JPH0621950B2 - Photosensitive element for color diffusion transfer method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a light-sensitive element for a color diffusion transfer method, and more specifically, it releases a diffusible dye or its precursor as a function of oxidation or reduction under alkaline conditions. Containing non-diffusible dye image-forming substances, especially fog, maximum density,
It relates to a photosensitive element for a color diffusion transfer process having an improved dye image forming rate.

[Prior art]

Generally, the color diffusion transfer method using a dye image forming substance is
It is already widely known in the art, and for related techniques, for example, U.S. Pat.Nos. 2,983,606 and 3,362,819,
Same 3,362,821, same 3,485,628, same 3,415,644, same 3,5
73,043, 3,594,164, 3,594,165, 3,705,18
No. 4, No. 3,243,294, No. 3,443,939, No. 3,443,940,
3,698,896, 3,628,952, 3,728,113, 4,0
76,529, 4,139,379, 4,139,389, 4,199,35
No. 4, No. 3,980,479, No. 4,199,354, No. 3,928,312,
4,135,929, 4,053,312, 4,198,235, 4,0
No. 13,633, No. 3,954,476, No. 3,929,760, No. 4,013,63
5, each specification of 4,195,993, British Patent No. 1,496,363
Publication, Research Disclosure 13024 (1975),
15157 (1976), JP-A-55-33141, 55-33142, 5
6-16131, 56-71072, 56-71060, 56-71061
No. 57, No. 57-85055, No. 57-105738, No. 58-37646, No. 5
9-68739, 54-130927, 56-142530, 56-1643
42, 57-119345, 58-37645, and 58-42043.

The dye image-forming substance used in the above color diffusion transfer method is a compound which gives an imagewise distribution of a diffusible dye in response to exposure as a result of development of a photosensitive silver halide emulsion brought about by imagewise exposure. There are various forms of dye image-forming substances as a method of producing a diffusible dye from the development of silver halide, and among these, a dye image used in a light-sensitive element for a color diffusion transfer method according to the present invention is used. The forming substance is a non-diffusible dye releasing redox compound (hereinafter referred to as a DRR compound) which undergoes a redox reaction with a developer or an electron transfer agent which is oxidized or not oxidized under alkaline conditions to release a diffusible dye.

In the system using this DRR compound (hereinafter referred to as the DRR system), a light-sensitive silver halide emulsion layer and a non-diffusible dye image forming substance combined with the emulsion layer, that is, DR
A light-sensitive element containing the R compound is imagewise exposed to form a latent image in the light-sensitive silver halide emulsion layer and then treated with an alkaline processing composition in the presence of a silver halide developer. It In the processing with the alkaline processing composition, the photosensitive element and the image receiving layer are in a state of being superposed, and the oxide of the silver halide developer is produced or not as a result of the processing with the alkaline processing composition. The DRR compound undergoes a redox reaction to release the diffusible dye or its precursor. The diffusible dye or its precursor released from the DRR compound is transferred to the image receiving layer by diffusion to form a dye image.

Generally, it is desirable that the photographic image obtained from these light-sensitive elements have sufficiently high maximum density and sufficiently low minimum density. preferable.

Further, since the DRR method is used for so-called instant photography which is usually developed in a camera, it is strongly required not only to have the above-mentioned good image quality, but also to be able to observe the image earlier. However, as is conventionally known, when the diffusion rate of the diffusible dye or its precursor from the DRR compound is fast, an image can be observed on the image receiving layer quickly, and a dye image with a high maximum density can be obtained. However, on the contrary, there is a drawback in that the minimum density is high and a good image quality cannot be obtained.
On the other hand, when the release rate of the diffusible dye or its precursor from the DRR compound is slow, a dye image having a low minimum density can be obtained on the image receiving layer, but on the contrary, the maximum density is low and the image receiving layer is also low. There is a drawback that it takes time to observe the dye image.

Further, a method of widely changing various properties of silver halide emulsion, a composition of a processing agent, an emulsion additive, etc. in order to obtain a desired gradation is well known from the past, and particularly, it is generally determined. A method of changing the properties of the silver halide emulsion has been adopted for the processing agent formulation.

However, in order to change the silver halide emulsion for the purpose of obtaining an appropriate gradation, many basic properties of the silver halide emulsion such as grain size, grain size distribution, crystal habit, composition and structure are widely used. It was very difficult to prepare the above emulsion. Furthermore, because of other performances required for the light-sensitive element, such as raw storability, developability, and sensitizing ability, the range of selection of the above emulsion including additives is remarkably narrowed to a desired level. It was even more difficult to get the key and it was impossible in practice.

On the other hand, the photosensitive element used for instant photography using the DRR system is processed under a wide range of processing temperatures because the processing is simple. Therefore, the conventional photosensitive element has a drawback in that the gradation of the image changes corresponding to the change of the processing temperature and the image quality is deteriorated. In particular, for example, JP-A-53
No. 20318, a DRR method using an internal latent image type direct positive silver halide emulsion containing a fogging agent, a negative type silver halide emulsion (as described in JP-A-49-90534) is used. ) Is softer at low temperature than the DRR method using
It has a drawback that it tends to become hard at high temperatures.

As a method of controlling such gradation, for example, a mixed emulsion in which emulsions having different gradation or sensitivity are mixed as described in U.S. Pat. No. 4,035,185 and Research Disclosure 151, No. 15162. Although a method using is also known, it is said that it is extremely difficult to obtain a stable image in this method because the gradation is also changed when the processing temperature changes.

[Problems to be solved by the invention]

Accordingly, the present invention provides a light-sensitive element for a color diffusion transfer method which can obtain an image having a high maximum density and a low minimum density (fog), and the present invention also provides a dye image forming speed on an image receiving layer. The present invention provides a light-sensitive element for a color diffusion transfer method capable of observing a transferred image at a high speed, that is, after processing with an alkaline processing composition, and further, the present invention provides a basic element of a silver halide emulsion. To provide a photosensitive element for a color diffusion transfer method, which can control sensitometric characteristics, particularly gradation, by extremely simple means without changing the characteristics, and whose gradation does not change with processing temperature. is there.

[Means for solving problems]

According to the present invention, the above-mentioned object of the present invention is to have at least one light-sensitive silver halide emulsion layer, and to deal with imagewise exposure in combination with the light-sensitive silver halide emulsion layer, alkaline conditions are required. In a light-sensitive element for a color diffusion transfer process having a layer containing a non-diffusible dye image-forming substance capable of releasing a diffusible dye or a precursor thereof as a function of oxidation or reduction, a layer containing the dye image-forming substance. At least one of a plurality of layers, and a layer farther from the photosensitive silver halide emulsion layer among the plurality of layers has a higher concentration than the layer closer to the photosensitive silver halide emulsion layer. It has been found that a light-sensitive element for a color diffusion transfer process containing a diffusible dye image forming material can be a solution. Hereinafter, the present invention will be described in more detail.

The light-sensitive element for color diffusion transfer method of the present invention (hereinafter referred to as the light-sensitive element of the present invention) comprises a layer containing a non-diffusible dye image-forming substance combined with a light-sensitive silver halide emulsion layer as described above. In the case of a plurality of layers, for example, a two-layer structure, a layer far from the photosensitive silver halide emulsion layer, that is, a layer in which the first dye image-forming substance layer is close to the emulsion layer, That is, it is characterized in that it contains a higher concentration of the non-diffusible dye image-forming substance as compared with the second dye image-forming substance layer. It can be defined by the weight fraction C of the dye image-forming substance in the hydrophilic colloid and other constituent substances that form the layer containing the, and the concentration (C ₁ ) of the first dye image-forming substance layer and the second dye image. Ratio of forming material layer concentration (C ₂ ) C ₁ / It means that C ₂ is at least more than 1, preferably in the range of 1.5-30.

