JPS6014340B2 - Photographic materials for diffusion transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material for diffusion transfer which forms a diffusion transfer image of metallic silver or dye by diffusion transfer. The present invention relates to a novel photographic material for diffusion transfer (hereinafter referred to as diffusion transfer material) that reduces the number of particles.

Conventionally, silver salt diffusion transfer materials and dye diffusion transfer materials are known as diffusion transfer materials.

Silver salt diffusion transfer materials are made by exposing a photosensitive silver halide emulsion to light,
Developed with an alkaline processing composition, and the image-forming material in which unexposed areas of silver halide are made into a silver salt using a silver halide solvent or a coating agent is diffused into a silver precipitate layer (or image-receiving layer) to obtain a positive image. .

Dye diffusion transfer materials are made by exposing a light-sensitive silver halide emulsion to light,
Development is carried out with an alkaline processing composition and at the same time an imagewise distribution image is obtained with a dye image-forming material.

At least a portion of this dye image-forming material is transferred to an overlapping image-receiving layer to obtain a positive image. These silver salt and dye diffusion transfer materials are processed with alkaline processing compositions to obtain images.

If the alkaline processing composition is left in the system after transfer imaging, undesirable diffusion of imaging materials and contaminants into the image receiving layer will occur.

To obtain good images, to stop development at a favorable point, and to obtain a lower p.
It is known to use a layer containing a neutralizing agent (hereinafter referred to as a neutralizing layer) in order to obtain H. These neutralizing layers may be provided anywhere in the diffusion transfer material, but are generally provided between the image-receiving layer and the image-receiving layer support, between the photosensitive layer and the photosensitive layer support, and on the processing sheet.

As the neutralizing agent used in this neutralizing layer, it is described in, for example, US Pat. However, these polymer acids or low-molecular-weight acids have disadvantages such as distortion of the resulting images, deterioration of the neutralization function due to the influence of humidity and temperature during long-term storage, and deformation of the photographic material. It will be done. Furthermore, it seems likely that so-called yellow stain may occur in the formed image. An object of the present invention is to provide a diffusion transfer material containing a novel neutralizing agent for use in a neutralizing layer. Another object of the present invention is to provide a novel neutralizing agent for obtaining images with no distortion, excellent storage stability, high color density and color purity, less staining, and excellent photostability. An object of the present invention is to provide a diffusion transfer material containing the following. As a result of studies, the present invention has developed a copolymer containing as a copolymerization component an ethylenically unsaturated monomer having at least one carboxyl group or a group that can be hydrolyzed to produce a carboxyl group, and a monomer having at least one fluorine atom. It has been found that the above object can be achieved by using a neutralizing layer containing a neutralizing agent made of a polymer (hereinafter referred to as the compound of the present invention).

In the compound of the present invention, the monomer component having at least one carboxyl group or a group that generates a carboxyl group by hydrolysis is preferably represented by the following general formula [1
] The monomer components shown are listed.

General formula [1] [In the formula, R is a hydrogen atom, a lower alkyl group, one COOR
4, or a phenyl group substituted with one COOR4, R
2 and R3 each represent a hydrogen atom, a halogen atom, a lower alkyl group or -(CH2)n-, COOR4, R4 represents a hydrogen atom or a lower alkyl group, and n represents an integer of 1 to 2.

However, R,, R2 and R3 may be the same or different groups, but at least one is a carboxyl group or a group that generates a carboxyl group by hydrolysis, and two carboxyl groups are further cyclized to form an anhydride. may be formed. ] In the present invention, representative examples of monomer components having at least one carboxyl group or a group that can be hydrolyzed to produce a carboxyl group include acrylic acid, methacrylic acid, Q-fluoroacrylic acid, and itaconic acid. , maleic acid, crotonic acid, fumaric acid,
Examples include itaconic anhydride, maleic anhydride, mo/alkyl maleate such as monoethyl maleate or mono-n-butyl maleate, ethylenically unsaturated carboxylic acids such as citraconic anhydride, and mo/ethyl fumarate.

Furthermore, the monomer component having at least one fluorine atom in the compound of the present invention is preferably represented by the following general formula [
One monomer component represented by D] is mentioned. General formula [0
[In the formula, R5, R6, R7 are each a hydrogen atom or a halogen atom, R8 is a hydrogen atom, a halogen atom,
an alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, a phenyl group which may be substituted with a fluorine atom,
A phenyl group having a lower alkyl group which may be substituted with a fluorine atom, 1 (C ratio) n-, COOR9, 1 (CH2
)n-, COOR9, -OCOR9, or -0-R9
, R9 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkyl group having 1 to 18 carbon atoms to which a carbon-carbon bond is bonded via an oxygen atom, or R , o is a lower alkyl group which may be substituted with a fluorine atom, n is 1 or 2, and k is an integer of 1 to 5.

However, R5, R6, R7 and R8 may be the same or different groups, but at least one of them is a group containing a fluorine atom. ]Next, typical specific examples of monomer components having at least one fluorine atom preferably used in the present invention include CF2=CF2, CQ=CF2, C
HF=CF2, CH2=CHF, CHF=CHF, CH
2=CF-CH3, CH2=CH-CF3, CF2:C
F-CF3, CC〆2 = CF2, CFC so = CH2,
CFC so = CF2, CH2 = CH-C ratio (CF2) nH
(n=2-8), C ratio=CF-COOC ratio, CH2=C
HCOOCF3, CH2= CF - COOCH2C
H2F, CH2 = OH-COOCH2CF2
CHFCF3, CH2=CH-COOCH2 (CF2)
3CHF2, CH2=CH-COOC (CF2) nH
(n=2-8), etc.

The compound of the present invention, that is, a copolymer containing as a copolymerization component a monomer having a carboxyl group or a group that can be hydrolyzed to produce a carboxyl group and a monomer having at least one fluorine atom, can be used as a copolymer. It may also contain a polymeric component.

In this case, it is preferable that the total molar ratio of the monomer having a carboxyl group or a group that can be hydrolyzed to produce a carboxyl group and the monomer having at least one fluorine atom to the copolymer is 50% or more, More preferably, the former monomer having a carboxyl group or a group that can be hydrolyzed to produce a carboxyl group is 90%
The latter monomer having at least one fluorine atom accounts for 60 to 10 mol%, and the other copolymer components account for 50 to 0 mol%. Note that the form of copolymerization is not particularly limited, and any form of copolymerization exhibits the same effect. Typical monomers as copolymerization components other than those mentioned above in the compound of the present invention include, for example, unsaturated vinyl aliphatic carboxylates such as vinyl acetate and pinyl butyrate, methyl acrylate, and acrylic C ratio = CHCOOCQC day 2
0CH2CF3, CQ=CHCOOCQCH20CF sunset F2, C ratio=CHCOOCQCF2CF20 (CF2
)3CF3, C ratio=CHOC○(CF2)J(n31~
8), C ratio = CHCOOCH2C day 20CQCF2CF
2 days, CH2=CHOCH2CF3 ethyl, n-butyl acrylate, methyl methacrylate, n-butyl methacrylate, methyl Q-chloroacrylate, 2-hydroxyethyl acrylate, 2-N,N-dimethylaminoester acrylate Acrylic acid esters such as chill, olefins such as ethylene, propylene, isobutylene, etc.
halogenated olefins such as vinyl chloride, pinylidene chloride, etc., diens such as butadiene, isoprene, etc., nitriles such as acrylonitrile, methacrylonitrile, etc., aromatic unsaturated hydrocarbons such as styrene, methylstyrene, etc., acrylamide, methacrylamide, N
Included are acrylamides such as monomethyl acrylamide, N,N-dimethylacrylamide, diacetone acrylamide, etc., vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, etc., N-vinylpyrrolidone, and the like.

