JPH0377980B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an image receiving element used in diffusion transfer photography, and more particularly to an image receiving element in which silver deposition nuclei are finely dispersed in a matrix material permeable to an alkaline processing composition. be. More specifically, the present invention relates to an image receiving element for diffusion transfer that has improved film strength and storage stability. (Prior Art) Diffusion transfer photography using silver salts such as silver halides is well known to those skilled in the art. In such photographic methods, fine particles of a photosensitive silver salt such as silver halide are dispersed in a hydrophilic binder such as gelatin, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, methylcellulose, etc. A photographic light-sensitive element is formed by coating a support such as baryta paper, or a film of a polymeric material such as polyethylene terephthalate, cellulose diacetate, cellulose triacetate, cellulose nitrate, polycarbonate, polyvinyl chloride, etc., with its light-sensitive layer. is imagewise exposed as a function of incident electromagnetic radiation and developed by contacting it with a processing solution containing a developer. At this time, the exposed silver halide in the photosensitive layer is reduced (developed) and becomes non-diffusible silver. Simultaneously or subsequently, when the photosensitive element is brought into contact with a water-soluble silver complex-forming agent, unexposed silver halide reacts with the water-soluble silver complex-forming agent to form a water-soluble silver complex compound. At this time, an image receiving element having a layer (image receiving layer) containing a substance (silver deposition nuclei, so-called physical development nuclei) dispersed in a hydrophilic binder as a catalyst for the reduction reaction of the water-soluble silver complex compound is used. When brought into close contact with the photosensitive layer,
The silver complex compound generated in the photosensitive layer is diffused by the processing solution, transferred from the photosensitive layer to the image-receiving layer, and is reduced to silver by the action of development nuclei in the image-receiving layer. That is,
When viewed as a whole on the image-receiving surface, a silver image is formed as if the image was transferred from the photosensitive layer to the image-receiving layer. Considering this technical content, the above-mentioned photographic method is called silver salt diffusion transfer photographic method. Diffusion transfer photographic receiver elements comprising silver deposition nuclei in a matrix material permeable to alkaline processing compositions are known and are described, for example, in British Patent No. 1,149,921. In the technical field of silver salt diffusion transfer photography, various studies have been conducted on image-receiving elements used in this photography method. For example, as silver deposition nuclei, metal sulfides, metal selenium, and colloids of heavy metals or precious metals, which are generally sparingly soluble in water, are used, but it is desirable that the silver deposition nuclei of this image-receiving element have high activity. . For example, U.S. Pat.
No. 2,698,237 describes a method of mixing a water-soluble metal salt and a water-soluble sulfide in fine silica to form a precipitation of the water-insoluble metal sulfide to obtain highly active silver precipitation nuclei. In addition, in Tokuko Sho 44-32754,
After impregnating an alkali-impermeable polymer material with a silver deposition core material by vacuum evaporation, this polymer material is dissolved in a solvent, coated on a support, dried, and then the surface of this polymer layer is coated. Image-receiving elements are described which are prepared by chemically treating the layer, such as hydrolysis, to render it permeable to alkali. Japanese Patent Publication No. 56-44418 (corresponding to U.S. Pat. No. 3,607,269) discloses that a hydrolyzable material containing () a diffusible agent suitable for modifying the photographic properties of a silver transfer image is deposited on a support. , an image-receiving material comprising a cellulose ester, polyvinyl ester, or polyvinyl acetal layer that becomes permeable to alkali upon hydrolysis, and a regenerated cellulose layer containing () silver deposition nuclei thereon, in which the first layer is free of silver deposition nuclei. discloses a silver salt diffusion transfer image-receiving material characterized in that the second layer does not contain the above-mentioned diffusible agent. As the diffusible drug, an organic mercapto compound is described. According to the specification of Japanese Patent Publication No. 56-44418, the purpose is to position the diffusible agent under the image forming layer before the diffusion transfer process, and to extract it from the lower layer before the diffusion transfer process. It is stated that toning agents and stabilizers are released during the diffusion transfer process, thus increasing the effect of these agents during the diffusion transfer process (Japanese Patent Publication No. 56-44418). (column 2, lines 25-37). In addition, Column 6, line 44 to Column 7 of the specification of Tokko Sho
Line 19 states that these layers are not independent or separate layers, but are partially modified depths of a single continuous layer, and that these layers are multiple continuous layers. It is also specified that when the coating is made by coating with a common solvent, the interface between these layers is not formed as a result and becomes a single layer. It is understood as technology. According to this method, at least the toning agent is present in the first layer at the very early stage of development,
As development progresses, it diffuses from layer to layer and acts as a toning agent. As is well known to those skilled in the art, toning agents act during the formation of developed silver to alter the color of the image by affecting the surface topography and other optical properties of the resulting developed silver. It is natural that it will have no effect unless it acts by diffusing from the lower layer while the developed silver is being formed. However, the method described in Japanese Patent Publication No. 56-44418 is extremely conceptual and has many fatal problems in reality, and is difficult to implement, at least for researchers in the field. It's obvious to us. That is, in the process of producing an image-receiving material, even if only the second layer contains a diffusible agent, mercapto-substituted compounds such as 1-phenyl-5-mercaptotetrazole and imidazolidine-thione, It is extremely easily soluble in the organic solvent used for coating, and when the second layer is applied, the second layer is swollen by the coating solvent of the second layer, the diffusible agent is diffused into the second layer, and is almost evenly distributed between the first and second layers. Secondly, the diffusible drug in the second layer is eluted into the hydrolysis solution and removed by the hydrolysis process, but
Before the manufactured image-receiving material is actually used by a user, the diffusive agent diffuses from layer to layer, degrading photographic performance. If the amount of agent added to the second layer is reduced in order to achieve this, satisfactory modification of the photographic properties of the transferred image will not be achieved. This fatal problem arises because interdiffusion of substances between the two layers is easy, especially since the first and second layers are composed of very closely similar components that do not form an interface. come. As a way to improve this fatal problem, a special application was made in 1983.
-148979 includes a first hydrolyzable compound containing at least one diffusable organic solvent soluble agent suitable for modifying the photographic properties of a silver transfer image formed in a thin layer of an alkali-permeable polymer. between the alkali-impermeable polymer layer and the image-receiving layer comprising silver deposition nuclei made alkali-permeable by hydrolyzing at least a portion of a second hydrolyzable alkali-impermeable polymer; A silver salt diffusion transfer photographic receiving element is disclosed having a single layer of hydrophilic polymer. However, in the method described in Japanese Patent Application No. 58-148979, by hydrolyzing at least a portion of the first hydrolyzable alkali-impermeable polymer layer or the second hydrolyzable alkali-impermeable polymer layer, The adhesion between the image-receiving layer containing alkali-permeable silver deposition nuclei and at least one hydrophilic polymer layer provided therebetween is weak, resulting in film peeling failure during the image-receiving element manufacturing process, or failure after image formation. The drawback is that the scratch resistance of the image receiving element is insufficient. (Object of the Invention) An object of the present invention is to provide an image-receiving element for silver salt diffusion transfer method, which has improved film strength and storage stability. Another object of the present invention is to provide an image-receiving element for silver salt diffusion transfer in which the adhesion between the first alkali-impermeable polymer layer and the image-receiving layer is improved. Another object of the present invention is to provide an image-receiving element for the silver salt diffusion transfer method that is easy to manufacture and does not cause peeling of the film during the manufacturing process. Another object of the present invention is to provide a silver salt diffusion transfer photographic product with improved scratch resistance. (Structure of the Invention) As a result of extensive research, the present inventors have found that a hydrate containing at least one diffusible organic solvent-soluble agent capable of modifying the photographic properties of a silver transfer image formed in a layer of an alkali-permeable polymer. an image receiving layer comprising silver deposition nuclei made alkali permeable by hydrolyzing at least a portion of a first degradable alkali impermeable polymer layer and a second hydrolyzable alkali impermeable polymer; In a silver salt diffusion transfer photographic image-receiving element having at least one hydrophilic polymer layer between the silver salt diffusion transfer method and the hydrophilic polymer layer, the hydrophilic polymer layer contains at least one polymer having vinyl sulfone or a precursor thereof in a side chain. It has been found that the above-mentioned drawbacks can be significantly improved by a silver salt diffusion transfer photographic image-receiving element characterized by the following. As the polymer having vinyl sulfone or its precursor in the side chain used in the present invention, a polymer having a repeating unit represented by the following general formula () is generally used. General formula () In the formula, A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q is an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, -CO ₂ -, or

Represents [formula]. L is −CO ₂ −,

[Formula] A divalent group containing at least one bond and having 3 to 15 carbon atoms, or -O-,