According to an embodiment of the present invention, the dihydroxybenzene derivative (described later) is added to the dye image-forming substance layer close to the emulsion layer to the extent that the dye image transfer density is not substantially reduced.
Can also be included.

The present invention can not only solve the above-mentioned problems of the present invention by using the light-sensitive element of the present invention as described above, but also because the rate of releasing the diffusible dye or its precursor is too fast, the minimum concentration is It enables the use of non-diffusible dye image-forming substances which could not be used in the past because of the high price, and further, the basic properties of the silver halide emulsion such as grain size and grain size distribution. , Easily realizing a desired shape of the gradation curve of the dye image obtained on the image receiving layer, without widely changing the crystal habit, composition, production or the like or changing other parameters such as developing conditions. It has an excellent effect in that it can be performed.

The non-diffusible dye image-forming substance used in the color diffusion transfer method of the present invention may already contain a completed dye portion, and the dye portion is formed in the development and the subsequent process which occurs at the same time. Further, the components essential for dye formation may move to the image receiving layer, and the dye may be formed there.

The dye image-forming substance itself used in the light-sensitive element of the color diffusion transfer method of the present invention is preferably non-diffusible in the light-sensitive element during the steps of manufacturing, storing and exposing the light-sensitive element.

In the present invention, a dye image-forming substance according to various combinations of the above-mentioned development-to-dye conversion system, dye image-forming method and diffusibility can be used, but as a particularly useful dye image-forming substance, It is a DRR compound that undergoes a redox reaction with a developer or an electron transfer agent that is oxidized or not oxidized under alkaline conditions to release a diffusible dye. Examples of such DRR compounds include those that act negatively, for example, US Pat. No. 3,928,312,
4,135,929, 4,053, 312, 4,198,235, 4,01
3,633, 3,954,476, 3,929,760, 4,013,635
No. 4,195,933, each specification of British Patent No. 1,496,363, Research Disclosure No. 13024 (1975), the same.
15157 (1976), JP-A-55-33141, 55-33142, 56-
16131, 56-71072, 56-71060, 56-71061
No. 57, No. 57-85055, No. 57-105738, No. 57-119345, No. 57-119345
58-37645, 58-37646, 58-42045, 59-68739
Those described in each publication of the issue can be used.

The following are typical examples of negatively acting DRR compounds.

(Example of compound) N- (1) N- (2) N- (3) N- (4) N- (5) N- (6) N- (7) N- (8) N- (9) N- (10) N- (11) N- (12) N- (13) N- (14) N- (15) N- (16) N- (17) N- (18) N- (19) N- (20) N- (21) Next, as a DRR compound that works positively, for example, JP-A-54
-130927, 56-142530, 56-164342, U.S. Pat.Nos. 4,139,379, 4,139,380, 4,199,354, 3,9
The compounds disclosed in the specification of each publication of No. 80,479 are known.

The following are typical examples of positively acting DRR compounds.

(Example of compound) P- (1) P- (2) P- (3) P- (4) P- (5) P- (6) P- (7) P- (8) P- (9) P- (10) P- (11) P- (12) P- (13) P- (14) P- (15) P- (16) P- (17) P- (18) P- (19) P- (20) P- (21) P- (22) P- (23) P- (24) P- (25) P- (28) P- (29) P- (30) P- (31) P- (32) P- (33) P- (34) P- (35) P- (36) P- (37) P- (38) P- (39) P- (40) P- (41) P- (42) P- (44) P- (45) P- (46) P- (47) P- (48) P- (49) P- (50) P- (51) P- (52) P- (54) P- (55) P- (56) P- (57) P- (58) P- (59) P- (60) P- (61) According to the present invention, the amount of the DRR compound according to the present invention used is 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol / mol as the coating amount when the DRR compounds contained in the plurality of dye image-forming substance layers are combined.
m ² is preferably in the range of 2 × 10 ^{-4 to} 2310 ^-3 mol / m ² .

Various dispersion methods are known as a method for dispersing the DRR compound according to the present invention in the constituent layers of the photosensitive element of the present invention, and typical dispersion methods include the methods described below. You can

A method in which a non-diffusible dye image-forming substance is dissolved in a substantially water-insoluble high boiling point solvent and finely dispersed in a hydrophilic protective colloid.

Particularly useful high-boiling solvents include N-n-butylacetanilide, N, N-diethyllaurylamide, dibutyllaurylamide, dibutylphthalate, tricresyl phosphate, N-dodecylpyrrolidone and the like.

A low boiling point solvent or an organic solvent which is easily dissolved in water can be used to assist the above dissolution.

As the low boiling point solvent, ethyl acetate, methyl acetate, cyclohexanone, acetone, methanol, ethanol, tetrahydrafuran, etc., and as the organic solvent easily soluble in water, 2-methoxyethanol, dimethylformamide, etc. can be used. . These low boiling point solvents and organic solvents that are easily dissolved in water can be removed by washing with water, coating and drying, or the like.

By gradually adding a polymer latex fillable in a solution of a non-diffusible dye image-forming substance in a water-miscible organic solvent and sufficient water to render the non-diffusible dye image-forming substance in said solvent insoluble. A method of incorporating a non-diffusible dye image-forming material into a loadable polymer latex particle.

The water-miscible organic solvent and the fillable polymer latex are described in detail in JP-A-51-59942 and JP-A-51-59943.

A method in which a non-diffusible dye image-forming substance is mechanically atomized using a sand grinder or a colloid mill and then dispersed in a hydrophilic colloid.

After dissolving the non-diffusible dye image-forming substance in a water-miscible organic solvent, it is preferably precipitated in water in the presence of a surfactant,
A method in which the precipitate is dispersed in a hydrophilic colloid, for example, a method described in JP-A-53-139532.

A method of dissolving a non-diffusible dye image forming substance together with a polymer in an alkaline aqueous solution, adjusting the pH with an acid to precipitate the non-diffusible dye image forming substance, and dispersing the non-diffusible dye image forming substance in a hydrophilic colloid.

In the present invention, various methods can be arbitrarily used without being limited to the above methods.

In the present invention, as described above, it is preferable that a layer close to the silver halide emulsion layer, for example, in the case of a two-layer structure, the second dye image-forming substance layer contains a dihydroxybenzene derivative. Examples of the dihydroxybenzene derivative used in the present invention include dihydroxybenzene in which at least one linear or branched alkyl group is substituted, preferably one or two, and hydroquinone and catechols are preferable.
Further, this dihydroxybenzene derivative may further have a sulfo group, a carboxyl group, a halogen atom, an acyl group or the like as a substituent, for example, US Pat. No. 2,360,290.
Nos. 2,418,613, 2,403,721 and 3,96
No. 0,570 discloses monosubstituted alkylhydroquinones, and the use of monobranched alkylhydroquinones is described in US Pat.
West German patent application (OLS) 2,149,789, JP-A-50-156438
And 49-106329. Further for di-substituted alkyl hydroquinones, see US Pat.
No. 8,659, No. 2,732,300, No. 3,243,294, British Patent No. 752,146 and "Chemical Abstract"
56, 6367h, etc., and dibranched alkyl-substituted hydroquinone is described in US Pat.
No. 2,732,300, No. 3,243,294, the aforementioned "Chemical Abstracts" magazine, JP-A-50-156438, and No. 53-
9528, 54-29637 and JP-B-50-21249. For other substituted hydroquinones, U.S. Patent Nos. 2,701,197, 2,710,801 and 2,704,
It is also described in 713 and JP-A-55-43521.

