JPS62141549A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To form a heat developable color photosensitive material which has good developability, prevents color clouding and has good film properties during heat development by incorporating a high-polymer hardening agent into a photograph constituting layer. CONSTITUTION:This photosensitive material contains the high-polymer hardening agent in at least one photograph constituting layer. The high-polymer hardening agent refers to the homomonomer or copolymer of polymerizable ethylenic unsatd. monomers having a group reactive with gelatine, active halide group and epoxy group and the polymer compd. having preferably 10-5,000 pieces of the above-mentioned groups reactive with gelatin in the molecule. The polymers having the active vinyl groups or the groups which can be the precur sor thereof are more preferable as the high-polymer hardening agent and above all, the polymer having the repeating unit expressed by formula (I) is more particularly preferable. A in the formula denotes the monomer unit copo lymerized with the copolymerizable ethylenic unsatd. monomer.

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, it has good heat-developability, prevents brownish turbidity, and has good heat-developability during heat development. The present invention relates to a heat-developable color photosensitive material with improved film properties.

[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.

Regarding such heat-developable photosensitive materials, for example,
No. 4921 and No. 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, a reducing agent, and a binder, which is commercialized as dry silver by 3M Company.

Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods.

For example, U.S. Pat. No. 3,531,286;
No. 761.270 and No. 3,764,328, etc. describe a method for forming a dye image by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler, Research Disclosure (Research D 1s).
closure) 15108 and 15127,
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 described in U.S. Pat. No. 4,021,240, etc. Method, as disclosed in British Patent No. 1,590,956, using an organic imino silver salt having a dye portion, releasing the dye in a heat development section and releasing a dye image on a separately provided receiver F14WIJ. , also JP-A-52-52-1O5
A method for obtaining a positive dye image by a silver dye bleaching method disclosed in U.S. Pat. No. 3,985,56
No. 5, No. 4,022,617, No. 4,452,8
Various methods have been proposed, such as the method of obtaining a dye image using an O-ico dye disclosed in 83@, JP-A-59-206831@, etc.

However, these proposals regarding the heat-developable color light-sensitive materials have the disadvantages that it is difficult to bleach-fix the black, white, and silver images that are formed at the same time, that it is difficult to obtain clear color images, and that it is difficult to obtain clear color images. Since these methods require post-processing, they are still unsatisfactory for practical use.

In recent years, as a new type of color image forming method by heat development, special rIaFjB57-179840 and 57
-186744, 57-198458, 57-
No. 207,250 and the like disclose a method of obtaining a color image by transferring a diffusible dye released by thermal development.

Then, by further improving these methods, for example,
A method of releasing a diffusible dye by oxidizing a non-diffusible reducible dye-donating substance disclosed in JP-A-58-58543@, JP-A-59-168439, etc.;
No. 8-79247, No. 59-174834, No. 59-
No. 12431, No. 59-159159, Go-29
A system in which a diffusible dye is released by coupling with an oxidized developing agent as disclosed in JP-A-58-149046 and JP-A-58-14904.
No. 7, No. 59-124339, No. 59-18134
No. 5, Go-2950, Patent Application No. 59-181604
No. 59-182506, No. 59-18, 25
No. 07, No. 59-272335, etc.! A method using a non-diffusible compound that reacts with an oxidized image agent to form a diffusible dye, and further disclosed in JP-A-59
-152440, 59-124327, 9-
No. 154445, Ji5159-. No. 186954, etc., non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, or conversely, non-diffusible dye-donating substances that release diffusible dyes when reduced. Some methods have been proposed, including methods that include

The basic structure of a color type heat-developable photosensitive material that obtains a color image using these emitted or formed diffusive dyes is as follows:
It consists of a light-sensitive element and an image-receiving element, and the light-sensitive element basically contains a light-sensitive silver halide, an organic silver salt, a reducing agent, a dye-providing substance,
It consists of 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 receiving element is referred to as an image receiving member.

The above-mentioned heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed light-spreading dye onto the image-receiving layer of an image-receiving member provided on the same support or another independent support. It was improved in many respects compared to previous heat-developable color photosensitive materials in terms of image sharpness, stability, etc.

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 not well 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 a temperature of 80°C or higher or 100°C, or pressure-applied heaters, electrodes, etc. The gelatin layer is processed under mechanical stress due to drums, rollers, etc., which may cause breakage of the gelatin layer, so-called film collapse, during heat development. 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 deterioration of the film.

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, thermal development In an attempt to prevent the film from deforming during wet processing, the hardening agent described in JP-A No. 60-119554 was used to increase the degree of hardening until the degree of swelling in wet processing was extremely low, but the film did not deform. without being improved,
It was found that the problem was that the developability deteriorated.

[Object of the Invention J] Therefore, an object of the present invention is to provide a heat-developable color photosensitive material which has good developability, prevents brown 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. This has been achieved by a heat-developable color photosensitive material having a photographic constituent layer consisting of at least a non-photosensitive layer of IJIl, in which at least one of the photographic constituent layers contains a polymer hardener.

[Specific Structure of the Invention] The polymer hardener in the present invention is a homopolymer or copolymer of a polymerizable ethylenically unsaturated monomer having a group reactive with gelatin, an active halide group, an epoxy group, etc. The molecule contains at least 2 or more groups, preferably 10 to 5, that are reactive with gelatin. It is a polymer compound having Goo or more.

Examples of polymer hardeners corresponding to these (hereinafter referred to as hardeners of the present invention) include U.S. Patent No. 3.396,0
Polymers having aldehyde groups (e.g. copolymers of acrolein, etc.) described in US Pat. No. 3,623.
Polymers with epoxy groups described in No. 878, Research Disclosure Magazine 16°725 (1978)
, U.S. Patent No. 4,161,407, Japanese Patent Publication No. 54-6
Examples include polymers having an active vinyl group or a group that can be a precursor thereof, as described in No. 5033 and No. 56-142524, and polymers having active ester groups as described in No. 56-66841.

In the polymer hardener of the present invention, a polymer having an active vinyl group or a group that can be a precursor thereof is preferable, and among them, a polymer having the following general formula (I) as described in JP-A-56-142524 is preferable. Particularly preferred are polymers having repeating units.

The following is a blank general formula (I) S O2-R2 In the formula, A represents one monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer.

However, as ethylenically unsaturated monomers, ethylene,
Propylene, 1-butene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, α-methylstyrene, vinyltoluene, N-vinylacetamide, N-vinylpyrrolidone, fatty acid Monoethylenically unsaturated esters (e.g. vinyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid), maleic anhydride, ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium D-toluenesulfonate, ethylenically unsaturated monocarboxylic or dicarboxylic acids) Amides of acids (e.g. acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate,
N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine) and the like.

R1 is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, butyl group,
(n-hexyl group), of which a hydrogen atom or a methyl group is particularly preferred.

