JPS5913729B2 - Color diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to color diffusion transfer processes, and more particularly to color diffusion transfer processes using novel polymeric mordants with ultraviolet absorption capabilities.

In more detail, without adversely affecting photographic performance,
The present invention relates to a color diffusion transfer method which has excellent mordant properties, is excellent in film formation whether used alone or in combination with a binder, and shows no deterioration in image storage stability. In color diffusion transfer, a light-sensitive element containing a silver halide emulsion and a dye image-forming material is exposed to light to form a latent image in the silver halide, followed by a processing agent (alkaline processing liquid). It is developed and processed. During processing with this processing agent, the photosensitive element and an image receiving element having an image receiving layer in which a dye image forming substance can be mordanted are in a superposed state, and the dye image forming substance is transferred to the image receiving layer by diffusion,
A dye image is obtained. Examples of such color diffusion transfer methods include silver halide developable and exposed...
A dye developer, which is a dye that can develop a silver halide emulsion, is
The method described in U.S. Pat. No. 2,983,606 is a dye image-forming material, and the method described in U.S. Pat. Examples include the method described in No. 2774668 and the like.

The image-receiving element used in such a color diffusion transfer method is one in which an image-receiving layer containing a water-permeable and alkali-permeable polymer mordant is coated on an opaque or transparent support. There is. The polymer mordant contained in the image-receiving layer is disclosed in US Pat. No. 314
The polymer 4-vinylpyridine described in the specification of No. 8061 and various vinyl quaternary salt polymers described in the specification of British Patent No. 1,261,925 are known.

The polymeric mordant in the image-receiving layer is preferably one that will produce a dye image on the image-receiving layer in a short period of time when the dye image-forming material is transferred to the image-receiving element by diffusion. On the other hand, once a good image is formed on the image-receiving layer, it is required that the image remain substantially unchanged forever;
Reduction of the alkalinity of the image-receiving layer by neutralization of the processing agent (alkaline processing solution) results in the termination of silver halide development and associated dye formation and diffusion.
However, these dye images are subject to changes or fading and deterioration over time. In particular, the deterioration of dye images due to sunlight, mainly ultraviolet rays, is remarkable and sometimes even negates the commercial value of the resulting color photographic material. As a countermeasure against this, for example, U.S. Pat. No. 3,249,435 discloses that an ultraviolet absorber (hereinafter referred to as UV absorber) is incorporated into an image receiving element, a photosensitive element, or a processing agent, and U.S. Pat. No. 3,460,942 discloses that It has been proposed to provide an alkali-insoluble layer on the image-receiving layer and to contain a UV absorber in this layer.

A UV absorber as used herein refers to a compound that absorbs and blocks light with a wavelength substantially shorter than 400 nm, preferably 380 to 390 nm, which is harmful to photographic performance, and does not impart the energy of these ultraviolet rays to the dye image of a color photographic material. This property is called ultraviolet absorption ability. However, even when conventional UV absorbers are used, the effect of preventing fading of dye images dyed on the image-receiving layer is still not sufficient. It has the disadvantage of adversely affecting performance. That is, the first object of the present invention is to provide a color diffusion transfer method that has an excellent effect of preventing fading.

The second object of the present invention is to provide a color diffusion transfer method using an image-receiving layer that can mordant dye image-forming substances when they migrate to an image-receiving element due to diffusion during development processing and form a good dye image in a short time. The goal is to provide the following. The third object of the present invention is to provide color diffusion using an image-receiving layer that prevents the dye image from fading and deterioration caused by light and maintains good image storage stability after a good image is formed on the image-receiving layer upon completion of processing. The purpose of the present invention is to provide a transcription method.

A fourth object of the present invention is to provide an image receiving element or processing sheet for use in a color diffusion transfer method that exhibits an excellent mordant effect without adversely affecting photographic performance and has a layer that has an anti-fading effect. .

These objects and other objects of the invention described below are directed to a copolymer comprising at least one vinyl monomer having ultraviolet absorbing ability and at least one monomer having tertiary nitrogen or quaternary nitrogen as copolymer components. This is achieved by using the polymer-containing layer as an image-receiving layer and/or scavenger layer in color diffusion transfer processes, or as other mordanting layers.

A copolymer (hereinafter referred to as the compound of the present invention) containing as a copolymer component a vinyl monomer having ultraviolet absorbing ability and a vinyl monomer containing at least one type of tertiary nitrogen or quaternary nitrogen used in the present invention.

) may be used as an image-receiving layer of an image-receiving element, a scavenger layer of an image-receiving element, a processing sheet, or a photosensitive element, and may also be used as a mordant other layer in an image-receiving element, a processing sheet, or a photosensitive element. good. Further, it can be used as a single layer of an image-receiving layer, a scavenger layer, or another mordanting layer, or it can be used as a layer of two or more of these layers.
That is, the compound of the present invention is contained only in the image-receiving layer of the image-receiving element, and the compound of the present invention is contained in the scavenger layer provided in this image-receiving layer and at least one of the image-receiving element, the processing sheet, and the photosensitive element. containing the compound of the present invention in only one scavenger layer provided in at least one of the image-receiving element, the processing sheet, and the photosensitive element; The compound of the present invention may be contained in other mordanting layers.
The compounds of this invention have no adverse effect on silver halide emulsions and are therefore useful as scavenger layers or mordanting other layers (other than silver halide emulsion layers) in light-sensitive elements.

) may be used as a layer containing the polymeric mordant of the present invention. The compound of the present invention may be any compound containing as copolymerization components at least one monomer having ultraviolet absorbing ability and at least one monomer having tertiary nitrogen or quaternary nitrogen. These compounds of the present invention may be used alone or in combination of two or more. The compound of the present invention may be used in combination with other polymer mordants as long as it does not adversely affect the functions and effects of the present invention.

The vinyl monomer having ultraviolet absorbing ability used in the present invention is preferably a monomer represented by the following general formula [1] or [].

General formula [1] In the above general formula [1] and [ ], R
1, R2 and R3 are hydrogen atoms, halogen atoms (e.g., fluorine, chlorine, bromine, etc.) or lower alkyl groups (e.g., methyl, ethyl, propyl, etc.), R4 and R5 are hydrogen atoms, halogen atoms (for example, each of the aforementioned atoms), an alkyl group (for example, each group such as methyl, ethyl, propyl, amyl, octyl, dodecyl, octadecyl, etc.),
Acyl groups (e.g. acetinoyl, ZO ropionoyl, butyroyl, valeroyl, octanoyl, benzoyl, etc.), acyloxy groups (e.g. acetyloxy, propionoyloxy, butyroyloxy, valeroyloxy, octanoyloxy, benzoyloxy, etc.) ),
Hydroxyl group or amino group, A is a simple bond or divalent organic group, B is a hydrogen atom, -0R6 or -0C
0R7, D is R6 is a hydrogen atom, an alkyl group (e.g. each of the above groups) or an aryl group (e.g. phenyl group), R7
is an alkyl group (e.g. each of the above groups), an aryl group (e.g. the above groups) or a heterocyclic group (e.g. imidazolyl,
benzimidazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, pyridyl, piperazinyl, oxazinyl, furyl, morpholino, triazolyl, pyrimidinyl, etc.), R8 and R9 are hydrogen atoms, halogen atoms (for example, each of the above atoms), Alkyl groups (e.g., the above groups), alkoxy groups (e.g., methoxy, ethoxy, butoxy, octoxy, dodecyloxy, etc.), acyl groups (e.g., the above groups), acyloxy groups (e.g., the above groups), or hydroxyl group,
m represents an integer of 0 to 3, and n represents an integer of 0 to 4.