These dihydroxybenzene derivatives are dispersed in the constituent layers of the photosensitive element of the present invention by various methods depending on the type,
Can be included. For example, a compound having a dissociative group such as a sulfo group or a carboxyl group can be added to the hydrophilic colloid solution after being dissolved in water or an alkaline aqueous solution. In the case of a compound that is difficult to dissolve in an aqueous medium, it can be dispersed and contained in the same manner as the DRR compound according to the present invention.

As the hydrophilic colloid, the same ones as those used in the silver halide emulsion described later can be used.

The light-sensitive element of the present invention contains, as described above, at least one light-sensitive silver halide emulsion layer coated on a support and a plurality of DRR compounds according to the present invention in combination with the emulsion layer. It is based on a structure having layers.
Therefore, in the light-sensitive element of the present invention, in addition to the case where the layer combined with the light-sensitive silver halide emulsion layer has a two-layer structure of the first dye image-forming substance layer and the second dye image-forming substance layer as described above, It may have a three-layer structure or a four-layer structure. In such a multi-layer structure, it is necessary to contain a higher concentration of the non-diffusible dye image forming substance in a layer farther from the silver halide emulsion layer. It is said that

The photosensitive silver halide emulsion according to the present invention comprises, for example, a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof. The silver halide grains used in this silver halide emulsion may be fine grains or coarse grains, and it is useful that the average grain size is in the range of about 0.1 to about 2 microns.

The silver halide emulsion can be prepared by any known method, and for example, a single jet emulsion such as Lippmann emulsion, thiocyanate or thioether ripening emulsion and the like can be used.

Also, an emulsion containing silver halide grains having substantial surface sensitivity is used, and an emulsion containing silver halide grains having substantial photosensitivity inside is also used.

In the present invention, a negative type emulsion or a direct positive emulsion can be used.

As the hydrophilic colloid used in the silver halide emulsion, gelatin is preferably used, but other examples include gelatin modified with an acylating agent, gelatin grafted with a vinyl polymer, casein, albumin. Protein, hydroxyethyl cellulose,
Hydroxypropylcellulose, carboxymethylcellulose, cellulose derivatives such as methylcellulose, partial hydrolysates of polyvinyl alcohol or polyvinyl acetate, polyvinylpyrrolidone, polyacrylamide, polyvinyl ethers, for example, polymeric non-electrolytes such as polymethyl vinyl ether, polyacrylic acid, Anionic synthetic polymers such as a partial hydrolyzate of polyacrylamide and a copolymer of vinyl methyl ether and maleic acid can be used. These hydrophilic colloids can be used alone or in combination. Further, these hydrophilic colloid layers may contain a latex polymer dispersion of a hydrophobic monomer such as alkyl acrylate.

These hydrophilic colloids, particularly polymers having functional groups such as amino groups, hydroxyl groups and carboxyl groups, can be insolubilized by various curing agents without losing the penetrability of the treating agent. Particularly useful curing agents include aldehyde compounds such as formaldehyde and mucohalogen acid.
N, N′-bis (1-aziridine-carbonyl) -hexamethylenediamine, β-bis-vinylsulfonylethane, a reaction product of tetrakis- (vinylsulfonylmethyl) methane and β-aminoethylsulfonate.
N, N ', N "-tri-acryloyl-hexahydro-
S-triazine and N, N ', N "-tri-acryloyl-hexahydro-s-triazine in combination with N, N'-bis (1-aziridine-carbonyl) -hexamethylenediamine, N, N', N ″ -Tri-acryloyl-
A combination of hexahydro-s-triazine and β-bis-vinylsulfonylethane can be mentioned. Further, these hydrophilic colloid layers may contain a curing accelerator such as carbonate in addition to the curing agent.

The silver halide emulsion used in the present invention is sensitized with a natural sensitizer or a chemical sensitizer contained in gelatin, such as a reducing agent, a sulfur, selenium or tellurium compound, gold, platinum or palladium compound, or a combination thereof. can do.

The silver halide emulsions used in the present invention can use speed-increasing compounds such as polyalkylene glycols, cationic surfactants and thioethers or combinations thereof. The silver halide emulsion used in the present invention can be protected against the generation of fog and can be stabilized against the reduction in sensitivity during storage. Suitable antifoggants and stabilizers used alone or in combination include thiazolium salts,
Azaindenes, mercury salts, urazoles, sulfocatechols, oximes, nitrones, benztriazoles,
Examples thereof include nitroindazoles, mercaptotetrazoles, polyvalent metal salts, thiuronium salts, palladium, platinum and gold salts. Among these compounds, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaine is particularly preferable. Den and sodium 2-mercaptobenzimidazole-5-sulfonate are preferred.

The silver halide emulsion used in the present invention can use an optical sensitizing dye in order to impart additional photosensitivity. For example, a silver halide emulsion may be treated with an organic solvent for a sensitizing dye, or the dye may be in the form of a dispersion in U.S. Pat.
In addition, additional optical sensitization can be achieved as described in the publication. For optimum results, it is desirable to add the dye to the emulsion at the final step or some step earlier. Sensitizing dyes useful for sensitizing such silver halide emulsions include cyanines, merocyanines, styryls,
Hemicyanines (eg, enamine hemicyanine), oxonol and hemioxonols are included. Dyes of cyanines include, for example, thiazoline, oxazoline,
It is desirable to include basic nuclei such as pyrroline, pyridine, oxazole, thiazole, selenazole and imidazole. Such a nucleus is an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group,
It may contain an aminoalkyl group or an enamine group, etc., and may be condensed with a carbocyclic ring or a heterocyclic ring, and these rings are a halogen atom, a phenyl group, an alkyl group, a haloalkyl group, a cyano group or It may be substituted with an alkoxy group. These dyes are symmetrical or asymmetrical in the methylene or polymethylene chain with an alkyl group,
It may have a phenyl group, an enamine group or a heterocyclic substituent. The merocyanine dye contains, in addition to the basic nucleus as described above, an acidic nucleus such as thiohydantoin, rhodanine, oxazolidendione, thiazolidenedione, barbital acid, thiazolinone and malononitrile. The acid nucleus may be substituted with an alkyl group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamino group or a heterocyclic nucleus. Combinations of the above dyes can be used if desired.

