JPH07128763A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material having a stretchable primer layer enhanced in adhesiveness, transparency, and antistatic effect, and prevented from occurrence of adverse effects on photographic performances, and having a dye layer formed uniformly and firmly and an easily reusable support. CONSTITUTION:The photographic sensitive material having a support and at least one silver halide emulsion layer is provided with the primer layer composed of at least a composition comprising (a) a water-soluble electrically conductive polymer, (b) a copolymer or a composition composed essentially of a water- soluble polyester or a water-soluble polyester and a vinyl type polymer, and (c) a composition containing at least polyglycerol, and the dye layer formed successively on the support.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material having a dye layer and having an antistatic property.

[0002]

BACKGROUND OF THE INVENTION In a photographic light-sensitive material, a photographic emulsion layer or other layers are colored to absorb a specific wavelength to improve the image quality of the photographic light-sensitive material. A coloring layer is provided between the emulsion layer and the support or on the support opposite to the photographic emulsion layer, and the light passing through the photographic emulsion layer is reflected at the boundary surface of the photographic light-sensitive material and is again in the photographic emulsion layer. It has been attempted to improve the sharpness of the photographic light-sensitive material by preventing the image from being blurred due to the incidence on the photographic material. The coloring layer for preventing the blurring of the image due to the light passing through the photographic emulsion layer being reflected on the boundary surface of the photographic light-sensitive material and entering the photographic emulsion layer again is called an antihalation layer. .

The colored layer is usually made of a hydrophilic colloid and contains a dye. This dye needs to satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) Photochemically inactive. In other words, do not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense (sensitivity reduction, latent image regression, fog). (3) No detrimental residual color is left on the photographic post-processed light-sensitive material by being decolorized or dissolved and removed in the developing / fixing process.

In a light-sensitive material such as a X-ray light-sensitive material in which a silver image is directly observed and diagnosed and evaluated, the color tone of the silver image is extremely important in order to enhance psychological transparency, and discoloration or color contamination may occur. Yes, if the psychological transparency is reduced, it not only gives an unpleasant impression to the observer, but also leads to misdiagnosis.Therefore, there is a psychological transparency and it is strongly possible to stably obtain a pure black tone silver image. desired.

In recent years, the color tone of a silver image tends to be a warm black tone because a tabular silver halide emulsion which has been put into practical use for the purpose of silver saving and high image quality is widely used. In order to improve the above drawbacks, a so-called toning agent is added to the support, or it is added to the silver halide emulsion layer or an intermediate layer between the silver halide emulsion layer and the support. The method of coloring is used.

The color tone required for an X-ray photosensitive material is X
It depends on the characteristics required for the line photosensitive material.
Usually, a toning agent is added to the support, but the concentration of the toning agent required for the X-ray photosensitive material differs depending on the type of the X-ray photosensitive material, and is required for these X-ray photosensitive materials. It is difficult to prepare in advance a support having all the color tones, so basically a support to which the required toning agent is added is manufactured in advance, and the necessary color tone is added later. The method is taken.

In this case, if a toning agent is added to the silver halide emulsion layer, a considerable photographic desensitization is forced by its optical absorption, so that the silver halide emulsion layer and the support are usually used. The method of adding to the intermediate layer between is adopted.

In the X-ray light-sensitive material, a method is generally used in which a photosensitive emulsion layer is provided on both sides of a support and sandwiched between fluorescent intensifying screens to enhance the absorption efficiency of transmitted X-rays. In this case, the light passing through one emulsion layer spreads through the thick support until it reaches the other emulsion layer, and the sharpness is lowered. A colored layer is provided between the photographic emulsion layer and the support for the purpose of preventing the sharpness from being lowered due to the crossover effect.

The dyes used in these colored layers also need to satisfy the following conditions, like the antihalation layer. (1) It has a proper spectral absorption according to the purpose of use. (2) Photochemically inactive. In other words, do not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense (sensitivity reduction, latent image regression, fog). (3) No detrimental residual color is left on the photographic post-processed light-sensitive material by being decolorized or dissolved and removed in the developing / fixing process.

In order to achieve the above object, US Pat.
130, 429, JP-A-61-116354 and JP-A-61-116349, a magenta dye or a yellow dye is added to an ortho-type photosensitive material to cut crossover light and sharpness. Techniques for improving the are disclosed.

As described above, in the photographic light-sensitive material, the function can be enhanced by providing a coloring layer containing a dye between the support and the silver halide emulsion layer.

In recent years, rapid processing has been required for photographic light-sensitive materials. For example, in the case of X-ray light-sensitive materials,
Processing from development to drying is performed in 90 seconds or less. In such a situation where the processing of the photographic light-sensitive material is required to be quick, it is not preferable that the drying property is deteriorated because the required speed cannot be satisfied.

The thickness of the colored layer is preferably as thin as possible in order not to deteriorate the drying property. Further, the coloring layer should not have uneven coloring.

Japanese Unexamined Patent Publication Nos. 62-70830 and 5
Japanese Patent Laid-Open No. 5-33172 discloses a means for fixing a water-soluble dye to a subbing layer of a support using a basic polymer mordant. According to these methods, the diffusion of the dye from the undercoat layer provided on the support to the silver halide emulsion layer can be prevented, and desensitization and deterioration of photographic performance caused by the diffusion of the dye can be prevented. it can.

Various plastic materials have been used as supports for photographic light-sensitive materials, but since these supports lack adhesiveness with hydrophilic colloids, colored layers made of hydrophilic colloids are used for these supports. When it is directly provided on the surface, the adhesion between the support and the colored layer is not sufficient, which may cause a trouble such as peeling during the treatment.

Particularly, a polyester film typified by a biaxially stretched polyethylene terephthalate film is characterized by excellent transparency, dimensional stability, mechanical properties, electrical properties, chemical resistance, etc. However, since these biaxially stretched polyester films have high crystallinity and poor adhesiveness, it was difficult to directly provide a hydrophilic colloid layer on the support.

In order to enhance the adhesiveness between the support and the hydrophilic colloid layer, it has been customary to provide a primer layer on the support, but when a conventionally known primer layer is provided, the support is Although the adhesiveness between the body and the primer layer can be obtained, the adhesiveness with the hydrophilic colloid layer is not sufficient. It is necessary to provide an intermediate layer containing a hydrophilic colloid having an affinity for both the layer and the above-mentioned primer layer, or to cure the layer forming the hydrophilic colloid layer, and to add water resistance to the aziridine-based coating solution in order to impart water resistance. It was necessary to use a highly active hardener such as a triazine-based hardener.

Providing an intermediate layer containing a hydrophilic colloid not only increases the number of steps, but also deteriorates the drying property, and the coating solution for forming the hydrophilic colloid has an aziridine-based or triazine-based coating. When using hardeners with high activity such as hardeners, these hardeners with high activity have a short life, and over time, the activity of the hardener is lost and the effect as a hardener is lost, so a large amount of hardener is used. It is not possible to make the coating liquid in advance, so make the coating liquid little by little,
There was a problem that it had to be replaced or replenished.

When the primer layer is provided on the support, it is preferable in the manufacturing process to provide the primer layer between the film forming steps of the support. However, if the primer layer is provided on the support and then the film is stretched, it is conventionally known. There is a risk of cracks, peeling, etc., in the existing primer layer.

When a plastic material typified by a polyester film is used as a base material for a photographic light-sensitive material, since the base material itself is an electrical insulator, accumulation of static electricity is a serious problem for photographic performance. Therefore, research on imparting antistatic properties to plastic materials has been conventionally conducted, and various methods have been developed.For example, anionic surfactants, acrylic copolymers and sulfonated polystyrene, metal powders, and oxides are contained in plastic materials. Although tin-antimony-based conductive agents and the like are kneaded, and coating agents containing these are applied to a polyester film, these antistatic agents have transparency, adhesiveness,
The effects on photographic performance and the antistatic property are still insufficient, and improvement thereof has been desired.

It is also known to use a water-soluble conductive polymer for imparting antistatic properties, but when these water-soluble conductive polymers are used, the water-soluble conductive polymer forms a support and a photographic light-sensitive material layer. There was a problem with the adhesiveness.

Therefore, there has been a demand for a technique capable of obtaining a film having excellent adhesiveness, transparency and antistatic property and excellent performance which does not adversely affect the photographic performance by the ordinary stretching process.

In recent years, it has been demanded to reuse resources, and also in photographic light-sensitive materials, a support occupying most of the volume of used photographic light-sensitive materials is recovered,
There is a demand for reuse.

When recovering the resin used for the support from the photographic light-sensitive material provided with the dye layer, the problem is peeling of the dye layer including the light-sensitive layer strongly bonded to the support. If it cannot be completely removed, the recovered resin will be mixed with the hydrophilic colloid layer, and the recovered resin will be colored or the color tone will change from the original resin, limiting the reuse of the recovered resin. It will be.

Therefore, there is a technique capable of obtaining a photographic light-sensitive material provided with a primer layer which is excellent in adhesiveness, transparency and antistatic property, has no adverse effect on photographic performance, and is easy to reuse resources. Was wanted.

[0026]

Therefore, the first object of the present invention is to have a primer layer which is excellent in adhesiveness, transparency and antistatic property, has no adverse effect on photographic performance, and can be stretched, and has a dye layer. It is to provide a photographic light-sensitive material that is uniformly and firmly provided, and a second object is to provide a photographic light-sensitive material in which the support can be easily reused.

[0027]

The above objects of the present invention are: (1) In a photographic light-sensitive material having a support and at least one silver halide emulsion layer, (a) a water-soluble conductive polymer, (b) on the support. ) A primer layer and a dye layer each comprising a water-soluble polyester or a copolymer or composition containing a water-soluble polyester and a vinyl polymer as constituent elements, and (c) a composition containing at least polyglycerin are sequentially provided. Photosensitive material to be. (2) A copolymer or composition comprising a water-soluble polyester and a vinyl polymer as constituent elements is characterized in that the trunk polymer is a water-soluble polyester and the branch polymer is a vinyl polymer. The photographic light-sensitive material as described in (1) above. (3) A copolymer or composition comprising a water-soluble polyester and a vinyl-based polymer as constituent elements is a polymer obtained by polymerizing a vinyl-based monomer in the presence of the water-soluble polyester. The photographic light-sensitive material as described in 1) or (2). (4) The copolymer or composition comprising a water-soluble polyester and a vinyl-based polymer as constituent elements is obtained by dispersion-polymerizing a vinyl-based monomer in an aqueous solution of the water-soluble polyester. The photographic light-sensitive material as described in (1) or (3). (5) The photographic light-sensitive material as described in (1) to (4) above, wherein the dye layer is a hydrophilic colloid layer. (6) The photographic light-sensitive material as described in (1) to (5) above, which is a photographic light-sensitive material for X-rays. Achieved by

The present invention will be described in detail below.

First, a composition containing at least a water-soluble conductive polymer forming a primer layer, a water-soluble polyester or a copolymer obtained by modifying a water-soluble polyester with a vinyl polymer, and polyglycerin (hereinafter referred to as the composition of the present invention. The water-soluble conductive polymer that constitutes the object) will be described.

