EP0695968A2 - Viscosity reduction in a photographic melt - Google Patents
Viscosity reduction in a photographic melt Download PDFInfo
- Publication number
- EP0695968A2 EP0695968A2 EP95112023A EP95112023A EP0695968A2 EP 0695968 A2 EP0695968 A2 EP 0695968A2 EP 95112023 A EP95112023 A EP 95112023A EP 95112023 A EP95112023 A EP 95112023A EP 0695968 A2 EP0695968 A2 EP 0695968A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- viscosity
- cyclodextrin
- solution
- photographic
- 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.)
- Withdrawn
Links
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- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 18
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- NFZDIOLJNMZZNS-UHFFFAOYSA-N n-[1-(2,5-dichlorophenyl)-5-oxo-4h-pyrazol-3-yl]-2-methylprop-2-enamide Chemical compound O=C1CC(NC(=O)C(=C)C)=NN1C1=CC(Cl)=CC=C1Cl NFZDIOLJNMZZNS-UHFFFAOYSA-N 0.000 description 1
- KUWCVCMJPABJDI-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid;dihydrate Chemical compound O.O.OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 KUWCVCMJPABJDI-UHFFFAOYSA-N 0.000 description 1
- FECCTLUIZPFIRN-UHFFFAOYSA-N n-[2-[2-amino-5-(diethylamino)phenyl]ethyl]methanesulfonamide;hydrochloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C(CCNS(C)(=O)=O)=C1 FECCTLUIZPFIRN-UHFFFAOYSA-N 0.000 description 1
- VILFVXYKHXVYAB-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000002245 particle Substances 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
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
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
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
Definitions
- This invention relates to a method for the preparation of a photographic element, and in particular to a method of controlling the viscosity of a photographic melt.
- Photographic elements typically comprise a support having thereon at least one light-sensitive layer.
- Color photographic elements typically comprise at least one layer sensitive to blue light, at least one layer sensitive to green light and at least one layer sensitive to red light.
- a color photographic element also contains various other layers, such as subbing layers, interlayers, antihalation layers and the like. Each layer of a photographic element is applied, generally simultaneously with other layers, to an appropriate support in a coating process.
- photographic coating compositions comprising emulsions, dispersions, and/or other photographic addenda for each layer are coated from aqueous solutions which contain a hydrophilic colloid, such as gelatin.
- a hydrophilic colloid such as gelatin.
- coating takes place at temperatures between about 35° to about 50°C.
- the photographic emulsions and dispersions are prepared, chill-set and stored until needed for coating. At that time they are then heated to about 35° to about 50°C to melt the chill-set emulsion or dispersion to provide the fluid coating compositions which are frequently called “melts", "coating melts" or "photographic melts".
- the second primary method is the curtain coating process.
- photographic addenda such as masking couplers, oxidized developer scavengers, filter dyes, optical brighteners, ultraviolet radiation absorbers, dye transfer dyes, etc.
- Such materials are usually fully water soluble, or are soluble to the extent of about 5-20% by weight, in water containing 5 to 20% by weight of a water miscible auxiliary solvent such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, or the like.
- a water miscible auxiliary solvent such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, or the like.
- Such materials behave also in a similar manner in the presence of a hydrophilic colloid.
- amphiphilic addenda disclosed in the '435 patent are block oligomeric compounds comprising hydrophobic polyoxypropylene blocks (A) and hydrophilic polyoxyethylene blocks (B) joined in the manner of A-B-A, B-A-B, A-B, (A-B) n -G-(B-A), or (B-A) n -G-(A-B), where G is a connective organic moiety and n is between 1 and 3.
- amphiphilic addenda examples include Ono et al. U.S. Patent No. 3,860,425 and in Visconte et al. US Patent 5,300,418.
- An object of this invention is to reduce the high viscosity of photographic gelatin-containing melts, which contain an anionically charged, hydrophobic group-containing photographic addenda that are water soluble, or rendered water soluble by assistance of a water-miscible organic auxiliary solvent.
- One aspect of this invention comprises an aqueous photographic coating composition
- an aqueous photographic coating composition comprising an aqueous solution comprising gelatin and an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, wherein the composition further comprises a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- Another aspect of this invention comprises a photographic element comprising a support having thereon a layer comprising:
- Another aspect of this invention is a method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- a further aspect of this invention is a method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution without reducing in the surface tension of the composition.
- This invention enables one to adjust the viscosity of a photographic coating composition without using undesirably large amounts of water to dilute the composition or adding a nonionic surfactant, including sugar based surfactants, as taught by the prior art, which may reduce the surface tension of the composition and/or cause undesired sensitometric changes in the resulting photographic element.
- Fig. 1 illustrates the physical configuration of a cyclodextrin molecule.
- Fig. 2 is a graph showing the surface tension of an aqueous solution of the anionically charged, hydrophobic group-containing compound, SC-1, obtained as described in the examples provided below.
- Fig. 3 is a graph showing shows the effect of adding ⁇ -cyclodextrin to an aqueous solution of SC-1, obtained as described in the examples provided below.
- the invention is generally accomplished by providing a melt for coating of a layer of a photographic element and which contains a hydrophilic colloid and an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, and adding to the solution an amount of a cyclodextrin effective to reduce the viscosity of the solution.
- Illustrative hydrophilic colloids include water-soluble polymers, gelatin, gelatin derivatives, cellulose esters, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers and mixtures thereof.
- the cellulose esters include hydroxyl propyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose.
- the latex polymers include vinyl chloride copolymers, vinylidene chloride copolymers, acrylic ester copolymers, vinyl acetate copolymers and butadiene copolymers. Among them, gelatin is most preferred.
- the amount of hydrophilic colloid in the solution is preferably about 2 to about 20 wt.%, based on the weight of the solution.
- Illustrative anionically charged, anhydrophobic group-containing addenda include sodium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium or potassium salt of octadecyl hydroquinone sulfate, or a compound of the formula:
- the anionically charged hydrophobic group-containing compound is preferably present in the solution in an amount of from about 0.1 to about 10 wt.%, based on the weight of the solution.
- the viscosity of the aqueous hydrophilic colloid solution is decreased by addition of a cyclodextrin.
- Cyclodextrins are torus shaped cyclic oligosaccharides formed by the linking of 6, 7 or 8 glucopyranose units by a, (1-4) linkages (called ⁇ -, ⁇ - and ⁇ -cyclodextrin respectively). Cyclodextrins have the following structural formula: wherein n is as defined below.
- a cyclodextrin molecule is shown as torus, 1, having a cavity 2, which has a diameter d.
- Cyclodextrins can be thought of as "molecular buckets" as they are toroidal-shaped, rigid structures with a well-defined cavity as illustrated in Fig. 1.
- cyclodextrins Due to the hydrophobic nature of the cavity, cyclodextrins are known to form various inclusion complexes in aqueous solutions and solid state with apolar (hydrophobic) molecules which fit into cyclodextrin's cavity without teh formation of a covalent bond. Further, polar compounds and certain inorganic ions have also been found to bind with cyclodextrin. (Takisawa, N.; Shirahama, K.; Tanaka, I. Colloid and Polymer Science 271(1993)499-503; Bender, K. L.; Komiyama, M. in Cyclodextrin Chemistry , Springer-Verlag, Berlin.; Saenger, W., Angew Chem. Int. Ed.
- the cyclodextrin is added in an amount effective to reduce the viscosity of the melt.
- the cyclodextrin is added to the melt preferably in an amount sufficient to provide a mole ratio of cyclodextrin to anionically charged, hydrophobic group-containing addenda of 1 to about 6, more preferably 1 to about 4 and most preferably about 3 to about 4.
- the cyclodextrin is generally added after the photographic emulsion or dispersion has been heated to form a coating melt.
- the viscosity of one layer of a multiple layer coating depends of the viscosities of the adjacent layers.
- the photographic composition or melt of the invention can be used in any of the ways and in any of the combinations known in the art.
- the invention materials are coated as a layer on a support to form part of a photographic element.
- the photographic elements can be single color elements or multicolor elements.
- Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum.
- the layers of the element, including the layers of the image-forming units can be arranged in various orders as known in the art.
- the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
- a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
- the element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
- the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure , November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth; Hampshire P010 7DQ, ENGLAND.
- the silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through IV. Color materials and development modifiers are described in Sections V and XXI. Vehicles are described in Section IX, and various additives such as brighteners, antifoggants, stabilisers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described , for example, in Sections V, VI, VIII, X, XI, XII, and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVIII.
- Coupling-off groups are well known in the art. Such groups can determine the chemical equivalency of a coupler, i.e., whether it is a 2-equivalent or a 4-equivalent coupler, or modify the reactivity of the coupler. Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording material, by performing, after release from the coupler, functions such as dye formation, dye hue adjustment, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation, color correction and the like.
- the presence of hydrogen at the coupling site provides a 4-equivalent coupler, and the presence of another coupling-off group usually provides a 2-equivalent coupler.
- Representative classes of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo.
- Image dye-forming couplers may be included in the element such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as: U.S. Pat. Nos. 2,772,162, 2,895,826, 3,002,836, 3,034,892, 2,474,293, 2,423,730, 2,367,531, 3,041,236, 4,883,746 and "Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitannonen, Band III, pp. 156-175 (1961).
- couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent.
- Couplers that form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Pat. Nos. 2,600,788, 2,369,489, 2,343,703, 2,311,082, 3,152,896, 3,519,429, 3,062,653, 2,908,573 and "Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitannonen, Band III, pp. 126-156 (1961).
- couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents.
- Couplers that form yellow dyes upon reaction with oxidized and color developing agent are described in such representative patents and publications as: U.S. Pat. Nos. 2,875,057, 2,407,210, 3,265,506, 2,298,443, 3,048,194, 3,447,928 and "Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961).
- Such couplers are typically open chain ketomethylene compounds.
- couplers any of which may contain known ballasts or coupling-off groups such as those described in U.S. Patent 4,301,235; U.S. Patent 4,853,319 and U.S. Patent 4,351,897.
- the coupler may also be used in association with "wrong" colored couplers (e.g. to adjust levels of interlayer correction) and, in color negative applications, with masking couplers such as those described in EP 213.490; Japanese Published Application 58-172,647; U.S. Patent 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Patents 4,070,191 and 4,273,861; and German Application DE 2,643,965.
- the masking couplers may be shifted or blocked.
- the photographic element may also contain materials that accelerate or otherwise modify the processing steps e.g. of bleaching or fixing to improve the quality of the image.
- Bleach accelerator releasing couplers such as those described in EP 193,389; EP 301,477; U.S. 4,163,669; U.S. 4,865,956; and U.S. 4,923,784, may be useful.
- Also contemplated is use of the compositions in association with nucleating agents, development accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. 4,859,578; U.S.
- antifogging and anti color-mixing agents such as derivatives of hydroquinones; aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
- the materials of the invention may replace or supplement the materials of an element comprising a support bearing the following layers from top to bottom:
- the photographic elemtns may comprise a support bearing the following layers from top to bottom:
- the photographic element may comprise a support bearing the following layers from top to bottom:
- the invention materials may also be used in combination with filter dye layers comprising colloidal silver sol or yellow, cyan, and/or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with "smearing" couplers (e.g. as described in U.S. 4,366,237; EP 96,570; U.S. 4,420,556; and U.S. 4,543,323.) Also, the compositions may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
- the photographic element may also contain image-modifying compounds such as "Developer Inhibitor-Releasing” compounds (DIR's).
- DIR's useful in conjunction with the compositions of the invention are known in the art and examples are described in U.S. Patent Nos.
- the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure , November 1979, Item 18716, available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England.
- Materials of the invention may be coated on pH adjusted support as described in U.S. 4,917,994; with epoxy solvents (EP 0 164 961); with nickel complex stabilizers (U.S. 4,346,165; U.S. 4,540,653 and U.S. 4,906,559 for example); with ballasted chelating agents such as those in U.S.
- the average useful ECD of photographic emulsions can range up to about 10 microns, although in practice emulsion ECD's seldom exceed about 4 microns. Since both photographic speed and granularity increase with increasing ECD's, it is generally preferred to employ the smallest tabular grain ECD's compatible with achieving aim speed requirements.