Q is either -CO2-1-〇ON- or an arylene group having 6 to 10 carbon atoms and L is -CO2-
A divalent group containing at least one 1-CON- bond and having 3 to 15 carbon atoms, or -〇-1-N-1-CO-1-SO-
It is any divalent group containing at least one 1-8O2-1-8O3-1 and having 1 to 12 carbon atoms. (However, R1 represents the same as described above.) L includes the following groups.

-CH2CO2CH2CH2- -CH2NHCOCH2- fCH2?1oNHCOCH2CH2--502CH2
CH2SO2CH2CH2--SO2NHCH2CH2
CO2CH2CH2--NHCONHCH2CH2- R2 represents a vinyl group or a functional group serving as a precursor thereof, and is either -CH=CH2 or -C82CH2X. X is substituted by a nucleophile or HX by a base
Represents a group that can leave in the form of

R2 includes the following groups.

-CH-CH2, -CH2CH2Sr.

-C82C82Cj! Delicious. x, ■ represent mole percentage, X is 0 to 99,
y takes a value from 1 to 100.

Preferably, X takes a value from 0 to 75, and y takes a value from 25 to 100.

Specific examples of the polymer hardener of the present invention are shown below.

Margin below P-18 -HcHyo-cH廿 1 + ct-+, -ct-+-i c.

T'-20()l.

Be (Hi-c- 揄 ’　(.

((Ht-, CF4S O wood -5o2CJ-4=CH2 0CH.

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 has two or more functional groups reactive with gelatin as described above. A polymeric hardener can also be mixed with a polymer that provides a molecular hardener to form a polymeric hardener in the coating layer. Examples of low-molecular hardening agents used in this case include, for example, JP-A No. 49-13
563, No. 53-41221, etc., and examples of polymers include those described in JP-A No. 563-41221.
Examples include those described in No. 6-4141.

In the present invention, those having an aldehyde group and those having a dichlorotriazine group interact W/811 with other photographic additives such as anti-capri agents and dye-providing substances, which not only impairs the curing effect but also reduces capri. This is not preferable because it may cause deterioration of photographic performance such as increase in density or decrease in density or sensitivity, or may be unstable and have poor storage stability.

The molecular weight of the polymer hardener of the present invention is preferably about 104 to 105 in terms of number average molecular weight.

The method for synthesizing the polymer hardener of the present invention includes the aforementioned U.S. Patent No. 3,396,029, U.S. Pat.
978), U.S. Pat.
It can be synthesized according to the methods described in each specification of No. 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 5 x 10' to 5 x 1 functional groups involved in hardening action are used per 1 g of gelatin.
An amount corresponding to 0-4 equivalents is used, particularly preferably I
X 10' to 2X10-current 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-donating 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. Mention may be made of a nucleus-containing layer, a filter layer, an image-receiving layer, and layers located between these layers.

The polymeric hardener according to the present invention may be added to any of these photographic constituent layers, but the hardening agent may be added to any of these photographic constituent layers, but the degree of hardening of the layer that does not contain photosensitive silver halide or a 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. I like it a lot.

Deterioration of each layer film during heat development can be determined by heat-developing the photothermographic material of the present invention in a heat development machine (e.g., Developer Module 217 manufactured by 3M Company) at various humidity and time. It can be evaluated by observing it with 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 point aqueous 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 the photothermographic material to increase the roughness of the surface of the photosensitive material and make it matte. be.

Methods of using matting agents to prevent adhesion that occurs during manufacturing, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and peeling between materials of the same or different types are known in the art. It is well known. Specific examples of matting agents include silicon dioxide described in JP-A-50-46316, JP-A-53-7231, JP-A-58-66937,
Alkali-soluble matting agents such as alkyl methacrylate/methacrylic acid copolymers described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341M, JP-A-58-145935 Combination of two or more types of fine particle powders with different Mohs hardnesses, combination of oil droplets and fine particle powders as described in JP-A-58-147734, two or more types of different average particle sizes as described in JP-A-59-149356 Combined use of spherical matting agent, JP-A-56-4
The combination of a fluorinated surfactant and a matting agent described in No. 4411, British Patent No. 1,055.713, U.S. Pat. No. 1,939,213, U.S. Pat. No. 2,221,873,
No. 2,268,662, 2,322. ．． No. 037,
No. 2,376,005, No. 2,391,181,
No. 2,701,245, No. 2,992,101, No. 3,079,257, No. 3,262,782, No. 3,443,946, No. 3,516,832, No. 3
, 539.344, 3,591゜379, same.
3,754,924, 3,767,448@, organic matting agents described in JP-A-49-106821, JP-A-57-14835, etc., West German Patent No. 2,529.3
No. 21, British Patent No. 760.775, British Patent No. 1,260.
No. 772, U.S. Patent No. 1,201,905, U.S. Patent No. 2,1
No. 92,241, No. 3,053,662, No. 3,06
No. 2,649, No. 3,257,206, No. 3.322
．． No. 555, No. 3.353.958, No. 3,370.
No. 951, No. 3,411,907, No. 3.437.
No. 484, No. 523,022, No. 3,615,
No. 554, No. 3,635,714, No. 3.769,
No. 020, No. 4,021,245, No. 4,029,5
Inorganic matting agents described in JP-A-46-7781, JP-A-49-10682j, JP-A-51
-8017, No. 53-116143, No. 53-10
No. 0226, No. 57-14835, No. 5? -8283
No. 2, No. 53-70426, No. 59-149357
No., Special Publication No. 57-9053 and EP-107,
A matting agent having physical properties such as those described in the specification of No. 378 and the like is preferably used.

In the protective layer of the present invention, the amount of the matting agent added is 10110/2.0 (+ is preferable, and more preferably 20+a to 1.0 g per 1f. The particle size of the matting agent is 0.5
~10μm is preferable, more preferably 1.0~6μm
It is.

The matting agents may be used in combination of two or more.

Examples of the slippery agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, French Patent No. 2.1
No. 80.465, British Patent No. 955,061, No. 1,
No. 143,118, No. 1,270,578, No. 1,
No. 320.564, No. 1,320,757, JP-A-4
No. 9-5017, No. 51-141623, No. 54-1
No. 59221, No. 56-81841, Research Disclosure
re ) 13969, U.S. Patent No. 1,263.7
No. 22, No. 2.588.765, No. 2,739,89
No. 1, No. 3,018.178, No. 3,042,52
No. 2, No. 3,080,317, No. 3.082,08
No. 7, No. 3,121,060, No. 3,222,1
No. 78, No. 3,295,979, No. 3,489,56
No. 7, No. 3,516.832, No. 3.658.573
No. 3,679,411, No. 3,870,521, etc. can be preferably used.

