JPS5914738B2 - Color diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to color diffusion transfer processes, and more particularly to color diffusion transfer processes using novel polymeric mordants.

In more detail, without adversely affecting photographic performance,
This invention relates to a color diffusion transfer method which has excellent mordanting properties, excellent film forming properties whether used alone or together with a binder, and which shows no deterioration in image storage stability. In the color diffusion transfer method, a light-sensitive element containing a silver halide emulsion and a dye image-forming substance is exposed to light to form a latent image in the silver halide, which is then developed with a processing agent (alkaline processing solution). It is processed.

During processing with this processing agent, the above photosensitive element and an image receiving element having an image receiving layer in which a dye image forming substance can be mordanted are superimposed, and the dye image forming substance is transferred to the image receiving layer by diffusion, and the dye image is is obtained. An example of such a color diffusion transfer process is US Pat.
U.S. Pat. No. 2,647,049, U.S. Pat. No. 2,647,049 utilizing the method described in U.S. Pat.
Examples include the method described in the specification of No. 4668 and the like.

The image-receiving element used in such a color diffusion transfer method is one in which an image-receiving layer containing a water-permeable and alkali-permeable polymer mordant is coated on an opaque or transparent support. There is. The polymer mordant contained in the image-receiving layer is disclosed in US Pat. No. 314
Poly4-vinylpyridine described in the specification of No. 8061, various vinyl quaternary salt polymers described in the specification of British Patent No. 1,261,925, etc. are known.

The polymer mordant in the image-receiving layer is preferably one that forms a dye image on the image-receiving layer in a short period of time when the dye image-forming substance moves to the image-receiving element by diffusion, and the resulting dye image has a high density.

On the other hand, once a good image is formed on the image-receiving layer, it is required that the image remains substantially unchanged, so the alkalinity of the image-receiving layer is reduced by neutralizing the processing agent (alkaline processing liquid). Although silver halide development and associated dye formation and diffusion are stopped by the process, excess dye and dye precursors and contaminants formed after obtaining a good image are not necessarily fixed. In such cases, excessive amounts of dyes and dye precursors as well as contaminants will gradually diffuse into the image-receiving layer, causing gradual changes in image quality after processing is complete. For this reason, the above-mentioned drawbacks have conventionally been eliminated by using, in addition to the image-receiving layer, a layer containing a scavenging substance (so-called scavenger layer). As this scavenger layer, the isocyanate tobisulfite adduct described in U.S. Pat. No. 3,725,063 can be used, and the resorcinol scavenger described in U.S. Pat. , same 3rd
It is known to use a polymer scavenger as described in Japanese Patent Laid-Open No. 501-142233, and to provide a scavenger layer in addition to the image-receiving layer as described in Japanese Patent Application Laid-open No. 501-142233. It is known that this scavenger layer may be provided on the image receiving element or on other photographic elements called processing sheets. The present inventor has discovered that the grafted polymer described below is extremely effective as a mordant for dye image-forming substances, and furthermore,
It has been discovered that such a polymer is effective for use in any layer including an image-receiving layer, a scavenger layer, and other mordant layers, leading to the completion of the present invention. That is, the first object of the present invention is to provide a color diffusion transfer method with excellent mordant effect.

A second object of the present invention is to mordant the dye image-forming substance that migrates to the image receiving element by diffusion during the development process, thereby producing a good dye image in a short period of time and reducing the density of the produced dye image. It is an object of the present invention to provide a color diffusion transfer method using a highly image-receiving layer. A third object of the present invention is to prevent excessive dyes and dye precursors and contaminants from diffusing into the receiving element after a good image has been formed in the receiving layer upon completion of processing, thereby improving image archivability. It is an object of the present invention to provide a color diffusion transfer method using a single layer of scavenger that can maintain good quality. A fourth object of the present invention is to provide an image-receiving element or processing sheet for use in color diffusion transfer processes that has a layer that exhibits excellent mordant effect without adversely affecting photographic performance.

A fifth object of the present invention is to provide a color diffusion transfer method using a layer containing a polymeric mordant that has excellent film-forming properties when used alone or with a binder.

A sixth object of the present invention is that the silver halide emulsion can be used in an image-receiving layer in an image-receiving element and as a scavenger layer in an image-receiving element, a processing sheet or a light-sensitive element without having an adverse effect on the silver halide emulsion. Of course,
It is an object of the present invention to provide a color diffusion transfer process using a polymeric mordant that may be used in any mordanting layer in the image receiving element, processing sheet or photosensitive element.

Such objects and other objects of the invention as set forth below are directed to
A dry polymer is a polymer containing a monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom as a polymerization component, and includes a polymer grafted or graft-polymerized with 5 mol% or more of a vinyl monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom. This is accomplished by using the layer as a color diffusion transfer delta image-receiving layer and/or as a scavenger layer or as other mordanting layer.

In the present invention, preferred examples of the monomer component containing a tertiary nitrogen atom that can be used as a salt of an organic or inorganic acid include compounds represented by the following general formula [1] or [].

General formula [1] [In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 represent a lower alkyl group, phenyl group or an aralkyl group, and R2 and R3 form a 5- or 6-membered ring containing a nitrogen atom. A may represent a simple bond or a bonding group consisting of at least two atoms of a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom.

Al. Zl and Z2 represent atoms necessary to complete a 5- or 6-membered ring containing a nitrogen atom. ] Next, as typical examples of the monomer component containing a tertiary nitrogen atom which can be made into a salt of an organic or inorganic acid and preferably used in the present invention, the following may be mentioned.

In the present invention, the vinyl monomer component containing a tertiary nitrogen atom or a quaternary nitrogen atom is preferably a compound represented by the following general formula [] or [].

General formula [] [In the formula, R4 and R7 are each a hydrogen atom, a rogen atom or a methyl group, R5 and R8 are each a lower alkyl group, a phenyl group, or an aralkyl group, and R6 and R are each a lower alkyl group or an aralkyl group. group, RlO is a hydrogen atom, a lower alkyl group or an aralkyl group, B. B' each represents a simple bond, a bonding group consisting of at least two hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms, XO represents an anion, and R5, R6, and R
8 and RlO may form a 5- or 6-membered ring containing a nitrogen atom.

B1, Z3 and Z4, and B/, Z5 and Z6 represent atoms forming a 5- or 6-membered ring containing a nitrogen atom. ]Next, typical examples of the vinyl monomer component containing a tertiary nitrogen atom or a quaternary nitrogen atom preferably used in the present invention include the compound of the present invention, that is, a salt of an organic or inorganic acid. A polymer containing a monomer containing a tertiary nitrogen atom that can be used as a polymerization component is used as a backbone polymer, and 5 mol% or more of a vinyl monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom is grafted or grafted. The polymerized polymer may contain other polymers.