- Emulsion tabularity increases markedly with reductions in tabular grain thickness. It is generally preferred that aim tabular grain projected areas be satisfied by thin (t ⁇ 0.2 micron) tabular grains. To achieve the lowest levels of granularity it is preferred that aim tabular grain projected areas be satisfied with ultrathin (t ⁇ 0.06 micron) tabular grains. Tabular grain thicknesses typically range down to about 0.02 micron. However, still lower tabular grain thicknesses are contemplated. For example, Daubendiek et al U.S. Patent 4,672,027 reports a 3 mole percent iodide tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 micron.
- tabular grains of less than the specified thickness account for at least 50 percent of the total grain projected area of the emulsion.
- tabular grains satisfying the stated thickness criterion account for the highest conveniently attainable percentage of the total grain projected area of the emulsion.
- tabular grains satisfying the stated thickness criteria above account for at least 70 percent of the total grain projected area.
- tabular grains satisfying the thickness criteria above account for at least 90 percent of total grain projected area.
- Suitable tabular grain emulsions can be selected from among a variety of conventional teachings, such as those of the following: Research Disclosure, Item 22534, January 1983, published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Patent Nos.
- the emulsions can be surface-sensitive emulsions, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or the emulsions can form internal latent images predominantly in the interior of the silver halide grains.
- the emulsions can be negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
- Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image and can then be processed to form a visible dye image.
- Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
- the processing step described above provides a negative image.
- the described elements can be processed in the known C-41 color process as described in The British Journal of Photography Annual of 1988, pages 191-198. Where applicable, the element may be processed in accordance with color print processes such a the RA-4 process of Eastman Kodak Company as described in the British Journal of Photography Annual of 1988, Pp 198-199.
- the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable.
- a direct positive emulsion can be employed to obtain a positive image.
- Preferred color developing agents are p-phenylenediamines such as: 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-( ⁇ -(methanesulfonamido) ethyl)aniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate, 4-amino-3- ⁇ -(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
- Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
- any reference to a substituent by the identification of a group containing a substitutable hydrogen e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.
- a substitutable hydrogen e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.
- the substituent will have less than 30 carbon atoms and typically less than 20 carbon atoms.
- Example 1 illustrates the reduction of viscosities of a coating melts by the addition of cyclodextrins.
- Example 1 is a melt that has no SC-1, and shows the aqueous gelatin solution containing 10.1 wt.% gelatin has a viscosity of 23.1 cP RBT (Rolling Ball Time). Incorporation of SC-1 (0.21 wt %, based on the weight of the solution) in the melt raises the viscosity to 44.5 cP. However, it is seen that the addition of the compound ⁇ -cyclodextrin hydrate (commercially available from Aldrich Chemical Company) to the melt in progressively greater amounts, reduces the viscosity of the melts (Example 3, 4 and 5) to virtually the value of that of the melt that has no (SC-1).
- SC-1 Rolling Ball Time
- Fig. 3 it can be seen that the addition of increasing amounts of SC-1 to an aqueous solution of ⁇ -cyclodextrin (10 ⁇ 3 M), results in a drop in surface tension only after the molar amount of SC-1 approaches the number of moles of ⁇ -cyclodextrin. Assuming a 1:1 type association, the binding constant is about 990 M ⁇ 1.
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Abstract
Description
- This invention relates to a method for the preparation of a photographic element, and in particular to a method of controlling the viscosity of a photographic melt.
- Photographic elements typically comprise a support having thereon at least one light-sensitive layer. Color photographic elements typically comprise at least one layer sensitive to blue light, at least one layer sensitive to green light and at least one layer sensitive to red light. Generally, a color photographic element also contains various other layers, such as subbing layers, interlayers, antihalation layers and the like. Each layer of a photographic element is applied, generally simultaneously with other layers, to an appropriate support in a coating process.
- In conventional photographic coatings, photographic coating compositions comprising emulsions, dispersions, and/or other photographic addenda for each layer are coated from aqueous solutions which contain a hydrophilic colloid, such as gelatin. Usually, coating takes place at temperatures between about 35° to about 50°C. Generally, the photographic emulsions and dispersions are prepared, chill-set and stored until needed for coating. At that time they are then heated to about 35° to about 50°C to melt the chill-set emulsion or dispersion to provide the fluid coating compositions which are frequently called "melts", "coating melts" or "photographic melts".
- Generally, in the photographic art there are two primary methods of coating photographic materials. One is the bead coating process. U.S. Patent 2,761,417 - Russell et al, U.S. Patent 2,681,294 - Beguin, and U.S. Patent 4,525,392 - Ishizaki, illustrate simultaneously applying multiple layers of photographic materials by the bead coating process, and apparatus for practicing that process.
- The second primary method is the curtain coating process. U.S. Patent 3,632,374 - Greiller, and U.S. Patent 4,569,863 - Koepke et al, illustrate apparatus and process for curtain coating.
- It is well known that adjustment and control of viscosities of melts of individual layers can improve layer thickness uniformity of finished coated products. It is also known that layer viscosities outside optimum ranges may cause undesired variations in layer thickness during flow on the slides of the coating hopper or on a non-horizontal web path after coating.
- Certain photographic addenda, such as masking couplers, oxidized developer scavengers, filter dyes, optical brighteners, ultraviolet radiation absorbers, dye transfer dyes, etc., when admixed in a melt containing a hydrophilic colloid, produce excessively high viscosity, which can result in non-uniform coatings. Such photographic addenda are in general molecules with large hydrophobic groups and are usually solubilized with one or more fully ionized anionic groups, such as -SO₃⁻ (i.e., sulfonate) groups, -SO₄= (i.e.,sulfate) groups or COO⁻ (i.e., carboxy) groups. Such materials are usually fully water soluble, or are soluble to the extent of about 5-20% by weight, in water containing 5 to 20% by weight of a water miscible auxiliary solvent such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, or the like. Such materials behave also in a similar manner in the presence of a hydrophilic colloid.
- It is known from U.S. Patent No. 3,409,435, that certain amphiphilic addenda, such as polyalkylene oxide block oligomers or polymers, when added to melts containing the mentioned viscosity-increasing photographic addenda, produce moderation of melt viscosity. The amphiphilic addenda disclosed in the '435 patent are block oligomeric compounds comprising hydrophobic polyoxypropylene blocks (A) and hydrophilic polyoxyethylene blocks (B) joined in the manner of A-B-A, B-A-B, A-B, (A-B)n-G-(B-A), or (B-A)n-G-(A-B), where G is a connective organic moiety and n is between 1 and 3.
- Other examples of such amphiphilic addenda are disclosed in Ono et al. U.S. Patent No. 3,860,425 and in Visconte et al. US Patent 5,300,418.
- However, such prior art materials that contain a large number of polyalkylene oxide groups produce adverse photographic (sensitometric) effects in some photographic products. Sugar surfactants discussed by Visconte et al. U.S. Patent No. 5,300,418 do not have the adverse photographic effects, but because they, and other amphiphiles, are surface active, they are unable to reduce the viscosity without reducing the surface tension of the melt.
- One of the ways of reducing high viscosities of melts is by dilution with water. However, such a procedure leads to increased water load in the drier, which is undesirable under high speed coating conditions, used for high volume film and paper products. Therefore, dilution is not always a desirable approach.
- Therefore, there is a need for photographic melts (of the aforesaid photographic addenda) which have sufficiently low viscosity, and adequate concentration of the hydrophilic colloid, such that no excessive drier wet load is encountered during manufacturing of photographic paper and film products, and such that no, or substantially no, adverse effect is produced on the desired sensitometric behavior of the photographic element. Furthermore, it is desirable to be able to reduce viscosity without reducing surface tension as the relative values of surface tension (including dynamic surface tension under flow conditions) of individual layers in multilayer packs coated simultaneously (as taught in the above mentioned patents) are important in order to avoid undesired non-uniformities in thicknesses of layers during the coating process caused by surface tension driven flow.
- An object of this invention is to reduce the high viscosity of photographic gelatin-containing melts, which contain an anionically charged, hydrophobic group-containing photographic addenda that are water soluble, or rendered water soluble by assistance of a water-miscible organic auxiliary solvent.
- One aspect of this invention comprises an aqueous photographic coating composition comprising an aqueous solution comprising gelatin and an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, wherein the composition further comprises a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- Another aspect of this invention comprises a photographic element comprising a support having thereon a layer comprising:
- (i) gelatin,
- (ii) an anionically charged, hydrophobic-group containing compound that is (a) soluble in water or a mixture of water and a water- miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, and
- (iii) a cyclodextrin.
- Another aspect of this invention is a method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- A further aspect of this invention is a method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution without reducing in the surface tension of the composition.
- This invention enables one to adjust the viscosity of a photographic coating composition without using undesirably large amounts of water to dilute the composition or adding a nonionic surfactant, including sugar based surfactants, as taught by the prior art, which may reduce the surface tension of the composition and/or cause undesired sensitometric changes in the resulting photographic element.
- Fig. 1 illustrates the physical configuration of a cyclodextrin molecule.
- Fig. 2 is a graph showing the surface tension of an aqueous solution of the anionically charged, hydrophobic group-containing compound, SC-1, obtained as described in the examples provided below.
- Fig. 3 is a graph showing shows the effect of adding α-cyclodextrin to an aqueous solution of SC-1, obtained as described in the examples provided below.
- The invention is generally accomplished by providing a melt for coating of a layer of a photographic element and which contains a hydrophilic colloid and an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, and adding to the solution an amount of a cyclodextrin effective to reduce the viscosity of the solution.
- Illustrative hydrophilic colloids include water-soluble polymers, gelatin, gelatin derivatives, cellulose esters, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers and mixtures thereof. The cellulose esters include hydroxyl propyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose. The latex polymers include vinyl chloride copolymers, vinylidene chloride copolymers, acrylic ester copolymers, vinyl acetate copolymers and butadiene copolymers. Among them, gelatin is most preferred.
- The amount of hydrophilic colloid in the solution is preferably about 2 to about 20 wt.%, based on the weight of the solution.
-
- The anionically charged hydrophobic group-containing compound is preferably present in the solution in an amount of from about 0.1 to about 10 wt.%, based on the weight of the solution.
- In accordance with this invention the viscosity of the aqueous hydrophilic colloid solution is decreased by addition of a cyclodextrin.
-
- The torroidal shape of a cyclodextrin is illustrated in Fig. 1. In Fig 1, a cyclodextrin molecule is shown as torus, 1, having a
cavity 2, which has a diameter d. The cyclodextrins are defined as:
α-cyclodextrin: wherein n=6, d=4.5Å
β-cyclodextrin: wherein n=7, d=7.0Å
γ-cyclodextrin: wherein n=8, d=8.5Å
Cyclodextrins can be thought of as "molecular buckets" as they are toroidal-shaped, rigid structures with a well-defined cavity as illustrated in Fig. 1. Due to the hydrophobic nature of the cavity, cyclodextrins are known to form various inclusion complexes in aqueous solutions and solid state with apolar (hydrophobic) molecules which fit into cyclodextrin's cavity without teh formation of a covalent bond. Further, polar compounds and certain inorganic ions have also been found to bind with cyclodextrin. (Takisawa, N.; Shirahama, K.; Tanaka, I. Colloid and Polymer Science 271(1993)499-503; Bender, K. L.; Komiyama, M. in Cyclodextrin Chemistry, Springer-Verlag, Berlin.; Saenger, W., Angew Chem. Int. Ed. Engl. 19 (1980) 344. Kaifer, A. E. in Advances in Supramolecular Chemistry,volume 2, pages 1-24, 1992, JAI Press Inc.; Satake, I; Ikenoue, T; Takeshita, T. Bull. Chem Soc. Jpn. 58 (1985) 2746; Schlenk, H; Sand, D. J. Am. Chem Soc. 83 ( 1961) 2312). While not wishing to be bound by any theory, it is believed that the cyclodextrins bind the anionically charged, hydrophobic group-containing addenda within the cavity of the cyclodextrin toroidal structure. Since cyclodextrins are not surface active, they thus reduce the viscosity of the gelatin melt without reducing the surface tension thereof. - The cyclodextrin is added in an amount effective to reduce the viscosity of the melt. The cyclodextrin is added to the melt preferably in an amount sufficient to provide a mole ratio of cyclodextrin to anionically charged, hydrophobic group-containing addenda of 1 to about 6, more preferably 1 to about 4 and most preferably about 3 to about 4.
- The cyclodextrin is generally added after the photographic emulsion or dispersion has been heated to form a coating melt. As mentioned above, the viscosity of one layer of a multiple layer coating depends of the viscosities of the adjacent layers.