[Formula] −CO−, −SO −, −SO ₂ −, −SO ₃ −,

【formula】

【formula】

[Formula] Any divalent group containing at least one bond and having 1 to 12 carbon atoms. (However, R ₁ represents the same thing as mentioned above.) R ₂ is −CH=CH ₂ or −
Represents _CH2 − _CH2X . X represents a group which can be substituted by a nucleophilic group or can be eliminated by a base in the form of HX. n represents 0 or 1. x, y represent mole percentage, x is 0 to 99, y is 1 to
Takes a value of 100. A is a monomer unit copolymerized with a monomer having at least one ethylenically unsaturated group copolymerizable with component y, and examples of the ethylenically unsaturated monomer include olefins (e.g. ethylene, propylene, - butenes, vinyl chloride, vinylidene chloride, isobutene, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, vinyl propionate,
esters of ethylenically unsaturated acids (e.g. methyl methacrylate, 2-hydroxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate,
Butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-sulfopropyl methacrylate, N,N,N-trimethyl-N-methacryloyloxyethylammonium, p-toluenesulfonate, benzyl methacrylate, phenyl methacrylate, octyl methacrylate, N, N-diethyl-N-acetate ammonioethyl methacrylate, methacryloyloxyethyl phosphonate, cyanoethyl acrylate, methoxyethyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, maleic acid monomethyl ester, maleic acid dibutyl ester, diethyl fumarate ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate),
Amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N,
N-dimethylacrylamide, N-methylolacrylamide, N-(N,N-dimethylaminopropyl)acrylamide, N,N,N-trimethyl-N-(N-acryloylpropyl)ammonium p-toluenesulfonate, 2-acrylamide- Sodium 2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N,
N-dimethyl-N'-acryloylpropanediamine propionate betaine, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine), styrenes (e.g. styrene,
α-methylstyrene, chlorstyrene, chloromethylstyrene, hydroxymethylstyrene, vinyltoluene, dichlorostyrene, potassium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N-vinylbenzylpiperidine, N,N,
N-trimethylammoniomethylstyrene chloride, N,N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, etc.), unsaturated nitriles (e.g. acrylonitrile, methacrylonitrile, crotonitrile, etc.), maleic anhydride, anhydride Itaconic acid, 4-vinylpyridine, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl-2-methylimidazole, N
-vinylacetamide, N-vinyloxazolidone, 1-(2-hydroxyethyl)-3-vinylimidazolium chloride, N-benzyl-4-vinylpyridinium chloride, sodium vinylsulfonate, and the like. A is arbitrarily selected depending on the purpose of use and properties (eg, solubility, glass transition point, ionicity, etc.) of the polymer of the present invention. Further, as a polymer, A may contain two or more types of monomer units in order to exhibit multiple functions. In order to increase the solubility in water, A
Preferred examples include ionic monomers, or water-soluble monomers such as N-vinylpyrrolidone, acrylamide, and N-vinylacetamide. Furthermore, when the polymer of the present invention is used as a crosslinked latex, it is advantageous to use a copolymerizable monomer having at least two ethylenically unsaturated groups as A. Examples of copolymerizable monomers having at least two ethylenically unsaturated groups are, for example, ethylene glycol dimethacrylate, diethylene glycol methacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate. Methacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, methylenebisacrylamide, methylenebismethacrylamide, trivinylcyclohexane , divinylbenzene, N,N-bis(vinylbenzyl)-N,N
-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-
(vinylbenzyl)ammonium chloride, N,
Examples include N,N',N'-tetraethyl-N,N'-bis(vinylbenzyl)-p-xylylene diammonium dichloride. The polymer having vinyl sulfone or its precursor in the side chain used in the present invention is preferably water-soluble. Therefore, as the monomer used for component A, ionic monomers or N-vinylpyrrolidone, methacrylamide, acrylamide, N-vinylacetamide, etc. are preferable. Particularly preferred are anionic monomers and acrylamide. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, n-hexyl group, etc.);
A hydrogen atom or a methyl group is particularly preferred. Q is an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms,
an aralkylene group having 7 to 11 carbon atoms, -
CO ₂ − or

Represents [formula]. Q includes, for example, the following groups. −CO ₂ −, −CONH−,

【formula】

【formula】

[Formula] −CH ₂ −,

【formula】

【formula】

【formula】 【formula】

Among these, −CO ₂ −, −CONH−,

【formula】

【formula】

[Formula] is particularly preferred. L is −CO ₂ −,

[Formula] A divalent group containing at least one bond and having 3 to 15 carbon atoms, or -O-,

[Formula] −CO−, −SO −, −SO ₂ −, −SO ₃ −,

【formula】 【formula】

[Formula] Any divalent group containing at least one bond and having 1 to 12 carbon atoms. (However, R ₁ represents the same as described above.) L includes, for example, the following groups. −CH ₂ CO ₂ CH ₂ − −CH ₂ CO ₂ CH ₂ CH ₂ − −CH ₂ CH ₂ CO ₂ CH ₂ CH ₂ − (—CH ₂ )— ₅ CO ₂ CH ₂ CH ₂ − (—CH ₂ )— ₁₀ CO ₂ CH ₂ CH ₂ − −CH ₂ NHCOCH ₂ − −CH ₂ NHCOCH ₂ CH ₂ − (—CH ₂ )— ₃ NHCOCH ₂ CH ₂ − (—CH ₂ )— ₅ NHCOCH ₂ CH ₂ − (—CH ₂ )― ₁₀ NHCOCH ₂ CH ₂ − −CH ₂ OCH ₂ − −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −

【formula】

[Formula] −COCH ₂ CH ₂ − −CH ₂ COCH ₂ CH ₂ − −SOCH ₂ CH ₂ − −CH ₂ SOCH ₂ CH ₂ − −SO ₂ CH ₂ CH ₂ − −SO ₂ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ − -SO ₃ CH ₂ CH ₂ CH ₂ - -SO ₃ CH ₂ CO ₂ CH ₂ CH ₂ - SO ₃ CH ₂ CH ₂ CO ₂ CH ₂ CH ₂ - -SO ₂ NHCH ₂ CO ₂ CH ₂ CH ₂ - -SO ₂ NHCH ₂ CH ₂ CO ₂ CH ₂ CH ₂ − −NHCONHCH ₂ CH ₂ − −CH ₂ NHCONHCH ₂ CH ₂ −NHCO ₂ CH ₂ CH ₂ − −CH ₂ NHCO ₂ CH ₂ CH ₂ − Also, L is the polymer of the present invention The polymer can be arbitrarily selected depending on its properties (e.g. cationicity, anionicity, nonionicity, solubility, hydrophilicity, hydrophobicity, glass transition point) or form (e.g. water-soluble polymer or polymer dispersion (latex)). Ru. _R2 represents a vinyl group or a functional group serving as a precursor thereof, and is either -CH= _{CH2 or -CH2CH2X} . X represents a group which can be substituted by a nucleophilic group or can be eliminated by a base in the form of HX. R ₂ includes, for example, the following groups. −CH=CH ₂ , −CH ₂ CH ₂ Cl, −CH ₂ CH ₂ Br, −
CH ₂ CH ₂ O ₃ SCH ₃ ,

【formula】

−CH ₂ CH ₂ OH, −CH ₂ CH ₂ O ₂ CCH ₃ , −
CH ₂ CH ₂ O ₂ CCF ₃ , −CH ₂ CH ₂ O ₂ CCHCl ₂ . Among these, −CH=CH ₂ , −CH ₂ CH ₂ Br, −
_{CH2CH2Cl ,}

