Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
  • G03C1/89—Macromolecular substances 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
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion

Definitions

• the present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material whose layer physical properties are improved without affecting its photographic characteristics.
• the hydrophilic colloid layer of a silver halide photographic light-sensitive material is required not only to have no bad influence upon its photographic characteristics but also to have a necessary performance for its layer physical/antistatic properties. Therefore, various attempts have conventionally been made, when coating on a support a hydrophilic colloid layer such as a silver halide emulsion layer, an interlayer or a protective layer, to improve the hydrophilic colloid layer's physical properties such as dimensional stability, scratch resistance, elasticity, pressure resistance and drying characteristic in the manner of incorporating a polymer latex formed by polymerization of various monomers into the hydrophilic colloid layer; and other attempts to improve the antistatic characteristics of the hydrophilic colloid layer by preventing the phenomenon called static marks, appearing in the form of spots or branched or feather-like marks when the light-sensitive emulsion layer is exposed to discharge of static electricity having accumulated and then processed, in the manner of dispersing the accumulated static charge by adding a surfactant to the surface of the hydrophilic colloid layer
• JP O.P.I. Japanese Patent Publication Open to Public Inspection
• JP O.P.I. Japanese Patent Publication Open to Public Inspection
• JP O.P.I. Nos. 50240/1980, 52882/1973 and 52883/1973, and JP E.P. Nos. 47371/1980 and 19772/1979 describe techniques that use a polymer latex obtained by using a water-soluble high-molecular material at the time of its polymerization. Such techniques, although useful for improving photographic characteristics, are not enough for improving physical properties, and leave the problems of devitrification, viscosity increase in coating, deterioration of scratch resistance and deterioration of antistatic characteristics, so that the polymer latex can not be used in a sufficient amount.
• JP O.P.I. No. 135335/1990 discloses a technique to use a methacrylic acid polymer, but its improving effect is insufficient and it largely affects the antistatic characteristics of the light-sensitive material.
• a silver halide photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer and optionally a hydrophilic colloid layer, in which at least one of the silver halide emulsion layer and hydrophilic colloid layer contains a latex of polymer comprising a repeating unit derived from a monomer having a solubility in water at 25°C of not higher than 0.025% by weight.
• the content of the repeating unit derived from a monomer having a solubility in water at 25°C of not higher than 0.025% by weight in the polymer is not less than 50% by weight of the polymer of latex.
• the above monomer is preferably an acrylate compound, and more preferably an acrylate compound used in combination with a methacrylate compound.
• the number average particle size of the polymer latex of the invention is preferably not more than 300nm.
• the polymerization of the polymer latex of the invention is preferably carried out in the presence of a water-soluble polymer and/or a surfactant.
• At least one of the monomers for use in forming the polymer latex of the invention has a solubility in water at 25°C of preferably not more than 0.025% by weight, and more preferably not more than 0.015% by weight.
• the ethylenic monomer include acrylates such as hexyl acrylate, 2-ethyl-hexyl acrylate, octyl acrylate, tert-octyl acrylate, nonyl acrylate, iso-nonyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, lauryl acrylate and tridecyl acrylate; methacrylates such as hexyl methacrylate, 2-ethyl-hexyl methacrylate, octyl methacrylate, iso-octyl methacrylate, tert-octyl methacrylate, nonyl methacrylate, iso
• solubility in water at 25°C of the monomer for use in forming the latex of the invention can be measured according to the method described in the 'Shin Jikken Kagaku Koza, Kihon Sosa 1, p.223-250' ('New Experimental Chemistry Course: Basic Operations 1') (Maruzene Kagaku, 1975).
• the solubility in water at 25°C of, e.g., 2-ethyl-hexyl acrylate is 0.01% by weight, 2-ethyl-hexyl methacrylate 0.005 by weight, cyclohexyl methacrylate 0.00% by weight, whereas in the case of comparative monomers, styrene 0.03% by weight, butyl acrylate 0.32% by weight and butyl methacrylate 0.03% by weight.
• the polymer latex used in the invention copolymerization of the above monomer compound with different other monomer compounds may be carried out.
• the content of repeating unit derived from the monomer, having a solubility in water at 25°C of not larger than 0.025% by weight, in the polymer be not lower than 50%.
• Examples of copolymerizable ethylenic monomer compounds with the above monomer compounds of the invention include acrylates, methacrylates, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, acryl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids. From the above compounds one or two or more are selected to be used in combination as monomers for copolymerization.
• examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate,
• methacrylate examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, -2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethyleneglycol monomethacrylate, dipropylene-glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acet
• vinyl ester examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinylmethoxy acetate, vinylphenyl acetate, vinyl benzoate and vinyl salicylate.
• olefin examples include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene and 2,3-dimethylbutadiene.
• styrene examples include styrene, methylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, bromostyrene, trifluorostyrene and vinylmethyl benzoate.
• crotonic acid ester examples include butyl crotonate.
• Examples of the itaconic acid diester include dimethyl itaconate, diethyl itaconate and dibutyl itaconate.
• maleic acid diester examples include diethyl maleate, dimethyl maleate and dibutyl maleate.
• fumaric acid diester examples include diethyl fumarate, dimethyl fumarate and dibutyl fumarate.
• acrylamide examples include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, ⁇ -cyanoethylacrylamide and N-(2-acetacetoxyethyl)acrylamide.
• methacrylamide examples include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, ⁇ -cyanoethylmethacrylamide and N-(2-acetacetoxyethyl)methacrylamide.
• allyl compound examples include allyl acetate, allyl caproate, allyl laurate and allyl benzoate.
• vinyl ether examples include methylvinyl ether, butylvinyl ether, hexylvinyl ether, methoxyethylvinyl ether and dimethylaminoethylvinyl ether.
• vinyl ketone examples include methylvinyl ketone, phenylvinyl ketone and methoxyethylvinyl ketone.
• vinyl-heterocyclic compound examples include vinylpyridine, N-vinyl-imidazole, N-vinyl-oxazolidone, N-vinyl-triazole, N-vinyl-pyrrolidone.
• glycidyl ester examples include glycidyl acrylate and glycidyl methacrylate.
• Examples of the unsaturated nitrile include acrylonitrile and methacrylonitrile.
• Those of the polyfunctional monomer include divinylbenzene, methylenebisacrylamide and ethyleneglycol dimethacrylate.
• These acids may be used in the form of salts of alkali metals such as Na, K or of ammonium ions.
• alkali metals such as Na, K or of ammonium ions.
• crosslinking monomers as described in U.S. Patent Nos. 3,459,790, 3,438,708, 3,554,987, 4,215,195 and 4,247,673, and JP O.P.I. No. 205735/1982.
• Examples of the crosslinking monomer include N-(2-acetacetoxyethyl)acrylamide and N-(2-(2-acetacetoxyethoxy) ethyl)acrylamide.
• the suitably usable among the above monomers compounds are acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins.
• Surfactants usable in the invention may be any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants, and are preferably anionic and/or nonionic surfactants.
• anionic surfactants and/or nonionic surfactants various compounds known to those skilled in the art may be used, but particularly, anionic surfactants are preferred. The following are useful examples of the surfactant for the invention.
• the water-soluble high molecular material preferably used for the invention includes synthetic water-soluble polymer materials and natural water-soluble polymer materials; either may be suitably used in the invention.
• the synthetic water-soluble polymer materials include ones having a nonionic group, ones having an anionic group, ones having a cationic group, ones having both nonionic and anionic groups, ones having both nonionic and cationic groups, and ones having both anionic and cationic groups in their respective molecular structures.
• the nonionic group includes an ether group, an alkyleneoxide group, a hydroxy group, an amido group and an amino group.
• the anionic group includes a carboxyl group and its salts, a phospho group and its salts, a sulfo group and its salts.
• the cationic group includes a quaternary ammonium salt group and a tertiary amino group.
• the natural water-soluble polymer materials also include ones having a nonionic group, ones having an anionic group, ones having cationic group, ones having both nonionic and anionic groups, ones having both nonionic and cationic groups and ones having both anionic and cationic groups in their respective molecular structures.
• water-soluble polymer either synthetic or natural, any of those having an anionic group or both nonionic and anionic groups may be suitably used.
• the water-soluble polymer is one having a solubility of preferably not less than 0.05g, and more preferably not less than 0.1g in 100g of water at 20°C.
• the synthetic water-soluble polymer includes those containing repeating units represented by the following Formula (1) and/or Formula (2) in a ratio of to to 100 mol% per polymer molecule thereof.