As the sensitizing dye particularly preferably used in the present invention, 3,3'-di- (3-sulfopropyl) -5,5 '
-Diphenyl-9-ethyloxacarbocyanine hydroxide, 3,3'-di- (3-sulfopropyl) -11
-Ethyl-4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide, 3,3'-di- (3-sulfopropyl) -5,5'-dichloro-9-ethylthiacarbocyanine hydroxide, 3,3'-di- (3-sulfopropyl) -5,5'-dimethyl-9-ethylthiacarbocyanine hydroxide, 3,3'-di- (3-sulfopropyl) -9-ethyl-4, 5,4 ', 5'-dibenzothiacarbocyanine hydroxide, 3-ethyl-
(3-sulfopropyl) -5,5'-dichloro-9-ethylthiacarbocyanine hydroxide, 5- (1-ethyl-2-pyridylidene) -3-ethylrhodanine,
3,3'-di- (3-sulfopropyl) selenacyanine hydroxide, 3-phenyl-5-[(3-methyl-
2-Benzoxazolidine) ethylidene] -1-ethyl-2-thiohydantoin, 3,3′-diethyl-5,6
-Dimethyl-5'-phenyl-9-methyloxathiacarbocyanine iodide, and 3,3'-di- (3-
Sulfopropyl) -5,5'-diphenyl-9-ethyloxacarbocyanine hydroxide and 3,3'-di-
(3-Sulfopropyl) -11-ethyl-4,5,4 ',
Combined use with 5'-dibenzothiacarbocyanine hydroxide, 3,3'-di- (3-sulfopropyl) -5,
5'-dichloro-9-ethylthiacarbocyanine hydroxide and 3,3'-di- (3-sulfopropyl) -9
-Ethyl-4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide in combination, 3-ethyl-1'-ethyl-3'-(3-sulfopropyl) -5'-trifluoromethyl-benz A combination of imidazolo-4,5-benzothiacarbocyanine hydroxide and 3,3′-di- (3-sulfopropyl) -5,5′-dichloro-9-ethylthiacarbocyanine hydroxide can be mentioned.

Furthermore, in the present invention, if desired, a supersensitizing additive that does not absorb visible light, such as an ascorbic acid derivative,
Azaindenes, cadmium salts or organic sulfonic acids can also be included.

When a positive type silver halide emulsion is used in the present invention, a direct positive type silver halide emulsion is preferable, and as the direct positive type silver halide emulsion, for example, the entire surface can be developed in advance by exposure or chemical treatment. And
An example of the silver halide emulsion is an imagewise undevelopable state upon imagewise exposure.

As another direct positive type silver halide emulsion, a direct positive type silver halide emulsion having photosensitivity mainly inside the silver halide grains can be mentioned. In the present invention, the latter direct positive type silver halide milk described in US Pat. No. 3,761,276 is preferred. When this direct positive type silver halide emulsion is imagewise exposed, a latent image is formed mainly inside the silver halide grains, and a positive silver image is formed when surface development is carried out under fog conditions.

There are various methods for development processing under such fog conditions. For example, West German Patent No. 850,383 and US Patent No.
The so-called air fog developer described in 2,497,875 or the like may be used, or flash exposure may be applied to the entire surface during development. This method is described in West German Patent No. 854,888, US Patent No. 2,592,298, British Patent Nos. 1,150,553, 1,195,838 and 1,187,029. Further, development processing may be carried out in the presence of a fogging agent. Fog agents that can be used for this include hydrazine-based compounds, N-substituted quaternary ammonium salts and the like, and these can be used alone or in combination. As these fog agents, 1- [4- (2-formylhydrazino) phenyl] -3-phenylthiourea and β-acetylphenylhydrazine in combination with t-butylaminoborane are preferably used. The amount of the fogging agent can be widely varied depending on the purpose, but when it is added to the development processing solution, it is generally 0.
1 to 2.0 g per 1 m ² when added to the photosensitive element
It is 0.05 mg to 0.1 g.

In the present invention, the above-mentioned negative type silver halide emulsion or various inversion methods can be used, and a negative or positive dye image can be optionally obtained on the image receiving layer in combination with the DRR compound. At this time, the DRR compound is preferably contained in a layer located on the side opposite to the exposure direction with respect to the silver halide emulsion layer so as not to reduce the sensitivity of the photosensitive silver halide emulsion, but a leuco dye image formation is carried out. In the layer positioned in the exposure direction with respect to the silver halide emulsion layer, the sensitivity of the emulsion is not decreased in the substance, the short wavelength shift type dye image forming substance or the dye image forming substance having no dye structure at the time of exposure. It can also be contained in.

Generally, one or two light-sensitive elements each comprising a combination of a light-sensitive silver halide emulsion layer and a non-diffusible dye image-forming substance layer.
By using more than one group, a monochromatic or multicolor dye image can be obtained on the image receiving layer. At this time, the photosensitive element of the present invention can be arbitrarily substituted for all or a part of the above-mentioned photosensitive elements.

Sensitive wavelength range of the photosensitive silver halide emulsion layer and absorption wavelength of the dye image formed on the image receiving layer by the diffusible dye or its precursor released from the non-diffusible dye image forming substance combined with the emulsion layer. The areas may be the same or different and can be used in so-called pseudo color photography, but when used in ordinary natural color photography, the yellow non-diffusible dye image forming substance is contained in the blue sensitive emulsion layer. , The magenta non-diffusible dye image-forming substance is combined with the green-sensitive emulsion layer, and the cyan non-diffusible dye image-forming substance is combined with the red-sensitive emulsion layer. At this time, the maximum absorption long wave of the dye image formed on the image-receiving layer by the non-diffusible dye image forming substance is 400 to 500 mμ when the non-diffusible dye image forming substance is yellow, and 500 to 600 mμ when it is magenta, 600-700m for cyan
It should be in the range of μ.

When performing multicolor photography in the present invention, it is advantageous to use an interlayer in the photosensitive element. The intermediate layer prevents undesired interactions between emulsion layer units having different color sensitivities and controls the diffusivity of the alkaline processing composition.
For this intermediate layer, a system of gelatin, calcium alginate, vinyl acetate-crotonic acid copolymer, isopropyl cellulose, hydroxypropylmethyl cellulose, polyvinylamides, polyvinylamide graft copolymer, latex liquid and penetrant is useful. This intermediate layer may contain an interlayer interaction inhibitor selected depending on the dye image-forming substance used and the type of alkaline processing composition. For example, a non-diffusible hydroquinone derivative such as di-
A reducing agent such as t-octylhydroquinone or potassium 2-octadecylhydroquinone-5-sulfonate, a non-diffusible coupler capable of fixing by reacting with an oxide of a developer, an amidrazone compound, a hydrazone compound, etc. are developed between emulsion layer units. Used to prevent undesired interactions of agent oxides.

In coating each of the above layers, it is advantageous to include a coating aid in the coating composition in order to facilitate coating. It is also possible to add a thickener.

Useful coating aids include saponin, alkyl etherified sucrose, monoalkyl etherified glycerin, p.
-Ethoxyethylene adduct of nonylphenol, sodium dodecylsulfate, sodium salt of dioctylsulfosuccinate, sodium p-dodecylbenzenesulfonate, betaine compounds described in the specifications of British Patent 1,159,825 and U.S. Pat. Kosho 49-46733
And the fluorine compounds described in JP-A-51-32322.

As a thickener, poly-p-sulfostyrene potassium salt,
Examples thereof include cellulose sulfate, polyacrylamide, acrylic acid polymers described in US Pat. No. 3,655,407, and the like.

As a method for applying the above-mentioned coating composition, various methods such as a slide hopper method, a curtain method, a dip method, a roller method, an air knife method can be used, but the slide hopper method is applied simultaneously with other layers. It is preferable.

