JPH01306842A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH01306842A JPH01306842A JP13725688A JP13725688A JPH01306842A JP H01306842 A JPH01306842 A JP H01306842A JP 13725688 A JP13725688 A JP 13725688A JP 13725688 A JP13725688 A JP 13725688A JP H01306842 A JPH01306842 A JP H01306842A
- Authority
- JP
- Japan
- Prior art keywords
- compd
- photographic
- silver halide
- light
- ultraviolet rays
- 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 12
- -1 Silver halide Chemical class 0.000 title claims description 22
- 229910052709 silver Inorganic materials 0.000 title claims description 16
- 239000004332 silver Substances 0.000 title claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000001875 compounds Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000006096 absorbing agent Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 108010010803 Gelatin Proteins 0.000 abstract description 2
- 229920000159 gelatin Polymers 0.000 abstract description 2
- 239000008273 gelatin Substances 0.000 abstract description 2
- 235000019322 gelatine Nutrition 0.000 abstract description 2
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 16
- 238000009835 boiling Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000010186 staining Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 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 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- 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
- 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 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- ZJOJXRSMJNWWRN-UHFFFAOYSA-N 3-amino-6-[2-(4-aminophenyl)ethenyl]benzene-1,2-disulfonic acid Chemical class C1=CC(N)=CC=C1C=CC1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O ZJOJXRSMJNWWRN-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
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- CYCBAKHQLAYYHQ-UHFFFAOYSA-N imidazo[4,5-c]pyrazole Chemical compound N1=NC2=NC=NC2=C1 CYCBAKHQLAYYHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- YRJYANBGTAMXRQ-UHFFFAOYSA-N pyrazolo[3,4-h]quinazolin-2-one Chemical compound C1=C2N=NC=C2C2=NC(=O)N=CC2=C1 YRJYANBGTAMXRQ-UHFFFAOYSA-N 0.000 description 1
- VNAUDIIOSMNXBA-UHFFFAOYSA-N pyrazolo[4,3-c]pyrazole Chemical compound N1=NC=C2N=NC=C21 VNAUDIIOSMNXBA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、紫外線吸収剤を含有するハロゲン化銀写真感
光材料に関するものである。さらに詳しくは、写真製品
に好ましく用いることのできる紫外線吸収剤に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material containing an ultraviolet absorber. More specifically, the present invention relates to ultraviolet absorbers that can be preferably used in photographic products.
［発明の背景］ 紫外線が写真製品に与える影響は数多く知られている。[Background of the invention] There are many known effects of ultraviolet light on photographic products.
例えば、写真製品の塗布乾燥時および搬送時に生じるス
タチック光により写真製品が好ましくない感光を起こす
ことや、撮影時の様々な光源における紫外線強度が異な
ることによる色再現性の劣化をおこすこと等が挙げられ
る。For example, static light generated during coating and drying of photographic products and transport can cause undesirable exposure of photographic products, and color reproducibility can deteriorate due to differences in the intensity of ultraviolet light from various light sources during photography. It will be done.
また、金属銀以外の色素により画像を形成する写真製品
においては、紫外線による色素画像の褪色が特に大きい
ので、写真製品を観賞用にデイスプレィした場合等にお
いて、紫外線を多量に含む太陽光線により著しい変褪色
が生じる。In addition, in photographic products in which images are formed using pigments other than metallic silver, fading of the pigment image by ultraviolet rays is particularly large, so when displaying photographic products for ornamental purposes, sunlight containing large amounts of ultraviolet rays may cause significant discoloration. Fading occurs.
さらに、特にポリエチレン被覆紙を支持体として使用し
た場合、紫外線によるポリエチ１／ンの劣化を生じ、支
持体のひび割れ（クラッキング）等が起きてしまう。Further, especially when polyethylene-coated paper is used as a support, the polyethylene 1/N deteriorates due to ultraviolet rays, resulting in cracking of the support.
これら以外にも写真製品中には様々な有機添加剤が導入
されており、光分解反応により生じる光分解生成物が着
色していることが多いために、特に非画像部の汚れを生
じることもしばしば見られる現象である０例えば、カラ
ー印画紙の未発色部（白地）が光照射により黄変を起こ
すことら知られており（光スティンと称されている）、
その改良が望まれている。In addition to these, various organic additives are introduced into photographic products, and the photodecomposition products produced by photodecomposition reactions are often colored, which can cause stains, especially in non-image areas. For example, it is known that the uncolored areas (white background) of color photographic paper turn yellow when exposed to light (referred to as photo stain).
Improvements are desired.
紫外線による上記の諸影響を緩和するために、写真製品
中のハロゲン化銀乳剤層または非感光性写真層に紫外線
吸収剤を導入することは周知であり広く用いられている
。そして、この用途のなめに非常に数多くの紫外線吸収
剤が従業されており、一般に次の特性を有することが必
要とされている。It is well known and widely used to incorporate ultraviolet absorbers into silver halide emulsion layers or non-light-sensitive photographic layers in photographic products in order to alleviate the above-mentioned effects of ultraviolet radiation. A large number of ultraviolet absorbers are used for this purpose, and they are generally required to have the following properties.
