JPH087426B2 - Diffusion transfer photographic element - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a silver salt diffusion transfer method and a color diffusion transfer method. More specifically, the so-called peeling type (peel apartment
Type) Diffusion transfer photographic element and a color diffusion transfer photographic element capable of being processed in a light chamber for observing a dye image without passing through a support after peeling after processing the integral type film unit.

(Prior Art) An image receiving element and a photosensitive element for forming a transferred image by a silver salt diffusion transfer method or a color diffusion transfer method, and a chemical reaction mechanism leading to image formation are well known. The conventional silver salt diffusion transfer photographic film unit and color diffusion transfer photographic film unit are roughly classified into a peeling type and a peeling-free type. One typical example of peeling type is peel apart type,
This is because the light-sensitive layer and the dye image-receiving layer are coated on separate supports, and after imagewise exposure, the light-sensitive element and the dye image-receiving element are superposed, the processing composition is developed therebetween, and then the dye image-receiving element is developed. By peeling off, the dye image transferred to the dye image-receiving layer is obtained.

The feature of this form is that the paint image formed on the image-receiving layer coated on the support can be observed directly, so there is no deterioration in image quality as seen in the peel-free type described below, and very excellent color. It is to show the reproduction. On the other hand, there is an inconvenience in that the light-sensitive element and the image-receiving element are superposed on each other in the camera, and the alkaline processing liquid becomes sticky after peeling and easily adheres to the surroundings, which is inconvenient in handling the processed film.

On the other hand, in the peel-free type, a dye image-receiving layer and a silver halide emulsion are coated between a transparent support and the other support, but the image-receiving layer and the silver halide emulsion layer are the same transparent. There are a form coated on a support and a form coated on another support.

In the former case, a white reflective layer is coated between the image receiving layer and the silver halide emulsion layer, and in the latter case, the processing composition developed between the image receiving layer and the silver halide emulsion layer is By containing the white pigment, the dye image transferred to the image receiving layer can be observed by reflected light.

The features of these stripping-free types are that they are very easy to handle because there is no sticking of the processing liquid and no inconvenience in handling due to the lamination of the film sheets as in the above-mentioned stripping type. However, on the other hand, since the color image is observed through the transparent support, the color saturation is reduced due to surface reflection, and the whiteness of the white background is insufficient due to insufficient reflectance of the white reflective layer. Inevitably lowers.

Further, since the used emulsion layer, pot, cover sheet and the like are not peeled off, there is a disadvantage that the thickness of the obtained print is too hot.

A high-quality image obtained by a peeling type color diffusion transfer unit and a diffusion transfer unit having the excellent handling property of a peeling-free type color diffusion transfer unit, at least on the same support, a dye image receiving layer, a peeling layer, The second release type is a type in which photosensitive elements are sequentially provided, and after the development of the alkaline processing composition, the dye image receiving element is peeled off at the release layer portion to obtain a transferred dye image. (Hereinafter, the second peelable type is referred to as a peelable monosheet type.) In the peelable monosheet type, the dye image formed on the image receiving layer coated on the support can be directly observed. Therefore, the image quality is not deteriorated and the color reproduction is very excellent. In addition, since the treatment liquid is not in contact with the release layer, the treatment liquid after peeling has no stickiness, and further, there is no inconvenience in handling due to the lamination of the film sheets.

In the peel-apart type diffusion transfer photographic method, in order to facilitate peeling when the image receiving sheet is peeled off from the photosensitive sheet, and to prevent the processing solution from forming a film and adhering and remaining on the image receiving layer. It is known that a release layer is provided as a film on the image receiving layer (however, on the developing solution development side).

Gum arabic (US Pat. Nos. 2,759,825 and 4,009,031) as materials for this type of release layer: hydroxyethyl cellulose (US Pat. No. 2,759,825, JP-A-47-8237)
No.): Methylcellulose, ethylcellulose, nitrocellulose (US Pat. No. 2,759,825): Cellulose acetate (Canada Patent 681,777): Cellulose acetate hydroenphthalate (Canada Patent 681,777)
JP, JP-A-47-41623): Carboxymethyl cellulose (British Patent No. 2,012,064): Cellulose derivative (JP-B-45-24075): Starch ether (JP-B-50-35820)
No.): Galactomannan (UK Patent 869,190): Pectin (US Pat. No. 2,759,825): Phthalated gelatin (Japanese Patent Publication No. 45-24075, Japanese Patent Publication No. 54-74431, 54-1265).
35): Sodium alginate (US Pat. No. 2,759,825
No.): Polyvinyl alcohol (US Pat. No. 2,759,825
No., British Patent No. 2,012,064, Japanese Patent Publication No. 45-24075): It is customary to use a water-soluble or hydrophilic polymer such as polymethacrylic acid (US Pat. No. 2,759,825).
The physical development nuclei in the image receiving layer are often altered due to its hygroscopicity, and the density and color tone of the transferred image are changed.Moreover, as the materials used as described above are many natural products, they are stored as raw materials. If it deteriorates easily, such as when it decomposes or molds while it is being used, there is concern about its stability over time, and since the coating solvent is water-based, the drying load is large and it takes a long time to dry. There were some drawbacks such as.

Further, the transferred silver image often has a metallic luster, or the transfer density is lowered due to transfer inhibition, which often causes problems.

In order to improve these points, vinyl acetate-maleic anhydride copolymer, methyl methacrylate-acrylic acid copolymer (above JP-B-45-15902): barbituric acid-formalin condensate (JP-B-49-4333): hydantoin-formalin condensation (JP-B-49-4334): Gelatin sufficiently reacted with dicarboxylic acid anhydride such as phthalic anhydride, and a graft copolymer with a monomer such as vinyl ester, vinyl ether, acrylic ester or a mixture thereof (JP It has been proposed to use a water-insoluble synthetic polymer such as JP-A-56-65133) as a material for the release layer.

As another improvement, US Pat. No. 4,366,227 discloses a release layer obtained by dispersing a terpolymer of ethylene, acrylic acid (or methacrylic acid) and methyl methacrylate (or methyl acrylate) in a water-soluble polymer such as hydroxyethyl cellulose. The use of is suggested.

However, these polymers have poor film-forming properties and it is difficult to form a thin and uniform coating film. As a result, there is a drawback that the image obtained by developing using an image receiving sheet using the polymer as a release layer is poor in uniformity, and undesired image unevenness is generated, resulting in a marked decrease in commercial value. or,
Regardless of the above-mentioned water-soluble or water-insoluble polymer, when an image receiving sheet using the polymer as a release layer is subjected to development processing at a temperature lower than room temperature, the adhered processing liquid component is dried and crystallized on the image surface to form an image. Has the drawback of being cloudy white, loose "dust" or cloudy.

Further, when an image receiving sheet using the polymer as a release layer is subjected to development processing at a temperature higher than room temperature, the release layer of the processing liquid is bad and the processing liquid adheres to the surface of the image receiving sheet.

In order to solve these problems, Japanese Patent Laid-Open No.
A polymer having a carboxylic acid-containing monomer unit of mol% or more and having a glass transition temperature (Tg) of less than 90 ° C. is proposed,
Butyl acrylate-co-methacrylic acid, butyl methacrylate-co-acrylic acid, hydroxyethyl methacrylate-co-acrylic acid and the like are used as preferred compounds.

When these are used, they are excellent in film-forming property, have no adverse effect on image formation, exhibit not only good releasability, but also improve various points such as residual treatment liquid on an image, image unevenness, and dusting.