In this case, for this polymer, a polymer containing as a polymerization component a monomer containing a tertiary nitrogen atom that can be made into a salt of an organic or inorganic acid is used as the backbone polymer,
It is preferable that the molar ratio of the polymer grafted or graft-polymerized with 5 mol% or more of a vinyl monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom is 25% or more. Note that the form of copolymerization is not particularly limited, and any form of copolymerization exhibits the same effect. Typical monomers as other copolymerization components in the compound of the present invention include saturated aliphatic vinyl carboxylates such as vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, methacrylate, etc. Methyl acrylate, n-butyl methacrylate, methyl α-chloroacrylate, 2-hydroxyethyl acrylate, 2-N acrylate
- Acrylic acid esters such as N-dimethylaminoethyl, olefins such as ethylene, propylene, isobutylene, etc., halogenated olefins such as vinyl chloride, vinylidene chloride, etc., dienes such as butadiene, isoprene, etc., acrylonitrile, methane, etc. Nitriles such as acrylonitrile, aromatic unsaturated hydrocarbons such as styrene, methylstyrene, acrylamide, methacrylamide, N-methylacrylamide, N-N-dimethylacrylamide, diacetone acrylamide, etc., vinyl methyl ether , vinyl ethers such as vinyl ethyl ether, fluorinated vinyl compounds such as N-vinylpyrrolidone, and the like. Although the molecular weight of the polymer mordant of the present invention is arbitrary, it is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000. Furthermore, a polymer containing a monomer containing a tertiary nitrogen atom, which can be made into a salt of an organic or inorganic acid, as a polymerization component can also be used as a backbone polymer. Even if a monomer other than the monomer is grafted or graft polymerized, no effect will be exerted on the purpose of the present invention. The main polymer is a polymer containing as a polymerization component a monomer containing a tertiary nitrogen atom that can be used as a salt of an organic or inorganic acid, and a tertiary nitrogen atom or a quaternary nitrogen atom is used as a backbone polymer. A layer containing a polymer grafted or graft-polymerized with 5 mol % or more of a vinyl monomer (hereinafter referred to as the polymer mordant of the present invention) may be used as an image-receiving layer of an image-receiving element, a processing sheet, or a photosensitive element. In addition to being used as a scavenger layer, it may also be used as a mordant or other layer in an image receiving element, processing sheet or photosensitive element.

Further, it can be used as a single layer of an image-receiving layer, a scavenger layer, or another mordanting layer, or it can be used as a layer of two or more of these layers. That is, the polymer mordant of the present invention is contained only in the image-receiving layer of the image-receiving element, and the polymer of the present invention is added to the scavenger layer provided in at least one of the image-receiving layer, the image-receiving element, the processing sheet, and the photosensitive element. containing a mordant; containing the polymer mordant of the present invention only in one scavenger layer provided in at least one of the image receiving element, the processing sheet, and the photosensitive element; each of the above three examples, the image receiving element, and the processing sheet; Alternatively, the polymer mordant of the present invention may be contained in other mordant layers in the photosensitive element. Since the polymer mordant of the present invention has no adverse effect on silver halide emulsions, it can be used as a scavenger layer in a light-sensitive element or in other mordant layers (excluding silver halide emulsion layers) according to the present invention. A layer containing a polymeric mordant may also be used. The polymer mordant of the present invention has a copolymer containing as a copolymerization component a monomer containing a tertiary nitrogen atom that can be made into a salt of an organic or inorganic acid. Any polymer may be used as long as it is grafted or graft-polymerized with 5 mol % or more of a vinyl monomer containing nitrogen atoms.

These polymer mordants of the present invention may be used alone or in combination of two or more. The polymer mordant of the present invention may be used in combination with other polymer mordants as long as it does not adversely affect the functions and effects of the present invention.

Next, typical examples of the polymer mordant of the present invention will be given, but the polymer mordant used in the present invention is not limited to these. Exemplary Compounds The polymer mordants of the present invention are described, for example, in POlymer, Vol. 16, p. 94 (1975) or Bulletin
ndesSOci6t6ChimiqusdeFran
ce] 1972, Part 2, p. 640, the desired product can be synthesized.

The polymeric mordant-containing layer of the invention is used as an image-receiving layer and/or as a scavenger layer.

When used as the image-receiving layer of the former image-receiving element, a layer containing the polymer mordant of the present invention may be coated as an image-receiving layer on the support of the image-receiving element. For example, it is desirable to use the polymer mordant of the present invention or its solution by coating it on a support coated with a neutralizing layer and an intermediate layer containing a neutralizing agent such as a polymeric acid. The polymer mordant of the present invention or its solution may be directly coated on the support without coating the sum layer and the intermediate layer. When the polymer mordant of the present invention is used as a solution, it is preferably used as a 2 to 20% solution, and examples of the solvent include, but are not limited to, water, methanol, ethanol, acetone, methylcellosolve, dioxane, N- Hydrophilic organic solvents such as N-dimethylformamide can be used alone or in combination. Various materials can be used as the support for the image receiving element, such as baryta paper, paper laminated with resin such as polyethylene, cellulose organic acid such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, etc. Ester sheets, such as inorganic acid ester sheets such as cellulose nitrate, polyester sheets such as polyethylene terephthalate, polyvinyl ester sheets such as polyvinyl acetate, sheets of polyvinyl acetals such as polyvinyl acetal,
For example, polyalkylene sheets such as polystyrene, polypropylene, polyethylene, etc. can be used depending on the purpose.

The neutralizing layer that can be used in the present invention may be one that contains a neutralizing layer and lowers the pH in the system after development processing, so the material used as a neutralizing agent is 1
Film-forming polymeric acids having one or more carboxyl groups, sulfonic groups, or groups capable of forming carboxyl groups upon hydrolysis are preferred, and any such polymeric acid can be used. The polymeric acid used in the present invention preferably has a molecular weight of about 10,000 to about 100,000 and is, for example, a 1:1 mixture of maleic anhydride and ethylene as described in U.S. Pat. No. 3,362,819. Polymeric monobutyl ester of maleic anhydride and methyl vinyl ether 1
:1 copolymer monobutyl ester, monoethyl ester, monopropyl ester, monopentyl ester and monohexyl ester of 1:1 copolymer of maleic anhydride and ethylene, 1:1 copolymer of maleic anhydride and methyl vinyl ether Copolymers of monoethyl ester, monopropyl ester, monopentyl ester and monohexyl ester, polyacrylic acid, polymethacrylic acid and copolymers of various ratios of acrylic acid and methacrylic acid, other of acrylic acid and methacrylic acid Copolymers in various ratios with vinylic monomers, i.e. acrylic esters,
Copolymers containing at least 30 mol %, preferably 50 to 90 mol % of acrylic acid or methacrylic acid, such as methacrylic esters and vinyl esters, can be used. In addition, Research Disclosure
Metals, monomer acids, ballasted organic acids, alkyl phosphates, polyalkyl phosphates, poly(1-acroyl-2,
2,2-trimethylhydrazinium p-toluenesulfonate) and the like can also be used in combination with a binder if necessary. Further, if necessary, a polymer acid, a monomer acid, or a polymer acid and an organic amine may be used in combination. These polymer acids, monomer acids, organic amines and binder polymers include alcohols such as methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone,
It can be dissolved in ketones such as diethyl ketone, cyclohexanone, etc., esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, etc., or mixtures thereof, and coated on the support.

The thickness of this neutralization cannot be determined unconditionally because it varies depending on the composition and amount of the processing agent used and the material contained in the neutralization layer used, but it is generally 5. A range of ~30μ is suitable. The above-mentioned neutralizing layer can be provided at any desired location depending on the layer structure of the photographic element for diffusion transfer.

For example, US Patent No. 3415644, US Patent No. 347392
No. 5, No. 3415646 and No. 3415645
It may be provided between the image-receiving layer and the image-receiving layer support as described in the specifications of U.S. Pat. It may be provided between the photosensitive layer support, or it may be provided in the processing sheet or between the image-receiving layer and the image-receiving layer support as described in U.S. Pat. , and further U.S. Patent No. 3615
In the case of the layer structure described in No. 421, it may be provided between the photosensitive layer and the photosensitive layer support and/or between the image receiving layer and the image receiving layer support.