• R1 represents a hydrogen atom, an alkyl group, a halogen atom or a -CH2COOM group, and preferably an alkyl group having 1 to 4 carbon atoms
• L1 represents a divalent linkage group such as -CONH-, -NHCO-, -COO-, -OCO-, -CO- or -O-
• J is an alkylene group, an arylene group or an oxyalkylene group
• Q1 represents -OM, -NH2, -SO3M, -COOM, a hydrogen atom or R3. Out of these, -COOM and -SO3 are preferred, particularly -SO3M is most suitably usable.
• M represents a hydrogen atom or a cation (such as an alkali metal ion, an ammonium ion);
• R3, R4, R5, R6, R7, R8, R9 and R10 each represent an alkyl group having 1 to 20 carbon atoms;
• X represents an anion;
• m1 and n1 each represent an integer of 0 or 1;
• Y represents a hydrogen atom or -(L2)m2-(J2)n2-Q2, wherein L2, J2, Q2, m2 and n2 are the same as defined for L1, J1, m1 and n1, respectively.
• R21, R22, R23, R24, R25 and R26 each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms or a -SO3X group, wherein X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or an amino group; provided at least one of R21, R22, R23, R24, R25 and R26 is -SO3X.
• Examples of the natural water-soluble polymer includes preferably lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminarin, lichenine, nigellon and their derivatives.
• As derivatives of these natural water-soluble polymers there may be preferably used those sulfonated, carboxylated, phosphated, sulfoalkylenated, carboxyalkylenated, alkyl-phosphated and salts thereof, and more preferably glucose, gelatin, dextran, cellulose and their derivatives.
• the polymer latex used in the invention can be produced easily by any one of various methods, such as by emulsion polymerization and redispersing a polymer that has been obtained in the emulsion polymerization, solution polymerization or block polymerization process.
• water is used as a dispersion medium, and a monomer in an amount of 10 to 50% by weight of water, a polymerization initiator in an amount of 0.05 to 5% by weight of the monomer and a dispersing agent in an amount of 0.1 to 20% by weight of the monomer are used to be subjected to polymerization reaction at about 30 to 100°C, preferably at 60 to 90°C, with stirring over a period of 3 to 8 hours, whereby the polymer latex can be obtained.
• concentration of the monomer, amount of the plymerization initiator, the reaction temperature, and the duration of the reaction may be broadly, easily changed.
• the initiator examples include water-soluble peroxides such as potassium peroxide, ammonium peroxide; water-soluble azo compounds such as 2,2'-azobis-(2-amidinopropane)-hydrochloride.
• dispersing agent examples include water-soluble polymers, anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. These may be used alone or in combination, and preferably in combination of a water-soluble polymer with a nonionic surfactant or with an anionic surfactant.
• a mixture of monomers in appropriate concentrations normally a mixture of monomers in amounts not more than 40% by weight, preferably 10 to 25% by weight of the solvent, is heated at an appropriate temperature, e.g., at 40 to 120°C, preferably 50 to 100°C, in the presence of a polymerization initiator, such as benzoyl peroxide, azobisisobutyronitrile or ammonium peroxide, to thereby effect the copolymerization of the monomers.
• a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or ammonium peroxide
• the obtained product is dissolved in a solvent capable of solving the copolymer but insoluble in water, such as ethyl acetate or butanol, and then vigorously dispersed in the presence of a dispersing agent, such as a surfactant or a water-soluble polymer, and then the solvent is distilled off to thereby obtain an objective polymer latex.
• a solvent capable of solving the copolymer but insoluble in water such as ethyl acetate or butanol
• a dispersing agent such as a surfactant or a water-soluble polymer
• the glass transition point Tg of the polymer to form the polymer latex used in the invention is preferably not higher than 60°C, and more preferably not higher than 40°C.
• a Tg value calculated according to the above formula has a precision of ⁇ 5°C.
• the polymer latex of the invention has an average particle size of preferably 0.5 to 300nm, and more preferably 30 to 250nm.
• the average particle size means number average of particle sizes.
• Measurement of the average particle size of the polymer latex of the invention may be made according to the electron-microscopic photography method, described in the 'Polymer Latex Chemistry' (Kobunshi Kanko Kai, 1973).
• the molecular weight of the polymer latex used in the invention is preferably from 1,000 to 1,000,000, and more preferably 2,000 to 500,000 in terms of the weight average molecular weight.
• the polymer latex of the invention may, either as it is or in the state of being dispersed in water, be incorporated into photographic component layers, preferably into emulsion layers.
• the polymer latex content of the layer it is preferably added in an amount of 5 to 70% by weight of the binder of the photographic component layer; i.e., an emulsion layer or another hydrophilic colloid layer.