However, the use of these release layer materials is at a level that is sufficiently satisfactory for the problem that the image is easily damaged by external force such as scratching in the case of release type (peeling apart type) sensitive material in which the image receiving layer is exposed. However, the improvement was strongly desired.

On the other hand, in the peelable monosheet type, a peeling layer is provided between the emulsion layer combined with the dye image-forming substance, the dye and the white image-receiving layer, and the emulsion layer is peeled off after the treatment. Therefore, the peeling layer in this case must maintain the adhesion between the image-receiving layer and the emulsion layer in an untreated state and be easy to peel after the treatment.

For this purpose, using the release layer material,
The following disadvantages were found.

First, the peelable mono-sheet type requires peeling from the state in contact with both upper and lower layers, so peeling is more difficult than peel-apart type. It was difficult to peel it off. As described above, the existence of the peeling time dependency of the peeling property significantly impairs the commercial value of the peelable diffusion transfer photograph. Further, as in the case of the peeling type (peel-apart type), this case also has a drawback that the image is easily damaged.

(Object of the present invention) The first object of the present invention is to provide a novel release layer showing a good release property over a wide processing temperature range and regardless of the elapsed time after the processing. To provide a transfer photographic element.

A second object of the present invention is to provide a diffusion transfer photographic element which provides a novel release layer which is less susceptible to damage to the image surface after release, i.e. which exhibits good scratch resistance.

Thirdly, an object of the present invention is to provide a photographic film unit for peeling type (peel apartment type and peelable monosheet type) diffusion transfer method, which includes the above-mentioned diffusion transfer photographic element. .

(Means for Solving Problems) An object of the present invention is to provide a diffusion transfer photographic unit having at least an image-receiving layer and a release layer made of a copolymer on a support, wherein the copolymer has the following general formula [I]. It was achieved by a diffusion transfer photographic element characterized by being a compound represented by

General formula [I] In the formula, X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Y represents a monovalent group containing at least one hydrocarbon group having 7 or more carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer whose homopolymer is soluble in water and / or aqueous alkali solution.

B represents a repeating unit derived from an ethylenically unsaturated monomer other than the above.

x, y and z represent the weight composition of each monomer component, and x
Is 10 to 90% by weight, y is 90 to 10% by weight, and z is 0.
To 30% by weight.

(Detailed Description of the Invention) Copolymer comprising a monomer containing at least one hydrocarbon group having 7 or more carbon atoms and a monomer whose homopolymer is soluble in water and / or aqueous alkali solution. It was an unexpected effect that I was able to overcome the above-mentioned problem using.

It has been confirmed that the release layer surface in the present invention forms a non-polar surface, which gives good release properties regardless of the length of the aging time after developing the treatment liquid or the treatment temperature. It is presumed to be the cause.

Further, in the release layer of the present invention, it is recognized that the release layer does not substantially diffuse even after release, and remains as a layer on the image-receiving sheet, which gives excellent scratch resistance. It is speculated that this is probably the reason.

Further, the present copolymer contains a large amount of repeating units having extremely hydrophobic groups, but on the other hand, its homopolymer such as acrylic acid is soluble in water and / or aqueous alkali solution. Since it contains various monomer components, it has moderate hydrophilicity and is free of image-forming substances that accompany or diffuse in the processing solution when the alkaline processing solution is developed during development. Therefore, it is considered that it does not hinder the formation of an image.

Furthermore, since the release layer copolymer of the present invention is a synthetic copolymer, it has excellent stability over time during production and storage.

Since the coating of the release layer can be performed by using an organic solvent such as alcohols, it is one of the features of the present invention that the drying load at the time of film formation is small.

The compound represented by formula (I) of the present invention will be described in detail below.

General formula [I] In the formula, X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group), and preferably a hydrogen atom or a methyl group.

Y represents a monovalent group containing at least one hydrocarbon group having 7 or more carbon atoms.

As the hydrocarbon group, an alkyl group having 7 or more carbon atoms (for example, n-octyl group, 2-ethylhexyl group,
n-decyl group, n-dodecyl group, n-hexadecyl group,
n- octadecyl) having 7 or more alkylene group having a carbon (e.g., CH _{2 n,} those _{n = 7,8,10,14,16, CH 10 H 21} CHCH 2 -), having 7 or more aralkyl group having a carbon ( For example Aralkylene groups having 7 or more carbon atoms (for example, Aryl groups having 7 or more carbon atoms (for example, tolyl group, 2-t
-Butylphenyl group, 4-t-butylphenyl group, 2,5
-Di-t-amylphenyl group, 4-t-octylphenyl group), arylene group having 7 or more carbon atoms (for example, Can be given. These groups may further have a substituent.

Among these, an alkyl group having 7 or more carbon atoms, an alkylene group, and an aryl group are preferable, and an alkyl group is particularly preferable. Particularly, those having 10 or more carbon atoms are preferable.

Represented by the general formula [I] of the present invention, As the ethylenically unsaturated monomer giving the repeating unit represented by, acrylic acid esters, methacrylic acid esters, substituted acrylamides, substituted methacrylamides, vinyl esters, and substituted styrenes are preferable.

Represented by the general formula [I] of the present invention, Examples of the ethylenically unsaturated monomer giving the repeating unit represented by the following are listed below, but are not limited thereto.

above The ethylenically unsaturated monomer that gives the repeating unit represented by the formula (1) may be used as the copolymer component only in one kind or in two or more kinds.

A represents a repeating unit derived from an ethylenically unsaturated monomer whose homopolymer is soluble in water or an aqueous alkali solution.

The term "soluble" as used herein means that the homopolymer is soluble in distilled water or a 1 mol / l sodium hydroxide aqueous solution at a concentration of 10% by weight or more.

Representative examples of this monomer are listed below, but are not limited thereto.

The ethylenically unsaturated monomer represented by A may be used alone or in combination of two or more as a copolymer component.

Preferable examples of the ethylenically unsaturated monomer providing the repeating unit represented by B are esters derived from acrylic acid or α-alacrylic acid (for example, methacrylic acid) or (for example, n-butyl acrylamide, t-butyl). Acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, t
-Butyl acrylate, iso-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl acrylate,
2-methoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate,
2-butoxyethyl acrylate, 2-n-propyloxyethyl methacrylate, 2- (2-methoxy) ethoxyethyl acrylate], vinyl ester (for example, vinyl acetate), acrylonitrile, methacrylonitrile,
Dienoic acid (for example, butadiene, isoprene), aromatic vinyl compound (for example, styrene), vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), ethylene, propylene, 1-butene, isobutene and the like, but are not limited thereto. Not something.

Two or more ethylenically unsaturated monomers used herein can be used together.

x, y and z represent the weight composition ratio of each monomer component, x is 10 to 90% by weight, y is 90 to 10% by weight, z
Is 0 to 30% by weight, preferably x is 30 to 90% by weight, y is 70 to 10% by weight and z is 0 to 10% by weight.

Preferred examples of the compound represented by the general formula [I] of the present invention are listed below, but the invention is not limited thereto.

