JP2884446B2 - Color diffusion transfer type photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer method and, more particularly, to a dye-diffusion-resistant dye which releases a diffusible dye in response to a reaction in which silver halide is reduced to silver. The present invention relates to an instant color diffusion transfer type photosensitive material capable of obtaining a color image having a high maximum density using a compound.

[0002]

2. Description of the Related Art As a method for directly forming a positive image by a color diffusion transfer method, there are two methods: A) a direct positive silver halide emulsion and a diffusible dye corresponding to a reaction in which silver halide is reduced to silver. (B) a conventional silver halide emulsion (a silver halide emulsion having a negative-positive response) and a method in which silver halide is reduced to silver. A non-diffusible compound that becomes diffusible by itself in response to a reaction that reacts with itself or a compound that releases a diffusible dye in response to a reaction in which silver halide is reduced to silver (these compounds are positive). (Referred to as a type dye-donating compound).

In the method A), for example, British Patent No. 1,3
30,524, JP-B-48-39165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 4,483,914, which are capable of leaving a diffusible dye. (D) which releases a diffusible dye by a coupling reaction with an oxidized form of a reducing agent
DR coupler), US Patent No. 3,928,312,
No. 4,053,312, No. 4,055,428, No. 4,336,322, etc., which are reducible to silver halide and have a diffusivity when reduced. A compound that releases a dye (DRR compound) is used.

In the method B), US Pat.
No. 4,764, No. 3,362,819, No. 3,59
7,200, 3,544,545, 3,48
No. 2,972, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked (the dye developer is diffusible in an alkaline environment, but is non-diffusible when reacted with silver halide). As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide. Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat. No. 3,980,479;
199,354, etc., compounds which release diffusible dyes by intramolecular reversal of isoxazolone ring, US Pat. No. 4,559,290, EP 220,746 A2, US Pat. 783,396
And non-diffusible compounds that react with a reducing agent remaining without being oxidized by development to release a diffusible dye, as described in JP-A No. 5-2,199, and the like.

[0005] Among the above two methods, the method B) is preferable in that higher sensitivity is easily obtained.

[0006]

However, as in the above-mentioned image forming method, particularly in the above-mentioned B) -type image forming method, a dye-donating compound is used in combination with an electron donor in combination with a silver halide emulsion. In this case, there is a problem that the maximum density of the image is not sufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color diffusion transfer type photosensitive material for obtaining a color image having a high image density.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to provide at least a light-sensitive silver halide emulsion on a support, which emits a diffusible dye in reverse to the reaction in which silver halide is reduced to silver. In a color diffusion transfer type photosensitive material having a photosensitive element containing a dye-donating compound, an electron donor and a binder and being developed with an alkaline processing solution, the dye-donating compound and / or the electron donor have a water content of 0.1%. 4
%, And is dispersed in a high-boiling organic solvent having a value obtained by dividing the organic value by 3 or less.

In the present invention, in the high-boiling organic solvent having the above-mentioned physical properties, the dye-donating compound and the diffusion-resistant electron donor sufficiently react during development, and the stability of the dispersion is kept high. Further, a compound having a water content of 0.6% or more is more preferable, and a compound having an organic value divided by an inorganic value of 3 or less and 0.9 or more and a boiling point of 180 ° C. or more is particularly desirable.

The dye-donating compound and the diffusion-resistant electron donor can be dissolved and dispersed together in the high-boiling organic solvent of the present invention, or can be prepared as a separate dispersion. In the latter case, at least one is dispersed using the high-boiling organic solvent of the present invention, while the other is a known high-boiling solvent,
And / or a low-boiling solvent described later or JP-B-51-3
9853 and JP-A-51-59943 and the like.

The high-boiling organic solvents used in the present invention are illustrated below, but the present invention is not limited to these compounds.

[0012]

Embedded image

The organic value and the inorganic value in the present invention are defined in an organic conceptual diagram (by Yoshio Koda, published by Sankyo). The water content of the high-boiling organic solvent as defined in the present invention is determined by mixing the high-boiling organic solvent (1.5 cc) with water (6 cc) and shaking for 16 hours. It was determined by measuring at 25 ° C. with a trace moisture measuring device (CA-01 manufactured by Mitsubishi Kasei Corporation).

In the present invention, a dye-providing compound and / or an electron-donating agent are dissolved and dispersed in the high-boiling organic solvent. In this case, a low-boiling organic solvent having a boiling point of 50 ° C. to 150 ° C. may be used in combination. be able to. Polymers described in JP-B-51-39853 and JP-A-51-59943 may be used in combination. The amount of the high-boiling organic solvent of the present invention is 10 g or less, preferably 5 g or less, per 1 g of the dye-donating compound or the diffusion-resistant electron donor (when used in combination). Various surfactants, which are known to be used in dispersing hydrophobic compounds in hydrophilic colloids, can also be used in this case. For example, Japanese Patent Application Laid-Open No.
The surfactants listed on pages 7) to (38) can be used.

The dye-providing compound used in the present invention is a compound having a function of releasing or diffusing a diffusible dye imagewise. This type of compound can be represented by the following general formula [LI]. (Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like latent image. The difference in diffusivity of the compound represented by (Dye-Y) _n -Z is caused in correspondence to the photosensitive silver salt having the following formula, or Dye is released, and the released Dye and (Dye-Y) _{and n} represents a group having a property that causes a difference in diffusibility with respect to -Z, wherein n is 1
Or 2 and when n is 2, the two Dye-Ys may be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. U.S. Pat. Nos. 3,134,764;
Nos. 362,819, 3,597,200, 3,5
No. 44,545, No. 3,482,972, etc., a dye developer comprising a hydroquinone-based developer and a dye component linked thereto. The dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide or an oxidized form of an electron transfer agent. As described in U.S. Pat. No. 4,503,137, etc., a nondiffusible dye which releases a diffusible dye in an alkaline environment but loses its ability when reacted with an oxidized form of silver halide or an electron transfer agent. Compounds can also be used. Examples thereof include compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and isoxazolone described in US Pat. No. 4,199,354. Compounds that release a diffusible dye by an intramolecular ring rewinding reaction are included. U.S. Pat. No. 4,559,290
No. 4,220,746 A2, U.S. Pat.
Non-diffusible compounds that react with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used, as described in JP-A-783,396 and JP-A-87-6199.

For example, see US Pat. No. 4,139,
No. 389, No. 4,139,379, JP-A-59-18.
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. Nos. 4,232,107
No., JP-A-59-101649, and JP-A-61-88257.
No., Research Disclosure (Research)
Disclosure (hereinafter referred to as “RD”) 240
No. 25 (1984), etc., compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-1984.
No. 142,530, U.S. Pat. Nos. 4,343,893 and 4,619,884, compounds which release a diffusible dye by cleavage of a single bond after reduction; U.S. Pat. Examples include a nitro compound which releases a diffusible dye after electron acceptance described in US Pat. No. 223 and the like, and a compound which releases a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like.

More preferred are EP 220,746 A2, JP 87-6199, US Pat. No. 4,783,396, and JP-A-63-2016.
No. 53, No. 63-201654, etc., in each molecule, an NX bond (X represents an oxygen, sulfur or nitrogen atom)
And a compound having an electron-withdrawing group, JP-A-1-26842
SO ₂ -X (X is as defined above) in one molecule described in
And compounds having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule.
Compounds having a C—X ′ bond (X ′ has the same meaning as X or —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341 can be mentioned. Further, Japanese Patent Laid-Open No.
The compounds described in JP-A-161237 and JP-A-1-161342 that can release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are particularly preferred. Examples are EP 220,746 A2 or U.S. Pat.
Compounds (1) to (3) described in No. 83,396,
(7) to (10), (12), (13), (15),
(23)-(26), (31), (32), (35),
(36), (40), (41), (44), (53)-
(59), (64), (70), Published Technical Report 87-619
9 compounds (11) to (23).

In the present invention, particularly in the case of a dye donating compound, since the reducing agent competitively acts on the silver developing reaction and the dye releasing reaction, the present invention can significantly increase the maximum density of an image.

Each of these compounds can be synthesized by the methods described in the above-cited patent specifications.
The amount of the reducible dye-providing compound used depends on the extinction coefficient of the dye, but is in the range of 0.05 to 5 mmol / m ² , preferably 0.1 to 3 mmol / m ² . The dye donating compounds can be used alone or in combination of two or more. Also,
To obtain an image of black or a different hue,
As described in JP-A No. 0-162251, mobility having different hues such as mixing at least one cyan, magenta and yellow dye-donating compound in a layer containing silver halide or in an adjacent layer. Two or more dye-donating compounds that release a dye may be used in combination.

In the present invention, when the dye-donating compound is used, a non-diffusible electron donor is used (when the electron donor is used in the present invention, its precursor is also included).
For details of these compounds, see U.S. Pat.
No. 3,396, European Patent Publication No. 220,746A2, Japanese Patent Publication No. 87-6199, JP-A-2-22649, JP-A-2-32338, JP-A-2-35451, Japanese Patent Application No. 1-2
No. 69556 and the like.

The use amount of the electron donor has a wide range,
It is preferably in the range of 0.01 to 50 mol, particularly preferably 0.1 to 5 mol, per mol of the dye-providing compound. The amount is 0.001 to 5 mol, particularly preferably 0.01 to 1.5 mol, per mol of silver halide. The electron donor is preferably contained in the same layer as the dye-donating compound, but may be contained in an adjacent layer.

In the present invention, an intermediate layer is provided to prevent the oxidized form of the electron transfer agent formed as a result of development from diffusing into other photosensitive layers and the like, causing color turbidity and causing a decrease in density. A diffusion-resistant reducing agent capable of reducing the oxidized form of the electron transfer agent can be added to this layer. In the present invention, the compounds described in the following patents can be used as the diffusion-resistant reducing agent used for the intermediate layer. US Patent No. 2,36
0,290, 2,403,721, 2,41
8,618, 2,701,197, 2,72
8,659, 2,735,765, 2,73
No. 2,300, No. 3,700,453, Special Publication No. 59-
37497, 56-21145, 51-122
No. 50, JP-A-59-202465 and 55-721
No. 58, No. 55-43521, No. 57-22237
No. 58-156932, No. 59-5247, No. 62-103638, West German Patent Publication (OLS) 2,7
No. 32,971, JP-A-1-120553, 2-3
No. 2338, No. 2-46450, No. 2-64633
No. 2 and No. 2-110557. Further, the above-mentioned electron donors can also be used.

The amount of the reducing agent to be added is 0.01 to 10 mmol, preferably 0.1 to 5 mmol per 1 m ² of the support in each intermediate layer, and 0 to 1 mmol per 1 g of the binder in each intermediate layer. 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol. The reducing agent of the present invention can be added to the protective layer as needed. When added to the protective layer, the amount added is 0.01 to 10 mmol, preferably 0.1 to 5 mmol per 1 g of the binder in the protective layer.

When there are a plurality of intermediate layers in the present invention, the diffusion-resistant reducing agent added to each intermediate layer may be the same or different, or a plurality of compounds may be used in combination.

In the present invention, a development inhibitor precursor can be used for the purpose of improving image discrimination and color reproducibility. The development inhibitor precursor used in the present invention is described in JP-B-47-44805 and JP-B-54-173.
No. 69, No. 55-9696, No. 55-34927,
JP 54-39727, JP-A-57-135944,
No. 57-135945, No. 57-136640, No. 55-53330, No. 57-76541, No. 57-
No. 135949, No. 57-179842, No. 62-2
No. 15270, No. 61-67851, No. 61-124
No. 941, No. 61-147249, No. 61-1857
No. 43, No. 61-184539, No. 61-14724
No. 4, No. 61-188540, No. 61-182039
Nos., 61-185744 and 61-236548
Nos., 61-267045 and 61-267041
Nos. 61-269147 and 61-269143
No. 61-269148, No. 61-269147
And JP-A-2-64634 and JP-A-2-110557. In the present invention, the development inhibitor precursor can be used in any layer such as an emulsion layer, an intermediate layer, a dye-donating compound-containing layer, and a protective layer.

Hydrophobic additives such as a dye-providing compound and a diffusion-resistant electron donor can be introduced into a layer of a photosensitive element by a known method such as the method described in US Pat. No. 2,322,027. In the emulsification dispersion method, JP-A-59-831 is used.
No. 54, No. 59-178451, No. 59-17845
No. 2, 59-178453, 59-178454
And high-boiling organic solvents described in JP-A-59-178455, JP-A-59-178457, and the like, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. Further, after the emulsification and dispersion, the organic solvent having a low boiling point can be removed and used, if necessary, by ultrafiltration or the like.

Since the electron donor of the present invention has low diffusivity,
In order to promote electron transfer between the electron donor of the present invention and the developable silver halide, it is preferable to use an electron transfer agent and / or an electron transfer agent precursor in combination. As the electron transfer agent or its precursor, any one can be used as long as it cross-oxidizes the electron donor and does not substantially generate stain even when oxidized.
Specific compounds of these electron transfer agents include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferred because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-
p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3'-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and the like. Such electron transfer agents may be used alone or in combination of two or more, may be added to a processing solution described later, or may be incorporated in the photosensitive element. When incorporated in a light-sensitive element, it can be added in whole or in part to all layers (emulsion layer, intermediate layer, protective layer, etc.).

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The halogen composition in the grains may be uniform, or the grains may have a multiple structure having different compositions on the surface and in the inside (JP-A-57-154232, 58-1).
No. 08533, No. 59-48755, No. 59-522
37, U.S. Pat. No. 4,433,048 and EP 100,984). The particle thickness is 0.5 μm
Hereinafter, tabular grains having a diameter of at least 0.6 μm and an average aspect ratio of 5 or more (US Pat. No. 4,414,310)
No. 4,435,499 and West German Patent (OL)
S) No. 3,241,646A1) or a monodisperse emulsion having a nearly uniform particle size distribution (JP-A-57-17823).
No. 5, No. 58-100846, No. 58-14829
No. WO 83 / 02338A1, European Patent No. 6
4,412A3 and 83,377A1).

Two or more kinds of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. Two or more types of monodispersed emulsions having different grain sizes may be mixed to adjust the gradation. In the present invention, the average grain size of the silver halide grains is 0.001 μm.
The thickness is preferably from m to 10 μm, more preferably from 0.001 μm to 5 μm.

These silver halide emulsions may be prepared by any of an acidic method, a neutral method, and an ammonia method.
As a reaction form of the soluble silver salt and the soluble halogen salt,
Any of a one-side mixing method, a simultaneous mixing method, or a combination thereof may be used. An inverse mixing method in which grains are formed in excess of silver ions, or a controlled double jet method in which the pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open No. 55-142).
Nos. 329 and 55-158124; U.S. Pat.
No. 50, 757). Epitaxial junction type silver halide grains can also be used (JP-A-56-161).
24, U.S. Pat. No. 4,094,684).

In the step of forming the silver halide grains used in the present invention, ammonia may be used as a silver halide solvent, an organic thioether derivative described in JP-B-47-11386, or a sulfur-containing solvent described in JP-A-53-144319. Compounds and the like can be used. Cadmium salts, zinc salts, lead salts, thallium salts, and the like may coexist in the process of particle formation or physical ripening. Further, a water-soluble iridium salt such as iridium chloride (III, IV) and ammonium hexachloroiridate, or a water-soluble rhodium salt such as rhodium chloride can be used for the purpose of improving high illuminance failure and low illuminance failure. The soluble salts may be removed from the silver halide emulsion after the formation of the precipitate or after the physical ripening. Therefore, the silver halide emulsion can be subjected to the Nudel washing method or the sedimentation method.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, or the like can be used alone or in combination for an emulsion for a normal photosensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-21).
No. 5644).

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the surface of a grain or an internal latent image type in which a latent image is formed inside a grain.
A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,763.
1,276, JP-B-58-3534 and JP-A-5
No. 7,136,641. Preferred nucleating agents for combination in the present invention are U.S. Pat.
227,552, 4,245,037, 4,2
55,511, 4,266,013, 4,27
6,364 and West German Patent Publication (OLS) 2,63
No. 5,316 and the like.

