US3655389A - Color photographic light-sensitive material containing silver occlusion preventing agent - Google Patents
Color photographic light-sensitive material containing silver occlusion preventing agent Download PDFInfo
- Publication number
- US3655389A US3655389A US74521A US3655389DA US3655389A US 3655389 A US3655389 A US 3655389A US 74521 A US74521 A US 74521A US 3655389D A US3655389D A US 3655389DA US 3655389 A US3655389 A US 3655389A
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- US
- United States
- Prior art keywords
- copolymer
- sensitive material
- color photographic
- photographic light
- vinylpyrrolidone
- 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.)
- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 title abstract description 28
- 239000004332 silver Substances 0.000 title abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 23
- 239000003795 chemical substances by application Substances 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 74
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 30
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 9
- DWDJKTWRXOGHOS-UHFFFAOYSA-N 2-acetamidoethyl prop-2-enoate Chemical compound CC(=O)NCCOC(=O)C=C DWDJKTWRXOGHOS-UHFFFAOYSA-N 0.000 claims description 7
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 claims description 5
- SKPWGBMKZNVXFF-UHFFFAOYSA-N 2-acetamidoethyl acetate Chemical compound CC(=O)NCCOC(C)=O SKPWGBMKZNVXFF-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 9
- -1 silver halide Chemical class 0.000 abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 20
- 230000003287 optical effect Effects 0.000 description 13
- 238000004061 bleaching Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229940050271 potassium alum Drugs 0.000 description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102100040996 Cochlin Human genes 0.000 description 1
- 101000748988 Homo sapiens Cochlin Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical group O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/396—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
Definitions
- a color photographic silver halide light-sensitive material comprising a support having a silver halide light-sensitive emulsion layer thereon wherein a copolymer is incorporated in said light-sensitive emulsion layer or a non-light-sensitive auxiliary layer on said support, said copolymer being represented by the following formula:
- R represents hydrogen or methyl
- R represents hydrogen, methyl, ethyl, propyl or butyl
- R represents hydrogen, methyl, ethyl, propyl or butyl
- x/y varies from 95/5 to 20/80.
- This invention relates to a color photographic light-sensitive material. More particularly, it relates to a color photographic light-sensitive material of improved silver bleaching property.
- a color photographic light-sensitive material When a color photographic light-sensitive material is subjected to exposure and then to color development, a color image and a silver image are formed. The silver image is then removed by a silver bleaching treatment and a fixing treatment, thus obtaining only a dye image. If the step of silver bleaching is incomplete, however, a part of the silver image remains in the material. Such an occluded silver cloud makes the color photographic image obscure and remarkably degrades the color reproduction.
- Some methods have been proposed in order to improve the silver bleaching property. It is well known to incorporate some compounds in a color photographic light-sensitive material for the purpose of preventing such silver occlusion.
- a polymer containing vinylpyrrolidone is described as a silver occlusion inhibitor in British Pat. No. 1,052,487.
- the compound described in this patent has the disadvantage that the development of exposed silver halide grains is markedly suppressed so that a long time is necessary for development, although it has an effect of improving the silver removal.
- the above-mentioned object can be accomplished by incorporating in a color photographic light-sensitive material a copolymer of 2-(N-acyl)aminoethyl acrylate or 2-(N- acyl)aminoethyl methacrylate and N-vinylpyrrolidone.
- the non-lightsensitive auxiliary layer is a layer adjacent to the light-sensitive emulsion layer, for example, a protective layer, an intermediate layer, a filter layer or antihalation layer.
- the effect of the copolymer of N-vinylpyrrolidone and 2- (N-acyl) aminoethyl acrylate or 2-(N-acyl)aminoethyl methacrylate depends on its monomer ratio.
- the effect of improving the silver removing property increases with an in crease in the amount (y) of N-vinylpyrrolidone, whereas the development suppressing property decreases with the decrease of (y).
- acopolymer having an x/y ratio of /5 to 20/80, in particular 90/10 to 40/60, is preferably used.
- the effect of the copolymer-of the present invention is substantially independent from the degree of polymerization of the copolymer. Therefore, any copolymer capable of being dissolved or dispersed in colloidal state in water or aqueous alkaline solution can be used independently of its degree of polymerization.
- the copolymer of the present invention represented by the formula (I), is obtained by polymerizing, in a solvent, vinylpyrrolidone and a monomer represented by the formula:
- a suitable solvent is water or dimethylformamide.