Examples of the water-soluble conductive polymer that constitutes the composition of the present invention include polymers having a structural unit represented by the following general formula in the molecule. The polymer may be a homopolymer or a copolymer copolymerized with another monomer.

[0031]

[Chemical 1] [In the formula, n represents an integer and M represents a counter ion. ]

Other copolymerizable monomers forming the copolymer include, for example, aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; methyl acrylate, ethyl acrylate. , Butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-
Esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate; acrylic acid, methacrylic acid,
Mono- or dicarboxylic acid anhydrides such as crotonic acid, maleic acid, fumaric acid and itaconic acid; anhydrides of butadiene, isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3-butadiene, etc. Group conjugated dienes; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl chloride; vinylidene chloride; vinyl ethyl ketone; vinyl methyl ether; vinyl acetate;
Vinyl formate; allyl acetate; methallyl acetate; acrylamide; N-methylol acrylamide;
Glycidyl acrylate; glycidyl methacrylate; acrolein; allyl alcohol.

In the present invention, antistatic property, transparency,
From the viewpoint of adhesiveness, it is preferable that the water-soluble conductive polymer having the structural unit represented by the general formula in the molecule contains 10 to 50% of the copolymerizable monomer. The number average molecular weight of the water-soluble conductive polymer used in the present invention is not particularly limited, but it is preferably in the range of 500 to 1,000,000 from the viewpoint of transparency after biaxial stretching. More preferably, it is in the range of 1,000 to 100,000.

In the constitutional unit represented by the above general formula,
As the counter ion of sulfonic acid, H ⁺ , Na ⁺ , K ⁺ , N
Cationic ions such as H ₄ ⁺ , Li ⁺ and Ca ⁺⁺ are mentioned. Among them, H ⁺ and NH ₄ ⁺ ions are preferable in terms of antistatic property and transparency.

Next, the water-soluble polyester which constitutes the composition of the present invention and the copolymer or composition which comprises the water-soluble polyester and the vinyl polymer as the constituents will be explained.

In the present invention, the water-soluble polyester is
A substantially linear polymer obtained by polycondensation reaction of a polybasic acid or its ester-forming derivative and a polyol or its ester-forming derivative, which is water-soluble. In order to make the polyester water-soluble, a hydrophilic copolymerization component such as a component having a sulfonate, a diethylene glycol component, or a polyalkylene ether glycol component is used as the copolymerization component.

Examples of the polybasic acid component of the water-soluble polyester include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid can be used, and maleic acid,
Unsaturated polybasic acids such as fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used in small proportions.

As the polyol component, for example,
Ethylene glycol, diethylene glycol, 1,4-
Use of butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, trimethylolpropane, poly (ethylene oxide) glycol, poly (tetramethylene oxide) glycol. You can

In order to impart water solubility to the polyester, a component having a hydrophilic group, for example, a component having a sulfonate, a diethylene glycol component, a polyalkylene ether glycol component or the like is introduced into the polyester as a copolymerization component. Is an effective means. In particular, it is preferable to use a dicarboxylic acid component having a sulfonate as a component having a hydrophilic group. In this case, the dicarboxylic acid component having a sulfonate is 5 to 15 mol% with respect to the total dicarboxylic acid component of the polyester. It is preferable to contain it.

The dicarboxylic acid having a sulfonic acid salt is particularly preferably one having a group of a sulfonic acid alkali metal salt, and examples thereof include 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid,
Although alkali metal salts such as 5- (4-sulfophenoxy) isophthalic acid can be mentioned, among them, 5-sulfoisophthalic acid sodium salt is particularly preferable. From the viewpoint of water solubility and water resistance, it is particularly preferable to use 6 to 10 mol% of the dicarboxylic acid having these sulfonates based on the total dicarboxylic acid component.

Various methods can be used for synthesizing the water-soluble polyester of the present invention. For example, an initial condensate of a dicarboxylic acid and a glycol is formed by a transesterification method or a direct esterification method, and this is melt-polymerized. It can be obtained by the known polyester production method.
More specifically, for example, transesterification reaction is performed with an ester of dicarboxylic acid, for example, dimethyl ester of dicarboxylic acid and glycol, and after distilling methanol off, the pressure is gradually reduced and polycondensation is performed under high vacuum. How to do,
After the esterification reaction of dicarboxylic acid and glycol and distilling off the produced water, the pressure is gradually reduced, and under high vacuum,
Examples thereof include a polycondensation method, a transesterification reaction between an ester of a dicarboxylic acid and a glycol, an esterification reaction by adding a dicarboxylic acid, and a polycondensation under high vacuum.

Known transesterification catalysts and polycondensation catalysts can be used. Manganese acetate, calcium acetate, zinc acetate and the like can be used as the transesterification catalyst, and antimony trioxide and germanium oxide can be used as the polycondensation catalyst. , Dibutyltin oxide, titanium tetrabutoxide and the like can be used. However, various conditions such as the polymerization method and the catalyst are not limited to the above examples.

The copolymer or composition of the present invention comprising a water-soluble polyester and a vinyl-based polymer as constituent elements is prepared by polymerizing a vinyl-based monomer in the presence of the water-soluble polyester, for example, a water-soluble polyester. It can be obtained by dissolving or dispersing a vinyl monomer in an organic solvent solution or an aqueous solution of a water-soluble polyester and polymerizing the vinyl monomer.

In the present invention, in synthesizing the water-soluble polyester, an addition-polymerizable group such as a carboxylic acid group, a glycidyl group or an amino group is introduced in advance, and the vinyl-based monomer is present in the presence of the polyester. A branched polymer may be formed in the addition-polymerizable group by polymerizing the monomer.

It is not preferable to use an organic solvent for the polymerization of vinyl monomers in the presence of polyester, since the process equipment becomes complicated and the working environment is polluted. From this point of view, it is preferable that the water-soluble polyester is dissolved in hot water, the vinyl monomer is dispersed and added to the matrix of the water-soluble polyester, and emulsion polymerization or suspension polymerization is performed.

A polymerization initiator is used to polymerize the vinyl monomer. Examples of the polymerization initiator that can be used include ammonium persulfate, potassium persulfate, sodium persulfate, and benzoyl peroxide. Among these, ammonium persulfate is preferable.

The polymerization of the vinyl monomer in the water-soluble polyester matrix can be carried out without using a surfactant, but for the purpose of improving the polymerization stability,
It is also possible to use surfactants as emulsifiers. In this case, general nonionic and anionic surfactants can be used.

When the vinyl-based monomer is graft-polymerized on the water-soluble polyester, a graft polymer in which the vinyl-based polymer as the branch polymer is bonded to the water-soluble polyester as the trunk polymer is formed and the vinyl-based monomer is formed. Although the polymer of 1 is also formed, these formed vinyl-based polymers may or may not be removed.

To obtain a copolymer or composition having a water-soluble polyester and a vinyl-based polymer as constituents, a vinyl-based monomer is used as (water-soluble polyester) / (vinyl-based monomer).
Is preferably used within the range of 99/1 to 5/95. Further, the vinyl-based monomer is (water-soluble polyester) / (vinyl-based monomer) 97/3 to 50/50.
Is more preferably within the range of 95/5 to 80 /
It is particularly preferable that it is in the range of 20.

Examples of vinyl-based monomers that can be used include acrylic-based monomers such as alkyl acrylate and alkyl methacrylate (wherein the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2
-Ethylhexyl group, cyclohexyl group, phenyl group,
Benzyl group, phenylethyl group, etc.); hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide. Amide group-containing monomers such as N, N-methylacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-phenylacrylamide Amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; glycidyl acrylate and glycidyl methacrylate Epoxy group-containing monomers; monomers containing carboxyl groups such as acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt, ammonium salt, etc.) or salts thereof; styrenesulfonic acid, vinylsulfonic acid and them Containing a sulfonic acid group or a salt thereof such as a salt (sodium salt, potassium salt, ammonium salt, etc.); itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium salt) And the like, and a monomer containing a carboxyl group or a salt thereof. Examples of the non-acrylic monomer include epoxy group-containing monomers such as allyl glycidyl ether; styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.), etc. Monomers containing sulfonic acid groups or salts thereof; simple monomers containing carboxyl groups or salts thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium salt, etc.) Monomers; monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate; allyl isocyanate; styrene; vinyltrisalkoxysilane; alkyl maleic acid monoester; alkyl fumaric acid monoester; acrylonitrile; methacrylic acid Ronitrile; alkyl itaconic acid monoester Vinylidene chloride; vinyl acetate; vinyl chloride and the like. The above-mentioned monomers may be used alone or in combination of two or more.

Next, the polyglycerin constituting the composition of the present invention will be described.

As the above-mentioned polyglycerin, for example, compounds represented by the following general formula are preferable.

[0053]

[Chemical 2] [In the formula, n is an integer of 2 or more and 20 or less. In the present invention, polyglycerin is preferably used in the range of 0.01 to 50% by weight based on the total amount of the copolymer obtained by modifying the water-soluble conductive polymer and the water-soluble polyester with a vinyl-based polymer, Further, it is preferably used in the range of 5 to 40% by weight. In the present invention, by containing polyglycerin in the coating agent, pseudo-collection or gelation of the coating solution does not occur, and the transparency can be maintained even after biaxial stretching.

In the present invention, the copolymer obtained by modifying the water-soluble conductive polymer and the water-soluble polyester with a vinyl polymer is (water-soluble conductive polymer): (water-soluble polyester is a vinyl polymer. Copolymer modified by
It is preferably used in a ratio of 70 to 15:30 to 85 (weight ratio).

The composition of the present invention contains an anionic surfactant, a nonionic surfactant, an aliphatic polyhydroxy compound, a sulfonated compound, within a range that does not impair the effects of the present invention.
Carboxylated, phosphorylated, sulfoalkylenated, carboxylalkylenated or alkylphosphorylated natural water-soluble polymers and salts thereof; etc. can be added.
Moreover, these compounds can be used together.

Further, additives such as antiblocking agents, organic or inorganic fillers, pigments and ultraviolet absorbers can be added to the composition of the present invention.

The amount of the above compound added is preferably in the range of 0 to 20% by weight based on the total amount of the copolymer obtained by modifying the water-soluble conductive polymer and the water-soluble polyester with a vinyl polymer.

The concentration of the coating liquid for forming the primer layer of the present invention is usually preferably 20% by weight or less, more preferably 15% by weight or less. The coating amount is from 1 to 30 g, and further from 5 to 5 by weight of the coating liquid per 1 m ² of the support.
20 g is preferred.

Next, the dye layer will be described.

In the present invention, the dye refers to an organic compound having an absorption maximum in the visible spectrum region of 380 to 700 nm.

The dye used in the dye layer of the present invention is appropriately selected according to the required purpose.

In the photographic light-sensitive material, the dye layer is used for various purposes. The dye used in the dye layer takes into consideration the absorption spectrum region of the dye, decolorizing property in the processing liquid, etc. according to the purpose of use. Selected and used.