Further, in the case of the layer structure described in JP-A-47-3480 having a peeling means, it may be provided between the image-receiving layer and the image-receiving layer support. In the present invention, an intermediate layer (so-called timing layer) for controlling the decrease in pH can be provided together with the neutralizing layer.

This intermediate layer remains P until after the required development and transfer have taken place.
It works to delay the drop in H. That is, before the development of silver halide and the formation of a diffusion transferred image, the neutralization layer prevents an undesirable decrease in the density of the transferred image due to a rapid decrease in the pH within the system.

Various materials can be used as this intermediate layer,
For example, gelatin, polyvinyl alcohol as described in U.S. Pat. No. 3,362,819, partially acetalized polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, cyanoethylated polyvinyl alcohol as described in U.S. Pat. No. 3,419,389, and U.S. Pat. No. 34,336.
Hydroxypropyl methyl cellulose, isopropyl cellulose, Japanese Patent Publication No. 46-126 as described in the specification of No. 33
Polyvinylamides as described in Publication No. 7, Japanese Patent Publication No. 1973-
Polyvinylamide graft copolymer as described in JP-A-41214, JP-A-49-22935 and JP-A-4991
A combination of a latex liquid and a penetrant, as described in Japanese Patent No. 642, is useful.

On the other hand, when a layer containing the polymer-mordant of the present invention is used as a scavenger layer, the image-receiving element, the processing sheet,
A layer containing the polymer mordant of the present invention may be provided as a scavenger layer in any of the light-sensitive elements.

For example, US Patent No. 3415644, US Patent No. 347392
No. 5, No. 3573043, No. 3573042,
When forming a layer structure as described in the specifications of the same No. 3615421, there is a layer structure between the photosensitive layer (silver halide emulsion layer) and the support of the photosensitive element, or between the photosensitive layer and the image-receiving layer. The polymer mordant of the present invention or its solution may be applied between the two. Alternatively, the polymer mordant of the present invention or its solution may be contained in the intermediate layer or neutralization layer to be used as a scavenger layer. moreover,
U.S. Patent No. 3415645, U.S. Patent No. 3415646,
In the case of the layer structure described in the specifications of 3594164 and 3594165, the layer containing the polymer mordant of the present invention can also be used as a scavenger layer in the treated sheet. The polymer mordant of the present invention is
It can cure by itself to form a film that can be mordant, or it can also be used in combination with other binders to form a film that can be mordanted. Suitable binders include, but are not limited to, water-soluble polymers such as gelatin, polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, starch, polyacrylamide, polyvinylpyrrolidone, and the like. When these polymers are used together with the polymer mordant of the present invention, they can be used in any mixing ratio, but when the polymer mordant of the present invention is contained in the image receiving layer, the image receiving layer of the polymer mordant of the present invention It is desirable that the content in the layer is in the range of 10 to 100% by weight, and the same applies to the case where the polymer mordant of the present invention is contained in one layer of the scavenger and when it is contained in other layers that can be mordanted. It is desirable to use the polymer mordant of the present invention depending on the content of. The coating thickness of the layer containing the polymer mordant of the present invention can be varied depending on the purpose. For example, when the layer is an image-receiving layer,
The optimum thickness is about 10 microns, and if the layer is a single scavenger layer, it is desirable to have a thickness of 0.5 to 10 microns.

In the present invention, processing sheets can be used depending on the layer configuration of the photographic element.

As the treatment sheet, any one for the purpose of blocking light and/or one for the purpose of uniformly distributing the treatment agent and achieving good diffusion can be used. For the former, a sheet that can block light can be used, and for the latter, any sheet that can uniformly distribute and diffuse the processing agent can be used, regardless of whether it is transparent or opaque. When the treated sheet is provided with a single scavenger layer, a layer containing the polymer mordant of the present invention may be coated on the support of the treated sheet, or a neutralization layer and/or an intermediate layer may be provided on the treated sheet. In such cases, this layer may contain the polymer mordant of the present invention and be used as a scavenger layer. As the support for the processing sheet, any support similar to the support for the image-receiving element described above can be used depending on the purpose. A treated sheet used for the purpose of blocking light may contain a pigment such as carbon black or titanium oxide in the support, or may be coated on the support using a binder if necessary. The above-described image-receiving element faces the exposed light-sensitive element for color diffusion transfer, and a processing agent (alkaline processing liquid) is spread therebetween to develop the silver halide emulsion.
A color image is obtained by transferring the resulting dye image-forming material to an image-receiving layer.

Color diffusion transfer photosensitive elements consist of at least one silver halide emulsion layer provided on a support and a dye image-forming material combined with the silver halide of the silver halide emulsion layer.

In particular, it is desirable to sequentially stack a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on the support, and each emulsion is combined to form a cyan dye image-forming substance, a magenta dye image-forming substance, and a yellow single-dye image forming substance. It is desirable to have a substance. Also, if necessary, add a layer of yellow filter,
Layers such as antihalation layers, intermediate layers, and protective layers can be provided. Preferably, the support is a planar material that does not undergo significant dimensional changes during treatment due to the treatment composition. Although rigid supports such as glass can be used depending on the purpose, flexible supports are generally useful. As the flexible support, supports used in general photographic materials such as cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, etc. are advantageously used. . In addition, in the present invention, in order to help the water of the processing agent (alkaline processing liquid) developed after treatment to diffuse through the support, US Pat.
It is advantageous to use water vapor permeable supports such as those described in Patents No. 573,044 and No. 3,690,879. Furthermore, in order to prevent light leakage from the edge of the transparent support to the silver halide emulsion layer when the film unit is processed in a bright place, the transparent support is
It is desirable that the material be colored to an extent that does not interfere with imagewise exposure and observation, but can prevent the transmission of light in the surface direction. The support may optionally contain various photographic additives, such as plasticizers such as phosphate esters and phthalate esters;
It may contain an ultraviolet absorber such as 2-(2-hydroxy-4-tbutylphenyl)benztriazole and an antioxidant such as hindered phenol. In order to maintain the adhesion between the support and the layer containing the hydrophilic polymer, it is advantageous to provide an undercoat layer or to subject the surface of the support to preliminary treatment such as corona discharge treatment, ultraviolet irradiation treatment, flame treatment, etc. . Although the thickness of the support is not limited, it is usually 20 to 30
It is desirable to have a thickness of 0μ. When the support is used for the purpose of blocking light, pigments such as carbon black and titanium oxide may be contained in the support, or a binder may be used if necessary to coat the support. You may. The dye image forming method used in the color diffusion transfer method of the present invention can be carried out in various ways depending on the method in which the dye image-forming material releases the diffusible dye upon development of silver halide.