As a method for forming silver halide grains used in the present invention, a known single jet method or double jet method can be used. In the latter method, the pAg in the reaction solution is further kept constant. A so-called controlled double jet method can also be used. Further, a method of combining them may be used. In any of the silver halide emulsion forming methods described above, any of known single-stage addition methods or multi-stage addition methods may be used, and the addition rate may be a constant rate, or may be stepwise or continuously. The rate of change (for example, a method of changing the addition flow rate of the solution while keeping the concentration of the soluble silver salt and / or halide constant, or the method of dissolving the soluble silver in the addition liquid while keeping the addition flow rate constant) It can be achieved by a method of changing the concentration of salt and / or halide, or a method of combining them). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner. The coating amount of the photosensitive silver halide of the present invention is from 1 mg to 10% in terms of silver.
g / m ² .

As a protective colloid used in preparing the emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates,
Sugar derivatives such as sodium alginate and starch derivatives; mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Such various kinds of synthetic hydrophilic polymer substances can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, p30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic decomposition product of gelatin can also be used.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, and JP-A-59-180550.
No. 60-140335, RD17029 (197
8 years), sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 3,615,641 and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The reproduction of a natural color by the subtractive color method is carried out by combining the emulsion spectrally sensitized with the above-mentioned spectral sensitizing dye with the above-mentioned dye-donating compound which provides a dye having selective spectral absorption in the same wavelength range. At least two photosensitive layers are used. The emulsion and the dye-donating compound may be coated as separate layers, or may be mixed and coated as a single layer. In the case where the dye-donating compound is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, another layer is preferred. In this case, the layer of the reducible dye-providing compound is preferably located below the silver halide emulsion layer from the viewpoint of sensitivity. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, or an arbitrary layer may be provided between the emulsion layer and the dye-donating compound layer. The color image density can be increased by providing a partition layer described in JP-B-60-15267, or the reflective layer described in JP-A-60-91354 can be provided to increase the sensitivity of the photosensitive element. In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side.

When the present invention is used as a photographing material,
An ultraviolet absorbing layer can be provided on the uppermost layer of the photosensitive layer.
Various ultraviolet absorbers generally used in the technical field, such as a benzotriazole compound, a 4-thiazolidone compound, and a benzophenone compound, can be used for the absorbing layer.

As the binder for the constituent layers of the photosensitive element and the image receiving element, hydrophilic binders are preferably used. Examples thereof include pages (26) to (28) of JP-A-62-253159.
Page. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Polyvinylpyrrolidone, acrylamide polymer,
Other synthetic polymer compounds can be mentioned. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly preferably 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the photosensitive element or the image receiving element include dimensional stability, curl prevention, adhesion prevention,
Various polymer latexes can be contained for the purpose of improving film physical properties such as prevention of cracking of the film and prevention of pressure increase / decrease sensation. Specifically, JP-A Nos. 62-245258 and 62
Any of the polymer latexes described in JP-B-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, the image receiving layer can be prevented from cracking, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

US Pat. No. 4,678,739, No. 41, as a hardener for use in a constituent layer of a photosensitive element or an image receiving element.
Column, JP-A-59-116655 and JP-A-62-24526.
No. 1, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be mentioned.

In the constituent layers of the photosensitive element and the image receiving element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are described in JP-A-62-173463 and JP-A-6-173463.
2-183457 and the like.

The constituent layers of the light-sensitive element and the image-receiving element may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of the organic fluoro compounds include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, and JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

A matting agent can be used for the photosensitive element and the image receiving element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952.

In addition, the constituent layers of the photosensitive element and the image receiving element may contain an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the image-receiving element. Examples of the image formation accelerator include promoting a redox reaction between a silver halide and a reducing agent, accelerating a reaction such as formation of a dye from a dye-donating compound or decomposition of the dye or release of a diffusible dye, and a method of forming a dye from a photosensitive material layer. It has the function of promoting the transfer of the dye to the fixed layer. From the physicochemical function, it interacts with a base or a base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a surfactant, silver or silver ions. Classified as compounds having an effect. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. For details of these, see US Pat.
78, 739, columns 38-40.

Next, other components included in the present invention will be described. A) Support The support used in the present invention includes a transparent support, a white support, a black support and the like which are usually used as a smooth photographic support. The thickness of the transparent support is 50 to 350 μm,
Preferably, polyethylene terephthalate, cellulose acetate, polycarbonate or the like having a size of 70 to 210 μm is used. The transparent support may contain a minute amount of a pigment such as titanium dioxide or a small amount of a dye to prevent light piping.

The white support in the present invention refers to a support having at least a white color on the side on which the dye image-receiving layer is provided, and any support having sufficient whiteness and smoothness can be used. Can be done. For example, a particle size of 0.1 to 5 μm
Titanium oxide, barium sulfate, polymer film whitened by the formation of microvoids by the addition or stretching of white pigments such as barium sulfate, such as polyethylene terephthalate film formed by conventional sequential biaxial stretching, a film made of polystyrene, polypropylene or Synthetic paper and those obtained by laminating polyethylene, polyethylene terephthalate, polypropylene or the like on both sides of paper are preferably used. A white pigment such as titanium white may be kneaded in the laminate layer. The thickness of the support is 50 to 350
μm, preferably 70 to 210 μm, more preferably 8 μm
0 to 150 μm. If necessary, a light-shielding layer may be provided on the support. For example, a support obtained by laminating polyethylene containing a light-shielding agent such as carbon black on the back of a white support is used.

