JPH0575105B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable color photosensitive material on which an image is formed by heat development, and more specifically, the present invention relates to a heat-developable color photosensitive material that has good heat developability, prevents color turbidity, and has improved film properties during heat development. This invention relates to heat-developable color photosensitive materials. [Background of the Invention] In recent years, heat-developable photosensitive materials whose development process can be performed by heat treatment have attracted attention as photosensitive materials. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication No. 43-4921 and No. 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, a reducing agent, and a binder. It is commercialized by 3M as dry silver. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Pat. Research Disclosure
15108 and 15127, U.S. Pat. No. 4,021,240, etc., a dye image is formed by the reaction of a coupler with an oxidized form of a reducing agent (hereinafter also referred to as a developer or developing agent), which is a sulfonamide phenol or sulfonamide aniline derivative. A method of releasing a dye image on a separately provided image-receiving layer by using an organic imino silver salt having a dye part as disclosed in British Patent No. 1590956, and releasing a dye image on a separately provided image-receiving layer. JP-A-52-105821, No. 52-
105822, 56-50328, and U.S. Pat. No. 4,235,957, etc., methods for obtaining positive dye images by silver dye bleaching methods, as well as U.S. Pat. No. 3,180,731,
Same No. 3985565, Same No. 4022617, Same No. 4452883,
Various methods have been proposed, such as the method of obtaining a dye image using a leuco dye disclosed in Japanese Patent Application Laid-Open No. 59-206831. However, with these proposals regarding the heat-developable color photosensitive materials, it is difficult to bleach and fix the black, white, and silver images formed at the same time, and
It is difficult to obtain clear color images,
Furthermore, it required complicated post-processing, and was not yet satisfactory for practical use. In recent years, as a new type of color image forming method using heat development, Japanese Patent Laid-Open Nos. 57-179840 and 57-
No. 186744, No. 57-198458, No. 57-207250, etc. disclose methods for obtaining color images by transferring diffusible dyes released by heat development. These methods were further improved to produce diffusible dyes by oxidizing non-diffusible reducing dye-donating substances, such as those disclosed in JP-A-58-58543 and JP-A-59-168439. A method of emitting
JP-A No. 58-79247, No. 59-174834, No. 59-
12431, No. 59-159159, No. 60-2950, etc., in which a diffusible dye is released by coupling with an oxidized developing agent; No. 58-149047, 59
−124339, No. 59-181345, No. 60-2950, Patent Application No. 59-181604, No. 59-182506, No. 59-
A method using a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye as disclosed in No. 182507, No. 59-272335, etc.;
JP-A No. 59-152440, No. 59-124327, No. 59-
No. 154445, No. 59-166954, etc., are non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and conversely, non-diffusible dye-donating substances that release diffusible dyes when reduced. Some methods have been proposed, such as a method containing a pigment-providing substance. The basic composition of a color type heat-developable photosensitive material that produces a color image using these emitted or formed diffusive dyes consists of a light-sensitive element and an image-receiving element. It consists of a silver salt, a reducing agent, a dye-providing substance, and a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense, and the image receiving element is referred to as an image receiving member. The above heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto an image receiving layer of an image receiving member provided on the same support or another independent support. , image sharpness,
In terms of stability and other aspects, it has been improved in many respects compared to previous heat-developable color photosensitive materials. However, the above heat-developable color photosensitive materials also have the following problems. Many of the photographic constituent layers of heat-developable photosensitive materials contain gelatin as a main component of the binder. It is known that gelatin is usually hardened using a hardening agent in order to improve the scratch resistance of the gelatin layer. However, heat-developable photosensitive materials have specific characteristics during heat development, such as processing at temperatures of 80°C or higher or 100°C or higher, or pressure-applied heaters, electrodes, etc., and drums containing these. The gelatin layer is processed under mechanical stress using a roller or the like, and the gelatin layer sometimes breaks down during the heat development process, so-called film collapse. Conventionally used gelatin hardeners have been insufficiently effective in preventing film deformation during thermal development. Separately, in heat-developable photosensitive materials, it is known that heat solvents such as those described below are allowed to coexist with the gelatin binder in order to improve the properties of the formed dye image. It is thought that the mixture temporarily enters a mixed molten state, resulting in further worsening of the film collapse. Furthermore, the degree of hardness of the gelatin layer is generally expressed by the degree of swelling (the rate of increase in the thickness of the gelatin layer), but when these thermal solvents coexist with the gelatin binder, In an attempt to prevent film deterioration during heat development,
Even if the hardening agent described in No. 119554 is used to increase the degree of curing until the degree of swelling in wet processing becomes very low, film deterioration is not improved and developability is reduced. found. [Object of the Invention] Accordingly, an object of the present invention is to provide a heat-developable color photosensitive material that has good developability, is prevented from color turbidity, and has improved film properties during heat development. [Structure of the Invention] The above object of the present invention is to provide on a support at least two heat-developable photosensitive layers in which the sensitivity of the photosensitive silver halide and the hue of the dye formed from the dye-providing substance are different from each other. A heat-developable color photosensitive material having a photographic constituent layer consisting of at least one non-photosensitive layer, wherein at least one of the photographic constituent layers contains a polymer hardener represented by the following general formula (). This was achieved using color photosensitive materials. General formula ()

embedded image In the formula, A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q is −CO ₂ −,

[Formula] or represents an arylene group having 6 to 10 carbon atoms. L is −CO ₂ −,

[Formula] A divalent group containing at least one bond and having 3 to 15 carbon atoms, or -O-,

[Formula] −CO−, −SO −, −SO ₂ −, −SO ₃ −,

【formula】

【formula】

[Formula] represents a divalent group containing at least one bond and having 1 to 12 carbon atoms. R ₁ ′, R ₁ ″ represent the same as R ₁ described above. R ₂ represents -CH=CH ₂ or -CH ₂ -CH ₂ X. Therefore, it represents a group that can leave in the form of HX. x, y represent mole percentage, x is 0 to 75,
y takes a value from 25 to 100. [Specific Structure of the Invention] The polymer hardener in the present invention is a homopolymer of a polymerizable ethylenically unsaturated monomer having a group reactive with gelatin, a vinyl group, or a functional group serving as a precursor thereof. Alternatively, it refers to a copolymer, which is a polymer compound having at least 2 or more, preferably 10 to 5000 or more, groups reactive with gelatin in the molecule. In the general formula (), the ethylenically unsaturated monomer represented by A includes ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, and sodium vinylbenzylsulfonate. , α-methylstyrene, vinyltoluene, N-vinylacetamide,
N-vinylpyrrolidone, monoethylenically unsaturated esters of fatty acids (e.g. vinyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid), maleic anhydride, ethylenically unsaturated esters of monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, ethylenically unsaturated Amides of monocarboxylic or dicarboxylic acids (for example, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine), etc. R ₁ is a hydrogen atom or methyl group is particularly preferred. Q includes the following groups: -CO ₂ -, -CONH-,

【formula】

[Formula] is particularly preferred. L includes the following groups. −CH ₂ CO ₂ CH ₂ CH ₂ − −CH ₂ NHCOCH ₂ − (−CH ₂ ) − ₁₀ NHCOCH ₂ CH ₂ − −CH ₂ COCH ₂ CH ₂ −

[Chemical] -SO ₂ CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ - -SO ₂ NHCH ₂ CH ₂ CO ₂ CH ₂ CH ₂ - -NHCONHCH ₂ CH ₂ - R ₂ includes the following groups. −CH=CH ₂ , −CH ₂ CH ₂ Br, −CH ₂ CH ₂ C,

[Formula] is particularly preferred. Specific examples of the polymer hardener of the present invention are shown below.