The dye image-forming material may already contain completed dye moieties, the dye moieties may be formed during development and subsequent processes that occur simultaneously, or the components essential for dye formation may be added to the image-receiving layer. It may migrate and the dye may be formed there. Among the methods for converting development into dye, three representative methods that can be advantageously applied to the present invention will be described. The first representative method is the so-called dye developer method. The dye developer in this system is a compound that has both a dye coloring system and a silver halide developing group in one molecule, and
As a result of the oxidation of the dye developer as a dye image-forming material by silver halide, reduction of the silver halide and oxidation of the dye developer occur, resulting in a change in diffusivity in the processing composition. be. The oxidized dye developer has lower solubility and diffusivity in the processing agent than the reduced form of the dye developer, and is immobilized near the reduced silver halide.
Preferably, the dye developer is substantially insoluble in acidic to neutral aqueous media, but contains at least one dissociable residue sufficient to render the dye developer soluble and diffusible in the alkaline nature of the processing agent. Contains. Such dye developers are
It can be incorporated into a light-sensitive element, particularly in or adjacent to a silver halide emulsion layer, and combines the sensitive wavelength range of a silver halide emulsion with a dye developer having spectral absorption characteristics corresponding thereto. Used in photosensitive elements. By performing diffusion transfer from a photosensitive element having at least one photosensitive unit of this combination to an image receiving element, a monochrome or multicolor positive transfer image can be obtained in one development process. More specifically, in the color diffusion transfer method used in the first typical method, a silver halide latent image in a light-sensitive element is developed in the presence of a dye developer, and as a result of this development, a The dye developer is oxidized and becomes substantially fixed. It is believed that this fixation is due, at least in part, to changes in the solubility properties of the dye developer upon oxidation, particularly with respect to its solubility in alkaline solutions. In the unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and can diffuse, so that the image quality of the unoxidized dye developer in the processing agent is reduced as a function of the point-by-point exposure of the logenated emulsion. Provide distribution. At least a portion of this imagewise distribution of unoxidized dye developer is transferred to the superimposed image-receiving layer by imbivision. This transfer substantially eliminates oxidized dye developer. The image receiving element accepts imagewise diffusion of unoxidized dye developer from the developed emulsion without substantially disturbing the imagewise distribution of unoxidized dye developer to provide a reversal of the developed image. This first type of diffusion transfer method is covered by many patents, such as British Patent No. 8049.
It is described in the specification of No. 71, etc. Dye developers particularly useful in the present invention are those in which the silver halide developing group has a benzenoid group, and the preferred benzenoid group in such compounds is a hydroquinonyl group.

Typical dye developers include, for example, U.S. Pat. No. 298
No. 3606, No. 3345163, No. 325500
No. 1, No. 3218164, No. 3453107,
Same No. 3551406, Same No. 3135605, Same No. 3
No. 421892, No. 3597200, No. 3563
No. 739, No. 3482972, No. 3415644
No. 3,594,165.

Further, in the present invention, it is also possible to use a hydrolyzable dye developer and a short wavelength shift dye developer in which a hydrolyzable group is introduced into the dye developer. Representative specific examples of these include U.S. Patent No. 3,230,082, U.S. Pat. No. 3,329,670, U.S. Pat.
No. 9334, No. 3295973, No. 319601
Specifications of No. 4 and No. 3336287, Special Publication No. 1973-
No. 379, No. 36-12393, No. 37-2241, U.S. Pat. No. 3,312,682, U.S. Pat. No. 3,826
Compounds described in each specification of No. 801 can be mentioned. Furthermore, in the present invention, it is possible to effectively use a leuco dye developer whose dye portion has been reduced and temporarily converted into a colorless leuco body. Representative examples of these include U.S. Patent Nos. 2,909,430 and 3,
No. 320063, No. 2892710, No. 2992
Specifications of No. 105, JP-A-4866440, JP-A No. 48
Compounds described in various publications such as No.-66441 can be mentioned.

A typical second method involves the reaction of the silver halide oxidized product with the dye image-forming material to release diffusible dyes, specifically Type A, Type B, and Type B. C
It is classified into the following types. Among these, type A uses a reactive non-diffusible substance that can couple with an oxidized developing agent, and as a result of the coupling reaction, a soluble and diffusible dye is released from the processing agent. I can do it. This type of diffusible dye-releasing force plate contains a moiety in which the coupling reactive site is replaced by a residue that is cleaved off by oxidized developing agent. The electronically conjugated system of the dye to be released may be pre-incorporated into the coupler or may be formed by a coupling reaction.
The former couplers exhibit spectral absorption similar to the emitted dye. On the other hand, the latter couplers are, in principle, colorless, and even if they are colored, their absorption is temporary and is not directly related to the absorption of the emitted dye. Compounds used in type A above include US Pat. No. 3,227,550;
British Patent No. 3880658, British Patent No. 3765886, British Patent No. 840731, British Patent No. 904364, British Patent No. 904
Specifications of No. 365 and No. 1038331, Special Publication No. 4
It is described in Japanese Patent Application No. 515471, Japanese Patent Application No. 50-133879 and Japanese Patent Application No. 50-118480.

In the above type B, the dye residue contained in the substituent group is cleaved due to the intramolecular ring-closing reaction with the substituent group adjacent to the reaction point that occurs following the condensation reaction with the oxidized developing agent. It is a type of system that releases In particular, after oxidative coupling of an aromatic primary amino developer to the 4-position of phenol or aniline, an azine ring is formed with the sulfonamide group containing the dye moiety located at the 3-position, and diffusion with sulfuric acid occurs. It releases sex pigments. Compounds used in type B are described in the specifications of US Pat. No. 3,443,940 and US Pat. No. 3,734,726.

As a result of development, type C is oxidized by an oxidized auxiliary agent to close the ring or decompose with an alkali to release a diffusible dye. Oxidation of the dye-forming agent is achieved through auxiliary agents such as pyrazolidones. A representative example of this type of dye imaging material is U.S. Pat.
No. 62, No. 3698897, No. 3728113, No. 3443939, No. 3443940, No. 3245789, No. 3880658, Pelkey Patent Nos. 796041 and 796042,
JP-A-48-33826 and JP-A No. 49-114424
It is stated in each publication of the issue. A typical third method uses a dye-developing material that releases a diffusible dye upon cleavage with an alkali, but does not substantially cleave in the presence of an oxidized developer. Representative examples of dye image-forming substances are described in Japanese Patent Application Laid-Open No. 111628/1983.

In the representative first and third systems described above, a positive diffusion transfer dye image is obtained by performing a development process using a negative OJ type silver halide emulsion layer.

On the other hand, in the typical second method described above, a negative diffusion transfer dye image is obtained by performing a development process using a negative-working silver halide emulsion layer. Therefore, the second method requires an inversion method. For example, direct positive emulsions, such as internal latent image emulsions such as those described in U.S. Pat. No. 2,592,550, U.S. Pat. Fog type emulsions described in the specifications of US Pat. No. 2,005,837, US Pat. No. 2,541,472 and US Pat.

Alternatively, a layer containing a diffusible dye-releasing layer and physical development nuclei provided adjacent to a negative-working silver halide emulsion layer may be treated with a developer containing a silver halide emulsion. A specific example of this is US Pat. No. 3,243,294.
No. 3,630,731. Furthermore, a diffusible dye-releasing power coupler is provided adjacent to the negative-working silver halide emulsion layer containing a compound that reacts with the oxide of the developing agent to release a development inhibitor such as 1-phenyl-5-mercaptotetrazole. A layer containing a spontaneously reducible metal salt may also be provided. Specific examples of this include US Pat. Nos. 3,148,062 and 32,275
Specifications of No. 51, No. 3227554, No. 3364022, and No. 3701783, Japanese Patent Publication No. 43-21
It is described in publications such as No. 778 and No. 47-49611. Combinations of these emulsions and dye image-forming substances can be used in the present invention, and systems that provide negative and positive dye images can be selected. The dye image-forming substances used in the present invention include gelatin, which is a carrier for the silver halide emulsion layer or its adjacent layer in the light-sensitive element;
Depending on the type of dye image-forming material, it can be dispersed in a hydrophilic protective colloid such as polyvinyl alcohol in a variety of ways.