The support of the photosensitive element is preferably a planar material that does not undergo significant dimensional changes during processing with the processing composition. Although a rigid support such as glass can be used for some purposes, a flexible support is generally useful. And as the flexible support, those used for general photographic light-sensitive materials can be used, for example, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, baryta paper, etc. are advantageously used. used. It is also advantageous in the present invention to use a water vapor permeable support to help the water in the developed alkaline treatment composition to wick through the support after treatment. Whether the support is transparent or opaque is selected depending on various conditions such as the layer structure of the light-sensitive element and the image receiving layer, the direction of exposure, and whether it is processed in a bright place or a dark place. It When a transparent support is used and further processed in the light, the transparent support does not interfere with exposure and observation in order to prevent light leakage from the edges of the transparent support to the silver halide emulsion layer. It is preferably colored to the extent that the transmission of light in the surface direction can be prevented.

When an opaque support is used for the purpose of shielding light, for example, a pigment such as carbon black or titanium oxide may be contained in the support, and a binder may be used on the support if necessary. May be applied.

The support may optionally contain various photographic additives such as plasticizers such as phosphoric acid esters and phthalic acid esters, 2- (2'-vidroxy-4-t-butylphenyl) benztriazole. An ultraviolet absorber, an antioxidant such as hindered phenol may be contained. In order to maintain the adhesion between the support and the layer coated on it,
It is advantageous to provide an undercoat layer or to subject the surface of the support to a pretreatment such as a corona discharge treatment, an ultraviolet irradiation treatment, and a flame treatment. The thickness of the support is not limited, but is usually 20 to 300.
It is desirable to have a thickness of μ.

When the above-mentioned light-sensitive element is imagewise exposed and then treated with an alkaline processing composition, the diffusible dye is diffusely transferred to the image-receiving layer placed in a superposed relationship with the light-sensitive element in response to the imagewise exposure. The layer is dyed to form a color image. The image receiving layer preferably contains a mordant.

As the mordant suitable for the image-receiving layer, any mordant can be used as long as it has a preferable mordant effect on the diffusible dye or its precursor which is diffused and transferred.
Poly-4-vinylpyridine, poly-4-vinyl-N-benzylpyridinium-paratoluenesulfonate, cetyltrimethylammonium bromide, JP-A-54-1398
The compounds described in the publication are useful.

The mordant is an ordinary gelatin, polyvinyl alcohol,
Used in various dispersants such as polyvinylpyrrolidone, fully or partially hydrolyzed cellulose esters such as poly-N-methyl-2-vinylpyridine, N-methoxy-methyl-poly-hexylmethylene adipamide. ,
The image receiving layer is composed only of a dispersant having a mordant effect, such as a copolymer of vinyl alcohol and N-vinylpyrrolidone or a polymer mixture, partially hydrolyzed polyvinyl acetate, acetyl cellulose, gelatin, and polyvinyl alcohol. It is also possible to do so. The content ratio of the mordant in the image receiving layer is preferably in the range of 10 to 100% by weight.

Also, as a special example, a mordant can be included in the alkaline processing composition.

The image-receiving layer may further contain various additives commonly used in the photographic art such as an ultraviolet absorber and a fluorescent brightening agent.

If the diffusible dye diffused and transferred to the image-receiving layer is not a dye but a precursor of a diffusible dye such as a leuco dye, in order to convert these into dyes, for example, an oxidizing agent, a color developing agent or a diazonium compound is used. It is advantageous to include.

The image-receiving layer may be in a relationship of being superposed on the light-sensitive element at the time of the treatment with the alkaline processing composition, may be separated before the treatment, or may be a combination of both. Further, after the processing, the photosensitive element and the image receiving layer may be integrated, or the photosensitive element and the image receiving layer may be peeled off.

The image-receiving layer may be coated on the support of the above-mentioned light-sensitive element or may be coated on another support, but the light-sensitive element and the image-receiving layer are present separately before the treatment, or When the photosensitive element and the image receiving layer are subsequently peeled off, the image receiving layer is usually provided on a support separate from the photosensitive element.

As the support for the image receiving layer, the same support as the above-mentioned support for the photosensitive element can be used.

After the formation of the dye image on the image-receiving layer is substantially completed by applying the alkaline processing composition, the pH in the light-sensitive element and the image-receiving layer is lowered to around neutral to increase the stability of the dye image and It is desirable to effectively stop the image formation and prevent discoloration or contamination of the image that occurs at high pH. For this reason, it is preferable to use a neutralization layer containing a neutralizing agent that lowers the pH in the system. The material used as the neutralizing agent is preferably a film-forming polymer acid having one or more carboxyl groups, sulfone groups or groups capable of generating a carboxyl group by hydrolysis.

The polymeric acid used in the present invention is preferably about 10,000.
To a molecular weight of about 100,000, such as the monobutyl ester of a 1: 1 copolymer of maleic anhydride and ethylene, 1: 1 of maleic anhydride and methyl vinyl ether.
1-copolymer monobutyl ester as well as 1: 1 copolymer of maleic anhydride and ethylene 1: 1 copolymer monoethyl ester, monopropyl ester, monopentyl ester and monohexyl ester, maleic anhydride and methyl vinyl ether 1: 1 Polymer monoethyl ester, monopropyl ester, monopentyl ester and monohexyl ester, polyacrylic acid, polymethacrylic acid and copolymers of various ratios of acrylic acid and methacrylic acid, other vinyls of acrylic acid and methacrylic acid Copolymers in various ratios with the system monomers, that is, containing at least 30 mol%, preferably 50 to 90 mol% of acrylic acid or methacrylic acid, such as acrylic acid esters, methacrylic acid esters, vinyl ethers, etc. A copolymer or the like can be used. In addition to these, Research Disclosure, metal salts described in 12331, monomeric acids, ballasted organic acids, alkyl phosphates, polyacrylic phosphates, poly (1-acryloyl-2,2,2) (2-trimethylhydrazinium, p-toluenesulfonate) and the like can be used alone or in combination with a binder polymer as the case requires. If necessary, a polymer acid and a monomer acid, or a polymer acid and an organic amine may be used in combination. These polymeric acids, monomeric acids, organic amines and binder polymers include alcohols such as methanol, ethanol, propanol, butanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl acetate, etc. It can be dissolved in an ester such as ethyl acetate, isopropyl acetate, butyl acetate, etc., or a mixture thereof, and applied. or,
It can also be microencapsulated.

The thickness of the neutralization layer varies depending on the composition of the alkaline treatment composition used, the material contained in the neutralization layer used, and the like, so it cannot be unconditionally determined, but it is generally 5 to 30 μm. Range is suitable.

A timing layer (neutralization rate control layer) for controlling the decrease in pH may be provided together with the neutralization layer. This timing layer serves to delay the pH drop until after the desired development and transfer has taken place. That is, the neutralization layer prevents an undesired decrease in the density of the transfer dye image due to a rapid decrease in pH in the system before the development of silver halide and the formation of the diffusion transfer dye image.

As this timing layer, various ones can be used, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, cyanoethylated polyvinyl alcohol,
Combinations of hydroxypropylmethyl cellulose, isopropyl cellulose, polyvinyl amides, polyvinyl amide graft copolymers, latex solutions and penetrants are useful.

The neutralizing layer and the timing layer may be coated on the support of the photosensitive element described above, or may be coated on a support different from the support of the photosensitive element together with the image receiving layer, and further, Alternatively, it may be applied on a treatment sheet described later.

Where the image-receiving layer described above is integrally combined with the photosensitive element prior to processing, it is preferred to use processing sheets to evenly distribute the alkaline processing composition and provide good diffusion.