(Composition is expressed as weight percentage) These compounds can be synthesized by various well-known methods such as solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, etc., but are preferably synthesized by solution polymerization. It

<Synthesis Example of Copolymer for Release Layer> Synthesis Example of Polymer Acrylic Acid-Colauryl Methacrylate (Synthesis of Exemplified Compound 1) Stirrer, Reflux Cooling Tube,
1000 ml of ethyl acetate and 290 ml of ethanol were added to a 2 liter three-necked flask equipped with a dropping funnel, a mercury thermometer and a nitrogen introducing tube, and heated in a water bath. When the temperature in the flask reached 70 ° C and became stable, the polymerization initiator, 2,2'-azobis- (2,4
-Dimethylvaleronitrile) (1.6 g) was added, and then 320.0 g of lauryl methacrylate and 80.0 g of acrylic acid monomer mixture, which had been mixed in advance, were slowly added dropwise over 2 hours. After completion of dropping, 1.6 g of the above-mentioned polymerization initiator was added,
After 2 hours another 3.2 g was added. After that, stirring was continued at 70 ° C. for 3 hours to carry out polymerization.

After heating and stirring, cool the flask temperature to room temperature,
The contents were taken out.

Yield 1490g, polymer solids concentration 25.8% by weight, viscosity 14.
5cp (20% ethyl acetate / ethanol mixed solution (weight ratio 8 /
2), 25 ° C E-type viscometer) To form a release layer using these copolymers, alcohols (eg, methanol, ethanol, propanol, ethylene glycol, etc.), acetone, methyl ethyl ketone, acetonitrile, dioxane, formamide, tetrahydrofuran, It may be dissolved in an organic solvent such as ethyl acetate or a mixed solvent thereof, or a mixed solvent with water, and the solution may be coated on the support by a usual method.

In the release layer of the present invention, other substances, for example, a toning agent, an image stabilizer, an antistatic agent, a brightening agent, a matting agent, an antifoggant, etc. are added unless the effects of the invention are impaired. You may.

When the film thickness of the release layer of the present invention is too thick, "cloudiness" is likely to occur in the low temperature development process, and when the film thickness is too thin, the long time development process is performed. , about 0.001g / m ² ~1.0g / m ² about to adhesion failure of the treatment liquid increases are suitable, preferably from ^{0.01g / m 2 ~0.5g / m 2} .

The constitution of the peeling type diffusion transfer photograph (peel apartment type, peelable monosheet type) of the present invention and each component other than the peeling layer will be described in detail below.

In the peel apart type diffusion transfer method, a photographic film unit integrated with a light-sensitive sheet, that is, a light-sensitive sheet having at least one light-sensitive silver halide emulsion layer on a support and at least an image-receiving layer on another support are provided. It is most commonly used in the form of a film unit consisting of an image-receiving sheet and a container which can be ruptured by a pressure containing a processing liquid between these sheets, and the halogen unit is used in this film unit. After imagewise exposure of the silver emulsion layer, the film unit is usually passed between a pair of juxtaposed pressure rollers to rupture the container and develop the processing solution by spreading it between the two sheets. Be seen. As a result of this development, the image-forming substance is image-wise diffused from the emulsion-containing layer or a layer containing a dye-donor compound (hereinafter referred to as "coloring material") in combination with the emulsion layer into an image-receiving layer on another support. A transfer image is formed by being fixed. The image receiving sheet is peeled from the photosensitive sheet to obtain the desired positive print or slide.

The support constituting the image-receiving element may be a hard material such as glass or pottery, or a flexible material such as paper or film, but in any case, it is markedly dimensioned during storage and processing. It is important to choose one that does not change. Such a support may be transparent or opaque, for example, polyester film, polycarbonate film, polystyrene film, cellulose derivative film, paper, baryta paper, pigment coated paper such as titanium white, and the surface of the paper polyethylene, polystyrene, Examples include paper laminated with a polymer such as a cellulose derivative. Since the image receiving element is generally in the form of a sheet using such a flexible material as a support, the image receiving sheet will be described below as a representative.

In the silver salt diffusion transfer method, the preferred embodiment of the image receiving layer constituting the image receiving sheet is a material which is a catalyst for the reduction reaction of a water-soluble silver complex (called a silver deposition nucleus material or a development nucleus) and has an alkaline processing composition permeability. And a mordant layer for fixing a diffusible dye compound in the color diffusion transfer method.

As the silver deposit nuclear material, heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt and copper, precious metals such as palladium, platinum, silver and gold, or sulfides of these metals, All those conventionally known as silver deposition nuclei such as selenides and tellurides can be used. These silver-deposited nuclides reduce the corresponding metal ions to form metal colloidal dispersions, or by mixing a solution of metal ions with a soluble sulfide, selenide or telluride solution to form a water-insoluble metal. It is obtained by forming a colloidal dispersion of sulfides, metal selenides or metal tellurides.

In order to obtain an image-receiving element which gives an image of the desired tone, these silver-deposited nucleating materials are usually present in the image-receiving layer in an amount of 10 ^-10 to 1
0 ^-5 g / cm ² Preferably, it is contained at -10 ^-8 -10 ^-6 g / cm ² .

As the matrix material, there are also hydrophilic binders such as gelatin, polyvinyl alcohol, carboxymethylcellulose, and methylcellulose. Particularly, a matrix material having alkali-permeable by hydrolysis of an alkali-impermeable polymer is preferable. .

As the hydrolyzable alkali impermeable polymer,
Examples thereof include cellulose esters such as cellulose triacetate, cellulose diacetate, cellulose propionate and cellulose acetate butyrate, and polyvinyl esters such as polyvinyl acetate, polyvinyl propionate and polyvinyl chloroacetate.
The alkali impermeable polymer layer comprising at least one of these polymers becomes alkali permeable by hydrolysis with an alkali solution. In addition, polyvinyl acetals such as polyvinyl formal, polyvinyl acetal, and polyvinyl butyral can be used. In this case, alkali hydrolysis can be achieved by acidic hydrolysis.

To make alkali impermeable polymer layer alkali permeable by alkali hydrolysis, use alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide or tetraalkylammonium hydroxide and alcohol such as methanol or ethanol at 10 to 90%. A saponification solution is prepared by dissolving it in an aqueous alcohol solution containing a concentration of 1%, and the saponification solution is brought into contact with an alkali impermeable polymer layer such as cellulose ester. As a contact method, any conventionally known contact means such as brush coating, roller coating, far knife coating, spray coating or dipping in a saponifying solution bath of the saponifying solution can be applied. The surface of the alkali-impermeable polymer layer is saponified by the contact with the saponification solution.

The saponified layer becomes alkali-permeable and can be penetrated by the diffusion transfer method treatment liquid.

In order to form an image receiving layer for the silver salt diffusion transfer method, a method in which a cellulose ester, for example, cellulose diacetate, is made to contain a silver deposition nucleus by vapor deposition, and then coated on a support and subjected to alkali hydrolysis, a cellulose ester solution. Among them, for example, a method of reacting silver nitrate with sodium sulfide to prepare a silver deposition nucleus in-situ, coating on a support and then performing alkali hydrolysis, or a method of alkali-hydrolyzing a cellulose ester layer previously coated on the support. A method of embedding silver deposit nuclei in the hydrolyzed layer simultaneously with decomposition, and after alkali-hydrolyzing the cellulose ester layer into regenerated cellulose, for example, chloroauric acid and reduction in the hydrolyzed layer. For example, a method of reacting with an agent to form a silver deposit nucleus can be used.

The layer having a neutralizing function used in the image-receiving sheet is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried from the processing composition, and if necessary, a neutralization rate adjusting layer (timing layer). ), A multi-layered structure including layers such as an adhesion enhancing layer. The preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably the oleic acid described in US Pat. No. 2,983,606. Higher fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 3,362,819; acrylics as disclosed in French Patent 2,290,699 Copolymer of acid and acrylic ester; US Pat. No. 4,139,383
Issues and Research Disclosur
e) Latex-type acidic polymers as disclosed in No. 16102 (1977).