As the black support, polyethylene terephthalate, cellulose acetate, polycarbonate, polystyrene, and the like having a thickness of 50 to 350 μm, preferably 70 to 210 μm, containing a light shielding agent such as carbon black.
A thickness of 50 to 400 μm, preferably 70 to 70 μm, containing a light shielding agent such as polypropylene or carbon black.
A laminate obtained by laminating polyethylene, polyethylene terephthalate, polypropylene or the like on both sides of a paper support having a thickness of up to 250 μm is preferably used. As the carbon black raw material, for example, Donnel Vest “Ca
rbon Black "Marcel Dekker,
Inc. Any production method such as a channel method, a thermal method and a furnace method described in (1976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 °. The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the light-sensitive material to be shielded, but the optical density is 5 to 1
About 0 is desirable.

When a black support is used or the whiteness of a white support is insufficient, it is necessary to provide a white light reflecting layer between the support and the dye image-receiving layer, and the particle size is 0.1. It is preferable to provide a layer containing a white pigment such as titanium oxide, barium sulfate, and zinc oxide of up to 5 μm, or a hollow polymer latex.

B) Layer Having a Neutralizing Function The layer having a neutralizing function used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali introduced from the treatment composition. Accordingly, a multilayer structure including layers such as a neutralization rate control layer (timing layer) and an adhesion strengthening layer may be used. Preferred acidic substances are those containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), and more preferably olein described in US Pat. No. 2,983,606. Higher fatty acids such as acids, US Pat. No. 3,362,8
Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in Patent No. 19; acrylic acid as disclosed in French Patent No. 2,290,699 Acrylic acid ester copolymers; US Pat. No. 4,139,383 and RDN
o. 16102 (1977). In addition, U.S. Pat. No. 4,088,493;
No. 153739, No. 53-1023, No. 53-454
The acidic substances disclosed in Nos. 0, 53-4541 and 53-4542 can also be mentioned.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose acetate, hydrogen diphthalate, and the like. The polymer acid may be used alone or in combination with a hydrophilic polymer. Examples of such a polymer include polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred. Further, a polymer other than the hydrophilic polymer, such as cellulose acetate, may be mixed with the polymer acid.

The amount of the polymer acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymer acid to the alkali per unit area is preferably from 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0 to 1.3. When mixed with a hydrophilic polymer, the amount of the hydrophilic polymer is too large or too small, and the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is 0.1.
It is 1 to 10, preferably 0.3 to 3.0.

In the layer having a neutralizing function of the present invention, additives can be incorporated for various purposes. For example, hardeners well known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other, if necessary,
An antioxidant, a development inhibitor and a precursor thereof can also be added.

C) Neutralizing Timing Layer The timing layer used in combination with the intermediate layer may be, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like. Useful are polymers that lower alkali permeability; latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid monomer to increase the activation energy of alkali permeation; and polymers having a lactone ring. In particular, Japanese Patent Application Laid-Open No. 54-136328, U.S. Pat.
7,262, 4,099,030, 4,02
Timing layer using cellulose acetate disclosed in JP-A-9,849 and the like;
Nos. 6-69629, 57-6843, U.S. Patent Nos. 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256. Latex polymers prepared by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid disclosed in U.S. Pat. Nos. 827 and 4,268,604; lactones disclosed in U.S. Pat. No. 4,229,516 Polymer having a ring; Others, JP-A-56-25735 and JP-A-5-25735
Nos. 6-97346 and 57-6842, European Patent No. 3
1,957A1, 37,724A1, 48,4
The polymers disclosed in, for example, No. 12A1 are particularly useful.

In addition, those described in the following documents can also be used. U.S. Pat. Nos. 3,421,893 and 3,45
5,686, 3,575,701, 3,77
8,265, 3,785,815, 3,84
7,615, 4,088,493, 4,12
3,275, 4,148,653, 4,20
1,587, 4,288,523, 4,29
7,431, West German Patent Application (OLS) 1,622,9
No. 36, No. 2, 162, 277, RD 15162
No. 151 (1976). JP-A-59-20246
No. 3, U.S. Pat. Nos. 4,297,431 and 4,28.
8,523, 4,201,587, 4,22
9,516, JP-A-55-121438 and JP-A-56-121438.
No.166212, No.55-41490, No.55-54
No. 341, No. 56-102852, No. 57-1416
No. 44, No. 57-173834, No. 57-17984
No. 1, West German Patent Application Publication (OLS) 2,910,271
No., European Patent No. 31,957A1, RD No. 18
452 and the like.

The neutralization timing layer may be a single layer or multiple layers. In the timing layer made of these materials,
For example, U.S. Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, and 3,014,67.
No. 2, JP-A Nos. 54-155837 and 55-1387
No. 45, and the like, and a development inhibitor and / or a precursor thereof disclosed in U.S. Pat.
Hydroquinone precursor disclosed in No. 78,
Other useful photographic additives or precursors thereof can be incorporated.

D) Dye receiving layer The dye receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable. The polymer mordant used in the present invention is preferably a polymer having a secondary or tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group, or the like having a molecular weight of 5,000 or more. Is 10,000 or more.