Next, typical examples of the compounds of the present invention will be given.
The compounds used in the present invention are not limited to these.

Exemplary Compounds The compounds of the present invention can be described, for example, in Preparative Methods of Polymer Chemistry, co-authored by W. R. Sorenson and T. W. Campbem. '
'Preparative Methods of P
olymerChemi-sRozo' (JohnWile
Y & So ship, lm. , NnwYorkl961)
and C.E.S.
Childknecht) Vinyl and Related Polymers “Vinyl and Related
Pol Hada eN” (John Wiley & Sons,
Inc. Synthesis can be carried out by arbitrarily adopting various polymerization reactions and conditions such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization according to the method described in , New York 952 King), etc., but for reference, the following A synthesis example is shown.

Synthesis Example-1 [Synthesis of Exemplified Compound (1)] In a pressure-resistant container for polymerization, 9.8 g of maleic anhydride, 24.0 g of vinyl perfluorobutyrate, and 50 g of dioxane were placed, and 50 g of dioxane was added as a polymerization initiator. Add 0.5 liters of peroxide, maintain at 70°C, and polymerize for 2 hours.

After the reaction, the reaction solution is concentrated, washed with n-hexane, and dried under reduced pressure. Polymer 29, which is soluble in acetone and dioxane, is obtained. The specific viscosity of a 1% acetone solution at 3 P0 is 2.4.

Synthesis Example-2 [Synthesis of Exemplified Compound [7]] Methacrylic acid 11.2 hours, 1, 1, 3 minutes in a pressure-resistant container for polymerization
-trihydroperfluorobutyl methacrylate 17
．． Add 40% of dioxane and 40% of dioxane, add 0.12% of azobisisoputilonitrile as a polymerization initiator, and make 7000
Keep at room temperature for 2 hours to polymerize.

After the reaction, the reaction solution is concentrated, washed with n-hexane, and dried under reduced pressure. Polymer 26 which is soluble in acetone and dioxane is obtained. The specific viscosity of a 1% acetone solution at 30% is 3.1.

The compound of the present invention has a fluorine atom in its molecule, so it has moderate water repellency, excellent storage stability, high color density and color density, and can produce diffusion transfer images without staining or static. to provide a diffusion transfer material with

The compound of the present invention has sufficient film-forming properties when used alone, but as long as it is compatible with the compound of the present invention, it can be used in combination with any binder to form a neutralizing layer. Examples of binders that can be used in combination include: , gelatin, derivative gelatin modified with acylating agents, natural polymeric compounds such as casein, polyvinyl alcohol, hydroxyethylcellulose, hydride.

Xypropylcellulose, methylcellulose, ethylcellulose, cellulose acetate, polyvinyl acetate, partial hydrolyzate of polyvinyl acetate, voripinylpyrrolidone, methyl polymethacrylate, polyethyl methacrylate, polybutyl acrylate, polyethyl acrylate, poly Examples include synthetic polymer compounds such as acrylamide, polymethacrylamide, polydiacetone acrylamide, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and mixtures thereof. The neutralizing layer of the present invention is
Although the layer can be placed anywhere as long as it does not have a neutralizing function and prevent the formation of a transferred image, it is preferable to use the layer described in US Pat.
It may be provided between the image-receiving layer and the image-receiving layer support as described in U.S. Pat. No. 4, No. 3415645, U.S. Pat.
It may be provided between the photosensitive layer and the photosensitive layer support as described in U.S. Pat. No. 3 and U.S. Pat. It may be provided between the layer and the image-receiving layer support;
In the case of the layer structure described in the specification, 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 Tokushu No. 47-348, which has a peeling means, it may be provided between the image-receiving layer and the image-receiving layer support. The neutralizing layer of the present invention is preferably separated from the spreading treatment agent layer by an intermediate layer (also referred to as a timing layer).

This intermediate layer prevents an undesirable decrease in the density of the transferred image due to a rapid decrease in the pH of the processing composition due to the neutralization layer before the required development of the silver halide emulsion layer and formation of the diffusion transferred image. and serves to delay the pH drop until after the required development and transfer have taken place. The intermediate layer contains gelatin, polypynyl alcohol as described in U.S. Pat. No. 3,362,819, partially acetalized polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and cyanoethyl as described in U.S. Pat. Polyvinyl alcohol, hydroxypropyl methyl cellulose as described in U.S. Pat. No. 3,433,633, inpropyl cellulose, polyvinyl amides as described in Samurai Publication No. 46-12676, Tsubaki Publication No. 48-41214
Polyvinylamide graft copolymer as described in the publication,
A combination of a latex liquid and a penetrating agent is useful, as described in JP-A-49-22935 and JP-A-49-91642. These polymers used in the timing layer can also be cured by crosslinking reactions using aldehyde compounds such as formaldehyde, N-methylol compounds, epoxy compounds, etc. Diffusion transfer materials using the compounds of the present invention (hereinafter referred to as the present invention) A photosensitive element (hereinafter referred to as a photosensitive element according to the present invention) that can be used in a diffusion transfer material (referred to as a diffusion transfer material) includes a silver halide emulsion in a silver salt diffusion transfer material, and a silver halide emulsion and a color image forming substance in a dye diffusion transfer material. Silver halide emulsions contain silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, and the hydrophilic halogenated lines of these mixtures. It is a colloidal dispersion that can be prepared by various conventional emulsion methods, such as so-called double jet emulsions, compound emulsions, Lippmann emulsions, U.S. Pat.
No. 53, No. 2541472, No. 2563785, No. 2861885, No. 3367778, British Patent No. 723019 and French Patent No. 15208
It may be manufactured using any of the direct positive emulsions to which fog has been imparted in advance as described in the specification of No. 21.
Also, depending on the type of diffusion transfer material, silver halide grain size,
The content, mixing ratio, etc. will be different.

As the hydrophilic protective colloid which is a dispersant for silver halide, various natural or synthetic colloidal substances such as gelatin, gelatin derivatives or polyvinyl alcohol are used alone or in combination. The silver halide may also be used to activate gelatin, sulfur sensitizers such as furylthiocarbamide, thiourea, cystine, selenium sensitizers, noble metal sensitizers such as gold sensitizers, ruthenium, rhodium, iridium, etc. Depending on the sensitizing agent, it may be used alone or in combination as appropriate, or in US Pat.
Paper No. 990, No. 3297446, No. 329744
Chemical sensitization can be performed by the method described in No. 7 specification. Further, the silver halide emulsion can be optically sensitized, for example, by cyanine dyes and merocyanine dyes described in U.S. Pat. No. 2,526,632, U.S. Pat. Diffusion transfer materials can be obtained using three types of silver halide emulsions each having a different sensitivity wavelength range.
Further, this emulsion is disclosed in, for example, US Pat. No. 2,131,038, US Pat.
No. 97915, No. 2694716, No. 24446
No. 05, No. 2728663, No. 2839405, No. 28886437, No. 3220839, No. 3236652, No. 326 Iso 97, No. 328
No. 7135, No. 3397987 and British Patent No. 6
It can be stabilized with triazoles, tetrazoles, imidazoles, azaindenes, quaternary penzothiazoyl compounds, zinc or cadmium compounds as described in the specification of No. 23448, etc., and can also be stabilized with quaternary ammonium salt type, polyethylene glycol. Sensitizing compounds of the type or thioether type may also be included.