The protective layer of the present invention contains a high boiling point organic solvent (for example, U.S. Pat. No. 2,322,027, U.S. Pat.
No. 533,514, No. 2,1182.157, Japanese Patent Publication No. 46-23233, British Patent No. 958.441, No. 1,222,753, U.S. Patent No. 2,353,262
No. 3,676.142, No. 3,700,454, JP-A-50-82078, JP-A No. 51-27921,
Esters (e.g., phthalate esters, phosphoric acid esters, fatty acid esters, etc.), amides (e.g., fatty acid amide, sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc., described in No. 51-141623, etc. Examples include. ) may contain oil droplets in which a water-insoluble oil compound is emulsified and dispersed. Furthermore, these oil droplets may contain photographic additives for various purposes.

Examples of the binder used in the adhesive of the present invention include polyvinylbugral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, polyacrylamide, gelatin, and phthalate. One or a combination of two or more synthetic or natural polymeric substances such as gelatin can be used. In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecules 11 to 400.Goo are preferred) and polyoxosalines (molecular weight 1, Go
o~800,000 is preferable), polyvinyl alcohol (molecular weight 1,000~100.Goo is preferable)
A single binder or a combination of two or more of these binders are preferable, and a binder using gelatin alone or a combination of gelatin and a hydrophilic polymer having good compatibility with gelatin such as the above-mentioned polyvinylpyrrolidone, polyvinyl alcohol, and polyoxazoline is particularly preferable. Gelatin may be lime-treated, acid-treated, or ion-exchange treated, including ossein gelatin, big skin gelatin,
Hydrogelatin or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins may also be used.

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.

Further, in order to increase the film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. Protect! One way to make the hardness of a layer greater than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using it in the layer, only the hardness of the protective layer can be made higher than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners.
For example, US Pat. No. 3.057.723, US Pat. No. 3.396.
No. 029, No. 4,161,407, JP-A-58-50
Hardeners described in No. 528 and the like can be used.

Another way to control the degree of dura for each layer is to
By containing a diffusible hardener (for example, a vinyl sulfone hardener) only in the protective layer, or by making the content of the protective layer higher than that of the photosensitive layer, and quickly drying it after simultaneous multilayer coating, it is possible to improve the retention. The degree of hardness of the photosensitive layer can be made larger than that of the photosensitive layer.

The heat-developable photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, and (4) binder in one heat-developable photosensitive layer. It is preferable to contain (5) an organic silver salt as necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, a heat-developable photosensitive layer with 21
The components (1), (2), (4), and (5) above are contained in one side of the heat-developable photosensitive layer, and the dye-providing substance is contained in the other layer adjacent to this photosensitive layer. (3) may be contained separately in two or more constituent layers as long as they are in a state where they can react with each other. -Also, the heat-developable photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity fI layer, a high-density layer and a low-density layer, or the like.

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 in each photosensitive layer, dyes with different hues are formed or released by 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. layer, a green-light-sensitive layer, a red-light-sensitive layer, or sequentially on a support.
There are configurations such as a green photosensitive layer, a red photosensitive layer, and a blue photosensitive layer.

In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a heat-retaining layer, a filter layer, a backing layer, and a 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.

Namely, dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method,
There are methods and apparatuses for the bead method, extrusion method, stretch method, curtain method, etc.

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 in the photographic field, such as a single jet method or a double jet method. For example, by applying the method described in JP-A-54-48521, monodisperse silver halide grains can be obtained by the double jet method while keeping the pAQ constant. In this case, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, EIH, I)A ratio, temperature, etc. According to a further preferred embodiment, silver halide emulsions having shelled silver halide grains 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 used in the present invention refers to an emulsion having a particle size distribution in which the variation in the silver halide grain size contained in the emulsion is less than a certain percentage of 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 a uniform grain morphology and small variation in grain size is almost a normal distribution, the standard deviation can be easily determined. The width of the distribution of the silver halide grains involved is preferably 15% or less, more preferably monodispersity of 10% or less.

Also, for example, JP-A-58-111933, JP-A No. 58-1
No. 11934, No. 58-108526, Research Disclosure No. 22534, etc., each of which has two parallel crystal planes, and each of these crystal planes is larger than the other single crystal of this particle. It is also possible to use a silver halide emulsion comprising tabular silver halide grains having a large area and an aspect ratio, that is, a ratio of grain diameter to thickness of 5=1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces are not coupled in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592, 250, No. 3.206.313, No. 3
, No. 317,322, No. 3,511,662, No. 3
．． No. 447,927, No. 3,761,266, No. 447,927, No. 3,761,266, No.
As described in No. 3.703.584, No. 3.736.140, etc., this silver halide grain has a higher sensitivity inside the grain than the surface sensitivity of the silver halide grain. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above-mentioned patent, for example, by first preparing 1 grain of AgCl and then adding bromide or iodide thereto. A method in which a chemically sensitized silver halide core is coated with a non-chemically sensitized silver halide,
Alternatively, many methods are known, such as a method in which a chemically sensitized coarse grain emulsion is mixed with a chemically sensitized or non-chemically sensitized fine grain emulsion, and a fine grain emulsion is deposited on the coarse grain emulsion.

Also, U.S. Patent Nos. 3,271,157 and 3.44
No. 7.927 and No. 3.531, 291, silver halide emulsions having silver halide grains containing polyvalent metal ions;
Silver halide emulsions whose grain surfaces are weakly chemically sensitized containing silver halide grains containing dopants as described in No. 761.276, or JP-A-50-8524 and JP-A-50-8524.
Silver halide emulsions consisting of grains having a layered structure as described in JP-A No. 0-38525, etc., and other JP-A-52-1
These include silver halide emulsions described in No. 56614 and JP-A-55-127549.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such exacerbation methods include:
Various methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion may be coarse or fine, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm, and more preferably about 0.001 μm to about 1.5 μm. .01 μm to about 0.5 μm.

The photosensitive silver halide emulsion produced by DI 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 is H [i, NH41
or represents 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,
Examples include germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, Odium, palladium, osmium, iridium, platinum, and cerium. )
, halogen-containing metal complexes (e.g., K2 Pt CILs
, K2 Pt Br s , HAu Cj! +
.

(NH4)2 1r (1!s h (NH4)
3 1r Cj! 6゜(NH4)2 Ru Cj! s
, (NH4)3 Ru C16,.

(NH4)2 Rh Cff1s, (NH4>3
Rh Br6, etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosphonium) Quaternary phosphonium halides such as bromide, benzylethylmethylsulfonium bromide, 1-
tertiary sulfonium halides such as edylthiazolium bromide), halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo 2-
methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalate) Zinone, N-bromoacetanilide, N, N-
Dibromobenzenesulfonamide, N-ProU-N-
Methylbenzenesulfonamide, 1,3-dibromo-4
, 4-dimethylhydantoin, etc.) and other halogen-containing compounds (eg, triphenylmedyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halide and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 (1 to 50 a
It is preferable that it is, more preferably 0.1Q to 1
0 (J.

The heat-developable photosensitive material of the present invention has a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. You can also do that. Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer).
.

In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. I can do it.

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 dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain 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. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent.

In addition to the above basic nucleus, the merocyanine dye may have an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidione nucleus, a thiazolidinedione nucleus, a barbylic acid group, a thiazolinthione nucleus, a malononitrile nucleus, or a pyrazolone nucleus. .

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 U.S. Pat. No. 2,933,3
A supersensitizing additive that does not absorb visible light, such as those described in Mei aS, No. 90 and No. 2,937,089, can be used in combination.

These sensitizing dyes are added in an amount of 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide-forming component. More preferably, 1x i o-+mol-l
X10-1 mol.

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 those disclosed in Japanese Patent Publication Nos. 43-4921, 52626-1980, 141222-1982, 36224-1983, and 37610-1980, etc. Publications and US Patent 1
! No. 3,330,633, No. 3,794.496 @
Silver salts of long-chain aliphatic carboxylic acids, such as silver salts of carboxylic acids having a heterocyclic ring, such as silver laurate, silver myristate, etc. , silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc. No. 26582,
No. 45-12700, No. 45-18416, No. 45
-22185, JP-A-52-137321, JP-A-58-118638, JP-A-5G-118639, U.S. Patent No. 4. ．． There are silver salts of imino groups described in various publications such as No. 123, No. 27.4.

Examples of silver salts of imino groups include benztriazole silver. The penztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, alkyl-substituted benztriazole silver (preferably an alkyl group of 022 or less,
More preferably, silver substituted with an alkyl group of C4 or less, such as silver methylbenztriazole, silver ethylbenztriazole, silver n-octylbenztriazole, etc., silver alkylamide benztriazole (silver preferably substituted with a flukylamide group of 022 or less) silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulf 7-moylbenztriazole (preferably with an alkylsulfamoyl group of C22 or less) Substituted ones, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, silver 4-(N-diethylsulfamoyl)penztriazole,
-octylsulfamoyl)penztriazole silver, 4
silver salts of halogen-substituted benztriazoles (for example, silver 5-chlorobenztriazole, 5-(N-octylsulfamoyl)benztriazole, etc.), Silver alkoxybenztriazole (preferably substituted with an alkoxy group of C22 or less, more preferably an alkoxy group of C04 or less, such as 5-methoxybenztriazole silver, 5-ethoxybenztriazole silver, etc.) silver, etc.), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4-
Hydroxybenztriazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver,
Examples include silver 5-sulfobenztriazole.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1.2
．． Silver salts of other mercapto compounds such as 4-triazole silver, 1-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzo Silver oxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-4-phenyl-1,2,4-triazole, 4-hydroxy-6
-Methyl-1,3゜3a, 7-chitrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-
Examples include silver pentazaindene.

In addition, silver complex compounds with a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, and silver complex compounds as described in U.S. Pat. No. 4,168,980. A silver salt of dacilinthion is used.

Among the above organic silver salts, imino group silver salts are preferred;
Particularly preferred are silver salts of benzotriazole derivatives, more preferably 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. It is also effective to add an alkali to promote dissolution of organic compounds, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is usually preferably 0.01 to 50 mol, more preferably 0.1 to 100 mol, per mol of photosensitive silver halide. Moreover, it 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;
-79247, 58-149046, 58
-149047, 59-124339, 59-
A diffusible dye is released by coupling with an oxidized form of a reducing agent as disclosed in No. 181345, No. 6G-2950, etc. In the formula (1), R1 and R2 are hydrogen atoms. , or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R1 and R2 may be closed to form a heterocycle. R3, R4゜R5 and R6 each have a hydrogen atom, a halogen atom, a hydroxy group, an amine 1 alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 1 which may have a substituent.
30 (preferably 1 to 4) alkyl group, R3
and R1 and R5 and R2 may each be ring-closed to form a complex i. 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 a dye-donating substance that forms basic nitrogen atoms that can form inorganic salts and salts, and if it is a dye-donating substance that can be used as a reducing agent in the present invention. For example, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, U.S. Pat.
, 15108, same No. 15127 and Japanese Patent Application Laid-open No. 1983
Using p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoramidophenol-based, sulfonamide phenol-based developing agents, sulfonamide aniline-based developing agents, hydrazone-based color developing agents, etc. described in Publication No. 27132. I can do things. Also, U.S. Patent Nos. 3.342.599 and 3.719.492.
No., JP-A-53-135628, JP-A No. 54-79035
Color developing agent precursors and the like described in No. 1, etc. 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.

Below is a margin.Next, preferred specific examples of the reducing agent represented by the general formula (1) are shown below.

(R-5) ^^^ v -ノ
-no -no (R-20) (R, -21) (R-22) (R-23) The reducing agent represented by the above general formula (1) can be prepared by a known method,
For example, Houben Peil, Methotzian der Organitsien Hemi, Band XI/2 (Houben
-Weyl, Methoden der Oraan
ischen Chelie, Band X I
/2) It can be synthesized according to the method described on page 645.703.

Furthermore, it is also possible to use two or more of the above-mentioned reducing agents at the same time, or to use a black and white developing agent described below in combination for the purpose of increasing developability.

Further, the dye-providing substance used in the present invention may be
In the case of compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc. as shown in Nos. 9-152440 and 59-154445, etc. (or when simply obtaining a silver image), 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-benzene Sulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo 4-(
+)-toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone,
tert-butylhydroquinone, 2,6-dimethylhydroquinone, dioxyhydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-aminonaphthol, -methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6.6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2.2'-dihydroxy-1,1'-binaphthyl, 4.
4'-dimethoxy-1,1'-dihydroxy-2,2'
-binaphthyl, bis(2-hydroxy-1-naphthyl)
methane, etc.], methylene bisphenols [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-humanOxy3.5
-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-humanOxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-
di-tc+rt-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, lazones, 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 0°01 per mole of photosensitive silver halide
-1500 mol, preferably 0.1-20
It is 0 mole.

The support used in the heat-developable photosensitive material of the present invention includes:
For example, paper supports such as polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, photographic base paper, printing paper, baryta paper and resin coated paper; electron beam curable,
Examples include a support coated with a resin composition and cured.

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 together 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 a copolymer (including a graft copolymer) of vinylpyrrolidone and one or more other monomers copolymerizable with vinylpyrrolidone. ). These polymers can be used regardless of their synthesis. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
It is of 0.000. Other polymers that can be copolymerized with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates,
Examples include vinyl monomers such as vinyl imidazoles, (meth)acrylamides, vinyl carbinols, and vinyl alkyl ethers, but at least 20% (by weight, same hereinafter) of the composition ratio should be polyvinylpyrrolidone. preferable. Preferred examples of such copolymers are those having a molecular weight of s, ooo to 40G, goo.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the above binder, gelatin preferably accounts for 10 to 90% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
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 molecules B s, ooo to 40G, G
A mixture of the vinylpyrrolidone copolymer of oo 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,
Natural substances such as starch, polysaccharides such as gum arabic and the like can be mentioned. These range from 0 to 85%, preferably from 0 to 70%
% may be contained.

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 to stand).

The amount of binder used is usually from 0.05 to 50.0 g per layer per 1f of support, preferably from 0.1 g to 50.0 g.
It is 10g.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~10g, more preferably 0.2
It is 5 to 4 g.

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. Pat.
556, Japanese Patent Application No. 59-47787, etc., and those 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 (for example, 1.5-bentanediol, 1.6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are most 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. Ratio (“organic concept mouth” Yoshio Koda,
Sankyo Shuppan ■, 1984) is 0.5 to 3.01, preferably 0.7 to 2.5, particularly preferably 1.0 to 2.0. '0, and the solubility in water at room temperature is less than 1.

Specific examples of water-insoluble solid thermal solvents are shown below, but the invention is not limited thereto.

(, JMw = Φ%
CQ a'1u's
(J 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 hot solvent is not particularly limited, but it may be added by grinding and dispersing it using a ball mill, sand mill, etc.
There are methods such as adding it by dissolving it in an appropriate solvent, and adding it as an oil-in-water dispersion by dissolving it in a high boiling point solvent.
It is preferable to pulverize and disperse the solid particles using a ball mill, sand mill, etc. 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.

Addition of the water-insoluble heat solvent is usually done by adjusting the amount of the binder.
a% to 500% by weight, preferably 50% to 300% by weight
i1i5%.

Note that even when the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the thermal development temperature, the melting point is lowered by being added to the binder, so that 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 Shuin Patent No. 3.438.776; compounds such as polyalkylene glycols described in U.S. Patent No. 3.666, 477 and JP-A-51-19525; , -C〇-1-8O2- described in U.S. Pat. No. 3,667.959
There are non-aqueous polar organic compounds having a melting point of 20° C. or higher, such as lactones having 1-80- groups.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829 and JP-A-53-24829;
Phenol derivatives described in No. 60223, JP-A-5
Carboxylic acids described in No. 8-118640, polyhydric alcohols described in JP-A-58-198038,
Also included are sulfumoylamide compounds described in JP-A-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 color toning agent, for example, JP-A-46-4
No. 928, No. 46-6077, No. 49-5019,
49-5020, 49-91215, 4
No. 9-107727, No. 5G-2524, No. 5G-
No. 67132, No. 50-67641, No. 5G-114
No. 217, No. 52-33722, No. 52-99813
No. 53-1020@, No. 53-55115, No. 5
No. 3-76020, No. 53-125014, No. 54-
No. 156523, No. 54-156524, No. 54-
No. 156525, No. 54-156526, No. 55-
No. 4060, No. 55-4061, No. 55-32015
Publications such as No. 2,140,406 and West German Patent No. 2,140,406,
Same No. 2.141゜063, Same No. 2,220,618,
U.S. Patent No. 3,847,612, U.S. Patent No. 3,782,9
No. 41, No. 4,201,582 and JP-A-57-
No. 207244, No. 57-207245, No. 58-1
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, penzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazine, which are compounds described in the specifications of No. 89628, No. 58-193541, etc. Dione, 2,3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, human O-oxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H
-1,3-benzothiazine-2,4-(3H)dione,
Benzotriazine, mercaptotriazole, dimerkabutotetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazole phthalic acid, naphthalic acid, phthalamic acid, etc.; mixtures of one or more of these with imidazole compounds; Examples include mixtures of at least one acid or acid anhydride such as phthalic acid and naphthalic acid and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

Antifoggants include, for example, U.S. Pat. No. 3,645;
Higher fat 1 (e.g., behenic acid, stearic acid, etc.) described in No. 739, mercuric salts described in Japanese Patent Publication No. 47-11113, N described in Japanese Patent Publication No. 51-47419@
- halogen compounds (e.g. N-halogenoacetamide,
N-halogenosuccinimide, etc.), U.S. Patent No. 3, 70
0,457, mercapto compound-releasing compounds described in JP-A No. 51-50725, arylsulfonic acids (e.g. benzenesulfonic acid, etc.) described in JP-A No. 49-125016, carboxylic acids described in JP-A No. 51-47419. Lithium salts (e.g. lithium laurate), British Patent No. 1,
455,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A No. 50-101019@, sulfinic acids or thiosulfonic acids described in JP-A No. 53-19825, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-81124
Disulfide and polysulfide compounds described in No. 55-93149, O-dine or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxyl groups described in No. 51-104338. or a polymeric acid having a sulfonic acid group,
Thiazolinthione described in U.S. Patent No. 4,138,265, JP-A-54-51821, U.S. Patent No. 4,13
1,2,4-triazole or 5-mercapto-1,2,4-triazole described in No. 7,079, No. 55
Thiosulfinate esters described in No.-140833, 1.2.3.4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-5
Dihalogen compounds or trihalogen compounds described in No. 7233, No. 59-57234, and No. 59-1
Examples include thiol compounds described in No. 11636.

In addition, as other anti-capri agents, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (e.g., di-t
-octylhydroquinone, dodecanylhydroquinone, etc.) or the hydroquinone derivatives described in Japanese Patent Application No. 1983-66380M are preferably used in combination with benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carpoxybenzotriazole, etc.) be able to.

As a silver image stabilizer, U.S. Patent No. 3.707.31
The polyhalogenated organic oxidizing agent described in No. 7 Mei 1II (e.g., tetrabromobutane, triamoquinaridine, etc.),
5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768.071, monohe○ compounds described in JP-A-50-119624 (e.g., 2-bromo-2-tolylsulfonylacetamide, etc.) ), bromine compounds described in JP-A-50-120328 (e.g., 2-bromomethylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6-methyltriazine, etc.), and JP-A-53-46020 Examples include tribromoethanol, etc., described in No. Also, the 1970s
Various monohalogenated organic antifoggants for silver halide emulsions, such as those described in Japanese Patent Application No. 119624, can be used.

Other image stabilizers include U.S. Pat. No. 3.220;
No. 846, No. 4,082,555, No. 4,088
, No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, 151
No. 68, No. 15567, No. 15732, No. 15
Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, as described in No. 733, No. 15734, No. 15776, etc.; Galactonamide; Compounds such as fludonamide-based compounds, amine imides, 2-carboxycarboxamide, etc., as well as JP-A-56-130745 and JP-A-56-130745, JP-A-56-130745;
6-132332, a compound that generates an amine through an intramolecular nucleophilic reaction described in British Patent No. 2,079,480, JP-A No. 5
Fluvioxime carbamates described in No. 9-157637, hydroxamic acid carbamates described in No. 59-166943, etc., and bases described in No. 59-180537, No. 59-174830, No. 59-195237, etc. Examples include release agents and the like.