For example, see US Pat. No. 2,548,564.
Nos. 2,484,430 and 3,148,061
No. 3,756,814; vinylpyridine polymers and vinylpyridinium cationic polymers; vinylimidazolium cationic polymers disclosed in US Pat. No. 4,124,386; US Pat. Nos. 625,694, 3,859,096 and 4,128,538, British Patent 1,277,453.
No. 3,958,995, U.S. Pat.
Nos. 1,852 and 2,798,063,
No. 115228, No. 54-145529, No. 54-1
No. 26027, No. 54-155835, No. 56-17
Aqueous sol-type mordant disclosed in U.S. Pat. No. 352,352, etc .; water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088; U.S. Pat. Nos. 4,168,976, 4,20.
Reactive mordants capable of forming a covalent bond with the dyes disclosed in U.S. Patent No. 3,709,690.
Nos. 3,788,855 and 3,642,482
No. 3,488,706 and 3,557,066
No. 3,271,147, 3,271,148
JP-A-53-30328 and JP-A-52-155528.
Nos. 53-125, 53-1024, 53-
No. 107835 and British Patent No. 2,064,802. Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

Among these mordants, those which hardly migrate from the mordant layer to the other layer are preferred. For example, those which undergo a crosslinking reaction with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type Mordants are preferred. Particularly preferred is a latex dispersion mordant,
Particle size 0.01-2 μm, preferably 0.05-0.2 μ
m is preferred. The amount of mordant applied depends on the type of mordant, 4
0.5 to 10 g depending on the content of the class cationic group, the type and amount of the dye to be mordant, the type of binder used, and the like.
/ M ² , preferably 1.0 to 5.0 g / m ² , particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred. An anti-fading agent may be used in the image receiving layer. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. These are substantially contained in the image receiving layer and can be added to other layers if the effect can be obtained.

Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794) as ultraviolet absorbers,
4-thiazolidone compounds (US Pat. No. 3,352,6)
No. 81), benzophenone-based compounds (JP-A-46-
2784, etc.), and JP-A-54-48535,
There are compounds described in JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of the metal complex include U.S. Patent Nos. 4,241,155 and 4,24.
5,018, columns 3 to 36; 4,254,195, columns 3 to 8; JP-A Nos. 62-174741 and 61-88.
No. 256, pages 27 to 29, JP-A-1-75568
And JP-A-63-199248.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137). An anti-fading agent for preventing fading of the dye transferred to the image receiving element may be contained in the image receiving element in advance, or may be supplied to the image receiving element from the outside such as a photosensitive element or a processing composition. Good. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used in the photosensitive element and the image receiving element. In particular, whether the image receiving element contains a fluorescent whitening agent,
It is preferable that the toner is incorporated in a photosensitive element or a processing composition and supplied to an image receiving element during a processing step. As an example,
K. Weenkataraman ed. "The Chem
compound of Synthetic Dyes, Vol. V, Chapter 8, JP-A-61-143752, and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with an anti-fading agent.

E) Release Layer In the present invention, a release layer is provided, if necessary, to peel off the photosensitive element and the image receiving element after processing. Therefore, this release layer must be easily peelable after the treatment. Materials for this purpose include, for example, Japanese Patent Application Laid-Open No. 47-8237.
Nos. 59-220727 and 59-229555
No. 49-4653, U.S. Pat. No. 3,220,83.
No. 5,4,359,518, JP-A-49-4334.
Nos. 56-65133 and 45-24075; U.S. Pat. Nos. 3,227,550 and 2,759,825
Nos. 4,401,746 and 4,366,227 can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. For example, hydroxyethyl cellulose, cellulose acetate-phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, and the like. Other examples include various natural polymers, such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins such as acetylated gelatin and phthalated gelatin can also be used. Further, another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol,
Examples thereof include polyacrylate, polymethyl methacrylate, polybutyl methacrylate, and a copolymer thereof. The release layer may be a single layer or a plurality of layers as described in, for example, JP-A-59-220727 and JP-A-60-60642.

F) Processing Composition The processing composition used in the present invention is developed uniformly on the photosensitive element after exposure of the photosensitive element, and develops the photosensitive layer with the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a development accelerator for controlling development, a development inhibitor, an antioxidant for preventing deterioration of the developer, and the like. I do. The alkali is sufficient to adjust the pH of the treatment liquid to 12 to 14, and includes an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) and an alkali metal phosphate (eg, potassium phosphate). ), Guanidines, and hydroxides of quaternary amines (eg, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable. The thickener is necessary for developing the processing solution uniformly, for maintaining the close contact between the photosensitive element and the image receiving element during development, and for preventing the processing liquid component from remaining on the surface of the image receiving element during peeling. is there. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

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

In the present invention, the electron transfer agent can be added to the processing composition regardless of whether the electron transfer agent is contained in the photosensitive element or not.

The treatment composition described above is disclosed in US Pat.
No. 3,181, No. 2,643,886, No. 2,65
No. 3,732, No. 2,723,051, No. 3,05
Nos. 6,491, 3,056,492 and 3,15
It is preferable to fill and use a container that can be ruptured by pressure as described in 2,515 or the like.

Next, the structure of the photosensitive material will be described. A color diffusion transfer instant photosensitive material can be formed by combining the above-described elements. The color diffusion transfer instant film unit is roughly classified into a release type and a release-free type, and the release type has a photosensitive layer and a dye image-receiving layer coated on a separate support, and after image exposure, a photosensitive element, The dye image is transferred to the dye-receiving layer by superimposing the dye-receiving element, developing the processing composition therebetween, and then peeling off the dye-receiving element. On the other hand, in the non-peelable type, the dye receiving layer and the photosensitive layer are coated between the transparent support and the other support, but the image receiving layer and the photosensitive layer are coated on the same transparent support. There is a form that is coated on another support. In the former case, a white reflective layer is coated between the image receiving layer and the photosensitive layer, and in the latter case, a white pigment is applied to the processing composition developed between the image receiving layer and the silver halide emulsion layer. By containing the dye, the dye image transferred to the image receiving layer can be observed with reflected light.