Furthermore, U.S. Patent No. 2886437, U.S. Patent No. 29449
No. 0, No. 3046132 and No. 329454
Sensitizing compounds such as those described in Specification No. 0 and the like may also be included. and also suitable gelatin plasticizers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bisethoxyethylene glycol succinate, amides of acrylic acids, latex, etc. It can also contain formaldehyde, halogen-substituted fatty acids such as mucofromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, beesters of methanesulfonic acid, and aldehyde groups containing two
Gelatin hardeners such as sodium bisulfite derivatives of dialdehydes separated by 3 to 3 carbon atoms, N-methylol compounds, methylol compounds, epoxy compounds, aziridine compounds, or extenders such as saponins, or sulfosuccinic acids. It may contain various photographic additives such as coating aids such as salts. Furthermore, if necessary, antifoggants, ultraviolet absorbers, and various other additives used in constant speed photography can also be included. Furthermore, alcolpic acid derivatives that do not absorb visible light, azaindene compounds,
Cadmium salts, organic sulfonic acid compounds such as those described in US Pat. No. 2,933,39 and US Pat. In the silver salt diffusion transfer method used in the diffusion transfer material of the present invention, when an alkaline processing composition is applied, metallic silver is produced by reduction of silver halide in exposed areas.

On the other hand, the silver halide in the unexposed area can be treated with, for example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanides such as sodium thiocyanide and potassium thiocyanide; silver halide solvents such as thiourea and ammonia, or silver salts. The forming agent forms a diffusible silver rust salt and diffuses. Various methods can be used to form the dye image used in the diffusion transfer material of the present invention, depending on the manner in which the dye image-forming material releases the diffusible dye upon development of silver halide.

The dye image-forming material may already contain finished dye moieties, dye moieties may be formed during development and/or subsequent processing, and the components essential for dye formation may migrate to the image-receiving layer where they are formed. A dye may be formed. Among the systems in which dyes are formed during development and/or subsequent processes, the first typical system is the so-called dye developer system. A dye developer is a compound that has both a dye part and a silver halide developer part in one molecule, and as a result of oxidation of the dye developer as a dye image forming substance by silver halide, an alkaline processing composition is formed. It changes into a diffusible pigment in a substance. The oxidized dye developer has lower solubility and less diffusivity in the processing composition compared to the original dye developer and is fixed 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 processing composition. Contains. Such dye developers can be incorporated into the light-sensitive element, particularly in or adjacent to the silver halide emulsion layer, and are dyes having spectral absorption characteristics corresponding to the sensitive wavelength range of the silver halide emulsion. Used in negative elements combined with developer. By performing diffusion transfer from a negative element having at least one stitched photosensitive unit to an image receiving element, a monochrome or multicolor positive transferred image can be obtained in one development process. This first type of diffusion transfer material has been described in many patent specifications, such as British Patent No. 80497.
It is stated in the Specification No. 1, etc. Typical dye developers include, for example, U.S. Pat.
No. 5605, No. 3218164, No. 325500
No. 1, No. 3415644, No. 3421892, No. 3453107, No. 348
No. 2972, No. 3551406, No. 35 73y
No. 35, No. 165 and No. 3597200. Further, in the present invention, a hydrolyzable dye developer in which a hydrolyzable group is introduced into a dye developer may be a short wavelength shift dye developer. Representative examples of these include U.S. Patent Nos. 3196014, 3230082, 3230083, and 32
300 Private No. 3230085, Same No. 329597
No. 3, No. 3307947, No. 3312682,
Same No. 3329670, Same No. 3336287, Same No. 3
579 Payment No. 3826801 Specification, Kimiaki Tsubaki 3
No. 6-37y, No. 36-12393, No. 37-224
Compounds described in Publication No. 1 and the like can be mentioned. Furthermore, in the present invention, it is also possible to effectively use a leuco dye developer whose dye portion has been reduced and temporarily converted into a colorless leuco form. Representative examples of these include U.S. Pat.
Specification No. 2992105, No. 3320063,
Compounds described in Tokkan Sho 48-6 Nezumi No. 40, Sho 48-6 Tetsu No. 41, and Sho 50-91324 can be mentioned. A typical second method is one in which a developing agent oxidized by silver halide reacts with a dye image-forming substance to release a diffusible dye.
, B and C.

Type A is an active non-diffusible substance (so-called diffusible dye-releasing coupler) that can couple with the oxidized developing agent.
The coupling reaction results in the release of soluble and diffusible dyes into the alkaline processing composition. Diffusible dye-releasing couplers of this type may also be so-called two-equivalent type couplers in which the coupling reaction site in the coupler is replaced by a group that is removed by an oxidized developer. 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 coupler exhibits spectral absorption characteristics similar to those of the emitted dye, whereas the latter coupler, in principle, exhibits spectral absorption characteristics similar to those of the emitted dye, even if the compound is colorless or colored. There is no direct relationship with the spectral absorption of the dye. Diffusible dye-releasing couplers used in type A above include US Pat. No. 3,227,550, US Pat.
Spot 06 ball, British Patent No. 840731, British Patent No. 9043
No. 64, No. 904365, No. 10 Spotted Powder No. 1 Specification, Taruko Sho 45-15471, Tsubakibuta Sho 50-13 Paper 7y
No. 50-11848 and the specification of No. 50-11848. Type B is formed by a condensation reaction between the oxidized developing agent and the diffusible dye-releasing coupler, followed by an intramolecular ring closure reaction with a substituent adjacent to the reactive site of the coupler.
The dye residue contained in the substituent group dissociates to release a diffusible dye. In particular, after oxidative coupling of an aromatic primary amino developer to the 4-position of the aniline nucleus, the phenol nucleus or the sulfonamide group containing the dye moiety located at the 3-position of the phenol nucleus or the aniline nucleus. As a result, a diffusible dye having a sulfinic acid group is released. The diffusible dye-releasing coupler used in this type B is US Pat. No. 3,443.
No. 940 and No. 3734726, Japanese Patent Publication No. 48-32129, etc. As a result of development, Type C is oxidized by an oxidized auxiliary agent to open the ring, and is decomposed with an alkali to release a diffusible dye. Compounds such as hydroquinones and 3-pyrazolidones can be used as auxiliary agents that open the ring by this oxidation. Dye image-forming materials of this type are described in U.S. Pat.
No. 062, Mukai No. 3728113, Mukai No. 3880658
Belgian Patent No. 796041, Belgian Patent No. 796042
No. Specification, Tokuseki No. 48-33826 and No. 49-1
It is described in Publication No. 14424 and the like. The third method is
This method uses a dye image-forming substance that releases a diffusible dye that is cleaved with an alkali, but does not substantially cleave in the presence of an oxidized developer. It is described in Publication No. 49-111628.

As the dye moiety in the above-mentioned various dye image-forming materials, various dyes such as azo dyes, azomethine dyes, anthraquinone dyes, azine dyes, and indophenol dyes can be used. Leuco dyes as shown in Japanese Patent Publications No. 48-66440 and No. 49-1111628, auxochromes as shown in Japanese Patent Publication No. 36-1123, Japanese Patent Application Laid-open No. 111628-1980, No. 50-115528, etc. It is also possible to use shift-type dyes obtained by acylating such as diazonium compounds such as those described in Tokkokki No. 49-10035, or couplers that can react with oxidation of a color developing agent to form a dye. . In the first and third methods, if a negative silver halide emulsion is used for development, a positive diffusion transfer image is obtained.