[Formula] is particularly preferred. x, y represent mole percentage, x is 0 to
99, y takes a value from 1 to 100. x and y are arbitrarily selected depending on the purpose of the present invention. The polymer having vinyl sulfone or its precursor in the side chain of the present invention is preferably hydrophilic, x
takes a value from 0 to 75, and y takes a value from 25 to 100. Although n is 0 or 1, n is preferably 1 in view of the reactivity of vinyl sulfone or its precursor. Among the polymers of the present invention having repeating units represented by the general _formula ( It can be obtained by polymerizing an ethylenically unsaturated monomer represented by the formula (). Further, a polymer in which R ₂ is a vinyl group can be easily obtained by treating a polymer in which R ₂ is a precursor of a vinyl group with a base such as triethylamine or pyridine. General formula () (However, R ₁ , Q, L, R ₂ and n are the same as those described above.) Among the ethylenically unsaturated monomers represented by the general formula (), the following are preferred. The synthesis of the polymer having vinyl sulfone or its precursor in the side chain used in the present invention is described in, for example, JP-A-54
-65033 and 56-142524, and polymers not described in these can be easily achieved by conventional methods with reference to the above-mentioned Japanese Patent Application Laid-Open No. Specific examples of polymers having vinyl sulfone or its precursor in the side chain used in the present invention include:
Examples include: 1 Acrylic acid-methacryloyloxyethoxycarbonylethyl, chloroethyl sulfone copolymer. Copolymer 1a 1b 1c Molar ratio 70:30 75:25 80:20 (Copolymer 1a is a copolymer of acrylic acid, methacryloyloxycarbonylethyl, and chloroethyl sulfone in a molar ratio of 70:30. ) 2 2-Acrylamido-2-methylpropanesulfonic acid sodium methacryloyloxyethoxycarbonylethyl vinyl sulfone copolymer. Copolymer 2a 2b 2c Molar ratio 50:50 60:40 75:25 3 Acrylic acid-(3-methacrylamidopropyl)carbamoylethyl, chloroethylsulfone copolymer. Copolymer 3a 3b 3c Molar ratio 65:35 75:25 90:10 4 2-Acrylamide-2methylpropanesulfonic acid sodium (3-methacrylamidopropyl) carbamoylethyl vinyl sulfone copolymer. Copolymer 4a 4b 4c Molar ratio 30:70 50:50 66:34 5 Potassium methacryloyloxypropanesulfonate-(3-methacrylamidopropyl)carbamoylethyl, vinylsulfone copolymer. Copolymer 5a 5b 5c Molar ratio 40:60 50:50 70:30 6 Acrylic acid-acrylamidomethylcarbamoylethyl, chloroethylsulfone copolymer. Copolymer 6a 6b 6c Molar ratio 60:40 70:30 90:10 7 Acrylamide-acrylamide methyl carbamoylethyl vinyl sulfone copolymer. Copolymer 7a 7b 7c Molar ratio 66:34 80:20 90:10 8 Sodium 2-acrylamido-2-methylpropanesulfonate-acrylamidomethylcarbamoylethylvinylsulfone copolymer. Copolymer 8a 8b 8c Molar ratio 45:55 66:34 80:20 9 Acrylic acid-acrylamidopropylcarbamoylethylchloroethyl sulfone copolymer. Copolymer 9a 9b 9c Molar ratio 70:30 85:15 90:10 10 2-acrylamide-2methylpropanesulfonic acid-acrylamidopropylcarbamoylethyl, chloroethylsulfone copolymer. Copolymer 10a 10b 10c Molar ratio 56:44 65:35 80:20 11 2-acrylamide-potassium 2-methylpropanesulfonate-acrylamidopropylcarbamoylethyl vinyl sulfone copolymer. (Molar ratio a66:34, b75:25, c85:15) Copolymer 11a 11b 11c Molar ratio 66:34 75:25 85:15 12 Potassium vinylbenzenesulfonate-2-acrylamidomethylcarbamoylethyl vinylsulfone copolymer . Copolymer 12a 12b 12c Molar ratio 60:40 70:30 80:20 13 2-acrylamide-2-methylpropanesulfonic acid-3-(p-vinylphenylsulfonylethyl)-2-hydroxypropyl, chloroethylsulfone Polymer. Copolymer 13a 13b 13c Molar ratio 50:50 64:36 78:22 14 2-acrylamide-2-methylpropanesulfonic acid soda vinylbenzylcarbamoylethylvinylsulfone copolymer. Copolymer 14a 14b 14c Molar ratio 60:40 74:26 82:18 The amount of the polymer having vinyl sulfone or its precursor in the side chain used in the present invention can be arbitrarily used as necessary, but is preferably is 0.1 to 500% by weight, particularly preferably 1 to 50% by weight, based on the hydrophilic polymer. The hydrophilic polymer used between the first and second alkali-impermeable polymer layers of the present invention includes:
Water-soluble or water-swellable polymers are used. Examples of the hydrophilic polymer include natural polysaccharides and their derivatives, natural proteins and their derivatives, and synthetic hydrophilic polymers. More specifically, natural polysaccharides or derivatives thereof include, for example, guar gum, locust bean gum, carrageenan, pectin, gum arabic, algin, (alginic acid) , sodium alginate, etc.) cellulose derivatives (carboxymethyl cellulose, cellulose sulfate salts (sodium salt, potassium salt, quaternary ammonium salt, etc.),
methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl cellulose acetate phthalate, hydroxyethyl carboxymethyl cellulose, etc.), starches and derivatives (starch, pregelatinized starch, carboxymethyl starch, hydroxypropyl starch, dialdehyde starch, etc.),
Dextran, Dextran Sodium Sulfate, Pullulan, Sansan Gum, Konyakunan, Karaya Gum, Gum Ghatti, Gum Tragacanth
Examples of natural proteins and their derivatives include gelatin, phthalated gelatin, gluten, casein, albumin, and glue. Examples of synthetic hydrophilic polymers include polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, polyvinylacetamide, polyvinyl sulfonates (sodium, potassium, quaternary ammonium salts, etc.), polyacrylates, polyacrylamide, poly-N -Methylacrylamide, poly-
Hydroxyalkyl-(meth)-acrylates (e.g., poly-2-hydroxyethyl acrylate, poly-2-hydroxyethyl methacrylate, poly-2-hydroxyethyl methacrylate, etc.), polyglutamine soda, polystyrene sodium sulfonate, polyvinylbenzyl-trimethyl ammonium chloride, etc., and copolymers thereof (e.g., acrylamide-sodium acrylate copolymer, acrylamide-N,N-dimethylacrylamide copolymer, acrylamide-N-
Methoxymethylacrylamide copolymer, acrylamide-2-hydroxyethyl methacrylate copolymer, 2-hydroxyethyl acrylate-
2-hydroxyethyl methacrylate copolymer,
Examples include methyl vinyl ether-sodium maleate copolymer, styrene-sodium maleate copolymer, vinyl acetate-vinyl alcohol copolymer, vinyl acetate-sodium maleate copolymer, and vinylpyrrolidone-acrylamide copolymer. You may mix and use these as needed. Among these, natural polysaccharides and their derivatives, and synthetic hydrophilic polymers are preferred from the viewpoint of coating surface condition, coating properties, solubility, and interlayer adhesion with the first and second alkali-impermeable polymer layers, among which dextran and derivatives are preferred. , agarose, starch, alginate, gum arabic, acrylamide polymers (single and multiple) are suitable, especially for water resistance,
Starch and acrylamide polymers (single and multi-component) are excellent in terms of hardening properties to ensure adhesion. The hydrophilic polymer layer used in the present invention is useful in the process of producing a photographic image-receiving element, and in improving the water resistance of the photographic image-receiving element.
In addition, it is desirable to harden the film to ensure adhesion with adjacent layers. Hardening agents are well known to those skilled in the art and include, for example, Research Disclosure.
Those described in the section "Hardeners" on page 26 of Vol. 176 (17643) can be used as desired. Among them, aldehyde-based (e.g., formalin, glyoxal, glutaraldehyde, dialdehyde starch, etc.) and N-methylol (or alkoxymethyl)-based (e.g., dimethylolurea, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, poly-N- methylol acrylamide,
poly-N-methoxymethylacrylamide, etc.)
Hardeners are preferred. The hydrophilic polymer used in the present invention is defined as a polymer that is substantially soluble in water at 1% or more. Further, the hydrophilic polymer used in the present invention has a characteristic of being permeable to alkali, and it is particularly preferable that the permeability thereof has appropriate resistance to aqueous alkaline solutions. That is, when image processing is performed by spreading the photographic processing composition between the image receiving element of the present invention and the exposed photosensitive material, it has the property of increasing the storage stability of the formed silver image. Then, since the agent having the property of inhibiting development is contained in the first hydrolyzable alkali-impermeable polymer layer, if the alkali permeability of the hydrophilic polymer layer is high, silver Before image formation is completed, a portion of the first alkali-impermeable polymer layer is hydrolyzed by the alkali that has passed through the hydrophilic polymer layer, and the drug contained in this first layer is absorbed by the alkali. It then becomes soluble and diffuses into the second layer, undesirably affecting the formation of the silver image. Therefore, by using a hydrophilic polymer layer that retards alkali permeation, it is possible to advantageously use a drug that has both the property of increasing the storage stability of silver images and the property of inhibiting development, which was difficult to use in the past. be able to. Water is used as the solvent for coating the hydrophilic polymer layer of the present invention, but if necessary, water such as alcohol, (methanol, ethanol, propanol, ethylene glycol, etc.), acetone, acetonitrile, dioxane, formamide, tetrahydrofuran, etc. A soluble organic solvent may be used in combination with water. It is desirable to use a coating aid in coating the hydrophilic polymer layer of the present invention. Application aids include, for example, Research Disclosure.