• the polymer latex may be added to any photographic component layer regardless of whether it is a light-sensitive or non-light-sensitive hydrophilic colloid layer.
• the polymer latex of the invention includes also functional polymers such as polymer couplers or polymer UV absorbing agents which are added in the form of latexes.
• the white crystals were filtered, dried, and then dissolved in 100ml of ethyl acetate. This solution was added with vigorously stirring to 500ml of distilled water containing 2g of Sf-19, and then the ethyl acetate was removed, whereby an objective polymer latex having an average particle size of 180nm was obtained.
• the obtained latex was filtered by using a GF/D filter, manufactured by Whotman Co., and water was added to make the whole liquid 50.5kg, whereby a monodisperse Latex (L) having an average particle size of 250nm was obtained.
• polymer latex according to the invention examples are listed below, wherein each suffixed number represents the content percentage of each monomer unit, and the water solubility of each monomer is shown underneath the structural formula thereof.
• the using amount of the polymer latex is preferably not less than 10% and not more tha 300% by weight, and more preferably not less than 30% and not more than 200% by weight of the weight of gelatin. Further, the water-soluble polymer used in the invention accounts for preferably not less than 5% and not more than 30% by weight, and more preferably not less than 1% and not more than 15% by weight of the polymer of the latex.
• gelatin and gelatin derivatives are advantageously usable.
• gelatin in addition to lime-treated gelatin there may be used those acid-treated gelatin products as described in Bull. Soc. Sci. Phot. Japan No.16, p.30 (1966), and also hydrolyzed products or oxygen-decomposed products of gelatin.
• gelatin derivative there may be used those obtained by the reaction of gelatin with various compounds such as acid halides, acid unhydrides, isocyanates, bromoacetates, alkane-sultones, vinylsulfonamides, maleimide compounds, polyalkyleneoxide or epoxy compounds; particular examples of which are described in U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846 and 3,321,553; British Patent Nos. 861,414, 1,033,189 and 1,005,784; and JP E.P. No. 26845/1967.
• the silver halide for the silver halide emulsion used in the invention may be any arbitrary one of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride which are used in ordinary silver halide emulsions.
• the silver halide grain may be either one having a uniform silver halide composition distribution throughout the inside thereof or of the core/shell type with difference in the silver halide composition between the inside phase and the surface phase thereof, and further, it may be either one forming a latent image principally on the surface or one forming a latent image principally in the innerside thereof.
• the silver halide grain for the silver halide emulsion used in the invention may be either of a regular crystal form such as a cubic, octahedral or tetradecahedral form or of an irregular crystal form such as a spherical or tabular form, but most preferably a tabular crystal form.
• each individual grain may take the form of a complex of these grains, or the silver halide may be a mixture of diverse crystal-form grains.
• the average grain size of the silver halide (expressed in terms of the diameter of a circle equivalent in the area to projected grain image) is preferably not more than 5 ⁇ m, and more preferably not more than 3 ⁇ m.
• the silver halide emulsion used in the invention may be of any grain size distribution.
• Either a broader grain-size distribution-having emulsion called a polydisperse emulsion or a narrower grain-size distribution-having emulsion called a monodisperse emulsion may be used.
• the monodisperse emulsion herein implies an emulsion which, when the standard deviation of its grain diameter distribution is divided by its average grain diameter, has a quotient value of not more than 0.20.
• the grain diameter, in the case of a spherical grain, is its diameter, while in the case of a non-spherical grain, is the diameter of a circle equivalent in the area to its projected image.
• the polydisperse emulsion and the monodisperse emulsion may be mixedly used.
• the silver halide emulsion used in the invention may be a mixture of two or more different emulsions separately prepared.
• the silver halide emulsion used in the invention may be chemically sensitized in the usual manner; i.e., the emulsion may be subjected to chemical sensitization treatment by either single use or combined use of methods of sulfur sensitization, selenium sensitization, reduction sensitization, and noble metal sensization that uses gold compounds or other noble metal compounds.
• Silver halide emulsion layers may contain dye-forming couplers to be used to form a color light-sensitive material.
• the silver halide photographic light-sensitive material of the invention can apply to X-ray light-sensitive materials, lith-type light-sensitive materials, black-and-white light-sensitive materials for camera use, color negative light-sensitive materials, color reversal light-sensitive materials and color photographic papers.
