JP2001042484A - Heat developable color photographic material and color image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a good image nearly free from image noise such as unevenness and dislocation in transfer by disposing photosensitive silver halide, a binder and a base precursor on a composite support obtained by sticking a biaxially oriented film to at least one face of a substrate. SOLUTION: The top of a composite support comprising at least a substrate and a biaxially oriented film stuck to at least the emulsion layer side (surface side) of the substrate by way of an adhesive layer is coated with photosensitive silver halide, a binder and a base precursor. Cellulose fiber paper, synthetic paper, a polymer, woven polymer fibers or cloth or a laminated body of those may be used as the substrate. The adhesive used for sticking the biaxially oriented film to the substrate may be any adhesive but a polyethylene adhesive is preferably used. The silver halide may be silver chloride, silver bromide, silver iodobromide or silver chlorobromide and any of surface latent image type and internal latent image type silver halide emulsions may be used.

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 photographic material (photosensitive material and image receiving material), and more particularly to a color photographic material having improved image quality and a color image forming method.

[0002]

2. Description of the Related Art Photothermographic materials are known in the art. For details of the photothermographic material and its process, see, for example, "Basics of Photographic Engineering", Non-Silver Salt Photo Edition (1982, Corona Co., Ltd.), pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, a method of forming a dye image by a coupling reaction between an oxidized form of a developing agent and a coupler is described in US Pat. A method of forming a positive color image by a photosensitive silver dye bleaching method is described in U.S. Pat. No. 4,235,957.

Recently, there has been proposed a method in which a diffusible dye is released or formed in an image form by thermal development, and the diffusible dye is transferred to a dye fixing element. In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-donating compound to be used or the type of silver halide to be used. More specifically, U.S. Pat. Nos. 4,500,626 and 4,483,914,
03137 and 4559290, JP-A-58-14
No. 9046, JP-A-60-133449 and 59-2
Nos. 18443, 61-238056, EP-A-220746A2, JP-A-87-6199, and EP-A-210660A2.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, U.S. Pat. No. 4,559,290 discloses that a compound obtained by converting a so-called DRR compound into an oxidized form having no ability to emit a color image coexists with a reducing agent or a precursor thereof, and the developing agent is subjected to heat development in accordance with the exposure amount of silver halide. A method has been proposed in which a diffusible dye is released by being oxidized and reduced by a reducing agent remaining without being oxidized. EP-A-220746A and JP-A-87-6199 (Vol. 12, No. 22) describe an NX bond (X
Represents a oxygen atom, a nitrogen atom or a sulfur atom.

In such a method of obtaining a color image by diffusing a dye from a photosensitive material to an image receiving material, a cause of noise generated in the image is often a transfer process. Noise generated in the transfer step includes, for example, mottle, transfer unevenness, transfer deviation, and the like, resulting in significantly impairing image quality.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable color photographic light-sensitive material capable of obtaining a good image with less image noise such as mottle, transfer unevenness and transfer deviation. It is to provide.

[0008]

The above object is achieved by the following. (1) A heat-developable color light-sensitive material in which a photosensitive silver halide, a binder, and a base precursor are coated on a support having at least one surface adhered to a biaxially stretched film. (2) A heat-developable color image-receiving material in which a mordant polymer and a base generator are coated on a paper support having at least one surface adhered to a biaxially stretched film. (3) The support of the material of (1) or (2) is 2
Heat-developable color light-sensitive material obtained by bonding an axially stretched film,
Or an image receiving material. (4) A color image was formed by using at least one of the materials defined in (1) to (3).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The composite support referred to in the present invention comprises at least a substrate and a biaxially stretched film having an adhesive layer on the emulsion layer side (surface side) of the substrate.

The composite support of the present invention comprises, as a substrate, cellulose fiber paper, synthetic paper, polymer, woven polymer fiber,
Alternatively, a cloth or a laminate thereof can be used. It may be polyethylene terephthalate having micropores as described in U.S. Pat. No. 4,912,333. Paper comprising cellulose fibers is particularly preferred as the substrate. The thickness of the substrate is preferably from 30 to 400 μm, more preferably from 50 to 200 μm.

The material of the biaxially stretched film used for the composite support of the present invention includes polyolefins, polyesters, polyamides, polycarbonates, cellulose esters, polystyrene, polyvinyl resins, polysulfonamides, polyethers, polyimides , Polyvinylidene fluoride, polyurethanes, polyphenylene sulfides, polytetrafluoroethylene, polyacetals, polysulfonates, polyester ionomers, and polyolefin ionomers. Copolymers of these polymers and / or mixtures of these polymers can also be used. In particular,
Polyolefins are preferred, and specifically include polypropylene, polyethylene, polymethylpentene, and mixtures thereof. Polyolefin copolymers, including copolymers of propylene and ethylene such as hexene, butene and octene, may be used. Of the polyolefins, polyethylene or polypropylene is most preferred. Furthermore, polypropylene is most preferred in terms of strength, surface properties and cost. The thickness of the biaxially stretched sheet is preferably 10 to 150 μm, and more preferably 15 to 150 μm.
~ 70 µm is preferred.