- Potassium persulfate, hydrogen peroxide or azobisisobutyronitrile may be used as a polymerization initiator.
- isopropanol may be used so as to control the degree of polymerization.
- Synthesis of a monomer represented by formula (II) may be carried out by the reaction of (l) 2-(N-acyl)aminoethyl alcohol with acrylic acid or methacrylic acid, (2) the alcohol with acrylic chloride or methacrylic chloride, (3) the alcohol with ,B-propiolactone or (4) the alcohol with acrylic acid ester or methacrylic acid ester.
- Synthetic Example 1 a Synthesis of 2-(N-formyl-N-methyl)aminoethyl acrylate 52 g of 2-(N-formyl-N-methyl)aminoethyl alcohol was charged into a flask of 500 ml equipped with a stirrer with g of triethylamine, 200 ml of acetone and 1.5 g of hydroquinone as a polymerization inhibitor and, while keeping the temperature at 5 C. and stirring, 46 g of acrylic chloride was dropwise added. After the reaction, the salt was removed and l g of hydroquinone was added followed by distillation. The compound obtained had the following structure which was identified by elementary analysis, NMR, mass spectrometry and infrared spectrum.
- the quantity to be added of the copolymer used in the present invention depends on its properties, the variety of layers into which it is added and, the variety and quantity of the coupler and other additives.
- good results can generally be obtained by employing about 5 percent by weight of the copolymer based on the weight of the binder. Ordinarily, 1-5 percent by weight is preferred since the color-forming efficiency and physical properties of the layer decrease when the addition quantity exceeds 20 percent by weight.
- the copolymer of the present invention may be added to a dispersion during the dispersing of the coupler or it may be added with other additives during the preparation of a coating solution.
- a suitable protective colloid may be used, for example, gelatin, polyvinyl alcohol or its derivative, polyacrylamide or its derivative, cellulose derivative, casein or alginate. Gelatin is most suitable.
- Color development solution sodium hexametaphosphate 2 g. sodium sult'tte (anhydrous) 4 gv Z-methyl-4-N, N-diethylaniline sulfate 3 g. sodium carbonate (monohydrate) 20 g. potassium bromide 2 g. water to make I liter Fixing solution sodium thiosulfate (anhydrous) 153 g. sodium sulfite (anhydrous) l5 g. acetic acid 48 g. boric acid 7.5 g. potassium alum l5 g. water to make 1 liter Bleaching solution potassium bromide 20 g. potassium bichromate 5 g. potassium alum 40 g.
- EXAMPLE 2 The same procedure as in Example l was repeated except that 4.3 g of l-(2,4,6-trichlorophenyl)-3-(3-(N-butyltetradecaneamide)-propaneamide) pyrazoline-S-on was used as a magenta coupler in place of the yellow coupler of Example l and a copolymer of 2-(N-formyl-N-methyl)-aminoethyl methacrylate and N-vinylpyrrolidone (monomer ratio: 6 4) was used as the copolymer.
- a color image of magenta was present together with a cloud of silver and was considerably obscure.
- the optical density of the two films was measured by a red light substantially free from absorption of the color image of magenta.
- the film containing no copolymer gives a high optical density due to the absorption of silver.
- Example 2 The same procedure as in Example 1 was repeated except that 2.4 g of l-hydroxy-4-chlor -2-N-dodecylnaphthamide was used as a cyan coupler in place of the yellow coupler of Example 1 and a copolymer of 2-(N-formyl-N- methyl)aminoethyl acrylate and N-vinylpyrrolidone(monomer ratio: 6 4) was used as the copolymer.
- a color image of cyan was present together with a cloud of silver and was considerably obscure.
- the optical density of the two films was measured by a blue light substantially free from absorption of the color image of cyan. As is evident from the results shown in Table 3, the film containing no copolymer gives a high optical density due to the absorption of silver.
- R represents hydrogen or methyl
- R represents hydrogen, methyl, ethyl, propyl or butyl
- R represents hydrogen, methyl, ethyl, propyl or butyl
- x/y varies from /5 to 20/80.
- the color photographic light-sensitive material as A rolidone of a monomer ratio of 6 4.
- copolymer is a copolymer of 2-(N-forrnyl-N-methyl)aminoethyl methacrylate and N-vinylpyrrolidone of a monomer ratio of 6 4.
