JPH0554110B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to photographic elements, and more particularly to novel polymer mixtures that are good mordants for dyes used in photographic elements, and photographic elements using the same. More particularly, it relates to a mordant layer for fixing imagewise produced diffusible dyes and color photographic elements employing this novel mordant layer. In the field of photography, the use of various quaternary ammonium salt polymers in mordant layers for the immobilization of anionic dyes is well known, as described in US Pat. No. 3,709,690 by Cohen et al.
Various polymer mordants are disclosed in the following publications. However, since this type of mordant does not have sufficient mordant properties for dyes, it has had drawbacks such as difficulty in increasing the density of the dye image and the density of the image decreasing over time. To improve mordanting properties, Cohen
water-insoluble polymeric mordant, or Campbell, as described in U.S. Pat. No. 3,898,088 by
proposed a water-dispersible polymer mordant described in US Pat. No. 3,958,995. However, although this type of mordant exhibits good mordanting properties for dyes, it has another drawback in that it has a poor ability to retain mordanted dyes in a stable form. In other words, photographic systems containing dye images mordanted with this type of mordant have the disadvantage that the mordanted dye images are susceptible to chemical changes or decomposition when irradiated with fluorescent lights or sunlight. Accordingly, it is a primary object of the present invention to provide a photographic element in which mordanted dye images undergo less chemical change or degradation due to light. A second object is to provide a photographic element that provides a highly concentrated dye image. The above purpose is to apply a mixture of a polymer having a monomer unit represented by the general formula () as a constituent component and a polymer having a monomer unit represented by the general formula () as a constituent component to a photographic element used in a mordant layer as a mordant. It was finally achieved. General formula () (-A)- _x (-C)- _y [In the general formula (), A represents a vinyl manomer unit having a tertiary amine. C represents a vinyl monomer unit having neither tertiary amine nor quaternary ammonium salt. x is 2 to 100 mol%, and y is 0 to 98 mol%. ] General formula () (-B) _-u (-D) _-v [In the general formula (), B represents a vinyl monomer unit having a quaternary ammonium salt. D is the same as that represented by C in the general formula (). u is 2 to 100 mol%, and v is 0 to 98 mol%. ] In the above formula, A, B, C, and D may contain two or more types of monomers as long as they each satisfy the definitions. That is, when conventional quaternary ammonium salt polymers are used as mordants, good mordant properties for dyes can be obtained, but the mordanted dye images are susceptible to chemical changes or decomposition by light.
On the other hand, tertiary amine polymers have extremely low mordanting properties for anionic dyes. However, by using these two types of mordants with different characteristics together, although the detailed reason is not clear, good mordant properties for anionic dyes can be achieved.
It was possible to obtain a mordant layer that simultaneously has the property of stably retaining the mordanted dye. Specifically, the vinyl monomer unit (-A-) in the general formula () of the present invention is preferably represented by the following general formula () or general formula (). General formula () [In the formula, R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. L represents a divalent linking group having 1 to 20 carbon atoms. E represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom. n is 0 or 1
It is. ] General formula () [In the formula, R ₁ , L, and n represent the same as in the general formula (). R ₄ and R ₅ are each the same or different 1
It represents an alkyl group having up to 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ₄ and R ₅ may be interconnected to form a cyclic structure together with the nitrogen atom. n is 0 or 1. ] In the general formula (), R ₁ is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, etc. , and a hydrogen atom or a methyl group is particularly preferred. L is a divalent linking group having 1 to about 20 carbon atoms, such as an alkylene group (e.g., methylene, ethylene, trimethylene, hexamethylene, etc.), a phenylene group (e.g., O-phenylene,
p-phenylene group, m-phenylene group, etc.), arylene alkylene group (e.g.

[Formula] or

[Formula] etc. However, R ₂ represents an alkylene group having 1 to about 12 carbon atoms. ), -CO ₂ -, -CO ₂ -R ₃ - (wherein R ₃ represents an alkylene group, phenylene group, or arylene arekylene group), -CONH-R ₃ - (however, R ₃ is the same as above). ),

[Formula] (however, R ₁ and R ₃ represent the same as above), etc.