Those described in the section "Coating aids" on page 26 of Vol. 176 (17643) are used. Furthermore, the hydrophilic polymer layer of the present invention can contain various additives as necessary.
For example, preservatives (glycerin, ethylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, pentaerythritol, triacetin, etc.), fluorescent brighteners, antistatic agents, plasticizers, etc. may be included. The thickness of the hydrophilic polymer layer used between the first and second alkali-impermeable polymer layers of the present invention is not particularly limited; From the viewpoint of water resistance of the image receiving element, it is preferable to apply the coating in a range of 0.05 to 20 g/m ² , particularly preferably 0.05 to 5 g/m ²
It is. Diffusable organic solvent soluble agents suitable for modifying the photographic properties of the silver transfer image formed in the polymer layer used in the first hydrolyzable alkali-impermeable polymer layer of the present invention include: For example, organic mercapto compounds (including their tautomerism),
There are imino compounds and iodine compounds, which are particularly effective in improving the storage stability of silver images. In particular, mercapto compounds and imino compounds are known to have an excellent effect on protecting silver images from tarnishing and fading. In the present invention, various conventionally known mercapto compounds and imino compounds can be used, and the present invention is not particularly limited by the types thereof. However, the mercapto and imino compounds used in the present invention need to be diffusive in nature. This is because the effect of the present invention is that after the development process, the mercapto compound and imino compound can be diffused by the permeated alkali of the developing solution, and are diffused into the image-receiving layer, thereby preventing denaturation of the silver image. This is because it will be achieved. Next, some examples of compounds will be given, but as mentioned above, the present invention is not limited to these compounds. (1) imidazolidinethiones, e.g. unsubstituted, and 1-alkyl or aryl substituted imidazolidinethiones; (2) mercaptoimidazoles, e.g. unsubstituted,
and 1-alkyl or aryl substituted 2-mercaptoimidazole, unsubstituted, and 5-alkyl, aryl or nitro substituted 2-mercaptobenzimidazole (3) Triazoles, e.g. unsubstituted and 4-
and/or 5-substituted 3-mercapto-
4H-1,2,4-triazole (alkyl group or aryl group as a substituent), unsubstituted,
and 5-alkyl, nitro or halogen substituted benztriazoles (4) tetrazoles such as unsubstituted and 1-alkyl or aryl substituted 5-mercapto-1H
Tetrazole (5) Mercaptopyrimidines, such as unsubstituted and 4- and/or 6-substituted 2-mercaptopyrimidine (substituents include alkyl groups,
hydroxyl group or mercapto group) (6) Mercaptotetrazapentalenes, e.g.
unsubstituted and substituted at the 3- and/or 6-positions 1,4-dimercapto-3H, 6H-2,3a,
5,6a-tetrazapentalene (alkyl group or aryl group as a substituent) (7) Imidazoles such as unsubstituted and 5-
Alkyl, nitro or halogen substituted 1H-imidazole, unsubstituted and 5-alkyl, nitro or halogen substituted benzimidazoles (8) Benzothiazoles, such as unsubstituted and 5- and/or 6-substituted benzothiazoles (substituents (9) Cysteine (10) Mercaptotetrazaindenes such as unsubstituted and 6-alkyl, hydroxy or mercapto substituted 4-mercapto-1,3,3a,7-
Natrazaindene In these compounds, the alkyl group preferably has 12 or less carbon atoms, and may be either a straight chain or a branched alkyl group. Diffusivity decreases in compounds having an alkyl group having 13 or more carbon atoms. Examples of the aryl group include phenyl and substituted phenyl groups such as tolyl. In addition, various mercapto compounds described in Japanese Patent Publication No. 45-3835 can also be suitably used in the present invention. Specific examples of representative compounds include the following. Namely, 2-imidazolidinethione, 1-ethyl-2-imidazolidinethione, 1-3'-methylphenyl-2-imidazolidinethione, 2-mercaptoimidazole, 3-phenyl-2-mercaptoimidazole, 3-mercapto-4H-1,2,4 -triazole, 4-
Phenyl-3-mercapto-4H-1,2,4-
Triazole, 5-propyl-2-mercaptobenzimidazole, 5-phenyl-2-mercaptobenzimidazole, 5-nitro-2-mercaptobenzimidazole, 2-mercaptobenzimidazole, 1-ethyl-5-mercapto-
1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 5-mercapto-1H
-tetrazole, 2-mercaptopyridine, 4-
Ethyl-2-mercaptopyridine, 4-hydroxy-2-mercaptopyrimidine, 2,4-dimercaptopyrimidine, 6-methyl-2-mercaptopyrimidine, 6-hydroxy-2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 4
-Ethyl-6-ethyl-2-mercaptopyrimidine, 4-methyl-6-hydroxy-2-mercaptopyrimidine, 4-nonyl-2,6-dimercaptopyrimidine, 4-hydroxy-2,6-dimercaptopyrimidine, 4 ,6-dihydroxy-2-
Mercaptopyrimidine, 1,4-dimercapto-
3H, 6H-2,3a,5,6a-tetrapentalene,
3,6-diphenyl-1,4-dimercapto-
3H,6H-2,3a,5,6a-tetrazapentalene, benzotriazole, 6-nitrobenzotriazole, 6-chlorobenzotriazole, 6-
Bromobenzotriazole, 6-octyl-benzotriazole, 1H-indazole, 5-nitro-1H-imidazole, 5-chloro-1H-imidazole, 5-bromo-1H-indazole, 5
-Iodo 1H-imidazole, 5-methyl-1H
- indazole, benzimidazole, 5-nitrobenzimidazole, 5-methylbenzimidazole, 2-mercaptobenzthiazole, 2-
Mercaptobenzimidazole, cysteine, 4
-mercapto-1,3,3a,7-tetrazaindene, 6-methyl-4-mercapto-1,3,
3a,7-tetrazaindene, 6-nonyl-4-
Mercapto-1,3,3a,7-tetrazaindene, 6-lauryl-4-mercapto-1,3,
Examples include 3a,7-tetrazaindene. As the organic mercapto compound or imino compound included in the present invention, precursors of mercapto compounds or imino compounds that dissociate or decompose under alkaline conditions, or metal salts of organic mercapto compounds or imino compounds can also be used. Examples of mercapto compound precursors include:
2-morpholinomethyl-4-phenyl-1,
2,4-triazole-3-thione, 1-morpholinomethyl-4-phenyltetrazole-5-thione, 2-phenyl-4-hydroxymethyl-
1,2,4-triazole-3-thione, 2-acetylthioimidazole, 5-ethoxycarbonylthio-3-methyl-4-phenyl-1,2,4
-triazole, 5-ethoxycarbonylthio-
4-phenyltetrazole, α-thioctic acid, cystine, 3-morpholinomethylbenzothiazoline-2-thione, 5-methyl-3-morpholinomethyloxazolidine-2-thione, 1-morpholinomethyl-4 -(4'-methylphenyl)tetrazol-2-yne-5-thione, 4-piperidinomethyl-1-phenyltetrazol-2-yne-5-thione, 4-morpholinomethyl-2-phenyl-1,3, 4-Oxadiazole-2-yne-5-thione, 3-piperazinomethyl-4-
Thiazolidine-2-thione, 2-amino-4-morpholinomethyl-1,3,4-thiazole-2-
Examples include yne-5-thione and 4-methyl-3-morpholinomethyl-4-thiazoline-2-thione. As the metal salt of the organic mercapto compound, salts or complex compounds of the mercapto compound and various metal ions can be used. As metal ions,
For example, gold, lead, platinum, cadmium, zinc,
There are ions such as iron, cobalt, sodium, potassium, calcium, lithium, and barium. The amount of these diffusible compounds that can change the properties of the silver image added to the layer is usually about 10 ^-6 to ^{10 -2} mol/m ² , although the effective amount varies depending on the type of compound.
and preferably 10 ⁻⁴ to 5×10 ⁻³ mol/m ² . Generally well-known organic solvents are used. Two or more types of solvents can also be used. Next, preferred organic solvents are listed. Alcohols such as methanol, ethanol,
Ketones such as propanol, ethylene glycol, diethylene glycol, glycerin, etc.
Acetone, methyl ethyl ketone, cyclohexanone, etc., esters such as methyl acetate, ethyl acetate, ethyl formate, methyl butyrate, etc., halogenated hydrocarbons, such as methylene chloride, dichloroethane, dichloroethylene, trichloroethane, chloroform, etc., ethers, such as diethyl ether, Tetrahydrofuran, dioxane, amides such as formamide, dimethylformamide, etc., hydrocarbons such as pentane, hexane, heptane, cyclohexane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc. Examples of the first and second hydrolyzable alkali-impermeable polymers used in the present invention include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose propionate, and cellulose acetate butyrate, polyvinyl acetate, Examples include polyvinyl esters such as polyvinyl propionate and polyvinyl chloroacetate. An alkali-impermeable polymer layer made of at least one of these polymers can be made alkali-permeable by hydrolysis with an alkaline solution. Further, polyvinyl acetals such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral can also be used for the second alkali-impermeable polymer layer. In this case, it can be made permeable to alkali by acidic hydrolysis. In the first and second hydrolyzable alkali-impermeable polymer layers used in the present invention, at least a portion of the second alkali-impermeable polymer is alkali-impermeable before being applied to the silver salt diffusion transfer photographic receiving element. It is necessary to make it permeable. Furthermore, an embodiment in which a part (surface) of the first alkali-impermeable polymer layer is hydrolyzed is also within the scope of the present invention. By hydrolyzing a portion of the first alkali-impermeable polymer layer, the adhesion between the first and second hydrolyzable alkali-impermeable polymer layers and the hydrophilic polymer layer provided therebetween is further improved. can be done. To make an alkali-impermeable polymer layer alkali-permeable by alkali hydrolysis, an alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or tetraalkylammonium hydroxide is added.