Others, U.S. Pat.No. 4,088,493, JP-A-52-153,739
No. 53-1,023, No. 53-4,540, No. 53-4,541,
The acidic substances disclosed in No. 53-4,542 and the like can also be mentioned.

Specific examples of the acidic polymer include copolymers of vinyl monomers such as ethylene, vinyl acetate and vinyl methyl ether with maleic anhydride, and n-butyl ester thereof,
Examples thereof include copolymers of butyl acrylate and acrylic acid, cellulose acetate acetate hydrogen phthalate, and the like.

The polymer acid can be used as a mixture with a hydrophilic polymer. Such polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol, (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable. Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be added to the polymer acid.

The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9-2.0. When the amount of the polymer acid is too small, the hue of the transfer dye is changed, or stain is generated on the white background portion, and when the amount is too much, the hue is changed,
Alternatively, it causes inconvenience such as deterioration of light resistance. A more preferred equivalent ratio is 1.0-1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymer acid is 0.
It is 1-10, preferably 0.3-3.0.

Additives can be incorporated into the layer having a neutralizing function for various purposes. For example, hardeners known to those skilled in the art to harden this layer and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin to improve the brittleness of the film can be added. In addition, if necessary, an antioxidant, a fluorescent whitening agent, a bluing dye, a development inhibitor, and a precursor thereof may be added.

Timing layers used in combination with the neutralization layer include polymers that reduce alkali permeability such as gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like; A latex polymer made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers to increase the activation energy of alkali permeation;
Polymers having a lactone ring are useful.

Among them, JP-A-54-136328 and U.S. Pat. No. 4,267,262.
No. 4,009,030, No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-12
8335, 56-69,629, 57-6,843, U.S. Pat.
56,394, 4,061,496, 4,199,362, 4,250,24
Nos. 4,229,51 and 4,256,827, and 4,268,604, etc., a latex polymer produced by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid;
Polymers having a lactone ring disclosed in No. 6; Others, JP-A Nos. 56-25735, 56-97346, 57-6842, European Patents (EP) 31,957A1, 37,724A1, 48, Four
The polymers disclosed in 12A1 and the like are particularly useful.

 In addition, those described in the following documents can also be used.

U.S. Patents 3,421,893, 3,455,686, 3,575,701
No.3, No.3,778,265, No.3,785,815, No.3,847,615,
4,088,493, 4,123,275, 4,148,653, 4,2
01,587, 4,288,523, 4,297,431, West German patent application (OLS) 1,622,936, 2,162,277, Research Disc
losure 15,162 No.151 (1976) The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

Further, for the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164
No. 3,014,672, JP-A No. 54-155837, and No. 55-13874.
No. 5, etc., development inhibitors and / or precursors thereof, and hydroquinone precursors disclosed in US Pat. No. 4,201,578, other additives useful for photography or their precursors can also be incorporated. .

The portion of the cellulose ester layer containing acetylcellulose that has not been hydrolyzed as an embodiment of the image receiving sheet for silver salt diffusion transfer method is suitable for improving the color tone, stability or other photographic properties of the silver transferred image. One or more mercapto compounds may be included. Such a mercapto compound is used by being diffused in the invisibility from the position where it was originally placed. This type of image-receiving element is designed by Richard W. Yo.
U.S. Pat. No. 3,607,269 and Japanese Patent Application No. 58-148979.

In addition, between a layer of hydrolyzed cellulose ester containing silver deposition nuclei and a layer of lower layer cellulose ester or partially hydrolyzed cellulose ester (which may contain the above-mentioned mercapto compound) if necessary. You may provide another hydrophilic polymer layer in. Examples of the polymer used for the hydrophilic polymer layer include gelatin, derivative gelatin (eg phthalated gelatin), sugars (eg starch, galactomannan, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, pullulan, hydroxypropyl cellulose, etc.). ), Hydrophilic synthetic polymers (for example,
Polyacrylamide, polymethylacrylamide, poly-N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, etc.).

The dye image receiving layer for color diffusion transfer method (mordanting layer) contains a mordant in a hydrophilic colloid. This may be a single layer or may have a multi-layered structure in which mordants having different mordant strengths are applied in layers. Regarding this, JP-A-61-1
252551. As the mordant, a polymer mordant is preferable.

Polymer mordants are polymers containing secondary and tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, and these 4
Polymers having a primary cation group or the like and having a molecular weight of 5,000 or more, particularly preferably 10,000 or more.

For example, U.S. Patents 2,548,564, 2,484,430, 3,
Vinyl pyridine polymers disclosed in 148,061 and 3,756,814, etc., and vinylpyridinium cation polymers; Vinyl imidazolium cationic polymers disclosed in U.S. Pat. No. 4,124,386; U.S. Pat. No. 4,128,538, a polymer mordant capable of crosslinking with gelatin and the like disclosed in British Patent No. 1,277,453; US Pat. No. 3,958,995,
2,721,852, 2,798,063, JP-A-54-115,228
54, 145, 529, 54-126, 027, 54-155, 83.
5, sol type mordanting agents disclosed in the above-mentioned 56-17,352 specifications; water-insoluble mordanting agents disclosed in US Pat. No. 3,898,088; US Pat. Nos. 4,168,976 and 4,20
Reactive mordants capable of forming a covalent bond with dyes disclosed in 1,840 and the like; US Pat. Nos. 3,709,690 and 3,7
88,855, 3,642,482, 3,488,706, 3,
No. 557,066, No. 3,271,147, No. 3,271,148, JP-A-53-30328, JP-A-52-155528, JP-A-53-125, JP-A-53-125
The mordants disclosed in, for example, No. 1024, No. 53-107,835 and British Patent No. 2,064,802 can be mentioned.

In addition, mordants described in US Pat. Nos. 2,675,316 and 2,882,156 can also be mentioned.

The image-receiving sheet may have a photosensitive layer on the same support, but it is preferable not to include it. That is, the photosensitive layer is preferably a constituent element of a photosensitive sheet coated on a support different from the image receiving sheet, and in particular, the image receiving sheet and the photosensitive sheet contain a treatment liquid between the two sheets. It is preferably in the form of a photographic film unit in which a pressure rupturable container is arranged.

The photosensitive layer is preferably composed of a silver halide emulsion, but in this case, it may be a so-called surface latent image type or an internal latent image type. When the coloring material used in combination with the light-sensitive layer is a coupler or redox compound of the type that reacts with an oxidizing agent to release a diffusible dye (or its precursor) as a result of development, an internal latent image type direct positive The use of silver halide emulsions is preferred.

The constituent elements of the photosensitive layer in the color diffusion transfer method will be described below.

(1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or has a diffusivity of itself. Is changing, and the theory of the photographic process “The Theo”
ry of the Photographic Process ", 4th edition. All of these compounds can be represented by the following general formula (II).

DYE-Y (I) Here, DYE represents a dye or its precursor, and Y represents a component that gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of Y, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area.

Specific examples of the negative type Y include those that are oxidized as a result of development and cleaved to release a diffusible dye.

Specific examples of Y include U.S. Pat. Nos. 3,928,312 and 3,993,638,
4,076,529, 4,152,153, 4,055,428, 4,0
53,312, 4,198,235, 4,179,291, 4,149,89
No. 2, No. 3,844,785, No. 3,443,943, No. 3,751,406,
3,443,939, 3,443,940, 3,628,952, 3,9
80,479, 4,183,753, 4,142,891, 4,278,75
0, 4,139,379, 4,218,368, 3,421,964,
4,199,355, 4,199,354, 4,135,929, 4,3
36,322, 4,139,389, JP-A-53-50736, 51-
104343, 54-130122, 53-110827, 56-12
No. 642, No. 56-16131, No. 57-4043, No. 57-650,
57-20735, 53-69033, 54-130927, 56
-164342, 57-119345 and the like.