• color photographic light-sensitive materials it can be used as either a monochromatic color light-sensitive material or a multicolor light-sensitive material.
• the multicolor light-sensitive material usually has dye image-forming component units separately sensitive to three primary color spectral regions, and the component units may be comprised of their respective single emulsion layers or multi-emulsion layers each consisting of plural sublayers, preferably differeing in the sensitivity, sensitive separately to individual specific spectral regions, and may also have other layers such as filter layers, intermediate protective layers and a subbing layer.
• the layers of the light-sensitive material can be coated in various orders as known to those skilled in the art.
• coating may be made from the support side in the order of a subbing layer, antihalation layer, cyan color-forming red-sensitive layer, intermediate layer, magenta color-forming green-sensitive layer, intermediate layer, yellow color-forming blue-sensitive layer and protective layer, and the latex in the invention can be incorporated into each of the above layers.
• the color-forming layers each may be of a high/low-sensitivity double-layer construction.
• a support having thereon a cyan dye image-forming component comprised of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, a magenta dye image-forming component comprised of a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler and a yellow dye image-forming component comprised of a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, along with other non-light-sensitive layers.
• a cyan dye image-forming component comprised of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler
• a magenta dye image-forming component comprised of a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler
• a yellow dye image-forming component comprised of a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler
• the yellow coupler include open-chain keto-methylene compounds such as pivaloyl-acetanilide-type and benzoyl-acetanilide-type yellow couplers.
• magenta coupler examples include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers such as pyrazolotriazole couplers, and open-chain acylacetonitrile couplers.
• cyan coupler includes naphthol couplers and phenol couplers.
• a colorless dye-forming coupler called a competing coupler may also be incorporated.
• the silver halide emulsion layers may, in addition to the above couplers, also contain a DIR compound capable of releasing a development accelerator or a precursor thereof, such as diffusible DIR compound, a timing DIR compound, or a hydroquinone derivative for preventing the layers from undesirable fogging or staining due to the aerial oxidation of a developing agent.
• a DIR compound capable of releasing a development accelerator or a precursor thereof such as diffusible DIR compound, a timing DIR compound, or a hydroquinone derivative for preventing the layers from undesirable fogging or staining due to the aerial oxidation of a developing agent.
• a backing layer with coated weight of gelatin: 2.0g/m2 On one side of a subbed polyethylene terephthalate support of 100 ⁇ m in thickness were coated a backing layer with coated weight of gelatin: 2.0g/m2, using the following backing layer coating liquid, and a backing protective layer with coated weight of gelatin: 1.5g/m2, using the following backing protective layer coating liquid, and on the opposit subbed side of the support were coated an emulsion layer with coated weight of gelatin: 2.0g/m2, and an emulsion protective layer with coated weight of gelatin: 1.0g/m2, using the following silver halide light-sensitive material coating liquid, in the 4-layer simultaneous coating manner, and then dried to thereby prepare light-sensitive material Samples 101 through 117.
• a silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows:
• An aqueous solution containing potassium pentabromorhodium in an amount of 23.9mg per 60g of silver nitrate, sodium chloride and potassium bromide and an aqueous solution of silver nitrate were added spending 25 minutes at 40°C in a double-jet method to an aqueous gelatin solution with stirring, thereby preparing a silver chlorobromide emulsion having an average grain size of 0.20 ⁇ m.
• the emulsion after adding 20 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene thereto, was subjected to sulfur sensitization. After that, gelatin was added, 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer, and water was added to make the whole 260ml to thereby complete the emulsion.
• Gelatin was swelled in water and dissolved at 40°C, to this were added an aqueous 1% Compound Z solution as a coating aid, an aqueous 1% solution of Compound Sf-20, Compound C as a filter dye and Compound D in the described order, and then citric acid was used to adjust pH of the mixture to 6.0.
• a matting agent amorphous silica having a particle diameter of 4.0 ⁇ m
• Hardener H-1 and further a compound of the invention, as shown in Table 1, were added thereto, whereby an emulsion protective layer coating liquid was prepared.
• the obtained samples were each exposed through a sensitometric stepwedge to white light and then processed in the following procedure, and on the other hand the same samples, remaining unexposed, were processed likewise, and thus two kinds of processed samples, exposed and unexposed, were prepared.
• Composition A is a composition having the following properties:
• Composition B
• compositions A and B were dissoled in the order given in 500 milliliters of water, and water was added to make the whole one liter.