For example, when a dye layer is provided for the purpose of preventing halation, crossover in an X-ray photographic light-sensitive material, etc., the dye remaining in the dye layer after the development process colors the photograph and deteriorates the image quality of the image. Therefore, a dye that is decolorized during development or fixing is used, and when the dye layer is provided for the purpose of enhancing psychological transparency in the X-ray photographic light-sensitive material, it is A dye that is not decolorized by development or fixing is used because decolorization is not a problem.

The dyes may be used alone or in combination of two or more. For example, when one dye cannot provide the required absorption spectral range, two or more dyes can be combined to obtain the required absorption spectral range.

The dye layer is formed by applying a coating solution prepared by adding a dye to a binder solution. It is preferable to use a hydrophilic colloid as the binder. Examples of the hydrophilic colloid used include gelatin,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; alginic acid,
Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole and other homopolymers or copolymers thereof. The synthetic hydrophilic high molecular weight substance can be used.

The preferred binder is gelatin. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull Society Science Photography Japan (Bull. Soc. Sci. Pho.
t. Japan), No. 16, page 30 (1966), oxygenated gelatin may be used,
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used. Furthermore, a gelatin derivative or a graft polymer of gelatin and another polymer can be used.

The binders can be used alone or in combination.

In the present invention, JP-A-60-2694 is used.
It is useful to incorporate the water-soluble methyl cellulose described in No. 4 into the dye layer. The water-soluble methyl cellulose is contained in the binder in a weight ratio of about 1% to 99%, preferably 2% to 50%, and more preferably 3% to 30%.

The substitution degree of the methyl group of the water-soluble methyl cellulose is preferably 0 to 2.5, more preferably 0.5 to 2.5, and particularly 1.0 to 2.5 has an excellent combined effect. . As the degree of polymerization of the water-soluble methyl cellulose, one having a degree of polymerization that gives a viscosity capable of coating may be selected.

The dye layer can be used to increase the film strength by using a hardening agent. Examples of such hardening agents include aldehyde type, aziridine type, isoxazole type, epoxy type, vinyl sulfone type and acryloyl type. , Carbodiimide type, triazine type, polymer type, other maleimide type,
Each of the acetylene-based and methanesulfonic acid ester-based hardening agents can be used alone or in combination.

These hardeners may be directly added to the dye layer, or may be designed to be added to the primer layer of the present invention and hardened by migration.

When the dye is water-soluble, the coating liquid containing the dye can be obtained by adding the dye or the dye aqueous solution to the binder aqueous solution, and the dye is soluble in the alkaline aqueous solution. In some cases, the dye can be obtained by dissolving the dye in an alkaline aqueous solution, adding this to an aqueous binder solution and precipitating it.In addition, when the dye is soluble in an organic solvent, the dye is dissolved in the organic solvent. However, when a hydrophilic colloid is used as the binder, the dye is preferably used by dissolving it in a solvent compatible with the hydrophilic colloid. For example, the coating solution can be obtained by dissolving the dye in water or a hydrophilic organic solvent (eg, methanol, acetone, etc.) and adding it to the solution of the hydrophilic colloid.

The dye may be dispersed in a solvent and added to the binder solution. A mechanical dispersion method using a ball mill, a sand mill, a homomixer or the like can be used to disperse the dye. It is also possible to obtain a dispersion liquid of a dye by dissolving the dye in a solvent capable of dissolving the dye and adding and dispersing this in a solvent in which the dye is insoluble.

Further, the dye can be added to the hydrophilic colloid using a dispersion method of dispersing the color coupler used in the art in the hydrophilic colloid.

The method for adding the dye to the hydrophilic colloid is as follows. The dye is dissolved in a substantially water-insoluble high-boiling point organic solvent, if necessary in combination with a low-boiling point organic solvent or a water-soluble solvent, It is a method of adding to a hydrophilic colloid by mixing with a hydrophilic colloid aqueous solution containing an agent and emulsifying and dispersing with an emulsifying device such as a colloid mill, a homogenizer, and an ultrasonic dispersing device.

Examples of the high-boiling point organic solvent that can be used include carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers and substituted hydrocarbons. Specifically, di-n -Butylphthalic acid ester, di-isooctylphthalic acid ester, dimethoxyethylphthalic acid ester, di-n-butyladipic acid ester, di-isooctylazelaic acid ester, tri-n-butylcitrate ester, butyllauric acid ester , Di-n-butyl sebacate, tricresyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, N, N'-diethylcaprylic acid amide, N, N'-dimethylpalmitic acid amide, n -Butyl-pentadecyl phenyl ether, ethyl-2,4-tert -Butyl phenyl ether,
There are succinic acid ester, maleic acid ester, chlorinated paraffin and the like, and these can be used alone or in combination of two or more kinds.

As the low boiling point organic solvent and water-soluble solvent which can be used, ethyl acetate, butyl acetate, cyclohexane, propylene carbonate, methanol,
There are sec-butyl alcohol, tetrahydrofuran, dimethylformamide, benzene, chloroform, acetone, methyl ethyl ketone, diethyl sulfoxide methyl cellosolve and the like, and one or more of these may be used if necessary.

The surfactants that can be used include anionic surfactants and nonionic surfactants, such as alkylbenzene sulfonate, sulfosuccinate ester salt, saponin and the like. Two or more kinds of these surfactants can be used in combination.

It is also possible to form a dye layer by adding a polymer latex colored with a dye to a binder solution to prepare a coating solution.

The dye layer of the present invention can be formed by applying the coating solution obtained as described above on the primer layer.

When a water-soluble dye is used, it is also preferable to add a mordant to the dye layer. The mordant can prevent the dye from diffusing from the dye layer and prevent the dye from diffusing into the silver halide emulsion layer, causing desensitization and degrading photographic performance.

Diffusion of the dye into the silver halide emulsion layer can be prevented by providing an intermediate layer on the dye layer. However, if the intermediate layer is provided, the thickness of the hydrophilic layer increases and the drying property is increased. Is aggravated, which is not preferable.

Examples of the water-soluble dye that can be used with the mordant include the following.

[0084]

[Chemical 3]

[0085]

[Chemical 4]

[0086]

[Chemical 5]

[0087]

[Chemical 6] In addition, examples of the mordant that can be used in the present invention include the following.

[0088]

[Chemical 7]

[0089]

[Chemical 8]

[0090]

[Chemical 9]

[0091]

[Chemical 10]

[0092]

[Chemical 11]

[0093]

[Chemical 12]

[0094]

[Chemical 13]

[0095]

[Chemical 14]

[0096]

[Chemical 15]

[0097]

[Chemical 16]

[0098]

[Chemical 17] Furthermore, although preferable dyes used in the present invention will be described, the dyes that can be used in the present invention are not limited to these.

Examples of the dye that can be used in the present invention include dyes represented by the following general formula [I].

[0100]

[Chemical 18] [Wherein R _A and R _B are an alkyl group having 1 to 7 carbon atoms, a carboxyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an amino group, an acylamino group, or a trifluoromethyl group, and M is a hydrogen atom or an alkali. Represents a metal atom or an ammonium group. n is 1 or 3. ] The above-mentioned dyes are exemplified in, for example, US Pat. No. 1,884,
It is easily synthesized by the method described in Japanese Patent Publication No. 035, JP-B-39-22069 and the like.

Examples of the dye that can be used in the present invention include silver salts and silver complexes formed by the reaction of the dyes represented by the following general formulas [II] to [VI] with silver ions. . These dyes can be solubilized in the fixing solution, diffused in the processing solution, and decolorized.

[0102]

[Chemical 19][In the formula, R₁, R ₂Is a hydrogen atom, alkyl group, alkenyl
A group, an aryl group or a heterocyclic group, X₁, X₂Is oxygen source
Represents a child and a sulfur atom. L₁~ L_FiveRepresents a methine group, n
₁, N₂Represents an integer of 0 to 2. Also, E₁Is an acidic nucleus
Represents a group having. ]

[0103]

[Chemical 20] [In the formula, R ₃ and R ₄ have the same meanings as R ₁ and R ₂ in the general formula [II], and X ₃ and X ₄ are X ₁ and X ₂ in the general formula [II].
Is synonymous with. L _{6 to} L ₉ represent a methine group, and n _{3 to} n ₅ represent an integer of 0 to 2. R ₅ represents an alkyl group or an alkenyl group, and Q ₁ represents a non-metal atom group necessary for forming a 5- or 6-membered heterocycle. ]

[0104]

[Chemical 21] [In the formula, R ₆ and R ₇ have the same meanings as R ₁ and R ₂ in the general formula [II], and X ₅ and X ₆ have the same meanings as X ₁ and X ₂ in the general formula [II]. R ₈ to R ₁₀ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a sulfo _{group, -COR 11, -CON (R 11} ) (R
_{12), - N (R 11} ) (R 12), - OR 11, -SOR 11,
_{-SO 2 R 11, -SO 2 N} (R 11) (R 12), - N
_{(R 11) COR 12, -N} (R 11) SO 2 R 12, -N (R
_{11) CON (R 12) (} R 13), - SR 11, -COOR 11
And R _{11 to} R ₁₃ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. ]

[0105]

[Chemical formula 22] [Wherein R ₁₄ and R ₁₅ have the same meanings as R ₁ and R ₂ in formula [II], and X ₇ and X ₈ represent X ₁ and X ₂ in formula [II].
Is synonymous with. L _{10 to} L ₁₂ represent a methine group, and n ₆ is 0
Represents an integer of 6; R _{16 to} R ₁₈ have the same meanings as R _{8 to} R ₁₀ in formula [IV]. ]

[0106]

[Chemical formula 23] [Wherein R ₁₉ and R ₂₀ have the same meanings as R ₁ and R ₂ in the general formula [II], and X ₉ and X ₁₀ represent X ₁ and X in the general formula [II].
Synonymous with ₂ . W ₁ represents an aryl group or a heterocyclic group. ] Specific examples of the dyes represented by the above general formulas [II] to [V] are shown below.

[0107]

[Chemical formula 24]

[0108]

[Chemical 25]

[0109]

[Chemical formula 26]

[0110]

[Chemical 27]

[0111]

[Chemical 28]

[0112]

[Chemical 29]

[0113]

[Chemical 30]

[0114]

[Chemical 31]

[0115]

[Chemical 32]

[0116]

[Chemical 33]

[0117]

[Chemical 34]Further, as the dye that can be used in the present invention,
The following general formula [I '] ~ General formula [V ’]
Can be mentioned.