In the general formulas [I] and [], the divalent organic group includes an alkylene group (e.g., methylene, ethylene, trimethylene, hexanotylene, octamethylene, propylene, butylene, etc.), an arylene group (e.g., phenylene group) , a divalent group in which at least one alkylene group and at least one arylene group are bonded (e.g., tolylene, xylylene, etc.), 1COO(CH+10-
(k represents a hydrogen atom, a hydroxyl group, or a hydroxymethyl group) is mentioned as a preferable group. Next, typical examples of vinyl monomers having ultraviolet absorbing ability used in the present invention will be listed.

Next, the vinyl monomer having tertiary nitrogen or quaternary nitrogen used in the present invention preferably has the following general formula [
] Examples include monomers represented by the following.

General formula [] In the above general formula [], RlO and Rll are hydrogen atoms, halogen atoms (e.g., fluorine, chlorine, bromine, etc. atoms), or lower alkyl groups (e.g., methyl, ethyl,
propyl, etc.), E is a simple bond, an alkylene group (e.g. methylene, ethylene, trimethylene, hexamethylene, octamethylene, propylene, butylene, etc.), an arylene group (e.g. phenylene group), at least one A divalent group in which an arylene group and at least one alkylene group are bonded together (e.g., tolylene, xylylene, etc.), Rl2 is an alkylene group (e.g., each group mentioned above), Rl3, Rl4, Rl5, and Rl7 are an alkyl group ( For example, groups such as methyl, ethyl, butyl, hexyl, octyl, dodecyl, octadecyl, etc.), cycloalkyl groups (such as cyclopentyl, cyclohexyl, etc.), or alkoxy groups (such as methoxy, ethoxy, butoxy, octyloxy, dodecyloxy, etc.) ), Rl6 is a hydrogen atom or an alkyl group (for example, each group mentioned above), Rl8 is a hydrogen atom, and Xe is an anionic residue (for example, a halide such as chloride, bromide, iodide, methyl nalphate, ethyl sulfate, etc.). represents an aryl sulfonate such as alkyl sulfate, p-toluenesulfonate, benzenesulfonate, an acetate group, a sulfate group, or a nitrate group), and E is cyclized with RlO or Rl8 to form an N-alkylene maleimide ring. Good too.

Next, vinyl monomers having tertiary nitrogen or quaternary nitrogen used in the present invention include vinyl monomers containing nitrogen-containing heterocycles such as pyridine and imidazole rings, and cations obtained by quaternizing the nitrogen of nitrogen-containing heterocycles. vinyl monomers containing a tertiary amino group such as a dimethylaminoethyl group and a guanidine group.

Next, typical examples of vinyl monomers having tertiary or quaternary nitrogen will be listed.

4-vinylpyridine, 2-vinylpyridine, 4-vinylpyridine methyltonrate, 5-vinyl-2-methylpyridinemethyltonrate, 4-vinylpyridiniumtonlate, 5-vinyl-2N-benzylpyridinium bromide, vinylbenzylpyridinium chloride , vinylbenzyl-N-methylmonopolinium chloride, vinylbenzyltrimethylammonium chloride, methylbenzyltrimethylammonium chloride, vinylbenzyltrihexylammonium chloride, p-vinylbenzyltriethylammonium chloride, p-
Vinylbenzyl triethyl andimethylaminoethyl methacrylate nitrate, β-(trimethylamino)
Ethyl methacrylate methyl sulfate, β-(trimethylamino)ethyl methacrylate nitrate, 2
monomethyl-N-vinylimidazole, β-(trimethylamino)ethyl methacrylate nitrate and biguazinostyrene-2-dimethylaminoethyl methacrylate, N-(3-maleimidopropyl)-N#N-dimethyl-N-(4- phenylbenzyl)ammonium chloride, N-(3-acrylamidopropyl)-N-N
-dimethyl N-(4-nitrobenzyl)ammonium chloride, N-benzyl-N-N-dimethyl-N(3-
maleimidopropyl) ammonium chloride, β-trimethylaminoethyl acrylamide chloride, N-
(Examples include β-trimethylaminoethynol-N-methylacrylamide chloride, β-vinyloxycarbonylmethyltrimethylammonium chloride, etc.

In the present invention, any copolymer containing the aforementioned vinyl monomer having ultraviolet absorbing ability and a vinyl monomer having tertiary nitrogen or quaternary nitrogen as copolymerization components can be used for the purpose of the present invention. It is valid for

The compounds of the invention may also contain other copolymers.

In this case, it is preferable that the total molar ratio of the vinyl monomer having ultraviolet absorbing ability and the vinyl monomer having tertiary nitrogen or quaternary nitrogen is 50% or more, and further,
1 to 20 mol% of vinyl monomer with ultraviolet absorption ability
, 30 to 99 mol % of the vinyl monomer having tertiary nitrogen or quaternary nitrogen, and 50 to 0 mol % of the other copolymer. However, the form of copolymerization is not particularly limited, and any form of copolymerization exhibits the same effect. Typical monomers as other copolymerization components in the compound of the present invention include saturated aliphatic vinyl carboxylates such as vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, methacrylate, etc. Methyl acrylate, n-butyl methacrylate, α-
Acrylic acid esters such as methyl chloroacrylate, 2-hydroxyethyl acrylate, 2-N-N-dimethylaminoethyl acrylate, ethylene, propylene,
Olefins such as isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, dienes such as butadiene and isoprene, acrylonitrile,
Nitriles such as methacrylonitrile, styrene,
Aromatic unsaturated hydrocarbons such as methylstyrene, acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, N-N-dimethylacrylamide, diacetone acrylamide, etc., vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, etc. N-vinylpyrrolidone, CF2-CF2, CH
2-CF2, CHF-CF2, CH2=CH-CF,,
CH2=CH-CH, (CF2)NH (n=2-8),
CH2-CH-COOCH2(CF2)NH(n=2~
8), CH2=C-COOCH2(CF,)NHCO(
Included are fluorinated vinyl compounds such as CF2)NH(n-1 to 8), divinylbenzene, and the like. Next, typical examples of the compounds of the present invention will be listed, but the compounds used in the present invention are not limited to these. Exemplary Compounds The compounds of the present invention are, for example, US Pat. No. 3,183,219, US Pat.
3921 specification, Japanese Patent Application Laid-open No. 47-560, Journal of Applied Polymer Science (JO
urnalOfApplledPOlymerScie
nce) Volume 9, Page 903 (1965), Volume 10
Vol. 663 (1966), Industrial Chemistry Journal Vol. 74, p. 1462 (1971) W.R. SOrenson, T.W. Campbell Author: Preparative Methods of Polymer Chemistry (1)
Pre[RativeMethOdsOfPOlyme
rChemistry) (JQhnWileyWile
y & SOns. Inc. NewYOrkl96l)
, Research Disclosure
It can be easily synthesized by arbitrarily adopting any polymerization method or reaction conditions such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization according to the method described in ScLOsure) No. 14103, etc., but the following is for reference. An example of its synthesis is given below.

Synthesis Example 1 Synthesis of exemplified compound [1] 14.27 (0.05 mol), vinylbenzyl chloride 71,37 (0.5 mol), styrene 46.87 (0
．． 45 mol) and 0.57 mol of α·α7-azobisisobutyronitrile were dissolved in 600 ml of dimethylformamide and heated and stirred at 110° C. for 7 hours in a nitrogen stream.