Among Y of the negative type dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Y are illustrated below, but the present invention is not limited thereto.

For positive-type compounds, see Angevante / Hemi / Internal / Edition / Ingredients.
v. Chem. Inst. Ed. Engl.), 22, 191 (1982).

Specific examples thereof include compounds (dye developers) that are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. Representative examples of Y effective for this type of compound are those described in US Pat. No. 2983606.

Another type is a type in which a diffusible dye is released by self-ring closure under alkaline conditions, but the dye is substantially not released when it is oxidized during development. For a specific example of Y having such a function,
U.S. Patent 3,980,479, JP-A-53-69033, JP-A-54-130927,
It is described in U.S. Pat. Nos. 3,421,964 and 4,199,355.

Another type is one that does not itself release a dye but releases a dye when reduced. This type of compound can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor which is imagewise oxidized by the silver phenomenon. Regarding the atomic group having such a function, for example, US Pat.
183,753, 4,142,891, 4,278,750, 4,139,379,
4,218,368, JP-A-53-110827, U.S. Pat.
4,356,249, 4,358,525, JP-A-53-110827, 54-13
No. 0927, No. 56-164342, Technical Report 87-6199, European Patent Publication 220746A2 and the like.

Specific examples thereof will be illustrated below, but the present invention is not limited thereto.

When this type of compound is used, it is preferably used in combination with a diffusion resistant electron donating compound (known as an ED compound) or its precursor. ED
Examples of the compound include, for example, U.S. Pat.
78,750, JP-A-56-138736 and the like.

Specific examples of other types of dye image-forming substances include the following.

(In the formula, DYE represents a dye having the same meaning as described above or a precursor thereof.

The details are described in US Pat. Nos. 3,719,489 and 4,098,783.

On the other hand, specific examples of the dye represented by the above general formula DYE are described in the following documents.

Examples of yellow dyes: US Pat. Nos. 3,597,200, 3,309,199 and 4,013,63
No. 3, No. 4,245,028, No. 4,156,609, No. 4,139,383,
4,195,992, 4,148,641, 4,148,643, 4,3
No. 36,322: JP-A-51-114930, JP-A-56-71072: Resear
ch Disclosure 17630 (1978) and 16475 (1977).

Examples of magenta dyes: US Pat. Nos. 3,453,107, 3,545,545 and 3,932,380
No. 3, No. 3,931,144, No. 3,932,308, No. 3,954,476,
4,233,237, 4,255,509, 4,250,246, 4,1
42,891, 4,207,104, 4,287,292: JP-A-52
-106,727, 52-106727, 53-23,628, 55
-36,804, 56-73,057, 56-71060, 55-1
The one described in No. 34.

Examples of cyan dyes: U.S. Patents 3,482,972, 3,929,760, 4,013,635
No., No. 4,268,625, No. 4,171,220, No. 4,242,435,
4,142,891, 4,195,994, 4,147,544, 4,1
48,642; British Patent 1,551,138; JP-A-54-99431,
No. 52-8827, No. 53-47823, No. 53-143323, No. 54
-99431, 56-71061; European Patent (EPC) 53,
037, 53,040; Research Disclosure 17,630 (1978)
And those described in No. 16,475 (1977).

(2) Silver Halide Emulsion The silver halide emulsion used in the present invention may be a negative type emulsion which mainly forms a latent image on the surface of silver halide grains, or an inside which forms a latent image on the inside of silver halide grains. A latent image type direct positive emulsion may be used.

The internal latent image type direct positive emulsion includes, for example, a so-called "convergence type" emulsion formed by utilizing the difference in solubility of silver halide, or a metal ion doped or chemically sensitized, or both of them. There is a "core / shell type" emulsion in which at least a light-sensitive site of a silver halide inner core (core) grain is coated with a silver halide outer shell (shell), which is disclosed in US Pat. ,twenty five
0, 3,206,313, British patent 1,027,146, U.S. patent 3,761,2
76, same 3,935,014, same 3,447,927, same 2,497,875, same 2,56
3,785, 3,551,662, 4,395,478, West German Patent 2,728,1
08, U.S. Pat. No. 4,431,730 and the like.

Further, when an internal latent image type direct positive emulsion is used, it is necessary to give fog nuclei to the surface by using light after image exposure or a nucleating agent.

As a nucleating agent therefor, U.S. Pat.
Hydrazines described in 2,588,982, U.S. Patent 3,227,5
Hydrazides and hydrazones described in 52, UK patent
1,283,835, JP-A-52-69613, U.S. Pat.
3,719,494, 3,734,738, 4,094,683, 4,115,122 and the like, heterocyclic quaternary salt compounds, US Patent 3,718,470
, A sensitizing dye having a substituent having a nucleating action in the dye molecule, U.S. Patents 4,030,925, 4,031,127, 4,
245,037, 4,255,511, 4,266,013, 4,276,364, thiourea-bonded acylhydrazine compounds described in British Patent 2,012,434, and U.S. Patents 4,080,270, 4,27.
An acylhydrazine compound having a thioamide ring or a heterocyclic group such as triazole or tetrazole described in 8,748 and British Patent 2,011,391B as an adsorption group is used.

In the present invention, a spectral sensitizing dye is used in combination with these negative type emulsion and internal latent image type direct positive emulsion. Specific examples thereof include JP-A-59-180550, JP-A-60-140335, Research Disclosure (RD) 17029, and US Pat.
6,300, 2,078,233, 2,089,129, 2,165,338, 2,
231,658, same 2,917,516, same 3,352,857, same 3,411,916, same
2,295,276, 2,481,698, 2,688,545, 2,921,067,
Same 3,282,933, same 3,397,060, same 3,660,103, same 3,335,01
0, same 3,352,680, same 3,384,486, same 3,623,881, same 3,718,
470 and 4,025,349.

(3) Structure of photosensitive layer For reproduction of natural color by the subtractive color method, the dye image-forming substance for providing a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye. And a photosensitive layer comprising at least two of The emulsion and the dye image forming substance may be coated as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable.
The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image-forming substance. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541 and a partition layer described in JP-B-60-15267 may be provided to increase the color image density, and
It is also possible to increase the sensitivity of the photosensitive element by providing a reflective layer described in 60-91354.

In a preferable multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side.

An arbitrary layer can be provided between each emulsion layer unit as needed. In particular, it is preferable to provide an intermediate layer in order to prevent the unfavorable influence of the development effect of one emulsion layer on other emulsion layer units.

When the developing agent is used in combination with a non-diffusible dye image forming substance, the intermediate layer preferably contains a non-diffusing reducing agent in order to prevent diffusion of the oxidized product of the developing agent. Specific examples thereof include non-diffusible hydroquinone, sulfonamide phenol, sulfonamide naphthol, and the like, and more specifically, JP-B-50-21249, 50-23813 and JP-A-49-10.
6329, 49-129535, U.S. Patents 2,336,327, 2,360,29
0, 2,403,721, 2,544,640, 2,732,300, 2,782,
659, 2,937,086, 3,637,393, 3,700,453, British Patent 557,750, JP-A-57-24941 and 58-21249. Further, regarding the dispersion method thereof, JP-A-60-23
8831, Japanese Examined Patent Publication No. 60-18978.