[0118]

[Chemical 35]General formula [I '] ~ General formula [V ′], R³⁵ Is al
Represents a kill group or an alkenyl group, R³⁶ And R³⁷ Is alkyl
Group, alkenyl group, aryl group, heterocyclic group, halogen atom
Child, cyano group, sulfo group, -COR³⁸ , -CON
(R³⁸ ) (R³⁹ ), -N (R³⁸ ) (R³⁹ ), -OR³⁸ ,
-SOR³⁸ , -SO₂R³⁸ , -SO₂N (R³⁸ )
(R³⁹ ), -N (R³⁸ ) COR³⁹ , -N (R³⁸ ) SO₂
R³⁹ , -N (R³⁸ ) CON (R³⁹ ) (R⁴⁰ ), -S
R³⁸ , -COOR³⁸ Represents R³⁸ ~ R⁴⁰ Is a hydrogen atom,
Shows alkyl, alkenyl, aryl and heterocyclic groups.
You

A is a group represented by the following general formula [A ₁ ] to general formula [A ₄ ] and A'is a group represented by the following general formula [A ' ₁ ] to general formula [A' ₄ ]. Represents

[0120]

[Chemical 36]General formula [A₁] ~ General formula [A_Four] And the general formula [A ′₁] ~
General formula [A '_Four], R⁴¹ , R⁴² , R⁴⁴ And R
⁴⁶ Is a hydrogen atom, alkyl group, alkenyl group, aryl
Group, a heterocyclic group, R⁴³ Is an alkyl group, alkenyl
Group, aryl group, heterocyclic group, cyano group, -COR⁴⁷ ,-
CON (R⁴⁷ ) (R⁴⁸ ), -N (R⁴⁷ ) (R⁴⁸ ), -O
R⁴⁷ , -SOR⁴⁷ , -SO₂R⁴⁷ , -SO₂N (R⁴⁷ )
(R⁴⁸ ), -N (R⁴⁷ ) COR⁴⁸ , -N (R⁴⁷ ) SO₂
R⁴⁸ , -N (R⁴⁷ ) CON (R⁴⁸ ) (R⁴⁹ ), -S
R⁴⁷ , -COOR⁴⁷ Represents R⁴⁷ ~ R⁴⁹ Is a hydrogen atom,
Shows alkyl, alkenyl, aryl and heterocyclic groups.
You R⁴⁵ Is R³⁶ And R³⁷ Is synonymous with. X₁₃Is oxygen source
Child, sulfur atom, selenium atom, = NR⁵⁰ Represents R⁵⁰
Is R⁴¹ Is synonymous with. X₁₄, X₁₅And X₁₆Is an oxygen atom,
Represents a sulfur atom.

L represents a methine group, and E represents a group having an acidic nucleus. Q ₂ represents a group of non-metal atoms necessary for forming a heterocycle. W ₂ represents an aryl group or a heterocyclic group. n ₇
And n ₈ represent an integer of 0 to 3, n ₉ and n ₁₀ represent an integer of 0 to _2, and l ₂ and l ₃ represent an integer of 0 to 3.

The compounds represented by the general formulas [I '] to [V'] will be described.

R above³⁵ ~ R⁵⁰ As an alkyl group represented by
Are, for example, methyl group, ethyl group, propyl group, iso
Propyl group, n-butyl group, tert-butyl group, cyclope
And a cyclohexyl group. these
The alkyl group may be a hydroxy group, a cyano group or a sulfo group.
Groups, carboxyl groups, halogen atoms (eg fluorogen
Child, chlorine atom, bromine atom), alkoxy group (for example,
Toxy group, ethoxy group), aryloxy group (for example,
Phenoxy group, 4-sulfophenoxy group, 2,4-dis
Ruphophenoxy group), aryl groups (eg phenyl
Group, 4-sulfophenyl group, 2,5-disulfophenyl
Group), an alkoxycarbonyl group (eg, methoxycarl)
Bonyl group, ethoxycarbonyl group), aryloxy groups
Due to a carbonyl group (eg, phenoxycarbonyl group), etc.
May be replaced.

R³⁶ ~ R⁵⁰ And W₂An aryl group represented by
Examples of include a phenyl group and a naphthyl group.
It These groups are R³⁵ ~ R⁵⁰ An alkyl group represented by
And a group similar to the substituent represented as the substituent of the alkyl group
Can be replaced by

R³⁶ ~ R⁵⁰ And W₂And a heterocyclic group represented by
Are, for example, pyridyl group, thiazolyl group, oxazol group.
Ryl group, imidazolyl group, furyl group, pyrrolyl group, pyra
Dinyl group, pyrimidinyl group, pyridazinyl group, purinyl
Group, selenazolyl group, sulforanyl group, piperidinyl
Group, pyrazolyl group, tetrazolyl group and the like. This
These groups are R³⁵ ~ R⁵⁰ An alkyl group represented by
A group similar to the substituent shown as the substituent of the alkyl group is used.
Can be replaced.

R³⁵ ~ R⁵⁰ As an alkenyl group represented by
Are, for example, a vinyl group and an allyl group. this
These groups are R³⁵ ~ R⁵⁰ An alkyl group represented by
By a group similar to the substituent shown as the substituent of the kill group,
Can be replaced.

Examples of the group having an acidic nucleus represented by E in the general formula [I '] include, for example, JP-A-61-2812.
A group having a bone nucleus described on page 11, line 20 to page 14, line 15 of Japanese Patent Publication No. 35, a group having a nucleus represented by the general formula [A ′ ₁ ] to general formula [A ′ ₄ ]; Examples thereof include groups represented by the following formulas 6 to 8.

[0128]

[Chemical 37][In the formula, R⁵¹ Is R⁴¹ Is synonymous with R⁵² , R⁵³ Is hydrogen
Child and R first³⁶ Represents the group shown as. ]

[0129]

[Chemical 38][In the formula, R⁵⁴ Is R⁴¹ Is synonymous with R⁵⁵ Is a hydrogen atom and
R first³⁶ Represents the group shown as. ]

[0130]

[Chemical Formula 39][In the formula, R⁵⁶ Is R⁴² Is synonymous with R⁵⁷ Is R⁴³ Synonymous with
is there. ] In the general formula [II ′], Q₂A heterocycle formed by
For example, in JP-A-61-282832, 23
~ Heterocycles described on page 26 and

[0131]

[Chemical 40][In the formula, R⁵⁸ Is R⁴¹ Is synonymous with R⁵⁹ Is R³⁶ Synonymous with
is there. l_FourIs an integer of 0 to 3. ] A heterocycle represented by can be mentioned.

Typical examples of the dyes represented by the above general formulas [I '] to [V'] are shown below.

[0133]

[Chemical 41]

[0134]

[Chemical 42]

[0135]

[Chemical 43]

[0136]

[Chemical 44]

[0137]

[Chemical formula 45]

[0138]

[Chemical formula 46]

[0139]

[Chemical 47]

[0140]

[Chemical 48]

[0141]

[Chemical 49] Further, as the dye that can be used in the present invention,
Examples thereof include dyes represented by the following general formula [VII] (hereinafter referred to as methine compounds).

These dyes can be used as silver salts and silver complexes formed by reaction with silver ions.

[0143]

[Chemical 50] [In the formula, Dye represents an atom group having a methine dye structure, J represents a divalent linking group having a skeleton of an atom or an atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and Sal is Represents a group which forms a sparingly soluble salt with silver ion, l ₅ represents 1 or 2, m ₁ represents 0 or 1, and n ₁₁ represents 1, 2, 3 or 4. In the general formula [VII], the group represented by Dye represents an atom group having a methine dye structure, for example, cyanine,
It is a group having a dye structure in which a methine chain such as merocyanine, merostyryl, styryl, oxonol, and triarylmethane is conjugated with a double bond. Specific examples of these dyes include cyanine dyes described in JP-A-63-202665, Soviet Patent No. 653,257, JP-A-52-29727 and JP-A-52-19272.
No. 60825, No. 52-135335, No. 56-27.
No. 146, No. 56-29226, No. 59-10944.
No. 59-15934, No. 59-11847,
63-34539, U.S. Pat. No. 2,944,8.
96, JP-A-3,148,187 and the like, merocyanine dyes described in JP-A-59-211041, JP-A-59-211041.
-211042, 60-135936, 60-
No. 135937, No. 61-204630, No. 61-2
05934, 62-56958, 62-708.
No. 30, No. 62-92949, No. 62-185758.
JP-A-50-14
No. 5125, No. 55-33103, No. 55-1206
No. 60, No. 55-161233, No. 62-18575.
5, No. 63-139949, No. 63-231445.
No. 63-264745, U.S. Pat. No. 4,18.
No. 7,275, British Patent No. 1,521,083, Belgian Patent No. 869,677 and other oxonol dyes, JP-A-59-55437 and JP-A-59-22.
8250, U.S. Pat. Nos. 4,115,126 and 4,359,574, and the like, and triarylmethane dyes, and further, TH James edited "Th.
eory of Photographic Process ”1977 Macmillan, FM Harmer“ Heterocyclic compounds Cyanine
dyes and related compounds ”John Wiley & Sons (Ne
w York London) 1964, DM Sturmer “The Chem
istry of Heterocyclic Compounds ”ed. A. Weissberger
and ECTaylor, 1977, “The Chemistry of Synt
hetic Dyes ”Academic Press (New York London) Vol.I
I, 1952, Vol. IV, selected from those listed in books published in 1971.

J represents a divalent linking group having a skeleton of an atom or atomic group selected from carbon atom, nitrogen atom, oxygen atom and sulfur atom. Preferred groups are alkylene groups (eg,
Methylene group, ethylene group, propylene group, pentylene group etc.), arylene group (eg phenylene group etc.), alkenylene group (eg ethylene group, propenylene group etc.), sulfonyl group, sulfinyl group, ether group, thioether group, carbonyl Group, -N (R ⁶⁰ ) -group (R ⁶⁰
Is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), -N = group, a heterocyclic divalent group (for example, triazine-2,4-diyl group, pyrimidine-).
2,4-diyl group, thiazole-2,4-diyl group, benzoxazole-2,5-diyl group and the like), which is a divalent linking group having 20 or less carbon atoms and formed by combining one or more thereof. , May have a substituent. Examples of the substituent include common ones such as a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.), aralkyl group ( For example, benzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, etc.), alkylthio group, hydroxy group,
Carboxy group, sulfo group, sulfonyl group (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, N-methylcarbamoyl group, morpholinocarbonylamino group, etc.), acyl group (eg,
Acetyl group, benzoyl group, etc.), acylamide group (eg, acetamide group), sulfonamide group (eg,
Methanesulfonamide group, butanesulfonamide group, etc.), cyano group, amino group (for example, ethylamino group,
Any group such as dimethylamino group) and ureido group is selected.

L ₅ is 1 or 2, m ₁ is 0 or 1,
n ₁₁ represents 1, 2, 3 or 4. Sal represents a group forming a sparingly soluble salt with silver ion, and examples thereof include a mercapto group, an acetylene group, a thiocarbonyl group, a thioamide group,
Thiourethane group, thioureido group (for example, 3-ethylthioureido group, 3-phenylthioureido group, etc.), or saturated or unsaturated 5- to 7-membered heterocyclic group containing at least one nitrogen atom in the ring. Examples include ring residues. Preferable groups include groups represented by formulas (VIII) and (IX) described in JP-A-2-97937, or general formulas (II) to (VI) described in JP-A-2-225476. The group shown by these is mentioned.

Typical specific examples of the above methine compounds are shown below.

[0147]

[Chemical 51]

[0148]

[Chemical 52] Furthermore, the dyes that can be used in the present invention include the following dyes.