The biaxially stretched film used in the present invention comprises:
It is preferable to have micropores. As used herein, “micropores” refer to bubbles made of gas (air) in a film.
Micropores can be generated by dispersing and containing pore-inducing particles in a polymer before stretching the film and stretching the film. Such production methods are disclosed, for example, in U.S. Patent Nos. 4,377,616, 4,758,462, and 4,632,869. As the vacancy inducing substance, a polymer material or an inorganic material can be used. As the porogen-inducing substance, a substance which is mixed with a polymer serving as a matrix and which forms dispersed particles when the solution is cooled is preferable. Nylon, polybutylene terephthalate, polypropylene, and the like are known as examples of the polymer material used as the pore-inducing particles. Examples of inorganic materials include particles such as glass spheres, metal or ceramic beads, clay, talc, barium sulfate, and calcium carbonate. In order to generate pores having a desired shape and size, the pore-inducing particles preferably have a diameter of 0.1 to 10 μm and are spherical. The porogen-inducing substance is preferably about 5 to 50% by weight based on the matrix polymer. The vacancy-inducing particles may be produced by any method, but in particular, particles having a uniform size using a process such as suspension polymerization or limited fusion are preferred. Further, the vacancy inducing substance is preferably used after being coated with a reagent for promoting vacancy formation. Suitable reagents for this use include colloidal silica, colloidal alumina, and metal oxides such as tin oxide and aluminum oxide. Colloidal silica and alumina are preferred, and silica is more preferred. The size of the micropores created during stretching depends on the extent of stretching in the machine and transverse directions. Usually, the shape of this hole is a disk like a lens,
The thickness of the disk is approximately the diameter of the vacancy inducer. The pores are preferably closed cells one by one, and it is not preferable that a plurality of cells are connected to each other by a cavity and continuous and penetrate from one surface to the other surface of the film as an air layer.

Further preferred biaxially stretched films include:
A multilayer film having a skin layer having no pores on one or both sides of a core layer having micropores. The skin layer having no pores may be the same polymer material as the core layer, or may be a polymer material different from the core layer. The core layer is 15-95% of the total sheet thickness, and further 30-85%
It is preferable that Therefore, the total thickness of the skin layer having no pores is 5 to 85% of the total film thickness, preferably 1%.
5 to 70%. Density (specific gravity) of this composite film
Is preferably 0.5 to 1.2, and more preferably 0.8 to 1.
15 is preferred. The total thickness of the composite film is 12 to 1
00 μm is preferable, and further preferably 20 to 70 μm.

Further additives may be added to the core layer and / or the skin layer of the biaxially stretched film. For example, in order to improve whiteness, adding a white pigment such as titanium dioxide, barium sulfate, clay or calcium carbonate, a fluorescent whitening agent or a bluish dye or pigment, for example, ultramarine, color of white background such as cobalt blue A taste modifier can be added. In order to adjust the charge amount, a conductive substance or a charge control agent can be added.

These composite films are co-extruded, quenched,
It can be achieved by any method known in the art for producing stretched sheets, such as a flat film process or a bubble or tubular process, consisting of stretching and heat setting. For example, in a flat film process, the formulation is extruded from a slit die and the core matrix polymer portion and skin portion of the film are quenched below their vitrification temperature on a cooled casting drum of the extruded web. The film is then biaxially stretched perpendicular to each other at a temperature above the glass transition temperature of the matrix polymer but below the melting temperature. As a stretching method, after stretching in one direction, stretching may be performed in a vertical direction or may be simultaneously performed in two directions. After stretching the film, it is manufactured by heating to a temperature at which the polymer crystallizes or anneals, while suppressing shrinkage of the film.

The biaxially stretched film is preferably provided with a core layer having micropores and a skin layer on one or both surfaces, but may further have additional layers. Examples of such layers include color control agents, antistatic substances, adhesives, or curling control layers. The biaxially stretched film may be subjected to a corona discharge treatment or a flame treatment in order to modify the surface.

In the composite support, any adhesive can be used for bonding the base and the biaxially stretched film, as long as both the base and the biaxially stretched film can be bonded. In the case of the present invention, a particularly preferred material is polyethylene. The thickness of the polyethylene used as the adhesive is 5 to 50 μm,
30 μm is preferred. As a method for producing a composite support from a substrate and a biaxially stretched film, there is known a production method in which a polyethylene film is sandwiched between a substrate and a biaxially stretched film, nipped and melted. Particularly preferred is a production method in which a polyethylene layer is provided in advance on the surface of either the substrate or the biaxially stretched film, and is nipped and heated to a temperature at which the polyethylene melts.

A preferred composite support is one having a biaxially stretched film on both sides of a substrate.
The same biaxially stretched film may be used on both sides, or may be different, but it is preferable that at least the thickness be different. More preferably, a biaxially stretched film having a skin having micropores in the core layer and having no micropores on both sides on the front surface side of the substrate, and biaxial stretching having no micropores on the back surface side is used. This is the case where a film is used. In the present invention, a composite support particularly preferably used comprises a paper support having a thickness of 120 to 250 μm having polyethylene layers on both sides as a substrate, a core layer having micropores on the surface side, and a surface layer having no pores. The composite biaxially stretched film having a thickness of 15 to 50 μm is formed from a biaxially stretched film having no micropores of 15 to 50 μm on the back side.

In the present invention, the surface resistivity of the back surface of the support is preferably 10 ¹² Ω · cm or less, and a back layer containing a conductive substance can be provided if necessary.

The heat-developable color photographic light-sensitive material referred to in the present invention is sensitive to at least three different spectral regions in order to obtain a wide range of colors in a chromaticity diagram using three primary colors of yellow, magenta and cyan. Are used in combination. These sensitivities may be in the visible region, the infrared region or the ultraviolet region. Further, a combination of these may be used, and each photosensitive layer may be divided into two or more layers as necessary.