On the other hand, the second method provides a negative diffusion transfer image by performing development using a negative silver halide emulsion.
For this reason, since the second method requires an inversion operation, for example, a direct positive emulsion, that is, US Pat.
No. 982, No. 259255 and No. 32275
Internal latent image type emulsions as described in British Patent No. 443245, Oka No. 462730, U.S. Patent No. 2005837, U.S. Patent No. 2541472 and U.S. Pat. A coupler emulsion is used. Alternatively, a layer containing a diffusible dye-releasing coupler and physical development nuclei provided adjacent to a negative-working silver halide emulsion layer may be treated with a developer containing a silver halide solvent. Specific examples of this are described in US Pat. No. 3,243,294 and US Pat. No. 3,630,731. Additionally diffused adjacent to the negative-working silver halide emulsion layer containing compounds (so-called DIR substances) that react with the oxidation products of the development agent to release development inhibitors such as 1-phenyl-5-mercaptotetrazole. A layer containing a dye-releasing coupler and a spontaneously reducible metal salt may be provided. Specific examples of this include U.S. Patent Nos. 3,148,062, 3,227,551, and 3
No. 227554, No. 3364022, No. 3701
Specification No. 783, Tsubaki Kosho No. 43-21778 and No. 4
It is described in Publication No. 7-49611 and the like. The present invention
Any combination of negative-working silver halide emulsions and dye image-forming substances may be used, and any method for providing negative and positive dye images may be selected. The dye image-forming substance used in the present invention is contained in a hydrophilic protective colloid such as gelatin or polyvinyl alcohol, which is a carrier of the silver halide emulsion layer or its adjacent layer in the light-sensitive element, depending on the type of the dye image-forming substance. It can be dispersed in various ways.

For example, the color image-forming substance used in the present invention is dissolved in as little organic solvent as possible, and is dissolved in a hydrophilic protective colloid such as gelatin or polyvinyl alcohol, which is a carrier for the silver halide emulsion layer or its adjacent layer in the photosensitive element. distributed to

As the organic solvent, a high boiling point solvent, a low boiling point solvent that can be removed from the dispersion by evaporation, or an easily soluble organic solvent can be used alone or in combination. Particularly useful high-boiling solvents in the present invention include N-n-butylacetanilide, diethyl laurylamide, dibutyl laurylamide, dibutyl phthalate, tricresyl phosphate, triphenyl phosphate, and the like.

As the low boiling point solvent, ethyl acetate, methyl acetate, 4-methylcyclohexanone, etc. are useful. After coating, low-boiling solvents are removed by evaporation during drying, or prior to coating,
It can also be removed by the method described in No. 801171. As the organic solvent that is easily soluble in water, 2-methoxyethyl, dimethylformamide, etc. can be used, and these solvents can be removed by the method described in US Pat. No. 3,396,027. Also, various lipophilic polymers can be used instead of or in addition to the high boiling point solvent. Examples of this type of lipophilic polymer include polyvinyl acetate, polyacrylic ester, and polyester consisting of a polyhydric alcohol and a polybasic acid. Tokuko Sho 43-13837
The methods described in No. 48-32131, Mochiseki No. 50-17637, or U.S. Patent No. 32173 are useful for dispersing color image-forming substances used in the method of the present invention. . Also, carboxyl group or
Color image-forming substances having water-soluble groups such as sulfo groups can be used by dissolving them in water or an alkaline aqueous solution and then dispersing them in a hydrophilic protective coid. Can be used together. Further, the color image forming substance used in the present invention is disclosed in Japanese Patent Publication No. 48-32131
They may be directly dispersed in the hydrophilic protective colloids described in US Pat.

The amount of color imaging material that can be used in the present invention can vary widely depending on the compound used and the desired result, but may, for example, range from about 0.5% to 0.5% in the water-soluble organic colloid coating solution being applied. Preferably, about 10 weight percent is used.

Additionally, sulfites, such as those described in U.S. Pat. No. 3,287,133, may be present to stabilize the dispersed color imaging material.

When performing three-color color photographic processes, it is advantageous to use an interlayer in the light-sensitive element.

The intermediate layer may include hydrophilic polymers such as gelatin, derivative gelatin, polyacrylamide, partially hydrolyzed polyvinyl acetate, hydroxypropyl cellulose, or mixtures thereof, as well as those described in U.S. Pat. No. 3,625-5. The base is made of a porous polymer formed from a latex of a hydrophilic polymer and a hydrophobic polymer. In order to prevent color mixing due to diffusion of the oxidizing agent into other layers, a coupler, JP-A-48-1, is placed in the middle.
An amidrazone compound described in Japanese Patent No. 5532, a hydrazone compound described in West German Patent No. 2123268, or a so-called interlayer interaction inhibitor can also be added. Examples of the support for the photosensitive element of the present invention include paper, glass, cellulose nitrate, cellulose acetate, polypynylacetal, polystyrene, polyethylene terephthalate,
Various natural or synthetic polymers such as polypropylene and polyethylene can be used and may be transparent or opaque depending on the purpose.
The water vapor permeable supports or oxygen barrier supports described in the above specification can also be used advantageously. Furthermore, when a transparent support is used, it should be colored to the extent that it does not interfere with exposure and observation of the formed image, but prevents the silver halide emulsion layer from being fogged during processing due to light rays passing from the edges of the support. can be done. After exposure, the photosensitive element described in detail above is superimposed with an image receiving element described below, and generally processed by spreading an alkaline processing liquid between the two elements.

When using a dye developer as a color image forming substance in a dye diffusion transfer material, when an alkaline processing liquid is applied,
Ha in the exposed area. Reduction of silver genide and oxidation of dye developer occur, and the oxidized dye developer has low diffusivity in the alkaline processing solution and is fixed near the reduced silver halide. On the other hand, unoxidized dye developer is generally insoluble in a neutral aqueous solution, but becomes soluble and diffusible in an alkaline processing solution, and when the dye developer in the unexposed area is exposed to the alkaline processing solution, it becomes Functions as a diffusible dye. (Thus, the term diffusible dye in the description above and below is defined to include the diffusible dye developer in alkaline as well as the diffusible dye released from the color image-forming material.) Also. When a non-diffusible coupler that can undergo a coupling reaction with the oxidized developing agent described above is used as a dye image-forming substance, application of an alkaline processing solution results in a coupling reaction between the oxidized form of the developing agent and the coupler, or A subsequent closure reaction releases the soluble and diffusible dye into the alkaline processing solution. In addition, when a non-diffusible compound that releases a diffusible dye upon decomposition with an alkali is used as a dye image-forming substance, the reduction of silver halide in the exposed area and the conversion of the dye image-forming substance are performed. Oxidation occurs and the oxidized dye imaging material releases diffusible dye as a result of further ring closure reactions. Alternatively, an alkaline processing solution is allowed to act in the presence of a silver halide developer, whereby the developer is oxidized, the oxidized developer oxidizes the dye image forming material, and the oxidized dye image is formed. The substance decomposes and releases a diffusible dye.