【formula】

【formula】

【formula】

[Formula] −CO ₂ −, −CONH−, −CO ₂ −CH ₂ CH ₂ −, −CO ₂
−CH ₂ CH ₂ CH ₂ −, −CONHCH ₂ −, −
CONHCH ₂ CH ₂ -, -CONHCH ₂ CH ₂ CH ₂ - and the like are particularly preferred. E is a heterocycle containing a nitrogen atom having a double bond with a carbon atom as a constituent, such as an imidazole ring (e.g.

【formula】

【formula】

【formula】

[Formula] etc. ),bird Azole ring (e.g.

【formula】

【formula】 Such. ), pyrazole rings (e.g.

【formula】

[Formula] etc. ), pyridine ring (e.g.

【formula】

【formula】

【formula】

[Formula] etc. ), Piri midine rings (e.g.

[Formula] etc. ), and an imidazole ring is particularly preferred. Specific examples of preferred monomer units represented by the general formula () are shown below.

【formula】

【formula】

【formula】

【formula】

【formula】 In the general formula (), R ₄ and R ₅ are alkyl groups having 1 to 12 carbon atoms, such as unsubstituted alkyl groups (methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc.), substituted alkyl groups (methoxyethyl group, 3-cyanopropyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydroxyethyl group, 2- butenyl group, etc.), or an aralkyl group having 7 to 20 carbon atoms, such as an unsubstituted aralkyl group (benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.), substituted aralkyl group (4-
Methylbenzyl group, 4-isopropylbenzyl group, 4-methoxybenzyl group, 4-(4-methoxyphenyl)benzyl group, 3-chlorobenzyl group, etc. ) etc. Further, as an example in which R ₄ and R ₅ are interconnected to form a cyclic structure with a nitrogen atom, for example,

[Formula] (where m represents an integer from 4 to 12) Was. ),

Examples include [Formula]. Specific examples of preferred monomer units represented by the general formula () are shown below. The vinyl monomer units (-C-) and (-D-) in the general formulas () and () of the present invention each represent a vinyl monomer unit having neither tertiary amine nor quaternary ammonium, and among them, Preferably something that does not. Preferred examples of the vinyl monomer unit (-C-) include ethylene, propylene, 1-butene,
Isobutene, styrene, α-methylstyrene, vinyltoluene, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate, etc.), monoethylenically unsaturated amides of aliphatic acids (e.g. N-vinylacetamide, N - vinylpyrrolidone, etc.), esters of ethylenically unsaturated mono- or dicarboxylic acids (e.g. methyl methacrylate, ethyl acrylate, n-
butyl acrylate, n-butyl methacrylate, benzyl acrylate, diethyl maleate, diethyl itaconate, etc. ), ethylenically unsaturated monocarboxylic acid amides (e.g. acrylamide, dimethylacrylamide, methacrylamide, diacetone acrylamide, acryloylmorpholine, etc.), monoethylenically unsaturated compounds (e.g. acrylonitrile), or dienes (e.g. butadiene, isoprene). etc.) etc.
Among these, styrene, ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acid amides, and the like are particularly preferred. Furthermore, when a crosslinked latex is made of a polymer having monomer units represented by the general formula () or () as a constituent component, vinyl monomer units (-
C-) or (-D-) is a vinyl monomer unit that does not have either a tertiary amine or a quaternary ammonium, and a unit that has two or more copolymerizable unsaturated bonds in one molecule can be used. . Preferred specific examples of the vinyl monomer unit are divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylene bisacrylamide, ethylene glycol diacrylate, etc. Among them, divinylbenzene,
Particularly preferred are ethylene glycol dimethacrylate and ethylene glycol diacrylate. In the general formula (), x is 2 to 100 mol%,
y is 0 to 98 mol%, preferably x is 60 to 98 mol%
100 mol%, y is 0 to 40 mol%. Preferred specific examples of the polymer having a monomer unit represented by the general formula () of the present invention as a constituent component are shown below. T-1 T-2 T-3 T-4 T-5 T-6 T-7 T-8 T-9 T-10 T-11 T-12 Specifically, the vinyl monomer unit (-B-) in the general formula () of the present invention is preferably represented by the following general formula () or general formula (). general formula [In the formula, R ₁ , L, and n represent the same as in the general formula (). G represents a heterocycle which is quaternized and contains as a constituent a nitrogen atom having a double bond with a carbon atom. X represents a monovalent anion. n is 0 or 1. ] General formula () [In the formula, R ₁ , L, and n represent the same as in the general formula (). R ₄ and R ₅ represent the same thing as in the general formula (). R ₆ is selected from the same ones representing R ₄ and R ₅ . X represents the same thing as in general formula (). R ₄ , R ₅ and R ₆ may be interconnected to form a cyclic structure together with the nitrogen atom. n is 0 or 1. ] In the general formula (), G represents a quaternized heterocycle containing a nitrogen atom having a double bond with carbon as a constituent, an example of which is imidazolium salt (