[ka]

[ka]

[ka]

[ka]

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[ka]

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[ka]

[ka]

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[Chemical] In addition to using a polymer having two or more functional groups reactive with gelatin as described above as the polymer hardening agent of the present invention, it is also possible to use a polymer that reacts with a low-molecular hardening agent. It is also possible to form a polymeric hardener in the coating layer by mixing it with a polymer that provides a polymeric hardener. Examples of low-molecular hardeners used in this case include JP-A-49-13563 and JP-A-49-13563;
Examples include those described in No. 53-41221, etc.
Examples of the polymer include those described in JP-A-56-4141. In the present invention, those having an aldehyde group and those having a dichlorotriazine group interact with other photographic additives such as antifoggants and dye-providing substances, which not only impair the curing effect but also increase fog. It is undesirable because it has disadvantages such as deterioration of photographic performance such as a decrease in density and sensitivity, and instability and poor storage stability. The molecular weight of the polymer hardener of the present invention is preferably about 10 ⁴ to 10 ⁵ in terms of number average molecular weight. The method for synthesizing the polymer hardener of the present invention includes the aforementioned U.S. Pat. No. 3,396,029, U.S. Pat. No. 56-
It can be synthesized according to the methods described in the specifications of No. 142524 and No. 56-66841. The polymer hardener can be added by dissolving it in water or an organic solvent and directly adding it to the layer to be hardened. The amount of the polymer hardener of the present invention to be used can be arbitrarily selected depending on the purpose, but usually the amount of functional groups involved in hardening action is 5×
An amount corresponding to 10 ⁻⁶ to 5×10 ⁻⁴ equivalents is used, particularly preferably 1×10 ⁻⁵ to 2×10 ⁻⁴ equivalents. Further, the polymer hardener of the present invention may be used alone, or may be used in combination with other polymer hardeners, or may be additionally used with a low molecular hardener. The heat-developable color photosensitive material of the present invention comprises at least two heat-developable photosensitive layers in which the sensitivity of the photosensitive silver halide and the hue of the dye formed from the dye-donating substance are different from each other, and at least one non-photosensitive layer. It has a photographic constituent layer consisting of a transparent layer, and at least one of the photographic constituent layers contains the polymer hardening agent. In addition to the heat-developable photosensitive layer having the photosensitive silver halide emulsion described above, there may be various types of these photographic constituent layers depending on the use of the photosensitive material, the types and properties of the photosensitive silver halide and the dye-providing substance, etc. Examples of the non-photosensitive layer include a layer containing a dye-providing substance, a layer containing a color clouding prevention agent, an intermediate layer, a protective layer, an antihalation layer, a subbing layer, an opaque layer, a light reflection layer, a thermal solvent supply layer, and a physical development layer. Examples include a nucleus-containing layer, a filter layer, an image-receiving layer, and a layer located between these layers. The polymer hardening agent according to the present invention may be added to any of these photographic constituent layers, but it is preferable that the hardening degree of the layer not containing photosensitive silver halide or dye-providing substance is relatively high. It is preferable to contain it in such a way that the uppermost layer when viewed from the support, which does not contain a photosensitive silver halide or a dye-providing substance (hereinafter referred to as the protective layer of the present invention), has the highest degree of curing. is even more preferable. Deterioration of each layer film during heat development was determined by heat developing the photothermographic material of the present invention in a heat developing machine (for example, Deiberotsu Parmodule 277, manufactured by 3M Company) at various humidity and times. Afterwards, the sample can be evaluated by observing it under a microscope. Various additives used in the photographic field can be used in the protective layer of the present invention. The additives include various matting agents, colloidal silica, slipping agents, organic fluoro compounds (especially fluorosurfactants), antistatic agents, ultraviolet absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, Examples include polymer latex, surfactants (including polymeric surfactants), organic silver salt particles, non-photosensitive silver halide particles, and the like. The matting agent used in the protective layer of the present invention is fine particles of inorganic or organic substances that are incorporated into a heat-developable photosensitive material to increase the roughness of the surface of the photosensitive material and make it matte. be. A method of using a matting agent to prevent adhesion that occurs during production, storage, use, etc. of photosensitive materials, and to prevent charging caused by contact, friction, and peeling between materials of the same or different types is as follows: Well known in the industry. As a specific example of a matte agent, JP-A-Sho
Silicon dioxide described in No. 50-46316, JP-A-53-
Alkali-soluble matting agents such as alkyl methacrylate/methacrylic acid copolymers described in No. 7231, No. 58-66937, and No. 60-8894; alkalis having anionic groups described in JP-A-58-166341; Soluble polymer, combination of two or more types of fine particle powders with different Mohs hardnesses, described in JP-A-58-145935, JP-A-58-145935
Combination of oil droplets and fine particle powder described in No. 147734, JP-A-Sho
59-149356, a combination of two or more spherical matting agents with different average particle diameters, a combination of a fluorinated surfactant and a matting agent described in JP-A-56-44411, British Patent No. 1055713, U.S. Patent No. 1939213;
No. 2221873, No. 2268662, No. 2322037, No. 2221873, No. 2268662, No. 2322037, No.
No. 2376005, No. 2391181, No. 2701245, No. 2376005, No. 2391181, No. 2701245, No.
No. 2992101, No. 3079257, No. 3262782, No.
No. 3443946, No. 3516832, No. 3539344, No.
No. 3591379, No. 3754924, No. 3767448, JP-A-Sho
Organic matting agents described in No. 49-106821, No. 57-14835, etc., West German Patent No. 2529321, British Patent No. 760775, No. 1260772, U.S. Patent No. 1201905
No. 2192241, No. 3053662, No. 3062649,
3257206, 3322555, 3353958, 3353958, 3322555, 3353958,
No. 3370951, No. 3411907, No. 3437484, No.
No. 3523022, No. 3615554, No. 3635714, No. 3635714, No. 3615554, No. 3635714, No.
Inorganic matting agents described in No. 3769020, No. 4021245, No. 4029504, etc., or JP-A-46-
No. 7781, No. 49-106821, No. 51-6017, No. 53-
No. 116143, No. 53-100226, No. 57-14835, No.
No. 57-82832, No. 53-70426, No. 59-149357,
Matting agents having physical properties as described in Japanese Patent Publication No. 57-9053 and EP-107378 are preferably used. In the protective layer of the present invention, the amount of the matting agent added is preferably 10 mg to 2.0 g per ^square meter, more preferably 20 mg to 1.0 g. The particle size of matte agent is 0.5
~10 μm is preferred, more preferably 1.0 ~ 6 μm. The matting agent may be used in combination of two or more types. Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, examples include French Patent No. 2180465 and British Patent No.
No.955061, No.1143118, No.1270578, No.955061, No.1143118, No.1270578, No.
No. 1320564, No. 1320757, JP-A-49-5017, No.
No. 51-141623, No. 54-159221, No. 56-81841,
Research Disclosure
Disclosure) No. 13969, U.S. Patent No. 1263722,
No. 2588765, No. 2739891, No. 3018178, No.
No. 3042522, No. 3080317, No. 3082087, No.
No. 3121060, No. 3222178, No. 3295979, No.
No. 3489567, No. 3516832, No. 3658573, No.
Those described in No. 3679411, No. 3870521, etc. can be preferably used. The protective layer of the present invention contains a high boiling point organic solvent (for example, US Pat.
No. 2322027, No. 2533514, No. 2882157, Tokko Akira
46-23233, British Patent No. 958441, British Patent No. 1222753
No. 2,353,262, U.S. Pat. No. 3,676,142, U.S. Pat.
No. 3700454, Japanese Patent Application Publication No. 50-82078, No. 51-27921,
51-141623 etc., esters (e.g. phthalate esters, phosphate esters, fatty acid esters, etc.), amides (e.g. fatty acid amides,
(sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ) may contain oil droplets in which a water-insoluble oily compound is emulsified and dispersed. Furthermore, these oil droplets may contain photographic additives for various purposes. Binders used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate,
One or a combination of two or more synthetic or natural polymeric substances such as cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, polyacrylamide, gelatin, and phthalated gelatin can be used. In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (preferably molecular weight 1000-400000) and polyoxosaline (molecular weight 1000-400000)
800,000), polyvinyl alcohol (preferably molecular weight 1,000 to 100,000) alone or in combination of two or more of these binders are preferable, and gelatin alone or gelatin is compatible with gelatin such as the above-mentioned polyvinylpyrrolidone, polyvinyl alcohol, and polyoxazoline. Particularly preferred is a binder in which a hydrophilic polymer with good properties is used. Gelatin may be treated with lime, acid, or ion exchange, and may be ossein gelatin, pitguskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. good. The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers. The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) in one heat-developable photosensitive layer.
It is preferable to contain a reducing agent, (3) a dye-providing substance, (4) a binder, and further contain (5) an organic silver salt if necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example,
The heat-developable photosensitive layer is divided into two layers, and the above (1), (2), (4),
The component (5) is contained in the heat-developable photosensitive layer on one side,
The dye-providing substance (3) may be contained separately in two or more constituent layers as long as they can react with each other, such as by containing the dye-providing substance (3) in the layer on the other side adjacent to this photosensitive layer. In addition, the heat-developable photosensitive layer is divided into a high-sensitivity layer and a low-sensitivity layer.
It may be divided into two or more layers such as a high concentration layer and a low concentration layer. The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, it generally has three heat-developable photosensitive layers with different color sensitivities, and each photosensitive layer forms or releases dyes with different hues upon heat development.