Also, when using a dye image-forming material that releases a diffusible dye when treated with an alkali, but in the presence of an oxidized developer, cleavage does not substantially occur, the cleavage occurs in the phosphorescent area due to the reduction of silver halide. Due to the presence of oxidized developer, no diffusible dye is produced, but in the unexposed areas, since no oxidized developer is present, the dye image-forming material is cleaved by alkali to produce a diffusible dye.

The image receiving element carrying the silver rust salt or diffusible dye diffusely transferred from the photosensitive element can be appropriately selected depending on the purpose as described below.

As the support for the image-receiving element, various materials similar to those for the photosensitive element can be used depending on the purpose.

The support of the image receiving element may also be transparent or opaque. It is essential that the image receiving element has an image receiving layer containing a silver precipitant or mordant.

As the silver precipitant or soot beam agent suitable for the image-receiving layer of the image-receiving element, any agent can be used as long as it has a favorable mordanting effect on the silver salt or diffusible dye that is diffused and transferred. Examples of silver precipitants that can be used in the photographic material for silver salt diffusion transfer of the present invention include sulfide, selenide, polysulfide, polyselenide,
Known silver such as thioureas, heavy metals, heavy metal salts, stannous halides, fogged silver halides, curly silver and salts of heavy metals with compounds such as thioacetamides, dithiooxamides and dithioburets. Precipitating agents are included.

Examples of silver precipitants and image receiving elements containing such silver precipitants as described above include U.S. Pat. No. 2,698,237;
No. 82, No. 2698245, No. 2774667, No. 2823122, No. 3396018, and No. 3369901. especially,
Colloids of noble metals such as silver, gold, platinum, palladium, etc. are useful as silver precipitants. A silver precipitant is made in the presence of a proteinaceous colloid such as gelatin and applied onto the image receiving sheet. The silver precipitant can be formed in the image-receiving layer or can be applied by precipitating or vapor depositing a suitable silver precipitant onto the surface of the image-receiving layer or sheet. Also, for example, silica, bentonite,
Colloids and colloidal particles such as diatomaceous earth, fine glass, metal oxides such as titanium dioxide, colloidal alumina, fine particles of aluminum oxide, and zirconium oxide can also be contained in the image-receiving layer together with a silver precipitant.Dye diffusion of the present invention As a mordant that can be used in the transfer material, when an acidic dye or an anionic dye is used as a mordant, as a soot dye, a polymer of an aminoguanidine derivative of vinyl methyl ketone, as described in U.S. Pat. No. 2, No. 2,156; Poly 4-vinylpyridine as described in U.S. Pat. No. 3,148,061, U.S. Pat. No. 37,096
Styrene/N-(3-maleimidopropyl(-N,N-dimethyl-N-(4-phenylbenzyl)ammonium chloride polymer) as described in U.S. Pat.
Polymers containing N-substituted maleimide units as described in U.S. Pat. , cetyltrimethylammonium bromide, methyltri-n-lauryl ammonium para-toluenesulfonate, methyl-ethyl-cetylsulfonium iodide, benzyl-toluene-phenylphosphonium chloride, and the like are useful.

In addition to these soot staining compounds, compounds containing polyvalent metals such as thorium, aluminum, and zirconium also have a soot beam effect on anionic dye image forming substances. These carrier compounds include films such as gelatin, derivative gelatin such as acid-treated gelatin, polyvinyl alcohol, polyacrylamide, polypynyl methyl ether, hydroxyethyl cellulose, N-methoxymethyl polyhexyl methylene adipamide, polyvinyl pyrrolidone, etc. Preferably, the film is formed together with a forming compound. When the dye image-forming substance is a dye-forming component such as a diffusible coupler, the image-receiving layer contains other coupling components that react with this component to form the dye, such as p-phenylenediamine derivatives and oxidizing agents or diazonium compounds. Contains.
Image-receiving elements containing this type of image-receiving layer include US Pat.
No. 98244, No. 2698798, No. 28027
No. 35, No. 3676124, British Patent No. 11584
40 and No. 1157507 can be used. Further, a toning agent can also be used to improve the color tone of the transferred image. This color toning agent is added in the alkaline processing composition, in the halogenated emulsion,
It is added to the image-receiving layer or to a layer above the image-receiving layer. Examples of color toners used include 2-mercaptothiazonine, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-thionimidazo-1''dene, 2-mercapto-2-methyloxazoline, and 2-thionimidazoline. Included are selenotetrazole and 5-captotetrazole as described in US Pat. No. 3,295,971 and US Pat. No. 2,699,393. Furthermore, as described in Japanese Patent Application Laid-Open No. 50-477626, which is a special example, a method of incorporating a soot agent into the alkaline processing liquid can also be advantageously used in the method of the present invention.

If what is diffusely transferred to the image-receiving layer is not a dye but a leuco dye or a dye precursor, an oxidizing agent, a color developing agent, or a diazonium compound may be contained in order to convert these into dyes. is necessary. As an image receiving element containing these oxidizing agents, color developing agents, diazonium compounds, etc., US Pat.
4y, French Patent No. 26 Group 7, French Patent No. 3676124, French Patent No. 2232776, French Patent No. 2232777, Samurai Sekisho No. 50-80131, etc. Compounds that convert dyes or dye precursors into dyes can also be used. Furthermore, the method of causing an oxidizing agent to be present in the alkaline processing solution as described in French Patent No. 32776, French Patent No. 32777, Japanese Patent Application Laid-Open No. 50-104023, etc. can also be used for the diffusion transfer material of the present invention. It can be used for. In addition, the image-receiving element may also contain various additives commonly used in photographic technology, such as ultraviolet absorbers and optical brighteners.

Furthermore, it is also possible to provide intermediate layers between the silver halide emulsion layers, color image-forming material layers, soot-dyed layers, etc. constituting the light-sensitive element and the image-receiving element.

In addition to hydrophilic colloids such as gelatin, these intermediate layers can contain various additives used in ordinary diffusion transfer materials. The alkaline processing composition used in the present invention contains components necessary for developing the silver halide emulsion and forming a diffusible dye, has strong alkalinity, and generally has a pH
It is more than IO.

The alkaline treatment composition contains compounds such as alkali metal or alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, or sodium carbonate, diethylamine, and the like. Antifoggants such as penzotriazole can also be added to the alkaline processing composition. Also, Tokuiso Raku 50-1
It is also possible to contain the dissolution promoter described in No. 24727. The alkaline treatment composition may also contain viscosity increasing compounds such as high molecular weight viscosity increasing compounds which are inert to alkaline solutions such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

The concentration of the viscosity enhancer is preferably about 1-5% by weight of the alkaline treating composition, which is about 100% by weight of the alkaline treating composition.
It provides a viscosity of ~200,000 centipoise, which not only facilitates uniform spread of the alkaline processing composition during processing, but also concentrates the alkaline processing composition by transferring aqueous solvent to the light-sensitive and image-receiving elements during processing. When used, a non-flowing film is formed to help unite the film 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. The alkaline processing composition may also contain a light-absorbing substance such as carbon black to prevent the silver halide emulsion from being fogged by external light during processing. It is desirable in the present invention to add onium compounds, such as quaternary ammonium, to the composition. Particularly useful onium compounds include 1-benzyl-2-picolinium bromide, 1-(3-bromopropyl)
-2-picolinium-p-toluenesulfonic acid, 1-phenethyl-2-picolinium bromide, 2,4-dimethyl-1-phenethylpyridinium bromide, Q-picolin-B-naphthoylmethyl bromide, N,N-diethyl piberi Typical preferred compounds include dinnium bromide, phenethyltrimethylphosphonium bromide, dodecyldimethylsulfonate p-toluenesulfonium, and onium bromide as described in U.S. Pat. Nos. 3,173,786 and 3,411,904. Compounds can also be used in the invention. In the second system, in which the silver halide oxidized product described above reacts with a coupler, a dye image-forming substance, to release a diffusible dye, a dye image is formed in the presence of an aromatic primary amine. However, developing agents such as aromatic primary amines are included in the alkaline processing composition.