After cooling, the reaction solution was poured into 1.51 liters of ether to obtain a white solid polymer 87.07. Obtained polymer 87
．． 07 was dissolved in benzyl alcohol, 87.4y (0.33 mol) of N-N-N-trihexylamine was added, and the mixture was reacted at 120° C. for 16 hours in a nitrogen stream. After cooling, the mixture was poured into ether 21 to solidify, and then dried under reduced pressure to obtain 84.0y of the desired product as a white solid. The target substance is soluble in water and methanol and has a molecular weight of 36,000. Synthesis example
2 Synthesis of Exemplified Compound [2] 28.37 (0.1 mol), distilled 4-pynylpyridine 94.5y (0.9 mol) and α・α7-azobisisobutyronitrile 10y were mixed and dissolved in a solution. , 80
An aqueous solution of sodium dodecylbenzenesulfonate 27 and glue 6f7 in 01ni water was heated at 60°C in a nitrogen stream.
While heating and stirring, add in 3 portions.

Thereafter, the mixture was heated and stirred at 60° C. for 4 hours. After cooling the reaction solution, it was poured into water in Step 51 to obtain a pale yellow solid. The obtained solid material is immersed in a large amount of water and left for several days to wash out residual monomers. Repeat this operation several times until the pyridine odor disappears. Thereafter, it was dried under reduced pressure to obtain a pale yellow solid Q-polymer/polymer 116.77. This polymer dissolves in acidic water. The molecular weight is 58,000. Synthesis Example 3 Exemplified compound [10] was synthesized, and 6.37 (0.015 mol), vinylbenzyl chloride 35.6y (0.25 mol), styrene 23.9 (0
．． 23 mol), 1.3 y (0.01 mol) of divinylbenzene, and 3.6 ml of Trax H-45 (surfactant) were added to 100 ml of degassed water, and the mixture was heated and stirred at 60°C in a nitrogen stream.

To this, 0.277 f of potassium persulfate and 0.09 f of sodium bisulfite, which are polymerization initiators, are dissolved in 3 ml of degassed water and added, followed by heating and stirring at 60° C. for 3 hours. After heating, lower to room temperature. This latex liquid 130
150 ml of distilled water and 867 ml of isopropanol were added to f, and then 12.6 V of dimethylbenzylamine was added over 30 minutes. After the addition was completed, the mixture was heated and stirred at 60° C. for 6 hours. After heating, cool to room temperature. white latex liquid, 3
Get 601. The dry product of this polymer is water, methanol,
Insoluble in tetrahydrofura. The molecular weight of the compound of the present invention is arbitrary, but preferably 5,000 to 500,000.
, more preferably 10,000 to 300,000.

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

When used as the image-receiving layer of the former image-receiving element, a layer containing the compound of the present invention may be coated as an image-receiving layer on the support of the image-receiving element. For example, it is desirable to use the compound of the present invention or its solution by coating it on a support coated with a neutralization layer and an intermediate layer containing a polymeric acid. The compound of the present invention or its solution may be applied directly to the support soil without coating. When the compound of the present invention is used as a solution, it is preferably used as a 2 to 20% solution, and examples of the solvent include, but are not limited to, water, methanol, ethanol, methylcellosolve, dioxane, N-N-dimethyl Organic solvents such as formamide, acetone, methyl ethyl ketone, ethyl acetate, and butyl acetate can be used alone or in combination.

Various materials can be used as the support for the image receiving element, such as baryta paper, paper laminated with resin such as polyethylene, cellulose organic acid such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, etc. Ester sheets, e.g. inorganic acid ester sheets such as cellulose nitrate, polyester sheets such as polyethylene terephthalate, polyvinyl ester sheets such as polyvinyl acetate, sheets of polyvinyl acetals such as polyvinyl acetal, e.g. polystyrene. Polyalkylene sheets such as , polypropylene, polyethylene, etc. can be used depending on the purpose.

The neutralizing layer that can be used in the present invention may be one that contains a neutralizing agent and lowers the pH in the system after development processing. The material used as the neutralizing agent is preferably a film-forming polymeric acid having one or more carboxyl groups, sulfonic groups, or groups that produce carboxyl groups upon hydrolysis; , anything can be used. The polymeric acids used in the present invention preferably have about 10,000 or about 100
Monobutyl ester of a 1:1 copolymer of ethylene with maleic anhydride, having a molecular weight of 0.000 and described for example in U.S. Pat. No. 3,362,819. 1
In addition to copolymer monobutyl esters, monoethyl esters, monopropyl esters, monopentyl esters, and monohexyl esters of 1:1 copolymers of maleic anhydride and ethylene, and 1:1 copolymers of maleic anhydride and methyl vinyl ether. Coalescing monoethyl esters, monopropyl esters, monopentyl esters and monohexyl esters, polyacrylic acid, polymethacrylic acid and copolymers of various ratios of acrylic acid and methacrylic acid, other vinyl-based acrylic acid and methacrylic acid Copolymers containing at least 30 mol %, preferably from 50 to 90 mol % acrylic or methacrylic acid in various ratios with monomers, e.g. acrylic esters, methacrylic esters, vinyl ethers, etc. A copolymer or the like can be used. In addition, Research Disclosure 1233
Metal salts, monomer acids, ballasted organic acids, alkyl phosphates, polyalkyl phosphates, poly(-1-acryloyl-2.2) described in No. 1
-2-trimethylhydrazinium, p-toluenesulfonate), etc. can also be used in combination with a binder polymer, if necessary. Further, if necessary, a polymer acid and a monomer acid, or a polymer acid and an organic amine may be used in combination. These polymer acids, monomer acids, organic amines and binder polymers include alcohols such as methanol, ethanol, propanol, butanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, etc., methyl acetate, ethyl acetate, etc. , esters such as isopropyl acetate, butyl acetate, etc., or mixtures thereof, and coated on the support. The thickness of this neutralization layer cannot be determined in general because it varies depending on the composition of the processing agent used and the material contained in the neutralization layer, but it is generally 5 to 30μ. The range is suitable. The neutralizing layer can be provided at any location depending on the layer structure of the photographic element for diffusion transfer.

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

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

This intermediate layer remains at PH until after the required development and transfer have taken place.
It works to delay the decline. That is, before silver halide development and formation of a diffusion transfer image are performed, the neutralization layer prevents an undesirable decrease in the density of the transferred image due to a rapid decrease in the pH within the system. Various materials can be used as this intermediate layer, such as gelatin, polyvinyl alcohol as described in US Pat. No. 3,362,819, partially acetalized polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and US Pat. No. 3,4193.
Cyanoethylated polyvinyl alcohol as described in No. 89, hydroxypropyl methyl cellulose and isopropyl cellulose as described in U.S. Pat. No. 3,433,633, polyvinyl amides as described in Japanese Patent Publication No. 46-1267, Japanese Patent Publication No. 48-41214 Polyvinylamide graft copolymer as described, JP-A-49-
Combinations of latics and penetrants are useful, as described in Japanese Patent Nos. 22935 and 49-91642.

On the other hand, when a layer containing the compound of the present invention is used as a scavenger layer, the layer containing the compound of the present invention is provided as a scavenger layer in any photographic element, such as an image receiving element, a processing sheet, or a photosensitive element. It's okay.