Furthermore, U.S. Patent No. 3,301,678, U.S. Pat.
．． No. 444, No. 3.824.103, No. 3.844
．． Illithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in No. 788, RD12035, and RD18016 may be used for the purpose of stabilizing images, and in general, U.S. Patent No. 3,669,670, U.S. Patent No. 4,012,260,
No. 4,060,420, No. 4,207,392,
Nitrogen-containing organic bases called activator stabilizers and activator stabilizer precursors described in RD No. 15109, R017711, etc., such as α-sulfonylacetic acid R salt or tri-90 acetate of 2-aminothiazoline, acylhydrazine compounds, etc., respectively. It can be used for the purpose of accelerating development or for stabilizing images.

Also, for example, JP-A-56-130745 and JP-A-59-2
Developing may be done in the presence of a small amount of water as described in U.S. Pat. 3,
312,550M and the like, development may be carried out using hot steam, hot air containing moisture, or the like. Also, compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-26
Compounds containing water of crystallization such as those described in No. 582, such as sodium phosphate dodecahydrate and ammonium alum diquadrate, may be incorporated into 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.

The heat-developable light-sensitive material of the present invention includes a heat-developable light-sensitive material and/or a non-photosensitive It! material for the purpose of improving film properties. Colloidal silica can be used for (eg, undercoat layer, intermediate layer, fief, etc.).

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 component is 5iO2 (silicon dioxide).
It is. Regarding colloidal silica, for example, JP-A-56-109336, JP-A-53-123916, JP-A-5
It is described in No. 3-112732, No. 53-100226, etc. The maximum use of colloidal silica is from 0.05 to 0.05 in dry weight ratio to the binder of the layer to be mixed and coated.
A range of 2.0 is preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
An organic fluoro compound can be used for the undercoat layer, intermediate layer, protective layer, etc.).

Regarding the organic fluoro compounds used in the present invention, US Pat.
No. 3,754.924, No. 3.775.126, No. 3.850.640, West German patent publication number 1,942
, No. 665, No. 1,961,638, No. 2.124.
No. 262, British Patent No. 1,330,356) Lt.
Key N W l 742, 680J! Namihini JP-A-46-7781, JP-A-48-9715, JP-A-49-4
No. 6733, No. 49-133023, No. 50-995
No. 29, No. 5G-11322, No. 50-160034
No. 51-43131, No. 51-129229,
No. 51-106419, No. 53-84712, No. 53-84712, No. 53-84712, No. 53-84712, No.
No. 54-111330, No. 56-109336, No. 59-30536, No. 59-45441, and Special Publication No. 47-9303, No. 48-43130, No. 59-
Examples include compounds described in No. 5887, etc., and these compounds can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an antistatic agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1
, No. 466.600, Research Disclosure t-
(Research Disclosure) 1
No. 5840, No. 16258, No. 16630, U.S. Patent No. 2,327,828, U.S. Patent No. 2,861,056,
No. 3,206,312, No. 3,245,833, No. 3,428,451, No. 3.775.126, No. 3
, No. 963.498, No. 4,025,342, No. 963.498, No. 4,025,342, No.
No. 4,025,463, No. 4.025,691, No. 4
, No. 025.704, etc., and these can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an ultraviolet absorber can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, those described in JP-A-46-2784, U.S. Pat. No. 3,215,530, and U.S. Pat. No. 3,6911.907), butadiene compounds (for example, , U.S. Pat. No. 4,045,229), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794;
3.352,681), benzotriazole compounds substituted with aryl groups [VA, such as those described in Japanese Patent Publication Nos. 36-10466, 41-1687, and 42-
No. 26187, No. 44-29620, No. 48-415
No. 72, JP-A No. 54-95233, JP-A No. 57-1429
No. 75, U.S. Patent No. 3,253,921@, U.S. Patent No. 3,53
No. 3,794, No. 3,754,919, No. 3.7
No. 94.493, No. 4, No. 009.038, No. 4,22
No. 0,711, No. 4.323.633, Research
Disclosure (Research Disclosure)
ure) 22519], benzoxidol compounds (e.g., U.S. Pat. No. 3,700.4)
55), cinnamate ester compounds (for example, U.S. Pat. No. 3.705.805, U.S. Pat. No. 3.707.
No. 375 and JP-A No. 52-49029). Additionally, U.S. Patent No. 3.499.
762 and JP-A-54-48535 can also be used. UV-absorbing couplers (e.g.
α-naphthol cyan dye-forming couplers) and ultraviolet-absorbing polymers (e.g., JP-A-58-11194
No. 2, No. 178351, No. 181041, No. 59-
No. 19945, No. 23344, and those described in the official gazette).

In the heat-developable photosensitive material of the present invention, a polymer latex is used in the heat-developable photosensitive layer and/or the non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. be able to.

Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, polylobyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of nylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. Examples include copolymers, 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 0.02μl
~0.2 μm. The company using the polymer latex has a dry weight ratio of 0.0 to the binder of the added layer.
3 to 0.5 is preferred.

In the heat-developable photosensitive material of the present invention, various surfactants are added to the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving coating properties. Agents 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
-carboxy groups, sulfo groups, such as acyl-N-furkyltaurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a phospho group, a sulfuric acid ester group, or a phosphoric acid ester 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 phosphonium or sulfonium salts containing aliphatic or heterocyclic rings are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides.

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 gelicol alkylamines or amides, polyethylene oxide adducts of silicone),
Preferred are glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like.

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, etc.) for the purpose of improving developability, improving image dye transferability, improving optical properties, etc. ,
A non-photosensitive silver halide grain can be included in the silver halide grains.

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 grain size of the non-photosensitive silver halide grains is about 0.
．． It is 3 μm or less.

Also, the amount added is 0.00% in terms of silver matrix for the layer to be added.
A range of 02 to 3 G/i' is preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (undercoat layer,
(intermediate layer, protective layer, etc.), for example, JP-A-51-10433.
Vinyl polymers having carboxyl groups or sulfo groups as described in No. 8 can be included.

The vinyl polymer used preferably has a dry 1 affi ratio of 0.05 to 2.0 relative to the binder of the layer to which it is added.

When the heat-developable photosensitive material of the present invention is a color type, a dye-providing substance is used.

Hereinafter, one dye-donating substance that can be used in the present invention will be explained. 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 their reaction form, negative-acting dye-donors act on a positive function (i.e., form a negative dye image when negative-working silver halide is used) and positive-acting substances act on a negative function. It can be classified as a dye-providing substance (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are further classified as follows.

Release type compound　　　Formation type compound Each dye-providing substance will be further explained.

Examples of the reducible dye-releasing compound include compounds represented by general formula (2).

General formula (2) % formula % In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of the photosensitive silver halide and/or the organic silver salt used as necessary. , Dy
e 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 No. 58-116537.
No. 9-60434, No. 59-65839, No. 59-7
No. 1046, No. 59-87450, No. 59-8873
No. 0, No. 59-123837, No. 59-165054
No. 59-165055, Specification 1, etc., and examples thereof include the following compounds.