【formula】

【formula】

【formula】

[Formula] etc. ), triazolium salts (e.g.

[Formula] etc. ), pyridinium salts (e.g. Ba

【formula】

【formula】

【formula】

[Formula] etc. ), among which imidazolium salts and pyridinium salts are particularly preferred. Here R ₄ is the general formula ()
, and methyl, ethyl, and benzyl groups are particularly preferred. X represents an anion, such as a halogen ion (e.g. chloride ion, bromide ion, iodine ion), an alkyl sulfate ion (e.g. methyl sulfate ion, ethyl sulfate ion), an alkyl or arylsulfonate ion (e.g. methanesulfonic acid, ethanesulfonate). acid, benzenesulfonic acid, p
-toluenesulfonic acid), acetate ions, and sulfate ions, with chloride ions and p-toluenesulfonic acid ions being particularly preferred. Specific examples of preferable vinyl monomer units (-B-) represented by the general formula () are shown below. (Here, p-TsO represents p-toluenesulfonic acid anion.) In the general formula (), as an example in which R ₄ and R ₅ are interconnected to form a cyclic structure with the nitrogen atom, for example,

[Formula] (where m is an integer from 4 to 12 represents a number. ),

Examples of forming a cyclic structure with R ₄ , R ₅ , and R ₆ include [Formula].