- The photographic composition or melt of the invention can be used in any of the ways and in any of the combinations known in the art. Typically, the invention materials are coated as a layer on a support to form part of a photographic element. The photographic elements can be single color elements or multicolor elements. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
- A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
- If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth; Hampshire P010 7DQ, ENGLAND.
- In the following discussion of suitable materials for use in the photographic elements of this invention, reference will be made to Research Disclosure, December 1989, Item 308119, available as described above, which will be identified hereafter by the term "Research Disclosure." The Sections hereafter referred to are Sections of the Research Disclosure.
- The silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through IV. Color materials and development modifiers are described in Sections V and XXI. Vehicles are described in Section IX, and various additives such as brighteners, antifoggants, stabilisers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described , for example, in Sections V, VI, VIII, X, XI, XII, and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVIII.
- Coupling-off groups are well known in the art. Such groups can determine the chemical equivalency of a coupler, i.e., whether it is a 2-equivalent or a 4-equivalent coupler, or modify the reactivity of the coupler. Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording material, by performing, after release from the coupler, functions such as dye formation, dye hue adjustment, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation, color correction and the like.
- The presence of hydrogen at the coupling site provides a 4-equivalent coupler, and the presence of another coupling-off group usually provides a 2-equivalent coupler. Representative classes of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo. These coupling-off groups are described in the art, for example, in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 3,880,661, 4,052,212 and 4,134,766; and in U.K. Patents and published application Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755A and 2,017,704A.
- Image dye-forming couplers may be included in the element such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as: U.S. Pat. Nos. 2,772,162, 2,895,826, 3,002,836, 3,034,892, 2,474,293, 2,423,730, 2,367,531, 3,041,236, 4,883,746 and "Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, Band III, pp. 156-175 (1961). Preferably such couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent.
- Couplers that form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Pat. Nos. 2,600,788, 2,369,489, 2,343,703, 2,311,082, 3,152,896, 3,519,429, 3,062,653, 2,908,573 and "Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, Band III, pp. 126-156 (1961). Preferably such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents.
- Couplers that form yellow dyes upon reaction with oxidized and color developing agent are described in such representative patents and publications as: U.S. Pat. Nos. 2,875,057, 2,407,210, 3,265,506, 2,298,443, 3,048,194, 3,447,928 and "Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, Band III, pp. 112-126 (1961). Such couplers are typically open chain ketomethylene compounds.
- It may be useful to use a combination of couplers any of which may contain known ballasts or coupling-off groups such as those described in U.S. Patent 4,301,235; U.S. Patent 4,853,319 and U.S. Patent 4,351,897. The coupler may also be used in association with "wrong" colored couplers (e.g. to adjust levels of interlayer correction) and, in color negative applications, with masking couplers such as those described in EP 213.490; Japanese Published Application 58-172,647; U.S. Patent 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Patents 4,070,191 and 4,273,861; and German Application DE 2,643,965. The masking couplers may be shifted or blocked.
- The photographic element may also contain materials that accelerate or otherwise modify the processing steps e.g. of bleaching or fixing to improve the quality of the image. Bleach accelerator releasing couplers such as those described in EP 193,389; EP 301,477; U.S. 4,163,669; U.S. 4,865,956; and U.S. 4,923,784, may be useful. Also contemplated is use of the compositions in association with nucleating agents, development accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. 4,859,578; U.S. 4,912,025); antifogging and anti color-mixing agents such as derivatives of hydroquinones; aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
- For example, in a color negative element, the materials of the invention may replace or supplement the materials of an element comprising a support bearing the following layers from top to bottom:
- (1) one or more overcoat layers containing ultraviolet absorber(s);
- (2) a two-coat yellow pack with a fast yellow layer containing "Coupler 1": Benzoic acid, 4-chloro-3-((2-(4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1- imidazolidinyl)-3-(4-methoxyphenyl)-1,3-dioxopropyl)amino)-, dodecyl ester and a slow yellow layer containing the same compound together with "Coupler 2": Propanoic acid, 2-[[5-[[4-[2-[[[2,4-bis(1,1-dimethylpropyl)phenoxy]acetyl]amino]-5-[(2,2,3,3,4,4,4-heptafluoro-1-oxobutyl)amino]-4-hydroxyphenoxy]-2,3-dihydroxy-6-[(propylamino)carbonyl ]phenyl]thio]-1,3,4-thiadiazol-2-yl]thio]-, methyl ester and "Coupler 3": 1-((dodecyloxy)carbonyl) ethyl(3-chloro-4-((3-(2-chloro-4-((1-tridecanoylethoxy) carbonyl)anilino)-3-oxo-2-((4)(5)(6)-(phenoxycarbonyl)-1H-benzotriazol-1-yl)propanoyl)amino))benzoate;
- (3) an interlayer containing fine metallic silver;
- (4) a triple-coat magenta pack with a fast magenta layer containing "Coupler 4": Benzamide, 3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydro-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-,"Coupler 5": Benzamide, 3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4',5'-dihydro-5'-oxo-1'-(2,4,6-trichlorophenyl) (1,4'-bi-1H-pyrazol)-3'-yl)-,"Coupler 6": Carbamic acid, (6-(((3-(dodecyloxy)propyl) amino)carbonyl)-5-hydroxy-1-naphthalenyl)-, 2-methylpropyl ester , "Coupler 7": Acetic acid, ((2-((3-(((3-(dodecyloxy)propyl)amino) carbonyl)-4-hydroxy-8-(((2-methylpropoxy)carbonyl) amino)-1-naphthalenyl)oxy )ethyl)thio)-, and "Coupler 8" Benzamide, 3-((2-(2,4-bis(1,1-dimethylpropyl) phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydro-4-((4-methoxyphenyl) azo)-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; a mid-magenta layer and a slow magenta layer each containing "Coupler 9": a ternary copolymer containing by weight in the ratio 1:1:2 2-Propenoic acid butyl ester, styrene, and N-[1-(2,4,6-trichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl]-2-methyl-2-propenamide; and "Coupler 10": Tetradecanamide, N-(4-chloro-3-((4-((4-((2,2-dimethyl-1-oxopropyl) amino)phenyl)azo)-4,5-dihydro-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)amino)phenyl)-, in addition to Couplers 3 and 8;
- (5) an interlayer;
- (6) a triple-coat cyan pack with a fast cyan layer containing Couplers 6 and 7; a mid-cyan containing Coupler 6 and "Coupler 11": 2,7-Naphthalenedisulfonic acid, 5-(acetylamino)-3-((4-(2-((3-(((3-(2,4-bis(1,1-dimethylpropyl)phenoxy) propyl)amino)carbonyl)-4-hydroxy-1-naphthalenyl) oxy)ethoxy)phenyl)azo)-4-hydroxy-, disodium salt; and a slow cyan
layer containing Couplers 2 and 6; - (7) an undercoat layer containing Coupler 8; and
- (8) an antihalation layer.
- In a color paper format, the photographic elemtns may comprise a support bearing the following layers from top to bottom:
- (1) one or more overcoats;
- (2) a cyan layer containing "
Coupler 1": Butanamide, 2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-N-(3,5-dichloro-2-hydroxy-4-methylphenyl)-, "Coupler 2": Acetamide, 2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-N-(3,5-dichloro-2-hydroxy-4-, and UV Stabilizers: Phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)-;Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1-dimethylethyl)-;Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1-dimethylethyl)-6-(1-methylpropyl)-; and Phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)- and a poly(t-butylacrylamide) dye stabilizer; - (3) an interlayer;
- (4) a magenta layer containing "
Coupler 3": Octanamide, 2-[2,4-bis(1,1-dimethylpropyl)phenoxy]-N-[2-(7-chloro-6-methyl-1H-pyrazolo[1,5-b][1,2,4]triazol-2-yl)propyl]- together with 1,1'-Spirobi(1H-indene), 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapropoxy-; - (5) an interlayer; and
- (6) a yellow layer containing "
Coupler 4": 1-Imidazolidineacetamide, N-(5-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-2-chlorophenyl)-.alpha.-(2,2-dimethyl-1-oxopropyl)-4-ethoxy-2,5-dioxo-3-(phenylmethyl)-. - In a reversal format, the photographic element may comprise a support bearing the following layers from top to bottom:
- (1) one or more overcoat layers;
- (2) a nonsensitized silver halide containing layer;
- (3) a triple-coat yellow layer pack with a fast yellow layer containing "
Coupler 1": Benzoic acid, 4-(1-(((2-chloro-5-((dodecylsulfonyl)amino)phenyl) amino)carbonyl)-3,3-dimethyl-2-oxobutoxy)-, 1-methylethyl ester; a mid yellowlayer containing Coupler 1 and "Coupler 2": Benzoic acid, 4-chloro-3-[[2-[4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1-imidazolidinyl]-4,4-dimethyl-1,3-dioxopentyl]amino]-, dodecylester; and a slow yellow layer also containingCoupler 2; - (4) an interlayer;
- (5) a layer of fine-grained silver;
- (6) an interlayer;
- (7) a triple-coated magenta pack with a fast magenta layer containing "Coupler 3": 2-Propenoic acid, butyl ester, polymer with N-[1-(2,5-dichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl]-2-methyl-2-propenamide; "Coupler 4": Benzamide, 3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydro-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; and "Coupler 5": Benzamide, 3-(((2,4-bis(1,1-dimethylpropyl)phenoxy)acetyl)amino)-N-(4,5- dihydro-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; and containing the stabilizer 1,1'-Spirobi(1H-indene), 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapropoxy-; and in the slow magenta layer Couplers 4 and 5 with the same stabilizer;
- (8) one or more interlayers possibly including fine-grained nonsensitized silver halide;
- (9) a triple-coated cyan pack with a fast cyan layer containing "Coupler 6": Tetradecanamide, 2-(2-cyanophenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1-oxobutyl)amino)-3-hydroxyphenyl)-; a mid cyan containing"Coupler 7": Butanamide, N-(4-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-2-hydroxyphenyl)-2,2,3,3,4,4,4-heptafluoro- and "Coupler 8": Hexanamide, 2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1-oxobutyl)amino)-3-hydroxyphenyl)-;
- (10) one or more interlayers possibly including fine-grained nonsensitized silver halide; and
- (11) an antihalation layer.
- The invention materials may also be used in combination with filter dye layers comprising colloidal silver sol or yellow, cyan, and/or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with "smearing" couplers (e.g. as described in U.S. 4,366,237; EP 96,570; U.S. 4,420,556; and U.S. 4,543,323.) Also, the compositions may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
- The photographic element may also contain image-modifying compounds such as "Developer Inhibitor-Releasing" compounds (DIR's). DIR's useful in conjunction with the compositions of the invention are known in the art and examples are described in U.S. Patent Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications: 272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613. Such compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR) Couplers for Color Photography," C.R. Barr, J.R. Thirtle and P.W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969).
- It is also contemplated that the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure, November 1979, Item 18716, available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England. Materials of the invention may be coated on pH adjusted support as described in U.S. 4,917,994; with epoxy solvents (EP 0 164 961); with nickel complex stabilizers (U.S. 4,346,165; U.S. 4,540,653 and U.S. 4,906,559 for example); with ballasted chelating agents such as those in U.S. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with stain reducing compounds such as described in U.S. 5,068,171. Other compounds useful in combination with the invention are disclosed in Japanese Published Applications described in Derwent Abstracts having accession numbers as follows: 90-072,629, 90-072,630; 90-072,631; 90-072,632; 90-072,633; 90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,337; 90-079,338; 90-079,690; 90-079,691; 90-080,487; 90-080,488; 90-080,489; 90-080,490; 90-080,491; 90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670; 90-087,360; 90-087,361; 90-087,362; 90-087,363; 90-087,364; 90-088,097; 90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668; 90-094,055; 90-094,056; 90-103,409; 83-62,586; 83-09,959.
- Especially useful in the photographic elements of this invention are tabular grain silver halide emulsions. Specifically contemplated tabular grain emulsions are those in which greater than 50 percent of the total projected area of the emulsion grains are accounted for by tabular grains having a thickness of less than 0.3 micron (0.5 micron for blue sensitive emulsion) and an average tabularity (T) of greater than 25 (preferably greater than 100), where the term "tabularity" is employed in its art recognized usage as
- The average useful ECD of photographic emulsions can range up to about 10 microns, although in practice emulsion ECD's seldom exceed about 4 microns. Since both photographic speed and granularity increase with increasing ECD's, it is generally preferred to employ the smallest tabular grain ECD's compatible with achieving aim speed requirements.