The heat development diffusion transfer type color light-sensitive 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.

Hereinafter, the silver halide emulsion used in the heat-developable diffusion transfer type color light-sensitive material of the present invention will be described in detail.

The silver halide emulsion includes silver chloride, silver bromide,
Any of silver bromoiodide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion 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 or light fogging. Further, a so-called core-shell emulsion in which the inside and the surface of the grain have different phases may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and is disclosed in JP-A-1-167,743,
As described in JP-A-223,463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm.
The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and tabular shapes having a high aspect ratio, and those having twin planes. Those having such twin defects, or composites thereof, or any other materials may be used. Specifically, US Pat. No. 4,500,626, column 50, 4,628,021
No. 17, 029 (1978), Research Disclosure Magazine (hereinafter abbreviated as RD), No. 17,
643 (December 1978), pp. 22-23, No. 1
8, 716 (November 1979), p. 648, ibid.
07, 105 (November 1989) pp. 863-865,
JP-A Nos. 62-253,159 and 64-13,546.
JP-A-2-236546, 3-110,55
No. 5, Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemieet Phisique Photog)
raphique, Paul Montel, 1967), "Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry, Focal Press, 196
6), "Manufacture and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al., Making and C).
oating Photographic Emulsion, Focal Press, 196
Any of the silver halide emulsions prepared by the methods described in 4) and the like can be used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637 and JP-A-4-126629 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B No. 47-1
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

Other conditions are described in the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel., 1697), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al.
L. Zelikman et al., Making and Coating Photographic
Emulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can also be used.

The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to impart blue-sensitive, green-sensitive, and red-sensitive color sensitivity to the photosensitive silver halide used in the present invention,
The photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. If necessary, the infrared sensitivity may be subjected to spectral sensitization. The dyes used include cyanine dyes,
Merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are included. Specifically, US Pat. No. 4,617,257,
JP-A Nos. 59-180,550 and 64-13,546.
And sensitizing dyes described in JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . 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. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before chemical ripening, or before or after nucleation of silver halide grains according to U.S. Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The amount of addition is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a step and known photographic additives which can be used in the photothermographic material and the dye fixing material of the present invention are described in the above-mentioned RD Nos. 17, 643 and RD No.
No. 18, 716 and No. 307, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer ~ page 649 right column 4. Fluorescent brightener 24 page 648 page right column 868 5. Fog prevention 24 ~ 25 page 649 right column 868 ~ 870 agent, stabilizer 6. 26Page 26 649 Right column Page 873 Filter 左 Page 650 Left column Dye, UV absorber 7.Dye image 25 650 Page Left column 872 Stabilizer 8.Hardening agent 26 Page 651 Left column 874-875 9. Binder page 26 page 651 left column 873-874 10. plasticizer, page 27 650 page right column 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12 Static page 27 page 650 right column pages 876-877 Inhibitor 13. Matting agent

As the binder for the constituent layers of the photothermographic material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75).
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,
Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also, U.S. Pat.
No. 0,681, JP-A-62-245260, etc., ie, -COOM or -SO
_A homopolymer of a vinyl monomer having 3M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

In the present invention, a system for performing thermal development after supplying a small amount of water is desirable. In this case, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g to
A suitable amount is 0.5 g.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. U.S. Pat. No. 4,500,626 is an example of a reducing agent used in the present invention.
Nos. 49-50, 4, 839, 272, 4,
330,617, 4,590,152, 5,0
17,454,5,139,919, JP-A-60
Nos. 140, 335, pp. (17) to (18), ibid.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
Nos. 0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181,742, No. 61-259,253
Nos. 62-201,434 and 62-244,04
Nos. 4, 62-131, 253, 62-131, 2
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
Nos. 2-234, 158 and 3-160, 443
And reducing agents and precursors described in EP-A-220,746 at pages 78 to 96 and the like. Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, in order 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. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Further, a method of stably introducing the compound into the layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher 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) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols,
No. 110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, compounds described as electron donors, and a non-diffusible and reducing dye described later. Donor compounds and the like. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, the above-mentioned reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixing, improvement of color reproduction, improvement of white background, and prevention of silver transfer to the dye fixing material. Specifically, European Patent Publication No. 52
4,649,357,040, JP-A-4-24
9,245, 2-64,633, 2-46,4
No. 50 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
And JP-A-2-64,634, JP-A-3-43,735, and EP-A-451,833.

In the present invention, the amount of the reducing agent added is 0.001 to 20 mol, particularly preferably 0.1 to 1 mol, per mol of silver.
01 to 10 mol.

In the present invention, when silver ions are reduced to silver under a high temperature condition, a compound which generates or releases a mobile dye in response to this reaction or in reverse thereof, ie, a dye donor The compound may also contain an acidic compound.

Examples of the dye-donating compound that can be used in the present invention include compounds (couplers) that form a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. See THJames for specific examples of color developers and couplers.
"The Theory of the Photographic Process" 4th edition 2
Pages 91 to 334, and pages 354 to 361,
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
No. 24399, No. 59-174835, No. 59-23
No. 1539, No. 59-231540, No. 60-295
Nos. 0, 60-2951, 60-14242, 60-23474, and 60-66249.