すなわち、 （１）可視光領域に吸収を持たな、いこと。That is, (1) Must have no absorption in the visible light region.
（２）写真製品に対して諸影響であること。(2) It has various effects on photographic products.
（３）高沸点有１ｓ溶媒に対する溶解性が高いこと。(3) High solubility in 1s solvents with high boiling points.
また、長時間の光照射の影響を抑制する目的で用いるた
めには、
（４） それ自身の光堅牢性が高いこと。In addition, in order to use it for the purpose of suppressing the effects of long-term light irradiation, (4) It must have high light fastness.
等が挙げられる。etc.
これらの紫外線吸収剤の代表的化合物は、例えば米国特
許第３，２５３，９２１号、特公昭５０−２５３３７号
、同４８−５４９１３号、同４８−４１５７２号、同５
５−１２５８７号、同５５−Ｈ９８４号、特開昭５８−
２１４１２５号に記載されている。Representative compounds of these ultraviolet absorbers are disclosed in, for example, U.S. Pat.
No. 5-12587, No. 55-H984, JP-A-58-
No. 214125.
しかしながら、これらの化合物は高温高湿条件下での保
存性が悪く、光スティンを生じやすい。However, these compounds have poor storage stability under high temperature and high humidity conditions and are prone to photo staining.
また、発色色素の褪色防止効果としても充分でないなど
の欠点を有している。Further, it has drawbacks such as an insufficient effect of preventing fading of coloring dyes.
Ｅ発明の目的〕
本発明の第１の目的は、写真製品に適用したとき、高温
高湿下においても紫外線吸収効果を失わない紫外線吸収
剤を提供することである７本発明の第２の目的は、写真
製品に適用したとき、高温高湿下でら光スティンの発生
が抑制された紫外線吸収剤を提供することである。E. Purpose of the Invention The first object of the present invention is to provide an ultraviolet absorber that does not lose its ultraviolet absorbing effect even under high temperature and high humidity conditions when applied to photographic products.7 Second object of the present invention An object of the present invention is to provide an ultraviolet absorber that suppresses the occurrence of light staining under high temperature and high humidity conditions when applied to photographic products.
本発明の第３の目的は、安定して高い紫外線吸収効果を
与えることのできる紫外線吸収剤を提供する、二とであ
る。A third object of the present invention is to provide an ultraviolet absorber that can stably provide a high ultraviolet absorption effect.
Ｅ発明の構成」
上記目的は、
支持体重に少なくとも１層のハロゲン化銀乳剤層を含む
写真構成層を有するハロゲン化銀写真感光材料において
、前記写真構成層の少なくとも１層に下記一般式［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。E. Structure of the Invention The above object is to provide a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer in the weight of the support, in which at least one of the photographic constituent layers has the following general formula [I ]
A silver halide photographic material containing at least one compound represented by:
一般式［Ｉ］
Ｈ
（式中、Ｒ３は、炭素数６以上の直５Ｘまたは２級炭素
原子を有するアルキル基を表す、Ｒ２は、炭素数５のア
ルキル基を表す。Ｒ３は、水素原子、ハロゲン原子、ア
ルキル基、アルコキシ基、アリール基を表す、）
によって達成された。General formula [I] H (wherein, R3 represents an alkyl group having a straight 5X or secondary carbon atom having 6 or more carbon atoms, R2 represents an alkyl group having 5 carbon atoms, R3 is a hydrogen atom, ), which represents a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
［発明の具体的構成］ 一般式［Ｉ］で表される化合物について説明する。[Specific structure of the invention] The compound represented by general formula [I] will be explained.
一般式［Ｉ］において、Ｒ４で表される炭素数６以上の
直鎖または２級炭素原子を有するアル≧ル基としては、
ｎ−ヘキシル基、５ｅｃ−ヘキシル基、ｎ−オクチル基
、ｉ−オクチル基、５ｅｃ＝オクチル基、２−エチルヘ
キシル基、ｎ−ドデシル基、５ｅｃ−ドデシル基、ｎ−
オクタデシル基などが挙げられる。In the general formula [I], the alkyl group having a straight chain or secondary carbon atom having 6 or more carbon atoms and represented by R4 is,
n-hexyl group, 5ec-hexyl group, n-octyl group, i-octyl group, 5ec=octyl group, 2-ethylhexyl group, n-dodecyl group, 5ec-dodecyl group, n-
Examples include octadecyl group.
これらのうちで好ましいものは、炭素数８〜１２の根元
２級炭素原子を有するアルキル基である。Among these, preferred is an alkyl group having a secondary carbon atom at the base of 8 to 12 carbon atoms.
Ｒ２で表される炭素数５のアルキル基は、直鎖でもまた
分岐のあるものでもよい。The alkyl group having 5 carbon atoms represented by R2 may be linear or branched.