In this method, Hakama Kosho No. 41-17184, No. 4
The alkaline processing composition additives described in JP-A No. 3-21778, JP-A-47-325, and the like are useful in the present invention. Furthermore, the treatment composition may contain titanium dioxide, barium sulfate, zinc oxide, alumina, barium stearate, calcium carbonate, kaolin, magnesium oxide, etc. as a light reflecting agent.

In addition, as a light reflection method, Tokukan Sho 46-486 and Sho 47
A method such as that described in Japanese Patent No.-447 may also be used. Furthermore, optical brighteners such as stilbene, coumarin, triazine, oxazole, etc. may be used in combination with the light reflecting agent. Carbon black and indicator dyes such as those described in Hakamakai Publications No. 47-26, No. 47-27, and No. 47-28 can also be added to the alkali treatment composition as opacifying agents. It is also possible to include development inhibitors, such as 1-phenyl-5-mercaptotetrazole, benzylaminopurine, etc., either in the light-sensitive element, the image-receiving element or the alkali processing composition.

It is also advantageous in the present invention to include an auxiliary developer such as a hydroquinone derivative such as p-tolylhydroquinone, a catechol derivative, or a phenidone either in the photosensitive element, the image receiving element or the alkaline processing composition. Samurai Publication No. 35-17383, U.S. Pat.
Any of the auxiliary developers described in the specifications such as No. 8, No. 49-8344, No. 49-842, and No. 50-634 can be advantageously used in the present invention. The auxiliary developer can be added to the light-sensitive element or image-receiving element by being dispersed in a manner similar to the dispersion of the dye image-forming material. Further, an auxiliary developer may be uniformly contained in the image-receiving element as described in Japanese Patent Application Publication No. 49-131134. Also, U.S. Patent No. 357933
Desensitizers such as those described in No. 3 can also be used. The alkaline treatment composition used in the present invention is preferably housed in a breakable container.

Such containers contain the alkaline treatment composition in a cavity created by folding a sheet of liquid- and air-impermeable material and sealing each bridge, so that when the film unit passes through the pressurized odor, Advantageously, the internal pressure applied to the alkaline treatment composition causes it to rupture at a defined point to release its contents. Materials used to form the container include a laminate of polyethylene terephthalate/polyvinyl alcohol/polyethylene, a laminate of lead foil/vinyl chloride-vinyl acetate copolymer, and the like. These containers are preferably secured along the front edge of the film unit and are adapted to spread the contained liquid substantially in one direction onto the surface of the photosensitive element. Preferred examples of containers are described in U.S. Pat. 2543
No. 181, No. 2643886, No. 2653732
No. 2723051, No. 3056491, No. 305 92, No. 3152515 and No. 3
It is described in the specification of No. 173580 and the like. In the present invention, it is sufficient to apply an alkaline processing liquid to the photosensitive element and the image receiving element, which have been imagewise exposed as described above, in a superimposed state. may exist separately before exposure, or may be a unit in which both are combined.

After processing, the photosensitive element and the image receiving element may be integrated, or the photosensitive element and the image receiving element may be separated. U.S. Patent No. 3415644, U.S. Patent No. 3415645, U.S. Patent No. 3415646, U.S. Patent No. 3473925, U.S. Patent No. 357
No. 3042, No. 3573043, No. 35941M
Any of the film units described in Belgian Patent No. 3594165, Belgian Patent No. 3615421, Belgian Patent No. 75795y or Belgian Patent No. 75796p can be used in the present invention. In the practice of the present invention, the surface layer of the image-receiving element may contain hydrophilic colloids such as gelatin, derivatized gelatin, starch, dextran, polyvinylpyrrolidone, gum arabic, ruboboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, guar gum, gum acacia, etc. A hydrophilic binder layer containing .

When the photosensitive element and the image-receiving element are separated to obtain an image after the development process, a so-called release agent is used. The stripping agent is contained on the surface of the silver halide emulsion layer, on the image receiving layer containing the silver precipitant or soot beam agent, or in the processing composition. As a suitable release agent, one having a composition different from that of the binder used in the silver halide emulsion layer is generally used. For example, alkali-permeable polysaccharides,
hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, 4,4'-dihydroxyphenol glucose, sucrose, sorbitol,
inositol, resorcinol, ficate sodium salt, zinc oxide, microparticle polyethylene, microparticle polytetrafluoroethylene, polypynylpyrrolidone/polyvinylhydrodiene phthalate as described in U.S. Pat. No. 3,325,283, U.S. Pat. No. 3,376,137 As described in the specification, ethylene-maleic anhydride copolymers and the like are useful. Each layer constituting the diffusion transfer material of the present invention contains a surfactant,
For example, sapinin, anionic surfactants such as alkylarylsulfonic acid series as described in US Pat. No. 260-81, amphoteric surfactants as described in US Pat. No. 313-16, and British Patent No. A coating composition containing a water-soluble adduct of Gridol and alkyl fer/fer as described in No. 878 is produced by a coating method as described below. Furthermore, to facilitate the above-mentioned application, the coating composition may contain various thickening agents, such as acrylic acid-based polymers such as high molecular weight polyacrylamide, and other bondable polymers in the coating composition. Anionic polymers that exhibit a thickening effect through interaction with the polymer are effective.

The diffusion transfer material of the present invention can be manufactured by applying various coating methods such as a dip coating method, an air knife method, a curtain coating method, or an extrusion coating method using a hopper as described in U.S. Pat. No. 2,681,294. .

If desired, two or more layers can be added to the U.S. Pat.
1791 and British Patent No. 837,095. The present invention can also be effectively applied to the method of obtaining a silver halide emulsion layer by vacuum deposition as described in British Patent No. 9 Ori 453 and US Pat. No. 3,219,451. Each of the curable layers constituting the diffusion transfer material of the present invention can be cured using an inorganic or organic curing agent alone or in combination as appropriate.

Examples of curing agents used in the present invention include aldehydes such as formaldehyde and succinic aldehyde, blocked aldehydes, ketones, carboxylic acid converters, carbonic acid derivatives, sulfonate esters, sulfonyl halides, vinyl sulfones, and activated Examples include halides, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, and mixed functional curing agents.

The present invention will be explained in more detail with reference to Examples below.
The embodiment of the present invention is not limited to this.

Example 1 1 A neutralizing layer containing the following various neutralizing agents was coated on a transparent polyethylene terephthalate film base having a film thickness of 100 mm.

63 parts of poly(ethylene-maleic anhydride), 129 parts of n-butyl alcohol, and 0.2 parts of 85% phosphoric acid were mixed and refluxed for one hour.

Then, 20 parts of acetone was added to 10 parts of the refluxed mixture.
0' was added to give a dry film thickness of 23 r'.
'B' A coating solution consisting of a mixed solvent of acetone and ethyl acetate containing Exemplary Compound '71 and polydiacetone acrylamide in a weight ratio of 2:1 was adjusted to a viscosity of 200 centipoise and coated to a thickness of 23 mounds of dried pus.