For example, a dye image-forming substance having a dissociable group such as a sulfo group or a carboxyl group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic protective colloid solution. A dye image-forming substance that is difficult to dissolve in an aqueous medium and easy to dissolve in an organic solvent can be dissolved in an organic solvent, and a solution obtained can be added to a hydrophilic protective colloid solution and dispersed into fine particles by stirring or the like. The organic solvent can be used alone or in combination with a low boiling point solvent that can be removed from the dispersion by evaporation or with an organic solvent that is easily soluble in water. . For example, the method described in Japanese Patent Publication No. 43-13837 can be effectively used for dispersing the dye image-forming substance in the present invention. Particularly useful high-boiling solvents in the present invention include Nn-butylacetanilide, diethyl laurylamide, dibutyl laurylamide, dibutyl phthalate, tricresyl phosphate, triglycerides of higher fatty acids, dioctyl adipate, and the like. Low boiling point solvents include ethyl acetate, methyl acetate,
4-methylcyclohexanone, tetrahydrofuran, methyl ethyl ketone, etc. are used. Additionally, to stabilize the dispersion of dye image-forming materials, U.S. Pat.
Sulfites may also be present as described in No. 3 specification.
Furthermore, the dye image-forming substance used in the present invention is disclosed in Japanese Patent Publication No. 48
As described in Japanese Patent No. 32131 and US Pat. No. 3,832,173, dye image-forming particles may be directly dispersed in a hydrophilic protective colloid without using a high boiling point solvent or the like.

The amount of dye image-forming material used in the present invention can vary widely depending on the compound used and the results desired, but for example, from about 0.5 to about 10 percent by weight of the hydrophilic protective colloid coating solution being applied. It is preferable to do so. When performing multicolor photography in the process of the present invention, it is advantageous to use an interlayer in the photosensitive element. The interlayer prevents undesirable interactions between emulsion layer units of different color sensitivities, and the dye image-forming material controls the diffusivity of the alkaline processing composition. This middle layer is gelatin,
Calcium alginate or U.S. Patent No. 3384
Any item described in specification No. 483, Japanese Patent Publication No. 45-18
Vinyl acetate-crotonic acid copolymer, isopropylcellulose, hydroxypropylmethylcellulose as described in Japanese Patent Publication No. 435, polyvinylamide as described in Japanese Patent Publication No. 47-47606, polyvinylamide graft as described in U.S. Pat. No. 3,575,700. Polymer, Japanese Patent Publication No. 49-20972 and U.S. Patent No. 3756
Latex liquid and penetrant systems such as those described in the '816 patent are useful.

This interlayer may contain interlayer interaction inhibitors selected depending on the type of dye imaging material and processing agent used. For example, in dye imaging materials of the type that release diffusible dyes by developer oxides, non-diffusible couplers that can react with and fix reducing agents and oxidation products, such as non-diffusible hydroquinone derivatives, are used in the emulsion. It is effective in preventing undesired exchange of developer oxidation products between layer units. The silver halide emulsion used in the present invention may be composed of, for example, a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof.

The silver halide emulsions may be fine-grained or coarse-grained, and usefully have an average grain size in the range of about 0.1 micron to about 2 microns. The silver halide emulsion can also be prepared by any known method, such as a single jet emulsion, a double jet emulsion, such as a Lippmann emulsion, an ammoniacal emulsion, a thiocyanate emulsion or a thioether-ripened emulsion, such as US Pat.
No. 2264, No. 3320069 and No. 3271
This includes those described in each specification of No. 157. Emulsions containing silver halide grains with substantial surface photosensitivity are used, and emulsions containing silver halide grains with substantial photosensitivity inside the grains are also used; these silver halide emulsions are used, for example, in the US Patent No. 2592250
No. 3206313 and No. 3447927.

In the present invention, negative emulsions can be used, or U.S. Pat. No. 2,184,013, U.S. Pat.
French Patent No. 1520821, US Patent No. 2563
No. 785, No. 2456953 and No. 28618
Direct positive emulsions such as those described in US Pat. No. 85, etc. can also be used.

The silver halide emulsions used in the present invention may be sensitized with natural sensitizers contained in gelatin or chemical sensitizers such as reducing agents, sulfur, selenium or tellurium compounds, gold, platinum or palladium compounds, or combinations thereof. can do.

Suitable sensitization methods are described in U.S. Pat.
No. 399083, No. 3297447 and No. 32
It is described in each specification of No. 97446.

The silver halide emulsions used in the present invention may contain speed-enhancing compounds such as polyalkylene glycols, cationic surfactants and thioethers or combinations thereof, such as U.S. Pat.
No. 32, No. 2944900 and No. 329454
Those described in the specification of No. 0 can be used.

The silver halide emulsions used in the present invention can be protected against the development of force ribs and can be stabilized against loss of sensitivity during storage. Suitable antifoggants and stabilizers, used alone or in combination, include:
U.S. Patent Nos. 2,131,038 and 2,694,716
thiazolium salts as described in the specifications of U.S. Pat. No. 2,886,437 and U.S. Pat.
Mercury salts as described in US Pat. No. 8,663, U.S. Pat.
urazoles as described in U.S. Pat. No. 87135, sulfocatecols as described in U.S. Pat. Mercaptotetrazoles as described in US Pat. No. 2,403,927, mercaptotetrazoles as described in US Pat. No. 3,266,897 and US Pat. No. 3,397,987, polyvalent metal salts as described in US Pat. , thiuronium salts as described in U.S. Pat. No. 3,220,839, U.S. Pat. No. 2,566
Palladium, platinum, and gold salts as described in the specifications of No. 263 and No. 2,597,915 are included.

The processing agent permeable layers such as the silver halide emulsion layer, the layer containing the dye image-forming substance, the layer containing the mordant, the protective layer or the intermediate layer used in the present invention contain a hydrophilic polymer as a binder. It is desirable to be present. For example, gelatin, gelatin modified with an acylating agent, gelatin grafted with a vinyl polymer,
Proteins such as casein, albumin, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, partial hydrolysates of polyvinyl alcohol or polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polyvinyl ethers such as polymethylvinyl ether. Examples include polymeric nonelectrolytes such as polyacrylic acid, partial hydrolysates of polyacrylamide, and anionic synthetic polymers such as copolymers of vinyl methyl ether and maleic acid. These hydrophilic polymers can be used alone or in combination. Furthermore, these hydrophilic polymer layers may contain latex-like polymer dispersions of hydrophobic monomers such as alkyl acrylates and alkyl methacrylates. In the present invention, these hydrophilic polymers, especially polymers having functional groups such as amino groups, hydroxyl groups, carboxyl groups, etc., can be made insolubilized by various curing agents without losing their permeability to processing agents. I can do it. Particularly useful curing agents include formaldehyde, glyoxal, aldehydes such as glutaraldehyde, N-methylol compounds such as N-hydroxymethylphthalimide, 1-hydroxymethylbenzotriazole, 2,5-hexadione, 1,2-cyclo Ketones such as pentadione, methylol compounds such as N-polymethylol urea and hexamethylol melamine, epoxy compounds such as 1,4-bis(2,3-epoxypropoxy) diethyl ether, and aziridine compounds such as triethylenephosphamide. , 3-hydroxy-5-chloro-
Examples include polymeric materials such as 8-triazinylated gelatin. Furthermore, these hydrophilic polymer layers may contain a curing accelerator such as carbonate or resorcinol in addition to the curing agent. The silver halide emulsions used in the present invention can use optical sensitizing dyes to provide additional photosensitivity.