[0149]

[Chemical 53]

[0150]

[Chemical 54]

[0151]

[Chemical 55]

[0152]

[Chemical 56]

[0153]

[Chemical 57]

[0154]

[Chemical 58]

[0155]

[Chemical 59]

[0156]

[Chemical 60]

[0157]

[Chemical formula 61]

[0158]

[Chemical formula 62]

[0159]

[Chemical formula 63]

[0160]

[Chemical 64]

[0161]

[Chemical 65]

[0162]

[Chemical formula 66] Further, as the dye that can be used in the present invention,
Examples thereof include dyes represented by the following general formula [A].

[0163]

[Chemical formula 67] [In the formula, R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ , R ₆₆ and R ₆₇
Is hydrogen atom, hydroxyl group, nitro group, halogen atom, -O
M, —SO ₃ M (M is a hydrogen atom, an alkali metal atom, an ammonium group), —COR ₆₈ (R ₆₈ represents a substituent), a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, Represents an alkoxy group. Examples of the halogen atom represented by R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ , R ₆₆ and R ₆₇ include a chlorine atom and a fluorine atom, and as a substituted or unsubstituted alkyl group, Is, for example, methyl group, ethyl group, n-propyl group, β
-Carboxyethyl group, γ-carboxypropyl group, γ
Examples include -sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoethoxyethyl group, cyclopentyl group and cyclohexyl group. Examples of the alkoxy group include methoxy group and ethoxy group.

Further, examples of the substituent of the amino group include an aliphatic group and an aromatic group.

Examples of these aliphatic groups include alkyl groups having 1 to 18 carbon atoms (methyl group, ethyl group, n-
Propyl group, octyl group, n-dodecyl group, etc.), alkenyl group (allyl group, butenyl group, octenyl group, etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.), and the like. Based on
Further, examples of the substituent include an alkoxy group (methoxy group, ethoxy group, etc.), aryl group (phenyl group, tolyl group, etc.), aryloxy group (phenoxy group, etc.), amino group, dialkylamino group (dimethylamino group, diethylamino group). Groups, etc.), hetero rings (N-morpholino groups, N-piperidino groups, etc.), halogen atoms (chlorine atoms, fluorine atoms, etc.), nitro groups, hydroxy groups, carbuxyl groups, sulfo groups, and alkoxycarbonyl groups (methoxycarbonyl). Group, ethoxycarbonyl group, etc.) and the like.

The aromatic group is preferably a phenyl group or a naphthyl group. The aromatic group may further have a substituent, and examples of the substituent include an alkyl group (methyl group, ethyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), a hydroxy group, Halogen atom (chlorine atom, fluorine atom, etc.), acylamino group (acetylamino group, benzoylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), succinimide group, carbamoyl group (carbamoyl group, methylcarbamoyl group) Etc.) and nitro groups.

The substituent represented by R ₆₈ is, for example,
Phenyl group, cyclohexyl group, alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, β
-Carboxyethyl group, γ-carboxypropyl group, γ
-Sulfopropyl group, phenyl group, and cyclohexyl group.

Examples of the alkali metal atom represented by M include sodium and potassium.

As the blue dye used in the present invention, among the compounds represented by the above general formula [A], the compound represented by the following general formula [B] is particularly preferable.

[0170]

[Chemical 68] [Wherein R ₆₉ , R ₇₀ , R ₇₁ , R ₇₂ and R ₇₃ are hydrogen atoms,
Hydroxyl group, alkyl group,

[0171]

[Chemical 69] The alkyl group represented by R ₆₉ , R ₇₀ , R ₇₁ , R ₇₂ and R ₇₃ is preferably a methyl group, an ethyl group or a propyl group.

Typical specific examples of the dye represented by the above general formula [A] are shown below.

[0173]

[Chemical 70]

[0174]

[Chemical 71]

[0175]

[Chemical 72] The above-mentioned dyes are commercially available from Side Co., Ltd. under the trade name of, for example, Terrazol Blue, and can be easily obtained.

Further, the following dyes can be used as well as the above dyes.

[0177]

[Chemical formula 73]

[0178]

[Chemical 74] Next, the support will be described.

The support of the present invention may be of any type, and may be a single-layer plastic film or a laminate of the plastic films. Examples of applicable plastic films or laminates of plastic films include cellulose films such as cellulose triacetate and cellulose diacetate, polyolefin films such as polyethylene films, polyester films, polycarbonate films, polystyrene films, and polyethylene laminated paper. However, in the present invention, it is preferably applied to a polyester film which has strength and is useful as a photographic support.

When the photographic light-sensitive material is an X-ray light-sensitive material, a color-tone adjusting agent which enhances psychological transparency may be added to the support.

The polyester constituting the polyester film is a linear saturated polyester mainly synthesized from an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative. Specific examples of such polyesters include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), and polyethylene-2,6-naphthalene dicarboxylate.
These polyesters also include copolymers and blends of these polyesters with small proportions of other resins.

The polyester film is formed by melt-extruding the above polyester resin into a film by a conventional method and stretching it.
It can be obtained by orientation crystallization. The polyester film may also be a coextrusion laminate.

In the present invention, as the polyester film, a differential scanning calorimeter may be used to obtain a polyester film in a nitrogen stream at 10 ° C.
The value of the heat of fusion of crystal measured at a temperature rising rate of 4 / min is 4c
It is preferable that the crystal orientation is such that it exhibits al / g or more.

The primer layer of the present invention may be provided on a biaxially stretched and heat-fixed polyester film by means of coating or the like, or by means of coating or the like during the film forming step for forming the polyester film. You may provide using.

When the biaxially stretched and heat-set polyester film is provided with a primer layer, the adjusted coating solution is applied to the biaxially stretched and heat-fixed polyester film at a desired stretching ratio, and hot air at 80 ° C. to 160 ° C. is applied. The primer layer can be formed by drying at a temperature and forming a continuous film on the film. Then, a coating liquid for forming a dye layer is subsequently applied, and the coating liquid is applied at 80 ° C to 160 ° C in the same manner as the primer layer.
It is dried at a hot air temperature of ° C to form a continuous coating layer having a two-layer structure on the film.

When the primer layer is formed in the course of the film forming process for forming the polyester film, the prepared coating solution is applied to the polyester film before completion of crystal orientation, followed by drying, stretching, heat setting, etc. The primer layer can be formed by carrying out the step (1) to form a continuous film on the film. Like the primer layer, the dye layer may be formed by coating during the film forming process, but may be separately formed and separately provided from the film forming process.

When a primer layer is provided by means of coating or the like during the film forming step for forming a polyester film, the polyester film during the film forming step for forming the primer layer is melt extruded from the polymer to form a film. May be an unstretched film, or a stretched film that has not been stretched to the final stretching ratio, for example, a uniaxially stretched film stretched in either the longitudinal direction or the transverse direction, and further stretched in the longitudinal or transverse direction. It may be a biaxially stretched film stretched in the two directions of the longitudinal and transverse directions to such an extent that orientation crystallization can be completed.

The method of providing the primer layer by means of coating or the like in the course of the film-forming step for forming the polyester film is, for example, by applying to uniaxially stretched polyester which has been longitudinally stretched at a magnification of 2 to 5 times. It can be carried out by providing a primer layer by using it, guiding it to a stenter, laterally stretching it at a magnification of 2 to 5 times, and further thermally fixing it. The dye layer is on the primer layer created in this way,
A coating liquid for forming a dye layer is applied and dried to form a two-layered continuous coating layer on the film.

The solid content concentration of the aqueous primer coating solution is usually 30% by weight or less, preferably 10% by weight or less. The coating amount is preferably 0.5 to 20 g, and more preferably 1 to 10 g in terms of coating liquid weight per 1 m ² of the support.

Conditions for oriented crystallization of polyester film,
For example, as the conditions such as stretching and heat setting, the conditions conventionally accumulated in the art can be adopted.

In the present invention, when the primer layer is formed by coating, a surface active agent such as an anionic surface active agent, a cationic surface active agent or a nonionic surface active agent, such as polyoxyethylene alkylphenyl ether or polyoxyethylene. -Fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap,
Alkyl sulfate, alkyl sulfonate, alkyl sulfosuccinate, quaternary ammonium chloride salt, alkyl amine hydrochloride are added in the required amounts to reduce the surface tension of the coating solution to 40 dyne / cm or less and wet the polyester film. Is preferably promoted.

In order to improve the adhesiveness between the primer layer and the dye layer, corona discharge treatment, glow discharge treatment, electron beam irradiation treatment, or ultraviolet irradiation treatment is performed on the surface of the primer layer before coating and forming the dye layer. Doing is preferred.

The dye layer can be formed by forming a primer layer on a polyester film which is biaxially stretched and heat-set at a desired stretch ratio, and then applying the dye layer. It is also possible to form a primer layer on the polyester film before the completion of crystal orientation, and then stretching, heat setting, etc., and then applying a dye layer coating solution.

More specifically, for example, a coating solution for the primer layer is applied to a uniaxially stretched polyester film which has been longitudinally stretched at a magnification of 2 to 5 times, and then introduced into a stenter and stretched horizontally at a magnification of 2 to 5 times. Stretch and heat set. In this way, a continuous film of the primer layer is formed on the polyester film, and subsequently, the primer layer and the polyester film provided with the dye layer by coating and drying the adjusted dye layer coating solution on the primer layer. Obtainable.

Various known methods can be used for coating the primer layer and the dye layer. For example, a roll coating method, a gravure roll coating method, a roll brushing method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method and a curtain coating method can be used alone or in combination.

The silver halide emulsion used in the photographic light-sensitive material of the present invention may be any silver halide emulsion that is commonly used, for example, silver bromide emulsion, silver iodobromide emulsion or a small amount. The silver iodochlorobromide emulsion containing silver chloride may be used, but the silver iodobromide emulsion is preferable from the viewpoint of obtaining high sensitivity.

Further, as the silver halide emulsion of the present invention, it is advantageous to use a silver halide emulsion having tabular silver halide grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more. Aspect ratio is preferably 3.5
Or more, and more preferably 3.5 or more and 8.0 or less.

The silver halide emulsion having these tabular silver halide grains is said to have improved spectral sensitization efficiency and improved image graininess and sharpness, and is disclosed, for example, in US Pat. No. 4,386,156. , No. 4,504,570,
4,478,929, 4,414,304, 4,411,986, 4,400,463, 4,414,306, 4,439,520, 4 , 433,048, 4,434,226, 4,413,053, 4,459,353, 4,490,458, 4,399,215 and the like. The silver halide emulsion having tabular silver halide grains can be prepared by the methods described therein.

The silver halide emulsion may be a surface latent image type which forms a latent image on the surface of a grain or an internal latent image type which forms a latent image on the inside of a grain. It may be of a type that forms a latent image on the.

These silver halide emulsions are prepared, for example, at the stage of grain preparation or physical ripening, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its salt. Complex salts may be added.

Soluble salts can be removed from the silver halide emulsion by the Nudel water washing method, the flocculation sedimentation method or the like. As a preferable method for removing soluble salts, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, and a polymer flocculant described in JP-A-63-158644. A method using certain exemplified G-3, G-8 and the like can be mentioned.

