JP3473816B2 - Silver halide photographic materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to providing a photographic paper having improved surface gloss and devitrification. It is generally known that a silver halide emulsion contains a water-soluble fluorescent whitening agent and a water-soluble polymer such as polyvinylpyrrolidone in order to improve the whiteness of photographic printing paper. Technology. However, when a nonionic water-soluble polymer such as gelatin and polyvinylpyrrolidone is used in the drying step after coating, gelatin and the polymer are liable to undergo phase separation, resulting in problems such as lowering of gloss and devitrification. there were. As a method for improving the surface gloss and devitrification of photographic printing paper, there is a method of containing a specific polymer latex as described in, for example, JP-A-63-198047. The effect was not observed in the silver halide emulsion. [0004] From the above, it is an object of the present invention to provide a silver halide photographic light-sensitive material, and in particular, to provide a photographic paper having improved surface gloss and devitrification. is there. [0005] The object of the present invention is to provide at least one silver halide photosensitive layer on a reflective support and at least one non-photosensitive layer on the silver halide photosensitive layer. A silver halide photographic material, wherein the silver halide photosensitive layer contains gelatin and a nonionic water-soluble polymer, wherein the non-photosensitive layer contains a polymer latex having at least a methacrylate ester as a monomer unit. This has been achieved by a silver halide photographic light-sensitive material characterized in that: Hereinafter, the present invention will be described in detail. The nonionic water-soluble polymer used in the present invention includes vinylpyrrolidone and vinyl alcohol-based polymers represented by the above general formula. In particular, the polyvinylpyrrolidone-based polymer represented by the above general formula, which is used as a whitening enhancer of a water-soluble fluorescent whitening agent, has low compatibility with gelatin and easily separates during the drying process after coating. There is a problem that gloss is reduced and devitrification occurs. In particular, when the average molecular weight was 100,000 or more, the occurrence of the above problem was remarkable. As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by including a specific polymer latex in the non-photosensitive layer on the silver halide emulsion layer. The polymer latex used in the present invention has at least methacrylate as a monomer unit. The latex may be a homopolymer of methacrylate or a copolymer with other components. The copolymer is not particularly limited, such as methacrylates, copolymers with acrylates, copolymers with styrene, and the like. Preferred are the homopolymers, copolymers with acrylates, and copolymers with methacrylates. In the case of a copolymer, the content ratio by weight of methacrylic acid ester as a monomer is preferably at least 5% or more. The ester residue includes methyl, ethyl, n
-Propyl and iso-propyl are preferred. Further, other monomer components may be contained within a range that does not substantially impair the effects of the present invention. The particle size of the polymer latex is preferably 0.1 μm or less. The polymer latex used in the present invention has an effect even when used in an intermediate layer or the like of a light-sensitive material, but is particularly effective when added to an outermost layer, for example, a protective layer. In an embodiment of the present invention, a polymer latex is used with another binder (eg, gelatin). At this time, the amount of addition to gelatin can be set arbitrarily, but is preferably 30 to 85% by weight based on gelatin,
More preferably, it is particularly effective when used in an amount of 40 to 75% by weight. The nonionic water-soluble polymer used in the present invention is preferably a polymer represented by the above formula (1). Among them, particularly, polyvinylpyrrolidone improves the fluorescent whitening property when used in combination with a water-soluble fluorescent whitening agent. The molecular weight of the water-soluble polymer is suitably about 40,000 to 1.5 million, preferably 500,000 to 1.2 million. The addition amount is 0.3 to 5 g / m ² approximately,
Preferably, it is about 1 to 3 g / m ² . When used in combination with a water-soluble fluorescent whitening agent, the same amount or more, preferably three times or more, of the water-soluble fluorescent whitening agent is used. Gelatin is mainly used as a binder or protective colloid which can be used in the hydrophilic colloid layers such as the emulsion layer, protective layer and intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids are also usable. Can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and hydrolyzate or enzyme-decomposed product of gelatin can also be used. In the present invention, the silver halide emulsion layer may contain a water-soluble fluorescent whitening agent in order to improve the whiteness of the photographic printing paper. Examples of the water-soluble fluorescent whitening agent include those described in JP-A-62-115444. The surface protective layer in the present invention preferably contains an appropriate hardener and a surfactant. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and microbenzione, and bis (2-chloroethyl urea) -2-hydroxy-4,6-. Dichloro-
1,3,5-triazine, U.S. Pat. No. 3,635,71
8, a compound having a reactive halogen, such as divinyl sulfone, described in US Pat.
N-methylol compounds as described in No. 16,
Isocyanates as described in U.S. Pat. No. 3,103,437; U.S. Pat. No. 3,017,280.