Examples include [Formula]. Specific examples of preferable vinyl monomer units (-B-) represented by the general formula () are shown below. (Here, p-TsO represents p-toluenesulfonic acid anion.) In the general formula (), u is 2 to 100 mol%, v is 2 to 98 mol%, preferably u is 40 to 100 mol%, v is 0 to 60 mol%. Preferred specific examples of the polymer having a monomer unit represented by the general formula () of the present invention as a constituent component are shown below. Q-1 Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 Q-8 Q-9 Q-10 (Here, p-TsO represents p-toluenesulfonic acid anion.) The molecular weight of the polymer having the monomer unit represented by the general formula () or () of the present invention as a constituent component is determined in terms of photographic properties, coating suitability, etc. from a point
It is preferably 10,000 or more. When using this polymer as a solution, the molecular weight is preferably 1,000,000 or less, particularly 300,000 or less from the viewpoint of coating properties, but vinyl monomer units (-C
-) or (-D-) when using a vinyl monomer unit having two or more copolymerizable unsaturated bonds in one molecule, the molecular weight of the polymer becomes infinite, and from the viewpoint of coating properties, dispersion is difficult. used as a thing. The following examples further illustrate specific examples of the invention. Synthesis Example 1 Synthesis of poly(N-vinylimidazole) T-1 N-vinylimidazole 94 was placed in a 300 ml reaction vessel.
Add 94g of DMF and 94g of DMF, and replace thoroughly with nitrogen gas.
Heated to 60°C. When the temperature became constant, 1.243 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. Then after 2 hours 2,
1.243 g of 2'-azobis(2,4-dimethylvaleronitrile) was added, and heating was continued for an additional 2 hours.
After the reaction solution was cooled to room temperature, it was added to the acetone in step 5, and the precipitate was collected and dried under vacuum.
90g of white polymer was obtained. Yield 96% Synthesis Example 2 Synthesis of poly(N-,N-dimethylaminopropylacrylamide) T-6 156.26 g of N,N-dimethylaminopropylacrylamide and 450 ethanol in a 500 ml reaction vessel.
After thoroughly degassing with nitrogen gas, the mixture was heated to 80°C, and 1.25 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. Another 1 hour later, 1.25 g of the same substance was added, and heating and stirring were continued for 1 hour and 30 minutes. Cool the reaction sample to room temperature,
300 ml of distilled water was added, the mixture was placed in a cellulose dialysis chamber, and dialysis was continued for 2 days, followed by freeze-drying to obtain 140.1 g of a white polymer. Yield 89.7% Synthesis Example 3 Poly(N-benzylimidazolium chloride)
Synthesis of Q-2 24 g of poly(N-vinylimidazole) obtained in Chemical Example 1, 220 g of DMF, and 20 g of ethanol were mixed and heated to 90°C. Then, 40 g of benzyl chloride was gradually added dropwise and heated for 5 hours. This reaction solution was added to 3.5 g of acetone, and the precipitated crystals were collected and dried under vacuum to obtain 51 g of a white polymer. Yield: 92.4% Synthesis Example 4 Synthesis of poly(styrene-co-N-methyl-N-vinylbenzylpiperidinium chloride-co-divinylbenzene) Q-3 Synthesized by the method described in JP-A-53-30328. Synthesis Example 5 Poly(N-methyl-N-vinylbenzylmorpholinium chloride-co-divinylbenzene) Q
-4 Synthesis (i) Synthesis of poly(divinylbenzene-co-chloromethylstyrene) polymer dispersion Put 350ml of distilled water in a reaction vessel, degas with nitrogen gas, add 10ml of Triton 770, and 58.0g of chloromethylstyrene. (0.38 mol), divinylbenzene
2.6g (0.02mol) was added and heated to 60°C.
1.00 g of potassium persulfate was added to 20 ml of distilled water degassed with nitrogen gas, and 0.38 g of sodium bisulfite was added to 10 ml of degassed distilled water, and the mixture was heated and stirred for 5 hours. Then, the above mixture was cooled to room temperature,
A polymer dispersion (latex) was obtained. (ii) Quaternization reaction 150 g of the above latex having a solid content concentration of 14.0% and 50 g of distilled water were added to a reaction vessel, and 11.2 g of N-methylmorpholine was added at room temperature.
Thereafter, the temperature was slowly raised to 70°C, and the mixture was heated and stirred for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a polymer dispersion mordant. Solid content concentration: 14.0wt% The mordant layer of the present invention contains a polymer having a monomer unit represented by the general formula () as a constituent component and a polymer having a monomer unit represented by the general formula () as a constituent component. The mixing ratio (()/()) is preferably 0.1 to 0.1 by weight.
10, preferably between 0.2 and 8. The mixing ratio of the polymer mixture mordant and binder of the present invention and the application amount of the polymer mixture mordant are as follows:
A mordant/gelatin ratio of 20/80 to 80/20 can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mixture mordant, and the image forming process used. (weight ratio), mordant application amount is 0.2 to 15 g/m ² preferably
Preferably, it is used at 0.5-8 g/ ^m2 . The binders in the mordant layer used in the present invention can be contained alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinyl Contains synthetic polymeric materials such as pyrrolidone, water-soluble polyvinyl compounds of acrylamide polymers. Among these, gelatin and polyvinyl alcohol can be particularly effectively used. As the gelatin used for the mordant layer, various known gelatins are used. For example, it is also possible to use gelatin produced by different methods of producing gelatin, such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment. As the polyvinyl alcohol used for the mordant layer, various known polyvinyl alcohols are used.
Polyvinyl alcohols having various saponification degrees and polymerization degrees are used. Saponification degree is preferably 70%
Particularly preferably 80% or more is used. The degree of polymerization used is preferably 300 to 2000. Those having different saponification degrees and polymerization degrees can also be used in combination. Regarding the saponification method, there are two methods: acid saponification method and alkali saponification method, and materials subjected to either saponification treatment can be used in the present invention. Examples of products that meet these conditions include PVA-105, PVA-124, and PVA manufactured by Kuraray Co., Ltd.