これらのうちで好ましいものは、分岐のアルキル基であ
る。Preferred among these are branched alkyl groups.
Ｒ３は、水素原子、ハロゲン原子、アルキル基、アルコ
キシ基、アリール基を表す。R3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.
アルキル基としては、例えばメチル基、エチル基、ｎ−
ブチル基、５ｅＣ−ブチル基が挙げられる。Examples of the alkyl group include methyl group, ethyl group, n-
Examples include butyl group and 5eC-butyl group.
アルコキシ基としては、例えばメトキシ基、エトキシ基
が挙げられる。Examples of the alkoxy group include a methoxy group and an ethoxy group.
アリール基としては、例えばフェニル基、トリル基、ナ
フチル基が挙げられる。Examples of the aryl group include phenyl group, tolyl group, and naphthyl group.
これらのうちで好ましいものは水素原子である。Among these, hydrogen atoms are preferred.
上記アルキル基、アルコキシ基、アリール基には、置換
基を有するものも含まれる。The above alkyl groups, alkoxy groups, and aryl groups include those having substituents.
以下に本発明の具体的な化合物例を示すが、本発明の化
合物はこれらに画定されるものではない。Specific examples of compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.
以下余白
以下余白
以下に、本発明に係る一般式ロエ］で表される化合物の
代表的な合成法を示すか、他の化合物も同様の方法によ
り合成することか出来る。Below, in the space below, a typical method for synthesizing the compound represented by the general formula Loe according to the present invention will be shown, or other compounds can be synthesized by similar methods.
例示化合物４の合成
Ｏ−ニトロアニリン ６９ｇを氷５００ｆ、Ｊ塩酸２５
０ｇおよび亜硝酸ナトリウム ３５ｇを用いてジアゾ化
した。このジアゾニウム塩Ｂ’ＲをＯ〜５ ”Ｃでかき
まぜなから氷３５００ ｇ、２−ｓ−オクチル−４−し
−アミルフェノール１４６ｇ、苛性ソーダ２２ｇ、炭酸
ソーダ２５０ｇからなる溶液に加えた。析出した赤色油
状物を分離し、メタノールＳＯＯ、に溶解し、４０％苛
性ソーダ水溶液２５０ｇと亜鉛末１５０ｇを加え、かき
まぜながら加熱し、赤色が消えるまで加熱還流した。−
過後、酢酸を加え、析出した油状物をヘキサンで抽出し
、ヘキサン留去ｆ＆、残渣をカラムクロマトグラフィー
にかけ、目的物 ４７ｆを得た。Synthesis of Exemplified Compound 4 69 g of O-nitroaniline, 500 g of ice, 25 J hydrochloric acid
Diazotization was carried out using 0 g and 35 g of sodium nitrite. This diazonium salt B'R was stirred at O~5''C and then added to a solution consisting of 3500 g of ice, 146 g of 2-s-octyl-4-amylphenol, 22 g of caustic soda, and 250 g of soda carbonate. The oil was separated and dissolved in methanol SOO, and 250 g of a 40% aqueous sodium hydroxide solution and 150 g of zinc dust were added, heated while stirring, and heated under reflux until the red color disappeared.
After evaporation, acetic acid was added, the precipitated oil was extracted with hexane, the hexane was distilled off, and the residue was subjected to column chromatography to obtain the desired product 47f.
構造は、ｒＲ，ＦＤマススペクトル及びＮＭＲで同定し
た。The structure was identified by rR, FD mass spectra and NMR.
その他の化合物についても対応するフェノールを原料と
して同様の方法で合成した。Other compounds were synthesized in the same manner using the corresponding phenols as raw materials.
本発明に係る一般式［Ｉ］で表される化合物は、種々の
方法で本発明の怒光材料に含有せしめることかできるが
、乳化分散物として用いるのが好ましい。Although the compound represented by the general formula [I] according to the present invention can be incorporated into the light-emitting material of the present invention by various methods, it is preferably used as an emulsified dispersion.
本発明に係る一般式［Ｉ］で表される化合物の乳化分散
物を得るには写真業界にて一般的に用いられている方法
を用いることができ、例えば米国特許第２，３２２，０
２７号、同第２，８０１，１７０号、同第２゜８０１、
１７１号、同第２，８７０，０１２号および同第２，９
９１゜１７７号の各明細書に記載されているカプラーの
分散物の調製に準じればよい。In order to obtain an emulsified dispersion of the compound represented by the general formula [I] according to the present invention, methods commonly used in the photographic industry can be used, such as U.S. Patent No. 2,322,0
No. 27, No. 2,801,170, No. 2゜801,
No. 171, No. 2,870,012 and No. 2,9
The preparation of the coupler dispersion described in each specification of No. 91°177 may be followed.
すなわち、本発明に係る化合物を、沸点約１７５°Ｃ以
上の高沸点有機溶媒に、必要に応じて沸点約１５０°Ｃ
以下の低沸点有機溶媒を併用して溶解し、ゼラチン水溶
液などの親水性バインダー中に界面活性剤を用いて微分
散して乳化分散物を得る。That is, the compound according to the present invention is added to a high boiling point organic solvent having a boiling point of about 175°C or higher, and if necessary, a boiling point of about 150°C.