'C} A coating solution consisting of a mixed solvent of acetone and ethyl acetate containing exemplified compound {7- was adjusted to a viscosity of 200 centipoise and coated in a dry film thickness of 18 mounds.

(2) A coating solution consisting of an acetone-ethyl acetate mixed solvent containing exemplified compound (11) and polymethyl methacrylate in a weight ratio of 2:1 was adjusted to a viscosity of 200 centipoise and coated to a dry film thickness.

{E' A coating solution consisting of an acetone-ethyl acetate mixed solvent containing exemplified compound (11) was adjusted to a viscosity of 200 centipoise and coated to a dry film thickness of 19 centipoise. 'F
} A coating solution prepared by dissolving the exemplified compound in a mixed solvent of methyl ethyl ketone and ethanol was coated to a dry and thick coating of 23 mm.

(b) A coating solution prepared by dissolving exemplified compound (21) in an acetone-n-phthyl acetate mixed solvent was applied to give a dry film thickness of 23 peaks.

5) A coating solution prepared by dissolving exemplified compound (25) in an acetone-butyl cellosolve mixed solvent was applied to give a dry film thickness of 23 cm.

(1) A coating solution prepared by dissolving exemplified compound (34) in an acetone-cyclohexanone mixed solvent was coated to a dry film thickness of 23 mm.

0) A coating solution prepared by dissolving exemplified compound (36) in an acetone-cyclohexanone mixed solvent was applied to give a dry film thickness of 23 mm.

Next, on the neutralization layer of each of (J) obtained as above,
Butyl acrylate/diacetone acrylamide/styrene/methacrylic acid 60/30/4/6 as intermediate layer
copolymer and polyacrylamide to copolymer
/40 (weight ratio) to a dry film thickness of 5
I applied it so that it was smooth.

Furthermore, a coating liquid having the composition shown below was coated as an image-receiving layer on this intermediate layer so as to have a dry film thickness of 6 mm.

Coating liquid formulation for image-receiving layer Polypynyl alcohol 12 t water
340 [Poly-4 vinyl pyridine 6-glacial acetic acid
3 [Emalgen 1082% aqueous solution
Image-receiving element containing a neutralizing layer of {■～(J) in No.5
) was left in 25o0 relative humidity 60% for 7 days.

Image-receiving element (1) showed deformation in the coated film and became opaque, but no such phenomenon occurred in 'B' to (J). Furthermore, the light transmittance (%) at 60 km is shown in Table 1.
Table 1 From the results of Table 1, image receiving elements containing the compound of the present invention {B
- (J) exhibit higher transmittance than image-receiving element (2) containing a neutralizing agent other than the compound of the present invention.

Example 2 A photosensitive element was prepared by sequentially applying the following layers to baryta paper overcoated with gelatin-subbed cellulose acetate butyrate.

[1} A gelatin light-sensitive layer containing 1.6 μm/l of silver in a silver iodobromide emulsion and having a dry thickness of 6 μm was coated.

■ Gelatin was applied at a rate of 1.5 coats/day.

The image-receiving element was prepared by mixing liquids A and B having the following composition on the mother, legs and (H) of the image-receiving element prepared up to the above in Example 11 to prepare a coating liquid. Image-receiving elements (K), (L), (N) and (M) were prepared by applying the liquid to a wet film thickness of 50 mm.Liquid A Snowtex
50 I 0.1N sodium sulfide aqueous solution
0.5 [Liquid B 0.1N cadmium acetate aqueous solution
3. Allosol OTI% aqueous solution 2.
Water 20 [The alkaline treatment composition used had the following formulation.

Alkaline treatment composition formulation water 100% sodium sulfite 5.8% carboxymethyl cellulose 5.8% sodium hydroxide
2.7 Sodium cutiosulfate
3.3 Tahydroquine
5.0 Tametol
1.8 Emazol 5.Z A processing bag made of this alkaline processing composition is placed between the photosensitive element exposed by the wedge and the image receiving element, and pressure is applied with a roller pressure odor to destroy the processing bag and develop. Processed.

The photosensitive element and image-receiving element were peeled off after 6 rounds of development after room temperature development. The maximum density (Dm3x
) and minimum density (Dmin) were measured, and the results are shown in Table 10. Table {1 0 From the results of Table 0, the image receiving element (K) has low DMx and Dm
The image receiving elements (L) to (N) containing the compound of the present invention not only have a high OMx and a low D sail, but also have distortion in the obtained images. It was very clear.

Example 3 A photosensitive element was prepared by sequentially coating the following layers on a gelatin-subbed acetylcellulose film base.

[1' Cyan dye developer layer 1,4-bis(Q-methyl-3-hydroquinonylethylamide/)-5,8-dihydroxyanthraquinone in a mixed solvent of N-n-butylacetanilide and 4-methylcyclohexanone The dissolved solution was emulsified and dispersed in an aqueous gelatin solution containing Alkanol B as a dispersant, and the resulting dye developer dispersion was coated with 4.2 g of gelatin and 2.0 g of cyan dye developer.

'21 Red-sensitive emulsion layer A red-sensitive silver iodobromide emulsion containing 0.6 m/m of silver and 2.4 g/m of gelatin.
I applied it to give it a finishing touch.

'31 Middle class It was coated with gelatin 2.0 ml/glue.

'4} Magenta dye developer layer 2-[p-(8-hydroquinonylethyl)phenylazo]-41n-propoxy 1-naphthol with N-n-butylacetanilide and 4
- emulsifying and dispersing a solution dissolved in a mixed solvent of methylcyclohexanone in an aqueous gelatin solution containing alkanol B as a dispersant;
The magenta dye developer was coated at a rate of 1.3 coats/coat.

'51 Green-sensitive emulsion layer A green-sensitive silver iodobromide emulsion containing 1.2 g of silver and 1.2 g of gelatin.
Evening: I applied it to my pillow.

'61 middle class The gelatin was coated at a ratio of 1.5 coats/coat.

'7' Yellow dye developer layer 1-phenyl-3-N1n
-hexylcarboxamide 4-[P-2,5'-dihydroxyphenethyl)phenylazo]-15-pyrazolone dissolved in a mixed solvent of N,N-jethyl laurylamide and ethyl acetate was used as a dispersing agent in alkali. A dye developer solution obtained by emulsifying and dispersing a gelatin aqueous solution containing 1.12 parts of gelatin and 0.0 parts of yellow dye developer was added.
5th evening/Applyed to leave a lasting impression.

Leg: Blue-sensitive emulsion layer: Sound-sensitive silver iodobromide was coated at a ratio of 0.6 m/m of silver and 0.6 m/m of gelatin.

'91 Protective layer 4 - A solution of methylphenylhydroquinone dissolved in N,N-jetyl laurylamide was emulsified and dispersed in an aqueous gelatin solution with alkanol B as a dispersant, and the resulting coating liquid was added to the coating liquid loo'. 2% mucochloric acid aqueous solution 5'
After adding 4'-methylphenylhydroquinone 0.
The coating was applied so that the coating was coated at a coating rate of 5 coats/finish and gelatin was coated at a coating ratio of 0.6 coats/coat.