For example, US Patent No. 3415644, US Patent No. 347392
No. 5, No. 3573043, No. 3573042,
When forming a layer structure as described in the specifications of the same No. 3615421, it is necessary to have a layer structure between the photosensitive layer (silver halide emulsion layer) and the support of the photosensitive element, or between the photosensitive layer and the image-receiving layer. The compound of the present invention or its solution may be applied between the two.

Alternatively, the compound of the present invention or its solution can be contained in the intermediate layer or neutralization layer to be used as a scavenger layer. Additionally, U.S. Patent No. 341564
No. 5, No. 3415646, No. 3594164,
In the case of the layer structure described in each specification of the same No. 3594165, the layer containing the compound of the present invention can also be used as a scavenger layer in the treated sheet. The compound of the present invention can cure by itself to form a film that can be mordant, and can also form a film that can be mordant when used in combination with other binders.

Suitable binders include, but are not limited to, water-soluble polymers such as gelatin, polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, starch, polyacrylamide, polyvinylpyrrolidone, and the like. When these polymers are used in combination with the compound of the present invention, they can be used in any mixing ratio, but when the compound of the present invention is contained in the image-receiving layer, the compound of the present invention is added to the image-receiving layer. It is desirable that the content is in the range of IO to 100% by weight, and the same content as above is also used when the compound of the present invention is contained in the scavenger layer or in other mordanting layers. It is therefore desirable to use the compounds of the present invention. The coating thickness of the layer containing the compound of the present invention can be varied depending on the purpose. For example, when the layer is an image-receiving layer, the optimal thickness is about 3 to 10 μm; When the scavenger is a single layer, it is desirable to have a thickness of 0.5 to 10 microns.

Processing sheets can be used in the present invention depending on the layer configuration of the photographic element.

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

A light-sensitive element for color diffusion transfer comprises at least one silver halide emulsion layer provided on a support and a dye image-forming material combined with silver halide in the silver halide emulsion layer. Consisting of

In particular, it is desirable to sequentially stack a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on the support, and each emulsion is combined with a cyan dye image-forming material, a magenta dye image-forming material, and a yellow single-dye image forming material. It is desirable to have a forming substance. Further, layers such as a yellow filter layer, an anti-reaction layer, an intermediate layer, and a protective layer can be provided as necessary. Preferably, the support is a planar material that does not undergo significant dimensional changes during treatment due to the treatment composition. Although rigid supports such as glass can be used depending on the purpose, flexible supports are generally useful. The flexible support is preferably one used in general photographic materials, such as cellulose nitrate film, cellulose acetate film,
Polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, paper, laminated paper, etc. are advantageously used. In addition, in the present invention, the processing agent (
To help the water of the alkaline processing solution wick through the support, water vapor permeable supports such as those described in U.S. Pat. No. 3,573,044 and U.S. Pat. It's advantageous. Furthermore, when the film unit is processed in the bright light, the transparent support is used to prevent imagewise exposure and observation in order to prevent light leakage from the edges of the transparent support into the silver halide emulsion layer. However, it is desirable that the material be colored to the extent that it can prevent the transmission of light in the surface direction. The support may optionally contain various photographic additives, such as plasticizers such as phosphate esters and phthalate esters, 2(2-hydroxy-4-
It may contain an ultraviolet absorber such as t-butylphenylbenztriazole and an antioxidant such as hindered phenol. In order to maintain the adhesion between the support and the layer containing the hydrophilic polymer, it is advantageous to provide an undercoat layer or to subject the surface of the support to preliminary treatment such as corona discharge treatment, ultraviolet irradiation treatment, flame treatment, etc. . Although the thickness of the support is not limited, it is generally desirable to have a thickness of 20 to 300 microns. When the support is used for the purpose of blocking light, pigments such as carbon black and titanium oxide may be contained in the support, or a binder may be used if necessary to coat the support. You may. The dye image forming method used in the color diffusion transfer method of the present invention is as follows:
Various methods may be used depending on the manner in which the dye image-forming material releases the diffusible dye upon development of the silver halide.

The dye image-forming material may already contain completed dye moieties, the dye moieties may be formed during development and subsequent processes that occur simultaneously, or the components essential for dye formation may be added to the image-receiving layer. It may migrate and the dye may be formed there. Among the methods for converting development into dye, three representative methods that can be advantageously applied to the present invention will be described. The first representative method is the so-called dye developer method.

The dye developer in this system is a compound that has both a dye coloring system and a silver halide developing group in one molecule, and the dye developer as a dye image forming substance is oxidized by silver halide. As a result, reduction of the silver halide and oxidation of the dye developer occur, resulting in a change in diffusivity in the processing composition. The oxidized dye developer has lower solubility and diffusivity in the processing agent than the reduced form of the dye developer, and is immobilized near the reduced silver halide. Preferably, the dye developer is substantially insoluble in acidic to neutral aqueous media, but contains at least one dissociable residue sufficient to render the dye developer soluble and diffusible in the alkaline nature of the processing agent. Contains. Such dye developers 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 photosensitive elements in combination with developer. By performing diffusion transfer from a photosensitive element having at least one photosensitive unit of this combination to an image receiving element, a monochrome or multicolor positive transfer image can be obtained in one development process. More specifically, in the color diffusion transfer method according to the first typical method, a silver halide latent image in a photosensitive element is developed in the presence of a dye developer, and as a result of the second development, exposure The dye developer in the area is oxidized and substantially fixed. It is believed that this fixation is due, at least in part, to changes in the solubility properties of the dye developer upon oxidation, particularly with respect to its solubility in alkaline solutions. In the unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and can diffuse, so it is possible to create an imagewise distribution of unoxidized dye developer in the processing agent as a function of the point-by-point exposure of the halogenated emulsion. provide. At least a portion of this imagewise distribution of unoxidized dye developer is transferred through the superimposed image-receiving layer by imbivision. This transfer substantially eliminates oxidized dye developer. The image receiving element accepts imagewise diffusion of unoxidized dye developer from the developed emulsion without substantially disturbing the imagewise distribution of unoxidized dye developer to provide a reversal of the developed image. This first type of diffusion transfer method is covered by many patents, such as British Patent No. 8049.
It is described in the specification of No. 71, etc.

Dye developers particularly useful in the present invention are those in which the silver halide developing group is a benzenoid group, and the preferred benzenoid group in such compounds is a hydroquinonyl group. Typical dye developers include, for example, U.S. Pat. No. 2,983,606, U.S. Pat.
No. 255001, No. 3218164, No. 3453
No. 107, No. 3551406, No. 3135605
No. 3421892, No. 3563739, No. 3482972, No. 3415644, and No. 3594165.

Further, in the present invention, it is also possible to use a hydrolyzable dye developer and a short wavelength shift dye developer in which a hydrolyzable group is introduced into the dye developer. Representative specific examples of these include U.S. Patent No. 3,230,082, U.S. Pat. No. 3,329,670, U.S. Pat.
No. 9334, No. 3295973, No. 319601
Specifications of No. 4 and No. 3336287, Special Publication No. 1973-
No. 379, No. 36-12393, No. 37-2241, U.S. Pat. No. 3,312,682, U.S. Pat. No. 3,826
The compound proboscis described in each specification of No. 801 can be mentioned.

Furthermore, in the present invention, it is possible to effectively use a leuco dye developer whose dye portion has been reduced and temporarily converted into a colorless leuco body. Typical examples of these include U.S. Patent Nos. 2,909,430 and 3,320,063;
Compounds described in the specifications of JP-A No. 2892710 and JP-A No. 2992105, and the publications of JP-A-48-66440 and JP-A-48-66441 can be mentioned. A typical second method involves the reaction of the silver halide oxidized product with the dye image-forming material to release diffusible dyes, specifically Type A, Type B, and Type B. It is classified as type C. Among these, type A uses a reactive non-diffusible substance that can couple with an oxidized developing agent, and as a result of the coupling reaction, a soluble and diffusible dye is released from the processing agent. I can do it. This type of diffusible dye-releasing force plate contains a moiety in which the coupling reactive site is replaced by a residue that is cleaved off by oxidized developing agent. The electronically conjugated system of the dye to be released may be pre-incorporated into the coupler or may be formed by a coupling reaction. The former coupler &ζ exhibits a spectral absorption close to that of the emitted dye. On the other hand, the latter couplers are, in principle, colorless, and even if they are colored, their absorption is temporary and is not directly related to the absorption of the emitted dye. As a compound used for the above type A, US Pat. No. 3,227,550
British Patent No. 3880658, British Patent No. 3765886, British Patent No. 840731, British Patent No. 904364, British Patent No. 9
No. 04365, Specifications of No. 1038331, Japanese Patent Publication No. 15471/1971, Japanese Patent Application No. 133879/1983
No. 50-118480, etc. 0 above. In type B, the dye residue contained in the substituent group is dissociated due to the intramolecular ring-closing reaction with the substituent group adjacent to the reaction point that occurs following the condensation reaction with the oxidized developing agent. This is a type of system in which the gas is emitted.

In particular, after oxidative coupling of an aromatic primary amino developer to the 4-position of phenol or aniline, an azine ring is formed with the sulfonamide group containing the dye moiety located at the 3-position, and diffusion with sulfuric acid occurs. It releases sex pigments. Compounds used in type B include US Pat. Nos. 3,443,940 and 3,73,472.
It is stated in each specification etc. of No. 6. As a result of development, the above type C is oxidized by an oxidized auxiliary agent to close the ring or decompose with an alkali to release a diffusible dye.
Representative embodiments of dye image-forming materials via supplementary foliar agents such as 3-pyrazolidones are described in U.S. Pat. No. 3,725,062.
No. 3698897, No. 3728113, No. 3443939, No. 3443940, No. 32
45789, Pelkey Patent No. 3880658, Pelkey Patent No. 796041, Pelkey Patent No. 796042, and Japanese Patent Application Laid-Open Nos. 48-33826 and 49-114424.

A third typical method uses a dye image-forming material that is cleaved with an alkali to release a diffusible dye, but cleavage does not substantially occur in the presence of an oxidized developer. A typical example of a dye image-forming substance is disclosed in Japanese Patent Application Laid-Open No.
-111628, etc.

In the representative methods No. 1 and No. 3 described above, a positive diffusion transfer dye image is obtained by performing a development process using a negative silver halide emulsion layer. On the other hand, in the typical second method described above, a negative diffusion transfer dye image is obtained by performing a development process using a negative silver halide emulsion layer. Therefore, the second method requires reversibility. For example, direct positive emulsions, U.S. Pat.
Internal latent image emulsions such as those described in British Patent No. 88982 and British Patent No. 3227552, British Patent No. 443245, British Patent No. 462730, and US Pat.
No. 05837, No. 2541472 and No. 336
Fogged type emulsions described in each specification of No. 7778 can be used.

Alternatively, a layer containing a diffusible dye-releasing power 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. A specific example of this is U.S. Patent No. 324329.
It is described in the specifications of No. 4 and No. 3630731.

Furthermore, it reacts with the oxide of the developing agent to form 1-phenyl-5-
Adjacent to the negative-working silver halide emulsion layer containing a compound that releases a development inhibitor such as mercaptotetrazole, a layer containing a diffusible dye-releasing agent and a spontaneously reducible metal salt is provided. It may be provided. Specific examples include the specifications of U.S. Pat.
No. 47-49611 and the like. Combinations of these emulsions and dye image-forming substances can be used in the present invention, and methods for providing negative and positive dye images can be arbitrarily selected. The dye image-forming substances used in the present invention include gelatin, which is a carrier for the silver halide emulsion layer or its adjacent layer in the light-sensitive element;
Depending on the type of dye image-forming material, it can be dispersed in a hydrophilic protective colloid such as polyvinyl alcohol in a variety of ways.

For example, a dye image-forming substance having a dissociable group such as a sulfo group or a carboxyl group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic protective colloid solution. A dye image-forming substance that is difficult to dissolve in an aqueous medium and easily soluble in an organic solvent can be dissolved in an organic solvent, and a solution obtained can be added to a hydrophilic protective colloid solution and dispersed into fine particles by stirring or the like. As the organic solvent, a high boiling point solvent can be used alone or a combination of a low boiling point solvent that can be removed from the dispersion by evaporation or an organic solvent that is easily soluble in water and the high boiling point solvent can be used. . For example, the method described in Japanese Patent Publication No. 43-13837 can be effectively used for dispersing the dye image-forming substance in the present invention. Particularly useful high-boiling solvents in the present invention include N-n-butylacetanilide, diethyl laurylamide, dibutyl laurylamide, dibutyl phthalate, tricresyl phosphate, triglycerides of higher fatty acids, dioctyl adipate, and the like. As the low boiling point solvent, ethyl acetate, methyl acetate, 4-methylcyclohexanone, tetrahydrofuran, methyl ethyl ketone, etc. are used. Further, to stabilize the dispersion of dye image-forming materials, U.S. Pat.
Sulfites may also be present as described in the '133 specification. Further, the dye image forming substance used in the present invention is disclosed in Japanese Patent Publication No. 48-32131 and U.S. Patent No. 383217.
As described in the specification of No. 3, etc., the dye image-forming substance particles may be directly dispersed in a hydrophilic protective colloid without using a high boiling point solvent or the like. The amount of dye image-forming material used in the present invention can vary widely depending on the compound used and the desired result, but may, for example, be from about 0.5 to about 1
Preferably, 0 weight percent is used. When multicolor photography is carried out in the present invention, the interaction between photosensitive Z: double: - middle: lily and T - is prevented, and the diffusibility of the dye image forming substance and the alkali processing composition is adjusted.

This intermediate layer may be made of gelatin, calcium alginate or any material described in U.S. Pat. Kosho 47-47
Polyvinylamide as described in No. 606, polyvinylamide graft copolymer as described in U.S. Pat. No. 3,575,700, latex liquid and infiltration as described in Japanese Patent Publication No. 49-20972 and U.S. Pat. No. 3,756,816. A system of agents is useful.

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

The silver halide emulsion may be of fine grain or coarse grain, and usefully has an average grain size in the range of about 0.1 micron to about 2 micron. The silver halide emulsion can also be prepared by any known method, such as a single jet emulsion such as a Lippmann emulsion, a thiocyanate or thioether ripened emulsion, such as U.S. Pat.
Those described in the specifications of No. 271157 are included. Emulsions containing silver halide grains with substantial surface photosensitivity are used, and emulsions containing silver halide grains with substantial photosensitivity inside the grains are also used,
These silver halide emulsions are described, for example, in U.S. Pat. No. 2,592.
No. 250, No. 3206313, and No. 3447
It is described in each specification etc. of No. 927.

In the present invention, a negative emulsion can be used, or US Pat.
No. 3367778, British Patent No. 723019, French Patent No. 1520821, US Patent No. 256
No. 3785, No. 2456953 and No. 2861
Direct positive emulsions such as those described in US Pat. No. 885, etc. can also be used.