As the processing sheet, those similar to the above-mentioned support of the photosensitive element can be arbitrarily used according to the purpose, and may be transparent or opaque depending on the purpose. The treatment sheet may be coated with a layer containing a mordant as a scavenger, or may be provided with a neutralizing layer and a timing layer.

A peeling agent is preferably used when the image-receiving layer is integrated with the light-sensitive element before the treatment, and when the image is obtained by peeling the light-sensitive element and the image-receiving layer after the treatment. The releasing 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 have a different composition than the binder used in the light-sensitive element and the image-receiving layer. For example, alkali permeable polysaccharides, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, 4,4-dihydroxyphenol glucose, sucrose, sorbitol, inositol, resorcinol, sodium phytate, zinc oxide, fine particle polyethylene, fine particle poly-4-fluorine. Polyethylene, polyvinylpyrrolidone / polyvinylhydrogenphthalate, ethylene-maleic anhydride copolymer, etc. are useful.

The alkaline processing composition used in the present invention is a liquid composition containing processing components necessary for developing a silver halide emulsion and forming a diffusion transfer image, and the solvent of the alkaline processing liquid is mainly water. A hydrophilic solvent such as methanol or methyl cellosolve can be additionally used.
The alkaline processing composition contains the amount of alkaline agent required for development of the emulsion layer and dye image formation. As the alkaline agent, sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, sodium carbonate, sodium phosphate, diethylamine, etc. can be used, and the alkaline treatment composition has about p
It is desirable to have H12 or more. Thickening agents, such as polymeric thickening agents inert to alkaline solutions, such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, can be included in the alkaline processing composition. The concentration of the thickener is preferably about 1 to 10% by weight of the alkaline processing composition, so that the viscosity of the alkaline processing composition is about 100 to 3%.
It becomes 00,000 centipoise and the distribution of the alkaline processing composition during processing can be made uniform. It also has the effect of forming a non-fluidic film during processing and preventing unwanted image changes after substantial dye image formation. Also, the alkaline processing composition preferably contains a silver halide developer.

Typical silver halide developers that can be used in the present invention include 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,
4-dimethyl-3-pyrazolidone, 1-m-tolyl-3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-hydroxymethyl-4-
Methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1,4-dimethyl-3-pyrazolidone, 1-phenyl-4,4-bis- (hydroxy) Methyl) -3-pyrazolidone, 4-methyl-3-pyrazolidone, 1- (3-chlorophenyl) -4-methyl-3-pyrazolidone, 1-
(4-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (3-chlorophenyl) -3-pyrazolidone,
1- (4-chlorophenyl) -3-pyrazolidone, 1-
p-tolyl-4-methyl-3-pyrazolidone, 1-o-
Tolyl-4-methyl-3-pyrazolidone, 1-m-tolyl-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1- (2-trifluoroethyl)
-4,4-dimethyl-3-pyrazolidone, etc., hydroquinone compounds such as hydroquinone, 2,5-dichlorohydroquinone, 2-chlorohydroquinone, etc., catechol compounds such as catechol, 3-methoxycatechol, 4-cyclohexylcatechol, etc. Aminophenol-based compounds such as 4-aminophenol, 3-methyl-4-aminophenol, N-methylaminophenol, 3,5-dibromoaminophenol and the like, phenylenediamine-based compounds such as N, N-diethyl-p- Phenylenediamine, N, N-diethyl-3-methol-p-
Phenylenediamine, 3-methoxy-N-ethyl-N-
Ethoxy-p-phenylenediamine, N, N, N ',
N'-tetramethyl-p-phenylenediamine and the like.

Of these, generally, a black-and-white silver halide developer, particularly a 3-pyrazolidone-based developer, is preferred in order to reduce the occurrence of contamination in the dye image area to be formed.

Further, for example, as described in JP-A-51-111334, two or more kinds of silver halide developers can be used in combination.

The silver halide developer is generally contained in the alkaline processing composition, but it may be contained in at least one layer in the light-sensitive element in advance. Further, it can be contained both in the alkaline processing composition and in the light-sensitive element. When it is contained in the light-sensitive element in advance, it may be contained in the form of a precursor.

The layer in the photosensitive element is, for example, a silver halide emulsion layer,
And a dye image forming substance-containing layer, an intermediate layer, a protective layer, and the like. Further, in the alkaline treatment composition, a benzotriazole-based compound, for example, 5-methylbenzotriazole, a benzimidazole-based compound, for example, 5-nitrobenzimidazole, a tetrazaindene-based compound, for example, 4-
Hydroxy-5,6-cyclopenteno-1,3,3a,
7-Tetrazaindene, sulfite, potassium bromide and the like can be contained. Further, a fog agent, a silver halide solvent and the like can be added depending on the silver halide emulsion used.

The alkaline treatment composition used in the present invention is preferably contained in a destructible container. For example, a sheet of liquid and air impermeable material is folded, and the treatment agent is stored in a hollow container created by sealing each edge, and when the film unit passes through the pressure tool, the treatment agent becomes It is desirable that the alkaline processing liquid is released by breaking at a location determined by the applied internal pressure.

As the material forming the container, materials such as polyethylene terephthalate / polyvinyl alcohol / polyethylene laminate, lead foil / vinyl chloride-vinyl acetate copolymer laminate, etc. are advantageously used. Further, it is desirable that these containers are fixed along the front edge of the photosensitive element so that the stored liquid can be spread on the surface of the photosensitive element in substantially one direction.

As a background of the formed image, it is preferable to provide a light-reflecting agent layer having high whiteness on the side opposite to the viewing direction with respect to the image receiving layer. The position of the light reflector layer is not particularly limited, but after the treatment,
When the photosensitive element and the image receiving layer are not peeled off, it is preferable to provide a light reflecting agent layer between the photosensitive element and the image receiving layer. The light-reflecting agent layer may be provided as a layer in advance, or the light-reflecting agent layer may be contained in the alkaline treatment liquid to form the light-reflecting agent layer during the treatment. As the light reflecting agent, titanium dioxide, zinc oxide, barium sulfate, flake silver, alumina, barium stearate, zirconium oxide and the like can be used alone or in combination of two or more.
When it is provided in advance as a layer, it may be dispersed in any hydrophilic colloid permeable to an alkaline solution, such as gelatin or polyvinyl alcohol.

Stilbene, coumarin or the like may be added as a whitening agent to the light reflector layer. When the silver halide emulsion is developed in the light after exposure, it is preferable to provide an opacifying layer in order to protect the silver halide emulsion from light.
The opacifying agent layer may be provided as a layer in advance or may be formed at the time of treatment. Carbon black or an indicator dye may be added as an opacifying agent. It is also advantageous to use desensitizers.

The light-reflecting agent layer and the opacifying agent layer may be present as the same layer or may be present as separate layers adjacent to each other.

Various types of film units can be used as the film unit composed of the photosensitive element according to the present invention.
3,415,644, 3,415,645, 3,415,646, 3,47
3,925, 3,573,042, 3,573,043, 3,594,164
No., 3,594,165, 3,615,421, 3,576,626,
No. 3,658,524, No. 3,635,707, No. 3,672,890, No. 3,7
30,718, 3,701,656, 3,689,262, JP-A-50-6
Any of the film units described in the specifications and publications of 337, Belgian Patent No. 757,959 or No. 757,960 can be used in the present invention.