The following low boiling point organic solvents are used in combination to dissolve and finely disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant to obtain an emulsified dispersion.
より具体的に説明するならば、高沸点有機溶媒としては
有機酸アミド類、カルバメート類、エステル類、ケトン
類、高級アルコール類、尿素誘導体等から選ぶことがで
きる。More specifically, the high-boiling organic solvent can be selected from organic acid amides, carbamates, esters, ketones, higher alcohols, urea derivatives, and the like.
なお、乳化分散物中の上記一般式［Ｉ］で示される紫外
線吸収剤の混合物の含有量は、セラチンに対し、１〜２
０ （ｈｖｔ％、より好ましくは１０〜ｉｏ。In addition, the content of the mixture of ultraviolet absorbers represented by the above general formula [I] in the emulsified dispersion is 1 to 2% with respect to seratin.
0 (hvt%, more preferably 10-io.
＋、ｖｔ％である。+, vt%.
また、高沸点溶媒は、紫外線吸収剤に対し、１０〜３０
０１１ｖｔ％、より好ましくは３０〜１００＋、ｖｔ％
で用いられ、さらに低沸点溶媒は、紫外線吸収剤に対し
、５０〜１ｏｏｏｖｔ％で用いられることが好ましい。In addition, the high boiling point solvent is 10 to 30% relative to the ultraviolet absorber.
011vt%, more preferably 30-100+, vt%
The low boiling point solvent is preferably used in an amount of 50 to 1 ooovt% based on the ultraviolet absorber.
上記乳化分散物中には、必要に応じて、一般式［Ｉ］で
示される化合物以外の紫外線吸収剤、混色防止剤、発色
色素形成カプラー、現像と同時に抑制剤を放出するいわ
ゆるＤＩＲカプラー、色調調整剤等の疎水性有機化合物
を添加してもよい。The emulsified dispersion may contain, if necessary, an ultraviolet absorber other than the compound represented by the general formula [I], a color mixing inhibitor, a coloring dye-forming coupler, a so-called DIR coupler that releases an inhibitor at the same time as development, and a color tone Hydrophobic organic compounds such as regulators may be added.
上記の発色色素形成カプラーは、イエロー、マゼンタ及
びシアン染料形成タイプのものを包含する。The chromogenic dye-forming couplers mentioned above include yellow, magenta and cyan dye-forming types.
これらのカプラーは、例えば米国特許３．２７７、１５
５号および同３，４５８，３１５号明細書に記載されて
いるような、いわゆる４当量型のもの、またはカップリ
ング位がカップリング反応時に離脱することのできる宣
換基（スズリットオフ基）で置換されている２当量型の
ものであってもよい。These couplers are described, for example, in U.S. Pat.
No. 5 and No. 3,458,315, so-called 4-equivalent type, or substituted with a declarative group (tin-off group) whose coupling position can be removed during the coupling reaction. It may also be of the 2-equivalent type.
本発明において好ましいイエロー色素形成カプラーとし
ては、ベンゾイルアセトアニリド型、ピバロイルアセト
アニリド型カプラーがあり、マゼンタ色素形成カプラー
としては、５−ピラゾロン系、ピラゾロトリアゾール系
、イミダゾピラゾール系、ピラゾロピラゾール系、ピラ
ゾロテトラゾール系、ピラゾリノベンツイミダゾール系
、インダシロン系カプラーがあり、シアン色素形成カプ
ラーとしては、フェノール系、ナフトール系、ピラゾロ
キナゾロン系カプラーがある。Preferred yellow dye-forming couplers in the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta dye-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type, pyrazolopyrazole type, There are pyrazolotetrazole-based, pyrazolinobenzimidazole-based, and indasilone-based couplers, and cyan dye-forming couplers include phenol-based, naphthol-based, and pyrazoloquinazolone-based couplers.
これらのイエロー、マゼンタおよびシアン色素形成カプ
ラーの各具体例は、写真業界において公知であり、本発
明においては、これら公知のすべてのカプラーを用いる
ことができる。Specific examples of these yellow, magenta, and cyan dye-forming couplers are known in the photographic industry, and all of these known couplers can be used in the present invention.
次にイエローカプラーの代表的具体例を挙げる。Next, typical examples of yellow couplers will be given.