- Emulsion tabularity increases markedly with reductions in tabular grain thickness. It is generally preferred that aim tabular grain projected areas be satisfied by thin (t < 0.2 micron) tabular grains. To achieve the lowest levels of granularity it is preferred that aim tabular grain projected areas be satisfied with ultrathin (t < 0.06 micron) tabular grains. Tabular grain thicknesses typically range down to about 0.02 micron. However, still lower tabular grain thicknesses are contemplated. For example, Daubendiek et al U.S. Patent 4,672,027 reports a 3 mole percent iodide tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 micron.
- As noted above tabular grains of less than the specified thickness account for at least 50 percent of the total grain projected area of the emulsion. To maximize the advantages of high tabularity it is generally preferred that tabular grains satisfying the stated thickness criterion account for the highest conveniently attainable percentage of the total grain projected area of the emulsion. For example, in preferred emulsions, tabular grains satisfying the stated thickness criteria above account for at least 70 percent of the total grain projected area. In the highest performance tabular grain emulsions, tabular grains satisfying the thickness criteria above account for at least 90 percent of total grain projected area.
- Suitable tabular grain emulsions can be selected from among a variety of conventional teachings, such as those of the following:
Research Disclosure, Item 22534, January 1983, published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Patent Nos. 4,439,520; 4,414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012; 4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456; 4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322; 4,914,014; 4,962,015; 4,985,350; 5,061,069 and 5,061,616. In addition, use of [100] silver chloride emulsions as described in EP 534,395 are specifically contemplated. - The emulsions can be surface-sensitive emulsions, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or the emulsions can form internal latent images predominantly in the interior of the silver halide grains. The emulsions can be negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
- Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image and can then be processed to form a visible dye image. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
- With negative-working silver halide, the processing step described above provides a negative image. The described elements can be processed in the known C-41 color process as described in The British Journal of Photography Annual of 1988, pages 191-198. Where applicable, the element may be processed in accordance with color print processes such a the RA-4 process of Eastman Kodak Company as described in the British Journal of Photography Annual of 1988, Pp 198-199. To provide a positive (or reversal) image, the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable. Alternatively, a direct positive emulsion can be employed to obtain a positive image.
- Preferred color developing agents are p-phenylenediamines such as:
4-amino-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido) ethyl)aniline sesquisulfate hydrate,
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate,
4-amino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid. - Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
- It is understood thoroughout this specification and claims that any reference to a substituent by the identification of a group containing a substitutable hydrogen (e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.), unless otherwise specifically stated, shall encompass not only the substituent's unsubstituted form, but also its form substituted with any photographically useful substituents. Usually the substituent will have less than 30 carbon atoms and typically less than 20 carbon atoms.
- The following Example illustrates the reduction of viscosities of a coating melts by the addition of cyclodextrins.
- Solutions of gelatin, water and an isomeric mixture of a sulfonated oxidized developer scavenger (SC-1) having the structural formulas (a) and (b), given below, were prepared in the proportions given in Table 1.
Table I Summary of Effect of α-cyclodextrin on viscosity of gelatin melt containing SC-1 Example Gelatin (wt %) SC-1 (wt %) Viscosity reducing agent (α-CD, wt %) Mole ratio α-CD/SC-1 Viscosity at 40°C (cP) 1, no SC-1 (control) 10.1 0 0 - 23.1 2, (control) 10.1 0.21 0 ∞ 44.5 3, invention 10.1 0.21 0.42 1.05 44.5 4, invention 10.1 0.21 0.85 1.93 41.7 5, invention 10.1 0.21 1.28 2.91 31.3 6, invention 10.1 0.21 1.68 3.82 25.6 - Example 1 is a melt that has no SC-1, and shows the aqueous gelatin solution containing 10.1 wt.% gelatin has a viscosity of 23.1 cP RBT (Rolling Ball Time). Incorporation of SC-1 (0.21 wt %, based on the weight of the solution) in the melt raises the viscosity to 44.5 cP. However, it is seen that the addition of the compound α-cyclodextrin hydrate (commercially available from Aldrich Chemical Company) to the melt in progressively greater amounts, reduces the viscosity of the melts (Example 3, 4 and 5) to virtually the value of that of the melt that has no (SC-1).
- Surface tension studies show that addition of α-cyclodextrin to water does not reduce its surface tension; i.e., it remains at about 72 mNm⁻¹ as measured by the Wilhemy plate method.
- In Fig. 2, it can be seen that the surface tension of SC-1 (consisting of 31% of SC-1 (a) and 69% of SC-1 (b)) decreases to about 43 dynes/cm for a 5x10⁻⁴ M SC-1 solution. The sharp break in the curve at about 5 x 10⁻⁵ M
- In Fig. 3, it can be seen that the addition of increasing amounts of SC-1 to an aqueous solution of α-cyclodextrin (10⁻³ M), results in a drop in surface tension only after the molar amount of SC-1 approaches the number of moles of α-cyclodextrin. Assuming a 1:1 type association, the binding constant is about 990 M⁻¹.
- By comparing Fig. 2 and Fig. 3 it can be seen that the surface tension of a 5x10⁻⁴ M SC-1 in the absence of α-cyclodextrin is about 43 dynes/cm while it is significantly higher (69 dynes/cm) in the presence of 10⁻³ M α-cyclodextrin. Viewed another way, the data in Fig. 3 is also consistent with the conclusion that adding α-cyclodextrin to a solution of SC-1 would cause an increase in the surface tension of the solution as there would be less free SC-1.
Claims (7)
- An aqueous photographic coating composition comprising an aqueous solution comprising gelatin and an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, wherein the composition further comprises a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- A photographic coating composition in accordance with claim 1, wherein the anionically charged, hydrophobic group-containing compound is sodium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium or potassium salt of octadecyl hydroquinone sulfate, or a compound of the formula:
- A photographic coating composition in accordance with claim 1, wherein the anionically charged, hydrophobic group-containing compound is a sulfonated alkyl hydroquinone.
- A photographic coating composition in accordance with claim 1, wherein the cyclodextrin is α-cyclodextrin.
- A method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution.
- A method of reducing the viscosity of an aqueous gelatin solution containing an anionically charged, hydrophobic group-containing compound that is (a) soluble in water or a mixture of water and a water-miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, which method comprises adding to said solution a cyclodextrin in an amount sufficient to reduce the viscosity of the solution without causing a reduction in the surface tension of the composition.
- A photographic element comprising a support having thereon a layer comprising:(i) gelatin,(ii) an anionically charged, hydrophobic-group containing compound that is (a) soluble in water or a mixture of water and a water- miscible organic solvent, and (b) which confers an undesirably high viscosity to aqueous gelatin solutions, and(iii) a cyclodextrin.
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US28397894A | 1994-08-01 | 1994-08-01 | |
US283978 | 1994-08-01 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2332952A (en) * | 1997-12-30 | 1999-07-07 | Eastman Kodak Co | Reduced viscosity gelatin mixture used in a process for making a direct dispersion of a photographically useful material |
US6203973B1 (en) | 1999-03-25 | 2001-03-20 | Eastman Kodak Company | Polymer latexes with core-shell morphology |
CN109331784A (en) * | 2018-11-12 | 2019-02-15 | 中国石油大学(华东) | A kind of Chagerdβcyclodextrins derivative and its preparation and application method for removing organic pollutants |
Citations (199)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2298443A (en) | 1939-08-24 | 1942-10-13 | Eastman Kodak Co | Nondiffusing sulphonamide coupler for color photography |
US2311082A (en) | 1941-11-14 | 1943-02-16 | Eastman Kodak Co | Pyrazolone coupler for color photography |
US2343703A (en) | 1942-09-04 | 1944-03-07 | Eastman Kodak Co | Pyrazolone coupler for color photography |
US2367531A (en) | 1942-06-12 | 1945-01-16 | Eastman Kodak Co | Acylaminophenol photographic couplers |
US2369489A (en) | 1941-09-25 | 1945-02-13 | Eastman Kodak Co | Acylated amino pyrazolone couplers |
US2407210A (en) | 1944-04-14 | 1946-09-03 | Eastman Kodak Co | Color couplers |
US2455169A (en) | 1944-05-03 | 1948-11-30 | Eastman Kodak Co | Colored couplers |
US2474293A (en) | 1947-09-10 | 1949-06-28 | Eastman Kodak Co | 1-naphthol-2-carboxylic acid amide couplers for color photography |
US2600788A (en) | 1949-06-07 | 1952-06-17 | Eastman Kodak Co | Halogen-substituted pyrazolone couplers for color photography |
US2681294A (en) | 1951-08-23 | 1954-06-15 | Eastman Kodak Co | Method of coating strip material |
US2761417A (en) | 1955-02-23 | 1956-09-04 | Eastman Kodak Co | Multiple coating apparatus |
US2772162A (en) | 1954-11-03 | 1956-11-27 | Eastman Kodak Co | Diacylaminophenol couplers |
US2875057A (en) | 1954-12-20 | 1959-02-24 | Eastman Kodak Co | Benzoylacet-o-alkoxyanilide couplers for color photography |
US2895826A (en) | 1956-10-08 | 1959-07-21 | Eastman Kodak Co | Photographic color couplers containing fluoroalkylcarbonamido groups |
US2908573A (en) | 1956-07-25 | 1959-10-13 | Eastman Kodak Co | Photographic color couplers containing mono-n-alkyl groups |
US2983608A (en) | 1958-10-06 | 1961-05-09 | Eastman Kodak Co | Yellow-colored magenta-forming couplers |
US3002836A (en) | 1959-04-09 | 1961-10-03 | Eastman Kodak Co | Cyan color former for color photography |
US3034892A (en) | 1958-10-27 | 1962-05-15 | Eastman Kodak Co | Magenta-colored cyan-forming couplers |
US3041236A (en) | 1959-09-18 | 1962-06-26 | Herbert C Stecker | Germicides containing trifluoromethyl halogenated salicylanilides |
US3048194A (en) | 1958-11-26 | 1962-08-07 | Gen Fire Extinguisher Corp | Fire extinguisher head assembly |
US3062653A (en) | 1960-02-18 | 1962-11-06 | Eastman Kodak Co | Photographic emulsion containing pyrazolone magenta-forming couplers |
US3137578A (en) | 1962-02-07 | 1964-06-16 | Eastman Kodak Co | Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants |
US3148022A (en) | 1961-10-17 | 1964-09-08 | Du Pont | Process for extracting beryllium values from ores |
US3148062A (en) | 1959-04-06 | 1964-09-08 | Eastman Kodak Co | Photographic elements and processes using splittable couplers |
US3152896A (en) | 1963-02-18 | 1964-10-13 | Eastman Kodak Co | Magenta-forming couplers |
US3227551A (en) | 1959-04-06 | 1966-01-04 | Eastman Kodak Co | Photographic color reproduction process and element |
US3265506A (en) | 1964-05-04 | 1966-08-09 | Eastman Kodak Co | Yellow forming couplers |