To the silver halide emulsion used in the photographic light-sensitive material of the present invention, various photographic additives can be added during the physical ripening or the chemical ripening or before or after the ripening. Examples of the compound used in such a process include Research Disclosure (RD) No. 176.
43, (RD) No. 18716 and (RD) No. 3081
19 (December 1989). The types of compounds described in these three Research Disclosures (RD) and their locations are listed below.

[0203]

[Table 1] The photographic light-sensitive material of the present invention may be various photographic light-sensitive materials such as X-ray light-sensitive materials, printing light-sensitive materials, photographing light-sensitive materials and ornamental light-sensitive materials.

[0204]

EXAMPLES The present invention will be further described with reference to the following examples.

The silver halide emulsion coating solution and the protective layer coating solution used in the following examples were prepared according to the adjusting method described in the following Preparation of silver halide emulsion coating solution and preparation of protective layer coating solution.

[Preparation of Silver Halide Emulsion Coating Solution] The average silver iodide content was 0.8 mol%, the average diameter in terms of projected area was 0.98 μm, the coefficient of variation was 0.25, and the aspect ratio was 8.0. A tabular silver iodobromide emulsion was prepared. The resulting emulsion contained 5,5'-dichloro-9-ethyl-3,3'-di-
Anhydrous of (3-sulfopropyl) oxacarbocyanine sodium salt and 5,5'-di- (butoxycarbonyl)
Anhydrous of 1,1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt in a weight ratio of 200: 1 to give 500 mg per mol of silver halide. Was added. Then, chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening and dispersion in an aqueous solution containing gelatin. Further, the following wetting agent and inhibitor were added to the silver halide emulsion in an addition amount shown below per mol of silver halide to obtain a photosensitive silver halide emulsion coating solution.

Ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g 1-phenyl-5-mercaptotetrazole 10 mg [Preparation of protective layer coating solution] The additives used for the protective layer solution preparation are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Ocein gelatin 70 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (average particle size 3.5 μm) 1.1 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500 mg support The characteristics of the photographic light-sensitive material were measured by the following methods.

[Density unevenness of coated base] The uniformity of the density of the support provided with the primer layer and the dye layer was visually evaluated according to the following evaluation criteria. Evaluation Criteria ◯: The density is uniform, and the coating is even. Δ: Streaks or slight pinhole repelling occurs on a part of the coated surface, and density unevenness exists. X = Streaks or pinhole repelling are generated on the entire surface, and remarkable unevenness of density is present.

[Antistatic property of coating film] The antistatic property of the photographic light-sensitive material was evaluated by the surface resistivity. The evaluation was performed by measuring the surface specific resistance value (Ω / □) using an insulation resistance meter MODEL-R-503 (Kawaguchi Electric Co., Ltd.) shown below. (Indicated in the evaluation table as 1 og (Ω / □).) Measurement conditions; applied voltage 100 V, parallel electrodes 5 cm, electrode gap 1 cm Humidification conditions; 55% RH, 23 ° C. for 24 hours .

[Adhesiveness of Light-Sensitive Material] With respect to a sample in which the silver halide emulsion layer and the protective layer are provided on a support provided with a primer layer and a dye layer, a film in a dry state before development processing (see below) , With a raw film), with a film during the development process (hereinafter, referred to as a wet film), and with a film in a dry state after the development process (hereinafter, referred to as a dry film) were evaluated by the following evaluation methods. did.

(With raw film and dried film) The silver halide emulsion layer of the sample which had been dried before or after the development treatment was scratched with a razor at an angle of 45 ° to reach the polyester film, and cellophane adhesion was observed. The tape was pressure-bonded and rapidly peeled off to find the peeled area of the silver halide emulsion layer, and the presence of the raw film and the presence of the dried film were evaluated according to the following evaluation criteria. Evaluation criteria 1. The adhesion is very weak and the silver halide emulsion layer peels completely. 2. The peeled area is 50% or more and less than 100%. 3. The peeled area is 20% or more and less than 50%. 4. The adhesive strength is strong, and the peeled area is 5% or more and less than 20%. 5. The adhesion is very strong and the peeled area is less than 5%. If the evaluation is 4 or more, it can be considered that the film is sufficiently strong in practical use.

During the development-fixing-washing treatment (with wet film), the silver halide emulsion layer of the sample was scratched in a lattice pattern reaching the polyester film with a sharp needle to wet the emulsion layer. As it is, rub strongly with the hands with rubber gloves for 10 seconds. The area of the silver halide emulsion layer peeled at this time was compared with the lattice area, and the peeled area was evaluated according to the same evaluation criteria as those for the case with the raw film and the case with the dry film.

[Alkali resistance of adhesion] A sample in which the above-mentioned silver halide emulsion layer and a protective layer were provided on a support provided with a primer layer and a dye layer was subjected to an aqueous solution of 1.5 wt% sodium hydroxide at 50 ° C. The mixture is allowed to stand still and the time until the silver halide emulsion layer slides off is measured. (Unit: second) 180
If it is more than a second, it is considered that there is no practical problem.

[Photographic Performance-Sensitivity] A sample having a silver halide emulsion layer and a protective layer on both sides of a support having a primer layer and a dye layer on both sides was prepared as an X-ray intensifying screen KO.
250 (manufactured by Konica Corporation), X-ray irradiation through Penetrometer B type, and then XD-SR, XF-SR using SRX-502 automatic processor (manufactured by Konica Corporation)
Processing was carried out at 32 ° C. for 45 seconds with a developing solution (manufactured by Konica Corporation). The sensitivity was evaluated for each of the samples developed as described above. The sensitivity was evaluated based on the current product SR-G (manufactured by Konica Corporation), and the value decreased by the relative value according to the evaluation criteria shown below. Evaluation standard: Sensitivity reduction of 1.25% or more occurs. 2. Sensitivity reduction occurs within the range of 10% or more and less than 25%. The sensitivity decreases in the range of 3.5% or more and less than 10%. The sensitivity decreases within the range of 4.1% or more and less than 5%. 5. No reduction in sensitivity occurs.

[Evaluation of Remaining Coloring Property] An unexposed quartet size sample in which the silver halide emulsion layer and the protective layer were provided on both sides of a support provided with a primer layer and a dye layer on both sides,
Using SRX-502 automatic developing machine, XD-SR, XF-
The sample was treated with an SR developing solution at 32 ° C. for 45 seconds, and the residual color of the treated sample was visually evaluated on a light source stand for photographic observation according to the following evaluation criteria. Evaluation Criteria A: There is no residual dye. B: There is a slight residual dye, but this does not hinder the diagnosis. C: Dye residue is present to the extent of annoying diagnosis. D: Remaining dye remains, which hinders diagnosis.

[Silver tone test after development] Primer
A sample having a size of 30 cm × 30 cm in which the silver halide emulsion layer and the protective layer are provided on both sides of a support having a layer and a dye layer provided on both sides so that the transmitted light density after development is 1.0 After exposure, XD-using the automatic processor SR-502
Processing was carried out at 32 ° C. for 45 seconds with SR and XF-SR development processing solutions. Each sample developed as described above was heated at 50 ° C. for 8 hours.
After standing for 7 days under the condition of 0% RH, the silver color tone by the transmitted light was visually evaluated on Schaukasten according to the following evaluation criteria. Evaluation Criteria A: Black. B: A slightly reddish black color. C: Reddish black. D: Black with a slight yellowish red tint. E: Black with a yellowish red tint.

[Photographic Performance-Activity] A sample having a silver halide emulsion layer and a protective layer on both sides of a support having a primer layer and a dye layer on both sides was subjected to an intensifying screen KO for X-ray photography.
・ I took a picture of the chest with 250 scissors. The processing is SRX-
Processing was carried out at 32 ° C. for 45 seconds with an XD-SR and XF-SR development processing solution using a 502 automatic developing machine.

With respect to each of the samples developed as described above, the real image forming property was visually observed and evaluated according to the evaluation criteria shown below. Evaluation criteria 1. I can't put it into practice. 2. Although it is within a practical range, it is not preferable. 3. Can be put to practical use. 4. It is good. 5. Very good.

However, for the evaluation of the actual image, a comprehensive evaluation including color tone, sharpness, and graininess is performed.

[Color tone after recovery and reuse] After photographic light-sensitive material samples were cut into strips with a width of 1 cm, they were cut at 1.5% at 50 ° C.
The solution was immersed in a NaOH aqueous solution and stirred for 3 minutes, the NaOH aqueous solution was removed by decantation, the obtained NaOH aqueous solution was neutralized with hydrochloric acid, and then silver was recovered and further treated with activated sludge. The remaining strip-shaped support was washed several times in pure water and then dried. This was immersed in liquid nitrogen and crushed with a crusher to obtain a flake-shaped resin. Further, this resin was melted at 280 ° C., extruded into a film shape from a T die, electrostatically applied, and rapidly cast on a cooling drum at about 30 ° C. to obtain an unstretched film (thickness: 1,575 μm).
Got The obtained unstretched film is preheated to 75 ° C., stretched 3 times in the machine direction and then stretched 3 times in the transverse direction at 100 ° C.
Heat treatment was performed at 20 ° C. to obtain a biaxially stretched polyester film.

The coloring of the obtained biaxially stretched polyester film was visually evaluated.

Evaluation Criteria A: Blue B: Slightly yellowish blue C: Yellowish blue

Example 1 <Preparation of Sample 1> 34.02 parts by weight of dimethyl terephthalate, 25.52 parts by weight of dimethyl isophthalate, 12.97 parts by weight of dimethyl sodium 5-sulfoisophthalate, 47.85 parts by weight of ethylene glycol. Parts, 1,4-cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight under a nitrogen stream at 170-22.
After transesterification while distilling off methanol at 0 ° C., 0.04 part by weight of trimethyl phosphate, 0.04 part by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. 22 parts
Esterification was carried out at a reaction temperature of 0 to 235 ° C. by distilling off almost the theoretical amount of water. Then, the pressure in the reaction system was further reduced over about 1 hour and the temperature was raised, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester copolymer (A).
The intrinsic viscosity of the obtained copolymer (A) was 0.35.

The resulting polyester copolymer (A) 90
0 g was dissolved by stirring in 6400 g of hot water at 95 ° C. for 3 hours. 100 g of styrene and 1.0 g of ammonium persulfate were added to this solution, and the mixture was reacted at 80 ° C. for 5 hours to obtain a polyester copolymer (A-
A solution of 1) was obtained.

The resulting modified polyester copolymer (A-
The following water-soluble conductive polymer (B-1) is added to the solution of 1),
The modified polyester copolymer (A-1) and the water-soluble conductive polymer (B-1) are in a weight ratio of [modified polyester copolymer (A-1)] / [water-soluble conductive polymer (B- 1)]
= 60/40 so that the solid content is 10% by weight
The adjustment liquid (AB) was prepared. The following polyglycerin (C-1) was added to 1,000 parts by weight of this adjusting liquid (AB) in an amount of 20.8 parts by weight based on the total solid content to obtain a first layer undercoating liquid.