Examples include -CS, PVA-HC (completely saponified), PVA-203, PVA-420, and L-8 (partially saponified). The mordant layer containing the mordant of the present invention can contain various surfactants in order to improve coating properties. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl fluphonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Surfactants: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium , heterocyclic quaternary ammonium salts such as imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocycles. Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide. Nonionic surfactants that meet the above conditions are
It is widely used outside the field, and its structure, properties, and synthesis method are well known. Representative known documents include Surfactant Science
Seriesvolume1.Nonionic Surfactants (Edited
by Martin J.Schick, Marcel Dekker
Inc.1967), Surface Active Ethylene Oxide
Adducts (Schoufeldt.N, Pergamon Press1969)
Among the nonionic surfactants described in these documents, those satisfying the above conditions are preferably used in the present invention. These nonionic surfactants can be used alone,
It can also be used as a mixture of two or more types. The image-forming dyes to be mordanted in the mordanting layer of the present invention include the following. That is, azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes having anionic groups such as phenolic hydroxyl groups, sulfonamide groups, sulfonic acid groups, and carboxyl groups. The mordant layer of the present invention is used to fix a dye in a color image forming method in which a diffusible dye is formed into an image, then diffused, and then fixed. The above color image forming method uses a developer at a temperature around room temperature (for example, the Belgian patent
There are various forms such as those described in JP-A No. 757959) and those that utilize heat development (for example, those described in JP-A No. 58-58543 and JP-A No. 58-79247), but the mordant layer of the present application cannot be used in any of them. sell. Photographic elements employing the mordant layer of the present invention are described in more detail below. The photographic element containing the mordant of the present invention usually consists of (1) a support, (2) a light-sensitive element, and (3) an image-receiving element, and development can be carried out by heating or by spreading a developer. In either case, after the photographic element has been imagewise exposed to light, the silver halide is developed and a corresponding diffusive dye is formed imagewise, which migrates to the image-receiving element. . The photographic element described above optionally further includes a developer,
Auxiliary developers and processing elements can be included. One preferred embodiment of the above embodiments is that disclosed in Belgian Patent No. 757959. Another preferred embodiment in which the mordant of the present invention can be used is disclosed in U.S. Pat.
No. 3415646, No. 3647487, and No. 3635707
German Patent Application (OLS) No. 2426980, etc. Other preferred embodiments using the mordant of the present invention are JP-A No. 58-58543, JP-A No. 58-79247, and Japanese Patent Application No. 57-1982.
-31976 and No. 57-32547, in which development is carried out by heating, and is particularly preferred. Example 1 A method for making a silver iodobromide emulsion will be described. Dissolve 40g of gelatin and 26g of KBr in 3000ml of water. The solution is kept at 50°C and stirred. Then silver nitrate
A solution of 34 g dissolved in 200 ml of water is added to the above solution over a period of 10 minutes. Then, a solution of 3.3 g of KI dissolved in 100 ml was added over 2 minutes. The pH of the silver iodobromide emulsion thus prepared is adjusted, and excess salt is removed by sedimentation. Thereafter, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g. Next, we will discuss how to make a benzotriazole silver emulsion. 28g gelatin and 13.2g benzotriazole in water
Dissolve in 3000ml. This solution is kept at 40°C and stirred. A solution of 17 g of silver nitrate dissolved in 100 ml of water is added to this solution over 2 minutes. Adjust the pH of this benzotriazole silver emulsion,
Allow to settle and remove excess salt. Then PH 6.0
A yield of 400 g of benzotriazole was obtained. Next, we will discuss how to make a gelatin dispersion of a dye-donating substance. Weigh out 5 g of a cyan dye donating substance with the following structure, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, and 5 g of tricresyl phosphate (TCP), add 30 ml of ethyl acetate,
Heat and dissolve at approximately 60°C to make a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, use a homogenizer for 10 minutes.
Disperses at 10000RPM. This dispersion is called a dispersion of a dye-providing substance (cyan). *Cyan dye-donating substance Next, we will discuss how to make a photosensitive coating. The following materials were mixed and dissolved, and then coated on a polyethylene terephthalate film in a wet film thickness of 30 μm and dried. (a) Silver benzotriazole emulsion 10g (b) Silver iodobromide emulsion 20g (c) Dispersion of the dye-providing substance (cyan) 33g (d) 5 ml of a 5% aqueous solution of guanidine trichloroacetic acid (e) 12.5 ml of a 10% ethanol solution of guanidine trichloroacetic acid (f) 4 ml of a 10% aqueous solution of H ₂ NSO ₂ N(CH ₃ ) ₂ (g) 7.5 ml of water On top of this, as a protective layer: The film thickness is
It was applied to a thickness of 25 μm and dried. (h) 35 g of 10% gelatin aqueous solution (i) 5 ml of 10% ethanol solution of guanidine trichloroacetic acid (j) 4 ml of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (k) 56 ml of water Next, dye fixing material I will explain how to make it. The above-mentioned T-1, 6 and Q-2, 3, 4 were added in the amounts shown in the table below, 200 ml of distilled water was added, 100 g of 10% lime-treated gelatin was added, and the mixture was mixed uniformly. This mixed solution was uniformly applied to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. This sample was dried and used as a dye fixing material.