US3379529A (en) | 1963-02-28 | 1968-04-23 | Eastman Kodak Co | Photographic inhibitor-releasing developers |
US3384657A (en) | 1960-04-28 | 1968-05-21 | Eastman Kodak Co | Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom |
US3432521A (en) | 1962-12-26 | 1969-03-11 | Eastman Kodak Co | 4-acyloxy-5-pyrazolones |
US3447928A (en) | 1965-07-26 | 1969-06-03 | Eastman Kodak Co | Silver halide emulsion containing twoequivalent yellow dye-forming coupler |
US3476563A (en) | 1965-08-30 | 1969-11-04 | Eastman Kodak Co | Photographic silver halide elements containing two equivalent cyan couplers |
US3519429A (en) | 1966-05-16 | 1970-07-07 | Eastman Kodak Co | Silver halide emulsions containing a stabilizer pyrazolone coupler |
US3615506A (en) | 1970-02-09 | 1971-10-26 | Eastman Kodak Co | Silver halide emulsions containing 3-cyclicamino-5-pyrazolone color couplers |
US3617291A (en) | 1967-10-10 | 1971-11-02 | Eastman Kodak Co | Two-equivalent couplers for photography |
US3620746A (en) | 1968-04-01 | 1971-11-16 | Eastman Kodak Co | Color photographic material comprising nondiffusing coupler and dir hydroquinone |
US3632374A (en) | 1968-06-03 | 1972-01-04 | Eastman Kodak Co | Method of making photographic elements |
US3733201A (en) | 1971-10-01 | 1973-05-15 | Eastman Kodak Co | Photographic compositions and elements comprising coupling compounds which on development release silver halidecomplexing materials and dyes |
US3860425A (en) | 1971-08-25 | 1975-01-14 | Fuji Photo Film Co Ltd | Dispersion containing nonionic surface acting agent with units of polyoxyethylene and polyoxypropylene |
US3880661A (en) | 1971-12-29 | 1975-04-29 | Eastman Kodak Co | Silver halide emulsion containing acylamidophenol photographic couplers |
GB1466728A (en) | 1973-05-25 | 1977-03-09 | Konishiroku Photo Ind | Two equivalent type colour couplers containing carbamoyloxy groups at their active positions and their use in photography |
DE2643965A1 (en) | 1975-09-30 | 1977-04-07 | Fuji Photo Film Co Ltd | Subtractive colour photographic material - contg. coloured coupler of aryl arylamino arylazo pyrazolone type to give satisfactory masking |
US4049455A (en) | 1975-08-15 | 1977-09-20 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
US4052212A (en) | 1974-02-08 | 1977-10-04 | Konishiroku Photo Industry Co., Ltd. | Photographic silver halide emulsion containing 2-equivalent cyan coupler |
US4070191A (en) | 1973-03-31 | 1978-01-24 | Konishiroku Photo Industry Co., Ltd. | Silver halide emulsion containing colored magenta coupler for photography |
US4095984A (en) | 1975-12-29 | 1978-06-20 | Fuji Photo Film Co., Ltd. | Development inhibitor releasing coupler and photographic element containing same |
GB1530272A (en) | 1975-02-21 | 1978-10-25 | Agfa Gevaert | 2-pyrazolin-5-ones and their use as colour couplers for silver halide photography |
GB1531927A (en) | 1975-06-11 | 1978-11-15 | Fuji Photo Film Co Ltd | Photographic cyan colour couplers and silver halide materials |
US4126459A (en) | 1976-05-14 | 1978-11-21 | Polaroid Corporation | Thioether substituted silver halide solvents |
GB1533039A (en) | 1975-08-08 | 1978-11-22 | Fuji Photo Film Co Ltd | Photographic silver halide materials and developers containing couplers |
US4134766A (en) | 1976-10-23 | 1979-01-16 | Konishiroku Photo Industry Co., Ltd. | Dye image forming process |
DE2842063A1 (en) | 1977-09-29 | 1979-04-05 | Ciba Geigy Ag | LIGHT SENSITIVE COLOR PHOTOGRAPHIC RECORDING MATERIAL |
US4149886A (en) | 1975-12-09 | 1979-04-17 | Fuji Photo Film Co., Ltd. | Light-sensitive material with coupler containing triazole coupling-off group |
GB2006755A (en) | 1977-09-22 | 1979-05-10 | Fuji Photo Film Co Ltd | Photographic silver halide light-sensitive material |
US4163669A (en) | 1977-04-27 | 1979-08-07 | Mitsubishi Paper Mills, Ltd. | Multilayer silver halide color photographic material |
GB2017704A (en) | 1978-03-31 | 1979-10-10 | Eastman Kodak Co | Ketomethylene yellow dye-forming couplers |
GB1560240A (en) | 1976-12-07 | 1980-01-30 | Fuji Photo Film Co Ltd | Photographic silver halide development in the presence of development inhibitor releasing coupling compound |
DE2937127A1 (en) | 1978-09-18 | 1980-03-27 | Ciba Geigy Ag | DEVELOPMENT INHIBITOR RELEASING CONNECTIONS AND THEIR USE IN PHOTOGRAPHIC MATERIALS |
GB2032914A (en) | 1977-08-12 | 1980-05-14 | Ciba Geigy Ag | Heterocyclyl-substituted phenacyl thioether derivatives for use as photographic development inhibitors |
US4211562A (en) | 1974-04-23 | 1980-07-08 | Polaroid Corporation | Photographic compositions with silver halide solvents containing thioether groups |
US4248962A (en) | 1977-12-23 | 1981-02-03 | Eastman Kodak Company | Photographic emulsions, elements and processes utilizing release compounds |
US4273861A (en) | 1973-06-19 | 1981-06-16 | Fuji Photo Film Co., Ltd. | Multilayer color photographic materials utilizing an interlayer correction coupler |
US4301235A (en) | 1979-09-05 | 1981-11-17 | Fuji Photo Film Co., Ltd. | Process and material for forming color photographic image |
US4346165A (en) | 1980-01-09 | 1982-08-24 | Fuji Photo Film Co., Ltd. | Process for improving light fastness of color images |
US4351897A (en) | 1980-08-12 | 1982-09-28 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
GB2097140A (en) | 1981-03-13 | 1982-10-27 | Fuji Photo Film Co Ltd | Silver halide photographic light-sensitive materials |
GB2099167A (en) | 1981-03-16 | 1982-12-01 | Fuji Photo Film Co Ltd | Silver halide color photographic light-sensitive material |
US4366237A (en) | 1980-07-04 | 1982-12-28 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
JPS589959A (en) | 1981-07-07 | 1983-01-20 | Sumitomo Metal Ind Ltd | Manufacture of ferroalloy |
JPS5862586A (en) | 1981-10-09 | 1983-04-14 | 株式会社日立製作所 | Movable head positioning device |
JPS58113935A (en) | 1981-12-26 | 1983-07-07 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
US4409323A (en) | 1980-02-15 | 1983-10-11 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic material |
JPS58172647A (en) | 1982-04-02 | 1983-10-11 | Konishiroku Photo Ind Co Ltd | Color photographic sensitive silver halide material |
US4414310A (en) | 1981-11-12 | 1983-11-08 | Eastman Kodak Company | Process for the preparation of high aspect ratio silver bromoiodide emulsions |
US4420556A (en) | 1980-09-11 | 1983-12-13 | Eastman Kodak Company | Photographic silver halide materials |
EP0096570A1 (en) | 1982-06-05 | 1983-12-21 | Olympus Optical Co., Ltd. | An optical system focus-state detector |
US4433048A (en) | 1981-11-12 | 1984-02-21 | Eastman Kodak Company | Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use |
US4439520A (en) | 1981-11-12 | 1984-03-27 | Eastman Kodak Company | Sensitized high aspect ratio silver halide emulsions and photographic elements |
GB2131188A (en) | 1982-09-16 | 1984-06-13 | Fuji Photo Film Co Ltd | Silver halide photographic material |
US4500634A (en) | 1982-08-24 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4525392A (en) | 1980-01-30 | 1985-06-25 | Fuji Photo Film Company, Limited | Method of simultaneously applying multiple layers to web |
US4540653A (en) | 1983-08-31 | 1985-09-10 | Konishiroku Photo Industry Co., Ltd. | Method of improving the light resistance of a dye image |
US4543323A (en) | 1982-12-18 | 1985-09-24 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
EP0164961A2 (en) | 1984-06-06 | 1985-12-18 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic elements employing novel coupler solvents |
US4569863A (en) | 1982-10-21 | 1986-02-11 | Agfa-Gevaert Aktiengesellschaft | Process for the multiple coating of moving objects or webs |
US4579816A (en) | 1984-07-24 | 1986-04-01 | Agfa-Gevaert Aktiengesellschaft | Yellow DIR coupler with 5-furyl(1,2,4-triazole) coupling off group |
US4607004A (en) | 1983-12-26 | 1986-08-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
EP0193389A2 (en) | 1985-02-28 | 1986-09-03 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Use of a coupler comprising a coupler moiety having a releasable bleach accelerator moiety |
US4618571A (en) | 1984-02-23 | 1986-10-21 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
JPS61258249A (en) | 1985-05-13 | 1986-11-15 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
US4643966A (en) | 1985-09-03 | 1987-02-17 | Eastman Kodak Company | Emulsions and photographic elements containing ruffled silver halide grains |
US4647528A (en) | 1983-09-16 | 1987-03-03 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0213490A2 (en) | 1985-08-24 | 1987-03-11 | Agfa-Gevaert AG | Colour-photographic recording material |
US4665012A (en) | 1982-11-29 | 1987-05-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4672027A (en) | 1985-10-23 | 1987-06-09 | Eastman Kodak Company | Multicolor photographic element with a minus blue recording tabular grain emulsion layer overlying a blue recording emulsion layer |
US4678739A (en) | 1984-12-20 | 1987-07-07 | Fuji Photo Film Co., Ltd. | Image forming method including heating step |
US4678745A (en) | 1984-06-15 | 1987-07-07 | Fuji Photo Film Co., Ltd. | Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same |
US4693964A (en) | 1985-10-23 | 1987-09-15 | Eastman Kodak Company | Multicolor photographic element with a tabular grain emulsion layer overlying a minus blue recording emulsion layer |
US4713320A (en) | 1985-12-19 | 1987-12-15 | Eastman Kodak Company | Low methionine gelatino-peptizer tabular grain silver bromide and bromoiodide emulsions and processes for their preparation |
US4722886A (en) | 1986-10-10 | 1988-02-02 | E. I. Du Pont De Nemours And Company | Process for preparing a photographic emulsion containing tabular grains having narrow size distribution |
DE3636824A1 (en) | 1986-10-29 | 1988-05-05 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A YELLOW DIR COUPLER |
US4746601A (en) | 1983-12-15 | 1988-05-24 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4746600A (en) | 1985-07-01 | 1988-05-24 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide color photographic material with non-diffusable light-insensitive dye layer |
EP0272573A2 (en) | 1986-12-24 | 1988-06-29 | Agfa-Gevaert AG | Colour-photographic recording material with a coupler liberating a photographically active compound |
US4755456A (en) | 1985-12-26 | 1988-07-05 | Fuji Photo Film Co., Ltd. | Method for preparing silver iodobromide emulsions having high aspect ratio |
DE3644416A1 (en) | 1986-12-24 | 1988-07-07 | Agfa Gevaert Ag | Colour-photographic recording material containing a coupler which liberates a photographically effective compound |
US4775617A (en) | 1985-07-18 | 1988-10-04 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing monodispersed tabular silver halide grains |
DE2706117C2 (en) | 1976-02-23 | 1988-10-13 | Agfa-Gevaert Ag, 5090 Leverkusen, De | |
US4782012A (en) | 1987-07-17 | 1988-11-01 | Eastman Kodak Company | Photographic material containing a novel dir-compound |
US4791049A (en) | 1986-04-25 | 1988-12-13 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a compound having an oxidation-reduction moiety and timing group |
US4797354A (en) | 1986-03-06 | 1989-01-10 | Fuji Photo Film Co., Ltd. | Silver halide emulsions comprising hexagonal monodisperse tabular silver halide grains |
US4801522A (en) | 1986-10-10 | 1989-01-31 | E. I. Du Pont De Nemours And Company | Process for preparing a photographic emulsion containing tabular grains exhibiting high speed |
EP0301477A2 (en) | 1987-07-27 | 1989-02-01 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material and method of processing thereof |
US4806461A (en) | 1987-03-10 | 1989-02-21 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic light-sensitive material using tabular grains having ten or more dislocations per grain |
US4835095A (en) | 1986-02-03 | 1989-05-30 | Fuji Photo Film Co., Ltd. | Photosensitive tabular core/shell silver halide emulsion |