ｊ
＼
Ｉ
＼
ＣＩ
ＣＩ
これらのイエローカプラーは、例えば***公開特許２，
０５７，９４１号、同２，１６３，８１２号、特開昭４
７−２６１３３号、同４８− ２９４３２号、同５０−
６５３２４号、同５１−３６３１号、同５１− ５０
７３４号、同５１− １０２６３６号、同４８− ６６
８３５号、同４８− ９４４３２号、同４９− １２２
９号、同４９− １０７３６号、特公昭５１− ３３４
１０号、同５２−２５７３３号等に記載されている化合
物を含み、かつ、これらに記載されている方法に従って
合成することができる。j \ I \ CI CI These yellow couplers are described in, for example, West German Published Patent Application No. 2,
No. 057,941, No. 2,163,812, Japanese Unexamined Patent Publication No. 4
No. 7-26133, No. 48-29432, No. 50-
No. 65324, No. 51-3631, No. 51-50
No. 734, No. 51-102636, No. 48-66
No. 835, No. 48-94432, No. 49-122
No. 9, No. 49-10736, Special Publication No. 51-334
10, No. 52-25733, etc., and can be synthesized according to the methods described therein.
次にマゼンタカプラーの代表的具体例を挙げる。Next, a typical example of a magenta coupler will be given.
以下余白 ＣＩ ＣＩ ＣＩ ｌ Ｃ２Ｈ。Margin below C.I. C.I. C.I. l C2H.
Ｈ３
Ｍ−８
ＣＩＩｌ（１）（１＋
４Ｈｓ
Ｃｓｌ（Ｉ７ｆｔ）
Ｉ
ｊ
Ｉ
Ｉ
Ｉ
これらのマゼンタカプラーは、例えば米国特許３．６８
４，５１４号、英国特許１，１８３，５１５号、特公昭
４０−６０３１号、同４０−６０３５号、同４４−１５
７５４号、同４５−４０７５７号、同４６−１９０３２
号、特開昭５０−１３０４４号、同５．３−１２９０３
５号、同５１−３７６４６号、同５５−６２４５４号、
米国特許３．７２５，０６７号、英国特許１，２５２゜
４１８号、同１，３３４，５１５号、特開昭５９−１７
１９５６号、同５９−１６２５４８号、同５ｏ−４３６
ｓｑ号、同６０−３３５５２号、リサーチ・ディスクロ
ージャーＮｏ２４６２６ ＜ １９８４）、特許“昭５
９−２４３００７号、同５９−２４３００８号、同５９
−２４３００９号、同５９−２４３０１２号、同６０−
７０１９７号、同６０−７０１９８号等に記載されてい
る化合物を含み、かつ、これらに記載されている方法に
従って合成することができる。H3 M-8 CIIl(1)(1+ 4Hs Csl(I7ft) I j I I I These magenta couplers are described, for example, in U.S. Pat.
No. 4,514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15
No. 754, No. 45-40757, No. 46-19032
No., JP-A-50-13044, JP-A No. 5.3-12903
No. 5, No. 51-37646, No. 55-62454,
U.S. Patent No. 3,725,067, British Patent No. 1,252゜418, British Patent No. 1,334,515, JP-A-59-17
No. 1956, No. 59-162548, No. 5o-436
sq No. 60-33552, Research Disclosure No. 24626 < 1984), patent “Sho 5
No. 9-243007, No. 59-243008, No. 59
-243009, 59-243012, 60-
No. 70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.
また、シアンカプラーについては特に制限はないが、フ
ェノール系シアンカプラーであることが好ましい。Furthermore, there are no particular limitations on the cyan coupler, but a phenolic cyan coupler is preferred.
シアンカプラーの代表的具体例を挙げる。A typical example of a cyan coupler is given below.
以下余白
ＣｓＨ＋ １ｆｔ）
Ｉ
Ｉ
Ｉ
Ｈ
Ｃ−５
Ｃ２Ｈｓ
これらのシアンカプラーは、例えば米国特許２゜４２３
、７３０号、同２，８０１，１７１号、特開昭５０−１
１２０３８号、同５０−１３４６４４号、同５３−１０
９６３０号、同５４−５５３８０号、同５６−６５１３
４号、同５６−８００４５号、同５７−１５５５３８号
、同５７−２０４５４５号、同５８−９８７３１号、同
５９−３１９５３号等に記載されている化合物を含み、
かつ、これらに記載されている方法に従って合成できる
。Below margin CsH+ 1ft) I I I H C-5 C2Hs These cyan couplers are disclosed in, for example, U.S. Pat.
, No. 730, No. 2,801,171, Japanese Unexamined Patent Publication No. 1973-1
No. 12038, No. 50-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
4, No. 56-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc.,
And, it can be synthesized according to the methods described therein.
本発明の方法において用いられる写真感光材料において
、ハロゲン化銀乳剤は一般に親水性コロイド中にハロゲ
ン化銀粒子を分散したものであり、ハロゲン化銀として
は塩化銀、臭化銀、沃化銀、塩臭化銀、沃臭化銀、塩沃
臭化銀およびこれらの混合物である。In the photographic light-sensitive material used in the method of the present invention, the silver halide emulsion is generally one in which silver halide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver iodide, Silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.
実施例１
表−１に示した層構成のカラー印画紙において、層４及
び層６の紫外線吸収剤を表−２に示すように変化させて
試料１〜７を作成した。Example 1 Samples 1 to 7 were prepared by using color photographic paper having the layer structure shown in Table 1, and changing the ultraviolet absorbers in layers 4 and 6 as shown in Table 2.