- copolymer is a copolymer of 2-(N-acetyl)amino-ethyl acrylate and N-vinylpyrrolidone of a monomer ration of 8 2.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
WHEREIN R1 represents hydrogen or methyl, R2 represents hydrogen, methyl, ethyl, propyl or butyl, R3 represents hydrogen, methyl, ethyl, propyl and x/y varies from 95/5 to 20/80.
A color photographic silver halide light-sensitive material comprising a support having a silver halide light-sensitive emulsion layer thereon wherein a copolymer is incorporated in said light-sensitive emulsion layer or a non-light-sensitive auxiliary layer on said support, said copolymer being represented by the following formula:
A color photographic silver halide light-sensitive material comprising a support having a silver halide light-sensitive emulsion layer thereon wherein a copolymer is incorporated in said light-sensitive emulsion layer or a non-light-sensitive auxiliary layer on said support, said copolymer being represented by the following formula:
Description
United States Patent Yasuda et al.
[151 3,655,389 [4 1 Apr. 11, 1972 [72] Inventors: Yukio Yasuda; Nobuo Tsuji; Takushi Miyazako, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd., Kanagawa,
Japan [22] Filed: Sept. 22, 1970 [2]] Appl. No.: 74,521
[30] Foreign Application Priority Data Sept, 22, 1969 Japan ..44/75465 [52] U.S. Cl ..96/100, 96/114 [51] Int. Cl ..G03c H40 [58] Field ofSearch ..96/114, 100
[56] References Cited UNITED STATES PATENTS 2,495,918 1/1950 Bolton ..96/114 3,360,373 12/1967 Shaller et al ..96/114 FOREIGN PATENTS OR APPLICATIONS 1,052,487 12/1966 Great Britain ..96/1 14 Primary Examiner-Ronald H. Smith Att0rneySughrue, Rothwell, Mion, Zinn and Macpeak ABSTRACT A color photographic silver halide light-sensitive material comprising a support having a silver halide light-sensitive emulsion layer thereon wherein a copolymer is incorporated in said light-sensitive emulsion layer or a non-light-sensitive auxiliary layer on said support, said copolymer being represented by the following formula:
wherein R represents hydrogen or methyl, R represents hydrogen, methyl, ethyl, propyl or butyl, R represents hydrogen, methyl, ethyl, propyl or butyl and x/y varies from 95/5 to 20/80.
12 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a color photographic light-sensitive material. More particularly, it relates to a color photographic light-sensitive material of improved silver bleaching property.
2. Description of the Prior Art One of the difficulties encountered in the processing of -a color photographic material is the phenomenon that silver bleaching is not complete. This is a serious problem, particularly in the case of a color photographic light-sensitive material using an oil-soluble coupler as disclosed in U.S. Pat. No. 2,322,027.
When a color photographic light-sensitive material is subjected to exposure and then to color development, a color image and a silver image are formed. The silver image is then removed by a silver bleaching treatment and a fixing treatment, thus obtaining only a dye image. If the step of silver bleaching is incomplete, however, a part of the silver image remains in the material. Such an occluded silver cloud makes the color photographic image obscure and remarkably degrades the color reproduction.
Some methods have been proposed in order to improve the silver bleaching property. It is well known to incorporate some compounds in a color photographic light-sensitive material for the purpose of preventing such silver occlusion. For example, a polymer containing vinylpyrrolidone is described as a silver occlusion inhibitor in British Pat. No. 1,052,487. However, the compound described in this patent has the disadvantage that the development of exposed silver halide grains is markedly suppressed so that a long time is necessary for development, although it has an effect of improving the silver removal.
It is the principal object of the present invention to prevent silver occlusion without suppressing the development in a color photographic light-sensitive material, in particular, containing an oil-soluble coupler.
SUMMARY OF THE INVENTION The above-mentioned object can be accomplished by incorporating in a color photographic light-sensitive material a copolymer of 2-(N-acyl)aminoethyl acrylate or 2-(N- acyl)aminoethyl methacrylate and N-vinylpyrrolidone.
DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the present invention, therefore, there is provided a color photographic light-sensitive material in which in a light-sensitive emulsion layer or in a non-light-sensitive auxiliary layer is incorporated a copolymer represented C l-l C H,, or C I-I and x/y=95/5-20/80. The non-lightsensitive auxiliary layer is a layer adjacent to the light-sensitive emulsion layer, for example, a protective layer, an intermediate layer, a filter layer or antihalation layer.