US4853319A (en) | 1986-12-22 | 1989-08-01 | Eastman Kodak Company | Photographic silver halide element and process |
US4853322A (en) | 1986-12-26 | 1989-08-01 | Fuji Photo Film Co., Ltd. | Light-sensitive silver halide emulsion and color photographic materials using the same |
US4857447A (en) | 1985-05-28 | 1989-08-15 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material containing a coupler having a dye moiety |
US4859578A (en) | 1988-06-21 | 1989-08-22 | Eastman Kodak Company | Photographic recording material providing improved granularity properties |
US4865959A (en) | 1987-06-25 | 1989-09-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing a bleach accelerator releasing compound |
US4865956A (en) | 1987-11-24 | 1989-09-12 | Eastman Kodak Company | Photographic elements containing a bleach accelerator precursor |
EP0335319A2 (en) | 1988-03-28 | 1989-10-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0336411A2 (en) | 1988-04-07 | 1989-10-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4880342A (en) | 1988-06-16 | 1989-11-14 | Millis Transfer, Inc. | Movable bulkhead |
US4883746A (en) | 1985-05-29 | 1989-11-28 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4886736A (en) | 1986-06-12 | 1989-12-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0346899A2 (en) | 1988-06-16 | 1989-12-20 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4906559A (en) | 1985-02-22 | 1990-03-06 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
JPH0272629A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Manufacture of semiconductor device |
JPH0272633A (en) | 1988-09-07 | 1990-03-12 | Mitsubishi Electric Corp | Manufacture of semiconductor device |
JPH0272630A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Manufacture of semiconductor device |
JPH0272632A (en) | 1988-09-08 | 1990-03-12 | Kawasaki Steel Corp | Manufacture of semiconductor device |
JPH0272631A (en) | 1988-09-08 | 1990-03-12 | Fuji Xerox Co Ltd | Wiring structure in electronic device and image sensor having this wiring structure |
JPH0272634A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Semiconductor device |
JPH0279338A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Shadow mask for color cathode ray tube |
JPH0279336A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Indirectly heated cathode structure |
JPH0279337A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Color cathode ray tube |
JPH0278229A (en) | 1988-09-13 | 1990-03-19 | Nec Corp | Field-effect transistor and its manufacture |
JPH0278230A (en) | 1988-09-14 | 1990-03-19 | Hitachi Ltd | Semiconductor integrated circuit device |
JPH0280488A (en) | 1988-09-16 | 1990-03-20 | Miyoshi Oil & Fat Co Ltd | Antistatic agent |
JPH0280489A (en) | 1988-09-19 | 1990-03-20 | Japan Vilene Co Ltd | Low-temperature insulation material |
JPH0280491A (en) | 1988-09-17 | 1990-03-20 | Sumitomo Metal Ind Ltd | Operation of continuous formed coke oven |
JPH0280487A (en) | 1988-09-15 | 1990-03-20 | Sumitomo Electric Ind Ltd | Carbon fibver-reinforced composite carbon material |
JPH0279690A (en) | 1988-09-16 | 1990-03-20 | Hitachi Ltd | Television signal forming method |
JPH0280494A (en) | 1988-09-16 | 1990-03-20 | Toyokazu Fukuoka | Removal of oil from bean-curd refuse |
JPH0280492A (en) | 1988-09-17 | 1990-03-20 | Sanii Denka:Kk | Welding tip or nozzle |
JPH0280490A (en) | 1988-09-17 | 1990-03-20 | Nagase Sangyo Kk | Highly heat-resistant photochromic material |
JPH0279691A (en) | 1988-09-16 | 1990-03-20 | Hitachi Ltd | Satellite broadcast receiver |
JPH0285928A (en) | 1988-09-22 | 1990-03-27 | Fujitsu Ltd | Automation system for system install job |
JPH0286669A (en) | 1988-09-22 | 1990-03-27 | Toyobo Co Ltd | Coating resin composition |
JPH0286670A (en) | 1988-09-22 | 1990-03-27 | Takamatsu Yushi Kk | Water-based coating composition |
US4912025A (en) | 1988-06-21 | 1990-03-27 | Eastman Kodak Company | Photographic recording material for accelerated development |
JPH0288097A (en) | 1988-09-27 | 1990-03-28 | Toshiba Corp | Washing drying machine |
JPH0287362A (en) | 1988-09-24 | 1990-03-28 | Sony Corp | Information read-out and reproducing device |
JPH0287363A (en) | 1988-09-22 | 1990-03-28 | Nec Home Electron Ltd | Sound recorder |
JPH0287364A (en) | 1988-09-22 | 1990-03-28 | Casio Comput Co Ltd | Access method for storage device |
JPH0287360A (en) | 1988-09-22 | 1990-03-28 | Alpine Electron Inc | Cartridge eject device in disk changer |
JPH0287361A (en) | 1988-09-21 | 1990-03-28 | Matsushita Electric Ind Co Ltd | Disk reproducing device |
US4914014A (en) | 1988-06-30 | 1990-04-03 | Eastman Kodak Company | Nucleation of tabular grain emulsions at high pBr |
JPH0293665A (en) | 1988-09-30 | 1990-04-04 | Fuji Xerox Co Ltd | Image output device |
JPH0293668A (en) | 1988-09-30 | 1990-04-04 | Ricoh Co Ltd | Automatic inverted document feeder for copying machine |
JPH0293666A (en) | 1988-09-30 | 1990-04-04 | Fuji Xerox Co Ltd | Image output device |
JPH0294056A (en) | 1988-09-30 | 1990-04-04 | Hitachi Ltd | Magnetic recording and reproducing device |
JPH0293664A (en) | 1988-09-30 | 1990-04-04 | Seiko Epson Corp | Wet type color image forming device |
JPH0293662A (en) | 1988-09-30 | 1990-04-04 | Canon Inc | Image forming device |
JPH0293663A (en) | 1988-09-30 | 1990-04-04 | Canon Inc | Image forming device |
JPH0294055A (en) | 1988-09-30 | 1990-04-04 | Hitachi Ltd | Magnetic recording and reproducing device |
EP0362870A2 (en) | 1988-10-06 | 1990-04-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
JPH02103409A (en) | 1988-06-24 | 1990-04-16 | Iwate Pref Gov Chiyuushiyou Kigyo Shinko Koushiya | Continuous detection and correction of defect of strip workpiece |
US4917994A (en) | 1988-03-01 | 1990-04-17 | Eastman Kodak Company | Color photographic reflection print material with improved keeping properties |
EP0365346A2 (en) | 1988-10-21 | 1990-04-25 | Toyo Ink Manufacturing Co., Ltd. | Diazo pigment composition |
EP0365252A2 (en) | 1988-10-15 | 1990-04-25 | Konica Corporation | A silver halide color photographic light-sensitive material for making color negatives |
US4923784A (en) | 1987-11-24 | 1990-05-08 | Eastman Kodak Company | Photographic elements containing a bleach accelerator precursor |
EP0373382A1 (en) | 1988-11-18 | 1990-06-20 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material |
US4937179A (en) | 1985-05-27 | 1990-06-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0376212A2 (en) | 1988-12-26 | 1990-07-04 | Fuji Photo Film Co., Ltd. | Silver halide color photographic photosensitive materials |
EP0377463A2 (en) | 1989-01-05 | 1990-07-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0378236A1 (en) | 1989-01-13 | 1990-07-18 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4946767A (en) | 1987-09-25 | 1990-08-07 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4948716A (en) | 1985-04-30 | 1990-08-14 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4952485A (en) | 1986-09-29 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Silver halide color negative photographic materials |
EP0384670A2 (en) | 1989-02-21 | 1990-08-29 | Konica Corporation | Method for processing light sensitive silver halide color photographic material |
US4956269A (en) | 1988-11-24 | 1990-09-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
US4959299A (en) | 1987-03-05 | 1990-09-25 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
US4962018A (en) | 1988-06-21 | 1990-10-09 | Eastman Kodak Company | Photographic materials containing DIR compounds and process of imaging |
US4962015A (en) | 1988-05-02 | 1990-10-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4966835A (en) | 1987-08-13 | 1990-10-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material |
EP0396486A1 (en) | 1989-05-04 | 1990-11-07 | International Business Machines Corporation | Receiver and level converter circuit |
EP0401613A2 (en) | 1989-06-06 | 1990-12-12 | Agfa-Gevaert AG | Colour photographic recording material with a DIR coupler |
EP0401612A2 (en) | 1989-06-06 | 1990-12-12 | Agfa-Gevaert AG | Colour photographic recording material with a DIR coupler |
US4985350A (en) | 1987-06-01 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4985336A (en) | 1985-07-24 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4994359A (en) | 1988-08-02 | 1991-02-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US5019492A (en) | 1989-04-26 | 1991-05-28 | Eastman Kodak Company | Photographic element and process comprising a blocked photographically useful compound |
US5061616A (en) | 1989-07-13 | 1991-10-29 | Eastman Kodak Company | Process of preparing a tabular grain silver bromoiodide emulsion |
US5061069A (en) | 1989-07-31 | 1991-10-29 | Allied-Signal Inc. | Fiber-optic bender beam interferometer accelerometer |
US5068171A (en) | 1988-07-16 | 1991-11-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material containing a two equivalent 5-pyrazolone magenta coupler and color photograph containing the same |
EP0534395A1 (en) | 1991-09-24 | 1993-03-31 | Eastman Kodak Company | High tabularity high chloride emulsions of exceptional stability |
US5300418A (en) | 1992-04-16 | 1994-04-05 | Eastman Kodak Company | Viscosity control of photographic melts |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0418743A3 (en) * | 1989-09-18 | 1991-05-15 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US5137571A (en) * | 1990-06-05 | 1992-08-11 | Rohm And Haas Company | Method for improving thickeners for aqueous systems |
HUT63704A (en) * | 1991-11-20 | 1993-09-28 | Forte Fotokemiai Ipar | Method for accelerating development of photo-materials |
US5352563A (en) * | 1992-01-21 | 1994-10-04 | Konica Corporation | Black-and-white silver halide photographic light-sensitive material and a method for processing the same |
EP0568850A1 (en) * | 1992-05-06 | 1993-11-10 | E.I. Du Pont De Nemours And Company | Photographic silver halide systems containing water soluble cyclodextrin-adjuvant adducts |
EP0675403A1 (en) * | 1994-03-22 | 1995-10-04 | Agfa-Gevaert N.V. | Photograhic material with effeciently used non-sensitizing dyes |
-
1995
- 1995-07-31 EP EP95112023A patent/EP0695968A3/en not_active Withdrawn
- 1995-07-31 JP JP19462695A patent/JPH08101477A/en active Pending
Patent Citations (209)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2298443A (en) | 1939-08-24 | 1942-10-13 | Eastman Kodak Co | Nondiffusing sulphonamide coupler for color photography |
US2369489A (en) | 1941-09-25 | 1945-02-13 | Eastman Kodak Co | Acylated amino pyrazolone couplers |
US2311082A (en) | 1941-11-14 | 1943-02-16 | Eastman Kodak Co | Pyrazolone coupler for color photography |
US2367531A (en) | 1942-06-12 | 1945-01-16 | Eastman Kodak Co | Acylaminophenol photographic couplers |
US2423730A (en) | 1942-06-12 | 1947-07-08 | Eastman Kodak Co | Acylamino phenols |
US2343703A (en) | 1942-09-04 | 1944-03-07 | Eastman Kodak Co | Pyrazolone coupler for color photography |
US2407210A (en) | 1944-04-14 | 1946-09-03 | Eastman Kodak Co | Color couplers |
US2455169A (en) | 1944-05-03 | 1948-11-30 | Eastman Kodak Co | Colored couplers |
US2474293A (en) | 1947-09-10 | 1949-06-28 | Eastman Kodak Co | 1-naphthol-2-carboxylic acid amide couplers for color photography |
US2600788A (en) | 1949-06-07 | 1952-06-17 | Eastman Kodak Co | Halogen-substituted pyrazolone couplers for color photography |
US2681294A (en) | 1951-08-23 | 1954-06-15 | Eastman Kodak Co | Method of coating strip material |
US2772162A (en) | 1954-11-03 | 1956-11-27 | Eastman Kodak Co | Diacylaminophenol couplers |
US2875057A (en) | 1954-12-20 | 1959-02-24 | Eastman Kodak Co | Benzoylacet-o-alkoxyanilide couplers for color photography |
US2761417A (en) | 1955-02-23 | 1956-09-04 | Eastman Kodak Co | Multiple coating apparatus |
US2908573A (en) | 1956-07-25 | 1959-10-13 | Eastman Kodak Co | Photographic color couplers containing mono-n-alkyl groups |
US2895826A (en) | 1956-10-08 | 1959-07-21 | Eastman Kodak Co | Photographic color couplers containing fluoroalkylcarbonamido groups |
US2983608A (en) | 1958-10-06 | 1961-05-09 | Eastman Kodak Co | Yellow-colored magenta-forming couplers |
US3034892A (en) | 1958-10-27 | 1962-05-15 | Eastman Kodak Co | Magenta-colored cyan-forming couplers |
US3048194A (en) | 1958-11-26 | 1962-08-07 | Gen Fire Extinguisher Corp | Fire extinguisher head assembly |
US3227554A (en) | 1959-04-06 | 1966-01-04 | Eastman Kodak Co | Photographic elements and processes utilizing mercaptan-forming couplers |
US3701783A (en) | 1959-04-06 | 1972-10-31 | Eastman Kodak Co | Certain mercaptan-forming couplers |
US3148062A (en) | 1959-04-06 | 1964-09-08 | Eastman Kodak Co | Photographic elements and processes using splittable couplers |
US3227551A (en) | 1959-04-06 | 1966-01-04 | Eastman Kodak Co | Photographic color reproduction process and element |
US3002836A (en) | 1959-04-09 | 1961-10-03 | Eastman Kodak Co | Cyan color former for color photography |
US3041236A (en) | 1959-09-18 | 1962-06-26 | Herbert C Stecker | Germicides containing trifluoromethyl halogenated salicylanilides |
US3062653A (en) | 1960-02-18 | 1962-11-06 | Eastman Kodak Co | Photographic emulsion containing pyrazolone magenta-forming couplers |
US3384657A (en) | 1960-04-28 | 1968-05-21 | Eastman Kodak Co | Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom |
US3148022A (en) | 1961-10-17 | 1964-09-08 | Du Pont | Process for extracting beryllium values from ores |
US3137578A (en) | 1962-02-07 | 1964-06-16 | Eastman Kodak Co | Photographic emulsions containing 2-heterocyclic benzimidazole antifoggants |
US3432521A (en) | 1962-12-26 | 1969-03-11 | Eastman Kodak Co | 4-acyloxy-5-pyrazolones |
US3152896A (en) | 1963-02-18 | 1964-10-13 | Eastman Kodak Co | Magenta-forming couplers |
US3379529A (en) | 1963-02-28 | 1968-04-23 | Eastman Kodak Co | Photographic inhibitor-releasing developers |
US3265506A (en) | 1964-05-04 | 1966-08-09 | Eastman Kodak Co | Yellow forming couplers |
US3447928A (en) | 1965-07-26 | 1969-06-03 | Eastman Kodak Co | Silver halide emulsion containing twoequivalent yellow dye-forming coupler |
US3476563A (en) | 1965-08-30 | 1969-11-04 | Eastman Kodak Co | Photographic silver halide elements containing two equivalent cyan couplers |
US3519429A (en) | 1966-05-16 | 1970-07-07 | Eastman Kodak Co | Silver halide emulsions containing a stabilizer pyrazolone coupler |
US3617291A (en) | 1967-10-10 | 1971-11-02 | Eastman Kodak Co | Two-equivalent couplers for photography |
US3620746A (en) | 1968-04-01 | 1971-11-16 | Eastman Kodak Co | Color photographic material comprising nondiffusing coupler and dir hydroquinone |
US3632374A (en) | 1968-06-03 | 1972-01-04 | Eastman Kodak Co | Method of making photographic elements |
US3615506A (en) | 1970-02-09 | 1971-10-26 | Eastman Kodak Co | Silver halide emulsions containing 3-cyclicamino-5-pyrazolone color couplers |
US3860425A (en) | 1971-08-25 | 1975-01-14 | Fuji Photo Film Co Ltd | Dispersion containing nonionic surface acting agent with units of polyoxyethylene and polyoxypropylene |
US3733201A (en) | 1971-10-01 | 1973-05-15 | Eastman Kodak Co | Photographic compositions and elements comprising coupling compounds which on development release silver halidecomplexing materials and dyes |
US3880661A (en) | 1971-12-29 | 1975-04-29 | Eastman Kodak Co | Silver halide emulsion containing acylamidophenol photographic couplers |
US4070191A (en) | 1973-03-31 | 1978-01-24 | Konishiroku Photo Industry Co., Ltd. | Silver halide emulsion containing colored magenta coupler for photography |
GB1466728A (en) | 1973-05-25 | 1977-03-09 | Konishiroku Photo Ind | Two equivalent type colour couplers containing carbamoyloxy groups at their active positions and their use in photography |
US4273861B1 (en) | 1973-06-19 | 1986-11-25 | ||
US4273861A (en) | 1973-06-19 | 1981-06-16 | Fuji Photo Film Co., Ltd. | Multilayer color photographic materials utilizing an interlayer correction coupler |
US4052212A (en) | 1974-02-08 | 1977-10-04 | Konishiroku Photo Industry Co., Ltd. | Photographic silver halide emulsion containing 2-equivalent cyan coupler |
US4211562A (en) | 1974-04-23 | 1980-07-08 | Polaroid Corporation | Photographic compositions with silver halide solvents containing thioether groups |
GB1530272A (en) | 1975-02-21 | 1978-10-25 | Agfa Gevaert | 2-pyrazolin-5-ones and their use as colour couplers for silver halide photography |
GB1531927A (en) | 1975-06-11 | 1978-11-15 | Fuji Photo Film Co Ltd | Photographic cyan colour couplers and silver halide materials |
GB1533039A (en) | 1975-08-08 | 1978-11-22 | Fuji Photo Film Co Ltd | Photographic silver halide materials and developers containing couplers |
US4049455A (en) | 1975-08-15 | 1977-09-20 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
DE2643965A1 (en) | 1975-09-30 | 1977-04-07 | Fuji Photo Film Co Ltd | Subtractive colour photographic material - contg. coloured coupler of aryl arylamino arylazo pyrazolone type to give satisfactory masking |
US4149886A (en) | 1975-12-09 | 1979-04-17 | Fuji Photo Film Co., Ltd. | Light-sensitive material with coupler containing triazole coupling-off group |
US4095984A (en) | 1975-12-29 | 1978-06-20 | Fuji Photo Film Co., Ltd. | Development inhibitor releasing coupler and photographic element containing same |
DE2706117C2 (en) | 1976-02-23 | 1988-10-13 | Agfa-Gevaert Ag, 5090 Leverkusen, De | |
US4150228A (en) | 1976-05-14 | 1979-04-17 | Polaroid Corporation | Thioether substituted silver halide solvents |
US4126459A (en) | 1976-05-14 | 1978-11-21 | Polaroid Corporation | Thioether substituted silver halide solvents |
US4134766A (en) | 1976-10-23 | 1979-01-16 | Konishiroku Photo Industry Co., Ltd. | Dye image forming process |
GB1560240A (en) | 1976-12-07 | 1980-01-30 | Fuji Photo Film Co Ltd | Photographic silver halide development in the presence of development inhibitor releasing coupling compound |
US4163669A (en) | 1977-04-27 | 1979-08-07 | Mitsubishi Paper Mills, Ltd. | Multilayer silver halide color photographic material |
GB2032914A (en) | 1977-08-12 | 1980-05-14 | Ciba Geigy Ag | Heterocyclyl-substituted phenacyl thioether derivatives for use as photographic development inhibitors |
GB2006755A (en) | 1977-09-22 | 1979-05-10 | Fuji Photo Film Co Ltd | Photographic silver halide light-sensitive material |
DE2842063A1 (en) | 1977-09-29 | 1979-04-05 | Ciba Geigy Ag | LIGHT SENSITIVE COLOR PHOTOGRAPHIC RECORDING MATERIAL |
GB2007662A (en) | 1977-09-29 | 1979-05-23 | Ciba Geigy Ag | Lightsensitive colour photographic material |
US4248962A (en) | 1977-12-23 | 1981-02-03 | Eastman Kodak Company | Photographic emulsions, elements and processes utilizing release compounds |
GB2017704A (en) | 1978-03-31 | 1979-10-10 | Eastman Kodak Co | Ketomethylene yellow dye-forming couplers |
DE2937127A1 (en) | 1978-09-18 | 1980-03-27 | Ciba Geigy Ag | DEVELOPMENT INHIBITOR RELEASING CONNECTIONS AND THEIR USE IN PHOTOGRAPHIC MATERIALS |
US4259437A (en) | 1978-09-18 | 1981-03-31 | Ciba-Geigy Ag | Development inhibitor releasing compounds and their use in photographic materials |
US4362878A (en) | 1978-09-18 | 1982-12-07 | Ciba-Geigy Ag | Substituted 1,2,4-triazoles as DIR compounds and their use in photographic materials |
US4301235A (en) | 1979-09-05 | 1981-11-17 | Fuji Photo Film Co., Ltd. | Process and material for forming color photographic image |
US4346165A (en) | 1980-01-09 | 1982-08-24 | Fuji Photo Film Co., Ltd. | Process for improving light fastness of color images |
US4525392A (en) | 1980-01-30 | 1985-06-25 | Fuji Photo Film Company, Limited | Method of simultaneously applying multiple layers to web |
US4409323A (en) | 1980-02-15 | 1983-10-11 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic material |
US4366237A (en) | 1980-07-04 | 1982-12-28 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4351897A (en) | 1980-08-12 | 1982-09-28 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
US4351897B1 (en) | 1980-08-12 | 1988-06-14 | ||
US4420556A (en) | 1980-09-11 | 1983-12-13 | Eastman Kodak Company | Photographic silver halide materials |
GB2097140A (en) | 1981-03-13 | 1982-10-27 | Fuji Photo Film Co Ltd | Silver halide photographic light-sensitive materials |
US4477563A (en) | 1981-03-16 | 1984-10-16 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
GB2099167A (en) | 1981-03-16 | 1982-12-01 | Fuji Photo Film Co Ltd | Silver halide color photographic light-sensitive material |
JPS589959A (en) | 1981-07-07 | 1983-01-20 | Sumitomo Metal Ind Ltd | Manufacture of ferroalloy |
JPS5862586A (en) | 1981-10-09 | 1983-04-14 | 株式会社日立製作所 | Movable head positioning device |
US4439520A (en) | 1981-11-12 | 1984-03-27 | Eastman Kodak Company | Sensitized high aspect ratio silver halide emulsions and photographic elements |
US4433048A (en) | 1981-11-12 | 1984-02-21 | Eastman Kodak Company | Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use |
US4414310A (en) | 1981-11-12 | 1983-11-08 | Eastman Kodak Company | Process for the preparation of high aspect ratio silver bromoiodide emulsions |
JPS58113935A (en) | 1981-12-26 | 1983-07-07 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
JPS58172647A (en) | 1982-04-02 | 1983-10-11 | Konishiroku Photo Ind Co Ltd | Color photographic sensitive silver halide material |
EP0096570A1 (en) | 1982-06-05 | 1983-12-21 | Olympus Optical Co., Ltd. | An optical system focus-state detector |
US4500634A (en) | 1982-08-24 | 1985-02-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
GB2131188A (en) | 1982-09-16 | 1984-06-13 | Fuji Photo Film Co Ltd | Silver halide photographic material |
US4569863A (en) | 1982-10-21 | 1986-02-11 | Agfa-Gevaert Aktiengesellschaft | Process for the multiple coating of moving objects or webs |
US4665012A (en) | 1982-11-29 | 1987-05-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4543323A (en) | 1982-12-18 | 1985-09-24 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
US4540653A (en) | 1983-08-31 | 1985-09-10 | Konishiroku Photo Industry Co., Ltd. | Method of improving the light resistance of a dye image |
US4647528A (en) | 1983-09-16 | 1987-03-03 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4746601A (en) | 1983-12-15 | 1988-05-24 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4607004A (en) | 1983-12-26 | 1986-08-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4618571A (en) | 1984-02-23 | 1986-10-21 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
EP0164961A2 (en) | 1984-06-06 | 1985-12-18 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic elements employing novel coupler solvents |
US4678745A (en) | 1984-06-15 | 1987-07-07 | Fuji Photo Film Co., Ltd. | Process for producing silver halide emulsion and silver halide photographic light-sensitive material containing the same |
US4579816A (en) | 1984-07-24 | 1986-04-01 | Agfa-Gevaert Aktiengesellschaft | Yellow DIR coupler with 5-furyl(1,2,4-triazole) coupling off group |
US4678739A (en) | 1984-12-20 | 1987-07-07 | Fuji Photo Film Co., Ltd. | Image forming method including heating step |
US4906559A (en) | 1985-02-22 | 1990-03-06 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material |
EP0193389A2 (en) | 1985-02-28 | 1986-09-03 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Use of a coupler comprising a coupler moiety having a releasable bleach accelerator moiety |
US4948716A (en) | 1985-04-30 | 1990-08-14 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
JPS61258249A (en) | 1985-05-13 | 1986-11-15 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
US4937179A (en) | 1985-05-27 | 1990-06-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4857447A (en) | 1985-05-28 | 1989-08-15 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material containing a coupler having a dye moiety |
US4883746A (en) | 1985-05-29 | 1989-11-28 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