It is preferable to use the following couplers. Yellow coupler: couplers represented by formulas (I) and (II) of EP 502,424A: EP 513,4
No. 96A, couplers represented by the formulas (1) and (2), and a coupler represented by the general formula (I) of claim 1 of Japanese Patent Application No. 4-134523: 45 of column 1 of US Pat. No. 5,066,576; Coupler represented by general formula D on line 55, coupler represented by general formula D in paragraph 0008 of JP-A-4-274425: coupler described in claim 1 on page 40 of EP498,38A1, and coupler 4 described in EP447,969A1. Coupler represented by formula (Y) on page 4, US 4,47
Formulas (I) to (I) on lines 36 and 58 in column 7 of 6,219
A coupler represented by V). Magenta couplers: JP-A-3-39737 and JP-A-6-4
No. 3611, 5-204106, JP-A-4-362
The coupler described in No. 6. Cyan coupler; JP-A-4-208443, JP-A-4
-43345. Polymer coupler: JP-A-2-44345.

US Pat. No. 4,366,237, GB 2, 12
5,570, EP 96,570, DE 3,234
No. 533 is preferred.

Further, the light-sensitive material of the present invention may contain the following functional coupler. Couplers for correcting unnecessary absorption of coloring dyes are disclosed in EP 456,257.
The yellow colored cyan coupler described in A1;
Yellow colored magenta coupler described in P, US
Magenta colored cyan couplers described in US Pat. No. 4,833,069, US Pat. No. 4,837,136 (2), WO92
/ 11575. Colorless masking couplers of formula (A) of claim 1 of claim 1 (especially the exemplified compounds on pages 36-45). In the present invention, it is preferable to use a coupler or another compound which releases a photographically useful compound by reacting with an oxidized form of the developing agent. Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: a compound represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, EP 43
No. 6,938A2, page 7, compound represented by formula (I), JP-A-5-307248, compound represented by formula (1), EP440,195A2, page 5, page 6 formula (I) , (II), and (III), a compound represented by formula (I) of claim 1 of JP-A-6-59411, a ligand-releasing compound, and a LIG described in claim 1 of US Pat. No. 4,555,478. A compound represented by -X.

In the light-sensitive material of the present invention, a color developing agent capable of forming a dye by coupling an oxidized product formed by silver development with the coupler described above can be incorporated. In this case, U.S. Pat. No. 3,531,256,
p-phenylenediamines developing agents and phenol or active methylene couplers;
A combination of a p-aminophenol developing agent and an active methylene coupler can be used. US Patent 4,0
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in JP-A Nos. 21 and 240 and JP-A-60-128438 is excellent in raw preservation when incorporated in a light-sensitive material, and is a preferable combination. When a color developing agent is incorporated, a precursor of the color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure Nos. 14,850 and 1
Schiff base type compounds described in 5,159, and 13,92.
4, aldol compounds, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

Further, a sulfonamide phenol-based active compound described in JP-A-9-15806 and JP-A-8-28634 are disclosed.
0 and JP-A-8-234388 are also preferred for use in the light-sensitive material of the present invention. In the present invention, it is preferable to use a compound described in JP-A-9-274295 as a developing agent. Among them, compounds of the general formula I or II are particularly preferably used.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Pat.
No. 9,919 and EP-A-418,743 are used. Also, JP-A-2-230143,
As described in JP-A-2-235,044, a method of stably introducing the compound into the layer is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,
040, JP-A-4-249,245, JP-A-2-46,
No. 450 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication 3-63,733
No., JP-A-1-150,135, JP-A-2-46,450
Nos. 2,64,634, 3-43,735 and EP-A-451,833 are also used.

It is also possible to use a developing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophilic reagent or heat during the development process. In addition, the following reducing agents may be incorporated in the light-sensitive material. Examples of the reducing agent used in the present invention include, for example, U.S. Pat. No. 4,500,626, columns 49 to 50, 4,839,272, and 4,33.
0,617, 4,590,152, 5,01
7,454,5,139,919;
Nos. 140,335, pp. (17)-(18), pp. 57-40, 2;
No. 45, No. 56-138, 736, No. 59-178,
No. 458, No. 59-53, 831, No. 59-182,
No. 449, No. 59-182, No. 450, No. 60-11
9,555, 60-128,436, 60-1
No. 28,439, No. 60-198,540, No. 60-
Nos. 181,742, 61-259,253, 62
-244,044, 62-131,253, 6
Nos. 2-131, 256 and 64-13, 546 (4
0) to (57), JP-A-1-120,553, and EP 220,746A2, pages 78 to 96, and the like. Also, U.S. Pat.
Combinations of various reducing agents, such as those disclosed in 039,869, can also be used. The developing agent or reducing agent may be incorporated in a processing sheet described later,
It may be built in a photosensitive material. In the present invention, the total amount of the developing agent and the reducing agent is 0.01 to 1 mol of silver.
-20 mol, particularly preferably 0.1-10 mol.

In the present invention, as the coupler, a 4-equivalent coupler and a 2-equivalent coupler can be selectively used depending on the type of the main drug. Also, a 4-equivalent coupler is used for the developing agent of the general formula I. The developing agent of the general formula I is
Since the coupling site is substituted by a sulfonyl group, and the sulfonyl group is released as sulfinic acid during coupling, the leaving group on the coupler side must be released as a cation. Therefore, it reacts with a 4-equivalent coupler capable of releasing a proton as a leaving group during coupling, but does not react with a 2-equivalent coupler whose leaving group is an anion. Conversely, two equivalent couplers are used for developing agents of general formulas II and III. General formula II, III
In the developing agent (1), the coupling site is substituted by a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during the coupling, so that the leaving group on the coupler side must be released as an anion. Therefore, it reacts with a 2-equivalent coupler capable of releasing an anion as a leaving group during coupling, but does not react with a 4-equivalent coupler whose leaving group is a proton. By using this combination, it is possible to prevent color smearing due to interlayer movement of the oxidized form of the developing agent. Specific examples of couplers include both 4-equivalent and 2-equivalent theory of the photographic process (4th Ed. TH James, edited by Macmillam, 1977), pages 291 to 334, and 35.
Pages 4 to 361, JP-A-58-12353, 58-
No. 149046, No. 58-149047, No. 59-1
Nos. 1114, 59-124399, 59-174
No. 835, No. 59-231539, No. 59-2315
No. 40, No. 60-2951, No. 60-14242,
The details are described in JP-A-60-23474 and JP-A-60-66249, and in the above-mentioned documents and patents.

As another example of the dye donating compound,
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI].

(Dye-Y) n-Z [L
I]

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 corresponds to a photosensitive silver salt having an image-like latent image. Alternatively, the diffusivity of the compound represented by (Dye-Y) n-Z is correspondingly changed, or D
ye, and the released Dye and (Dye-Y) n-
Z represents a group having a property that causes a difference in diffusibility with Z, and n represents 1 or 2, and when n is 2, 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 (a) to (e). The following (a) to (c) form a diffusible dye image (positive dye image) in reverse to the development of silver halide, and (d) and (e) show the silver halide A diffusive color image (negative dye image) is formed in accordance with the development of.

(A) US Pat.
No. 62819, No. 3597200, No. 3544545
No. 3,482,972, etc., a dye developing agent comprising a hydroquinone-based developing agent and a dye component linked to each other. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

(B) As described in US Pat. No. 4,503,137 and the like, a nondiffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. . Examples thereof include compounds described in US Pat. No. 3,980,479, which release a diffusible dye by an intramolecular nucleophilic substitution reaction, and US Pat.
Compounds which release a diffusible dye by an intramolecular reversion reaction of an isoxazolone ring described in No. 9354 and the like.

(C) US Pat. No. 4,559,290, EP 220746A2, US Pat. No. 4,783,396
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 No. 5-2,199, and the like.

As an example, see US Pat.
Nos. 9 and 4139379, JP-A-59-185333.
And compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat. No. 4,232,107, and JP-A-59-84453.
-101649, 61-88257, RD240
No. 25 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 308588A, JP-A-56-14.
No. 2530, U.S. Pat. Nos. 4,434,893 and 4,619.
No. 8450, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
Examples include a nitro compound which releases a diffusible dye after electron acceptance described in JP-A-223 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 220746A2, JP 87-6199, US Pat. No. 4,783,396, and JP-A-63-201653.
In one molecule described in JP-A-63-201654 and the like.
-X bond (X is oxygen, sulfur or a nitrogen atom) with a compound having an electron withdrawing group, SO ₂ -X in one molecule described in JP-A-1-26842 (X is as defined above) and Compound having an electron-withdrawing group, JP-A-63-271344
A compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in
No. 1341 describes a C—X ′ bond (X ′) in one molecule.
The X synonymous or or -SO ₂ - include compounds having a representative) and an electron attractive group.

Of these, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (2) described in European Patent No. 220746A2.
(3), (7)-(10), (12), (13), (15), (23)-(26), (3
1), (32), (35), (36), (40), (41), (44), (53)-(5)
9), (64), (70), and the compound (1
1) to (23).

(D) A compound having a diffusible dye as a leaving group and releasing a diffusible dye by reacting with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,542, JP-B-48-39165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 44.
83914 and the like.

(E) A compound (DRR compound) that is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312 and 4,053,312.
Nos. 4,055,428 and 4,336,322
And JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, No. 51-104343, R
D17465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-11637, 57-179840, U.S. Pat. 626, etc. D
Specific examples of the RR compound include the above-mentioned US Pat.
Compounds described in Columns 22 to 44 of U.S. Pat. No. 0,626 can be mentioned, and compounds (1) to (3), (10) to (13), and 16)-(1
9), (28)-(30), (33)-(35), (38)-(4
0) and (42) to (64) are preferred. U.S. Pat.
The compounds described in 639,408, columns 37 to 39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58). Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
5,957, Research Disclosure Magazine, 19
April, 76, pp. 30-32), leuco dyes (U.S. Pat. Nos. 3,985,565, 4,022,617, etc.) and the like can also be used.

A hydrophobic additive such as a dye-donating compound or a nondiffusible reducing agent can be introduced into a layer of a photothermographic material by a known method such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
Nos. 55,470, 4,536,466, 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. In addition, 1 cc or less per gram of the binder, further 0.5 cc
Below, especially 0.3cc or less is suitable. In addition, Tokiko Sho 51
-39,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,287.
No. 42 or the like and a method of adding it as a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No.
The surfactants described in Research Disclosure, pages 7 to 38, mentioned above, can be used. In the photothermographic material of the present invention, a compound which activates development and stabilizes an image at the same time can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In a system in which an image is formed by diffusion transfer of a dye, an unnecessary dye or coloring matter is fixed or made colorless in the constituent layers of the photothermographic material of the present invention, and the purpose is to improve the white background of the obtained image. Various compounds can be added. Specifically, EP-A-353,741
No. 461,416, JP-A-63-163,345.
And the compounds described in JP-A Nos. 62-203,158 can be used.

As the compound having a transmission density of 0.5 or more used in the present invention, when the above-mentioned dye-providing compound has absorption in the visible light region, it is preferable to use this compound.