The effect of the copolymer of N-vinylpyrrolidone and 2- (N-acyl) aminoethyl acrylate or 2-(N-acyl)aminoethyl methacrylate depends on its monomer ratio. The effect of improving the silver removing property increases with an in crease in the amount (y) of N-vinylpyrrolidone, whereas the development suppressing property decreases with the decrease of (y). Accordingly, acopolymer having an x/y ratio of /5 to 20/80, in particular 90/10 to 40/60, is preferably used.
The effect of the copolymer-of the present invention is substantially independent from the degree of polymerization of the copolymer. Therefore, any copolymer capable of being dissolved or dispersed in colloidal state in water or aqueous alkaline solution can be used independently of its degree of polymerization.
The copolymer of the present invention, represented by the formula (I), is obtained by polymerizing, in a solvent, vinylpyrrolidone and a monomer represented by the formula:
1 CH I J R7 70 O CHzCHnNf in which R R and R have the same meaning as in formula (I). A suitable solvent is water or dimethylformamide. Potassium persulfate, hydrogen peroxide or azobisisobutyronitrile may be used as a polymerization initiator. Furthermore, isopropanol may be used so as to control the degree of polymerization.
Synthesis of a monomer represented by formula (II) may be carried out by the reaction of (l) 2-(N-acyl)aminoethyl alcohol with acrylic acid or methacrylic acid, (2) the alcohol with acrylic chloride or methacrylic chloride, (3) the alcohol with ,B-propiolactone or (4) the alcohol with acrylic acid ester or methacrylic acid ester.
Synthetic examples of the copolymer used in the invention are as follows:
Synthetic Example 1 a. Synthesis of 2-(N-formyl-N-methyl)aminoethyl acrylate 52 g of 2-(N-formyl-N-methyl)aminoethyl alcohol was charged into a flask of 500 ml equipped with a stirrer with g of triethylamine, 200 ml of acetone and 1.5 g of hydroquinone as a polymerization inhibitor and, while keeping the temperature at 5 C. and stirring, 46 g of acrylic chloride was dropwise added. After the reaction, the salt was removed and l g of hydroquinone was added followed by distillation. The compound obtained had the following structure which was identified by elementary analysis, NMR, mass spectrometry and infrared spectrum.
Yield: 63.2 g (81.0%)
B.P.: 102l04 C./0.5 mm. Hg Analysis for C H N0 (molecular weight: 157.17)
c H N calculated 53.49 7.05 8.91 found 53.1 7.2 8.4
b. Synthesis of a copolymer of 2-(N-formyl-N- methyl)aminoethyl acrylate and N-vinylpyrrolidone Synthetic Example 2 a. Synthesis of 2-(N-acetyl)aminoethyl acrylate 76 g of 2- (N-acetyDaminoethyl acrylate was charged into a 1,000 ml flask equipped with a stirrer along with 250 ml of acetone, 150 g of triethylamine and 1.5 g of hydroquinone as a polymerization inhibitor, and then 68 g of acrylic chloride was added thereto dropwise while stirring and keeping the reaction temperature lower than 10 C. After being allowed to stand for one night, the triethylamine hydrochloride was filtered off and the reaction mixture was then distilled under reduced pressure. The compound obtained had the following structure which was identified by elementary analysis, NMR and infrared spectrum.
Yield: 78 g (66%) COCHs CHQ=CHC O O (CH )zN\ Analysis for C H NO (molecular weight: 157.17)
c H N calculated 53.49 7.05 8.91 found 53.9 6.9 8.5
b. Synthesis of a copolymer of 2-( N-acetyl)aminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 8 2) 31.4 g of Z-(N-acetyl) aminoethyl acrylate, 5.6 of N-vinylpyrrolidone, 200 ml of water, 2 ml of 30 percent aqueous ammonia, 0.3 ml of isopropanol and 185 mg of potassium persulfate as a polymerization initiator were charged into a flask of 300 ml equipped with a stirrer, rinsed with nitrogen and stirred at 60 C for 2 hours to effect polymerization. After the reaction, the solution was subjected to dialysis in a dialysis membrane for one night and then to freeze drying.