The alkaline treatment composition used had the following formulation. Alkaline treatment composition formulation water 100 [potassium hydroxide 11.2 tacarboxymethylcellulose 5] penzotriazole
7.0 N-phenethyl-Q-picolinium bromide 2.0 Penzylaminopurine 0.12 Titanium dioxide 50 It was placed between the image receiving element consisting of element wind (J), and after exposure with a wedge, pressure was applied with a roller pressure odor, the processing bag was destroyed, and development processing was carried out.

Bound photographic element 25qo, cyan using red, green and blue filters after storage for 78 hours in 60% relative humidity.
The maximum density (DMX) and minimum density (D ship n) of each dye image of ○, magenta (M), and yellow (Y) were measured, and the obtained results are shown in Taiichim. Table-m From the results of Table-m, the image receiving element ■ has a low ○ cape x, and Dmin
The image receiving elements 'B}~(J) containing the compound of the present invention were not only high but also distorted in the dye images obtained.
not only had a high Dm fence and a low Dmin, but also the obtained dye image was clear with no distortion.

Further, yellow stay was observed in the image-receiving element (1), but no stain was observed in the image-receiving elements [B' to (J)]. Example 4 A photosensitive element was prepared by sequentially coating the following layers on an acetylcellulose film base subbed with gelatin.

○｝ Line-sensitive silver bromide emulsion with silver 1.0% / finish, gelatin 2
．． 6/1-Phenyl-31 (3,5-disulfobenzamide) as a tiger and magenta pigment-forming diffusion puller
-4-(6-Hydroxy-4-bentadecylphenylazo)-15-pidrazolone potassium neutral salt 0.8 m/m was applied.

{21 Gelatin was coated to give a coating of 2.0 g/l. Samples of Example-1 coated up to the intermediate layer ■, {C', {E'
, (J) and (H), the following layers were sequentially applied to prepare image receiving elements (0), (P), (Q), (R) and (S). {1) Light reflective layer Titanium dioxide was coated 30 times a day and gelatin was coated 30 times a day.

'21 Image-receiving layer: 5 coats of gelatin and 2 coats of octadecyltributylammonium bromide were coated.

‘3} Protective layer The gelatin was coated to a thickness of 0.6.

The alkaline treatment composition used had the following formulation. Alkaline treatment composition formulation 4-Amino-N-ethyl-N-8-hydroxyethylaniline hydrochloride 3 Hydroxyethyl cellulose 3.2 Tapiveridinohexose reductone 0.08 Sodium hydroxide
A processing bag containing the alkaline processing composition was placed between the photosensitive element and the image-receiving element, and pressure was applied with a roller pressure tool to destroy the processing bag and development processing was carried out.

Three minutes after the development process, the photosensitive element and the image-receiving element are peeled off, and the peeled image-receiving element is placed in a
The samples were stored for several days, and Dmax and Dmin were measured, and the results are shown in Table-W. Table-W Image-receiving element (0) not only had low Dmax and high Dmln, but also showed distortion in the obtained dye image, but image-receiving elements (P) to (S) containing the compound of the present invention were ○ Not only was the m-value high and the Dm'n low, but the obtained dye image was clear and free of distortion.

Example-5 Samples of Example-1 coated up to the intermediate layer ■, Ni, 'E'
, (1), and (H) and coat the following layers on top of this layer in sequence to form the photographic elements, tB}, 'C}, ■, and 'E'.
Image-receiving layer 11 was prepared by applying poly(vinylbenzyltrimethylammonium) chloride 2 times a day and polyvinyl alcohol (Nippon Gohsenol NH-26) 4 times a day.

'2' Light reflective layer Titanium dioxide was applied 20 times a day and gelatin was applied 2 times a day.

■ Opacifying layer Gelatin was coated 2 times a day and carbon black was coated twice a day.

[41] Yellow dye image-forming substance-containing layer A yellow dye image-forming substance having the following structure was coated in a ratio of 1 coat/layer and gelatin 1 coat/layer.

The same sound-sensitive emulsion layer contains sound-sensitive silver iodobromide of 0.6 m/m of silver and 0.6 m/m of gelatin.
I applied it to finish it off.

■ Protective layer The gelatin was applied to a thickness of 0.5.

The cover sheet used a transparent polyethylene terephthalate film base.

The alkaline treatment composition used had the following formulation.

Alkaline treatment composition formulation Hydroxyethyl cellulose 2.5 Sodium hydroxide 6.0 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.8 Potassium todide 1 Female 5
-Methylbenzotriazole 80 ot-butylhydroquinone 80 ot Sodium sulfate 0.2 tacarbon black
4t water
A processing bag made of 100 W and this alkaline processing composition was placed between the photographic element and the cover sheet, and after wedge exposure, pressure was applied with a roller pressure odor to destroy the processing bag and development processing was carried out.

Photographic elements with color images were placed at 5-°C and 80% relative humidity.
The samples were stored for 3 days in a container, and Dmax and D skin were measured, and the results are shown in Table V. Table-V photo element bad is Dm pine is low D
Not only did the skin have a high Dmax, but distortion was observed in the obtained pigment image, but the photographic element leg ~ [E] containing the compound of the present invention not only had a high Dmax and a low D skin, but the obtained pigment image No distortion was observed and the image was clear.

Claims (1)

[Scope of Claims] 1. A neutralization layer for lowering the pH in the system after applying the alkaline treatment composition, and the neutralization layer contains at least one carboxyl group or hydrolyzes the carboxyl group. 1. A photographic material for diffusion transfer, comprising a copolymer containing an ethylenically unsaturated monomer having a forming group and a monomer having at least one fluorine atom as copolymer components. 2. Diffusion transfer according to claim 1, wherein the monomer having at least one carboxyl group or a group that generates a carboxyl group by hydrolysis is a compound represented by the following general formula [I]. Photographic materials. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom, a lower alkyl group, -COO
R_4, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or - Phenyl group substituted with COOR^4, R_2, R_
3 is a hydrogen atom, a halogen atom, a lower alkyl group, or -(CH_2)_n_-_1COOR_4, R_
4 represents a hydrogen atom or a lower alkyl group, and n represents an integer of 1 to 2. However, R_1, R_2 and R_3 may be the same or different groups, but at least one is a carboxyl group or a group that generates a carboxyl group by hydrolysis, and two carboxyl groups are further cyclized to form an anhydride. may be formed. [3] The photographic material for diffusion transfer according to claim 1, wherein the monomer having at least one fluorine atom is a compound represented by the following general formula [II]. General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_5, R_6, and R_7 may each be substituted with a hydrogen atom or a halogen atom, and R_8 may be substituted with a hydrogen atom, a halogen atom, or a fluorine atom, respectively. Number of carbon atoms: 1
~12 alkyl group, phenyl group optionally substituted with fluorine atom, phenyl group having lower alkyl group optionally substituted with fluorine atom, -(CH_2)_n_-_1C
OOR_9, -(CH_2)_n_-_1COR_9,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ -OCOR_9 or -OR_9, R_9 are hydrogen atoms, alkyl groups with 1 to 18 carbon atoms that may be substituted with fluorine atoms, and carbon-carbon bonds via oxygen atoms, respectively. The alkyl group having 1 to 18 carbon atoms or R_1_0 bonded to is a lower alkyl group which may be substituted with a fluorine atom, n is 1 or 2, and k is an integer of 1 to 5. However, R_5, R_6, R_7 and R_8 may be the same or different groups, but at least one of them is a group containing a fluorine atom. ]