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

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

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

The silver halide emulsions used in the present invention can be protected against the occurrence of fog and can be stabilized against loss of sensitivity during storage. Suitable antifoggants and stabilizers, used alone or in combination, include:
U.S. Patent Nos. 21,31038 and 269471
Thiazolium salts as described in the specifications of US Pat. No. 6, etc., azaindenes as described in the specifications of US Pat. No. 2,886,437 and US Pat.
Mercury salts as described in US Pat. No. 28,663, U.S. Pat.
urazoles as described in US Pat. No. 2,87135, sulfocatecol as described in US Pat. No. 3,236,652, oximes nitrones and nitrointazoles as described in UK Patent No. 623,448, US Pat. No. 2,403,927. Mercaptotetrazoles as described in U.S. Pat. No. 3,266,897 and U.S. Pat.
Mercaptrazoles as described in the specifications of US Pat. No. 397,987, polyvalent metal salts as described in US Pat. No. 2,839,405, thiuronium salts as described in US Pat. No. 3,220,839, and US Pat. No. 2,566,263.
Palladium, platinum, and gold salts as described in the specifications of No. 2,597,915 and the like are included.

The processing agent permeable layers such as the silver halide emulsion layer, the layer containing the dye image-forming substance, the layer containing the mordant, the protective layer or the intermediate layer used in the present invention contain a hydrophilic polymer as a binder. It is desirable to be present. For example, gelatin, proteins such as casein, albumin grafted with gelatinyl polymers modified with acylating agents, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, methylcellulose, etc. , polyvinyl alcohol or polyvinyl acetate partial hydrolyzate, polyvinylpyrrolidone, polyacrylamide, polyvinyl ethers, polymeric non-electrolytes such as polymethyl vinyl ether, polyacrylic acid, polyacrylamide partial hydrolyzate, vinyl methyl ether and Examples include anionic synthetic polymers such as copolymers of maleic acid. These hydrophilic polymers can be used alone or in combination. Additionally, these hydrophilic polymer layers may contain latex-like polymer dispersions of hydrophobic monomers such as alkyl acrylates. In the present invention, these hydrophilic polymers, especially polymers having functional groups such as amino groups, hydroxyl groups, and carboxyl groups, can be made insolubilized by various curing agents without losing their permeability to processing agents. Particularly useful curing agents include aldehydes such as formaldehyde, cryoxal, and gretaraldehyde, N-methylol compounds such as N-hydroxymethylphthalimide, 1-hydroxymethylbenzotriazole, 2,5-hexadione,
Ketones such as 1,2-cyclopentadione, methylol compounds such as N-polymethylol, hexamethylolmelamine, epoxy compounds such as 1,4-bis(2,3-epoxyproboxy)diethyl ether, triethylene phos Examples include aziridine compounds such as Famide, and polymeric compounds such as 3-hydroxy-5-chloro-8-triazinylated gelatin. Furthermore, these hydrophilic polymer layers may contain, in addition to the curing agent, a curing accelerator such as carbonate and L-zorcin. The silver halide emulsions used in the present invention can use optical sensitizing dyes to provide additional photosensitivity.

For example, silver halide emulsions may be treated with organic solvents of sensitizing dyes, or dyes may be prepared in the form of dispersions in British Patent No. 1154.
In addition, additional optical sensitization can be achieved as described in the '781 specification. For best results, it is desirable to add the dye to the emulsion in the final step or somewhat earlier. For example, US Patent No. 2526
No. 632, No. 2503776, No. 2493748, and No. 3384486. Optical sensitizers that can be effectively used in the present invention include cyanines, merocyanines, styryls, hemicyanines (eg, enamine hemicyanine), oxonols, hemioxonols, and the like. Examples of cyanine dyes include thiazoline, oxazoline, pyrroline,
It is desirable to include basic cores such as pyridine, oxazole, thiazole, selenazole and imidazole. Such a nucleus may contain an alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl or enamine group, and may be attached to a carbocyclic or heterocyclic ring. These rings may be substituted or unsubstituted with...rogen, phenyl group, alkyl group, haloalkyl group, cyano group or alkoxy group. These dyes may have alkyl, phenyl, eminane or heterocyclic substituents on the methylene or polymethylene chain in symmetrical or asymmetrical form. Merocyanine dye is
Basic nuclei such as those mentioned above, such as thiohydantoin, rhodanine, oxazolidenedione, thiazolidenedione,
Contains acidic cores such as barbituric acid, thiazolinone, and malononitrile. This acid nucleus is an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group,
It may also be substituted with an alkylamino group or a heterocyclic nucleus. Combinations of the above dyes can also be used if desired. Furthermore, the present invention may optionally contain supersensitizing additives that do not absorb visible light, such as ascorbic acid derivatives, azaindenes, cadmium salts or US Pat.
Organic sulfonic acids such as those described in the specifications of No. 33390 and No. 2937089 can be contained. As the processing agent (alkaline processing liquid) used in the present invention, any liquid composition can be used as long as it contains processing components necessary for developing the silver halide emulsion and forming a diffusion transfer image.

As the solvent for this treatment agent, any hydrophilic solvent such as water, methanol, methylcellosolve, etc. can be used. The processing agent desirably contains an alkaline agent in an amount sufficient to maintain the pH necessary for development of the emulsion layer and to neutralize acids generated during the development and image formation processes. As the alkali agent, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, etc. can be used, and the treatment agent should have a pH of about 2 or more at room temperature. is desirable. The processing agent used in the present invention may contain a thickening agent, for example, a polymeric thickening agent that is inert to alkaline solutions, such as hydroxyethyl cellulose and sodium carboxymethyl cellulose. The concentration of the thickener is preferably about 1 to 5% by weight of the processing agent, so that the concentration of the thickener is about 100 to 200% by weight.
000 centiboads of viscosity to the processing agent, which not only facilitates the uniform spread of the processing agent during processing, but also allows the aqueous solvent to migrate to the light-sensitive element and the image-receiving element during processing, thereby concentrating the processing agent. When used, a non-flowing film is formed to help unite the photographic element units after processing.
This polymer film can also serve to prevent image change by inhibiting further migration of image forming components to the image receiving layer after formation of the diffusion transferred image is substantially completed. It may be advantageous for the processing agent to contain a light-absorbing material, such as carbon black, to prevent the silver halide emulsion from being disturbed by external light during processing. Additionally, the processing agent contains processing components specific to the imaging material used. For example, in the case of dye developers, para-aminophenol, 4-methylphenylhydroquinone,
Auxiliary developers such as 1-phenyl 3-pyrazolidone, N
It is desirable to contain an onium-based development accelerator such as -benzyl-α-picolinium bromide, an antifoggant such as benizotriazole, and the like. In addition, in the case of a diffusible dye releasing agent, it is possible to contain an antioxidant such as an aromatic primary amino color developer, a silver halide solvent such as sodium thiosulfate or sodium thiocyanate, etc. desirable. In the color diffusion transfer method according to the present invention, development can also be carried out in the presence of a diffusible onium compound.

Examples of such onium compounds include quaternary ammonium compounds, quaternary phosphoric acid compounds, and quaternary sulfonium compounds, such as 1-benzyl-2-picolinium bromide, 1-(3-bromopropyl)-2-
Picolinium-p-toluenesulfonic acid, 1-phenethyl-2-picolinium bromide, 2,4-dimethyl-
Onium compounds such as 1-phenethylpyridinium bromide, α-picoline-β-naphtholmethyl bromide, N-N-diethylpiperidinium bromide, phenethyltrimethylphosphonium bromide, dodecyldimethylsulfonium-p-toluenesulfonium are used in the present invention. It is valid. The onium compound may be used anywhere in the photosensitive element or the image receiving element, but it is preferable to include it in the processing agent (alkaline processing liquid). For specific examples of onium compounds and examples of their use, see, for example, U.S. Pat.
It is described in the specifications of No. 411904 and No. 3173786.