When the dye-donating compound of the present invention has no absorption in the visible light range, various pigments and dyes used for the purpose of improving color separation properties and sensitization have a transmission density of 0.5.
It can be used by coating as described above.

Specifically, the compounds described in the above-mentioned Research Disclosure, and EP-A-479,167.
No. 502,508, JP-A-1-167,838
No., 4-343,355, 2-168,252
No., JP-A-61-20,943, and EP-A-47.
Compounds and layer configurations described in JP-A Nos. 9,167 and 502,508 can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with the photothermographic material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. 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 field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88,256, pages (32) to (41),
Mordants described in U.S. Pat. Nos. 4,774,162 and 4,619,883.
And Nos. 4,594,308 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The binder used in the dye fixing material of the present invention is preferably the above-mentioned hydrophilic binder. Further, it is preferable to use a combination of carrageenans as described in EP-A-443,529 and a latex having a glass transition temperature of 40 ° C. or lower as described in JP-B-3-74,820. Auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided on the dye fixing material as needed. It is particularly useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a sliding agent, or an agent for improving the releasability between the photosensitive material and the dye-fixing material. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils, particularly carboxy-modified silicone (trade name: X-22-3710) described in “Modified Silicone Oil” Technical Documents P6 to 18B issued by Shin-Etsu Silicone Co., Ltd. are effective. Also, silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are effective.

An anti-fading agent may be used in the photothermographic material or the dye fixing material. Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes. Dye image stabilizers and ultraviolet absorbers described in Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Patent Application Laid-Open
The compounds described in -159,644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), and benzophenone-based compounds (Japanese Unexamined Patent Publication No. 2,784), and JP-A Nos. 54-48,535 and 62-1.
36, 641 and 61-88, 256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3-36, No. 4,254,195, No. 3
Columns 8 to 8, JP-A-62-174,741 and JP-A-61-8
8, 256, pp. 27-29, pp. 63-199,
No. 248, JP-A Nos. 1-75,568 and 1-74,2
No. 72 and the like.

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or the dye may be supplied from outside such as a heat-developable photosensitive material or a transfer solvent described later. It may be supplied to the fixing material. The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination. A fluorescent whitening agent may be used in the photothermographic material or the 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 such as a photothermographic material or a transfer solvent. For example, K. Veenkataraman ed., "The Chemis
tryof SyntheticDyes ", Vol. V, Chapter 8, JP-A-61-1
And the compounds described in US Pat. 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 a fading inhibitor or an ultraviolet absorber. These anti-fading agents, ultraviolet absorbers,
Specific examples of the fluorescent whitening agent are described in JP-A-62-215272 (pages 125-137) and JP-A-1-161236.
Nos. (17) to (43).

Examples of the hardening agent used for the constituent layers of the photothermographic material and the dye fixing material include the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042, 1984-116,655
Nos. 62-245,261 and 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane),
N-methylol hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be used. These hardeners are
0.001 to 1 g, preferably 0.005 to 0.5 g, is used per 1 g of gelatin applied. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

In the constituent layers of the photothermographic material and the dye fixing material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-62-13546 (7). Pages (9), (57) to (71) and (8)
1) to (97), U.S. Pat. No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No. 63-264,747, JP-A-1-150,1
No. 35, No. 2-110, 557, No. 2-178, 65
No. 0, RD 17, 643 (1978) (24)-(2
5) Compounds described on page and the like. These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

In the constituent layers of the photothermographic material and the dye-fixing material, coating aids, improved releasability, improved slipperiness, antistatic,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in the aforementioned Research Disclosure, JP-A-62-173463, and JP-A-62-173463.
183,457. The constituent layers of the photothermographic material and the dye fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-209.
No. 44, 62-135826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as a fluorine oil or a solid fluorine compound resin such as an ethylene tetrafluoride resin described in No. 62-135826, etc. No.

A matting agent can be used in the photothermographic material or the dye-fixing material for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin and polymethacrylate, and JP-A-63-2747 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
Nos. 44 and 63-274952.
Other compounds described in Research Disclosure can be used. These matting agents are the top layer (protective layer)
In addition, it can be added to the lower layer as needed.
In addition, the constituent layers of the photothermographic material and the dye fixing material may contain a thermal solvent, an antifoaming agent, a germicide / antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), and
No. 11,338 and Japanese Patent Publication No. 2-51,496.

In the present invention, an image formation accelerator can be used in the photothermographic material and / or the dye fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as formation of a dye from a dye-providing substance or decomposition of the dye or release of a diffusible dye, and photothermographic exposure. It has the function of promoting the transfer of the dye from the material layer to the dye fixing layer, and from the physicochemical function, a base or base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant , Silver, or compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. An example is U.S. Pat.
Nos. 514,493 and 4,657,848.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, a method in which a base and / or a base precursor is contained in a dye-fixing material is preferred from the viewpoint of enhancing the storage stability of the photothermographic material. . In addition to the above,
EP 210,660, U.S. Pat. No. 4,74
No. 0,445, and combinations of compounds which can form a complex with metal ions constituting the hardly soluble metal compound (referred to as complex forming compounds), and JP-A-61-232,451. Electrolysis O4 described in
And urea derivatives, nitroaniline derivatives such as nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM).
-Oxide derivatives, JP-A-61-53462, 62
The compounds described in JP-A-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type,
Fiber types and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signal, C
An image signal created using a computer represented by G or CAD can be used.

The photothermographic material and / or the dye-fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of the dye. The heat generating element in this case is described in JP-A-61-14.
No. 5,544 and the like can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and particularly about 60 ° C. to 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the thermal development, or may be performed after the thermal development step. In the latter case, the transfer temperature can be in the range from the temperature in the thermal development step to the room temperature, but is particularly 50 ° C. or higher, and is about 10 ° C. lower than the temperature in the thermal development step.
Up to lower temperatures are preferred.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this method, the heating temperature is preferably 50 ° C. or higher and lower than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the section of the image formation accelerator). Described are used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
The device described in No. 5, etc. or water may be used.

These solvents can be applied to the photothermographic material, the dye fixing material, or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying this water,
For example, the methods described in JP-A-62-253,159 (page 5) and JP-A-63-85,544 are preferably used. In addition, the solvent is enclosed in the microcapsule,
It can also be used in the form of a hydrate incorporated in advance in the photothermographic material or the dye fixing element or both. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85544. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

In order to promote the dye transfer, a system in which a hydrophilic heat solvent which is solid at room temperature and dissolves at a high temperature is incorporated in the photothermographic material and / or the dye fixing material may be employed. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

As a heating method in the development and / or transfer step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far infrared lamp heater may be used. For example, or by passing through a high-temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application No. 4-277,517, 4
Devices described in JP-A-243,072 and JP-A-4-244,693 are preferably used. Further, as a commercially available apparatus, a Pictrostat 100, a Pictrostat 200, a Pictography 3000, a Pictography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

[0081]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Example 1 A method for forming a support will be described.

Preparation of Cellulose Support 1 A pulp completed material comprising 50% of bleached hardwood kraft, 25% of bleached hardwood sulphite, and bleached hardwood sulphite was subjected to double disc refiner and then Jordan conical refiner. A photographic support was prepared by purification to 200 cc Canadian Standard Freeness. The obtained knitted pulp furnish has an alkyl ketene dimer of 0.2 on a dry weight basis.
%, Cation starch corn starch. 0% polyamylene de epichlorohydrin 1.5%, was added anionic polyacrylamide 0.26%, and a TiO ₂ 5.0%. About 2
25kg / 1000m ² (46.51bf / 1000ft2 (ksf))
Absolutely dry base paper is made on a Ford Linier paper machine, wet-pressed to a solids content of 42%, dried to a moisture content of 42% with a steam heated dryer, and has a Sheffield Porosit of 160 Sheffield units.
y) and an apparent density of 0.70 g / cc. Then, the paper base is placed in a vertical size press for 1 hour.
The surface was glued with a 0% hydroxyethylated corn starch solution to achieve a starch loading of 3.3% by weight.
The surface-glued support was calendered to an apparent density of 1.04 g / cc.

Preparation of Cellulose Support 2 In the same manner as in the preparation of cellulose support 1, about 100 k
Using a g / 1000 m ² (20.6 bf / 1000 ft ² (ksf)) bone dry weight base paper, a cellulose support thinner than support 1 (about 45%) was made.

Support A (Comparative Support) Titanium dioxide was added to the above cellulose support 1 in an amount of 15% by weight.
Polyethylene to which a very small amount of ultramarine blue is added as a bluing dye is 25 g / m ² on the surface, and 30 g of transparent polyethylene is on the back
/ M ² to obtain a support A as a comparative example.

Support B (Support Supporting the Present Invention) The following sheet was extruded and laminated on the above-mentioned cellulose support 1 having a polyethylene laminate layer of 10 g / m ^{2 on} the front and back surfaces to prepare a support B. Front side sheet: a composite sheet having microvoided biaxially oriented polypropylene layers filled with titanium dioxide on both sides of a biaxially oriented polypropylene core having microvoids (about 73% of the total sheet thickness) ( 38μ thickness, d = 0.6
2 g / cc), and the vacancy inducing material is polybutylene terephthalate. Back side sheet: One side matte finished polypropylene sheet (18 μ thickness, d = 0.9 g / cc) consisting of a biaxially stretched polypropylene core.

Support C (Support Supporting the Present Invention) The following sheet was extruded and laminated on the above-mentioned cellulose support 1 having a polyethylene laminate layer of 10 g / m ^{2 on} the front and back surfaces to prepare support C. Front side sheet: Biaxially stretched polypropylene sheet filled with titanium dioxide (27 μ thickness, d = 0.76 g / c)
c) Back side sheet: One side matte finish sheet made of polyethylene (40 μ thickness, d = 0.78 g / cc).

Support D (Comparative Support) 25 g of polyethylene was applied to the surface of the cellulose support 2 above.
/ M ^2, was prepared a support D serving as a comparative example by laminating a 30 g / m ² transparent polyethylene on the back side.

Support E (Support Supporting the Present Invention) The following sheet was extruded and laminated on the above-mentioned cellulose support 2 having a polyethylene laminate layer of 10 g / m 2 on the front and back surfaces to prepare a support E. Front sheet: Biaxially stretched polypropylene sheet (20 μ thickness, d = 0.74 g / cc) Back sheet: Biaxially stretched polypropylene sheet with matte finish on one side (20 μ thickness, d = 0.74 g)
/ Cc).

Example 2 A method for producing a photosensitive material will be described. JP-A-10-97042 except that the support is changed to the paper supports D and E described above.
Light-sensitive materials 01D and 01E were prepared in exactly the same manner as the light-sensitive material 101 described in Example 1 therein.