In each of the various film units described above, a filter dye or the like suitable for improving photographic characteristics may be added to any position on the light incident side of the silver halide emulsion during exposure, if necessary. As the filter dye, it is possible to use a dye that is stable at a normal pH, but becomes colorless due to decomposition or the like when contacted with an alkaline treatment liquid.

In addition, after the dye image is diffuse-transferred to the image-receiving layer, the silver image and the image of the dye or its precursor remain on the photosensitive element in correspondence with the diffusion-transferred image. The residual silver and silver halide were formed on the image-receiving layer by treating with a bleaching bath and a fixing bath or a bleach-fixing bath to remove them, and further, if necessary, changing the dye precursor to a dye. It is also possible to obtain a dye image that is the reverse of the dye image.

The present invention will be described below based on examples, but the present invention is not limited to the following description.

Example 1 A 150μ thick opaque polyethylene terephthalate film support was coated sequentially with the following layers to give
A photographic element (I) according to the present invention was prepared.

(1) Styrene and N, N-dimethyl-N-benzyl-N-
Terpolymer of p- (methacryloylaminophenyl) methylammonium chloride and divinylbenzene (molar ratio 48/48/4) (2.7 g / m ² ) and gelatin (2.7 g / m ² ).
an image-receiving layer consisting of m ² ).

(2) Titanium dioxide (22 g / m ² ) and gelatin (2.2 g / m ² )
a white reflective layer containing m ² ).

(3) Carbon black (2.8 g / m ² ) and gelatin (1.
Light-shielding layer (opaque layer) containing 8 g / m ² ).

(4) Cyan DRR compound (0.5 g / m ² ) of the exemplified compound (N-15), N, N-diethyllaurylamide (1.0
g / m ² ) as well as a first cyan dye image-forming material layer containing gelatin (2.5 g / m ² ).

(5) The same cyan DRR compound used in (4) (0.025 g
/ M ² ), N, N-diethyllaurylamide (0.05 g /
m ² ), as well as a second cyan dye imager layer containing gelatin (0.5 g / m ² ).

(6) Red-sensitive internal latent image type direct positive emulsion (0.75 converted to silver
g / m ² ), 2-sec-octadecylhydroquinone-5
-Potassium sulfonate (0.08 g / m ² ), 1- [4- (2
-Formylhydrazino) phenyl] -3-phenylthiourea (25 mg per mol of silver) and gelatin (1.65 g /
a red-sensitive emulsion layer containing m ² ).

(7) An intermediate layer containing 2-acetyl-5-sec-octadecylhydroquinone (0.6 g / m ² ) and gelatin (1.25 g / m ² ).

(8) Magenta DRR compound (0.8 g / m ² ) of the exemplified compound (N-1), N, N-dimethyllaurylamide (0.8
First containing g / m ² ) and gelatin (2.5 g / m ² ).
Magenta dye image-forming material layer.

(9) Magenta DRR compound (0.04 g / m ² ) having the same structure as used in (8), N, N-diethyllaurylamide (0.
Second magenta dye image-forming material layer containing 04 g / m ² ) and gelatin (0.5 g / m ² ).

(10) Green-sensitive internal latent image type direct positive emulsion (converted to silver of 1.0
g / m ² ), 2-sec-octadecylhydroquinone-5
-Potassium sulfonate (0.1 g / m ² ), 1- [4- (2
-Formylhydrazino) phenyl] -3-phenylthiourea (25 mg per mol of silver) and gelatin (1.65 g /
m ² ) containing a green-sensitive emulsion layer.

(11) An intermediate layer containing 2-acetyl-5-sec-octadecylhydroquinone (0.6 g / m ² ) and gelatin (1.25 g / m ² ).

(12) Yellow DRR compound (1.0 g / m ² ) of the exemplified compound (N-17), N, N-diethyllaurylamide (1.0
First containing g / m ² ) and gelatin (2.5 g / m ² ).
Yellow dye image forming material layer.

(13) Yellow DRR compound (0.05 g / m ² ) having the same structure as used in (12), N, N-diethyllaurylamide (0.
A second yellow dye image-forming material layer containing 05 g / m ² ) and gelatin (0.5 g / m ² ).

(14) Blue-sensitive internal latent image type direct positive emulsion (converted to silver of 1.0
g / m ² ), 2-sec-octadecylhydroquinone-5
-Potassium sulfonate (0.1 g / m ² ), 1- [4- (2
-Formylhydrazino) phenyl] -3-phenylthiourea (25 mg per mol of silver) and gelatin (1.65 g /
a blue-sensitive emulsion layer containing m ² ).

(15) Gelatin (0.8 g / m ² ), methacrylate beads ( ^{2 to 4} μm 0.15 g / m ² ) Silica (0.45 μm) with a particle size of 0.2 μm
g / m ² ) and tetrakis (vinylsulfonylmethyl)
Protective layer consisting of methane (0.2 g / m ² ).

As a comparative sample to the photographic element (I) of the present invention, as the photographic element (I) except that the second dye image-forming substance layers (5), (9) and (13) were removed from the photographic element (I). Exactly the same comparative photographic element (II) was prepared.

Further, the first and second dye image-forming substance layers (4), (5), (8), (9), (12) and (13) were removed from the photographic element (I), and these layers were removed. Make sure to equalize the amount of substance formed below
A comparative photographic element (I) was prepared identical to photographic element (II) except that (4) ', (8)' and (12) 'were substituted, respectively.

(4) ′ The same cyan DRR compound (0.525 g / m ² ) used in the first cyan dye image-forming material layer (4), N,
A cyan dye image-forming material layer containing N-diethyllaurylamide (1.05 g / m ² ) and gelatin (3.0 g / m ² ).

(8) ′ The same magenta DRR compound (0.84 g / m ² ) used in the first magellanic dye image-forming substance layer (8),
N, N-diethyl lauramide (0.84g / m ²⁾ and gelatin (3.0g / m ²⁾ a magenta dye image-forming material layer containing a.

(12) ′ The same yellow DRR compound (1.05 g / m ² ) as that used in the first yellow dye image-forming substance layer (12),
A yellow dye image forming material layer containing N, N-diethyllaurylamide (1.05 g / m ² ) and gelatin (3.0 g / m ² ).

Further, in the layers (5), (9), and (13) of the above photographic element (I), 2-acetyl-5-sec-octadecylhydroquinone (0.1 g /
A photographic element (IV) identical to photographic element (I) except for the addition of m ² ) was made.

Next, a cover sheet was prepared by sequentially coating the following layers (1) and (2) on a transparent polyethylene terephthalate film support having a thickness of 100 μm.

(1) Copolymer of acrylic acid and ethyl acrylate (75/25
Wt%) (22 g / m ² ) neutralization layer.

(2) A timing layer made of cellulose diacetate (5 g / m ² ).

Each of the prepared photographic elements was exposed to light through a light wedge having a density difference of 0.15 in a single step, and then the above-mentioned processing sheets were superposed on each other. The pod was attached and the film unit was made. The pod was then ruptured by passing the film unit through a pair of pressure-wise juxtaposed rollers having a gap of about 340 μm, the contents of which were spread between the photosensitive element and the processing sheet.

The composition of the treatment composition used here was as follows.

After a few minutes a dye image was observed through the transparent support of the light sensitive element. The reflection density (using a Sakura photoelectric densitometer PDA-65 type) of the obtained dye image was measured, and the results shown in Table 1 below were obtained.