Alcohol such as methanol or ethanol from 10 to
A saponification solution dissolved in an aqueous alcohol solution containing a concentration of 90% is prepared, and this saponification solution is brought into contact with the polymer layer. Contact methods include brush application of saponification solution,
At least a portion of the cellulose ester layer is saponified by any conventional contact such as roller application, air knife application, spray application, or immersion in a saponifying liquid bath. The saponified layer becomes permeable to alkali and can be penetrated by a diffusion transfer processing solution.
Since the saponified layer becomes the image-receiving layer, the thickness of the image-receiving layer depends on factors such as alkali concentration, alcohol concentration, duration of saponification bath, and temperature, which influence the thickness of the saponified layer. Therefore, it can be controlled. The thickness of the image-receiving layer of the second polymer layer is suitably 0.1 to 20 microns, particularly 0.5 to 10 microns. If the thickness of the image-receiving layer is too thin, it will be difficult to obtain sufficient transfer density, and if it is too thick, a large amount of processing solution will soak into the image-receiving layer, causing oxidation of the developer and contaminating the image-receiving sheet. , there is a tendency to impair the storage stability of silver images. Preferably, the second alkali-impermeable polymer layer contains a silver deposition nucleating material. The silver deposition nucleating material can be included before or after making the second alkali-impermeable polymer layer alkali-permeable, or even simultaneously with the chemical treatment to make it alkali-permeable. These methods are well known to those skilled in the art, and are disclosed, for example, in Japanese Patent Publication No. 44-32754,
120634, Japanese Patent Publication No. 51-49411, U.S. Pat. Silver deposition nuclear materials include zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt,
All conventionally known silver deposition nuclei can be used, such as heavy metals such as copper, noble metals such as palladium, platinum, silver, and gold, or sulfides, selenides, and tellurides of these metals. These silver deposition nuclei can be prepared either by reducing the corresponding temperature ions to create a metal colloidal dispersion or by mixing a metal ion solution with a soluble sulfide, selenide or telluride solution to form water-insoluble metals. Obtained by making colloidal dispersions of sulfides, metal selenides or metal tellurides. The function of materials such as silver deposition nuclei in silver transfer processes is described, for example, in Edwin Etsch Rand et al., U.S. Pat. In order to obtain an image-receiving element giving a favorable tone image, these silver deposition nuclei are usually present on the image-receiving layer in an amount of 10 ^-10 to ^{10 -5} g/m ² , preferably
Contain 10 ^-8 to 10 ^-6 g/cm ² . In the silver salt diffusion transfer photographic image-receiving element of the present invention, it is preferable that the image-receiving layer containing silver deposition nuclei contain a toning agent, if necessary. A toning agent is a compound that can change the tone of the silver transfer image formed after photographic processing. As a color toning agent, for example, imidazolidine-2
-thione, perhydrodiazine-2-thione, benzimidazoles (e.g. benzimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole,
mercapto-5-chlorobenzimidazole, etc.) mercapto-imidazoles (e.g. 2-mercapto-imidazole, 2-mercapto-4-phenylimidazole, 1-methyl-2-mercapto-5-phenylimidazole, 1-benzyl-
2-mercaptoimidazole, 2-mercapto-
1-phenylimidazole, etc.) mercaptotriazoles (e.g., 3-mercapto-4,5
-dimethyltriazole, 4-p-tolyl-
4H-1,2,4-triazole-3-thiol, etc.) benzotriazoles (e.g., benzotriazole-2-thiol, etc.) tetrazole-5-thiols (e.g., 1-phenyl-5-thiol, etc.)
mercaptopyrimidines (e.g., α-mercaptopyrimidine, 2,4-dimercaptopyrimidine, 4-hydroxy-2,6-dimercaptopyrimidine, etc.)
Tetrazapentalenes (e.g. 1,4-dimercapto-3H,6H-2,3a,5,6a-tetrazapentalene, 3,6-diphenyl-1,4-dimercapto-3H,6H-2,3a , 5,6a-tetrazapentalene, etc.), and others, Andre´ Rott, Dipl
By Ing, and Edith Weyde, Dr Ing
Photographic Silver Halide Diffusion
Processes 3, 2, 4, chapters 61-65, U.S. Patent
3756825, German patent 1903741, British patent
Compounds described in French Patent No. 1230470 and French Patent No. 2090476 can also be effectively used. The amount of color toning agent used varies depending on the type of chemical, but if it is too small, the color tone of the silver transfer image will become reddish-black, and if it is too large, it will give a lead color or the overall optical density will decrease, so it is usually about 10 ^-9 to 10 ^-4 mol/
m ² , preferably 10 ⁻⁷ to 10 ⁻⁵ mol/m ² . Among the above color toning agents, benzimidazoles,
Mercaptoimidazoles or mercaptopyrimidines are preferred. Layer and layer thickness are typically 0.1 each
~20μ and 0.1-10μ, preferably 0.5-10μ and 0.5-5μ, respectively. If the layers and the thickness of the layers are too thin, the functions of each layer cannot be fully demonstrated. On the other hand, if the layer is too thick, a large amount of the processing solution will remain in the layer and in the layer coating, causing stains and impairing the image's shelf life. The image receiving element of the present invention is preferably supported on a support. Supports include paper, baryta paper, pigment-coated paper such as titanium white, cellulose acetate, cellulose nitrate, polyvinyl butyral, polyvinyl formal, cellulose butyrate, cellulose acetate butyrate, cellulose propionate, polyethylene, polystyrene, etc. Examples include paper coated with molecular substances by a method such as latky coating or emulsion coating, and films of polymer substances such as polyethylene terephthalate, cellulose diacetate, cellulose triacetate, nitrocellulose, polycarbonate, polyvinyl chloride, etc. Conventionally,
All supports that have been used in the photographic industry can be used. Furthermore, an alkali neutralizing agent layer may be provided if necessary. This alkali neutralizing agent layer has, for example,
48-33697 can be used.
The alkali neutralizer layer is preferably provided between the first alkali-impermeable polymer layer and the support supporting it. Preferred polymeric acids include maleic anhydride copolymers such as styrene-maleic anhydride copolymers, methyl vinyl ether-maleic anhydride copolymers, ethylene-maleic anhydride copolymers, (meth)acrylic acid (co) Examples of the polymer include acrylic acid-alkyl acrylate copolymer, acrylic acid-alkyl methacrylate copolymer, methacrylic acid-alkyl acrylate copolymer, and methacrylic acid-alkyl methacrylate copolymer. Furthermore, the provision of a thin layer of an alkali-permeable or alkali-soluble polymer material called a release layer on the surface of the layer, which is customary in conventional image-receiving elements, can be implemented in the same manner in the image-receiving material of the present invention. As the gelatin silver halide light-sensitive element used in combination in the present invention, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide emulsions can be used. and silver iodobromide are preferred. The average grain size of these silver halides is usually 0.1-10μ. Depending on the purpose, optical sensitizers, chemical sensitizers, antifoggants, gelatin hardeners, surfactants, etc. are added. In some cases, a developing agent for the development process may be added in advance to the silver halide photosensitive element. Hydroxyamine silver halide developers have been found to be particularly useful in producing silver transfer images requiring little or no post-processing, especially when used in combination with a regenerated cellulose silver receiving layer. Particularly useful hydroxylamine silver halide developers are N-alkyl and N-alkoxylalkyl substituted hydroxylamines. Many such hydroxylamines are
U.S. Patent No. 2857274, U.S. Patent No. 2857275, U.S. Patent No. 2857276,
No. 3287124, No. 3287125 and No. 3293034,