For example, silver halide emulsions may be treated with organic solvents of sensitizing dyes, or dyes may be prepared in the form of dispersions in British Patent No. 1154.
In addition, additional optical sensitization can be achieved as described in the '781 specification. For optimal results, it is desirable to add the dye to the emulsion at or before the final step. Sensitizing dyes useful for sensitizing such silver halide emulsions are described, for example, in U.S. Pat.
It is described in each specification of No. 384486. Optical sensitizers that can be effectively used in the present invention include cyanines,
Included are merocyanines, styryls, hemicyanines (eg, enamine hemicyanine), oxonols, hemioxonols, and the like. The cyanine dye preferably contains a basic core such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole and imidazole. Such a nucleus may contain an alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl or enamine group, and may be attached to a carbocyclic or heterocyclic ring. These rings may or may not be substituted with a halogen atom, phenyl group, alkyl group, haloalkyl group, cyano group or alkoxy group. These dyes may have alkyl groups, phenyl groups, enamine groups or heterocyclic substituents on the methylene or polymethine chains in symmetrical or asymmetrical form. Merocyanine dyes contain basic nuclei such as those mentioned above and acidic nuclei such as thiohydantoin, rhodanine, oxazolidenedione, thiazolidenedione, barbituric acid, thiazolinone, malononitrile. The acid nucleus may be substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamino group or a heterocyclic nucleus. Combinations of the above dyes can also be used if desired. Furthermore, in the present invention, if desired, supersensitizing additives that do not absorb visible light, such as ascorbic acid derivatives, azaindenes, cadmium salts or US Pat.
Organic sulfonic acids such as those described in the specifications of No. 90 and No. 2937089 can be included. As the processing agent (alkaline processing liquid) used in the present invention, any liquid composition can be used as long as it contains processing components necessary for developing the silver halide emulsion and forming a diffusion transfer image.

As the solvent for this treatment agent, any hydrophilic solvent such as water, methanol, methyl cellosolve, etc. can be used. The processing agent desirably contains an alkaline agent in an amount sufficient to maintain the pH necessary for development of the emulsion layer and to neutralize acids generated during the development and image formation processes. As the alkali agent, sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, sodium carbonate, monosodium phosphate, diethylamine, etc. can be used, and the treatment agent has a PHL of about 2 or more at room temperature. This is desirable. The processing agent used in the present invention may contain a thickening agent, for example, a polymeric thickening agent that is inert to alkaline solutions, such as hydroxyethyl cellulose and sodium carboxymethyl cellulose. The concentration of the thickener is preferably about 1 to 5% by weight of the processing agent, so that the concentration of the thickener is about 100 to 20,000
It is possible to give the processing agent a viscosity of 0 centiboads, which not only facilitates the uniform spread of the processing agent during processing, but also
When the aqueous solvent moves to the photosensitive element and the image receiving element during processing and the processing agent is concentrated, it forms a non-flowing film.
Assists in the integration of photographic element units after processing. This polymer film can also serve to prevent image change by inhibiting further migration of image forming components to the image receiving layer after formation of the diffusion transferred image is substantially completed. It may be advantageous for the processing agent to contain a light-absorbing material, such as carbon black, to prevent the silver halide emulsion from being disturbed by external light during processing. Furthermore, the processing agent contains processing components specific to the imaging material used. For example, in the case of dye developers, p-aminophenol, 4'methylphenylhydroquinone, 1-
It is desirable to contain an auxiliary developer such as phenyl-3-pyrazolidone, an onium-based development accelerator such as N-benzyl-α-picolinium bromide, and an antifoggant such as benzotriazole. In the case of a diffusible dye releasing agent, developers such as aromatic primary amino color developers, antioxidants such as sulfites or ascorbic acid, halides or 5-nitrobenzimidazole may also be used. It is desirable to contain an antifoggant, a silver halide emulsion such as sodium thiosulfate or sodium thiocyanate, and the like. In the color diffusion transfer method according to the present invention, development can also be carried out in the presence of a diffusible onium compound.

Examples of such onium compounds include quaternary ammonium compounds, quaternary phosphoric acid compounds, and quaternary sulfonium compounds, and in particular, for example, 1-benzyl-2-
Picolinium bromide, 1-(3-bromopropyl)
-2-picolinium-p-toluenesulfonic acid, 1-phenethyl-2-picolinium bromide, 2,4-dimethyl-1-phenethylpyridinium bromide, α-picolin-β-naphtholmethyl bromide, N-N-diethyl Onium compounds such as piperidinium bromide, phenethyltrimethylphosphonium bromide, and dodecyldimethylsulfonium-p-toluenesulfonium are effective in the present invention. The onium compound may be used anywhere in the photosensitive element or the image receiving element, but it is preferable to include it in the processing agent (alkaline processing liquid). Specific examples of onium compounds and examples of their use are described, for example, in the specifications of US Pat. No. 3,411,904 and US Pat. No. 3,173,786.

In the present invention, a light-reflecting material can be used to form a white background for the image formed on the image-receiving layer.
Suitable light-reflecting substances include titanium dioxide, barium sulfate, zinc oxide, barium alumina stearate, calcium carbonate, silicates, zirconium oxide, kaolin, magnesium oxide, etc., which may be used alone or in combination. be able to. Such light-reflecting materials may be preformed or as described in Pelkey Patent No. 768110 and
They may be formed in-situ from precursors that are distributed in photographic elements as described in No. 1 and others. Additionally, the light-reflecting material may be a hydrophilic polymer such as polyvinyl alcohol, gelatin, hydroxypropylcellulose, polyvinylpyrrolidone, or
As described in the specification etc., it may be contained in a layer using a vinyl polymer containing an anionic solubilizing group as a binder,
Furthermore, it can also be fixed in a dispersed state in a layer of a film-forming polymer such as hydroxyethyl cellulose or carboxymethyl cellulose, which is blended into a processing agent and formed by processing development. Fluorescent brighteners such as stilbenes, coumarins, triazines or oxazoles may be used in conjunction with such light-reflecting materials. Further, in the present invention, in order to protect the silver halide emulsion layer from ambient light during processing, Pelkey Patent Nos. 743,336, 768,107 and 76, together with a light reflective material, are used.
Indicator dyes such as those described in Patent No. 8109 and the like can be used. The processing agent (alkaline processing liquid) used in the present invention is preferably stored in a breakable container.

For example, when a processing agent is placed in a hollow container created by folding a sheet of liquid and air impermeable material and sealing each edge, when the photographic element is passed through a pressurizing device.
It is desirable that the treatment agent be released by breaking at a predetermined location due to the internal pressure applied to the treatment agent. As materials forming the container, materials such as polyethylene terephthalate/polyvinyl alcohol/polyethylene laminates, lead foil/vinyl chloride monovinyl acetate copolymer laminates, etc. are advantageously used. The containers are also secured along the leading edge of the photographic element;
Desirably, the storage liquid is adapted to be spread over the surface of the photosensitive element in a substantially unidirectional manner. Preferred examples of the container include U.S. Pat. No. 2,543,181, U.S. Pat. No. 2,643,886, U.S. Pat.
No. 56491, No. 3056492, No. 31525
No. 15 and No. 3173580. The image receiving element used in the present invention preferably uses a hydrophilic colloid as its surface layer.