ハロゲン化銀としては、塩臭化銀（塩化銀２０モル％）
を用いた。As silver halide, silver chlorobromide (silver chloride 20 mol%)
was used.
ここで用いたカプラー（Ａ）、ＣＢ）、（Ｃ）、（Ｃ′
）、混色防止剤（Ｄ）、色素画像安定剤（Ｅ）、（Ｆ）
、（Ｇ）、高沸点有機溶媒（ＨＢＳ−１）、（ＨＢＳ−
２＞および比較化合′＠１．２の化学構造式を以下に示
す。Couplers used here (A), CB), (C), (C'
), color mixing inhibitor (D), dye image stabilizer (E), (F)
, (G), high boiling point organic solvent (HBS-1), (HBS-
2> and comparative compound '@1.2 are shown below.
なお、上記において各成分の量は■／１００ａａである
。In addition, in the above, the amount of each component is 1/100aa.
以下余白
カプラー（Ａ）
カプラー（Ｂ）
カプラー（Ｃ′）
混色防止剤＜Ｄ）
Ｈ
Ｈ
色素画像安定剤（Ｅ）
色素画像安定剤（Ｆ）
ＱＣｓ）Ｉ＋７（ｎ）
色素画像安定剤（Ｇ）
高沸点有機溶媒（ＨＢＳ−４）
Ｈ３
□
高沸点有機溶媒（ＨＢＳ−２）
２ＨＳ
ノ
２Ｈ５
比較化合物１（特開昭５１２１５３７８号記載の化合物
）Ｈ
Ｃ５）Ｉ、 ｌ （ｔ）
比較化合物２（米国特許４，３８３，８６３号記載の化
合物）Ｈ
以上のようにして作成した試料１〜７を、未露光で、ま
た、感光計（コニカ株式会社製ＫＳ−７型）を使用して
、青色光、緑色光、赤色光のそれぞれを光楔を通して露
光し、下記の処理工程に従って処理を行い、未発色試料
と、三色分解試料（黄色、マゼンタ、シアン）を得た。The following margin coupler (A) Coupler (B) Coupler (C') Color mixing inhibitor <D) H H Dye image stabilizer (E) Dye image stabilizer (F) QCs) I+7 (n) Dye image stabilizer (G) High boiling point organic solvent (HBS-4) H3 □ High boiling point organic solvent (HBS-2) 2HS No. 2H5 Comparative compound 1 (compound described in JP-A-51215378) H C5) I, l (t) Comparative compound 2 (U.S. Compound described in Patent No. 4,383,863) H Samples 1 to 7 prepared as above were exposed to blue light using a sensitometer (Konica Corporation Model KS-7) without exposure to light. , green light, and red light through a light wedge and processed according to the following processing steps to obtain an uncolored sample and a three-color separated sample (yellow, magenta, cyan).
〈処理工程〉
処理時間 処理温度
発色現像 ３．５分 ３３°Ｃ漂白
定着 １．５分 ３３°Ｃ水
洗 ３分 ３３゛ｃ乾
燥 ８
０”Ｃく発色現像液組成〉
純水 ７００ ｍｌベ
ンジルアルコール １５ｏａｌジエチ
レングリコール １５０１１ヒドロキシ
ルアミン硫酸塩 ２ｇＮ−エチル−Ｎ−β
−メタン
スルホンアミドエチル−３−
メチル−４−アミンアニリン硫酸塩 ４．４ｇ炭酸カリ
ウム ３０ｇ臭化カリウム
０．４を塩化カリウム
０．５ｇ亜硫酸カリウム
２ｇ純水を加えて１１とする。（ｐ Ｈ＝
１０．２）く漂白定着液組成〉
漂白定着液１工中、
エチレンジアミンテトラ酢酸第２秩
アンモニウム ６１゜エチレ
ンジアミンテトラ酢酸２
アンモニウム ５ｇ千オ硫酸
アンモニウム １２５ｇメタ重亜硫酸ナ
トリウム １３ｇ−亜硫酸ナトリウム
２７ｇを含有、
（ｐＨ−７，２）次いで、得られた各試料について、３
０°Ｃｌ２ｏ％ＲＨと５０°Ｃｌ８ｏ％ＲＨとの雲囲気
下、キセノン光による光褪色試験を行い、光堅牢性およ
び光スティンを評価した。<Processing process> Processing time Processing temperature Color development 3.5 minutes 33°C bleach fixing 1.5 minutes 33°C water
Wash 3 minutes, dry at 33°C 8
0"C color developing solution composition> Pure water 700 ml Benzyl alcohol 15 oal diethylene glycol 15011 hydroxylamine sulfate 2 g N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.4g Potassium carbonate 30g Potassium bromide
0.4 potassium chloride
0.5g potassium sulfite
Add 2g of pure water to make 11. (pH=
10.2) Bleach-fix solution composition> In one process of bleach-fix solution, 61° diammonium ethylenediaminetetraacetate 5g ammonium 1000sulfate 125g sodium metabisulfite 13g - sodium sulfite
Contains 27g,
(pH-7,2) Then, for each sample obtained, 3
A photofading test using xenon light was conducted under a cloud atmosphere of 0°Cl2o%RH and 50°Cl8o%RH to evaluate light fastness and light stain.