• Composition A is a composition having the following properties:
• Composition B
• compositions A and B were dissolved in the order given in 500 ml of water, and water was added to make the whole one liter.
• This fixer solution had pH of about 4.3.
• Each unexposed sample processed was measured with respect to its haze by use of a turbidimeter Model T-2600DA, manufactured by Tokyo Denshoku Co., and the haze is shown in percentage.
• the exposed samples processed in the foregoing procedure were each subjected to sensitivity measurement with use of a sensitometer KS-1, manufactured by KONICA Corp.
• the sensitivity of each sample is a reciprocal of the exposure amount necessary to give a density of fog + 0.7, and is indicated as a speed relative to the immediate speed of the control sample set at 100.
• each sample was again put in the developer solution at a designated temperature to be subjected to a scratch test, wherein the sample's surface kept immersed therein was scratched by a weighted metallic needle to find the minimum needle weight necessary to damage the surface (scratch resistance).
• Latex LX-M was prepared in the same manner as in LX-L except that the following monomers and surfactant Sf-19 were used.
• the following backing layer 1 coating liquid was coated at a rate of 20 ml/m2, and then dried at 80°C in 5 minutes.
• Aluminasol AS-100 product of Nissan Chem. Ind.,Co.
• the following backing layer 2 coating liquid was coated at a rate of 20 ml/m2 and dried at 80°C in 5 minutes.
• Diacetyl cellulose 1.0g SiO2 fine particles (average particle size: 3.0 ⁇ m) 0.02g
• the following backing layer 3 coating liquid was coated at a rate of 20 ml/m2, and dried at 90°C in 5 minutes.
• Layer 1 Antihalation layer (HC) Black colloidal layer 0.15 UV absorbent UV-1 0.20 Colored cyan coupler CC-1 0.02 High-boiling solvent Oil-1 0.20 High-boiling solvent Oil-2 0.20 Gelatin 1.6
• Layer 2 Intermediate layer (IL-1) Gelatin 1.3
• Layer 4 High-speed red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average grain diameter: 0.7 ⁇ m, average iodide content: 7.5 mol%) 0.9 Sensitizing dye S-1 1.7x10 ⁇ 4 mol/mol Ag Sensitizing dye S-2 1.6x10 ⁇ 4 mol/mol Ag Sensitizing dye S-3 0.1x10 ⁇ 4 mol/mol Ag Cyan coupler C-2 0.23 Colored cyan coupler CC-1 0.03 DIR compound D-2 0.02 High-boiling solvent Oil-1 0.25 Additive SC-1 0.003 Gelatin 1.0
• Layer 5 Intermediate layer (IL-2) Gelatin 0.8 Layer 7
• the silver iodobromide emulsion used in Layer 10 was prepared in the following manner:
• a silver iodobromide emulsion was prepared according to a double-jet method with monodisperse silver iodobromide grains having a silver iodide content of 2 mol% and an average grain diameter of 0.33 ⁇ m used as seed crystals.
• Solutions ⁇ H-1> and ⁇ S-1> were added at an accelerated flow rate (final flow rate: 3.6 times the initial), spending 86 minutes.
• Controls of pAg and pH during the grain formation were carried out by using an aqueous potassium bromide solution and an aqueous 56% acetic acid solution. After the formation of grains, the grains were subjected to washing treatment according to the usual flocculation method, then redispersed by adding gelatin thereto, and then the pH and pAg thereof were adjusted at 40°C to 5.8 and 8.06, respectively.
• the obtained emulsion was a monodisperse emulsion of octahedral silver iodobromide grains having a silver iodide content of 8.5 mol%, an average grain diameter of 0.80 ⁇ m and a grain size distribution broadness of 12.4%.
• Solution ⁇ G-1> Osein gelatin 100.0g Compound [I], 10% by weight methanol solution 25.0ml 28% aqueous ammonia solution 440.0ml 56% aqueous acetic acid solution 660.0ml Water to make 5000.0ml Solution ⁇ H-1>: Osein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.0g Water to make 1030.5ml Solution ⁇ S-1>: Silver nitrate 309.2g 28% aqueous ammonia solution Necessary amount Water to make 1030.5ml Solution ⁇ S-2>: Silver nitrate 1130.0g 28% aqueous ammonia solution Necessary amount Water to make 3776.8ml
• the 'necessary amount' of the ammonia solution means the amount thereof necessary for making an ammoniacal silver nitrate solution.