Examples of hydrophilic colloids include gelatin, starch,
Dextran, polyvinylpyrrolidone, gum arabic,
It is desirable to use carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, guar gum, gum acacia, etc. In the method of the present invention, when an image is obtained by separating the photosensitive element and the image-receiving element, a releasing agent can be used.

The stripping agent can be contained on the surface of the silver halogenide emulsion layer, on the image receiving layer containing a mordant, or in the processing agent. Suitable release agents are those having a composition different from the binder used in the silver halide emulsion layer. For example, alkali-permeable polysaccharide, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, 4·l-dihydroxyphenol, glucose, sucrose, sorbitol, inositol, resorcinol, sodium phytate, zinc oxide, microparticle polyethylene, microparticle poly4 Fluorinated ethylene, polyvinylpyrrolidone/polyvinylhydrodiene phthalate as described in US Pat. No. 3,325,283, ethylene monomaleic anhydride copolymer as described in US Pat. No. 3,376,137, and the like are useful.

Additionally, the hydrophilic colloid surface layer on such image receiving elements may contain ultraviolet absorbing materials, such as U.S. Pat. No. 3,460,942.
No. 3,069,262, No. 3,330,680, and No. 3,330,656. Furthermore, if desired, a fluorescent whitening agent such as stilbene, coumarin, triazine, oxazole, etc. can be included. The photographic element layer consisting of the photosensitive element, image receiving element, processing sheet, etc. used in the present invention may optionally contain a surfactant, such as saponin, an anionic compound, such as U.S. Pat.
alkylaryl sulfonates, amphoteric compounds as described in U.S. Pat. No. 831, e.g.
Water-soluble adducts of glycidol and alkylphenols can also be included, such as those described in US Pat. No. 816, and as described in British Patent No. 1,022,878. Further, in order to facilitate the coating of the photographic element layer used in the present invention, the coating composition may contain various thickeners and the above-mentioned surfactants. Anionic polymers, such as high molecular weight polyacrylamide or acrylic acid-based polymers, which exhibit a thickening effect upon interaction with the binder polymer in the coating composition, are also effectively used in the present invention. The photographic element layers used in this invention can be coated by a variety of coating methods, such as dip coating, air knife coating, curtain coating, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294. .

If desired, two or more layers can also be applied simultaneously by methods such as those described in US Pat. No. 2,761,791 and British Patent No. 837,095.
The present invention is disclosed in British Patent No. 968,453 and US Pat.
It can also be used for vacuum-deposited silver halide layers as described in the specifications of No. 219451.

The photographic element layers used in this invention can be hardened with a variety of organic or inorganic hardeners, alone or in combination.

Suitable curing agents include, for example, aldehydes, flocked aldehydes, ketones, carboxylic acid derivatives,
Carbonic acid derivatives, sulfonate esters, sulfonyl halides, vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed functional hardeners and polymer hardeners such as dialdehyde starch and Included are oxidized polysaccharides such as oxyguar gum, and the like. The sensitizing dyes and other additives used in the invention can be added as an aqueous solution;
Alternatively, it can be added using a suitable organic solvent.
The above-mentioned sensitizing dye and other additives are disclosed in U.S. Patent No. 29123.
43, No. 3342605, No. 2996287, and No. 3425835.

Photographic element layers used in the present invention are described, for example, in U.S. Pat.
No. 253921, No. 2274782, No. 2527
583 and 2956879, etc., and filter dyes may be included.

If desired, such compounds can be mordanted as described in US Pat. No. 3,282,699. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereby.

Example 1 A photosensitive element was prepared by sequentially coating the following layers on a gelatin-subbed acetylcellulose film support.

(1) Cyan dye developer layer 1,4-bis(α-methyl-β-hydroquinonylethylamino)-5,8-dihydroxyanthraquinone with N-
It was dissolved in a mixed solvent of n-butylacetanilide and 4-methylcyclohexanone, emulsified and dispersed in an aqueous gelatin solution containing a dispersant Alkanol B (manufactured by DuPont), and applied.

Coating amount: gelatin 4.27/M2, cyan dye developer 2
．． It was set as 07/M2. (2) Red-sensitive emulsion layer Red-sensitive silver iodobromide emulsion contains silver 0.67/I and gelatin 2.4
7/Rrl.

(3) Middle class The gelatin was coated at a rate of 2.0 t/Trl.

(4) Magenta dye developer layer 2-[p-(β-hydroquinonylethyl)phenylazo]-4-n-propoxy-1-naphthol is dissolved in a mixed solvent of N-n-butylacetanilide and 4-methylcyclohexanone, It was emulsified and dispersed in an aqueous gelatin solution containing dispersant Alkanol B, and then applied.

The coating amount was 2.87/m'' of gelatin and 1.37/m of magenta dye developer. (5) Green-sensitive emulsion layer The amount of green-sensitive silver iodobromide was 1.2y/M of silver and 1.27/m of gelatin. I applied it to make it look like this.

(6) Middle class The gelatin was applied at a rate of 1.5 t/Rrl.

(7) Yellow one-dye developer layer 1-phenyl-3-N-n
-hexylcarbamoylamide-4-[(p-2'・5
'-dihydroxyphenethylphenylazo]-5-pyrazolone was dissolved in a mixed solvent of N-N-diethyl laurylamide and ethyl acetate, emulsified and dispersed in an aqueous gelatin solution containing alkanol B as a dispersant, and applied.

The coating amount was 1.17 t/Trl of gelatin and 0.5 t/d of yellow monochrome developer. (8) Blue-sensitive emulsion layer Blue-sensitive silver iodobromide: silver 0.67/TI, gelatin 0.6y
/M2.

(9) Protective layer 4'-Methylphenylhydroquinone was dissolved in N-N diethyl uralylamide, emulsified and dispersed in an aqueous gelatin solution, and after coating, 5 ml of a 2% mucochloric acid aqueous solution was added to 100 ml.
1 was added and then applied.

The coating amount is l-methylphenylhydroquinone 0.57/
A. Gelatin was set at 0.61/M2. The following processing agent (alkaline processing liquid) was prepared. A processing bag containing such a processing agent is used with the above photosensitive element and Table 1 below.
The various polymer mordants (comparative compounds and exemplified compounds) shown in the following were placed between image-receiving elements in which the image-receiving layer was contained, imagewise exposed, and then developed using a roller pressing tool.

The resulting photographic element was treated with cyan (C), magenta (M), and yellow (Y) using red, green, and blue filters, and the maximum density (4) Rnax) after 10 minutes had elapsed.
was measured. The obtained results are shown in Table-1. The image receiving element is
On a transparent film base of 100 μm thick made of polyethylene terephthalate, 3% by weight of the polymer mordant of the present invention (the above-mentioned exemplified compound) shown in Table 1 below, and polyvinyl alcohol (Nippon Gohsenol NH-2)
6) was prepared by adding 0.1y of polyoxyethylene nonyl phenyl ether to an aqueous solution 1007 containing 6% by weight, and applying the mixture to form an image-receiving layer having a dry film thickness of 5μ.