光堅牢・闇の尺度としては、色素残存率を用い、曝射前
反射濃度１．０に対する曝射後反射濃度の百分率を算出
した。この場合、白地部分の、曝射による黄変（光ステ
ィン）が影響するもの（特に黄色発色試料）においては
、その分を差し引いて曝射後の濃度とした９例えば、曝
射前、白地濃度０．００、黄色色素濃度１．００に調整
した場合、曝射後の白地濃度が０．１８、黄色色素濃度
が０．７８であれば、色素残存率は、
とした。As a measure of light fastness/darkness, the dye residual rate was used, and the percentage of the reflection density after exposure to the reflection density before exposure of 1.0 was calculated. In this case, if the yellowing (photostain) of the white background area due to exposure is affected (particularly yellow colored samples), that amount is subtracted to obtain the concentration after exposure.9For example, the white background density before exposure, 0.00, and when the yellow dye density was adjusted to 1.00, if the white background density after exposure was 0.18 and the yellow dye density was 0.78, the dye residual rate was as follows.
また、曝射後の白地濃度を光スティンとして表示した。In addition, the white background density after exposure was expressed as a light stain.
なお、上記の例では０．１８である。Note that in the above example, it is 0.18.
結果を表−２に示す、なお、表−２にはこの光スティン
の相対値が併記される６
以下余白
表−２の結果より、従来技術に係る紫外線吸収剤を適用
した試料１〜２においては、高温高温条件下で黄色、マ
ゼンタおよびシアン色素の光堅牢性の劣化と光スティン
の増加を生じている。The results are shown in Table 2. Table 2 also includes the relative values of this light stain.6 From the results in Table 2 below, it can be seen that in Samples 1 and 2 to which the conventional ultraviolet absorber was applied, has resulted in a deterioration of the light fastness of yellow, magenta and cyan dyes and an increase in light staining under high temperature conditions.
しかし、本発明に係る紫外線吸収剤を適用した試料３〜
７においては、高温高湿下でも常温低湿条件に比べて殆
ど色素の光堅牢性に影響を及ぼしていない。これは紫外
線吸収剤含有塗膜中の紫外線吸収剤が極めて安定に保持
されているためと考えられる。また、高温高温条件下は
もとより常温低湿条件内で比較してみても本発明に係る
試料３〜７の光スティンはかなり抑制されており、紫外
線吸収効果を有効に発揮していることがわかった。However, samples 3 to 3 to which the ultraviolet absorber according to the present invention was applied
In No. 7, even under high temperature and high humidity conditions, the light fastness of the dye was hardly affected compared to under normal temperature and low humidity conditions. This is thought to be because the ultraviolet absorber in the ultraviolet absorber-containing coating film is retained extremely stably. In addition, even when compared under high temperature and high temperature conditions as well as under normal temperature and low humidity conditions, the light staining of Samples 3 to 7 according to the present invention was considerably suppressed, indicating that they effectively exerted their ultraviolet absorption effects. .
実施例２
実施例１に使用した各ハロゲン化銀乳剤に代えて塩化銀
９９．５モル％の塩臭化銀乳剤を使用し、層４及び層６
の紫外線吸収剤を表−３に示す様に変化させた以外は実
施例１の試料１と同様にして試料８〜１３を作製した。Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and layers 4 and 6 were
Samples 8 to 13 were prepared in the same manner as Sample 1 of Example 1 except that the ultraviolet absorber was changed as shown in Table 3.
試ｆ１８〜１３を常法に従って光楔露光後、以下に示す
処理を行った。Samples f18 to f13 were subjected to light wedge exposure according to a conventional method, and then subjected to the following processing.
く処理工程〉
処理温度 処理時間
発色環＠ ３４．７±０．３°Ｃ４５秒漂白定着
３４，７±０．５°Ｃ４５秒安定化 ３０〜３４°
Ｃ９０秒
乾 燥 ６０〜８０°Ｃ６０秒〔発色現像液
〕
純水 ８００ｍ１トリ
エタノールアミン ８ｇＮ、Ｎ−ジエ
チルヒドロキシアミン ５ｇ塩化カリウム
２ｇＮ−エチル−Ｎ−β−メタンス
ルホン
アミドエチル−３−メチル−４−
アミンアニリン硫酸塩 ５ｇテトラポ
リリン酸ナトリウム ２ｇ炭酸カリウム
３０ｆ亜硫酸カリウム
０．２ｇ螢光増白剤（４，４’−ジアミ
ノ
スチルベンジスルホン酸誘導体）１ｇ：純水を加えて全
量を１ｊとし、ｐＨ１０，２に調整する。Processing process> Processing temperature Processing time Color development ring @ 34.7 ± 0.3°C 45 seconds Bleach fixing
34,7±0.5°C 45 seconds stabilization 30~34°
Dry at C for 90 seconds 60-80°C for 60 seconds [Color developer] Pure water 800 ml Triethanolamine 8 g N, N-diethylhydroxyamine 5 g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30f potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g: Add pure water to bring the total amount to 1j, and adjust the pH to 10.2.