It is described in No. 3362961 and No. 3740221. A particularly effective and preferred hydroxylamine silver halide developer is of the formula (wherein R ^1A represents alkyl, alkoxyalkyl or alkoxyalkoxyalkyl, and R ^2A represents hydrogen, alkyl, alkoxyalkyl, alkoxyalkoxyalkyl or alkenyl). Preferably alkyl, alkoxy and alkenyl groups contain 1 to 3 carbons. Particularly useful hydroxylamine silver halide developers include N,
Mention may be made of N-diethyl-hydroxylamine, N,N-bis-methoxyethyl-hydroxylamine and N,N-bis-ethoxyethyl-hydroxylamine. In addition, dihydroxybenzene compounds (e.g., hydroquinone, t-butylhydroquinone, methylhydroquinone, etc.) and U.S. Pat.
Reductone compounds described in US Pat. No. 4,128,425 and reductonic acid compounds described in US Pat. No. 3,615,440 are useful as silver halide developers. Further, the above developer can be used in combination with the auxiliary developer such as a phenidone compound, a p-aminophenol compound, and ascorbic acid. The silver halide solvent may be an alkali metal thiosulfate, such as sodium thiosulfate or potassium thiosulfate, preferably as described in U.S. Pat.
cyclic imides of the type described in detail in the above, such as uracil, urazol, 5-methyl-uracil and the like. The treatment composition contains an alkali, preferably an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide. If this is applied by distributing the processing composition as a thin layer between a superimposed photosensitive element and an image receiving element, and especially if these elements are distributed in a superimposed relationship. If so, the treatment composition preferably includes a polymeric film former, thickener or thickener. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose,
They are included in the processing composition in concentrations effective to provide the appropriate viscosity according to known principles of diffusion transfer photography. The processing composition may further contain other auxiliaries known in silver transfer processes, such as antifoggants, toning agents, stabilizers, and the like. Mercapto compounds, imidazole compounds, imidazole compounds, triazole compounds, etc. are useful as anti-fogging agents and color toning agents, and are particularly patented in the US.
3565619, 3756825, 3642473, UK patents
1122158 and West German Patent Application (OLS) 1804365, etc., are effective. In addition, as a stabilizer, in particular, oxyethylamino compounds,
For example, when triethanolamine is included,
They are useful in increasing the shelf life of treatment compositions as described in Sidney Kasman, US Pat. No. 3,619,185. The image receiving element of the invention can be applied in various ways.
One of them is known as a peelapart type light-sensitive material, in which the image-receiving material sheet and the light-sensitive material sheet are separated into separate sheets, and during the exposure stage, the image-receiving material are folded or rolled so as not to interfere with the exposure of the photosensitive material.
After exposure, the photosensitive material and the image-receiving material are placed one on top of the other, and a developing solution is spread between them for processing. After processing for a certain period of time, the image-receiving material and the photosensitive material are peeled off to obtain a positive image on the image-receiving material. On the other hand, there are diffusion transfer photosensitive materials that do not require peeling (integrate negative and positive type).
In this method, the image-receiving material and the photosensitive material are layered and integrated in advance.
In appearance, it forms one sheet. In this case, either the image-receiving material is light-transmissive to the extent that it does not interfere with the exposure of the light-sensitive material and the exposure is carried out through the image-receiving material, or the support of the light-sensitive material is light-transmissive and the image is transmitted through the support. When observed, only the positive image is visible because the negative image is blocked by the light-reflecting material layer of the processing solution. Therefore, in such a diffusion transfer photographic material, a positive image can be observed without finally peeling off the image-receiving photosensitive material. In addition to the above-mentioned method, methods having various layer structures are known for such diffusion transfer photographic materials that do not require peeling. The present invention is an image-receiving element that has been improved to produce a highly stable silver image and can be applied in all cases, regardless of the differences in these systems. (Operations and Effects of the Invention) When the silver salt diffusion transfer photographic image receiving element of the present invention is used, even if stored for a long time before image processing,
The effect is that the optical density of the silver image is extremely unlikely to decrease during image processing, and that discoloration and optical density decrease during storage of the obtained silver image are extremely unlikely to occur. Furthermore, by using a hydrophilic polymer layer,
It becomes easier to use many kinds of organic solvent-soluble agents to be contained in the first alkali-impermeable polymer layer, and it becomes easier to use various kinds of silver deposition nuclei to be contained in the second image-receiving layer. This is also one of the features of the present invention. Further, by using the hydrophilic polymer layer of the present invention, there can be obtained characteristics in which there are fewer failures due to film peeling during the manufacturing process of the image receiving element, and the scratch resistance of the image receiving element after image formation is significantly improved. The present invention is clearly different from Japanese Patent Publication No. 56-44418 in the following features of the present invention. (1) An intermediate layer made of a hydrophilic polymer, which is provided between the first layer containing an image stabilizer and the second layer containing silver deposition nuclei, and is insoluble in the organic solvent used to coat these layers. It does not swell and forms a clear interface with these layers, preventing unnecessary movement of the image stabilizer during the manufacture of the image-receiving sheet or until it is used by the user. It also has resistance to permeation of alkaline liquid,
Prevents hydrolysis from extending to the first layer during hydrolysis of the second layer, prevents image stabilizer from diffusing into the second layer during development, and preserves the image after development. It sometimes has the effect of gradually diffusing into the second layer. (2) Toning agent The amount of toning agent necessary to optimally adjust the color tone of the developed silver is added to the image-receiving layer containing silver deposition nuclei or to the processing solution from the beginning. Thus, during the diffusion transfer process, the effective concentration of toner in the image-receiving layer in which the transferred silver forms remains unchanged. As described above, by using the image-receiving material with the new structure of the present invention, (1) an image-receiving material containing a larger amount of image stabilizer can be obtained, and it can be stored extremely stably until it is used during the manufacturing process or by the user; , and the discoloration and fading of the obtained image during storage is improved. (2) During the development process, the necessary and sufficient amount of the toning agent is always retained in the layer where development is occurring and does not fluctuate, so images of constant quality can always be obtained. Next, the present invention will be explained with reference to Examples, but of course these Examples do not limit the present invention. (Examples) Example 1 (Preparation of image-receiving element A) Cellulose acetate with 0.12 g of 1-4-hexylcarbamoyl-phenyl-2-mercaptoimidazole dissolved on the surface of baryta coated paper (120 g/m ² , thickness 0.140 mm). A 10% acetone solution of (degree of acetylation 54%) was applied so that the dry coating amount was 5 g/m ² . On top of this, 5% dialdehyde starch (based on starch) was added to a 2% starch aqueous solution containing 10% Exemplified Compound 6c, and the coating was dried to obtain a dry coating amount of 0.6
g/ ^m2 . Furthermore, a 3% acetone solution of cellulose acetate was applied onto this to give a dry film thickness of 14 μm. An alkaline solution containing nickel sulfide as silver deposition nuclei was applied to the above-mentioned coating at a thickness of 25 ml/m ² , dried, washed with water and dried to prepare an image-receiving element A. The composition of the alkaline solution used for coating is as follows. 〓NaOH 20g H ₂ O 200ml Methanol 800ml Glycerin 30g NiS 0.06g The nickel sulfide contained in the above alkaline solution is 20% nickel nitrate aqueous solution and 20% nickel nitrate aqueous solution in glycerin.