[0227]

[Chemical 75] In addition, blue-colored polyethylene terephthalate having an intrinsic viscosity of 0.65 is melt extruded from a T-die at 280 ° C into a film, electrostatically applied, and rapidly cast on a cooling drum at about 30 ° C to cast an unstretched film (thickness). 1,575μ
m) was obtained. This unstretched film was preheated to 75 ° C., stretched 3 times in the machine direction, and then subjected to corona discharge treatment on both sides. Then, the above-mentioned first layer undercoating processing liquid was applied to this corona-discharge-treated film by a wire bar coater so that the coating thickness after biaxial stretching would be 0.3 μm, and then 100 ° C.
Was transversely stretched 3 times in the transverse direction and heat-treated at 220 ° C. to obtain a biaxially stretched polyester film (base concentration 0.153) provided with the primer layer of the present invention. Then, a second layer undercoating processing liquid prepared by dispersing a dye (the above-mentioned Exemplified Dye D-1) in a gelatin solution having a concentration of 2% was coated on the primer layer with a wire bar coater so that the coating amount was as follows.
After drying at 0 ° C for 1 minute, a biaxially stretched polyethylene terephthalate film (175 µm) having a primer layer and a dye layer on both sides was obtained.

Gelatin 150 mg / m ² Dye (Exemplary Dye D-1) 37.5 mg / m ² Further, the above silver halide emulsion coating solution was applied on both sides of the biaxially oriented polyethylene terephthalate film provided with this primer layer and dye layer. And the protective layer coating liquid on one side,
Sample 1 was obtained by coating so that the emulsion layer had a silver equivalent of 1.7 g / m ² and the protective layer had a gelatin coating amount of 0.99 g / m ² .

<Preparation of Sample 2> Two polyethylene terephthalates colored with blue having an intrinsic viscosity of 0.65 were applied from a T-die.
It is melt extruded into a film at 80 ° C, electrostatically applied, and rapidly cooled and cast on a cooling drum at about 30 ° C to preheat an unstretched film (thickness 1,575 μm) to 75 ° C and stretch 3 times in the machine direction. And then stretched 3 times in the transverse direction at 100 ° C,
Heat treatment was performed at 220 ° C. to obtain a biaxially stretched polyester film (thickness 175 μm, base concentration 0.153). Both sides of this biaxially stretched polyester film are subjected to corona discharge treatment, the first layer undercoating processing liquid and the second layer undercoating processing liquid are sequentially applied and dried, and a biaxially stretched film having the same undercoating structure as Sample 1. A finished polyethylene terephthalate film was obtained, and a silver halide emulsion layer and a protective layer were applied in the same manner as in Sample 1 to obtain Sample 2.

<Preparation of Sample 3> The modified polyester copolymer (A-1) and the water-soluble conductive polymer (B-1) were used in the first layer subbing liquid used in the preparation of Sample 1,
[Modified Polyester Copolymer (A-1)] / by Weight Ratio
Sample 3 was obtained in the same manner as Sample 1 except that the water-soluble conductive polymer (B-1) was changed to 85/15 and mixed.

<Preparation of Sample 4> The modified polyester copolymer (A-1) and the water-soluble conductive polymer (B-1) were added to the first layer subbing liquid used in the preparation of Sample 1,
[Modified polyester copolymer (A-1)] / by weight ratio
Sample 4 was obtained in the same manner as Sample 1 except that the water-soluble conductive polymer (B-1) was changed to 40/60 and mixed.

<Preparation of Sample 5> The dye (D-1) dispersed in the second layer subbing liquid used in the preparation of Sample 1 was replaced with (D
A sample 5 was obtained in the same manner as the sample 1 except that it was changed to -2).

<Preparation of Sample 6> The dye (D-1) dispersed in the second layer subbing liquid used in the preparation of Sample 1 was replaced with (D
A sample 6 was obtained in the same manner as the sample 1 except that it was changed to -3).

<Preparation of Sample 7> The dye (D-1) dispersed in the second layer subbing liquid used in the preparation of Sample 1 was converted into (D
A sample 7 was obtained in the same manner as the sample 1 except that it was changed to -4).

<Preparation of Sample 8> The polyglycerin (C-
Sample 8 was obtained in the same manner as Sample 1 except that 1) was changed to the following (C-2) and dye (D-1) dispersed in the second layer subbing processing liquid was changed to (D-5). It was

[0236]

[Chemical 76] <Preparation of Sample 9> A dye in which the amount of polyglycerin (C-1) used in the first layer subbing processing liquid used in the preparation of Sample 1 was changed to 25% by weight, and which was dispersed in the second layer subbing processing solution. Sample 9 was obtained in the same manner as sample 1 except that (D-1) was changed to (D-6).

<Preparation of Sample 10> A sample was prepared in the same manner as sample 1 except that the dye (D-1) dispersed in the second layer subbing liquid used in preparing sample 1 was changed to (D-7). 1
I got 0.

<Preparation of Sample 11> 500 g of the polyester copolymer (A) used in preparation of Sample 1 was dissolved in 3400 g of hot water at 95 ° C. with stirring for 3 hours. 100 g of glycidyl methacrylate (GMA) and 1.0 g of ammonium persulfate were added to this solution and reacted at 80 ° C. for 5 hours to obtain a solution of a polyester copolymer (A-2) modified with a vinyl polymer.

Sample 1 except that the above modified polyester copolymer (A-2) was used in place of the modified polyester copolymer (A-1) in the first layer subbing processing liquid used in the preparation of Sample 1. Sample 11 was obtained in the same manner as in.

<Preparation of Sample 12> 500 g of the polyester copolymer (A) used in preparation of Sample 1 was dissolved in 3400 g of hot water at 95 ° C. with stirring for 3 hours. To this solution, 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide
And 1.0 g of ammonium persulfate were added at 5 ° C at 5 ° C.
After reacting for a time, a solution of a polyester copolymer (A-3) modified with a vinyl polymer was obtained.

Sample 1 except that the above modified polyester copolymer (A-3) was used in place of the modified polyester copolymer (A-1) in the first layer undercoating processing liquid used in the preparation of Sample 1. Sample 11 was obtained in the same manner as in.

<Preparation of Sample 13> The acid component was terephthalic acid (49 mol%), isophthalic acid (49 mol%) and 5-sodium sulfoisophthalic acid (2 mol%), and the glycol component was ethylene glycol (50 mol%). %), Neopentyl glycol (45 mol%) and trimethylolpropane (5 mol%) in 5.4 parts by weight of methyl methacrylate (50 mol%), ethyl acrylate (37 mol%), butyl acrylate (8 mol). %) And acrylic acid (5 mol%), 3.6 parts by weight of an acrylic polymer are polymer-reacted to obtain a modified polyester copolymer (A-4) obtained by grafting an acrylic polymer on the polyester copolymer. Obtained. This modified polyester copolymer (A-4) is dissolved in an organic solvent and dispersed in water,
It was heated and distilled to obtain a dispersion liquid of the modified polyester copolymer (A-4).

Instead of the first layer subbing processing liquid used in the preparation of Sample 1, the above modified polyester copolymer (A-
Sample 1 was prepared in the same manner as Sample 1 except that the dispersion liquid of 4) was used.
Got 3.

<Preparation of Sample 14> 38.74 parts by weight of dimethyl terephthalate, 31.95 parts by weight of dimethyl isophthalate, and 1-dimethyl 5-sulfoisophthalic acid sodium salt 1
0.34 parts by weight, ethylene glycol 54.48 parts by weight, calcium acetate monohydrate 0.073 parts by weight, manganese acetate tetrahydrate 0.024 parts by weight under nitrogen flow,
After carrying out the transesterification reaction while distilling off methanol at 70 to 220 ° C., 0.05 part by weight of trimethyl phosphate,
As a polycondensation catalyst, 0.04 parts by weight of antimony trioxide and 17.17 parts by weight of 1,4-cyclohexanedicarboxylic acid were added, and at a reaction temperature of 220 to 235 ° C., a theoretical amount of water was distilled off for esterification. . Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised, and finally polycondensation was performed at 280 ° C. and 0.2 mmHg for 2 hours to obtain a polyester copolymer (A-0).
The intrinsic viscosity of the obtained copolymer (A-0) was 0.45.

Obtained polyester copolymer (A-0)
The following water-soluble conductive polymer (B-1) was added to the above solution, and the polyester copolymer (A-0) and the water-soluble conductive polymer (B
-1) in a weight ratio of [modified polyester copolymer (A
-0)] / [water-soluble conductive polymer (B-1)] = 60 /
The mixture was mixed so as to be 40, and the solid content was adjusted to 10% by weight to prepare a preparation liquid (A0-B). To 1,000 parts by weight of this adjusting solution (A0-B), polyglycerin (C
-1) was added in an amount of 20.8 parts by weight based on the weight of the total solid content to obtain a first-layer undercoat working liquid.

Sample 14 was obtained in the same manner as in Sample 1 except that the first layer undercoating working liquid was used in place of the first layer undercoating working liquid used in the preparation of Sample 1.

<Preparation of Comparative Sample 1> Butadiene (Bu
t) -styrene (St) (30% by weight / 70% by weight) copolymer latex / 2,4-dichloro-6-hydroxy-s-triazine sodium salt (= 97.5% by weight /
Comparative Sample 1 was obtained in the same manner as Sample 1 except that the dispersion liquid having a solid content of 2.5% by weight) was used as the first layer undercoating processing liquid.

<Preparation of Comparative Sample 2> Vinylidene chloride (V
dCl) -Methyl methacrylate (MMA) -acrylic acid (AA) (70 wt% / 25 wt% / 5 wt%) copolymer latex was used in the same manner as in Sample 1 except that the first layer subbing liquid was used. Comparative sample 2 was obtained.

<Preparation of Comparative Sample 3> An acrylic polymer composed of methyl methacrylate / ethyl acrylate (50 mol% / 50 mol%) into which 2.5 parts by weight of a carboxyl group and a methylol group were introduced (average molecular weight 50 10,000)
Same as Sample 1 except that an aqueous primer solution containing acrylic polymer / sulfonated polystyrene = 80/20 (weight ratio) with and sulfonated polystyrene (molecular weight 70,000) was used as the first layer subbing processing liquid. Comparative sample 3 was obtained.

<Preparation of Comparative Sample 4> Comparative Sample 4 was obtained in the same manner as Sample 1 except that the dye dispersed in the second layer undercoating processing liquid was omitted.

Regarding the obtained samples and comparative samples, the above-mentioned “uneven density of coated base”, “antistatic property of coating film”, “adhesive property of photosensitive material”, “alkali resistance of adhesion”, “photographic performance- According to the evaluation methods described in "Sensitivity", "Evaluation of residual color", "Photo-actual image quality", "Color tone after recovery and reuse", uneven density of coating film, charging property of coating film, and adhesion of photosensitive layer The properties, the alkali resistance of the photosensitive layer, the sensitivity, the residual color, the real image-forming property, and the color tone after collection were evaluated. The results are shown in Tables 2 and 3.