［漂白定着液］
漂白定着液１１中、
エチレンジアミンテトラ酢酸第２鉄
アンモニウム２水塩 ６０ｇエチレ
ンジアミンテトラ酢ｕ ３ｆチオ流酸ア
ンモニウム（７０％溶液） １００［＋１１亜Ｆ
ａ酸アンモニウム（４０％溶液） ２７．５ｍ＋
を含有、炭酸カリウムスは氷酢酸でＰＨ５，７に調整す
る。[Bleach-fix solution] In bleach-fix solution 11, 60 g ethylenediaminetetraacetic acid ferric ammonium dihydrate U 3f ammonium thiosulfate (70% solution) 100 [+11 F
Ammonium a-acid (40% solution) 27.5m+
Contains potassium carbonate, adjusted to pH 5.7 with glacial acetic acid.
「安定化液」
安定化液１」中、
５−り四ロー２−メチル−４−
インチアゾリン−３−オン １ｆ１−ヒド
ロキシエチリデン−１゜
１−ジホスホン酸 ２ｇを含有
、硫酸又は水酸化カリウムにてｐＨを７．０に調整する
。"Stabilizing liquid" Stabilizing liquid 1 contains 2 g of 5-ri-4-2-methyl-4-inthiazolin-3-one 1f1-hydroxyethylidene-1゜1-diphosphonic acid, which is mixed with sulfuric acid or potassium hydroxide. Adjust the pH to 7.0.
処理後の各試料を実施例１と同様にし評価しな。Each sample after treatment was evaluated in the same manner as in Example 1.
その結果を表−３に示す。The results are shown in Table-3.
表−３の結果より、実施例１と同様、本発明に帥る紫外
線吸収剤を適用した試料１０〜１３においては、高温高
湿下でも常温低湿条件に比べて殆ど色素の光堅牢性に影
響を及ぼしていない。これは紫外線吸収剤含有塗膜中の
紫外線吸収剤が極めて安定に保持されているためと考え
られる。また、高温高温条件下はもとより常温低湿条件
内で比較してみても本発明に係る試料１０〜１３の光ス
ティンはかなり抑制されており、紫外線吸収効果を有効
に発揮していることがわかった。From the results in Table 3, as in Example 1, in Samples 10 to 13 to which the ultraviolet absorber of the present invention was applied, even under high temperature and high humidity conditions, there was almost no effect on the light fastness of the dye compared to under normal temperature and low humidity conditions. It has not affected. This is thought to be because the ultraviolet absorber in the ultraviolet absorber-containing coating film is retained extremely stably. Furthermore, even when compared under high temperature and high temperature conditions as well as under room temperature and low humidity conditions, the light staining of Samples 10 to 13 according to the present invention was considerably suppressed, indicating that they effectively exerted their ultraviolet absorption effects. .
また析出・注もなく、分散安定性も良好であった。Further, there was no precipitation or dispersion, and the dispersion stability was good.
［発明の効果コ
本発明の紫外線吸収剤を用いたハロゲン化銀カラー写真
感光材料は、高温高温条件下においてら紫外線吸収効果
を失わず、かつ、光スティンの発生が抑制され、また、
安定した高い紫外線吸収効果か与えられるという効果を
奏する。[Effects of the Invention] The silver halide color photographic light-sensitive material using the ultraviolet absorber of the present invention does not lose its ultraviolet absorption effect even under high temperature conditions, and the generation of light stain is suppressed, and
It has the effect of providing a stable and high ultraviolet absorption effect.
Claims (1)
写真構成層を有するハロゲン化銀写真感光材料において
、前記写真構成層の少なくとも１層に下記一般式［ 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、炭素数６以上の直鎖または２級炭素
原子を有するアルキル基を表す。Ｒ＿２は、炭素数５の
アルキル基を表す。Ｒ＿３は、水素原子、ハロゲン原子
、アルキル基、アルコキシ基、アリール基を表す。）[Scope of Claims] In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the photographic constituent layers has the following general formula [I
A silver halide photographic material containing at least one compound represented by the following. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. (R_3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13725688A JPH01306842A (en) | 1988-06-06 | 1988-06-06 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13725688A JPH01306842A (en) | 1988-06-06 | 1988-06-06 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01306842A true JPH01306842A (en) | 1989-12-11 |
Family
ID=15194412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13725688A Pending JPH01306842A (en) | 1988-06-06 | 1988-06-06 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01306842A (en) |
-
1988
- 1988-06-06 JP JP13725688A patent/JPH01306842A/en active Pending
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