The image receiving element (1) is made of poly-4-
This is an example in which vinylpyridine is used, and the image receiving element (2) is an example in which a polymer mordant obtained by graphing 2 mol % of 4-vinylpyridine into poly-4-vinylpyridine is used.

From the results in Table 1, the DnlaX of the image-receiving element (1) containing a known polymer mordant is low, and the image-receiving element containing a polymer mordant in which 2 mol% of 4-vinylpyridine is grafted onto poly-4-vinylpyridine. (2) Dnl
It can be seen that the image receiving elements (3) to (8) containing the polymer mordants of the present invention exhibit high DnlaX, although the ax is also low.

Example 2 A photosensitive element was prepared by sequentially coating the following layers on a gelatin-subbed acetyl cellulose film support.

(1) Green-sensitive silver bromide was mixed with 1.0'il/Trl of silver, 2.67/M2 of gelatin, and 1-phenyl-3-(3,5-disulfonate) as a magenta dye-diffusive coupler. Benzamide)-4-(6-hydroxy-4-pentadecylphenylazo)-5 pyrazolone potassium neutral salt was applied at a ratio of 0.87/M2.

(2) Gelatin was coated in a ratio of 2,07/M2.

Image receiving elements (1), (3), (4) coated in Example 1,
Titanium dioxide 20.07/m" and gelatin 2,07/M2 were coated as a light reflecting layer on the image-receiving layers of (7) and (8). Furthermore, gelatin 0.67/T was applied as a protective layer on top of this.
An image-receiving element was prepared by applying the coating so as to obtain the following properties: rl. Next, the following processing agent was prepared and placed in a processing bag.

The processing bag was placed between the photosensitive element and the image-receiving element and subjected to imagewise exposure, and then developed using a roller presser.

The maximum density (Dnlax) of the dye image was measured 10 minutes after processing. The results obtained are shown in Table-2. As is clear from Table 2, the method of the present invention (image receiving element numbers (3), (4), (
It can be seen that in cases 7) and (8)), excellent maximum densities can be obtained even when a light reflecting layer is provided.

Example 3 A diffusion transfer photographic element was prepared by sequentially coating the following layers on a transparent acetylcellulose film support.

(1) Image-receiving layer Add 3% by weight of the polymer mordant of the present invention (the above-mentioned exemplified compound) shown in Table 3 below and 6% by weight of polyvinyl alcohol (Gohsenol NH-26 manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) to an aqueous solution 1007. Polyoxyethylene nonyl phenyl ether 0.1y was added to form an image-receiving layer having a dry thickness of 5 μm.

(2) Light reflective layer titanium dioxide 20.07/m", gelatin 2.07/R
It was applied so that it became RL.

(3) Opaque layer gelatin 2.07/A, carbon black 2.07/M
It was applied so that it became 2.

(4) Yellow dye image-forming substance-containing layer The following dye image-forming substances were mixed at 1.07/d and gelatin at 1.07/d.
07/A.

(5) Blue-sensitive emulsion layer containing blue-sensitive silver iodobromide of silver 0.67/m" and gelatin 0.67
/ I applied it to make it look good.

(6) Protective layer The gelatin ratio was applied to 0.57/Trl.

A transparent polyethylene terephthalate film was used as the treated sheet. The processing agent was prepared according to the following formulation.

Processing Agent Prescription A processing bag containing the above processing agent was placed between the above photographic component and the processing sheet for imagewise exposure, and then developed using a roller pressure tool.

Process the obtained color image using a blue filter 10
The maximum concentration (Dnlax) after minutes was measured. The results obtained are shown in Table 3. Furthermore, as a control,
A known poly-4-vinylpyridine was used in place of the polymer mordant of the present invention used in the above photographic element.

As is clear from Table 3, the method of the present invention (photographic element (self),
(O), 02) and 03)) exhibit excellent maximum density. Example 4 Same as Example 3 except that the treatment sheet was changed.

The treated sheet was prepared by sequentially applying the following layers onto a polyethylene terephthalate film support. (1) Scavenger: A polymer mixture consisting of 4 parts of polyacrylic acid and 1 part of polymer mordant was coated at a ratio of 20.07/Trl.

(2) Intermediate layer (timing layer) A polymer mixture consisting of 95 parts of cellulose acetate and 5 parts of styrene-maleic anhydride copolymer at 3.0y/M
It was applied so that it became 2.

Minimum density (Dnlin) after one day of development processing
is as shown in Table 4 below.

I know it can be controlled. Example 5 Polymer, a known polymer mordant, was used as an image-receiving layer material.
The same procedure as Example 4 was used except that an image receiving layer containing 4-vinylpyridine/gelatin in a weight ratio of 1:2 and having a dry thickness of 5 μm was used.

The Dmin after one day of development is as shown in Table 5. Note that poly-4-vinylpyridine was used as a control. From the results in Table 5, it can be seen that the method of the present invention (photographic elements 01 to Q'') suppresses the increase in Dmln to a low level. Example 6 Example 3 except that the light reflecting layer contained a polymer mordant (the above-mentioned exemplified compound) in an amount of 10% by weight based on the gelatin content.
is the same as

Dmax and Dmin were measured 10 minutes after the treatment, and the results are shown in Table 6. In addition, a known poly-4-vinylpyridine was used as a control.

As is clear from Table 6, the method of the present invention (photographic element QO) ~Q
According to 3)), it can be seen that Dmax is high and the increase in Dmin is kept low.

Claims (1)

[Claims] 1. As an image receiving and/or scavenger layer, a copolymer containing as a copolymer component a monomer containing a tertiary nitrogen atom that can be made into a salt of an organic or inorganic acid is used as a backbone polymer. A color diffusion transfer method characterized by using a layer containing a polymer grafted or graft-polymerized with 5 mol % or more of a vinyl monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom. 2. The third, which can be a salt of an organic or inorganic acid.
2. The color diffusion transfer method according to claim 1, wherein the monomer containing a nitrogen atom is a compound represented by the following general formula [I]. General formula [I]▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom or a methyl group, R_2, R
_3 represents a lower alkyl group, phenyl group or aralkyl group, A represents a simple bond or a bonding group consisting of at least two atoms of hydrogen, carbon, nitrogen and oxygen atoms, and B represents R_2 and/or R_3 Together, they may form a 5- or 6-membered heterocycle which may have a substituent, and the heterocycle may further contain a nitrogen atom or an oxygen atom. ]. 3. The vinyl monomer containing a tertiary nitrogen atom or a quaternary nitrogen atom is a compound represented by the following general formula [II] or [III] Color diffusion transfer method. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_4 and R_7 are hydrogen atoms, halogen atoms, or methyl groups, respectively, R_5, R_8 is a lower alkyl group, phenyl group or aralkyl group, R_6, R
_9 is a lower alkyl group or an aralkyl group, R
_1_0 represents a hydrogen atom, a lower alkyl group or an aralkyl group, B and B' each represent a simple bond, a bonding group consisting of at least two atoms of a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom, and R_5 and R_6 , R_
8 and R_9 may form a 5- or 6-membered ring containing a nitrogen atom, B may have a substituent with R_5 and/or R_6, and B' may have a substituent with R_8 and/or R_9.
A 6-membered or 6-membered heterocycle may be formed, and the heterocycle may further contain a nitrogen atom or an oxygen atom. ]. 4. A color diffusion transfer method according to claim 1, wherein the scavenger layer is included in the image receiving element, the processing sheet or the photosensitive element.