Margin below Un　e　　　　　　G OC+aHss ■ QC,, crow.

e @ IN (Jul Other reducing dye releasing compounds include, for example, general formula (3)
Examples include compounds represented by:

A.

In the formula, A I and A 2 each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye has the same meaning as Dye shown in general formula (2). Specific examples of the above compounds are given in JP-A-59
It is shown in the publication No.-124329.

As a coupled dye-releasing compound, general formula (4) is used.
Examples include compounds represented by:

General formula (4) % formula % In the formula, Cut is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a divalent bonding group. The bond between CI) + and J is cleaved by the reaction of the reducing agent with the oxidized product. n
l represents 0 or 1, and Dye has the same meaning as defined in general formula (2). Further, CI)+ is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has a carbon atom number of 8 depending on the form of the photosensitive material used. or more (more preferably 12 or more) organic groups, or hydrophilic groups such as sulfo groups or carboxy groups, or 8 or more (more preferably 12 or more) carbon atoms and hydrophilic groups such as sulfo groups or carboxy groups. It is a group that also has a 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 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159,
It is described in the specification of No. 59-231540, and includes, for example, the following compounds.

As the coupling dye-forming compound, general formula (5) is used.
Examples include compounds represented by:

General formula (5) % formula %) In the formula, CI)2 is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusive dye, F represents a divalent bonding group, and B represents a ballast group.

The molecular weight of the coupler residue represented by CI)2 is preferably 100 or less, more preferably 500 or less, in view of the diffusibility of the dye formed.

Further, 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 coupled 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) % formula %) In the formula, CD2 and F have the same meaning as defined in general formula (5), Y represents an alkylene group, an arylene group, or an aralkylene group, and 2 is 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 the coupled dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-1243
No. 39, No. 59-181345, No. 6G-295
No. 0, Japanese Patent Application No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
No. 7, each light m1l1, etc., and include, for example, the following compounds.

Margin below Exemplary dye-donor substances [phase] polymer M-1 PM-7 CH.

y: 50% by weight M-8 y: 50% by weight In the above general formulas (4), (5) and (6), Cp
More specifically, the coupler residue represented by t or CPt is preferably a group represented by the following general formula.

General formula (7) General formula (8) General formula (9
) General formula (10) General formula (11)
General formula (12) General formula (13)
General formula (14) General formula (15)
In the general formula (16) R9, R7, Re, R9 and R+o 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, amino group, alkoxy group, aryloxy group, cyam L alkylsulfonyl group, arylsulfonyl group, ureido group, alkylthio group, arylthio group, carboxy group, sulfonyl group represents a group or a heterocyclic residue, which further includes 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, and a carbamoyl group. , an imide group, a halogen atom, etc.

These substituents are selected depending on the purpose of Cut and CI)2, and as described above, one of the substituents in CD1 is preferably a ballast group, and in CI)2, it is preferable to In order to improve properties, the substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less.

As a positive dye-donating substance, for example, the following general formula (1
There is an oxidizable dye-releasing compound represented by 7).

General formula (17) In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring),
R11 represents an alkyl group or a hydrogen atom, and E is -N-
C(RI3) (in the formula, R12 represents an alkyl group or a hydrogen atom, R13 represents an oxygen atom or -N-) or -802-, r represents O or 1, and Dye represents the general formula (2 ) has the same meaning as defined in Specific examples of this compound are JP-A-59-166954 and JP-A No. 59-1.
It is described in specifications such as No. 54445, and includes, for example, the following compounds.

The following general formula (18) is used as a positive dye-providing substance according to the margin below.
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by:

General formula (18) In the formula, W2 represents a collection of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R''
, ' , E s D ye have the same meaning as defined in general formula (17). Specific examples of this compound are described in JP-A-59-124327 and JP-A-59-152440, and include the following compounds.

Margin below Exemplary dye-donor substances ■ OCR.

[Phase] Still another positive dye-providing substance has the following general formula (
Examples include compounds represented by 19).

General formula (19) In the above formula, W2, R'', and Dye are represented by general formula (1
It has the same meaning as defined in 8).

Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds.

The following margins are general formulas (2), (3), (4), (17) (18)
) and (19), the residue of the diffusible dye represented by Dye will be explained in further detail. The residual base of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less, for the sake of the diffusivity of the dye;
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
Chelatable dye residues described in No. 48765 and No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. The use thereof is not limited, and depends on the type of dye-providing substance, whether it is used for military purposes or in combination with two or more types, and 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. However, for example, the usage 1 is 0.0059 to 50 g, preferably 0.1 g to 10 (+) per 1 f.

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material using any method. Cresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.) and then neutralized with mineral acid (e.g., hydrochloric acid or nitric acid, etc.). Alternatively, it can be used after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.).

The heat-developable photosensitive material of the present invention usually has a temperature of 80°C to 20°C after imagewise exposure.
1 at a temperature range of 0°C, preferably 100°C to 170°C.
Seconds WA to 180°C, preferably 1.5 seconds to 12G!
It can be developed by simply heating it for a period of j. Transfer of the diffusible dye to the image-receiving layer may be performed simultaneously with heat development by bringing a passive member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development.
Alternatively, the image may be transferred by being brought into close contact with an image receiving member after thermal development and heated, or by being brought into close contact with an image receiving member after supplying water and further heated if necessary. Also, before exposure, 70℃~18℃
Preheating may be performed in a temperature range of 0°C. In addition, as described in Japanese Patent Application Laid-Open No. 60-443338@ and Japanese Patent Application No. 60-3644, the photosensitive material and image receiving member are heated at a temperature of 80°C to 250°C immediately before thermal development transfer to improve mutual adhesion. You may preheat each.

Various exposure means can be used for the heat-developable photosensitive material i according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources commonly used for color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, any method that can be used for ordinary heat-developable photosensitive materials can be used. For example, it can be brought into contact with a heated plotter or plate, brought into contact with a heated roller or drum, or passed through a high-temperature atmosphere. 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 the back surface of the image receiving member for thermal transfer, and the Joule heat generated by energization may be utilized. You can also. There are no particular restrictions on the heating pattern, including methods of preheating (breheating) and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, continuously increasing, decreasing, or repeating, and even discontinuously. Although heating is possible,
A simple pattern is preferable. Alternatively, a method in which exposure, light, and heating proceed simultaneously may be used.

The image receiving layer of the passive member that can be effectively used in the present invention includes:
It is sufficient that the polymer has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, for example, a polymer containing a tertiary amine or a quaternary ammonium salt, as described in US Pat.
, 709,690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene-co-N,N,Nl-ly-n-hexyl-N-vinyl-benzylammonyl cumylide is 1:4 to 4:1, preferably 1:1. belongs to.

Examples of polymers containing tertiary amines include polyvinylpyridine. A typical AWI 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 JP-A-57-207
The glass transition temperature described in No. 250 etc. is 40°C or higher,
Examples include those formed from organic polymeric substances that are heat resistant to 250° C. or lower.

These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support.