Typically, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer. The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. There is a structure in which a green-sensitive layer, a red-sensitive layer is formed, or a structure in which a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer are sequentially formed on a support. In addition to the heat-developable photosensitive layer, the photothermographic material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied. That is, there are methods and apparatuses for the dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method, bead method, extrusion method, stretch flow method, curtain method, and the like. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as a single jet method or a double jet method. For example, JP-A-54-48521
By applying the method described in the above publication, monodisperse silver halide grains can be obtained by a double jet method while keeping pAg constant. At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, PH, pAg, temperature, etc. According to a further preferred embodiment, silver halide emulsions having silver halide grains with shells can be used. Silver halide grains having shells can be obtained by sequentially growing shells on a core of silver halide grains having good monodispersity using the method described above. The monodisperse silver halide emulsion referred to in the present invention is
Variation in silver halide grain size contained in the emulsion refers to those having a grain size distribution below a certain ratio with respect to the average grain size as shown below. Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with uniform grain morphology and small grain size variations is almost a normal distribution, the standard deviation can be easily determined. When the width of the distribution is defined by the relational expression standard deviation/average grain size x 100 = width of distribution (%), the width of the distribution of the silver halide grains used in the present invention is 15% or less. The monodispersity is preferably 10% or less, and more preferably 10% or less. Also, for example, JP-A-58-111933, JP-A No. 58-111933;
As described in No. 111934, No. 58-108526, Research Disclosure No. 22534, etc.
A particle that has two parallel crystal planes, each of which has a larger area than other single crystals of the particle, and whose aspect ratio, that is, the ratio of the diameter to the thickness of the particle, is 5: Silver halide emulsions consisting of one or more tabular silver halide grains can also be used. Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. Regarding internal latent image type silver halide whose surface is not fogged in advance, for example, US Pat. No. 2,592,250, US Pat.
No. 3317322, No. 3511662, No. 3447927,
As described in No. 3761266, No. 3703584, No. 3736140, etc., it is a silver halide grain in which the sensitivity inside the grain is higher than the sensitivity on the surface of the grain. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above patent, for example, by first preparing AgC grains and then adding bromide or a small amount of iodide thereto. A method in which the center core of chemically sensitized silver halide is coated with non-chemically sensitized silver halide, or a method in which chemically sensitized coarse grain emulsion and chemical sensitization are performed. Many methods are known, such as a method in which a fine grain emulsion which has not been chemically sensitized is mixed and a fine grain emulsion is deposited on a coarse grain emulsion. Additionally, U.S. Patent No.
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 3,271,157, US Pat. No. 3,447,927 and US Pat. A silver halide emulsion containing weakly chemically sensitized silver halide grain surfaces, or JP-A-Sho
Silver halide emulsions comprising grains having a laminated structure as described in JP-A-50-8524 and JP-A-50-38525, and other JP-A-52-156614 and JP-A-Sho. 55
These include the silver halide emulsion described in No. 127549. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm,
More preferably, it is about 0.01 μm to about 0.5 μm. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, NH ₄ group or a metal atom, and X represents C, Br or I, n is 1 when M is an H atom or NH ₄ group, and the valence when M is a metal atom.Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, Gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium,
Examples include molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g., K ₂ PtC ₆ , K ₂ PtBr ₆ , HAuC ₄ , (NH ₄ ) ₂
IrC ₆ , (NH ₄ ) ₃ IrC ₆ , (NH ₄ ) ₂ RuC ₆ ,
(NH ₄ ) ₃ RuC ₆ , (NH ₄ ) ₂ RhC ₆ , (NH ₄ ) ₃
RhBr ₆ , etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosph quaternary phosphonium halides such as onium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g.
Iodoform, bromoform, carbon tetrabromide, 2-
bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromo-2-methylpropane, etc.),
-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N
-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) etc. can be given. These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amounts used are as ^follows :
The amount is preferably 0.001 g to 50 g, more preferably 0.1 g to 10 g. The heat-developable photosensitive material of the present invention has blue light, green light,
It is also possible to have a multilayer structure including each layer having sensitivity to red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. In addition, two or more photosensitive layers of the same color (for example, a high-sensitivity layer and a low-sensitivity layer)
It can also be divided into two parts. In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as US Pat. No. 2,933,390,
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these sensitizing dyes added is 1×10 ^-4 per mole of photosensitive silver halide or silver halide forming component.
mol to 1 mol. More preferably, 1×10 ⁻⁴
mole to 1×10 ⁻¹ mole. In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publication No. 43-4921 and Japanese Patent Application Laid-Open No. 49-52626.
No. 52-141222, No. 53-36224 and No. 53
Publications such as −37610 and U.S. Patent No. 3330633
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle as described in the specifications of No. 3794496, No. 4105451, etc.
For example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, α-(1-phenyltetrazolthio)
Silver aromatic carboxylates such as silver acetate, such as silver benzoate, silver phthalate, etc.,
No. 45-12700, No. 45-18416, No. 45-22185,
JP-A-52-137321, JP-A-58-118638, JP-A-58
There are silver salts of imino groups described in publications such as No. 118639 and US Pat. No. 4,123,274. Examples of silver salts of imino groups include silver benztriazole. The benztriazole silver may be substituted or unsubstituted. Representative examples of silver substituted benztriazoles include:
For example, alkyl-substituted benztriazole silver (preferably substituted with a _C22 or less alkyl group, more preferably a _C4 or less alkyl group, such as methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.) ), silver alkylamidobenztriazole (preferably substituted with an alkylamide group of up to _C22 , e.g. silver acetamidobenztriazole, silver propionamidobenztriazole, silver iso-butylamidobenztriazole,
silver laurylamide benztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably substituted with an alkylsulfamoyl group of C ₂₂ or less, for example, silver 4-(N,N-diethylsulfamoyl)benztriazole) , 4-
(N-propylsulfamoyl)benztriazole silver, 4-(N-octylsulfamoyl)benztriazole silver, 4-(N-decylsulfamoyl)benztriazole silver, 5-(N-octylsulfamoyl) benztriazole silver, etc.),
Silver salts of halogen-substituted benztriazoles (for example, silver 5-chlorobenztriazole, silver 5-bromobenztriazole, etc.), silver alkoxybenztriazole (preferably an alkoxy group of C ₂₂ or less, more preferably an alkoxy group of C ₄ or less) silver 5-methoxybenztriazole, silver 5-ethoxybenztriazole, etc.), silver 5-nitrobenztriazole, silver 5-aminobenztriazole, silver 4-hydroxybenztriazole, silver 5-carboxybenztriazole, 4-Sulfobenztriazole silver, 5
-silver sulfobenztriazole, and the like. Examples of other imino group-containing silver salts include imidazole silver, benzimidazole silver, 6
- nitrobenzimidazole silver, pyrazole silver,
urazole silver, 1,2,4-triazole silver,
Silver salts of other mercapto compounds such as 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, satucalin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzoxazole silver, mercaptooxadi Azole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-
Mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,
Examples include 3,3a,7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver. In addition, silver complex compounds with a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, imidazolinthion silver salts as described in U.S. Pat. No. 4,168,980, etc. are used. . Among the above organic silver salts, imino group silver salts are preferable, particularly silver salts of benzotriazole derivatives,
More preferred are 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives. The organic silver salts used in the present invention may be used alone or in combination of two or more. Further, a silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated salt may be dispersed in a binder by an appropriate means and used. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like. In addition, the method for preparing organic silver salts is generally to dissolve silver nitrate and raw organic compounds in water or an organic solvent and mix them, but if necessary, a binder may be added or a solution such as sodium hydroxide may be added. Adding alkali to promote the dissolution of organic compounds,
It is also effective to use an ammoniacal silver nitrate solution. The amount of the organic silver salt used is generally preferably 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol of photosensitive silver halide. Further, the amount is more preferably 0.3 to 30 mol. As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used. The dye-providing substance used in the heat-developable photosensitive material of the present invention is, for example, JP-A-57-186744;
No. 58-79247, No. 58-149046, No. 58-149047
No. 59-124339, No. 59-181345, No. 60-
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent as disclosed in No. 2950, etc., the reducing agent used in the present invention may be , for example, US Patent No. 3531286, US Patent No. 3761270, US Patent No.
3764328 specifications, RD No. 12146, and the same No.
15108, No. 15127 and JP-A-56-27132, p-phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenol type, sulfonamide phenol type developing agents, sulfonamide aniline type developing agents A developing agent, a hydrazone color developing agent, etc. can be used. Also, U.S. Patent No. 3342599, U.S. Patent No. 3719492
Color developing agent precursors described in Japanese Patent Application Laid-open Nos. 53-135628 and 54-79035 can also be advantageously used. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (1) described in No. General formula (1)

[Chemical formula] In the formula, R ¹ and R ² are hydrogen atoms, or carbon atoms having 1 to 30 carbon atoms (preferably 1 to 30), which may have a substituent.
-4) represents an alkyl group, and R ¹ and R ² may be ring-closed to form a heterocycle. R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, hydroxy groups,
Represents an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R ³ and R ¹ And R ⁵ and R ² may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming an inorganic salt and a salt, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, piperidine, and imidazole, which are well-known as typical examples of heterocyclic organic bases. It will be done. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. Next, preferred specific examples of the reducing agent represented by the general formula (1) are shown below.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Chemical formula] The reducing agent represented by the above general formula (1) can be prepared by a known method such as Heuben-Beil, Mesoden der Organitsien Chemie, Band XI/2.
(Houben-Weyl, Methoden der Organischen
Chemie, Band XI/2), pages 645-703. Furthermore, even if two or more of the above reducing agents are used simultaneously,
It is also possible to use a black and white developing agent described below in combination for the purpose of increasing developability. Further, the dye-donating substance used in the present invention is JP-A-57-179840, JP-A-58-58543, JP-A-59
-152440, 59-154445, etc., compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc. (or In the case where only a silver image is simply obtained, a developing agent as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1′ -dihydroxy group-2,2'-binaphthyl, 6,6'-dibromo-2,2-dihydroxy-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol,
α-phenyl-α,α-bis(2-hydroxy-
3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,
5,5-tetrakis(2-hydroxy-3,5-
dimethylphenyl)-2,4-ethylpentane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4- Hydroxy-
3,5-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones,
Mention may be made of pyrazolones, hydrazones and paraphenylenediamines. These developing agents mentioned above can also be used alone or in combination of two or more. The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide, the type of organic acid silver salt, and the type of other additives used, but usually is in the range of 0.01 to 1500 mol, preferably 0.1 to 200 mol, per 1 mol of photosensitive silver halide. Examples of the support used in the heat-developable photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coated paper. Examples include paper supports, and supports obtained by coating and curing an electron beam curable resin composition on these supports. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-59-229556. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including graft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1000
~400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates, vinyl imidazoles, (meth)acrylamides, Examples include vinyl monomers such as vinyl carbinols and vinyl alkyl ethers, but at least
It is preferable that 20% (weight %, same hereinafter) is polyvinylpyrrolidone. Preferred examples of such copolymers have a molecular weight of 5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pitgskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05 g to 50 g per layer per m ² of support, preferably
It is 0.1g to 10g. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of the dye-providing substance. When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, various heat solvents are preferably added to the photothermographic material and/or the image receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. These compounds are described in, for example, U.S. Patent No. 3,347,675, U.S. Pat. Examples include organic compounds with polarity,
Particularly useful in the present invention include, for example, urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g.,
acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-pentanediol, 1,
(6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycols. Among the above thermal solvents, water-insoluble solid thermal solvents described below are more preferably used. A water-insoluble solid thermal solvent is a compound that is solid at room temperature but becomes liquid at high temperatures (60°C or higher, preferably 100°C or higher, particularly preferably 130°C or higher and 250°C or lower), and is an inorganic/organic compound. The ratio of
3.0, preferably 0.7 to 2.5, particularly preferably 1.0 to
It is a compound in the range of 2.0, and the solubility in water at room temperature is less than 1. Specific examples of water-insoluble solid thermal solvents are shown below.
Not limited to these.

【table】

【table】

【table】

[Table] Many compounds used as water-insoluble solid heat solvents are commercially available, and can be easily synthesized by those skilled in the art. The method of adding the water-insoluble heat solvent is not particularly limited, but
There are methods such as adding by pulverizing and dispersing using a ball mill, sand mill, etc., adding by dissolving in a suitable solvent, and adding by dissolving in a high boiling point solvent and adding as an oil-in-water dispersion. It is preferable to pulverize and disperse the solid particles using a sand mill or the like and add them while maintaining the solid particle shape. Layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image-receiving layer of an image-receiving member, and the like, so that the respective effects can be obtained. The amount of water-insoluble heat solvent added is usually 10% to 500% by weight, preferably 50% to 50% by weight of the binder amount.
It is 300% by weight. In addition, even if the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the heat development temperature, the melting point will be lowered by being added to the binder.
It can be effectively used as a thermal solvent. The photothermographic material of the present invention may contain various additives in addition to the above-mentioned components, if necessary. For example, melt formers such as acetamide and succinimide described in U.S. Patent No. 3,438,776, compounds such as polyalkylene glycols described in U.S. Pat. There are non-aqueous polar organic compounds having a melting point of 20°C or higher, such as lactones having -CO-, _-SO2- , and -SO- groups. Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829, JP-A-53-
Phenol derivatives described in No. 60223, JP-A-Sho
Carboxylic acids described in No. 58-118640, JP-A-Sho
Examples include polyhydric alcohols described in No. 58-198038 and sulfamoylamide compounds described in JP-A No. 59-84236. Further, a color toning agent known in heat-developable photosensitive materials may be added as a development accelerator to the photothermographic material of the present invention. As a coloring agent,
For example, JP-A No. 46-4928, No. 46-6077, No. 49-
No. 5019, No. 49-5020, No. 49-91215, No. 49-
No. 107727, No. 50-2524, No. 50-67132, No. 50
−67641, No. 50-114217, No. 52-33722, No.
No. 52-99813, No. 53-1020, No. 53-55115, No. 53-55115, No.
No. 53-76020, No. 53-125014, No. 54-156523,
No. 54-156524, No. 54-156525, No. 54-156526
No. 55-4060, No. 55-4061, No. 55-32015
Publications such as No. 2140406 and West German Patent No. 2140406,
No. 2141063, No. 2220618, U.S. Patent No. 3847612,
No. 3782941, No. 4201582 and JP-A-57-
No. 207244, No. 57-207245, No. 58-189628, No. 58-189628, No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,
3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, aminomercaptotriazole, acylaminomercaptotriazole, phthalic acid, naphthalic acid, phthalamic acid, etc.
A mixture of one or more of these and an imidazole compound, a mixture of at least one acid or acid anhydride such as phthalic acid or naphthalic acid, or a phthalazine compound, furthermore, a mixture of phthalazine and maleic acid, itaconic acid, or quinoline. Examples include combinations of acids, gentisic acid, and the like. As an antifoggant, for example, US Pat.
Higher fatty acids (e.g. behenic acid, stearic acid, etc.) described in Japanese Patent Publication No. 3645739, mercuric salts described in Japanese Patent Publication No. 11113-1983, N-halogen compounds described in Japanese Patent Application Laid-open No. 47419-1983 (e.g. -halogenoacetamide, N-halogenosuccinimide, etc.), mercapto compound-releasing compounds described in U.S. Pat. oxidants (e.g. perchlorates, inorganic oxides, persulfates, etc.), sulfinic acids or thiosulfonic acids described in No. 53-19825, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, 51- No. 42529, No. 51-81124, No. 42529, No. 51-81124, No.
Disulfide and polysulfide compounds described in No. 55-93149, rosins or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxyl groups or sulfonic acid groups described in No. 51-104338. 1,2,4-triazole or 5-triazole as described in JP-A-54-51821 and U.S. Pat. No. 4,137,079;
Mercapto-1,2,4-triazole, 55
- Thiosulfinate esters described in No. 140833, 1,2,3,4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-57233
No. 59-57234, and the dihalogen compounds or trihalogen compounds described in No. 59-111636.
Examples include the thiol compounds described in No. In addition, as other anti-fogging agents,
Hydroquinone derivatives described in No. 56506 (e.g.
di-t-octylhydroquinone, dodecanylhydroquinone, etc.), hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole,
-carboxybenzotriazole, etc.) can be preferably used in combination. As a silver image stabilizer, U.S. Patent No. 3707377
5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768071, JP-A No. 768071; Monohalo compounds (e.g., 2-bromo-2-tolylsulfonylacetamide, etc.) described in JP-A-50-119624, bromine compounds described in JP-A-50-120328 (e.g., 2-bromomethylsulfonylbenzothiazole, 2, 4-bis(tribromomethyl)-6-methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, various monohalogenated organic antifoggants for silver halide emulsions described in JP-A-50-119624 can be used. Other image stabilizers include U.S. Pat.
No. 3220846, No. 4082555, No. 4088496, JP-A-Sho
50-22625, Research Disclosure (RD) No. 12021, RD No. 15168, RD No. 15567, RD No.
Compounds called activator precursors that release basic substances by heat, such as guanidinium, which releases a base by decarboxylation with heat, described in No. 15732, No. 15733, No. 15734, No. 15776, etc. Compounds such as trichloroacetate, aldnamide compounds such as galactonamide, amine imides, 2-carboxycarboxamide, etc.
In addition, sodium phosphate base generators described in JP-A-56-130745 and JP-A-56-132332, compounds that generate amines through intramolecular nucleophilic reactions described in British Patent No. 2079480, JP-A-56-130745 and JP-A-56-132332; Aldoxime carbamates described in No. 59-157637, No. 59-
Hydroxamic acid carbamates etc. described in No. 166943, No. 59-180537, No. 59-174830, No. 59-174830,
Examples include base releasing agents described in No. 59-195237 and the like. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444, U.S. Patent No.
No. 3824103, No. 3844788, No. RD12035, No. 3824103, No. 3844788, No. RD12035, No.
Illithiuronium compounds, s-carbamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in US Pat.
No. 4012260, No. 4060420, No. 4207392,
Activator stabilizer and nitrogen-containing organic base called activator stabilizer precursor described in RD15109 and RD17711, etc., such as α-sulfonylacetate or trichloroacetate of 2-aminothiazoline, acylhydrazine compound, etc., are developed. It can be used for the purpose of promoting or for stabilizing the image. Also, for example, JP-A-56-130745, JP-A No. 59-
Development may be carried out in the presence of a small amount of water as described in No. 218443, or water may be supplied by spraying a small amount of water or applying a certain amount of water before heating.
As described in US Pat. No. 3,312,550 and the like, development may be performed using hot steam, hot air containing moisture, or the like.
Compounds that release water into heat-developable photosensitive materials, such as compounds containing water of crystallization as described in Japanese Patent Publication No. 44-26582, such as sodium phosphate dodecahydrate,
Ammonium alum 24 hydrate salt or the like may be included in the photothermographic material. In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used. In the heat-developable photosensitive material of the present invention, colloidal silica may be used in the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving film properties. can. The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main components are:
It is SiO ₂ (silicon dioxide). Regarding colloidal silica, for example, JP-A-56-109336, JP-A No. 53-
It is described in No. 123916, No. 53-112732, No. 53-100226, etc. The amount of colloidal silica used is
The dry weight ratio to the binder of the layer to be mixed and coated is preferably in the range of 0.05 to 2.0. In the heat-developable photosensitive material of the present invention, an organic fluoro compound may be used in the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving film properties. I can do it. Regarding the organic fluoro compounds used in the present invention, US Pat. No. 3,589,906, US Pat.
3754924, 3775126, 3850640, West German Patent Publication No. 1942665, 1961638, 2124262,
British Patent No. 1330356, Belgian Patent No. 742680, and Japanese Patent Application Laid-open Nos. 46-7781, 48-9715, and 49-
No. 46733, No. 49-133023, No. 50-99529, No. 50
−11322, No. 50-160034, No. 51-43131, No.
No. 51-129229, No. 51-106419, No. 53-84712,
No. 54-111330, No. 56-109336, No. 59-30536
No. 59-45441 and Special Publication No. 47-9303, same.
Examples include compounds described in No. 48-43130 and No. 59-5887, and these compounds can be preferably used. In the heat-developable photosensitive material of the present invention, an antistatic agent can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). Antistatic agents used in the present invention include British Patent No. 1466600, Research Disclosure No. 15840, British Patent No. 16258
No. 16630, U.S. Patent No. 2327828, U.S. Pat.
No. 2861056, No. 3206312, No. 3245833, No.
No. 3428451, No. 3775126, No. 3963498, No.
No. 4025342, No. 4025463, No. 4025691, No. 4025342, No. 4025463, No. 4025691, No.
Examples include compounds described in No. 4025704 and the like, and these can be preferably used. In the heat-developable photosensitive material of the present invention, an ultraviolet absorber can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, JP-A No. 46-2784,
U.S. Pat. Nos. 3,215,530 and 3,698,907), butadiene compounds (e.g., U.S. Pat.
4045229), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794 and U.S. Pat. No. 3,352,681), benzotriazole compounds substituted with aryl groups [e.g., Japanese Patent Publication No. 36-10466,
No. 41-1687, No. 42-26187, No. 44-29620,
48-41572, JP-A No. 54-95233, JP-A No. 57-
142975, U.S. Patent No. 3253921, U.S. Patent No. 3533794,
Same No. 3754919, No. 3794493, No. 4009038, Same No.
No. 4220711, No. 4323633, Research Disclosure No. 22519], benzoxide compounds (e.g.
U.S. Pat. No. 3,700,455), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805;
No. 3707375, as described in JP-A-52-49029)
can be mentioned. Additionally, U.S. Patent No.
Those described in No. 3499762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (e.g., α-naphthol cyan dye-forming couplers) and ultraviolet absorbing polymers (e.g., JP-A-58-111942, JP-A No. 178-351, JP-A-181041, JP-A-59-59)
-19945, No. 23344, and those described in publications). The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.) for the purpose of improving film properties, etc.
Polymer latex can be used for this purpose. Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, poly-n-butyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of vinylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acetate and ethyl acrylate, copolymers of ethyl acrylate and 2-acrylamide, and the like. The preferred average particle size of the polymer latex is
It is 0.02 μm to 0.2 μm. The amount of polymer latex used is preferably 0.03 to 0.5 in dry weight ratio to the binder of the layer to which it is added. The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.) for the purpose of improving coating properties.
Various surfactants can be used. The surfactant used in the present invention may be any of anionic, cationic, amphoteric and nonionic surfactants. Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N- Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Those containing an acidic group are preferred. Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic phosphonium or sulfonium salts. etc. are preferred. Examples of amphoteric surfactants include amino acids,
Aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines,
Amine oxides and the like are preferred. Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl sugars Esters and the like are preferred. The heat-developable photosensitive material of the present invention includes, for the purpose of improving developability, improving image dye transferability, improving optical properties, etc.
Non-photosensitive silver halide grains can be contained in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). The non-photosensitive silver halide grains used in the present invention may have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Can be used. The preferred particle size of the non-photosensitive silver halide grains is about 0.3 μm or less. In addition, the amount added is calculated in terms of silver amount for the layer to be added.
A range of 0.02 to 3 g/m ² is preferred. In the heat-developable photosensitive material of the present invention, for the purpose of improving the physical properties of the film, a heat-developable photosensitive layer and/or a non-photosensitive layer (undercoat layer, intermediate layer, protective layer, etc.) may be added, for example, to JP-A No. 51-104338. It is possible to contain vinyl polymers having carboxyl groups or sulfo groups as described in the above. The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in terms of dry weight ratio to the binder of the layer to which it is added. When the photothermographic material of the present invention is a color type, a dye-providing substance is used. Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on its reaction form, negative-acting dye-donors that act in a positive function (i.e.
A positive dye-donor acting on a negative function (i.e., a positive dye image when using negative-working silver halide) can be classified as Negative dye-donating substances are further classified as follows.