In the present invention, a light-reflecting material can be used to form a white background of an image formed on the image-receiving layer.
Suitable light-reflecting substances include titanium dioxide, barium sulfate, zinc oxide, barium alumina stearate, calcium carbonate silicate, zirconium oxide, and magnesium kaolin oxide, which may be used alone or in combination. I can do it. Such light-reflecting materials may be preformed or as described in Pelkey Patent No. 768110 and
They may be formed in place from precursors that are distributed in the photographic element as described in the respective specifications of the present invention. moreover,
This light-reflecting material is polyvinyl alcohol, gelatin,
Hydrophilic polymers such as hydroxypropylcellulose and polyvinylpyrrolidone may be contained in a layer using a vinyl polymer containing an anionic solubilizing group as a binder as described in US Pat. No. 3,721,555, and further It can also be fixed in a dispersed state in a layer of a film-forming polymer such as hydroxyethyl cellulose or carboxymethyl cellulose, which is blended into a processing agent and formed by processing development. Fluorescent brighteners such as stilbenes, coumarins, triazines or oxazoles may be used in conjunction with such light-reflecting materials. Furthermore, in the present invention, in order to protect the silver halide emulsion layer from ambient light during processing, a light-reflecting material is used in conjunction with Pelkey Patent No. 74.
No. 3336, No. 768107 and No. 76810
Indicator dyes such as those described in Specification No. 9 can be used. Processing agent used in the present invention (
The alkaline processing liquid) is preferably stored in a breakable container.

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

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

The stripping agent can be contained on the surface of the silver halide emulsion layer, on the image-receiving layer containing a mordant, or in the processing agent. Suitable release agents are those having a composition different from the binder used in the silver halide emulsion. For example, alkali-permeable polysaccharides, carboxymethyl cellulose, hydroxyethyl cellulose
Hydroxypropylcellulose, 4,4'-dihydroxyphenolglucose, sucrose, sorbitol, inositol, resorcinol, sodium phytate, zinc oxide, particulate polyethylene, particulate poly-4-fluorinated ethylene, described in US Pat. No. 3,325,283 Useful examples include polyvinylpyrrolidone/polyvinylhydrodiene phthalate such as ethylene-maleic anhydride copolymer described in US Pat. No. 3,376,137.

Additionally, the hydrophilic colloid surface layer on such image receiving elements may contain ultraviolet absorbing materials, such as U.S. Pat. No. 3,460,942.
No. 3,069,262, No. 3,330,680, and No. 3,330,656. Furthermore, if desired, a fluorescent whitening agent such as stilbene, coumarin, triazine, oxazole, etc. can be included. The photographic element layer consisting of the photosensitive element, image receiving element, processing sheet, etc. used in the present invention may optionally contain a surfactant, such as saponin, an anionic compound, such as U.S. Pat.
alkylaryl sulfonates, amphoteric compounds as described in US Pat.
Water-soluble adducts of glycidol and alkylphenols such as those described in GB 1,022,878 and GB 1,022,878 can be included. Further, in order to facilitate the coating of the photographic element layer used in the present invention, the coating composition may contain various thickeners and the above-mentioned surfactants.

Anionic polymers, such as high molecular weight polyacrylamide or acrylic acid-based polymers, which exhibit a thickening effect upon interaction with the binder polymer in the coating composition, are also effectively used in the present invention. The photographic layers used in the present invention may be coated by a variety of coating methods, such as dip coating, air knife coating, curtain coating, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294.

If desired, two or more layers can also be applied simultaneously by methods such as those described in US Pat. No. 2,761,791 and British Patent No. 837,095.
The present invention is disclosed in British Patent No. 968,453 and US Pat.
Vacuum deposition as described in the specifications of No. 219451...
It can also be used for silver halide layers. The photographic element layers used in this invention can be hardened with a variety of organic or inorganic hardeners, alone or in combination.

Suitable curing agents include, for example, aldehydes, blocked aldehydes, ketones, carboxylic acid derivatives,
Carbonic acid derivatives, sulfonate esters, sulfonyl halides, vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed functional hardeners and polymer hardeners such as dialdehyde starch. and oxidized polysaccharides such as oxyguar gum. The sensitizing dye and other additives used in the present invention can be added as an aqueous solution or can be added using a suitable organic solvent. The sensitizing dye and other additives described above are described in US Pat.
3, No. 3342605, No. 2996287, and No. 3425835.

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

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

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

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

The coating amount was 4.2 t/Trl of gelatin and 2.0 y/Trl of cyan dye developer. (2) Red-sensitive emulsion layer A red-sensitive silver iodobromide emulsion contains 0.6 t of silver and 2.4 t of gelatin.
It was applied so that it became t/WI.

(3) Middle class It was coated to give a gelatin ratio of 2.0y/TI.

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

The coating amount was 2.87 gelatin/Tll magenta dye developer 1.37/M2. (5) Green-sensitive emulsion layer Green-sensitive silver iodobromide: silver 1.27/Rrl, gelatin 1.2t/Rrl
It was applied to make it look like this.

(6) Middle class The gelatin was coated at 1.57/d.

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

The coating amount was 1.17/Tll of gelatin/0.57/Tll of yellow monochrome developer. (8) Blue-sensitive emulsion layer Blue-sensitive silver iodobromide is mixed with silver 0.67/7TI1 gelatin 0.6
It was applied so that it was t/a.

(9) Protective layer 4'-Methylphenylhydroquinone was dissolved in N-N-diethyl laurylamide, emulsified and dispersed in an aqueous gelatin solution, and 5% of a 2% aqueous mucochloric acid solution was added to 100 ml of a coating solution.
After adding m1, it was applied.

The amount applied is 4'-methylphenylhydroquinone 0.57
/Trl and gelatin 0.6f/i. The processing agent (alkaline processing liquid) was prepared as follows. Then, it was developed using a roller pressure tool.

The obtained photographic element is processed into cyan (C), magenta (M), and yellow (Y) using red, green, and blue filters.
The maximum concentration (Dnlax) after 0 minutes was measured. This sample was irradiated with a xenon fademeter for 5 days, and the subsequent Dmax was measured, and the ratio of Dnlax on the same day was measured as light resistance. The results obtained are shown in Table-1. The image receiving element is made of polyethylene terephthalate and has a thickness of 10
On a 0μ transparent film base, 3% by weight of the compounds of the present invention shown in Table 1 below (the above-mentioned exemplified compounds) and polyvinyl alcohol (Nippon Gosei Gohsenol NH-2) were applied.
6) was added to an aqueous solution 1007 containing 6% by weight of polyoxyethylene nonyl phenyl ether and applied to form an image receiving layer having a dry film thickness of 5 μm.

As a control, poly-4 vinylpyridine [
A] was used.

The light resistance in Table 1 is the Dnlax after 5 days of irradiation when the same-day Dnlax is 100, and the larger this value is, the better the fading prevention effect is.

As is clear from Table 1, it can be seen that excellent light resistance can be obtained in the method of the present invention (image-receiving element numbers 2 to 5) having a layer containing the compound of the present invention as an image-receiving layer.