Yield: 35.8 g (96.8%)
The quantity to be added of the copolymer used in the present invention depends on its properties, the variety of layers into which it is added and, the variety and quantity of the coupler and other additives. In the case of adding the copolymer to a light-sensitive emulsion layer, good results can generally be obtained by employing about 5 percent by weight of the copolymer based on the weight of the binder. Ordinarily, 1-5 percent by weight is preferred since the color-forming efficiency and physical properties of the layer decrease when the addition quantity exceeds 20 percent by weight. In the case of adding the copolyer to a non-light-sensitive auxiliary layer, on the other hand, even an addition of 50 percent by weight, based on the weight of the binder of the copolymer, does not lower the color forming efficiency and physical properties of the layer.
The copolymer of the present invention may be added to a dispersion during the dispersing of the coupler or it may be added with other additives during the preparation of a coating solution.
As a binder for the emulsion used in the color photographic light-sensitive material of the present invention, a suitable protective colloid may be used, for example, gelatin, polyvinyl alcohol or its derivative, polyacrylamide or its derivative, cellulose derivative, casein or alginate. Gelatin is most suitable.
The following examples are provided to further illustrate the present invention in detail without limiting the same.
EXAMPLE l ml of a 5 percent aqueous solution of Z-(N-acetyl-N- methyl)aminoethyl acrylate N-vinylpyrrolidone copolymer (monomer ratio: 6 4) was added to 20 ml of a 10 percent aqueous solution of gelatin containing 2 ml of a 10 percent aqueous solution of sodium alkylbenzenesulfonate. Then, 3.0 g of 4-benzoylacetamide-N-butyl-N-octylbenzamide, dissolved by heating in 2.0 ml of dibutyl phthalate, and 3.0 ml of ethyl acetate were added thereto as a yellow coupler and stirred vigorously at 40-50 C. for 15 minutes by means of a homoblender, to thus obtain a coupler dispersion. All of the dispersion was mixed with a photographic emulsion containing 7.0 g of silver bromide and 5.0 g of gelatin and coated onto a film base followed by drying. The resulting light-sensitive material was exposed and subjected to the following treatments at 24 C.
Color development I l min. rinsing 1/4 min. fixing 2 min. water washing 1 min. bleaching 6 minv water washing 2 1/2 min. fixing 2 min. water washing 6 min. The treating solutions had the following composition:
Color development solution sodium hexametaphosphate 2 g. sodium sult'tte (anhydrous) 4 gv Z-methyl-4-N, N-diethylaniline sulfate 3 g. sodium carbonate (monohydrate) 20 g. potassium bromide 2 g. water to make I liter Fixing solution sodium thiosulfate (anhydrous) 153 g. sodium sulfite (anhydrous) l5 g. acetic acid 48 g. boric acid 7.5 g. potassium alum l5 g. water to make 1 liter Bleaching solution potassium bromide 20 g. potassium bichromate 5 g. potassium alum 40 g. pH adjusted to 3.1 with sulfuric acid water to make 1 liter In the resulting film, bleaching of silver was completely carried out with only a yellow color image remaining while in the same film but free from the copolymer, bleaching of silver was incomplete and there was a color image of yellow with a cloud of silver. The optical density of the two films was measured by a red light substantially free from absorption of the yellow image. As is evident from the results as shown in Table l, the film containing no copolymer gives a high optical density due to the absorption of silver.
TABLE 1 Presence of Copolymer Optical Density Yes 0.1 i No 053 Substantially similar results were also obtained in the case of using an aqueous solution containing g of potassium ferricyanide per 1 liter as a bleaching solution.
EXAMPLE 2 The same procedure as in Example l was repeated except that 4.3 g of l-(2,4,6-trichlorophenyl)-3-(3-(N-butyltetradecaneamide)-propaneamide) pyrazoline-S-on was used as a magenta coupler in place of the yellow coupler of Example l and a copolymer of 2-(N-formyl-N-methyl)-aminoethyl methacrylate and N-vinylpyrrolidone (monomer ratio: 6 4) was used as the copolymer. In the copolymer-free film, a color image of magenta was present together with a cloud of silver and was considerably obscure. The optical density of the two films was measured by a red light substantially free from absorption of the color image of magenta. As is evident from the results shown in Table 2, the film containing no copolymer gives a high optical density due to the absorption of silver.