[Table] Coupling dye Coupling dye Release type compound Formation type compound
Each dye-providing substance will be further explained. As the reducing dye releasing compound, for example, the general formula
Examples include compounds represented by (2). General formula (2) Car−NHSO ₂ −Dye In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of photosensitive silver halide and/or organic silver salt used as necessary. ), and Dye is a diffusible dye residue. Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840, JP-A-58-116537, and JP-A-59.
−60434, No. 59-65839, No. 59-71046, No.
No. 59-87450, No. 59-88730, No. 59-123837,
They are described in the specifications of No. 59-165054 and No. 59-165055, and include, for example, the following compounds.

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embedded image Another reducible dye-releasing compound includes, for example, a compound represented by the general formula (3). General formula (3)

[Formula] In the formula, A ₁ and A ₂ each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye is represented by general formula (2).
Synonymous with dye. Specific examples of the above compounds are given in JP-A-Sho.
No. 59-124329. Examples of the coupling dye-releasing compound include compounds represented by general formula (4). General formula (4) Cp ₁ - (J) - _o1 Dye In the formula, Cp ₁ is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, J is a divalent bonding group, and the bond between Cp ₁ and J is cleaved by reaction with the oxidized form of the reducing agent. n ₁ represents 0 or 1, and Dye has the same meaning as defined in general formula (2). Also
Cp ₁ is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms (or more) depending on the form of the photosensitive material used. (preferably 12 or more) organic groups or sulfo groups,
Hydrophilic groups such as carboxy groups, or 8 or more (more preferably 12 or more) carbon atoms and sulfo groups,
It is a group that also has a hydrophilic group such as a carboxy group. Another particularly preferred ballast group can include polymer chains. Specific examples of the compound represented by the above general formula (4) include JP-A-57-186744, JP-A-57-122596, and JP-A-57-122596;
No. 57-160698, No. 59-174834, No. 57-224883
No. 59-159159 and No. 59-231540, examples of which include the following compounds.

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[Chemical formula] Examples of the coupling dye-forming compound include compounds represented by the general formula (5). General formula (5) Cp ₂ -(F)--(B) In the formula, Cp ₂ is an organic group (so-called coupler) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. residue), and F
represents a divalent bonding group, and B represents a ballast group. The coupler residue represented by Cp ₂ preferably has a molecular weight of 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed. In addition, the ballast group is preferably the same as the ballast group defined in general formula (4), and particularly has 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Groups having both are preferred, and polymer chains are more preferred. The coupling dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (6). General formula (6) Cp ₂ -(F)--(Y)--(Z)--(L) In the formula, Cp ₂ and F have the same meanings as defined in general formula (5), and Y represents an alkylene group, an arylene group or an aralkylene group, represents 0 or 1, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. Specific examples of coupling dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-
No. 124339, No. 59-181345, No. 60-2950, Patent Application No. 179-179657, No. 59-181604, No. 59-182506
No. 59-182507, for example, the following compounds are mentioned.

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[C] In the above general formulas (4), (5) and (6), Cp ₁ or
More specifically, the coupler residue defined by Cp ₂ is preferably a group represented by the following general formula.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an alkylsulfonyl group. group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group,
It represents an amino group, an alkoxy group, an aryloxy group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, which can further be a hydroxyl group, a carboxy group. , a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, etc. These substituents are selected depending on the purpose of Cp ₁ and Cp ₂ , and as mentioned above, one of the substituents in Cp ₁ is preferably a ballast group, and in Cp ₂ , it is preferable to select one of the substituents according to the purpose of the dye to be formed. In order to increase the molecular weight, the substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less. Examples of positive dye-donating substances include oxidizable dye-releasing compounds represented by the following general formula (17). General formula (17)

[Chemical formula] In the formula, W ₁ represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring), R ¹¹ represents an alkyl group or a hydrogen atom, E is

[Formula] (In the formula, R ¹² represents an alkyl group or a hydrogen atom, and R ¹³ represents an oxygen atom or

Represents [formula]. ) or _-SO2- , r represents 0 or 1, and Dye has the same meaning as defined in general formula (2). Specific examples of this compound are described in the specifications of JP-A-59-166954 and JP-A-59-154445, and include the following compounds.

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[Chemical Formula] Another positive dye-providing substance is a compound represented by the following general formula (18), which loses its dye-releasing ability when oxidized. General formula (18)

[Formula] In the formula, W ₂ represents a group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R ¹¹ , r, E, and Dye represent the general formula (17 ) has the same meaning as defined in ). Specific examples of this compound are described in the specifications of JP-A-59-124327 and JP-A-59-152440, and include the following compounds.

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[Chemical formula] Still another positive dye-providing substance includes a compound represented by the following general formula (19). General formula (19)

[Formula] In the above formula, W ₂ , R ¹¹ , and Dye have the same meanings as defined in general formula (18). Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds.