It was created by reacting with an aqueous sodium sulfide solution while stirring well. Example 2 (Preparation of image-receiving element B) 18 g of cellulose acetate (degree of acetylation 53%), 0.15 g of 1-(p-hexylcarbamoyl phenyl)-2-mercaptoimidazole and 45% concentration of titanium oxide dispersion
A mixed solution of 0.33 g of methyl vinyl ether-maleic anhydride copolymer and 0.12 g of 2,5-bis(5'-tert-butylbenzoxazolyl-2)-thiophene in 169 ml of acetone, 65 ml of diacetone alcohol, and 60 ml of methyl ethyl ketone. was applied to a thickness of 100 ml/m ² and dried. To this coated material was added 7.3% by weight diluted with 1.2g of 1-(p-hexylcarbamoylphenyl)-2-mercaptoimidazole, 4g of methyl vinyl ether-monomethyl maleate copolymer, and 100g of cellulose acetate (oxidation degree 55%). Acetone alcohol acetone mixture (22/
78vol ratio) solution was applied so that the dry film thickness was 65mg/(dm) ² . Furthermore, a solution of 1% water-soluble 1 of a 9:1 mixture of polyacrylamide and Exemplified Compound 8b of the present invention to which 0.83 ml of formalin was added was added to N-(3-lauroylaminopropyl)-N,
Using N-dimethyl-N-carboxymethylammonium betaine as a coating aid, the dry film thickness was 0.4 g/
It was coated and dried to give a coating size of m ² (this coated material is designated as W). Furthermore, an acetone solution of cellulose acetate was applied on top of this, and the dry film thickness was 0.015 g/
(dm) ² . As in Example 1, an alkaline solution containing nickel sulfide was applied to a thickness of 20 ml/m ² and dried.
Then, it was washed with water and dried. Furthermore, a 1×10 ^-3 wt% methanol solution of 2-mercaptobenzimidazole was added.
Image receiving element B was prepared by coating at 18 ml/m ² and drying. Example 3 An image receiving element C was prepared in the same manner as in Example 1 except that gum arabic was used in place of the starch in Example 1 so that the dry film thickness was 1 g/m ² . Example 4 Image receiving element D was produced in the same manner as in Example 2 except that pullulan was used in place of the polyacrylamide in Example 2 so that the dry film thickness was 0.6 g/m ² . Example 5 (Preparation of image-receiving element E) 54 ml of a solution of 18 g of cellulose acetate (degree of acetylation 54%) and 12 g of styrene-maleic anhydride copolymer dissolved in 270 ml of acetone and 30 ml of methanol was placed on polyethylene laminated paper. It was applied to a thickness of m ² and dried. On top of this, 3,6-diphenyl-
1,4-dimercapto-3H,6H-2,3a,5,
6a-A 11% cellulose acetate acetone solution containing 0.598% tetrazapentalene was added to a dry film thickness of 5.
It was coated so that the amount was 2 g/m ² . Furthermore, on top of this, a 2% aqueous solution of polyacrylamide, an aqueous solution of Exemplified Compound 11b of the present invention (10%) and dimethylol urea (5%) were added.
aqueous solution and acetic acid (50%) at 10% and 5%, respectively.
It was added and mixed at a concentration of 1.25% (based on polyacrylamide) and coated at a coating thickness of 2.5 ml/m ² . Furthermore, a liquid in which palladium sulfide was finely dispersed in an acetone/methanol solution of cellulose acetate was applied on top of this. This coating solution contained 1-phenyl-5-mercaptoimidazole in a coating amount of 1.25×10 ⁻⁶ mol/m ² . The dry film thickness was 0.8 μm. Add 18ml/m ² of the following alkaline solution to this coating.
An image-receiving element E was prepared by coating the film at a ratio of 1, washing with water, and drying. The above palladium sulfide dispersion was prepared by adding a 7 x 10 ^-3 mol sodium sulfide methanol solution and a 7 x 10 ^-3 mol sodium palladium chloride methanol solution to a 5.3% acetone/metal mixed (9/1) solution of cellulose acetate. Add it and stir well. <Alkaline solution> Potassium hydroxide (purity 86%) 44.3g Water 200ml Methanol 800ml Example 6 On top of the applied material W in Example 2, acetic acid degree of 54.6 was added.
% cellulose acetate in a mixed solvent of acetone, diacetone alcohol, methanol, and water (71.3:25:
Palladium sulfide is added to the solution with a weight ratio of 2.2:1.5
A finely dispersed liquid at a ratio of 0.097% by weight (based on cellulose acetate) was applied so that the dry coating amount was 1.5 g/m ² . This coating solution contains 2.7×10 ^-3 g/m ²
1-phenyl-5-mercaptoimidazole was contained so that the coating amount was . further on top of this
An acetone solution of cellulose acetate containing finely dispersed palladium sulfide at a ratio of 3.9 × 10 ^-3 weight % (based on cellulose acetate) was applied in a dry coating amount of 0.2 g/m ²
It was applied so that The same alkaline solution as in Example 5 was applied to this coated material at a rate of 20 ml/m ² , followed by washing with water and drying. On top of this, add 2,
A solution containing 2% of 2,4-trimethylhexamethylene-1,6-diisocyanate (acrylic acid-n-butyl methacrylate copolymer) was applied to a dry coating amount of 0.04 g/m ² to form an image-receiving element. F was produced. The above palladium sulfide dispersion is 0.19% in a 6.6% acetone solution of cellulose acetate.
Add wt% sodium sulfide, water-acetone mixed solution (water:acetone 2:3 volume ratio) and 0.3 wt% sodium palladium chloride water-methanol mixed solution (water:methanol 1:9 vol ratio) and stir well. I made it. Example 7 (Production of image-receiving element G) The same procedure as in Example 6 was carried out except that acrylamide-N,N-dimethylacrylamide copolymer (copolymerization ratio 9:1) was used instead of polyacrylamide in Example 6. An image receiving element G was prepared in this manner. Example 8 (Production of image-receiving element H) Acrylamide-acrylic acid copolymer (copolymerization ratio 95:5) was used instead of acrylamide-N,N-dimethylacrylamide copolymer in Example 7.
Image receiving element H was produced in the same manner as in Example 7 except that . <Production of Comparative Image-Receiving Element> Comparative image-receiving elements were prepared in the same manner as in Examples 1 and 3, except that Exemplary Compound 6c in Examples 1 and 3 was removed. <Production of Comparative Image-Receiving Element> Comparative image-receiving elements and Comparative Image-Receiving Elements were prepared in the same manner as in Examples 2 and 4, except that Exemplary Compound 8b in Examples 2 and 4 was removed. <Preparation of comparative image-receiving element> A comparative image-receiving element was prepared in the same manner as in Example 5, except that Exemplary Compound 11b in Example 5 was removed. <Preparation of Comparative Image-Receiving Elements> Comparative image-receiving elements were prepared in the same manner as in Examples 6, 7, and 8, except that Exemplary Compound 8b in Examples 6, 7, and 8 was removed. Example 9 Diffusion transfer development was performed using the image-receiving elements A to H and the comparative image-receiving element ~ with the following photosensitive layer sheet and the following processing solution to obtain a positive image. (1) Preparation of photosensitive layer sheet A silver iodobromide emulsion having an average grain size of 1.0 μm was prepared by a conventional method. 100g of this was placed in a pot and dissolved in a constant temperature bath at 50°C. 3-{5- to this
Chloro-2-[2-ethyl-3-(3-ethyl-2
-Benzothiazolinylidene)propenyl]-3-
Benzoxazoliopropanesulfonate, 4
-{2-[3-ethylbenzothiazolin-2-ylidene)-2-methyl-1-propenyl]-3-benzothiazolio}propanesulfonate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaine 10 ml of a 1% by weight aqueous solution of DEN, 10 ml of a 1% by weight aqueous solution of 2-hydroxy-4,6-dichlorotriazine sodium salt, and 10 ml of a 1% by weight aqueous solution of sodium dodecylbenzenesulfonate were added and stirred. This completed emulsion was coated on a polyethylene terephthalate film base containing titanium oxide and undercoated to a dry film thickness of 5 microns and dried to obtain a sample. The amount of silver applied was 1.0g/
It was ^m2 . (2) Treatment liquid composition Potassium hydroxide (40% KOH aqueous solution) 323c.c. Titanium dioxide 3g Hydroxyethylcellulose 79g Zinc oxide 9.75g N,N-bis-methoxyethylhydroxyamine 75g Triethanolamine solution (for 6.2 parts of water) (4.5 parts of triethanolamine) 17.14 g Tetrahydropyrimidinethione 0.4 g 2,4-dimercaptopyrimidine 0.35 g Uracil 80 g Water 1193 g The photosensitive layer sheet was subjected to light wedge exposure using a sensitometer with a light source with a color temperature of 5400 K. . This exposed photosensitive layer sheet and the above image-receiving layer sheet were stacked and the above processing solution was spread between them to a thickness of 0.04 mm, and diffusion transfer development was performed. The sheet was peeled off to obtain a positive image. The image-processed image-receiving sheet was immersed in water, and after 1 minute, a diamond needle with a diameter of 1 mm was attached to a force coil type scratch strength meter, and the film strength was measured by changing the load from 0 g to 100 g.