The same procedure as in Example 1 was repeated except that 2.4 g of l-hydroxy-4-chlor -2-N-dodecylnaphthamide was used as a cyan coupler in place of the yellow coupler of Example 1 and a copolymer of 2-(N-formyl-N- methyl)aminoethyl acrylate and N-vinylpyrrolidone(monomer ratio: 6 4) was used as the copolymer. In the copolymer-free film, a color image of cyan was present together with a cloud of silver and was considerably obscure. The optical density of the two films was measured by a blue light substantially free from absorption of the color image of cyan. As is evident from the results shown in Table 3, the film containing no copolymer gives a high optical density due to the absorption of silver.
TABLE 3 Presence of Copolymer Optical density Yes 0.4] No 081 EXAMPLE 4 The same procedure as in Example 1 was repeated except that three kinds of copolymers of 2-(n-acetyl)aminoethyl acrylate and N-vinyl-pyrrolidone, differing in monomer ratio, were used. As is evident from the results shown in Table 4, the film containing the copolymer gives a lower red optical density than the film containing no copolymer.
This example is given for the illustration of the fact that the copolymer of the present invention has a low suppressing action of development. The ratio of optical densities when a film is exposed and developed for 3 minutes and for minutes was compared for the films containing the copolymers of Examples l to 4 and comparison films prepared in a manner similar to that of Example 1 but using copolymers of N-vinylpyrrolidone and vinyl acetate (monomer ratio: 7 3), and N- vinylpyrrolidone and sytrene (monomer ratio: 7 3). The larger this value, the less the suppressing action of development. As is evident from the results shown in Table 5, the copolymers of the present invention give less of a suppressing action of development as compared with the known copolymers.
TABLE 5 Copolymer Density ratio copolymer of Z-NmcetyLN-methyl)aminoethyl n if acrylate and N-vinylpyrrolidone (monomer ratio: 6 :4) 0.57 copolymer of 2-(N-formyl-N-methyl)aminoethyl methacrylate and N-vinylpyrrolidone (monomer ratio: 6 :4) 0.52 copolymer of 2-(N-formyl-N-methyl)aminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 6 4) 0.50 copolymer of 2-( N-acetyl)aminoethyl acrylate and N- vinylpyrrolidone (monomer ratio: 8 Z) 0.49 copolymer of Z-(N-acetylaminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 7 3) 0.43 copolymer of 2-( N-acetyl)aminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 4 6) 0.35 copolymer of N-vinylpyrrolidone and vinyl acetate (monomer ratio: 7 3) 0.23 copolymer of N-vinylpyrrolidone and styrene (monomer ratio: 7 3) 0.25 none 0.55
EXAMPLE 6 To 1 kg of a photographic emulsion containing 60 g of silver bromide and 60 g of gelatin was added 15 ml of a 2 percent (by weight) aqueous solution of a copolymer of Z-(N-acetyl- N-methyl)aminoethyl acrylate and N-vinylpyrrolidone (monomer ratio: 9 l). A copolymer-free coupler dispersion prepared by a procedure similar to that of Example 1 was added thereto, coated onto a film base and dried. For comparison, another film was prepared by the same procedure as mentioned above but using no copolymer. The two films were processed as in Example 1 and their red optical density was measured. As is evident from the results shown in Table 6, the film containing the copolymer of the invention gives a lower red optical density.
TABLE 6 Presence of Copolymer Red optical density Yes 0. l 7 No 0.54
wherein R represents hydrogen or methyl, R represents hydrogen, methyl, ethyl, propyl or butyl, R represents hydrogen, methyl, ethyl, propyl or butyl and x/y varies from /5 to 20/80.
2. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is incorporated in the light sensitive emulsion layer in an amount of up to 20 percent by weight, based on the weight of the binder of said layer.
3. The color photographic light-sensitive material of claim 2 wherein the amount of said copolymer varies from 1 to 5 percent, by weight, based on the weight of binder.
4. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is incorporated in a nofi-light-sensitive auxiliary layer in an amount of up to 50 percent by weight based on the weight of the binder of said layer.
5. The color photographic light-sensitive material as A rolidone of a monomer ratio of 6 4.
9. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-forrnyl-N-methyl)aminoethyl methacrylate and N-vinylpyrrolidone of a monomer ratio of 6 4.
10. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl)amino-ethyl acrylate and N-vinylpyrrolidone of a monomer ration of 8 2.
rolidone of a monomer ration of 9 l.
Claims (11)
- 2. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is incorporated in the light sensitive emulsion layer in an amount of up to 20 percent by weight, based on the weight of the binder of said layer.
- 3. The color photographic light-sensitive material of claim 2 wherein the amount of said copolymer varies from 1 to 5 percent, by weight, based on the weight of binder.