In the release type, the image receiving element and the photosensitive element are generally provided on separate supports, and a layer having a neutralizing function, a neutralization timing layer, a release layer, if necessary, in addition to a dye image receiving layer as an image receiving material. Is provided. As a support for the image receiving material,
It is preferable to use a white support having a light shielding function. On the other hand, the light-sensitive material is provided with a layer having a neutralization function and a neutralization timing layer, if necessary, in addition to the light-sensitive layer. It is preferable to use a black support having a light-shielding function as the support for the photosensitive material. The film unit is disclosed in
No. -47956 can be applied. Further, as a peeling type, JP-A-1-198747,
As described in Japanese Patent Application No. 1-68749, a film unit in which a dye image-receiving layer / a release layer / a photosensitive layer is provided on the same support in this order can be used.

When the photosensitive layer and the image receiving layer are provided on the same support, the release-free type is a cover sheet material provided with a layer having a neutralization function and a neutralization timing layer on another transparent support. Is used. As for the film unit, those described in JP-B-46-16356 and JP-A-50-13040 can be applied.

[0076]

The present invention will be described in more detail with reference to the following examples.

Example 1 A method for preparing a red-sensitive silver halide emulsion (I) will be described. To a well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride, and 30 mg of the following drug A in 800 cc of water and kept at 50 ° C.) was added as described in Table A below. Solution I) and solution (II) were simultaneously added at an equal flow rate over 30 minutes. Thereafter, solution (III) and solution (IV) shown in Table B below were simultaneously added over 30 minutes. In addition, 3 of the start of addition of (III) and (IV) solutions
After one minute, the following dye solution was added over 20 minutes. After washing with water and desalting, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.7, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3 were added.
a, 7-Tetrazaindene and chloroauric acid were added and optimally sensitized at 60 ° C. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.38 μm was obtained. The yield was 635 g.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

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<Dye Solution> A solution prepared by dissolving 67 mg of the following dye (a) and 133 mg of dye (b) in 100 cc of methanol.

[0082]

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Next, the green-sensitive silver halide emulsion (II) will be described. The gelatin solution (Table C), which was well stirred, was kept at 50 ° C., and the solutions (I) and (II) in Table D were added over 30 minutes. Next, liquid (III) and liquid (IV) in Table D were mixed with 3
It was added over 0 minutes, and one minute after the completion of the addition, the following dye solution was added. After washing with water and desalting, add 20 g of gelatin and p
H, pAg was prepared and triethylthiourea, chloroauric acid,
Optimum chemical sensitization was performed using 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. The resulting emulsion was a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.40 μm, and the yield was 630 g.

[0084]

[Table 3]

[0085]

[Table 4]

<Dye solution> 0.18 g of the following dye (c):
A solution obtained by dissolving 0.02 g of the dye (d) and 0.035 g of the dye (e) in 154 cc of methanol.

[0087]

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Next, how to prepare a blue-sensitive silver halide emulsion (III) will be described. A well-stirred aqueous gelatin solution [20 g of gelatin in 800 cc of water, potassium bromide 3
g, 0.03 g of the following chemical A, and HO (CH ₂ ) ₂
0.25 g of S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH was added and kept at 50 ° C.], and the solutions (1) and (2) in Table E below were added simultaneously over 30 minutes. . Thereafter, Solution (3) and Solution (4) shown in Table E below were simultaneously added over 20 minutes. After the addition of the solution (3) was started, the following dye solution was added in 18 minutes from 5 minutes. After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and p.
After adjusting the Ag to 8.5, sodium thiosulfate and 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimal chemical sensitization. Thus, 600 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.40 μm was obtained.

[0089]

[Table 5]

[0090]

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<Dye Solution> A solution prepared by dissolving 0.18 g of the following dye (f) and 0.06 g of the dye (g) in 160 cc of methanol.

[0092]

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Next, a method for preparing a gelatin dispersion of a dye-providing substance will be described. Yellow dye-donating compound (1)
^* The 2.2g, electron donor (1) ^* The 0.7 g, high-boiling organic solvent (1) ^* was 1.5g weighed, ethyl acetate 13c
c was added thereto and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and a 14% solution of lime-processed gelatin 12.4
g, 14 cc of water and 1.2 cc of a 5% aqueous solution of a surfactant (2) ^* , and then mixed with a homogenizer.
Dispersed at 10,000 rpm for minutes. This dispersion is referred to as a yellow dye-providing compound dispersion.

Dispersions of the magenta and cyan dye-donating compounds were prepared using the magenta dye-donating compound (2) ^* or the cyan dye-donating compound (3) ^* , like the yellow dye-donating compound.

Next, a method of preparing a gelatin dispersion of a diffusion-resistant reducing agent for the intermediate layer will be described. Reducing agent (1) ^* 20.
0 g, development inhibitor precursor (1) ^* 5.9 g, compound (1) ^* 1.8 g, high boiling point organic solvent (1) ^* 8.5 g are dissolved in ethyl acetate (26 cc) and cyclohexanone (13 cc) at about 60 ° C. and homogeneously. Solution. 100 g of this solution and a 10% solution of lime-processed gelatin, surfactant (2) ^*
After stirring and mixing 15 cc of a 5% aqueous solution of the above and 15 cc of a 1.7% aqueous solution of sodium bisulfite, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes.
This dispersion is referred to as a dispersion of the diffusion-resistant reducing agent for the intermediate layer.

