマリン(37%水溶液) 1.5+a(
2コニダツクス(コニカ株式会社製) 7.5011
2水を加えてlQとする。Holimarin (37% aqueous solution) 1.5+a (
2 Konidax (manufactured by Konica Corporation) 7.5011
2 Add water to make 1Q.
得られたピースから求めたカラーセンシトメトリー結果
を次の表−2に示す。The color sensitometric results obtained from the obtained pieces are shown in Table 2 below.
なお表中のカプリはペース濃度を差し引いた値で、感度
は比較試料16の自然放置3日の各感色性層を100と
して表した場合の相対感度である。Note that the capri in the table is the value after subtracting the pace concentration, and the sensitivity is the relative sensitivity when each color-sensitive layer of comparative sample 16 left for 3 days is expressed as 100.
表−2の結果から、本発明に係る試料は、多層カラー感
光材料においても苛酷な保存ならびに30°C以上の高
温現像条件下にも拘らず各感光層のバランスも良く、感
度低下のないカブリ抑制性が得られることが明らかであ
る。From the results in Table 2, it is clear that the samples according to the present invention have a good balance of each photosensitive layer even in multilayer color photosensitive materials, despite severe storage conditions and high-temperature development conditions of 30°C or higher, and fog without deterioration in sensitivity. It is clear that suppressive properties are obtained.
本発明の一般式(1)で表される化合物から選ばれる少
なくとも1つを、ハロゲン化銀乳剤層または隣接する親
水性コロイド層に添加含有せしめた本発明のハロゲン化
銀写真感光材料は、経時保存中高温下あるいは高温・高
湿下で貯蔵されてもカブリの発生が抑制されると共に、
感度の低下や階調の軟化をきたす恐れが少ない侵ttだ
写真感光材料である。The silver halide photographic light-sensitive material of the present invention contains at least one compound selected from the compounds represented by the general formula (1) of the present invention in a silver halide emulsion layer or an adjacent hydrophilic colloid layer. The occurrence of fog is suppressed even when stored at high temperatures or under high temperature and high humidity, and
It is a highly sensitive photographic material that is less likely to cause a decrease in sensitivity or softening of gradations.
Claims (1)
イド層中に、下記一般式〔 I 〕で表される化合物の少
なくとも1つを含有することを特徴とするハロゲン化銀
写真感光材料。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 〔式中、R^1はアルキル基、アリール基、アルコキシ
基、アリールオキシ基、または▲数式、化学式、表等が
あります▼を表し、R^3,R^4はそれぞれ水素原子
、アルキル基、アリール基を表し、R^2は水素原子、
ハロゲン原子を表す。〕[Scope of Claims] A silver halide photograph characterized in that a silver halide emulsion layer and/or an adjacent hydrophilic colloid layer contains at least one compound represented by the following general formula [I] photosensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents an alkyl group, aryl group, alkoxy group, aryloxy group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^3 and R^4 represent a hydrogen atom, an alkyl group, and an aryl group, respectively, and R^2 is a hydrogen atom,
Represents a halogen atom. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30858888A JPH02153346A (en) | 1988-12-05 | 1988-12-05 | Silver halide photographic sensitive material which is suppressed in generation of fogging |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30858888A JPH02153346A (en) | 1988-12-05 | 1988-12-05 | Silver halide photographic sensitive material which is suppressed in generation of fogging |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02153346A true JPH02153346A (en) | 1990-06-13 |
Family
ID=17982843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30858888A Pending JPH02153346A (en) | 1988-12-05 | 1988-12-05 | Silver halide photographic sensitive material which is suppressed in generation of fogging |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02153346A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5681837A (en) * | 1979-12-07 | 1981-07-04 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
-
1988
- 1988-12-05 JP JP30858888A patent/JPH02153346A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5681837A (en) * | 1979-12-07 | 1981-07-04 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS63301937A (en) | Silver halide photographic sensitive material | |
JPH02153346A (en) | Silver halide photographic sensitive material which is suppressed in generation of fogging | |
JPH02157745A (en) | Silver halide photographic sensitive material with which generation of fogging is suppressed | |
JPH09203992A (en) | Photographic element containing sensitizing dye | |
JP2631730B2 (en) | Silver halide photographic light-sensitive material with reduced fog | |
JP2717696B2 (en) | Silver halide photographic fog suppressant | |
JP2686804B2 (en) | Silver halide photographic fog suppressant | |
JP2663350B2 (en) | Silver halide photographic materials containing antifoggants | |
JP2663349B2 (en) | Silver halide photographic materials containing antifoggants | |
JP2896937B2 (en) | Silver halide photographic fog suppressant | |
JP2864428B2 (en) | Silver halide photographic fog suppressant | |
JPH0588812B2 (en) | ||
JP2678610B2 (en) | Silver halide photographic fog suppressant | |
JPH0895189A (en) | Silver halide material of color photograph | |
JPS61256346A (en) | Silver halide photographic sensitive material | |
JPS62189460A (en) | Photographic sensitive material improved in antistaticness | |
JPH0549087B2 (en) | ||
JPS63175853A (en) | Silver halide photographic sensitive material inhibiting fogging | |
JPH07181639A (en) | Reversal element having core-shell emulsion for forming internal latent image and processing method thereof | |
JPS62187842A (en) | Silver halide photographic sensitive material | |
JPH0239142A (en) | Silver halide photographic sensitive material | |
JPS62170951A (en) | Photographic recording material, generation of photographic image and triazol | |
JPH01291250A (en) | Silver halide color photographic sensitive material | |
JPS63301948A (en) | Silver halide photographic sensitive material having high sensitivity and excellent graininess | |
JPS63306440A (en) | Silver halide photographic sensitive material suppressing fog |