Here, the maximum density and the minimum density are those after 60 minutes of developing the treatment liquid, and the transfer time to.5 indicates the time to reach the density of 50% of the maximum density, which is a measure of the dye image forming speed.

From the above table, it can be seen that the photographic element (I) of the present invention has increased yellow density, magenta density, and cyan density as compared with the conventional photographic element (II) consisting of a single dye image-forming substance layer. Regardless, the minimum concentrations are all extremely low.

Also, a comparative photographic element (I) using a DRR compound and gelatin corresponding to the same amount as the photographic element (I) in the dye image forming material layer.
Compared to II), it can be seen that the minimum density of yellow, magenta and cyan and the dye image forming speed are significantly improved.

Further, it has been found that the photographic element (IV) in which the dihydroxybenzene derivative is contained in the second dye image-forming substance layer of the photographic element (I) according to the present invention is also highly effective.

From the above results, it has become clear that the photographic element of the present invention has the characteristics that the maximum density is high despite the low minimum density and the dye image forming rate is high.

Example 2 1- [4- (2-formylhydrazino) phenyl] -3-phenylthiourea (foggant) was used instead of the internal latent image type direct positive emulsion of the photographic element of Example 1 with a surface latent image type negative emulsion.
To prepare photographic elements (V) to (VIII) excluding photographic elements,
Exposure was performed in the same manner as in Example 1, and development processing was performed using the same processing sheet and processing composition as in Example 1, and the density was measured, and the results shown in Table 2 were obtained.

From the results shown in the above table, July 1984 by the same applicant
Photographic elements (V)-(VII prepared using a surface latent image type negative emulsion prepared by the method described in the patent application filed on 11th
Also in I), the photographic element of the present invention has a high maximum density despite a low minimum density as compared to conventional photographic elements (VI) and (VII) consisting of a single dye image-forming material layer and a high dye density. It was found that the image forming speed was also high.

Example 3 Photographic element (IX) of the present invention was prepared by sequentially coating the following layers on a 150 µ thick opaque polyethylene terephthalate film support.

(1) Yellow DRR compound (N-17) (0.8 g / m ² ),
A first yellow dye image-forming material layer containing N, N-diethyllaurylamide (0.8 g / m ² ) and gelatin (2.5 g / m ² ).

(2) The same yellow DRR compound (0.04 g / m ² ) as above,
A second yellow dye image-forming material layer containing N, N-diethyllaurylamide (0.04 g / m ² ) and gelatin (0.5 g / m ² ).

(3) Blue-sensitive internal latent image type direct positive emulsion (0.7g in terms of silver)
/ M ² ), 2-sec-octadecylhydroquinone-5
Potassium sulfonate (0.2 g / m ² ), 1- [4- (2-
Formylhydrazino) phenyl] -3-phenylthiourea (2.5 mg per silver mole) and gelatin (1.65 g /
a blue-sensitive emulsion layer containing m ² ).

(4) Gelatin (0.8 g / m ^2), methacrylate beads (2~4μm0.15g / m ^2), particle size 0.2μm silica (0.4
5 g / m ² ) and a protective layer consisting of tetrakis (vinylsulfonylmethyl) methane (0.2 g / m ² ).

A comparative photographic element identical to photographic element (IX) except that the second yellow dye image-forming material layer (2) was removed from photographic element (IX) as a comparative sample to photographic element (IX) of this invention. Created (X).

Also, the second yellow dye image-forming material layer of photographic element (IX)
The same photographic element (IX) as photographic element (IX) except that 2-acetyl-5-sec-octadecylhydroquinone (0.1 g / m ² ) was added to (2) as the dihydroxybenzene derivative according to the present invention. )made.

Then, a dye image receiving sheet was prepared by successively coating the following layers on an opaque paper support.

(1) Styrene and N, N-dimethyl-N-benzyl-N-
Tertiary copolymer of p- (methacryloylaminophenyl) methylammonium chloride and divinylbenzene (molar ratio 48/48/4) (2.7 g / m ² ), gelatin (2.7 g / m ² ).
And an image-receiving layer consisting of 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone (0.33 g / m ² ).

(2) Gelatin (1.2 g / m ² ), UV absorber; 2- (2-
Hydroxy-3-tert-butyl-5-n-butylphenyl) benzotriazole, 2- (2-hydroxy-3-)
tert-Butyl-5-methylphenyl) -6-chloro-benzotriazole, 2- (2-hydroxy-3,5-dibutylphenyl) benzotriazole and 2- (2-
Hydroxy-5-n-butylphenyl) benzotriazole mixture (0.8 g / m ² ) and glyoxal (0.0
An intermediate layer consisting of 6 g / m ² ).

(3) Protective layer of gelatin (0.65 g / m ² ).

(4) Gelatin (0.27 g / m ² ) and silica (1.4 g / m ² )
An overcoat layer consisting of.

The above photographic elements (IX) to (XI) are exposed to light through a wedge having a density difference of 0.15 and then dipped in an activator solution having the following composition for 20 seconds, and then a pair of pressures are applied. The image receiving sheet was superposed on the above image receiving sheet through the rollers. Processing is
It carried out at 18 degreeC, 24 degreeC, and 33 degreeC.

(Composition of activator solution) After 3 minutes, the photosensitive sheet and the image receiving sheet were peeled off. The reflection density of the yellow dye image obtained on the image receiving sheet was measured, and the obtained results are shown in Table 3 below.

In the above table, the gradation (γ) is represented by the tangent value of the inclination angle of the straight line connecting the two points of density 0.3 and 0.8 on the characteristic curve.

From the results shown in the above table, both the photographic element having the second yellow dye image-forming substance layer according to the present invention and the photographic element having the dye image-forming substance layer containing the dihydroxybenzene derivative were compared with the comparative photographic element. It is understood that not only the rate of change of the maximum density and the minimum density depending on the processing temperature is small, but also the gradation is stable. Further, in the photographic element (XI), the gradation value is higher than that in the photographic element (IX). Therefore, the shape of the gradation curve can be easily adjusted by the present invention without changing the basic properties of the silver halide emulsion. It turns out that it is controlled by.

〔The invention's effect〕

Having a plurality of dye image-forming substance layers combined with a light-sensitive silver halide emulsion layer, and comparing the concentration of the DRR compound contained in the dye image-forming substance layer of the layer far from the emulsion layer with other layers By increasing the density to a higher level, an image with a higher maximum density and a lower minimum density can be obtained, and further, the dye image forming speed on the image-receiving layer and the processing temperature dependency of gradation are remarkably improved. A light-sensitive material for diffusion transfer method can be obtained.

Claims (1)

[Claims] 1. As a function of oxidation or reduction under alkaline conditions in response to imagewise exposure in combination with at least one light-sensitive silver halide emulsion layer and in combination with said light-sensitive silver halide emulsion layer. In a photosensitive element for a color diffusion transfer process having a layer containing a non-diffusible dye image-forming substance capable of releasing a diffusible dye or a precursor thereof, at least one of the layers containing the dye image-forming substance is a plurality of layers. Of the plurality of layers, the layer farther from the light-sensitive silver halide emulsion layer has a higher concentration of the non-diffusible dye image-forming substance than the layer closer to the light-sensitive silver halide emulsion layer. A light-sensitive element for a color diffusion transfer method, which comprises: