JPH04218044A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To improve storage stability of the heat-developable color photosensitive material with the lapse of time and to stably obtain a color image high in image density and small in stains. CONSTITUTION:The heat-developable color photosensitive material contains a hardener for hardening it represented by general formula (I) in which R is H, or an alkyl, aralkyl, aryl, or heterocyclic group, and n is 0 or 1.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material which can provide color images with sufficient image density and low stain, and which has excellent storage stability.

0002

[Background Art] Heat-developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (published by Corona Publishing, 1982), pages 242-255. It is written on the page. Many methods have also been proposed for obtaining color images by heat development. For example, U.S. Patent No. 3,531,286
No. 3,761,270, No. 4,021,240, Belgian Patent No. 802,519, Research Disclosure magazine (hereinafter referred to as RD), September 1975, pages 31-32, etc. A method of forming a color image by combining an oxidized drug with a coupler has been proposed.

However, since the heat-developable photosensitive material for producing the above-mentioned color images is a non-fixing type, silver halide remains even after the image is formed, and the white background gradually becomes colored when exposed to strong light or stored for a long period of time. This poses a serious problem. Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high fog and low image density.

[0004] In order to improve these drawbacks, a method has been proposed in which a diffusive dye is formed or released in an image form by heating, and the diffusible dye is transferred to an image-receiving material having a mordant using a solvent such as water. ing. (U.S. Patent No. 4
, No. 500,626, No. 4,483,914, No. 4,
No. 503,137, No. 4,559,920, Japanese Unexamined Patent Publication No. 5
No. 9-165054, etc.) In the above method, the development temperature is still high and the stability of the photosensitive material over time is not sufficient. Therefore, a method of heat development in the presence of a base or a base precursor and a trace amount of water to transfer the dye is disclosed in JP-A-59-218443, which accelerates development, lowers the development temperature, and simplifies the process. 61-238056, European Patent No. 210,660A2, etc.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound is converted into an oxidized form without dye-releasing ability in the presence of a reducing agent or its precursor, and then thermally developed to form a compound that is in an oxidized form without dye-releasing ability. A method has been proposed in which a reducing agent is oxidized and the remaining unoxidized reducing agent is used for reduction to release a diffusible dye. Also, European Patent Publication No. 220,746,
Kokka Technical Report 87-6199 (Vol. 12, No. 22) describes a compound that releases a diffusible dye by a similar mechanism, including a reductive compound with an N-X bond (X represents an oxygen atom, nitrogen atom, or sulfur atom). A heat-developable color photosensitive material using a compound that releases a diffusible dye upon cleavage is described.

[0006]

Problems to be Solved by the Invention In the above-mentioned heat-developable photosensitive materials, since a development reaction occurs in a short time, there is a strong correlation between the physical properties of the coating film and the resulting photographic performance. In particular, in a system that simultaneously performs thermal development and dye transfer in the presence of a small amount of water, the development speed and transfer speed often vary depending on the physical properties of the film, especially the degree of hardness. Therefore, in order to maintain stable photographic performance of heat-developable photosensitive materials,
It is necessary to minimize changes in film properties. In particular, it is desirable to suppress changes in hardness as much as possible, but depending on the hardening agent used, the hardening reaction is slow, and a large amount must be used to obtain the desired hardness at the time of product shipment. Since the hardening reaction continues to occur gradually, the degree of hardening changes during storage of the product, resulting in the problem that photographic properties cannot be maintained constant.

[0007]

OBJECTS OF THE INVENTION An object of the present invention is to obtain a heat-developable color photosensitive material which has excellent storage stability and production stability.

[0008]

[Means for Solving the Problems] The object of the present invention is to provide a heat-developable color photosensitive material having at least a photosensitive silver halide, a binder, and a dye-providing compound on a support, which is represented by the following general formula (I). This was achieved using a heat-developable color photosensitive material characterized by having a layer hardened with a compound.

[0009]

[Case 2]

In the formula, R represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. n represents 0 or 1.

The hardening agent used in the heat-developable color photosensitive material of the present invention has a fast hardening reaction after coating and drying, provides stable film properties at the time of shipment, and has little change in film properties after shipment. Although it is an excellent hardener, it reacts quickly when added to the coating solution, so if it is not applied immediately, it will react with the gelatin binder over time, increasing the viscosity of the coating solution and causing poor coating. There is. To prevent this, there is a method in which a hardening agent is added and mixed with a pump while the coating solution is being transferred from a tank (especially just before coating), and then coated immediately. It is preferable to use this method for the production of.

Another method is to keep the pH of the coating liquid to which the hardening agent is added at 40°C below 6.5 and take advantage of the fact that the hardening reaction is relatively slow at low pH. There is a way. This method makes it possible to control the hardening speed of the coated film by increasing the pH of one of the layers that does not contain a hardening agent and neutralizing it when the layers are coated. The utility value will be even greater. The pH of the layer to which the hardener is added is 6.0 at 40°C.
The pH value is preferably 5 or less, but when lime-treated gelatin is used as the binder, a pH range of 4.8 to 6.5 is more preferable in order to prevent coacervation of gelatin.

Next, the hardening agent used in the heat-developable color photosensitive material of the present invention will be described in more detail. The compound represented by the general formula (I) used in the present invention will be explained. In general formula (I), R is a hydrogen atom, an alkyl group, an aralkyl group,
Represents an aryl group or a heterocyclic group. n represents 0 or 1. To explain in more detail, R is a hydrogen atom and has 1 carbon number.
~20 alkyl groups (including substituted ones, e.g. methyl, ethyl), aralkyl groups having 6 to 20 carbon atoms (
Including those that have been replaced. For example, benzyl, phenethyl), an aryl group having 5 to 20 carbon atoms (including substituted ones, such as phenyl and naphthyl), or a 5 to 6-membered nitrogen-containing heterocyclic group (such as pyridyl). Examples of substituents include sulfonic acid groups, hydroxyl groups, and carboxyl groups. Particularly preferred as R is a hydrogen atom. n represents 0 or 1. Specific examples of the compound represented by the general formula (I) of the present invention are listed below, but the present invention is not limited thereto.

[0014]

[Chemical formula 3]

[0015]

[C4]

The amount of the compound represented by the general formula (I) to be added is desirably selected depending on the type of compound, the type of gelatin, etc., and is 0.5 x 10-3 to 50 x 10 per 100 g of gelatin. -3 mol is appropriate;
Preferably it is 2 x 10-3 to 20 x 10-3 mol.

The compound represented by the general formula (I) used in the present invention is contained in at least one of the hydrophilic colloid layers such as the silver halide emulsion layer, the protective layer, and the intermediate layer. A method that does not allow coexistence with compounds (zinc hydroxide, zinc oxide, etc.) is preferred. Further, from the viewpoint of manufacturing suitability, the compound represented by the general formula (I) used in the present invention is preferably added by the mixing method immediately before coating as described in Example 1.

In the silver halide emulsion layer and/or other photographic constituent layers, a compound represented by the general formula (I) and a gelatin hardening agent commonly used in the art may be used in combination. Examples of such curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl urea), and 2-hydroxy-4
, 6-dichloro-1,3,5-triazine, and others U.S. Patent Nos. 3,288,775 and 2,732,303
British Patent No. 974,723, British Patent No. 1,167,20
Compounds having reactive halogens such as those shown in No. 7, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others U.S. Patent No. 3,635,718 , 3,232
, No. 763, No. 3,490,911, No. 3,642,
No. 486, compounds with reactive olefins such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent Nos. 2 and 7.
N-methylol compounds such as those shown in U.S. Pat. No. 32,316 and U.S. Pat. No. 2,586,168;
Isocyanates such as those shown in US Pat. No. 3,017,280, US Pat. No. 2,983,
Aziridine compounds as shown in No. 611 etc.,
U.S. Patent Nos. 2,725,294 and 2,725,29
Acid derivatives such as those shown in U.S. Pat.
, 100,704, epoxy compounds as shown in U.S. Pat. No. 3,091,537, U.S. Pat. No. 3,321,313, U.S. Pat. 3,543,292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or chromium alum as an inorganic hardening agent. , zirconium sulfate, etc.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, and a dye-providing compound (which may also serve as a reducing agent as described later) on a support. Furthermore, an organic metal salt oxidizing agent or the like may be contained as necessary. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination. . For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials. Further, each of these photosensitive layers may be divided into two or more layers as necessary. The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

The silver halide that 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 silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofog. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. The particle size is preferably 0.1 to 2 μm, particularly 0.2 to 1.5 μm. The crystal habits of silver halide grains are cubic, octahedral,
It may be a tetradecahedron, a flat plate with a high aspect ratio, or any other shape. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A No. 62-253159, etc. can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, selenium sensitization methods, etc. for emulsions for conventional light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-Open No. 62-25315
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m 2 in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the organic silver salt oxidizing agents described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 626, columns 52-53. Also, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 13235, and
Acetylene silver described in No. 249,044 is also useful. Two or more types of organic silver salts may be used in combination. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m 2 in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include azoles and azaindenes described in RD17643 (1978) pages 24-25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The 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. 60-140335, RD17029 (197
Examples include the sensitizing dyes described on pages 12 and 13 of 8th year). These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. ，
No. 615,641, JP-A No. 63-23145, etc.). These sensitizing dyes may be added to the emulsion during or before chemical ripening, or as described in U.S. Pat.
, 183,756 and 4,225,666 before or after nucleation of silver halide grains. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the light-sensitive material or the dye-fixing material. Examples include pages (26) to (2) of JP-A-62-253159.
Examples include those listed on page 8). Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and pullulan, and polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, super absorbent polymers described in JP-A No. 62-245260, etc.
That is, homopolymers of vinyl monomers having -COOM or -SO3 M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Sumikagel L-5H) manufactured by Kagaku Co., Ltd. is also used. Two or more of these binders can also be used in combination.

[0027] When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to rapidly absorb water. Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to another material after transfer. In the present invention, the amount of binder applied is preferably 20 g or less per m2, particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the photosensitive material or dye-fixing material may contain additives for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitization and desensitization. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A-62-245258, JP-A-62-136648, JP-A-62-110066, etc. can be used. especially,
Using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent the mordant layer from cracking, and using a polymer latex with a high glass transition point for the back layer can prevent curling. .

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donating compound having reducing properties, which will be described later, is also included (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include columns 49 to 50 of U.S. Pat. No. 4,500,626 and columns 30 to 50 of U.S. Pat.
Column 31, No. 4,330,617, No. 4,590,15
No. 2, JP-A No. 60-140335, Nos. (17) to (1)
8) page, No. 57-40245, No. 56-138736
No. 59-178458, No. 59-53831,
No. 59-182449, No. 59-182450, No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-198540,
60-181742, 61-259253, 62-244044, 62-131253 to 62-131256, European Patent No. 220,746
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. A2. Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

When using a diffusion-resistant reducing agent, an electron transfer agent and/or an electron transfer agent may be added as necessary to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below. In the present invention, the amount of reducing agent added is 0.00% per mole of silver.
0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, silver can be used as the image forming substance. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. can. Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a polymer chain. Specific examples of color developers and couplers are given by T. H. Jam
“The Theory of the
Photographic Process” No. 4
Edition pages 291-334 and 354-361, Japanese Patent Application Publication No. 1973.
No. 8-123533, No. 58-149046, No. 58
-149047, 59-111148, 59-
No. 124399, No. 59-174835, No. 59-2
No. 31539, No. 59-231540, No. 60-29
No. 50, No. 60-2951, No. 60-14242,
It is described in detail in No. 60-23474, No. 60-66249, etc.

[0032] As another example of the dye-providing compound,
Examples include compounds that have the function of releasing or diffusing diffusible dyes in an imagewise manner. This type of compound can be represented by the following general formula [LI]. Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a connecting group, and Z corresponds to or inversely corresponds to a photosensitive silver salt having a latent image in image form. to create a difference in the diffusivity of the compound represented by (Dye-Y)n-Z, or to release Dye and increase the diffusivity between the released Dye and (Dye-Y)n-Z. represents a group having the property of causing a difference in , n represents 1 or 2, and when n is 2, the two Dye-Ys may be the same or different. General formula [
Specific examples of the dye-providing compound represented by LI] include the following compounds (1) to (2). In addition, ■ to ■ below correspond inversely to the development of silver halide to form a diffusive dye image (positive dye image), and ■ and ■ correspond to the development of silver halide to form a diffusible dye image. It forms a dye image (negative dye image).

■US Patent No. 3,134,764, 3
, No. 362,819, No. 3,597,200, No. 3,
544,545, 3,482,972, etc., a dye developer in which a hydroquinone developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. ■As described in US Pat. No. 4,503,137, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. Examples include compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions described in U.S. Patent No. 3,980,479, and isoxazolone described in U.S. Pat. No. 4,199,354. Examples include compounds that release diffusible dyes through intramolecular rewinding reactions of rings.

■US Patent No. 4,559,290, European Patent No. 220,746A2, US Patent No. 4,783,
As described in No. 396, Kokai Technical Report 87-6199, etc., non-diffusible compounds that release diffusible dyes by reacting with the reducing agent remaining unoxidized during development can also be used. Examples include U.S. Patent No. 4,139,389, U.S. Pat.
No. 57-84453, etc., a compound that releases a diffusible dye by an intramolecular nucleophilic substitution reaction after being reduced, U.S. Patent No. 4,232,107, JP-A-59
-101649, 61-88257, RD240
25 (1984) etc., a compound which releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3,008,588A, JP-A-1988-1
42530, U.S. Pat. No. 4,343,893, U.S. Pat. No. 4,619,884, etc., compounds whose single bonds are cleaved after reduction to release a diffusible dye; U.S. Pat. No. 4,450; Nitro compounds that release diffusible dyes after accepting electrons, as described in U.S. Patent No. 223, etc.;
, 609,610, etc., which release a diffusible dye after electron acceptance.

[0035]More preferably, European Patent No. 220,746A2, Published Technical Report No. 87-6199, US Pat.
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in No. 653, No. 63-201654, etc., JP-A-1-268
42, a compound having SO2 -X (X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A-63-
PO-X bond (
X has the same meaning as above) and an electron-withdrawing group;
'Bond (X' is synonymous with X or represents -SO2 -)
and a compound having an electron-withdrawing group. Further, compounds described in JP-A-1-161237 and JP-A-1-161342, which release a diffusible dye by cleavage of a single bond by a π bond conjugated with an electron-accepting group after reduction, can also be used. Among these, compounds having an N-X bond and an electron-withdrawing group in one molecule are particularly preferred. Specific examples include European Patent No. 220,746A2 or U.S. Patent No. 4,78.
Compounds (1) to (3), (7) described in No. 3,396
) to (10), (12), (13), (15), (23
) ~ (26), (31), (32), (35), (36
), (40), (41), (44), (53) to (59
), (64), (70), and compounds (11) to (23) described in Kokai Technical Report 87-6199.

(2) A compound having a diffusible dye as a leaving group, which releases the diffusible dye upon reaction with an oxidized form of a reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, U.S. Pat.
No. 4,483,914, etc. ■A compound (D
RR compound). Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent. A typical example is U.S. Patent Nos. 3 and 9.
No. 28,312, No. 4,053,312, No. 4,05
No. 5,428, No. 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381
No. 9, No. 51-104343, RD17465, U.S. Patent No. 3,725,062, U.S. Patent No. 3,728,113
No. 3,443,939, Japanese Unexamined Patent Publication No. 11653/1983
No. 7, No. 57-179840, U.S. Patent No. 4,500
, No. 626, etc. Specific examples of DRR compounds include the aforementioned U.S. Pat. No. 4,500,626, No. 2.
Compounds described in columns 2 to 44 can be mentioned, among which compounds (1) to (3) described in the above-mentioned U.S. patents can be mentioned.
, (10) to (13), (16) to (19), (28)
〜(30),(33)〜(35),(38)〜(40)
, (42) to (64) are preferred. Also, U.S. Patent No. 4,
Also useful are the compounds described in No. 639,408, columns 37-39. In addition, the couplers mentioned above and the general formula [LI
] Examples of dye-donating compounds other than dye silver compounds that combine organic silver salts and dyes (Research Disclosure magazine, May 1978 issue, pages 54-58, etc.), azo dyes used in heat-developable silver dye bleaching methods ( U.S. Patent No. 4,235,9
No. 57, Research Disclosure, No. 4, 1976, pp. 30-32, etc.), Leuco dye (U.S. Patent No.
, No. 985,565, No. 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-providing compounds and diffusion-resistant reducing agents can be introduced into the layers of the light-sensitive material by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454,
59-178455, 59-178457, etc., as necessary.
It can be used in combination with a low boiling point organic solvent of 0°C to 160°C. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing compound used. Further, it is appropriate that the amount is 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less per 1 g of binder. Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59943
The dispersion method using polymers described in No. In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above. When dispersing hydrophobic compounds into hydrophilic colloids,
A variety of surfactants can be used. For example, those listed as surfactants on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Pat. No. 4,500,62.
No. 6, columns 51-52.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can also be applied to the present application. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat.
No. 00,626, columns 58-59 and JP-A-61-8825
The mordant described in No. 6, pages (32) to (41), JP-A-6
Examples include those described in No. 2-244043 and No. 62-244036. Also, U.S. Patent Nos. 4 and 4
Dye-receiving polymeric compounds such as those described in US Pat. No. 63,079 may also be used. The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improving agent between the light-sensitive material and the dye-fixing material. A specific example is JP-A No. 62-253159 (25
), No. 62-245253, etc. Furthermore, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used for the above purpose. Examples include various modified silicone oils, especially carboxy-modified silicone (trade name: X-
22-3710) etc. are effective. Also, JP-A-62-
Silicone oils described in No. 215953 and No. 63-46449 are also effective.

[0040] Anti-fading agents may be used in the light-sensitive materials and dye-fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (such as U.S. Patent No. 3,533,794), 4-thiazolidone compounds (such as U.S. Patent No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective. Examples of metal complexes include U.S. Pat. No. 4,241,155, U.S. Pat. No. 61-88256 (27
) to (29) pages, No. 63-199248, JP-A-1-
There are compounds described in No. 75568 and No. 1-74272.

[0041] Examples of useful anti-fading agents are disclosed in JP-A-62-21
No. 5272, pages (125) to (137). The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination. A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. An example is K. Edited by Veenkataraman “The
Chemistry of Syntheti
c.
Examples include compounds described in No. 52 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds,
Examples include carbostyryl compounds. Optical brighteners can be used in combination with antifade agents.

In addition to the above-mentioned hardening agents, the hardening agents used in the constituent layers of the dye-fixing material include those described in US Pat. No. 4,678,73.
No. 9, column 41, JP-A-59-116655, JP-A No. 62-
Examples include hardeners described in No. 245261 and No. 61-18942. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners (such as compounds represented by the following formula 5), and vinyl sulfone hardeners (N, N' -ethylene-bis(vinylsulfonylacetamide) ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157, etc.). It will be done.

[0043]

[C5]

Various surfactants can be used in the constituent layers of the light-sensitive material and the dye-fixing material for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like. Specific examples of surfactants are JP-A-62-173463;
It is described in No. 62-183457 and the like. An organic fluoro compound may be included in the constituent layers of the photosensitive material or the dye fixing material for the purpose of improving slipperiness, preventing static electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17, and Japanese Patent Publication No. 61-2094.
4, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye-fixing material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described in No. 1-88256 (page 29), JP-A-63-274944, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 63-274952. others,
The constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A No. 61-8825.
No. 6, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and silver. It is also classified as a compound that interacts with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40. Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. A specific example is U.S. Patent No. 4,511,493.
No. 62-65038, etc.

In a system in which thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye-fixing material in order to improve the storage stability of the light-sensitive material. In addition to the above, European Patent Publication No. 210,660, U.S. Patent No. 4,740,445
Combinations of poorly soluble metal compounds and compounds that can form complexes with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds), as described in JP-A No. 1986-
Compounds that generate bases by electrolysis as described in No. 232451 can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

In the present invention, various development stoppers can be used in the light-sensitive material and/or the dye-fixing material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development. The development stopper mentioned here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors. For more details, see JP-A-62-25
No. 3159, pages (31) and (32).

[0049] In the present invention, as a support for the light-sensitive material or dye-fixing material, one that can withstand the processing temperature is used. Generally, paper, synthetic polymer (film)
can be mentioned. Specifically, films made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), or films containing pigments such as titanium oxide, as well as polypropylene, etc. film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (
In particular, materials such as cast coated paper), metal, cloth, glass, etc. are used. These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition to this,
The supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, etc. A method of scanning and exposing an original image through a slit using an exposure device of a copying machine, a method of transmitting image information to a light emitting diode, various lasers, etc. via an electric signal, and a method of transmitting image information to a CRT, liquid crystal display, etc. There is a method of outputting the image to an image display device such as an electroluminescence display or a plasma display and exposing it directly or via an optical system.

[0051] As a light source for recording an image on a photosensitive material,
As mentioned above, U.S. Patent No. 4 for natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc.
, 500, 626, column 56 can be used. Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, BaB2 O4, etc., urea derivatives, nitroaniline derivatives, such as 3-methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and compounds described in JP-A-61-53462 and JP-A-62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful. The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. It is possible to use image signals created using a computer, such as signals, CG, and CAD.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye. In this case, the transparent or opaque heating element is
Those described in No. 45544 etc. can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step can be developed at about 50°C to about 250°C, and particularly useful is about 80°C to about 180°C. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 50° C. or higher and up to about 10° C. lower than the temperature in the heat development step.

[0053] Dye migration can also be caused by heat alone, but
A solvent may be used to facilitate dye transfer. Also,
As detailed in JP-A-59-218443 and JP-A-61-238056, it is also useful to carry out development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (especially water). be. In this method, the heating temperature is preferably at least 50°C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least 50°C and at most 100°C. Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may (Those listed in the section on formation accelerators are used)
can be mentioned. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt, and a complex-forming compound may be included in the solvent.

These solvents can be used in a method in which they are applied to a dye fixing material, a photosensitive material, or both. The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating). As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A No. 61-147244 (2)
There is a method described on page 6). Further, the solvent can be used by being incorporated in the photosensitive material, the dye fixing material, or both in advance, such as by encapsulating the solvent in microcapsules.

In order to promote dye transfer, a method may also be adopted in which a hydrophilic thermal solvent, which is solid at room temperature and dissolves at high temperature, is incorporated into the light-sensitive material or dye fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far-infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere. The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye-fixing material and bringing them into close contact are described in JP-A-61-1.
The method described in No. 47244, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Utility Model Application No. 62-259
The apparatus described in No. 44 and the like is preferably used.

[0058]

[Examples] Specific examples will be described below, but the present invention is not limited to these examples. <Example 1> A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.15 μm12.
5g, carboxymethylcellulose 1g as a dispersant,
0.1 g of sodium polyacrylate to 4% gelatin aqueous solution 1
00 ml and was ground in a mill for 30 minutes using glass beads with an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent (a) will be described. 10 g of the following electron transfer agent (a), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of Demol N (manufactured by Kao Soap Co., Ltd.)
was added to 100 ml of a 5% gelatin aqueous solution and ground for 60 minutes in a mill using glass beads with an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent (a) with an average particle size of 0.4 μm.

[0060]

[C6]

Next, a method for preparing a gelatin dispersion of a dye-providing compound will be described.

[0062]

[Table 1]

Yellow, magenta, and cyan dye-providing compounds were heated and dissolved at about 60° C. according to the recipe shown in Table A above to form a uniform solution. After stirring and mixing this solution with 100 g of a 10% aqueous solution of lime-treated gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water, the mixture was heated using a homogenizer for 10 minutes at 10,000 rpm.
It was dispersed. This dispersion is called a gelatin dispersion of a dye-providing compound.

[0064]

[C7]

[0065]

[Chemical formula 8]

[0066]

[Chemical formula 9]

[0067]

[Chemical formula 10]

[0068]

[Chemical formula 11]

[0069]

[Chemical formula 12]

[0070]

[Chemical formula 13]

[0071]

[Chemical formula 14]

Next, the preparation of a gelatin dispersion of the electron donor (2) for the intermediate layer will be described. The following electron donor ■20.
0g, 5.9g of the following compound, 1.8g of the following compound, and 8.5g of the above high boiling point solvent, and 30ml of cyclohexanone.
1 and heated to dissolve at 60°C to obtain a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, 0.8 g of sodium dodecylbenzenesulfonate, 0.3 g of sodium bisulfite, and 30 ml of water were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of electron donor (1).

[0073]

[Chemical formula 15]

[0074]

[Chemical formula 16]

[0075]

[Chemical formula 17]

Next, the method for preparing the photosensitive silver halide emulsion (I) (for blue-sensitive emulsion layer) will be described. A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and HO(CH2)2S(CH2 in 800 cc of water)
)2 Add 0.3g of S(CH2)2OH to 55
The following solutions (1) and (2) were added simultaneously over 30 minutes. Thereafter, the following solutions (3) and (4) were simultaneously added over 20 minutes. Also (3)
After starting addition of the liquid, a methanol solution of the following sensitizing dye (0.12 g each of sensitizing dye A and sensitizing dye B dissolved in 160 cc of methanol) was added over 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 pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3
, 3a,7-tetrazaindene, and chloroauric acid were added to perform optimal chemical sensitization. In this way, the average particle size is 0.4
600 g of a monodispersed tetradecahedral silver iodobromide emulsion of 0 μm was obtained.

[0077]

[Table 2]

[0078]

[Chemical formula 18]

[0079]

[Chemical formula 19]

Next, the method of preparing the photosensitive silver halide emulsion (II) (for green-sensitive emulsion layer) will be described. To a well-stirred aqueous solution (20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride, and 0.015 g of the following chemical A were added to 730 ml of water and kept at 60.0°C), the following solution (I) and ( Solution II) was simultaneously added at equal flow rates over 60 minutes. After the addition of solution (I) was completed, a methanol solution (III) of the following sensitizing dye C was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared. After washing with water and desalting, gelatin 2
After adding 0 g and adjusting the pH to 6.4 and the pAg to 7.8, chemical sensitization was performed at 60.0°C. The chemicals used at this time were 1.6 mg of triethylthiourea and 1.6 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
00 mg and the aging time was 55 minutes. The yield of this emulsion was 635 g.

[0081]

[C20]

[0082]

[C21]

[0083]

[Table 3]

Next, photosensitive silver halide emulsion (III) (
This section describes how to make a red-sensitive emulsion layer). A well-stirred gelatin solution (20 g of gelatin in 800 ml of water)
, 0.3 g of potassium bromide, 6 g of sodium chloride, and 30 mg of the following chemical A were added and kept at 65°C).The following solutions (I) and (II) were simultaneously added at equal flow rates over 30 minutes. After that, the following solution (III) and (IV
) was added at the same time over a period of 30 minutes. Also (III)
, 3 minutes after the start of addition of solution (IV), a methanol solution of the following sensitizing dye [a solution of 67 mg of sensitizing dye D and 133 mg of sensitizing dye E dissolved in 200 ml of methanol] 1
60ml was added over 20 minutes. After washing with water and desalting, add 20g of lime-treated ossein gelatin to adjust the pH to 6.0.
After adjusting the pAg to 7.7, sodium thiosulfate and 4
-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid were added to optimally chemically sensitize at 60°C. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.5 μm was obtained. The yield was 635g.

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[C22]

[0088]

[C23]

[0089]

[C24]

Next, a method for preparing a photosensitive silver halide emulsion (IV) (for red-sensitive emulsion layer) will be described. The procedure was exactly the same as that for photosensitive silver halide emulsion (III) except that the temperature of the aqueous gelatin solution was changed from 65°C to 40°C and the amount of methanol solution of the sensitizing dye was changed from 160ml to 220ml.
A light-sensitive silver halide emulsion for the red-sensitive emulsion layer was prepared. The average particle size was 0.31 μm and the yield was 635 g.

Using the above emulsion dispersion, a coating solution was prepared as follows. First layer (red-sensitive emulsion layer) 96 ml of water was added to 300 g of photosensitive silver halide emulsion (III) and 880 g of photosensitive silver halide emulsion (IV), and the mixture was dissolved at 38°C. Next, 260 ml of a 0.15% aqueous solution of the following antifoggant (1) was added, and after 5 minutes, 3,500 g of a gelatin dispersion of a cyan dye-providing compound was dissolved at 45°C.
62 ml of a 3% aqueous solution of thickener (10) was added to prepare a coating solution for the first layer.

[0092]

[C25]

[0093]

[C26]

2nd layer (middle layer) lime-treated gelatin 14
% aqueous solution 863 g, gelatin dispersion of electron donor ■ 59
9 g was added and dissolved at 38°C. Next, 715 g of zinc hydroxide dispersion was dissolved at 45°C, 50 ml of a 5% aqueous solution of the following anionic surfactant (11), 231 ml of a 5% aqueous solution of the following compound (12), polyvinyl alcohol (polymerized 231 ml of a 5% aqueous solution of
12% latex dispersion 462 of the following compound (13)
ml, and 57 ml of a 3% aqueous solution of thickener (10) were added.
It was used as a coating liquid for layers.

[0095]

[C27]

[0096]

[C28]

[0097]

[C29]

Third layer (green-sensitive emulsion layer) 1366 g of photosensitive silver halide emulsion (II) was dissolved at 38° C., 289 ml of a 0.15% aqueous solution of the above antifoggant (1) was added, and after 5 minutes, bromide was added. 300 ml of a 1% aqueous solution of potassium and after a further 5 minutes gelatin dispersion of a magenta dye-providing compound 4
171 g was dissolved at 45°C and added, and a thickener (10
) was added to prepare a coating solution for the third layer.

4th layer (middle layer) lime-treated gelatin 14
% aqueous solution 823g, dispersion of electron transfer agent (a) 185g
, 1312 g of water to 590 g of gelatin dispersion of electron donor
ml was added and dissolved at 38°C. Next, surfactant (11
), 138 ml of a 5% aqueous solution of compound (12), 77 ml of dextran, and 115 ml of a 3% aqueous solution of thickener (10) were added to prepare a fourth layer coating solution. The pH of this coating liquid was 6.8 at 40°C.

Fifth layer (blue-sensitive emulsion layer) 1375 g of photosensitive silver halide emulsion (I) was dissolved at 38°C, and 230 ml of a 0.14% methanol solution of the following antifoggant (14) was added.
1% aqueous solution of potassium bromide after 5 minutes.
After a further 5 minutes, 3819 g of gelatin dispersion of a yellow dye-providing compound was dissolved at 45°C, and 117 ml of a 3% aqueous solution of thickener (10) was added.
It was used as a coating liquid for layers.

[0101]

[C30]

6th layer (protective layer) lime-treated gelatin 14
% aqueous solution 890g, gelatin dispersion of silica matting agent (
81 g of silica (8 g of silica with an average particle size of 3 μm dispersed in an 8% gelatin aqueous solution) was dissolved by heating at 38°C, 1110 g of a dispersion of zinc hydroxide dissolved at 45°C was added, and a surfactant ( 98 ml of 5% aqueous solution of compound (11), 244 ml of 10% aqueous solution of compound (15), 151 ml of 5% aqueous solution of dextran, and 3% of thickener (10).
23 ml of the aqueous solution was added to form a coating solution for the sixth layer.

[0103]

[Chemical formula 31]

[0104] Using the above coating solution, coat the first to third layers on a support of polyethylene terephthalate (thickness 100 μm, with a carbon black antihalation layer as a back layer) so that the wet film thickness is as shown in Table-1. A photosensitive material 101 was prepared by applying six layers of coating liquid.

[0105]

[Table 6]

During the feeding of the coating solution to the fourth layer, a 2.5% methanol solution of the compound I-1 of the present invention was mixed immediately beforehand at a rate of 10% of the flow rate of the coating solution for the fourth layer. Added. In other words, a mixing tank equipped with stirring blades is provided at a position immediately before the coating of the liquid delivery system for the fourth layer coating liquid, and the fourth layer coating liquid and the methanol solution of the hardener are combined on the upstream side of this mixing tank and applied. I did it. Next, in the photosensitive material 101, a photosensitive material 102 was prepared in exactly the same manner except that the compound I-2 of the present invention was used instead of the compound I-1 of the present invention, and a photosensitive material 102 was prepared using the compound of the present invention as a comparison. Photosensitive material 103 was prepared in exactly the same manner as photosensitive material 101 except that the following compound (16) was used in place of I-1.