【table】

[Table] The values in the table indicate the load at which the film constituting the image receiving layer begins to break down. As is clear from these results, by using the polymer having vinyl sulfone or its precursor in the side chain of the present invention in the hydrophilic polymer layer, the film strength of the image-receiving sheet of the present invention is increased compared to the comparative image-receiving element. It can be seen that there is a noticeable improvement. Example 10 The positive image obtained in Example 9 was measured using a TCD type self-recording densitometer manufactured by Fuji Film Co., Ltd., and the minimum density of the highlight portion was determined. 300lux of this positive image
The sample was exposed to a fluorescent lamp for one week at an illuminance of 100 mL, and the density of the highlighted area was measured again to determine the increase in stain in the highlighted area.

【table】

[Table] The values in the table indicate the increase in optical density of the highlighted area after one week of exposure to fluorescent lamps. As is clear from these results, the image-receiving elements of the present invention have lower optical densities in highlighted areas due to exposure to fluorescent lamps than the corresponding comparative image-receiving elements, and exhibit good image preservation properties. Preferred Embodiment 1 In the claims, the first and second hydrolyzable alkali-impermeable polymers are
A silver salt diffusion transfer photographic receiving element that is acetylcellulose. 2. In the claims, a silver deposition nucleus produced by hydrolyzing at least a portion of the second hydrolyzable alkali-impermeable polymer layer with an alkaline solution containing a silver deposition nucleus material. A silver diffusion transfer photographic image-receiving element characterized in that it has an image-receiving layer consisting of an alkali-permeable polymer layer containing a substance. 3. In the claims, a silver salt diffusion layer having an image-receiving layer made by containing a silver deposition nucleating material in a second hydrolyzable alkali-impermeable polymer layer and hydrolyzing at least a portion thereof. Transfer method photographic image receiving element. 4. A silver salt diffusion transfer photographic element as claimed, wherein the polymer of the hydrophilic polymer layer comprises a natural polysaccharide and a derivative thereof. 5. A silver salt diffusion transfer photographic receiving element as claimed, wherein the polymer of the hydrophilic polymer layer comprises a synthetic hydrophilic polymer. 6. A silver salt diffusion transfer photographic image-receiving element as claimed in the claims, wherein the polymer of the hydrophilic polymer layer comprises a polyacrylamide polymer (single or multiple). 7. A silver salt diffusion transfer photographic image-receiving element as claimed in the claims, wherein the organic solvent-soluble drug contained in the first hydrolyzable alkali-impermeable polymer layer is an organic mercapto compound. 8. A silver salt diffusion transfer photographic image-receiving element according to embodiment 7, wherein the organic mercapto compound is a mercaptotetrazapentalene and/or a mercaptoimidazole. 9. A silver salt diffusion transfer photographic receiving element according to embodiment 2, wherein the polymer of the hydrophilic polymer layer comprises a natural polysaccharide or a derivative thereof. 10 In embodiment 2, the silver salt diffusion transfer photographic receiving element wherein the polymer of the hydrophilic polymer layer comprises a synthetic hydrophilic polymer. 11 In embodiment 10, the silver salt diffusion transfer photographic receiving element wherein the synthetic hydrophilic polymer comprises an acrylamide polymer (single or multiple). 12 In embodiment 3, the silver salt diffusion transfer photographic receiving element wherein the polymer of the hydrophilic polymer layer comprises a natural polysaccharide or a derivative thereof. 13 In embodiment 3, the silver salt diffusion transfer photographic receiving element wherein the polymer of the hydrophilic polymer layer comprises a synthetic hydrophilic polymer. 14. A silver salt diffusion transfer photographic receiving element according to embodiment 13, wherein the synthetic hydrophilic polymer comprises an acrylamide polymer (single or multiple). 15. A silver salt diffusion transfer photographic receiving element according to embodiment 2, wherein the organic solvent soluble drug contained in the first hydrolyzable alkali impermeable polymer layer is an organic mercapto compound. 16. A silver salt diffusion transfer photographic image receiving element according to embodiment 15, wherein the organic mercapto compound is a mercaptotetrazapentalene derivative and/or a mercaptoimidazole derivative. 17 In embodiment 16, the silver salt diffusion transfer photographic receiving element wherein the polymer of the hydrophilic polymer layer comprises an acrylamide polymer (single or multiple). 18. A silver salt diffusion transfer photographic image receiving element according to embodiment 3, wherein the organic solvent soluble drug contained in the first hydrolyzable alkali impermeable polymer layer is an organic mercapto compound. 19. A silver salt diffusion transfer photographic image receiving element according to embodiment 18, wherein the organic mercapto compound is a mercaptotetrazapentalene derivative and/or a mercaptoimidazole derivative. 20 In Embodiment 14, the organic solvent-soluble drug contained in the first hydrolyzable alkali-impermeable polymer layer is a mercaptotetrazapentalene derivative and/or a mercaptoimidazole derivative. element. 21 In Embodiment 2, the silver deposition nuclear material is silver sulfide,
A silver salt diffusion transfer photographic receiving element that is palladium sulfide or nickel sulfide. 22 In embodiment 10, the silver deposition nuclear material is silver sulfide,
A silver salt diffusion transfer photographic receiving element that is palladium sulfide or nickel sulfide. 23. A silver salt diffusion transfer photographic receiving element according to embodiment 16, wherein the silver deposition nucleus material is palladium sulfide or nickel sulfide. 24 In embodiment 17, the silver deposition core material is palladium sulfide or nickel sulfide.25 In embodiment 3, the silver deposition core material is a metal colloid of gold, silver, platinum and palladium. or silver salt diffusion transfer photographic receiving elements which are sulfides of nickel, silver, lead, platinum, and palladium. 26 In embodiment 12, the silver deposition core material is gold,
A silver salt diffusion transfer photographic receiving element that is a metal colloid of silver, platinum, and palladium, or a sulfide of nickel, silver, lead, gold, platinum, and palladium. 27 In embodiment 18, the silver deposition nuclear material is gold, silver,
A silver salt diffusion transfer photographic receiving element that is a metal colloid of platinum and palladium or a sulfide of nickel, silver, lead, gold, platinum, and palladium. 28 In embodiment 20, the silver deposition core material is gold,
A silver salt diffusion transfer photographic receiving element that is a metal colloid of silver, platinum, and palladium, or a sulfide of nickel, lead, gold, silver, platinum, and palladium. 29. A silver salt diffusion transfer photographic image-receiving element as claimed in the claims, having a layer containing a polymeric acid between the first alkali-impermeable polymer layer and the support. 30. A silver salt diffusion transfer photographic receiving element according to embodiment 29, wherein the polymeric acid-containing layer comprises acrylic acid, or a copolymer of methacrylic acid and an alkyl acrylate or alkyl methacrylate. 31 In embodiment 29, the polymeric acid-containing layer comprises a styrene-maleic anhydride copolymer, a methyl vinyl ether-maleic anhydride copolymer, or a mixture of an ethylene-maleic anhydride copolymer and cellulose acetate. A silver salt diffusion transfer photographic receiving element comprising: 32. A silver salt diffusion transfer photographic receiving element according to embodiment 2 having a layer containing a polymeric acid between the first alkali-impermeable polymer layer and the support. 33 In embodiment 32, the layer containing the polymeric acid is a silver salt comprising a (meth)acrylic acid (co)polymer, a maleic anhydride copolymer, or a mixture of each of the above polymers and cellulose acetate. Diffusion transfer photoreceptor element. 34. A silver salt diffusion transfer photographic image-receiving element according to embodiment 3, having a layer containing a polymeric acid between the first alkali-impermeable polymer layer and the support. 35 In embodiment 34, the polymeric acid-containing layer comprises a (meth)acrylic acid (co)polymer, a maleic anhydride copolymer, or a mixture of each of the foregoing polymers and cellulose acetate. Transfer method photographic image receiving element. 36 In embodiment 24, a layer consisting of a (meth)acrylic acid (co)polymer or a mixture of a maleic anhydride copolymer and cellulose acetate is provided between the first alkali-impermeable polymer layer and the support. A silver salt diffusion transfer photographic image receiving element having a silver salt diffusion transfer method. 37 In embodiment 28, a layer consisting of a (meth)acrylic acid (co)polymer or a mixture of a maleic anhydride copolymer and cellulose acetate is provided on the support side with respect to the first alkali-impermeable polymer layer. A silver salt diffusion transfer photographic image-receiving element. 38. A silver salt diffusion transfer photographic image-receiving element as claimed, wherein the image-receiving layer contains a toning agent. 39. A silver salt diffusion transfer photographic receiving element according to embodiment 38, wherein the toning agent is at least one compound selected from benzimidazoles, mercaptoimidazoles, and mercaptopyrimidines. 40. A silver salt diffusion transfer photographic image-receiving element according to embodiment 8, wherein the image-receiving layer contains a mercaptoimidazole as a toning agent. 41. A silver salt diffusion transfer photographic receiving element according to embodiment 40, wherein the polymer of the hydrophilic polymer layer comprises a polyacrylamide polymer (single or multiple). 42. A silver salt diffusion transfer photographic image-receiving element according to the claims, wherein the polymer having vinyl sulfone or its precursor in a side chain is a polymer having a repeating unit represented by the following general formula (). General formula () In the formula, A represents a monomer unit copolymerized with a water-soluble copolymerizable ethylenically unsaturated monomer.
R ₀ represents a hydrogen atom or a methyl group, Q is 6
arylene group with ~10 carbon atoms, 7-11
an aralkylene group having -CO ₂ - carbon atoms;
or

Represents [formula]. L is -O-, _-SO2- ,

【formula】

【formula】

[Formula] Any divalent group containing at least one bond and having 1 to 12 carbon atoms. R ₁ , R ₂ , X, x, and y represent the same as described above. 43 In Embodiment 1, the silver salt diffusion transfer photographic image-receiving element is characterized in that the polymer having vinyl sulfone or its precursor in the side chain is a polymer represented by the general formula () and having a repeating unit. . 44 In Embodiment 2, the silver salt diffusion transfer method photographic image-receiving element, wherein the polymer having vinyl sulfone or its precursor in a side chain is a polymer having a repeating unit represented by the general formula (). 45 In Embodiment 3, the silver salt diffusion transfer photographic image-receiving element is characterized in that the polymer having vinyl sulfone or its precursor in a side chain is a polymer having a repeating unit represented by the general formula ().

Claims (1)

[Claims] 1 a hydrolyzable first alkali-impermeable polymer layer containing at least one diffusable organic solvent-soluble agent capable of modifying the photographic properties of a silver transfer image formed in the alkali-permeable polymer layer; at least one layer of a hydrophilic polymer between the image-receiving layer and the image-receiving layer comprising silver deposition nuclei made alkali-permeable by hydrolyzing at least a portion of a hydrolyzable alkali-impermeable polymer. A silver salt diffusion transfer photographic image receiving element characterized in that the hydrophilic polymer layer contains at least one polymer having vinyl sulfone or a precursor thereof in a side chain. element.