A method for preparing an image receiving material will be described. The image receiving material R20 described in Example 1 in JP-A-10-97042, except that the support is changed to the paper supports A, B and C described above.
Image receiving materials 01A, 01B, and 01C were prepared in exactly the same manner as in Example 1.

(Image Forming Method) The above photosensitive material 01D,
01E and image receiving materials 01A, 01B, and 01C were processed using a Pictrostat 300 manufactured by Fuji Photo Film Co., Ltd. That is, an original image (a test chart with a density of 1.0 and the entire surface is gray) is placed on a platen of the Pictrostat 300, surface exposed by a normal operation, and the exposed photosensitive material is placed in water maintained at 40 ° C. for 2.5 days. After immersion for 2 seconds, the sheet was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other. Then, using a heat drum whose temperature was adjusted so that the temperature of the water-absorbing film surface became 80 ° C., the photosensitive material was heated for 17 seconds and peeled from the image receiving material to obtain a gray uniform image corresponding to the original image on the image receiving material.

Table 1 shows the results of evaluating the mottle (density unevenness) and the transfer deviation (conveyance deviation between the photosensitive material and the image receiving paper in the heat development process) of the image obtained by combining each photosensitive material and the image receiving material.

Table 1 Experimental Example No. Photosensitive Material Image Receiving Material Image Motor Transfer Misalignment 101 01D 01A Comparative Example 10 6 102 01D 01B Present Invention 6 4 103 01D 01C Present Invention 7 4 104 01E 01A Present Invention 5 2 105 01E 01B Present Invention 3 1 106 01E 01C The present invention 4 1

The evaluation of the mottle in Table 1 is based on the fluctuation of the density value measured by a micro densitometer and visual judgment.
Performed comprehensively in stages. The larger the number, the more noticeable the mottle is, and 1 is very good and 10 is inferior.
As can be seen from Table 1, Experimental Examples Nos. 102 to 10 of the present invention
6 shows that the image was less mottled compared to Comparative Experimental Example 101, and it was found that transfer deviation was less likely to occur. In particular, Experimental Example 10 using the support of the present invention for both the light-sensitive material and the image-receiving material
5 and 106 are preferable, and Experimental example 105 is particularly preferable.

Example 3 A method for producing a photosensitive material will be described. JP-A-11-84610 except that the support is changed to the above-mentioned paper supports D and E.
Light-sensitive materials 02D and 02E were prepared in exactly the same manner as the light-sensitive material 208 described in Example 2 therein.

A method for producing an image receiving material will be described. The image receiving material R10 described in Example 1 in JP-A-11-84610 except that the support is changed to the paper supports A, B, and C described above.
Image-receiving materials 02A, 02B, and 02C were prepared in exactly the same manner as in Example 1.

(Image Forming Method) The above photosensitive materials 02D,
02E and the image receiving materials 02A, 02B, and 02C, and a pictography 3000 manufactured by Fuji Photo Film Co., Ltd.
Processed using A test chart image of the entire surface having a density of 1.0 was exposed and exposed, and the exposed photosensitive material was immersed in water kept at 40 ° C. for 2.5 seconds. Were overlapped so that they touched each other. Then, using a heat drum whose temperature was adjusted so that the temperature of the film surface having absorbed water was 80 ° C., heating was performed for 35 seconds to peel off the photosensitive material from the image receiving material, whereby a gray uniform image corresponding to the original image was obtained on the image receiving material. This image was visually observed, and the “image mottle” was evaluated in the same manner as in Example 3. Similarly, signals were sent such that the yellow, magenta, and cyan colors give the highest density, and the same processing was performed to obtain a black uniform image. This image was visually evaluated, and transfer unevenness (transfer defect of white spots) was evaluated on a 10-point scale (the smaller the number, the better). Table 2 shows the results.

Table 2 Experimental example No. Photosensitive material Image receiving material Image mottle Transfer unevenness 201 02D 02A Comparative example 6 7 202 02D 02B Present invention 4 3 203 02D 02C Present invention 4 4 204 02E 02A Present invention 3 3 205 02E 02B Present invention 1 1 206 02E 02C The present invention 13

As can be seen from Table 2, Experimental Example No.
From 202 to 206, image mottle was smaller than in Comparative Experimental Example 201, and transfer unevenness was seen. In particular, Experimental Example 205 using the support of the present invention for both the photosensitive material and the image receiving material.
To 206 are preferable, and particularly in the case of transfer unevenness, Experimental Example 205 in which a transfer member is combined with an image receiving material using a support having a film having fine pores is preferable.

[0101]

As described above, in a heat-developable color photographic material comprising a photosensitive material and an image-receiving material, the image-receiving material and / or the photosensitive material can be provided with a support having at least one side adhered to a biaxially stretched film, whereby image quality can be improved. Improved, especially
The present invention can provide a heat-developable color photographic material that provides a good image with less image noise such as mottle, transfer unevenness, and transfer deviation, and a color image forming method.

Claims (5)

[Claims] 1. A heat-developable color light-sensitive material having a photosensitive silver halide, a binder and a base precursor on a composite support having at least one surface bonded to a biaxially stretched film. 2. A heat-developable color image-receiving material comprising a mordant polymer and a base generator on a composite support having at least one surface adhered to a biaxially stretched film. 3. A heat-developable color light-sensitive material in which the composite support has a biaxially stretched film bonded on both sides. 4. A heat-developable color image-receiving material, wherein the composite support has a biaxially stretched film bonded on both sides. 5. A method for forming a color image using one of the photosensitive material and the image receiving material defined in claim 1, 2 or 3.