[0107]

[C32]

Next, an image receiving material was prepared as shown in Table 2.

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

[Chemical formula 33]

[0112]

[C34]

[0113]

[C35]

[0114]

[C36]

[0115]

[C37]

[0116]

[C38]

[0117]

[C39]

[0118]

[C40]

[0119]

[C41]

Fluorescent brightener (1) 2,5-bis(5-tert-butylbenzoxazole (2)) Thiophene water-soluble polymer (1) Sumikagel L5-H (Sumitomo Chemical Co., Ltd.)
) water-soluble polymer (2) dextran (molecular weight 70,000)
Matting agent (1) Silica matting agent (2) Benzoguanamine resin (average particle size 15 μm)

The photosensitive materials 101 to 103 and the image-receiving material described above were processed using the image recording apparatus described in JP-A-2-84634. That is, an original image (a test chart recording wedges of Y, M, Cy, and gray whose densities are continuously changing) was scanned and exposed through a slit, and the exposed photosensitive material was kept at 35°C. 5 in the water
After dipping for a second, the film was squeezed with a roller, and then immediately stacked on top of each other so that the image-receiving material and the film surface were in contact with each other. The film was heated for 15 seconds using a heat drum whose temperature was adjusted so that the temperature of the surface of the film that had absorbed water was 80°C, and when it was peeled off from the image-receiving material, a clear color image corresponding to the original image was obtained on the image-receiving material. Next, the photosensitive materials 101 to 103 were stored for 10 days at 40° C. and 80% RH, and subjected to the same treatment. Also,
Swelling film thickness of photosensitive materials 101 to 103 at 40°C and 80% R
Measurements were taken before and after storage for 10 days. Measurement of swollen film thickness is as follows:
Water at 40℃ is poured onto the coating film, and the coating film is compared to the dry film.
We measured how much it swelled. Dmax and D of Y (yellow), M (magenta), and Cy (cyan) in the gray area
The measurement results of min and swollen film thickness are shown in Table 3.

[0122]

[Table 9]

From the above results, it can be seen that the photosensitive material 101 of the present invention
, 102 shows less variation in Dmax, Dmin, and swollen film thickness before and after the forced thermotest than Comparative Example 103, indicating that it is a photosensitive material with excellent shelf life. Further, even when I-3, I-5, and I-7 were used in place of I-1, the fluctuations in Dmax, Dmin, and swollen film thickness before and after the forced thermotest were smaller than in the comparative example.

<Example 2> The pH of the coating solution for the fourth layer of the photosensitive material 101 of Example 1 was adjusted to pH 6.2 at 40° C. using a 5% aqueous solution of citric acid. Other than that, photosensitive material 201 was produced in the same manner as photosensitive material 101. Furthermore, the pH was adjusted to 5.0 in the same manner, and the photosensitive material 202
made. When photosensitive materials 101, 201, and 202 were manufactured continuously for 24 hours and the surface condition of the coating film was inspected,
The results shown in Table 4 below were obtained.

[0125]

[Table 10]

From the above results, the photosensitive materials 201 and 202 in which the pH of the coating solution for the layer containing the compound represented by the general formula (I) of the present invention is set to 6.5 or less can be coated even during long-time coating. It can be seen that there are few failures and excellent manufacturing suitability.

<Example 3> A method for preparing emulsions (1) to (3) will be described. Solutions I and II in Table F were added to the well-stirred aqueous solution (Table E) at 60° C. over 20 minutes, and then solutions III and IV were added over 35 minutes. After washing with water and desalting, add 25g of gelatin and adjust the pH to 6.1.
After adjusting the pAg to 8.0, chemical sensitization was performed at 61°C. Chemical sensitization is triethylthiourea and 4-hydroxy-6
-Methyl-1,3,3a,7-tetrazaindene was used to optimally chemically sensitize the sample to obtain the highest score. 10-
Yield of emulsion with sensitivity obtained at 4 seconds exposure, grain size,
The crystals were as shown in Table G, and each was a monodisperse emulsion.

[0128]

[Table 11]

[0129]

[Table 12]

[0130]

[Table 13]

Next, a method for preparing a gelatin dispersion of a dye-providing substance will be described. Magenta dye-donating substance (A
), 1.2 g of the reducing agent, 0.15 g of the mercapto compound (1), 0.4 g of the surfactant (4), and 5.1 g of the high boiling point organic solvent (2) were weighed, and ethyl acetate was added. 70
cc was added and dissolved by heating to about 60°C to form a homogeneous solution. This solution and a 10% aqueous solution of lime-treated gelatin 100%
g and 60 cc of water were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of a magenta dye-providing substance.

7. Cyan dye-donating substance (B1).
Weighed 3g, 10.6g of (B2), 1.2g of reducing agent, 0.3g of mercapto compound (1), 1.5g of surfactant (4), and 9.8g of high boiling point organic solvent (1). Then, 40 cc of ethyl acetate was added, and the mixture was heated and dissolved at about 60° C. to form a homogeneous solution. 10% of this solution and lime-processed gelatin
After stirring and mixing 100 g of the aqueous solution and 60 cc of water, the mixture was dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of a cyan dye-providing substance.