[Table] The above photosensitive coating was imagewise exposed for 10 seconds at 2000 Lusk using a tungsten bulb. after that
The mixture was heated uniformly for 30 seconds on a heat block heated to 130°C. Next, after supplying 80 ml of water per 1 m ² to each membrane side of the dye-fixing material, the photosensitive coating material that has been heat-treated and the dye-fixing material to which the water has been supplied are stacked so that their membrane surfaces are in contact with each other. Combined. After heating for 5 seconds on a heat block at 80°C, the dye-fixing material was peeled off from the light-sensitive material, and a negative cyan dye was obtained on the dye-fixing material. The density of these negative images was measured using a Macbeth reflection densitometer (RD-
519). Next, a transparent film with an ultraviolet absorbing layer was superimposed on the film surface of the dye fixing material with these negative images, and using an Atlas CI65 weatherometer,
The color image was irradiated with xenon light (100,000 lux) for 3 days. The density of the color image was measured before and after irradiation with xenon light, and the fastness of the color image to light was evaluated. Table 1 shows the dye residual rate at each maximum density and reflection density of 1.0.

【table】

[Table] Dye concentration before light irradiation
As shown in Table 1, for cyan dyes, by co-dissolving a tertiary amine polymer and a quaternary ammonium salt polymer in the mordant layer, it is possible to maintain the high transfer density exhibited by the quaternary ammonium polymer alone, while maintaining the color image. was found to improve the light fastness of Example 2 The same operations and treatments as in Example 1 were carried out except that the cyan dye-donating substance in the dispersion of dye-providing substance in the photosensitive coating of Example 1 was replaced with a dye-donating substance having the following structure. I did it. The results are shown in Table 2. *Magenta dye-donating substance

[Table] Also, as shown in Table 2, for magenta dye, by using a tertiary amine polymer and a quaternary ammonium salt polymer together in the mordant layer,
It has been found that the quaternary ammonium salt polymer improves the light fastness of color images while maintaining the high transfer density exhibited by itself. Example 3 The operations and treatments were carried out in exactly the same manner as in Example 1, except that the cyan dye-donating substance in the dispersion of the dye-providing substance in the photosensitive coating of Example 1 was replaced with a dye-donating substance having the following structure. Ta. The results are shown in Table 3. *Yellow dye-donating substance