Nos. 2,983,611, aziridyl compounds, carbodiizide compounds described in U.S. Pat. No. 3,100,704, and U.S. Pat. No. 3,091,537. Compounds, halogen carboxaldehydes such as mucochromic acid, dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chrome alum, potassium alum, and zirconium sulfate. Species can be used, or two or more can be used in combination. Specific examples of surfactants include natural surfactants such as saponins, alkylene oxides, glycerins, nonionic surfactants such as glycidols, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as complex salts and sulfoniums, anionic surfactants containing acidic groups such as carboxylic acid, phosphoric acid, sulfate group, and phosphate group, amino salts, aminosulfonic acids, and sulfuric acid or phosphorus of amino alcohol There are amphoteric surfactants such as acid esters, and these can be used alone or in combination of two or more. The silver halide used in the practice of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. The silver halide may be fine grains having a grain size of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The silver halide emulsion which can be used in the present invention can be prepared by a known and conventional method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide salt may be any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, or a reverse mixing method. May be used. It is not limited by the pH, pAg, etc. of the silver halide emulsion. The silver halide emulsion used in the present invention may contain various additives. For example, when chemically sensitizing with a gold compound, other chemical sensitizers (eg, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers other than gold, reduction sensitizers) and the like may be used in combination. it can. Further, it may contain stabilizers, antifoggants, surfactants, developers, development accelerators, hardeners, hardeners, dye removal improvers, thickeners and the like. The silver halide emulsion may be an opaque support such as baryta coated paper, white polyester film, polyolefin (eg, polyethylene, polypropylene, etc.).
It is applied on something like coated paper. Various inorganic white pigments, inorganic color pigments, dispersants, fluorescent brighteners, antistatic agents, antioxidants, stabilizers and the like can be added to these supports. Further, the surface of the support may be subjected to a surface activation treatment such as a corona discharge treatment by a known method, and may be subjected to an undercoating process if necessary. The light-sensitive material of the present invention can be developed after exposure by a known method usually used. Developers include hydroxybenzenes used in ordinary photography, 3
-Developing agents such as pyrazolidones, aminophenols, 1-phenyl-3-pyrazolines, ascorbic acid and aminobenzenes can be used alone or in combination. In addition, generally other known preservatives, alkali agents, pH buffering agents, antifoggants, etc., further include a dissolution aid, a color tone agent, a development accelerator, a surfactant, an antifoaming agent, Water softeners, hardeners, viscosity modifiers, and other alkali metal salts such as sulfites, carbonates, bisulfites, bromides and iodides can be included. As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. If necessary, water-soluble aluminum may be contained as a hardening agent. The processing temperature may be between 18 and 50 ° C. which is generally used in all of the development, fixing and washing steps.
The temperature may be lower than 8 ° C or higher than 50 ° C. The processing time may be selected under conditions suitable for the processing temperature, but it is necessary to prevent fixing and washing from becoming insufficient. Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. EXAMPLE An average particle size of 0.6 μm adjusted by a usual method.
An emulsion composed of m cubic AgBrI (I; 1 mol%) grains was subjected to chemical ripening, and 0.3 mmol / mol AgX of a spectral sensitizing dye represented by the following formula (2) was added to prepare a silver halide emulsion. Embedded image In 100 g of this silver halide emulsion, silver 2
After adjusting the gelatin concentration to contain 4 g of gelatin and 1 g of gelatin, 1 mg of 1-phenyl-5-mercaptotetrazole was used as an antifoggant, 0.1 g of a water-soluble fluorescent whitening agent represented by the following formula 3, and water-soluble An emulsion coating solution was prepared by adding 1.5 g of polyvinylpyrrolidone having an average molecular weight of 1,000,000 as a polymer and 0.2 g of 2,4-dichloro-6-hydroxy-1,3,5-triazine as a hardener. It was coated on a 110 μm polyethylene laminated paper support at a coating silver amount of 1.5 g / m ² . Embedded image Next, 1.5 g of gelatin containing various polymer latexes corresponding to 50% by weight of gelatin was used.
Samples (1 to 7) were obtained by applying a protective layer made of m ² and heating at 40 ° C. for 1 day. For comparison, a sample to which no polymer latex was added was similarly coated to obtain a sample. This is designated as Sample (8). The unexposed product and the white light exposed product of each sample were developed with a D-72 developer (manufactured by Kodak Co.) at 20 ° C. for 90 seconds, and subjected to fixing, washing and drying. The resulting print was measured for white gloss and black gloss using a gonio-gloss meter VG-ID (manufactured by Nippon Denshoku Industries Co., Ltd.).
Shown in The obtained black gloss sample was visually observed. If no devitrification was observed, the sample was marked with a circle.
Also shown in Table 1 as marks. [Table 1] As shown in Table 1, the samples (1 to 4) to which the polymer latex used in the present invention was added were comparative samples (5 to 5).
Compared to 8), it is clear that the film is excellent in any of white gloss, black gloss and devitrification. According to the present invention, a photographic paper excellent in surface gloss and devitrification can be provided.

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Claims (1)

(57) Claims 1. A halogenated composition comprising at least one silver halide photosensitive layer on a reflective support and at least one non-photosensitive layer on the silver halide photosensitive layer . For silver photographic materials
Wherein the silver halide photosensitive layer is gelatin, water-soluble
Polyvinylpyrrolidone as rimer and water-soluble fluorescent enhancement
A silver halide photographic light-sensitive material containing a whitening agent, wherein the non-photosensitive layer contains a polymer latex having at least a methacrylate ester as a monomer unit.