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

(1) Green-sensitive silver bromide: silver 1.07/Rrl, gelatin 2
. 5-pyrazolone potassium neutral salt was applied at a ratio of 0.87/M2.

(2) Gelatin was coated at 2.0y/Trl.

On the image receiving layer of the image receiving element coated in Example 1, titanium dioxide 20.0y/Trll gelatin 2.0 was applied as a light reflecting layer.
7/m' was applied. Further, gelatin was coated thereon as a protective layer at a ratio of 0.67/l to prepare an image receiving element. Next, the following processing agent was prepared and placed in a processing bag.

After the processing bag was placed between the photosensitive element and the image receiving element and subjected to imagewise exposure, the roller pressing tool was subjected to development processing.

The maximum density (Dnlax) of the dye image was measured 10 minutes after processing. Thereafter, the light resistance of each sample was measured using a fedometer for 5 days. (Measurements are the same as in Example 1).
The results obtained are shown in Table 2. As is clear from Table 2,
It can be seen that the method of the present invention (image-receiving element numbers 2, 3, 4 and 5) provides excellent maximum density and light resistance even in the case of a method in which a light-reflecting layer is provided.

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

(1) Image-receiving layer An image-receiving layer having a dry film thickness of 5 μm was coated at a ratio of 1:1 (weight ratio) of the compound polymer mordant of the present invention (the above-mentioned exemplified compound) and gelatin shown in Table 3 below.

(2) Light reflective layer Titanium dioxide was coated in an amount of 20.0y/d1 and gelatin 2.0y/d1.

(3) Opaque layer Gelatin 2.

07/M2, carbon black was applied at a rate of 2.0 t/a.

(4) Yellow single-dye image forming substance containing layer The following compounds were mixed at 1.0f7/I and gelatin at 1.07/R.
It was applied so that it became RL.

(5) Blue-sensitive emulsion layer Blue-sensitive silver iodobromide is mixed with 0.67 t/a of silver and 0.6 t/a of gelatin.
It was applied so that it became WI.

(6) Protective layer The gelatin was coated at 0.57/7TI.

A transparent polyethylene terephthalate film was used as the treated sheet. The following processing agents were prepared.

The processing bag containing the processing agent was placed between the photographic component and the processing sheet and subjected to imagewise exposure, followed by development using a roller pressure tool.

Process the obtained color image using a blue filter 10
The maximum concentration (Dmax) after 5 minutes was measured, and then irradiated for 5 days with a Phedometer.
was measured, the rate of decrease in Dnlax was measured, and the light resistance was examined.
The results obtained are shown in Table 3. As a control, the following polymer mordant [B] was used in place of the compound of the present invention used in the above photographic element.

As is clear from Table 3, the method of the present invention (photographic element number 7,
8, 9, 10 and 11 are found to exhibit excellent maximum density and fire resistance.

Example 4 The procedure was the same as in Example 3 except that the treatment sheet was changed.

The treated sheet was prepared by sequentially coating the following layers on a polyethylene terephthalate film support. (1) Scavenger Single layer A polymer mixture consisting of 4 parts of polyacrylic acid and 1 part of polymer mordant was applied at a rate of 20.0 t/day.

(2) Intermediate layer (timing layer) A polymer mixture consisting of 95 parts of cellulose acetate and 5 parts of styrene inert water maleic acid copolymer was coated at a ratio of 3.0 y/y.

The minimum density (Dmin) after one day of development was as shown in Table 4 below.

As is clear from Table 4, it can be seen that the method of the present invention (photographic component numbers 13 to 15) suppresses the increase in Dmin.

Example 5 Dry film thickness 5μ containing polymer mordant poly-4-vinylpyridine/gelatin 1:2 (weight ratio) as real image layer material
This is the same as Example 4 except that the image receiving layer of .

Dmin after 1 day of development processing is shown in the table below. be.

5, and as is clear from Table 5, the method of the present invention (photographic element number 13)
~15) shows that the increase in Dnlln is suppressed.

Example 6 The same as Example 3 except that the light reflecting layer contained a polymer mordant in an amount of 10% by weight based on the gelatin content.

Dmax after 10 minutes of treatment. Dmin was measured and the results are shown in Table 6. As is clear from Table 6, according to the method of the present invention (photographic element numbers 13 to 15), DnlaX is high and Dml is high.

It can be seen that the increase has been suppressed. Example 7 The same as Example 6 except that an image-receiving layer containing a polymer mordant poly-4-vinylpyridine/gelatin 1:2 (weight ratio) and having a dry film thickness of 5 μm was used as the image-receiving layer material.

Dnlln was measured 10 minutes after the treatment, and the results are shown in Table 7.

As is clear from Table 7, the method of the present invention (Photographic element number 13
~15) shows that the increase in Dnlin is suppressed.

Claims (1)

[Scope of Claims] 1. A layer containing a copolymer containing a vinyl monomer having ultraviolet absorbing ability and a vinyl monomer having tertiary nitrogen or quaternary nitrogen as copolymer components, as an image-receiving layer and/or a scavenger layer. A color diffusion transfer method characterized by using. 2. In a copolymer containing a vinyl monomer having ultraviolet absorbing ability and a vinyl monomer having tertiary nitrogen or quaternary nitrogen as copolymerization components, the vinyl monomer having ultraviolet absorbing ability and the third The total molar ratio with monomers having quaternary nitrogen or quaternary nitrogen is 50
% or more, the color diffusion transfer method according to claim 1. 3 The monomer having ultraviolet absorbing ability has the following general formula [I
] or [II], the color diffusion transfer method according to claim 1 or 2, characterized in that the monomer is a monomer represented by [2] or [II]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2 and R_3 are hydrogen atoms, halogen atoms or lower alkyl groups, R_4 and R_5 are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, a hydroxyl group, or an amino group, and A is a simple bond, an alkylene group, an arylene group, or at least one alkylene group and at least one arylene group. A divalent group bonded with, -CONH-, -COO, -NH
CO-, -SO_2NH, -NHSO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (W represents a hydrogen atom, hydroxyl group, or hydroxymethyl group), B is a group selected from Hydrogen atom, -OR_6 or -
OCOR_7, D has ▲mathematical formulas, chemical formulas, tables, etc.▼
Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_6 is a hydrogen atom, an alkyl group or an aryl group, R_
7 is an alkyl group, aryl group or heterocyclic group, R_8
and R_9 is a hydrogen atom, a halogen atom, an alkyl group,
an alkoxy group, an acyl group, an acyloxy group or a hydroxyl group, m represents an integer of 0 to 3, and n represents an integer of 0 to 4; ]. 4. The color diffusion transfer method according to claim 1 or 2, wherein the vinyl monomer having tertiary nitrogen or quaternary nitrogen is a monomer represented by the following general formula [III]. General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc.
Alkylene group, arylene group, divalent group in which at least one arylene group and at least one alkylene group are bonded, COOR_1_2-, ▲ mathematical formula, chemical formula, table, etc. ▼ R_1_2- or -OCOR_1_2-, M is ▲ mathematical formula , chemical formulas, tables, etc. ▼R_1_5・X^■
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ NH_2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼・X^■, R_1
_2 is an alkylene group, R_1_3, R_1_4, R_1
_5 and R_1_7 are alkyl groups, cycloalkyl groups, or alkoxy groups, R_1_6 is a hydrogen atom or an alkyl group, R_1_8 is a hydrogen atom, and It may form a ring. ]. 5. The color diffusion transfer method according to claim 1 or 2, wherein the scavenger layer is included in the image receiving element, processing sheet or photosensitive element.