Thus, a comparative photosensitive element 101 having the structure shown in Table 1 below was prepared.

[0097]

[Table 6]

[0098]

[Table 7]

[0099]

[Table 8]

Matting agent (1) ^* Spherical latex of polymethyl methacrylate (average particle size 4 μm)

[0101]

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Surfactant (1) ^* Aerosol OT

[0103]

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High boiling organic solvent (1) ^* Tricyclohexyl phosphate Hardener (1) ^* 1,2-Bis (vinylsulfonylacetamide) ethane

[0105]

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[0106]

Embedded image

[0107]

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[0108]

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Further, the first layer, the fifth layer
The high-boiling organic solvents (1) ^* in the color layers of the first and ninth layers were replaced with the high-boiling organic solvents shown in Table 2 to prepare photosensitive elements 102 to 108 as comparative examples.

[0110]

[Table 9]

[0111]

[Table 10]

Next, the first layer, the fifth layer
And the ninth colorant layer, the high-boiling organic solvents (1) ^* were changed to the high-boiling organic solvents shown in Table 3 to obtain photosensitive elements 201 to 20.
5 was created.

[0113]

[Table 11]

The image receiving element was prepared as follows. Paper support: 150 μm thick paper laminated with polyethylene on both sides by 30 μm. To the polyethylene on the image receiving layer side, 10% by weight of titanium oxide based on polyethylene is dispersed and added.

Back side: (a) Carbon black 4.0
g / m ² , light-shielding layer of gelatin 2.0 g / m ² . (B) Titanium oxide 8.0 g / m ² , gelatin 1.0 g / m
white layer of m ^2. (C) A protective layer of 0.6 g / m ² of gelatin. (A) ~
(C) is applied in this order and is hardened by a hardener.

Image receiving layer side: (1) Average molecular weight of 50,000
Neutralizing layer containing 22 g / m ² of acrylic acid-butyl acrylate (molar ratio 8: 2). (2) Cellulose acetate having a degree of acetylation of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample), and styrene-maleic anhydride having an average molecular weight of about 10,000 (molar ratio) 1: 1) A second timing layer containing 4.5 g / m ^{2 of the} copolymer in a weight ratio of 95: 5. (3) An intermediate layer containing 0.4 g / m ^{2 of} poly-2-hydroxyethyl methacrylate. (4) Styrene / butyl acrylate / acrylic acid / N
-Methylol acrylamide in a weight ratio of 49.7 / 42.
A polymer latex emulsion polymerized at a ratio of 3/4/4;
A polymer latex obtained by emulsion polymerization of methyl methacrylate / acrylic acid / N-methylolacrylamide at a weight ratio of 93/3/4 is blended so that the solid content ratio is 6: 4, and the total solid content is 1.6 g. / M ² first timing layer. (5) with a compound of the following Formula 13 as a coating aid, an image receiving layer was coated with a polymer mordant 3.0 g / m ² gelatin 3.0 g / m ² having a repeating unit of the following Formula 14. (6) A protective layer coated with 0.6 g / m ² of gelatin. The above (1) to (6) are applied in this order and hardened with a hardener.

[0117]

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[0118]

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The treatment liquid formulation is shown below. 0.8 g of a treatment liquid having the following composition was filled in a container capable of bursting. 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 14.0 g potassium sulfite (anhydrous) 4.0 g hydroxyethylcellulose 40 g potassium hydroxide 64 g benzyl alcohol 2.0 g

The photosensitive elements 101 to 108 and 201
After exposing No. to 205 from the emulsion layer side through B, G, R and gray color separation filters, the image receiving layer side of the image receiving element is superimposed so that the processing solution has a thickness of 60 μm between both elements. Deployed with the help of a pressure roller.
The processing was performed at 25 ° C., and the photosensitive element and the image receiving element were peeled off after 1.5 minutes. The cyan reflection density of the maximum density portion of the gray portion transferred to each image receiving element was measured with a color densitometer.
Table 4 shows the results.

[0121]

[Table 12]

From Table 4, the comparative photosensitive elements 101 to 108 were obtained.
In, the dye-donating compound and the electron donor are supplied from the processing liquid because the water content is low or the value obtained by dividing the organic value by the inorganic value is dispersed in a high-boiling organic solvent exceeding 3. Since the aqueous alkaline solution hardly penetrates into the dispersion, the image density decreases. On the other hand, it was found that the photosensitive elements 201 to 205 using the high boiling point organic solvent of the present invention can obtain high image density.

[0123]

According to the present invention, a dye donating compound and / or
Alternatively, when the electron donor is dispersed in a high-boiling organic solvent having a water content of 0.4% or more and an organic value divided by an inorganic value of 3 or less, the effect of increasing the density of the obtained color image is obtained. Obtained.

Claims (1)

(57) [Claims] 1. A photosensitive silver halide emulsion comprising at least a photosensitive silver halide emulsion on a support, a dye-donating compound which emits a diffusible dye in response to a reaction in which silver halide is reduced to silver, and a non-diffusible electron donor. In a color diffusion transfer type photosensitive material having a photosensitive element containing a dye and a binder and developing with an alkaline processing solution, the dye-providing compound and / or the electron-donating agent have a water content of 0.4% or more and an organic value. Is dispersed in a high boiling organic solvent having a value obtained by dividing by 3 with an inorganic value of 3 or less.