• Emulsions different in the average grain diameter and silver iodide content used in the layers other than Layer 10 were prepared in the same manner as in the above emulsion except that the average grain diameter of seed crystals, temperature, pAg, pH, flow rate, adding period of time and halide composition were varied.
• emulsions were all core/shell-type monodisperse emulsions having a grain size distribution broadness of not more than 20%.
• Each of the emulsions was subjected optimal chemical ripening treatment in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and then to it were added sensitizing dyes and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene-1-phenyl-5-mercaptotetrazole.
• the above light-sensitive material samples each contain Compounds Su-1 and Su-2, Stabilizer ST-1, Antifoggants AF-1 and AF-2 (weight average molecular weights 10000 and 1100000), Dyes AI-1 and AI-2, and 4.9mg/m2 of Compound DI-1.
• Samples for the pressure fog measurement were prepared in the darkroom and were cut to 35mm x 111mm size pieces. Each piece was put in a rollfilm cartridge having an inside diameter of 22mm and loaded in a camera FT-1, manufactured by KONICA Corp. The sample remaining loaded in the camera was subjected to a one-full-day accelerated aging test at 23°C/80%RH.
• Each light-sensitive material sample was wound up, processed in the following steps, and then evaluated for pressure fog.
• Both the spotted fog's yellow density and the density of the fog-free area at the leading end of each sample were measured with a microdensitometer to find the density difference ⁇ D between them.
• Each unexposed light-sensitive material sample was placed with its protective layer side down on a rubber sheet; had its backing side squeezed with a rubber roller; and then peeled apart from the rubber sheet to cause static electricity to be discharged.
• the sample was then processed to make its discharged marks into visible static marks, and the degree of the marks generation was rated on the following 5-step evaluation basis. Those classified as A and B are acceptable for practical use.
• the samples containing the compound of the invention are excellent in respect of being free from comet-shaped defects due to lumps in coating as well as in the photographic characteristics (fog, speed) and scratch resistance.
• the following emulsion at 55°C was subjected to goldsulfur sensitization treatment by adding ammonium thiocyanate and hypo thereto. After completion of the sensitization 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added. In the final stage, the emulsion was divided into parts to add separately appropriate sensitizing dyes thereto to thereby prepare different color sensitivity-having emulsion coating liquids. To each emulsion coating liquid were added the following additives in the following amounts per mol of silver:
• hydrophobic particles of the invention shown in Table 3 were added, whereby the emulsion coating liquids were prepared.
• the reacting solution was desalted by the use of Demol N, a product of KAO-Ailas Co., and a magnesium sulfate solution.
• the thus obtained flocks of emulsion was redispersed in a gelatin solution.
• a potassium bromide solution was added through a nozzle spending 8 minutes, pAg was lowered to 11.0, and the mixing was completed 3 minutes after the addition potassium bromide.
• the obtained emulsion was of an average grain diameter of 0.55 ⁇ m, and the silver iodide content of the overall grain thereof was about 2.2 mol%.
• the liquid was kept at 40°C and to it were added 5g/mol Ag of naphthalene sulfonate-formalin condensate oligomer and 8g/mol Ag of MgSO4 with stirring for 5 minutes, and then the liquid was allowed to stand for a while.
• the supernatant was decanted off to make the volume of the liquid 200 ml per mol of Ag. Then, pure water at 40°C in an amount of 1.8 liter/mol Ag was added and the liquid was stirred for 5 minutes, followed by adding 20g/mol Ag of MgSO4 with stirring likewise and then decanting off the supernatant, thus effecting the desalting of the liquid. To the desalted liquid with stirring gelatin was added for redispersion of AgX, whereby the preparation of the emulsion was carried out.
• a matting agent comprising polymethyl methacrylate having an average particle size of 5 ⁇ m
• 70 mg of colloidal silica having an average particle size of 0.013 ⁇ m the compound of the invention shown in Table 3
• 8 mg of glyoxal and 6 mg of formalin were added to thereby prepare a protective layer coating liquid.
• the samples containing the compound of the invention are excellent in respect of being free from comet-shaped defects due to lumps in coating as well as in the photographic characteristics (speed, pressure fog), scratch resistance and antistatic characteristics.

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• 1993
  • 1993-03-04 JP JP4386593A patent/JPH06258749A/ja active Pending
• 1994
  • 1994-03-04 EP EP94301571A patent/EP0615158A1/en not_active Withdrawn

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