【table】

【table】

[Table] For yellow dyes, by using a tertiary amine polymer and a quaternary ammonium salt polymer together in the mordant layer, the light fastness of the dye can be improved while maintaining the high transfer density that the quaternary ammonium polymer alone exhibits. I found out that it can be improved. As is clear from Examples 1 to 3 above, when a quaternary ammonium salt is used alone in the mordant layer, a high transfer density can be obtained, but it is difficult to stably maintain the transferred color image. However, when a tertiary amine polymer is added to this mordant layer,
The light fastness of the dye image can be enhanced while maintaining a high transfer density. Therefore, according to the present invention, the transfer density is high;
It is shown that a mordant layer with excellent light fastness of the transferred dye image can be obtained. Example 4 A photosensitive sheet coated on a polyethylene terephthalate transparent support as follows: (1) Mordant 3.0 consisting of the same polymer composition as used in dye fixing materials 1 to 17 of Example 1.
g/m ² and a mordant layer containing 3.0 g/m ² of gelatin.
(Mordant layer 1 to 17) (2) Titanium oxide 20g/m ² and gelatin 2.0g/
White reflective layer containing m ² . (3) Carbon black 2.3g/m ² and gelatin
Light blocking layer containing 3.1g/ ^m2 . (4) 0.96 g/m ² of the following cyan dye image donor and 0.03 g/m 2 of 2,5-di-t-butylhydroquinone
A layer containing 1.6 g/m ² of N,N-diethyl laurylamide dissolved in g/m ² and 1.5 g/m ² of gelatin. (5) Red spectrally sensitized silver iodobromide internal latent image type direct reversal emulsion containing 1.9 g/m ² of silver (Japanese Patent Application Laid-Open No.
-3426 Example 1 emulsion), 0.040 g/m ² -
Red-sensitive emulsion layer containing (2-formylethyl)-2-methyl-benzothiazolium bromide and 1.4 g/m ² of gelatin. (6) 1.2 g/m dissolved in both 3.3 g/m ² gelatin, 0.030 g/m ² sodium bisulfite, 1.9 g/m ² tricresyl phosphate and 0.77 g/m ² dibutyl phthalate. ² of 2,5-di-t
- An intermediate layer containing octylhydroquinone. (7) 1.5 g/m ² of gelatin, 0.89 g/m ² of a magenta dye image donor having the following structure and 0.030 g/m 2 of a magenta dye image donor having the structure shown below.
A layer containing 1.5 g/m ² of N,N-diethyl laurylamide in which both m ² of 2,5-di-t-butylhydroquinone were dissolved. Magenta dye image donor: (8) Green spectrally sensitized silver iodobromide internal latent image type direct reversal emulsion containing 1.4 g/m ² of silver (patent application 50-
79893 Example 1 emulsion), 0.010 g/m ² of 3-
Green-sensitive emulsion layer containing (2-formylethyl)-2-methyl-benzothiazolium bromide and 1.0 g/m ² gelatin. (9) 3.7 g/m ² gelatin, 0.023 g/m ² sodium bisulfite, 0.94 g/m ² 2,5-di-t
-1.5g of dissolved octylhydroquinone/
m ² of tricresyl phosphate (solvent) and 0.61
Intermediate layer containing g/m ² dibutyl phthalate (solvent). (10) 2.1 g/m ² of gelatin, 1.5 g/m ² of the following yellow dye donor and 0.042 g/m ² of 2,5-di-t-butylhydroquinone were dissolved.
Layer containing 2.5 g/m ² of N,N-diethyl laurylamide. Yellow dye image donor: (11) Blue-sensitive internal latent image type silver iodobromide direct reversal emulsion containing 2.2 g/m ² of silver (emulsion of Example 1 of JP-A-52-3426), 0.014 g/m ² of 3-(2 -formylethyl)-2-methyl-benzothiazolium bromide and a blue-sensitive emulsion layer containing 1.7 g/m ² of gelatin. (12) Gelatin protective layer of 0.95g/ ^m2 . The following processing solution was spread between the photosensitive sheet and a cover sheet coated on a polyethylene terephthalate transparent support as follows, and the results shown in Table 4 were obtained. (Fastness to light was evaluated in the same manner as in Example 1.) Cover sheet: Polyacrylic acid (10% by weight aqueous solution, viscosity approximately 1000 cp) 15 g/m ² as a neutralized acidic polymer layer on a polyethylene terephthalate support. and on top of that acetylcellulose as a neutralization timing layer (100g of acetylcellulose was hydrolyzed to 39.4%
g of acetic acid) ⁾ and poly(styrene-co-maleic anhydride) (composition ratio, styrene:maleic anhydride = approximately 60:40, molecular weight approximately 50,000)
Coated with 0.2g/ ^m2 .

【table】

【table】

[Table] Even in the form of diffusion transfer type color photosensitive materials that use a developer at temperatures around room temperature, as shown in the table, a combination of a tertiary amine polymer and a quaternary ammonium salt polymer is used in the mordant layer. It has been found that the light fastness of color images can be improved by using it.

Claims (1)

[Scope of Claims] 1. At least one layer containing both a polymer having monomer units represented by the following general formula () as a constituent and a polymer having monomer units represented by the general formula () as constituent components. photo element. General formula () (-A)- _x (-C)- _y [In the general formula (), A represents a vinyl monomer unit having a tertiary amine. C represents a vinyl monomer unit having neither tertiary amine nor quaternary ammonium salt. x is 2 to 100 mol%, and y is 0 to 98 mol%. ] General formula () (-B) _-u (-D) _-v [In the general formula (), B represents a vinyl monomer unit having a quaternary ammonium salt. D is the same as that represented by C in the general formula (). u is 2 to 100 mol%, and v is 0 to 98 mol%. ]