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[Chemical Formula] The residue of the diffusible dye represented by Dye in the above general formulas (2), (3), (4), (17), (18) and (19) will be explained in further detail. As a residue of a diffusible dye,
Due to the diffusibility of the dye, the molecular weight is preferably 800 or less, more preferably 600 or less, and azo dyes,
Residues of azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc. can be opened. These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in Japanese Patent Application Laid-Open No. 59-48765,
The chelatable dye residue described in No. 59-124337 is also a preferred form. These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more types. You can decide accordingly, but for example, the usage amount is 1 m ²
It can be used in an amount of 0.005g to 50g, preferably 0.1g to 10g. Any method can be used to incorporate the dye-providing substance used in the present invention into the photographic constituent layer of the heat-developable photosensitive material.
For example, after dissolving in a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.), ultrasonic dispersion,
Alternatively, after dissolving in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.), it can be used by neutralizing it with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.).
Alternatively, it can be used after being dispersed with a suitable polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill. The heat-developable photosensitive material of the present invention usually has a temperature of 80°C after imagewise exposure.
In the temperature range ~200℃, preferably 100℃~170℃,
Developing is accomplished by simply heating for 1 second to 180°C, preferably 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development and heating. Alternatively, the transfer may be carried out by supplying water and then applying heat if necessary. Further, preheating may be performed in a temperature range of 70° C. to 180° C. before exposure. Also, JP-A-60-143338
As described in Japanese Patent Application No. 60-3644, the photosensitive material and the image-receiving member may be preheated at a temperature of 80°C to 250°C immediately before thermal development transfer in order to improve their mutual adhesion. . Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Light sources commonly used for regular color printing, such as tungsten lamps, mercury lamps, xenon lamps,
Laser beams, CRT beams, etc. can be used as light sources. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, high-frequency heating may be used, or furthermore, a conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or on the back surface of the image receiving member for thermal transfer to remove the Joule heat generated by energization. You can also use it. There are no particular restrictions on the heating pattern, including preheating and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time.
Although it is possible to continuously raise, lower, repeat, or even heat discontinuously, a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image-receiving layer of the image-receiving member effectively used in the present invention may have the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, such as a tertiary amine or quaternary ammonium salt. Among the polymers described in US Pat. No. 3,709,690 are preferably used. For example, as a polymer containing an ammonium salt, polystyrene-co-N,N,N-tri-n-hexyl-N-
The vinyl-benzylammonium chloride ratio is from 1:4 to 4:1, preferably 1:1. Examples of polymers containing tertiary amines include polyvinylpyridine. A typical image-receiving layer for diffusion transfer is obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. Another useful dye-receiving material is
The glass transition temperature described in No. 57-207250 etc. is 40
Examples include those formed from organic polymeric substances that are heat-resistant at temperatures above ℃ and below 250 ℃. These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support. Examples of the heat-resistant organic polymer substances include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole,
Polyacetals such as polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylallylamide, p-cyanophenyl group, Polyacrylate with pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate,
Polyesters such as poly-2-cyano-ethyl methacrylate and polyethylene terephthalate,
Examples include polysulfone, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook
Second Edition (edited by G.A. Brandlap and E.H. Inmargatsu) John John
Willie and Sons (Polymer Handbook)
2nd ed. (edited by J. Brandrup, EHImmergut)
Synthetic polymers with glass transition temperatures of 40°C or higher, as listed in John Wiley & Sons), are also useful. These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types as a copolymer. Useful polymers include cellulose acetates such as triacetate and diacetate; polyamides made from combinations such as heptamethylene diamine and terephthalic acid; fluorene dipropylamine and adipic acid; hexamethylene diamine and diphenic acid; hexamethylene diamine and isophthalic acid;
diethylene glycol and diphenylcarboxylic acid,
Examples include polyester, polyethylene terephthalate, and polycarbonate made of a combination of bis-p-carboxyphenoxybutane and ethylene glycol. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, etc. as a modifier is also effective. A particularly preferred image-receiving layer is JP-A-59-
Examples include a layer made of polyvinyl chloride described in No. 223425 and a layer made of polycarbonate and a plasticizer described in JP-A-60-19138. These polymers can also be used as a support and an image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or from multiple layers. . As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used, and examples thereof include films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, and polypropylene, and supports thereof. Supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments, cloth, glass, aluminum, etc. metals, etc., supports on which electron beam curable resin compositions containing pigments are coated and cured, and supports on which coating layers containing pigments are provided. Examples include the body. In particular, a support that is coated and cured with an electron beam curable resin composition containing a pigment on paper, or directly on paper or with a pigment coating layer and an electron beam curable resin on the pigment coating layer. The resin layer of the support coated with the composition and cured can itself be used as an image-receiving layer, so it can be used as is as an image-receiving member. When the present invention is applied to a heat-developable color light-sensitive material, the various polymers mentioned above can be used as a mordant for a dye image and as an image-receiving layer. It may be an image-receiving element or the image-receiving layer may be a single layer that is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflection layer) is provided in the photosensitive material.
can also be included, and such layers are used to reflect the desired amount of radiation, such as visible light, that can be used to view the dye image in the image-receiving layer. The opacifying layer (reflective layer) can contain various reagents that provide the necessary reflection, such as titanium dioxide. The image-receiving layer of the image-receiving member can also be formed into a type that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. Further, after imagewise exposure and uniform heat development of the heat-developable color light-sensitive material, an image-receiving layer may be superimposed and heated at a temperature lower than the development temperature to transfer the dye image released or formed from the dye-providing substance. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these embodiments. Example 1 Ossein gelatin 20
Solution A in which g is dissolved in 1000 ml of distilled water and ammonia, 11.62 g of potassium iodide and 130.9 g of potassium bromide.
By adding 500 ml of an aqueous solution containing B solution and 500 ml of an aqueous solution C containing 1 mol of silver nitrate and ammonia while keeping pAg and PH constant, and further controlling the addition rate of B solution and C solution. , a core grain with a silver iodide content of 7 mol % and a regular hexahedron and an average grain size of 0.25 μm was prepared, and then a shell with a silver iodide content of 1 mol % and a thickness of 0.05 μm was coated in the same manner. Core/shell type silver iodobromide grains having a regular hexahedral shape and an average grain size of 0.3 μm were prepared. (The monodispersity was 8%.) The yield after washing with water and desalting was 700 ml. Furthermore, using the silver iodobromide grains prepared above,
Silver halide emulsions spectrally sensitized to blue, green, and red sensitivities were prepared under the following conditions. Spectral sensitization conditions Core/shell type silver iodobromide grains 700ml 4-hydroxy-6-methyl-1,3,3a,
7-tetoazaindene 0.4g Gelatin 32g Sodium thiosulfate 10mg The following spectral sensitizing dyes 1% methanol solution 80ml Distilled water 1200ml The following spectral sensitizing dyes were used.