US4746600A (en) | 1985-07-01 | 1988-05-24 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide color photographic material with non-diffusable light-insensitive dye layer |
US4775617A (en) | 1985-07-18 | 1988-10-04 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing monodispersed tabular silver halide grains |
US4985336A (en) | 1985-07-24 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0213490A2 (en) | 1985-08-24 | 1987-03-11 | Agfa-Gevaert AG | Colour-photographic recording material |
US4643966A (en) | 1985-09-03 | 1987-02-17 | Eastman Kodak Company | Emulsions and photographic elements containing ruffled silver halide grains |
US4672027A (en) | 1985-10-23 | 1987-06-09 | Eastman Kodak Company | Multicolor photographic element with a minus blue recording tabular grain emulsion layer overlying a blue recording emulsion layer |
US4693964A (en) | 1985-10-23 | 1987-09-15 | Eastman Kodak Company | Multicolor photographic element with a tabular grain emulsion layer overlying a minus blue recording emulsion layer |
US4713320A (en) | 1985-12-19 | 1987-12-15 | Eastman Kodak Company | Low methionine gelatino-peptizer tabular grain silver bromide and bromoiodide emulsions and processes for their preparation |
US4755456A (en) | 1985-12-26 | 1988-07-05 | Fuji Photo Film Co., Ltd. | Method for preparing silver iodobromide emulsions having high aspect ratio |
US4835095A (en) | 1986-02-03 | 1989-05-30 | Fuji Photo Film Co., Ltd. | Photosensitive tabular core/shell silver halide emulsion |
US4797354A (en) | 1986-03-06 | 1989-01-10 | Fuji Photo Film Co., Ltd. | Silver halide emulsions comprising hexagonal monodisperse tabular silver halide grains |
US4791049A (en) | 1986-04-25 | 1988-12-13 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a compound having an oxidation-reduction moiety and timing group |
US4886736A (en) | 1986-06-12 | 1989-12-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4952485A (en) | 1986-09-29 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Silver halide color negative photographic materials |
US4722886A (en) | 1986-10-10 | 1988-02-02 | E. I. Du Pont De Nemours And Company | Process for preparing a photographic emulsion containing tabular grains having narrow size distribution |
US4801522A (en) | 1986-10-10 | 1989-01-31 | E. I. Du Pont De Nemours And Company | Process for preparing a photographic emulsion containing tabular grains exhibiting high speed |
DE3636824A1 (en) | 1986-10-29 | 1988-05-05 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A YELLOW DIR COUPLER |
US4853319A (en) | 1986-12-22 | 1989-08-01 | Eastman Kodak Company | Photographic silver halide element and process |
EP0272573A2 (en) | 1986-12-24 | 1988-06-29 | Agfa-Gevaert AG | Colour-photographic recording material with a coupler liberating a photographically active compound |
DE3644416A1 (en) | 1986-12-24 | 1988-07-07 | Agfa Gevaert Ag | Colour-photographic recording material containing a coupler which liberates a photographically effective compound |
US4853322A (en) | 1986-12-26 | 1989-08-01 | Fuji Photo Film Co., Ltd. | Light-sensitive silver halide emulsion and color photographic materials using the same |
US4959299A (en) | 1987-03-05 | 1990-09-25 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
US4806461A (en) | 1987-03-10 | 1989-02-21 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic light-sensitive material using tabular grains having ten or more dislocations per grain |
US4985350A (en) | 1987-06-01 | 1991-01-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
US4865959A (en) | 1987-06-25 | 1989-09-12 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing a bleach accelerator releasing compound |
US4782012A (en) | 1987-07-17 | 1988-11-01 | Eastman Kodak Company | Photographic material containing a novel dir-compound |
EP0301477A2 (en) | 1987-07-27 | 1989-02-01 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material and method of processing thereof |
US4966835A (en) | 1987-08-13 | 1990-10-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material |
US4946767A (en) | 1987-09-25 | 1990-08-07 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4923784A (en) | 1987-11-24 | 1990-05-08 | Eastman Kodak Company | Photographic elements containing a bleach accelerator precursor |
US4865956A (en) | 1987-11-24 | 1989-09-12 | Eastman Kodak Company | Photographic elements containing a bleach accelerator precursor |
US4917994A (en) | 1988-03-01 | 1990-04-17 | Eastman Kodak Company | Color photographic reflection print material with improved keeping properties |
EP0335319A2 (en) | 1988-03-28 | 1989-10-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0336411A2 (en) | 1988-04-07 | 1989-10-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
US4962015A (en) | 1988-05-02 | 1990-10-09 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0346899A2 (en) | 1988-06-16 | 1989-12-20 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
US4880342A (en) | 1988-06-16 | 1989-11-14 | Millis Transfer, Inc. | Movable bulkhead |
US4912025A (en) | 1988-06-21 | 1990-03-27 | Eastman Kodak Company | Photographic recording material for accelerated development |
US4962018A (en) | 1988-06-21 | 1990-10-09 | Eastman Kodak Company | Photographic materials containing DIR compounds and process of imaging |
US4859578A (en) | 1988-06-21 | 1989-08-22 | Eastman Kodak Company | Photographic recording material providing improved granularity properties |
JPH02103409A (en) | 1988-06-24 | 1990-04-16 | Iwate Pref Gov Chiyuushiyou Kigyo Shinko Koushiya | Continuous detection and correction of defect of strip workpiece |
US4914014A (en) | 1988-06-30 | 1990-04-03 | Eastman Kodak Company | Nucleation of tabular grain emulsions at high pBr |
US5068171A (en) | 1988-07-16 | 1991-11-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material containing a two equivalent 5-pyrazolone magenta coupler and color photograph containing the same |
US4994359A (en) | 1988-08-02 | 1991-02-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
JPH0272633A (en) | 1988-09-07 | 1990-03-12 | Mitsubishi Electric Corp | Manufacture of semiconductor device |
JPH0272629A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Manufacture of semiconductor device |
JPH0272630A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Manufacture of semiconductor device |
JPH0272634A (en) | 1988-09-07 | 1990-03-12 | Fujitsu Ltd | Semiconductor device |
JPH0272631A (en) | 1988-09-08 | 1990-03-12 | Fuji Xerox Co Ltd | Wiring structure in electronic device and image sensor having this wiring structure |
JPH0272632A (en) | 1988-09-08 | 1990-03-12 | Kawasaki Steel Corp | Manufacture of semiconductor device |
JPH0278229A (en) | 1988-09-13 | 1990-03-19 | Nec Corp | Field-effect transistor and its manufacture |
JPH0278230A (en) | 1988-09-14 | 1990-03-19 | Hitachi Ltd | Semiconductor integrated circuit device |
JPH0280487A (en) | 1988-09-15 | 1990-03-20 | Sumitomo Electric Ind Ltd | Carbon fibver-reinforced composite carbon material |
JPH0279337A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Color cathode ray tube |
JPH0279691A (en) | 1988-09-16 | 1990-03-20 | Hitachi Ltd | Satellite broadcast receiver |
JPH0280494A (en) | 1988-09-16 | 1990-03-20 | Toyokazu Fukuoka | Removal of oil from bean-curd refuse |
JPH0279690A (en) | 1988-09-16 | 1990-03-20 | Hitachi Ltd | Television signal forming method |
JPH0280488A (en) | 1988-09-16 | 1990-03-20 | Miyoshi Oil & Fat Co Ltd | Antistatic agent |
JPH0279336A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Indirectly heated cathode structure |
JPH0279338A (en) | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Shadow mask for color cathode ray tube |
JPH0280492A (en) | 1988-09-17 | 1990-03-20 | Sanii Denka:Kk | Welding tip or nozzle |
JPH0280490A (en) | 1988-09-17 | 1990-03-20 | Nagase Sangyo Kk | Highly heat-resistant photochromic material |
JPH0280491A (en) | 1988-09-17 | 1990-03-20 | Sumitomo Metal Ind Ltd | Operation of continuous formed coke oven |
JPH0280489A (en) | 1988-09-19 | 1990-03-20 | Japan Vilene Co Ltd | Low-temperature insulation material |
JPH0287361A (en) | 1988-09-21 | 1990-03-28 | Matsushita Electric Ind Co Ltd | Disk reproducing device |
JPH0286670A (en) | 1988-09-22 | 1990-03-27 | Takamatsu Yushi Kk | Water-based coating composition |
JPH0287363A (en) | 1988-09-22 | 1990-03-28 | Nec Home Electron Ltd | Sound recorder |
JPH0287364A (en) | 1988-09-22 | 1990-03-28 | Casio Comput Co Ltd | Access method for storage device |
JPH0287360A (en) | 1988-09-22 | 1990-03-28 | Alpine Electron Inc | Cartridge eject device in disk changer |
JPH0286669A (en) | 1988-09-22 | 1990-03-27 | Toyobo Co Ltd | Coating resin composition |
JPH0285928A (en) | 1988-09-22 | 1990-03-27 | Fujitsu Ltd | Automation system for system install job |
JPH0287362A (en) | 1988-09-24 | 1990-03-28 | Sony Corp | Information read-out and reproducing device |
JPH0288097A (en) | 1988-09-27 | 1990-03-28 | Toshiba Corp | Washing drying machine |
JPH0293665A (en) | 1988-09-30 | 1990-04-04 | Fuji Xerox Co Ltd | Image output device |
JPH0294056A (en) | 1988-09-30 | 1990-04-04 | Hitachi Ltd | Magnetic recording and reproducing device |
JPH0293668A (en) | 1988-09-30 | 1990-04-04 | Ricoh Co Ltd | Automatic inverted document feeder for copying machine |
JPH0293666A (en) | 1988-09-30 | 1990-04-04 | Fuji Xerox Co Ltd | Image output device |
JPH0294055A (en) | 1988-09-30 | 1990-04-04 | Hitachi Ltd | Magnetic recording and reproducing device |
JPH0293663A (en) | 1988-09-30 | 1990-04-04 | Canon Inc | Image forming device |
JPH0293662A (en) | 1988-09-30 | 1990-04-04 | Canon Inc | Image forming device |
JPH0293664A (en) | 1988-09-30 | 1990-04-04 | Seiko Epson Corp | Wet type color image forming device |
EP0362870A2 (en) | 1988-10-06 | 1990-04-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0365252A2 (en) | 1988-10-15 | 1990-04-25 | Konica Corporation | A silver halide color photographic light-sensitive material for making color negatives |
EP0365346A2 (en) | 1988-10-21 | 1990-04-25 | Toyo Ink Manufacturing Co., Ltd. | Diazo pigment composition |
EP0373382A1 (en) | 1988-11-18 | 1990-06-20 | Fuji Photo Film Co., Ltd. | Silver halide color photosensitive material |
US4956269A (en) | 1988-11-24 | 1990-09-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
EP0376212A2 (en) | 1988-12-26 | 1990-07-04 | Fuji Photo Film Co., Ltd. | Silver halide color photographic photosensitive materials |
EP0377463A2 (en) | 1989-01-05 | 1990-07-11 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
EP0378236A1 (en) | 1989-01-13 | 1990-07-18 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
EP0384670A2 (en) | 1989-02-21 | 1990-08-29 | Konica Corporation | Method for processing light sensitive silver halide color photographic material |
US5019492A (en) | 1989-04-26 | 1991-05-28 | Eastman Kodak Company | Photographic element and process comprising a blocked photographically useful compound |
EP0396486A1 (en) | 1989-05-04 | 1990-11-07 | International Business Machines Corporation | Receiver and level converter circuit |
EP0401612A2 (en) | 1989-06-06 | 1990-12-12 | Agfa-Gevaert AG | Colour photographic recording material with a DIR coupler |
EP0401613A2 (en) | 1989-06-06 | 1990-12-12 | Agfa-Gevaert AG | Colour photographic recording material with a DIR coupler |
US5061616A (en) | 1989-07-13 | 1991-10-29 | Eastman Kodak Company | Process of preparing a tabular grain silver bromoiodide emulsion |
US5061069A (en) | 1989-07-31 | 1991-10-29 | Allied-Signal Inc. | Fiber-optic bender beam interferometer accelerometer |
EP0534395A1 (en) | 1991-09-24 | 1993-03-31 | Eastman Kodak Company | High tabularity high chloride emulsions of exceptional stability |
US5300418A (en) | 1992-04-16 | 1994-04-05 | Eastman Kodak Company | Viscosity control of photographic melts |
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