When a compound capable of releasing a diffusible dye by silver ion as described in JP-B-55-7576 is used, it is preferable that the intermediate layer contains a compound which traps silver ion.

If necessary, an irradiation prevention layer, an isolation layer, a protective layer, etc. are coated.

The processing composition that can be used contains an alkali, a thickener, a developer, a development accelerator for controlling development, a development inhibitor, an antioxidant for preventing deterioration of the developer, and the like. .

Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and includes alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (eg potassium phosphate). ), Guanidines, and hydroxides of quaternary amines (eg, tetramethylammonium hydroxide), but potassium hydroxide and sodium hydroxide are preferred.

The thickener is required to spread the processing solution uniformly, and to maintain the close contact between the photosensitive layer and the cover sheet when the used photosensitive layer is peeled off together with the cover sheet.
For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used.

Preferred developers cross-oxidize dye image-forming substances,
Any substance can be used as long as it does not substantially generate stain even when it is oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain.

For example, 1-phenyl-3-pyrazolidinone, 1-p
-Tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-
4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxylmethyl-3-pyrazolidinone and the like can be mentioned.

When the image-receiving sheet is used in the silver salt diffusion transfer method, the hydroxylamine silver halide developing agent produces a silver transfer image requiring no or little post-treatment, particularly when used in combination with a regenerated cellulose silver image-receiving layer. It is especially useful for making. Particularly useful silver halide developers of hydroxylamine are N-alkyl and N-alkoxyalkyl-substituted hydroxylamines. Many such hydroxylamines are described in US Pat.
No. 2, 2857275, 2857276, 3287124, 32871
25, 3293034, 3362961, and 3740221. Particularly useful hydroxylamine silver halide developers include N, N-diethyl-hydroxylamine, N, N-bis-methoxyethyl-hydroxylamine and N, N-bis-ethoxyethyl-hydroxylamine. .

The silver halide solvent may be an alkali metal thiosulfate (for example, sodium thiosulfate or potassium thiosulfate), preferably US Pat. No. 3,857.
No. 274, No. 2857275 and No. 3857276, for example, cyclic imides such as lauryl, urazole and 5-methyl-
Urushiru and the like.

Further, in the peelable monosheet type diffusion transfer method, at least (a) a layer having a neutralizing function, on a white support,
(B) a dye image receiving layer, (c) a release layer, (d) a photosensitive element sequentially having at least one silver halide emulsion layer in combination with a dye image forming substance, an alkali processing composition containing a light shielding agent, and a transparent cover. The sheet comprises a sheet and has a layer having a light shielding function on the side of the emulsion layer opposite to the side where the processing composition is developed. That is, in the peelable mono-sheet type, the photosensitive layer and the dye image-receiving layer are coated on the same support, and after the image exposure, the processing composition is developed, and then the dye image-receiving element is peeled off to form a dye. This is to obtain a dye image transferred to the image receiving layer.

The white support means a support having a white color on at least the side on which the dye image-receiving layer is coated, and any support having sufficient whiteness and smoothness can be used. For example, a polymer film whitened by adding a white pigment having a particle size of 0.1 to 5 μm, such as titanium oxide, barium sulfate, or zinc oxide, or forming a microvoid by stretching, for example, polyethylene terephthalate formed into a film by a normal sequential biaxial stretching,
A film made of polystyrene or polypropylene or synthetic paper, or a paper obtained by laminating polyethylene containing titanium white, polyethylene terephthalate, polypropylene or the like on both sides of the paper is preferably used.

The thickness of the support is 50-350 μm, preferably 70-210 μm,
More preferably, it is 80 to 150 μm. Further, if necessary, a light-shielding layer can be provided in the support. For example, a support obtained by laminating polyethylene containing a light shielding agent such as carbon black on the back surface of a white support is used.

Examples of carbon black raw materials include Donnet Voet
Any method such as the channel method, thermal method and furnace method described in "Carlon Black" Marcel Dekker, Inc. (1976) can be used.

The particle size of carbon black is not particularly limited,
90 to 1800Å is preferable. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the light-sensitive material to be shielded, but an optical density of about 5 to 10 is desirable.

The layer having a neutralizing function, the dye image-receiving layer and the light-sensitive element are the same as above.

In peelable monosheet type diffusion transfer photography, the light-shielding layer in the light-sensitive element and the light-shielding processing liquid spread on the light-sensitive element during processing completely shield the light-sensitive layer from outside light during development processing. This enables processing under daylight. Specifically, a layer containing a light-shielding agent may be coated on the back surface of the support or between the emulsion layer and the support, or a layer containing a light-shielding agent may be provided in the support. As the light-shielding agent, any material having a light-shielding function is used, but carbon black is preferably used.

The binder for applying the light-shielding agent may be any binder capable of dispersing the carbon black, and is preferably gelatin.

The light-shielding of the photosensitive layer is performed by developing a processing composition having a light-shielding function on one side (side) of the photosensitive layer, and the opposite side (side) of the photosensitive layer is placed between the photosensitive layer and the white support. ,
It is carried out by providing a layer containing a light-shielding agent on the white support itself and / or on the back surface (the surface opposite to the photosensitive layer) of the white support to shield light. At this time, it suffices that all of and can shield light, and each of them may not have a sufficient light-shielding function.

The processing composition used for the peelable mono-sheet type diffusion transfer photograph is uniformly spread on the photosensitive element after exposure of the photosensitive element, and a light-shielding layer provided on the back of the support or on the side opposite to the processing solution of the photosensitive layer. In a pair, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this reason, in the composition:
The above-mentioned alkalis, thickeners, light-shielding agents, developers, other light-shielding agents such as development accelerators, development inhibitors for controlling development, antioxidants for preventing deterioration of the developer must be included. .

As the light-shielding agent, any dye or pigment can be used as long as the light-shielding agent does not diffuse to the dye image-receiving layer to produce stain, or a combination thereof. A typical example is carbon black, but a combination of titanium white and dye is also used. The dye may be a temporary light-shielding dye that becomes colorless after a certain time of treatment.

In peelable mono-sheet type diffusion transfer photography, a transparent cover sheet is used in order to uniformly spread the processing liquid on the photosensitive element. After processing, the carver sheet is peeled off together with the processing liquid and the used photosensitive layer. Therefore, surface treatment should be performed to ensure sufficient adhesion with the treatment liquid.
Alternatively, it is preferable to apply an appropriate adhesion layer. Further, the cover sheet may contain a filter dye to adjust the sensitivity of the photosensitive layer. The filter dye may be added directly to the support of the cover sheet, or may be coated as a separate layer.

The support of the cover sheet may be any smooth transparent support usually used for photographic light-sensitive materials, such as cellulose acetate, polystyrene, polyethylene terephthalate and polycarbonate, and may be provided with an undercoat layer.

For the undercoat layer, an undercoat liquid usually used in photographic light-sensitive materials is used. Further, the cover sheet may have a layer having a neutralizing function or a layer for capturing the dye diffused to the cover sheet side.

<Example-1> An image-receiving sheet of the present invention, an image-receiving sheet for comparison, and a photosensitive sheet were prepared by the following formulations.

Image receiving sheet Paper support: 150 μm thick paper laminated with polyethylene on both sides by 30 μm. To the polyethylene on the image receiving layer side, 10% by weight of titanium oxide is dispersed and added to polyethylene.

Back side: (a) Carbon black 4.0g / m ² , gelatin
2.0g / m ² light shielding layer.

(B) White layer of 8.0 g / m ^{2 of} titanium oxide and 1.0 g / m ² of gelatin.