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[Chemical formula] In addition, 28.8 g of silver 5-methylbenzotriazole obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-methanol mixed solvent,
16.0 g of poly-N-vinylpyrrolidone and 1.33 g of 4-sulfobenzotriazole sodium salt were dispersed in an alumina ball mill to adjust the pH to 5.5 to prepare 200 ml of a 5-methylbenzotriazole silver dispersion. Next, 62.0 g of exemplary dye-providing substance (PM-1) and 5.0 g of 2,5-di-t-octylhydroquinone
Dissolve in 200ml of ethyl acetate and add alkanol
(manufactured by Dupont) and 720 ml of an aqueous solution containing 30.5 g of phenylcarbamoylated gelatin (manufactured by Rousslow, type 17819PC), dispersed with an ultrasonic homogenizer, and after distilling off ethyl acetate, the pH was 5. 5 to prepare 795 ml of yellow dye-donor dispersion (1). 35.5 g of Exemplary Dye-Providing Substance (PM-4) and 62.0 g of Exemplary Dye-Providing Substance (PM-5) were prepared in the same manner as Magenta Dye-Providing Substance Dispersion (1) and Cyan Dye-Providing Substance Dispersion (1), respectively. ) was prepared. In addition, 23.3 g of exemplified reducing agent (R-11), poly(N
-vinylpyrrolidone) and 0.50 g of the following fluorine-based surfactant were dissolved in water to prepare 250 ml of reducing agent solution (1) at pH 5.5. Fluorine-based surfactant

[C] In addition, 25.0g of the following color clouding prevention agent (SC-1)
was dissolved in 80 ml of ethyl acetate, mixed with 50 ml of a 5% by weight aqueous solution of Alkanol 1) Prepared 320ml. Color clouding prevention agent (SC-1)

[C] Also, 20.0g of yellow filter dye with the following structure
Dissolve in 120 ml of ethyl acetate and add alkanol
Mix with 50 ml of an aqueous solution containing 50 ml of a wt% aqueous solution and 250 ml of an aqueous solution containing 9.0 g of phenylcarbamoylated gelatin, disperse with an ultrasonic homogenizer, and distill off ethyl acetate to obtain a yellow filter dye dispersion (1) 300
ml was prepared.

[Chemical formula] From these, heat-developable photosensitive materials () to () having a multilayer structure shown in Table 1 were prepared, and at this time, a curing agent shown in Table 2 was contained.

【table】

[Table] However, each layer also contains a small amount of surfactant as a coating aid.

【table】

[Table] However, the comparative hardeners (H-1) and (H-2) used in Table-2 are as follows. Comparative hardener (H-1) Tetra(vinylsulfonylmethyl)methane comparative hardener (H-2)

[C] Next, a tetrahydrofuran solution of polyvinyl chloride (n=1100, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto photographic baryta paper so that the coating amount of polyvinyl chloride was 12.0.
An image-receiving member (1) was prepared by coating the solution at an amount of g/m ² . The above-mentioned heat-developable color photosensitive materials () to () were exposed to 1600 CMS through a step wedge, combined with the image-receiving member (1), and then placed in a heat developing machine (Developer Module 277, manufactured by 3M Company). After thermal development was carried out at different temperatures and times, the photosensitive material and image receiving member were immediately peeled off. For each sample, the reflective dye density of the transferred dye image obtained on the polyvinyl chloride surface of the image receiving member was measured using a densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.).
The degree of film deterioration of the photosensitive material after processing was also observed. The results are shown in Table-3. At this time, the degree of membrane collapse was displayed in the next step. A: When observed under a microscope at 100 times magnification, no membrane deterioration was observed at all. B: When observed under a microscope at 100 times magnification, some or slight membrane deterioration is observed. C: Significant film deterioration is observed when observed under a microscope at 100 times magnification.

[Table] As is clear from Table 3, the photosensitive material using no hardening agent () had severe film deterioration, and the photosensitive material using a comparative hardening agent (H-1) () , (), film collapse occurs during thermal development regardless of the addition position, and Dmin is also higher than Dmax. On the other hand, in the photosensitive materials () to () using the polymer hardener of the present invention, the occurrence of film deterioration is improved, fogging (Dmin) is low, Dmax is high, and color turbidity is also improved. It can be seen that it has been done. This improvement effect is particularly remarkable in photosensitive materials (2003), and no film deterioration is observed even at high processing temperatures. Example 2 30.0 g of the exemplary dye-providing substance () was dissolved in 30.0 g of dimethyl lauramide and 90.0 ml of ethyl acetate,
After mixing with 460 ml of an aqueous solution containing the same surfactant and gelatin as in Example 1 and dispersing with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to
ml of yellow dye-donor dispersion (2) was prepared.
A magenta dye-providing substance dispersion (2) and a cyan dye-providing substance dispersion (2) were prepared using the same recipe for the exemplary dye-providing substance () and the exemplary dye-providing substance (2), respectively. In addition, 30.0g of the following color clouding prevention agent (SC-2),
15.0 g of tricresyl phosphate was dissolved in 90 ml of ethyl acetate and mixed with 560 ml of an aqueous solution containing 50 ml of a 5% by weight aqueous solution of Alkanol XC and 20.0 g of gelatin.
Dispersion was performed using an ultrasonic homogenizer, and ethyl acetate was distilled off to prepare 600 ml of color clouding preventive agent dispersion (2). Color clouding prevention agent (SC-2)

[Chemical formula] Using these and the same silver halide emulsion and 5-methylbenzotriazole silver dispersion as used in Example 1, heat-developable photosensitive materials () to () with the multilayer structure shown in Table 4 were prepared. did. At this time, a hardening agent shown in Table 5 was also included.

【table】

【table】

[Table] Next, an image receiving member (2) was prepared by sequentially coating the following layers on a paper support coated with polyethylene having a thickness of 200 μm. (1) Neutralization layer made of polyacrylic acid (7.0g/m ² ). (2) Timing layer consisting of cellulose acetate (4.0 g/m ² ). (3) 1:1 copolymer of styrene and N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl) ammonium chloride (3.0g/m ² )
and a layer consisting of acid-treated gelatin (3.0 g/m ² ). (4) A layer consisting of urea (4.0 g/m ² ) and polyvinyl alcohol (saponification degree 98%) (3.0 g/m ² ). However, each layer also contains a small amount of surfactant and hardening agent in addition to these. For the heat-developable photosensitive materials () to (),
After exposing the material to 1600 CMS through a step wedge and combining it with the image-receiving member (2), the photosensitive material and the image-receiving member are immediately separated. did.
For each sample, the reflected dye density of the transferred dye image obtained on the image-receiving member was measured using a densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.), and film deterioration of the photosensitive material after processing was measured. The degree of oxidation was observed and shown in Table 6 using the same display as in Example 1.

【table】

[Table] As is clear from Table 6, in photosensitive materials using hardeners other than those of the present invention, film deterioration occurs which causes image deterioration, and fogging (Dmin) is higher than Dmax. In contrast, in the present invention, it has been found that a high Dmax can be achieved while keeping fog low and without causing any film deformation during thermal development. Moreover, color turbidity was also improved.

Claims (1)

[Scope of Claims] 1. On a support, at least two heat-developable photosensitive layers and at least one layer in which the color sensitivity of photosensitive silver halide and the hue of a dye formed from a dye-providing substance are different from each other. A heat-developable color photosensitive material having a photographic constituent layer consisting of a non-photosensitive layer, characterized in that at least one of the photographic constituent layers contains a polymer hardener represented by the following general formula (). Developable color photosensitive material. General formula () [In the formula, A represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q represents -CO ₂ -, [Formula] or an arylene group having 6 to 10 carbon atoms. L is -CO ₂ -, [formula] a divalent group containing at least one bond and having 3 to 15 carbon atoms, or -O-, [formula] -CO-, -SO -, -SO ₂ -, -SO ₃ -, [Formula] [Formula] [Formula] Represents a divalent group containing at least one bond and having 1 to 12 carbon atoms. R ₁ ′, R ₁ ″ represent the same as R ₁ described above. R ₂ represents -CH=CH ₂ or -CH ₂ -CH ₂ X. Therefore, it represents a group that can leave in the form of HX. x, y represent mole percentage, x is 0 to 75,
y takes a value from 25 to 100. 2. The heat-developable color photosensitive material according to claim 1, wherein the heat-developable color photosensitive material further contains a heat solvent. 3. The heat-developable color photosensitive material according to claim 1, wherein the polymer hardener is contained in at least one of the non-photosensitive layers. 4. The heat-developable color photosensitive material according to claim 3, wherein the heat-developable color photosensitive material further contains a heat solvent.