- 4. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is incorporated in a non-light-sensitive auxiliary layer in an amount of up to 50 percent by weight based on the weight of the binder of said layer.
- 5. The color photographic light-sensitive material as claimed in claim 1 wherein x/y varies from 90/10 to 40/60.
- 6. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-formyl-N-methyl) aminoethyl acrylate and N-vinylpyrrolidone of a monomer ratio of 6 : 4.
- 7. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl)aminoethyl acrylate and N-vinylpyrrolidone of a monomer ratio of 4 : 6.
- 8. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl-N-methyl)aminoethyl acrylate and N-vinylpyrrolidone of a monomer ratio of 6 : 4.
- 9. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-formyl-N-methyl)aminoethyl methacrylate and N-vinylpyrrolidone of a monomer ratio of 6 : 4.
- 10. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl)amino-ethyl acrylate and N-vinylpyrrolidone of a monomer ration of 8 : 2.
- 11. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl)aminoethyl acetate and N-vinylpyrrolidone of a monomer ration of 7 : 3.
- 12. The color photographic light-sensitive material as claimed in claim 1 wherein said copolymer is a copolymer of 2-(N-acetyl-N-methyl)aminoethyl acrylate and N-vinylpyrrolidone of a monomer ration of 9 : 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP44075465A JPS4838417B1 (en) | 1969-09-22 | 1969-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3655389A true US3655389A (en) | 1972-04-11 |
Family
ID=13577066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US74521A Expired - Lifetime US3655389A (en) | 1969-09-22 | 1970-09-22 | Color photographic light-sensitive material containing silver occlusion preventing agent |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3655389A (en) |
| JP (1) | JPS4838417B1 (en) |
| DE (1) | DE2046682C3 (en) |
| GB (1) | GB1260609A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907572A (en) * | 1973-01-30 | 1975-09-23 | Mitsubishi Paper Mills Ltd | Color photographic photosensitive emulsion and color photographic material |
| US4201589A (en) * | 1974-08-26 | 1980-05-06 | Fuji Photo Film Co., Ltd. | Silver halide photo-sensitive material prepared with solvent and solvent soluble polymer |
| US5576165A (en) * | 1993-07-07 | 1996-11-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU523480B2 (en) * | 1977-08-04 | 1982-07-29 | Ppg Industries, Inc | Amide. acrylate compounds for use in radiation-curable coat img compositions |
| US4227979A (en) | 1977-10-05 | 1980-10-14 | Ppg Industries, Inc. | Radiation-curable coating compositions containing amide acrylate compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1052487A (en) * | 1963-06-10 | |||
| US2495918A (en) * | 1948-08-28 | 1950-01-31 | Du Pont | Poly-n-vinyl lactam photographic silver halide emulsions |
| US3360373A (en) * | 1962-12-04 | 1967-12-26 | Ciba Ltd | Process for the manufacture of silver halide emulsions by the flocculation method |
-
1969
- 1969-09-22 JP JP44075465A patent/JPS4838417B1/ja active Pending
-
1970
- 1970-09-22 DE DE2046682A patent/DE2046682C3/en not_active Expired
- 1970-09-22 GB GB45131/70A patent/GB1260609A/en not_active Expired
- 1970-09-22 US US74521A patent/US3655389A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2495918A (en) * | 1948-08-28 | 1950-01-31 | Du Pont | Poly-n-vinyl lactam photographic silver halide emulsions |
| US3360373A (en) * | 1962-12-04 | 1967-12-26 | Ciba Ltd | Process for the manufacture of silver halide emulsions by the flocculation method |
| GB1052487A (en) * | 1963-06-10 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907572A (en) * | 1973-01-30 | 1975-09-23 | Mitsubishi Paper Mills Ltd | Color photographic photosensitive emulsion and color photographic material |
| US4201589A (en) * | 1974-08-26 | 1980-05-06 | Fuji Photo Film Co., Ltd. | Silver halide photo-sensitive material prepared with solvent and solvent soluble polymer |
| US5576165A (en) * | 1993-07-07 | 1996-11-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2046682C3 (en) | 1975-02-13 |
| DE2046682B2 (en) | 1974-06-27 |
| DE2046682A1 (en) | 1971-04-01 |
| JPS4838417B1 (en) | 1973-11-17 |
| GB1260609A (en) | 1972-01-19 |
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