(C) Protective layer of gelatin 0.6 g / m ² .

(A) to (c) are applied in this order.

Image-receiving layer side: (1) A neutralization layer containing 22 g / m ^{2 of} an acrylic acid-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000.

(2) Cellulose acetate having a degree of oxidation of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample) and styrene-maleic anhydride having an average molecular weight of about 10,000 (molar ratio 1: 1) Combine at a ratio of 95: 5 by weight
A neutralization timing layer containing 4.5 g / m ² .

(3) Styrene-butyl acrylate-acrylic acid, N
-Polymer latex obtained by emulsion-polymerizing methylol acrylamide at a weight ratio of 49.7 / 42.3 / 4/4 and emulsion-polymerization of methyl methacrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 93: 3: 4. A layer containing polymer latex and a total solid content of 1.6 g / m ² blended so that the solid content ratio is 6: 4.

(4) below the polymer 3.0 g / m ² and gelatin 3.0 g / m ² comprises the image receiving layer.

(5) A release layer coated with 0.05 g / m ² of Exemplified Compound I of the present invention (lauryl methacrylate-co-acrylic acid, weight ratio 80:20).

The image receiving sheet is designated as 1-1.

Further, an image receiving sheet coated in the same manner as the image receiving sheet 1-1 was prepared except that the compounds used in the release layer (5) were changed to the exemplified compounds 2, 4 and 10 of the present invention, and the image receiving sheet 1-
It was set to 2 to 1-4.

The image-receiving sheet for comparison was replaced with the compound of the present invention used for the release layer, and butyl methacrylate-acrylic acid (molar ratio 1: 9) copolymer 0.1 g / m ² , methyl methacrylate-acrylic acid (molar ratio 1 : 9) Copolymer 0.1 g / m ² and hydroxyethyl cellulose (2% solution, viscosity of about 350 cps at 25 ° C.) 0.7 g / m ² except that the coating was the same as the image-receiving sheet 1-1 of the example. The image-receiving sheet was prepared as Comparative Example 1-5 to 1-7.

Photosensitive sheet Each layer was coated on a polyethylene terephthalate transparent support as follows to prepare a photosensitive sheet.

Back side: (a) Carbon black 4.0g / m ² , gelatin
Light-shielding layer having 2.0 g / m ² .

Emulsion layer side: (1) The following cyan dye-releasing redox compound 0.44 g / m ² , tricyclohexyl phosphate 0.09 g / m ²
m ^2, 2,5- di -t- pentadecylhydroquinone 0.008g /
layer containing m ^2, and gelatin 0.8 g / m ^2.

(2) Red-sensitive internal latent direct positive silver bromide emulsion (1.03 in terms of silver)
g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent 0.04 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone
Red-sensitive emulsion layer containing sodium salt 0.13 g / m ² .

(3) 2,5-di-t-pentadecylhydroquinone 0.
Layer containing 43 g / m ² , trihexyl phosphate 0.1 g / m ² and gelatin 0.4 g / m ² .

(4) Magenta dye-releasing redox compound of structural formula I (0.21 g / m ² ), Magenta dye-releasing redox compound of structural formula II (0.11 g / m ² ), tricyclohexyl phosphate (0.08 g / m ² ), 2,5-di -t- pentadecylhydroquinone (0.009g / m ²⁾ and a layer containing gelatin (0.9g / m ^2).

(5) Green-sensitive inner latent type immediately after positive silver bromide emulsion (0.82 in terms of silver amount)
g / m ² ), gelatin (0.9 g / m ² ), the same nucleating agent (0.03 mg / m ² ) as layer ( ² ) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.08 g / m ² ). m ² ) containing a green-sensitive emulsion layer.

(6) The same layer as (3).

(7) Yellow dye-releasing redox compound (0.53 g / m ² ) having the following structure, tricyclohexyl phosphate (0.13 g / m ² ).
g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014g / m ²⁾ and a layer containing gelatin (0.7g / m ^2).

(8) Blue-sensitive inner latent direct positive silver bromide emulsion (1.09 in silver amount)
g / m ² ), gelatin (1.1 g / m ² ), the same nucleating agent (0.04 mg / m ² ) as in layer ( ² ) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.07 g / m ² ). a blue-sensitive emulsion layer containing m ² ).

(9) A layer containing 1.0 g / m ² of gelatin.

The unprocessed photosensitive sheet was superposed on the image receiving sheet, and the processing solution was spread between both sheets so as to have a thickness of 65 μm (developing was performed with the help of a pressure roller).

The treatment was carried out at 25 ° C., and the photosensitive sheet and the image receiving sheet were peeled off 5 minutes after the treatment.

After the peeling, the surface haze of the obtained positive image was visually evaluated, and the scratch resistance 30 seconds after the peeling was evaluated.

The results are shown in Table 1. The scratch resistance test was carried out using a sapphire needle having a diameter of 1 mm, and the scratch strength was obtained by using the load applied to the needle when the image surface was destroyed and scratches remained.

From Table 1, it is clear that the film unit using the image-receiving sheet of the present invention gives an image excellent in gloss without surface haze after peeling. Further, it is clear that the obtained image has excellent scratch resistance and is not easily damaged.

<Example-2> The following (A) and (B) layers were formed on one side of a PET support containing a titanium white white pigment, and the following (1) to (2) were formed on the opposite side.
5) The photosensitive image-receiving sheet (2-
1) was produced.

(A) Carbon black 3.0 g / m ² and gelatin 4.5 g / m ²
A light-shielding layer containing.

(B) a white layer containing titanium white 3.0 g / m ² and gelatin 1.0 g / m ^2.

(1) Polyacrylic acid 4.0 g / m ² , polyvinyl alcohol
4.0 g / m ^2, and 1,4-bis (2,3-epoxypropoxy) - neutralizing layer containing butane 0.04 g / m ^2).

(2) Cellulose acetate with an oxidation degree of 55% and methyl half ester of methyl vinyl ether and maleic anhydride (molar ratio 1: 1) copolymer at a weight ratio of 95: 5, 6 g / m 2.
² including timing layer.

(3) An adhesion strengthening layer containing 0.4 g / m ^{2 of} hydroxyethyl methacrylate.

(4) Styrene-butyl acrylate-acrylic acid-N
Polymer latex obtained by emulsion polymerization of methylol acrylic acid amide at a weight ratio of 49.7 / 42.3 / 4/4 and polymer latex obtained by emulsion polymerization of methyl methacrylate-acrylic acid-N methylol acrylamide at a weight ratio of 93/3/4. A layer containing the blend of 2.5 g / m ² and the total amount of solids blended so that the solid content ratio is 6: 4.

(5) below the polymer latexes mordant 3 g / m ² and gelatin 3 g / m ² comprises a mordant layer.

(6) A release layer comprising 0.02 g / m ² of the compound 1 of the present invention (lauryl methacrylate-co-acrylic acid weight ratio 80:20).

(7) ethyl acrylate lattes try 1 g / m ^2, the layer (8) containing gelatin 2.5 g / m ² following cyan dye-releasing Redotsukusu compound 0.44 g /
m ² , tricyclohexyl phosphate 0.09 g / m ² , 2.5
- di -t- pentadecylhydroquinone 0.008 g / m ^2, the layer containing carbon black 0.05 g / m ² and gelatin 0.8 g / m ^2.