[0252]

[Table 2]

[0253]

[Table 3]

Example 2 <Preparation of Sample 15> The dye (D-1) dispersed in the second layer subbing processing liquid used in the preparation of Sample 1 in Example 1 was mixed with (A
A sample 14 was obtained in the same manner as the sample 1 of Example 1 except that it was changed to -1).

<Preparation of Sample 16> The dye (D) dispersed in the second layer subbing processing liquid used in preparation of Sample 2 of Example 1
Sample 2 of Example 1 except that -1) was changed to (A-1)
Sample 15 was obtained in the same manner as in.

<Preparation of Sample 17> The modified polyester copolymer (A-1) and the water-soluble conductive polymer (B-1) were mixed in the first layer subbing liquid used in the preparation of Sample 15, [Modified polyester copolymer (A-
1)] / [water-soluble conductive polymer (B-1)] = 85/1
Sample 17 was obtained in the same manner as sample 15, except that the mixture was changed to 5 and mixed.

<Preparation of Sample 18> The modified polyester copolymer (A-1) and the water-soluble conductive polymer (B-1) were mixed in the first layer subbing liquid used in the preparation of Sample 15. In a weight ratio, [modified polyester copolymer (A-
1)] / [water-soluble conductive polymer (B-1)] = 40/6
Sample 18 was obtained in the same manner as sample 15 except that the mixture was changed to 0 and mixed.

<Preparation of Sample 19> 500 g of the polyester copolymer (A) used in preparation of Sample 1 of Example 1
Was dissolved in 3400 g of hot water at 95 ° C. with stirring for 3 hours.
100 g of glycidyl methacrylate and 1.0 g of ammonium persulfate were added to this solution and reacted at 80 ° C. for 5 hours to obtain a solution of a polyester copolymer (A-5) modified with a vinyl polymer.

The modified polyester copolymer (A-1) was used in the first layer subbing processing liquid used in the preparation of Sample 13.
A sample 19 was obtained in the same manner as the sample 13 except that the modified polyester copolymer (A-5) was used instead of the above.

<Preparation of Sample 20> In the first layer undercoating processing liquid used in preparation of Sample 15, the modified polyester copolymer (A-1) was used and used in Preparation of Sample 12 in Example 1. Modified polyester copolymer (A-3)
A sample 20 was obtained in the same manner as the sample 15 except that was used.

<Preparation of Sample 21> In the first layer undercoating processing liquid used in preparation of Sample 20, the water-soluble conductive polymer (B-1) was replaced with the following water-soluble conductive polymer (B-
Sample 20 was obtained in the same manner as sample 20 except that 2) was used.

[0262]

[Chemical 77] <Preparation of Sample 22> First used in preparation of Sample 20
Sample 22 was obtained in the same manner as in Sample 20, except that the polyglycerin (C-1) shown below was used in place of the polyglycerin (C-1) in the underlayer processing liquid.

[0263]

[Chemical 78] <Preparation of Sample 23> First used in preparation of Sample 20
The same as Sample 20 except that the addition amount of the polyglycerin (C-1) was changed to 25 parts by weight with respect to the total solid content weight of 1,000 parts by weight of the adjusting liquid (A-B) in the substratum processing liquid. Then, a sample 23 was obtained.

<Preparation of Sample 24> A sample was prepared in the same manner as in sample 15 except that the dye (A-1) dispersed in the second layer subbing liquid used in preparing sample 15 was changed to (A-2). I got 24.

<Preparation of Sample 25> Sample 25 was prepared in the same manner as in Sample 15 except that the dye (A-1) dispersed in the second layer subbing liquid used in Preparation of Sample 15 was changed to (A-3). I got 25.

<Preparation of Sample 26> The addition amount of the dye dispersed in the second layer undercoating processing liquid used in preparation of Sample 15 was 2
Sample 26 was obtained in the same manner as sample 15 except that the amount was changed to 0.0 mg / m ² .

<Preparation of Sample 27> 38.74 parts by weight of dimethyl terephthalate, 31.95 parts by weight of dimethyl isophthalate, and 1-dimethyl 5-sulfoisophthalic acid sodium salt 1
0.34 parts by weight, ethylene glycol 54.48 parts by weight, calcium acetate monohydrate 0.073 parts by weight, manganese acetate tetrahydrate 0.024 parts by weight under nitrogen flow,
After carrying out the transesterification reaction while distilling off methanol at 70 to 220 ° C., 0.05 part by weight of trimethyl phosphate,
As a polycondensation catalyst, 0.04 parts by weight of antimony trioxide and 17.17 parts by weight of 1,4-cyclohexanedicarboxylic acid were added, and at a reaction temperature of 220 to 235 ° C., a theoretical amount of water was distilled off for esterification. . Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised, and finally polycondensation was performed at 280 ° C. and 0.2 mmHg for 2 hours to obtain a polyester copolymer (A-0).
The intrinsic viscosity of the obtained copolymer (A-0) was 0.45.

Obtained polyester copolymer (A-0)
The following water-soluble conductive polymer (B-1) was added to the above solution, and the polyester copolymer (A-0) and the water-soluble conductive polymer (B
-1) in a weight ratio of [modified polyester copolymer (A
-0)] / [water-soluble conductive polymer (B-1)] = 60 /
The mixture was mixed so as to be 40, and the solid content was adjusted to 10% by weight to prepare a preparation liquid (A0-B). To 1,000 parts by weight of this adjusting solution (A0-B), polyglycerin (C
-1) was added in an amount of 20.8 parts by weight based on the weight of the total solid content to obtain a first-layer undercoat working liquid.

Sample 27 was obtained in the same manner as in Sample 15, except that the above-mentioned first layer undercoating working liquid was used in place of the first layer undercoating working liquid used in the preparation of Sample 15.

<Preparation of Comparative Sample 5> Butadiene (Bu
t) -styrene (St) (30% by weight / 70% by weight) copolymer latex / 2,4-dichloro-6-hydroxy-s-triazine sodium salt (= 97.5% by weight /
Comparative sample 5 in the same manner as sample 15 except that the dispersion liquid having a solid content of 2.5% by weight) was used as the first layer undercoating processing liquid.
Got

<Preparation of Comparative Sample 6> Vinylidene chloride (V
dCl) -methyl methacrylate (MMA) -acrylic acid (AA) (70% by weight / 25% by weight / 5% by weight) copolymerized latex / 2,4-dichloro-6-hydroxy-s-
Comparative sample 6 was obtained in the same manner as in sample 15, except that the dispersion containing triazine sodium salt (= 97.5% by weight / 2.5% by weight solids) was used as the first layer undercoating processing liquid.

<Preparation of Comparative Sample 7> Comparative Sample 7 was obtained in the same manner as Sample 15 except that the dye dispersed in the second layer undercoating processing liquid was omitted.

Regarding the obtained samples and comparative samples, the above-mentioned “density unevenness of coated base”, “antistatic property of coating film”, “adhesive property of photosensitive material”, “alkali resistance of adhesion”, “after development treatment” According to the evaluation methods described in "Silver tone test", "Photo-sensitivity", "Photo-actual image quality", and "Color tone after recovery and reuse", uneven density of coating film, chargeability of coating film, and photosensitive layer The adhesiveness, the alkali resistance of the photosensitive layer, the silver color tone, the sensitivity, the real image transfer property, and the color tone after collection were evaluated. The results are shown in Table 4.

[0274]

[Table 4]

[0275]

【The invention's effect】

(1) The water-soluble polyester used for forming the primer layer of the present invention can be synthesized without using an organic solvent, and a copolymerized vinyl-based copolymer obtained by modifying the water-soluble polyester with a vinyl-based polymer. Since it can be performed by modification with an aqueous system, there is no danger of catching fire and there is no problem in the working environment. In addition, in use, the equipment can be simplified as compared with the case of using an organic solvent system. (2) From a water-soluble conductive polymer, a water-soluble polyester copolymer or a copolymer obtained by modifying a water-soluble polyester copolymer with a vinyl polymer and polyglycerin used for forming the primer layer of the present invention The resulting composition exhibits excellent dispersion stability. (3) In the photographic light-sensitive material of the present invention, the dye layer is firmly adhered to the support, and exhibits excellent adhesiveness even during development processing. Further, the dye layer can be formed without density unevenness. (4) From a water-soluble conductive polymer, a water-soluble polyester copolymer or a copolymer obtained by modifying a water-soluble polyester copolymer with a vinyl-based polymer and polyglycerin used for forming the primer layer of the present invention The composition has excellent film-forming properties and also has excellent antistatic properties. (5) In the photographic light-sensitive material of the present invention, the support can be easily recovered and reused, and the color tone of the recovered resin is the same as the original resin, and the resin can be easily reused.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03C 1/83 1/89 1/93 (72) Inventor Akihisa Nakajima 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company (72) Inventor Masaaki Taguchi 1 Sakura-cho, Hino City, Tokyo Konica Stock Company (72) Inventor Ryomichi Ozawa 3-22-19 Osaki Jiyugaoka, Hofu City, Yamaguchi Prefecture (72) Inventor Hitoshi Yamamoto 4-1 Kanebocho, Hofu-shi, prefecture (72) Inventor Hiroshi Naito 2265-5, Yoshiki, Yamaguchi-shi, Yamaguchi (72) Inventor Mitsuo Sato 22-23-206, Gunkeshinmachi, Takatsuki-shi, Osaka (72) Makoto Mohri, Osaka 6-7-1-102, Tomobuchi-cho, Miyakojima-ku, Yokohama (72) Inventor Katsuya Koyama 5-4-1 Senmon, 4-chome, Itami City, Hyogo Prefecture 202 (72) Inventor Yukio Ebisawa 1 Uenohigashi, Toyonaka-shi, Osaka Prefecture No. 204 of 3-27

Claims (6)

[Claims] 1. A photographic light-sensitive material having a support and at least one silver halide emulsion layer, the support comprising:
(A) a water-soluble conductive polymer, (b) a water-soluble polyester or a copolymer or composition having a water-soluble polyester and a vinyl polymer as components, and (c) a composition containing at least polyglycerin A photographic light-sensitive material characterized in that a primer layer and a dye layer are sequentially provided. 2. A copolymer or composition comprising a water-soluble polyester and a vinyl-based polymer as constituent elements is a copolymer in which the trunk polymer is a water-soluble polyester and the branch polymer is a vinyl-based polymer. The photographic light-sensitive material according to claim 1, wherein 3. A copolymer or composition comprising a water-soluble polyester and a vinyl-based polymer as constituent elements, wherein a vinyl-based monomer is polymerized in the presence of the water-soluble polyester. The photographic light-sensitive material according to claim 1. 4. A copolymer or composition comprising a water-soluble polyester and a vinyl-based polymer as constituent elements, wherein the vinyl-based monomer is dispersed and polymerized in an aqueous solution of the water-soluble polyester. The photographic light-sensitive material according to claim 1 or 3. 5. The photographic light-sensitive material according to claim 1, wherein the dye layer is a hydrophilic colloid layer. 6. The photographic light-sensitive material according to claim 1, wherein the photographic light-sensitive material is an X-ray photographic light-sensitive material.