15 g of yellow dye-providing substance (C)
, 1.2 g of reducing agent, 0.1 g of mercapto compound (1)
5 g, 1.5 g of surfactant (4), high boiling point organic solvent (
Weigh 1) to 7.5g, add 45cc of ethyl acetate,
The mixture was heated and dissolved at about 60°C to form a uniform solution. This solution, 100g of a 10% aqueous solution of lime-treated gelatin, and 60c of water
After stirring and mixing with c, mix with a homogenizer for 10 minutes.
Dispersion was performed at 0,000 rpm. This dispersion is called a yellow dye-providing substance dispersion. With these materials, a heat-developable color photosensitive material 301 as shown in Table 5 below can be constructed.

[0134]

[Table 14]

[0135]

[Table 15]

[0136]

[Table 16]

[0137]

[C42]

[0138]

[C43]

[0139]

[C44]

[0140]

[C45]

[0141]

[C46]

[0142]

[C47]

[0143] High boiling point organic solvent (1) triisononyl phosphate High boiling point organic solvent (2) trihexyl phosphate

[0144]

[C48]

[0145] Surfactant (1) Aerosol OT

0
146]

[C49]

[0147]

[C50]

[0148]

[C51]

[0149]

[C52]

[0150]

[C53]

[0151]

[C54]

[0152]

[C55]

[0153] During the feeding of the coating solution to the sixth layer, 2.5% methanol/water of compound I-1 of the present invention was added by direct mixing method so that the amount added was 0.066 g/m2. A mixed solution of (4:6) was added. In other words, a mixing tank equipped with stirring blades is provided at a position immediately before the coating of the liquid delivery system for the sixth layer coating solution, and the sixth layer coating solution and the methanol aqueous hardener solution are combined on the upstream side of this mixing tank and applied. I did this. Next, in the photosensitive material 301, a photosensitive material 302 was prepared in exactly the same manner except that the compound I-2 of the present invention was used instead of the compound I-1 of the present invention. Photosensitive material 3 was prepared in exactly the same manner as photosensitive material 301 except that the following compound (17) was used in place of I-1.
I made 03.

[0154]

[C56]

Next, the method of making the image-receiving material will be described. An image-receiving material was prepared by coating the composition shown in Table 6 on a paper support laminated with polyethylene.

[0156]

[Table 17]

[0157]

[Table 18]

[0158]

[C57]

[0159] Surfactant *2 Aerosol OT

01
60]

[C58]

[0161]

[C59]

[0162]

[C60]

Polymer *5 Vinyl alcohol sodium acrylate copolymer (75/25 molar ratio) Polymer *7 Dextran (molecular weight 70,000)

[0164]

[C61]

[0165] High boiling point organic solvent *8 Rheophos 95 (
Manufactured by Ajinomoto Co., Inc.)

[0166]

[C62]

Matting agent *10 Benzoguanamine resin (ratio of particles exceeding 10 μm is 18 vol%)

01
68 Next, evaluation was performed using the following exposure and processing. Using the laser exposure apparatus shown in Figure 2 of JP-A-2-129625, exposure was carried out under the conditions shown in Table 7. After immersing the exposed photosensitive material in water kept at 40°C for 2 seconds, it was exposed with a roller. After aperture, the image-receiving material and the film were immediately placed on top of each other so that the film surfaces were in contact with each other. Using a heat drum whose temperature was adjusted so that the temperature of the water-absorbed film was 82° C., the film was heated for 32 seconds, and when the image-receiving material was peeled off from the photosensitive material, a clear color image was obtained on the image-receiving material.

[0169]

[Table 19]

Next, photosensitive materials 301 to 303 were heated at 40°C.
It was stored for 10 days at 80% RH and treated in the same way. In addition, the swelling film thickness of the photosensitive materials 301 to 303 was set to 40
Measurements were taken before and after storage at 80% RH for 10 days. The swollen film thickness was measured by pouring water at 40° C. onto the coated film and measuring how much the coated film swelled compared to the dry film. D for each color Y (yellow), M (magenta), Cy (cyan)
The measurement results of max, Dmin and swollen film thickness are shown in Table 8.

[0171]

[Table 20]

From the above results, it can be seen that the photosensitive material 301 of the present invention
, 302 shows less variation in Dmax, Dmin, and swollen film thickness before and after the forced thermotest than Comparative Example 303, and is found to be a photosensitive material with excellent shelf life. Also, even if I-3, I-5, and I-7 are used instead of I-1, the Dmax and Dmi before and after the forced thermotest are lower than those of the comparative example.
There was little variation in n and swollen film thickness.

[0173]

Effects of the Invention By using the hardener of the present invention, the storage stability over time of heat-developable color photosensitive materials was improved, and color images with high image density and low stain could be stably obtained. Furthermore, 40% of the coating solution to which the hardener of the present invention is added
By controlling the pH at 6.5 or less at 0.degree. C., the heat-developable color photosensitive material having excellent storage stability over time could be stably produced.

Claims (2)

[Claims] Claim 1: A heat-developable color photosensitive material having at least a photosensitive silver halide, a binder, and a dye-providing compound on a support, which has a layer hardened with a compound represented by the following general formula (I). A heat-developable color photosensitive material characterized by: embedded image In the formula, R represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. n represents 0 or 1. 2. The heat-developable color photosensitive material according to claim 1, wherein the pH of the coating solution of the layer to which the compound represented by formula (I) is added is 6.5 or less at 40°C.