(9) Layer containing titanium oxide 2 g / m ² and gelatin 0.5 g / m ² (10) Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.0 μm (0.15 g / m 2 in silver amount) ² ), red-sensitive sensitizing dye,
Low-sensitivity red-sensitive emulsion layer containing 0.4 g / m ^{2 of} gelatin, 1.1 μg / m ^{2 of the following} nucleating agent (NA), and 0.02 g / m ² of 2-sulfo-5-n-pentadecylhydroquinone sodium salt. .

NA (11) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (0.55 g / m ^{2 in} terms of silver), red-sensitive sensitizing dye,
Gelatin 0.8 g / m ² , same nucleating agent (NA) as layer (10) 3.0 μg /
m ² and a high-speed red-sensitive emulsion layer containing a 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.04 g / m ^2.

(12) 2,5-di-t-pentadecylhydroquinone 1.2g /
m ^2, polymethyl methacrylate 1.2 g / m ² and color mixing prevention layer containing gelatin 0.7 g / m ^2.

(13) A layer containing 0.3 g / m ² of gelatin.

(14) 0.5 g / m of the following magenta dye-releasing redox compound
² , tricyclohexyl phosphate 0.1 g / m ² , 2,5-
Di -t- pentadecylhydroquinone 0.009 g / m ² and gelatin 0.9 g / m ² containing layers.

(15) Layer containing titanium oxide 1 g / m ² and gelatin 0.25 g / m ² (16) Octahedral internal latent image type direct positive silver bromide emulsion with grain size 1.0 μm (0.12 g / m ^{2 in} silver amount) ) Green sensitizing dye, gelatin 0.25g / m ² , same nucleating agent (NA) as layer (10) 1.1μg / m
A low-sensitivity green-sensitive emulsion layer containing ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.07 g / m ² .

(17) Octahedral internal latent image type direct positive silver bromide emulsion with a grain size of 1.6 μm (0.35 g / m ^{2 in} terms of silver amount), a green-sensitive sensitizing dye,
Gelatin 0.7 g / m ² , same nucleating agent (NA) as layer (10) 1.7 μg /
m ² and a high sensitivity green-sensitive emulsion layer containing a 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.04 g / m ^2.

(18) 2,5-di-t-pentadecylhydroquinone 0.8g /
m ^2, polymethyl methacrylate 0.8 g / m ² and color mixing preventing agent containing gelatin 0.45 g / m ² (19) layer (13) and the same layer (20) yellow dye-releasing Redotsukusu compound having the following structure (0.53 g / m ² ), tricyclohexyl phosphate (0.
13g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014g / m ²⁾ and a layer containing gelatin (0.7g / m ^2).

(21) Titanium oxide 0.7 g / m ² and the light reflective layer containing gelatin 0.18 g / m ^2.

(22) Octahedral internal latent image type direct positive silver bromide emulsion (grain size: 025 g / m ² ), blue-sensitive sensitizing dye,
Gelatin 0.4g / m ² layers, same nucleating agent (NA) as in (10) 2μg / m
A low-sensitivity blue-sensitive emulsion layer containing ² and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.045 g / m ² .

(23) Octahedral internal latent image type direct positive silver bromide emulsion (grain size: 0.42 g / m ² ), blue-sensitive sensitizing dye,
Gelatin 0.45 g / m ² , same nucleating agent (NA) as layer (10) 3.3 μg
/ m ² and a high sensitivity blue-sensitive emulsion layer containing a 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.025 g / m ^2.

(24) Each of the following UV absorbers, 4 x 10 ^-4 mol /
m ^2, and the ultraviolet absorbing layer containing gelatin 0.5 g / m ^2.

(25) A protective layer containing a matting agent and 1.0 g / m ² of gelatin.

Further, except that the compound 1 of the present invention used in the peeling layer (6) was changed to the compounds 2, 5 and 14 of the present invention, the light-sensitive image receiving sheet 2-1 was exactly the same, and the light receiving image sheets 2-2 to 2-2 were used. −
Created 4.

Furthermore, a comparative image-receiving sheet was prepared by using butyl methacrylate-acrylic acid (molar ratio 10:90) copolymer 0.7 g / m ² , hydroxyethyl cellulose (instead of the compound 1 of the present invention used in the release layer (6)). 2% solution viscosity at 25 ℃
350 cps) 0.7 g / m ² , except that the photosensitive image-receiving sheet was coated in exactly the same manner as the photosensitive image-receiving sheet 1-1 of the example, and prepared as comparative photosensitive image-receiving sheets 2-5 to 2-7. .

Next, an alkaline treatment liquid containing a light-shielding agent was prepared as described below and filled in the treatment liquid pot.

Treatment liquid 1-m-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10 g 1-phenyl-4-hydroxymethyl-4-methyl-3
-Pyrazolidone 4g 5-Methylbenzotriazole 1.2g Benzotriazole 6g Potassium sulfite 8g Carboxymethyl cellulose 45g Potassium hydroxide 64g Carbon black 150g Total amount 1kg with water Cover sheet containing gelatin for preventing dye dyeing Anti-piping on polyethylene terephthalate transparent support The following layers were coated on to prepare a cover sheet.

(1) A neutralization layer containing 3 g / m ^{2 of} cellulose acetate (oxidation degree: 55.5%) and a methyl vinyl ether-maleic anhydride copolymer 2 g / m ² .

(2) Weight ratio of styrene-n-butyl acrylate-acrylic acid-N methylol acrylamide to 49.7 / 42.3 / 4/4
The solid-type fraction of the polymer latex obtained by emulsion polymerization at a ratio of 3 to 5 and the polymer latex obtained by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylol acrylamide at a ratio of 93: 3: 4 by weight become 5: 5. Blended as above, layer containing 3.9 g / m ^{2 of} total solid content.

(3) A mordant layer containing 1 g / m ^{2 of the} same polymer latex mordant as layer (5) of the photosensitive image-receiving sheet and 1 g / m ² of gelatin.

The above-mentioned photosensitive sheets 2-1 to 2-7, the processing liquid pot, and the cover sheet were combined and processed into an integrated unit as shown in FIG.

The support on the side to which the processing solution pot was attached was provided with discontinuous perforations as described in JP-A-56-67840.

A color test chart was exposed through this film unit through a cover sheet, and then passed through a pair of rollers to uniformly spread the processing liquid in the processing pad between the photosensitive element and the cover sheet. After the treatment liquid was spread for a certain period of time, the perforated portion was strongly bent to cut and the cover sheet was peeled off. At this time, the wet peelability was evaluated by the area ratio at which the target image was obtained by being peeled off cleanly by the peeling layer. 10 when perfect peeling is done
Shown at 0%.

After 30 seconds from the peeling, the scratch resistance of the obtained positive image was evaluated by the same method as in Example 1.

 The obtained results are shown in Table 2.

From Table 2, it is clear that when the compound of the present invention is used as a release layer, the wet peelability is good and the obtained image is excellent in scratch resistance, so that the image is not easily damaged.

Further, it was found by visual evaluation that the release surface of the photosensitive image-receiving sheet using the compound of the present invention was excellent in gloss.

Claims (1)

[Claims] 1. A diffusion transfer photographic unit having at least an image receiving layer and a release layer made of a copolymer on a support,
A diffusion transfer photographic element, wherein the copolymer is a compound represented by the following general formula [I]. General formula [I] In the formula, X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Y represents a monovalent group containing at least one hydrocarbon group having 7 or more carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer whose homopolymer is soluble in water and / or aqueous alkali solution. B represents a repeating unit derived from an ethylenically unsaturated monomer other than the above. x, y and z represent the weight composition of each monomer component, and x
Is 10 to 90% by weight, y is 90 to 10% by weight, and z is 0.
To 30% by weight.