An example of the heat-resistant organic polymer substance is molecule m2.
000-85. Goo (7) HoIJ Suchi L/ >
, polystyrene derivatives having substituents having 4 or less carbon atoms, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyridine, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, Chlorinated polyethylene, polytrichlorinated butylene, polyacrylonitrile, polyN,N-dimethylallylamide, polyacrylate with p-cyanophenyl, pentachlorophenyl and 2,4-dichlorophenyl groups, polyacrylchloroacrylate1. Polyesters such as olimethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate Polycarbonates such as polysulfone, bisphenol A polycarbonate, polyanhydride, carbon
Examples include lyamides and cellulose acetates. In addition, Polymer Handbook Second Edition
ymer Handbook 2nd ed.

(J, Brandrup, E, H,
John Wiley &
Also useful are synthetic polymers with glass transition temperatures of 40° C. or lower, which are described in publications such as 5ons). These polymeric substances may be used alone or in a blend of two or more, or may be used as a copolymer in combination of two or more.

Useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as heptamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid; Examples include polyester, polyethylene terephthalate, and polycarbonate made of combinations of ethylene glycol and diphenylcarboxylic acid, bis-hydroxybenoxybutane and ethylene glycol, and the like. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4-benzenesulfonic acid, etc. as a modifier is also effective.

゛A particularly preferred image-receiving layer is disclosed in Japanese Patent Application Laid-Open No. 59-2234.
Examples include a layer made of polyvinyl chloride described in No. 25 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 (receiving member), in which case the support may be formed from a single layer or from multiple layers. good.

As the support for the image-receiving member, any material such as a transparent support or an opaque carrier may be used, and examples thereof include films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypyrene,
and supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, talc, etc., baryta paper, RC paper in which thermoplastic resin containing pigments is laminated on paper, cloth, Supports made of glass, metals such as aluminum, etc., and supports obtained by coating and curing electron beam curable resin compositions containing pigments on these supports, and coatings containing pigments on these supports. Examples include a support provided with a layer.

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 (reflective layer) can be included in the light-sensitive material;
It is used to reflect a desired amount of radiation, such as visible light, which can be used to observe the dye image in the dye. 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 2
09 in distilled water 100% (hQ and solution A dissolved in ammonia, potassium iodide 11.6217 and potassium bromide 13%)
8 liquids of 50 hQ of aqueous solution containing 0.90 and 1 silver nitrate
500 iQ of an aqueous solution containing mol and ammonia of C
The silver iodide-containing 1
7 mol %, regular hexahedral core particles with an average grain size of 0.25 μm were prepared, and then in the same manner, silver iodide content of 1 mol %,
Core/shell type silver iodobromide grains having a regular hexahedron shape and an average grain size of 0.3 μm were prepared by coating with a shell having a thickness of 0.05 μm. (The monodispersity was 8%.) The concentration after washing with water and desalting was TooIQ.

Furthermore, using the silver iodobromide grains prepared above, silver halide emulsions spectrally sensitized to blue, green, and red color sensitivities were prepared under the following conditions.

Spectral sensitization conditions Core/shell type silver iodobromide grains 700 vQ4-
Hydroxy-6-methyl-1゜3.3a, 7-tetoazaindene o, ag Gelatin, 32 g Sodium thiosulfate 10 mg Spectral sensitizing dye below 1% methanol solution go, g Distilled water
1200i12 The following spectral sensitizing dyes were used at this time.

Blue sensitizing dye Green sensitizing dye (CH,), SO, H''N (C2H5)! Red sensitizing dye C2H, C, H, Br3 In addition, 5-methylbenzotriazole and silver nitrate were mixed with water-
5-methylbenzotriazole silver 28.813 obtained by reaction in a methanol mixed solvent and poly-N-vinylpyrrolidone 16.0 (+ and 4-sulfobenzotriazole sodium salt 1.330) were dispersed in an alumina ball mill. , pH was adjusted to 5.5 to prepare 1 m of 5-methylbenzotriazole silver dispersion 20012.

Next, an exemplary dye-providing substance (PM-1) 62. Go and 5.0 g of 2.5-di-t-octylhydroquinone were dissolved in 200 mff1 of ethyl acetate, and alkanol xC (
DuPont) 5% by weight aqueous solution 124tQ and phenylcarbamoylated gelatin (Rouslow, Type 17)
819P C') 720i aqueous solution containing 3G, 5(l
After mixing with Q and dispersing with an ultrasonic homogenizer and distilling off ethyl acetate, a yellow dye-providing substance dispersion (1) having a pH of 795 d was prepared. 35.5 g of Exemplary Dye-Providing Material (PM-4) and Exemplary Dye-Providing Material (PM-5) 62. Regarding OQ, a magenta dye-providing substance dispersion (1) and a cyan dye-providing substance dispersion (1) were prepared, respectively, using the same formulation.

In addition, 23.3 g of exemplary reducing agent (R-11), poly(N-
Vinylpyrrolidone) 14.6111, the following fluorosurfactant 0.5017 was dissolved in water, pal 5.5
As reducing agent solution (1) 250mj2er! 4tJ
did.

In a fluorine-based surfactant solution, 25.0G of the following color clouding prevention agent (SC-1) was dissolved in 801g of ethyl acetate, and mixed with 50mQ of an aqueous solution of 5% by weight of Alkanol XC and 25ml of an aqueous solution containing 12.0g of gelatin. Disperse with an ultrasonic homogenizer, distill off ethyl acetate, and prepare a dispersion of color turbidity preventive agent (1
) 32 (hj2 was prepared.

Color clouding prevention agent (SC-1) (weight ratio) In addition, yellow filter dye 20.0Q having the following structure was dissolved in 120 d of ethyl acetate, and alkanol XC 5 weight a%
501 g of aqueous solution and 9.0 g/j of phenylcarbamoylated gelatin! by mixing with 250 mj2 of an aqueous solution containing
The mixture was dispersed using an ultrasonic homogenizer, and ethyl acetate was distilled off to prepare yellow filter dye dispersion (1) 5ooIQ in F14.

Yellow Filter Dye Using these materials, heat-developable photosensitive materials (I) to (■) having a multilayer structure as shown in Table 1 were prepared, but at this time they were made to contain a curing agent as shown in Table 2.

Below is a margin. However, the comparative hardening agent (H-1) used in Table-2
and (H-2) are as follows.

Comparative hardener (H-1) Tetra(vinylsulfonylmethyl)methane comparative hardener (
H-2”) OH.

Next, polyvinyl chloride (n) was applied onto photographic baryta paper.
-1,100, manufactured by Wako Saiyaku Kogyo ■) in a tetrahydrofuran solution with a coating amount of polyvinyl chloride of 12.0 g/12
An image receiving member (1) was prepared by applying the following.

The heat-developable color photosensitive materials (1) to (■) were exposed to 1,600 CMS through a step wedge, combined with the image-receiving member (1), and then placed in a heat developing machine (Developer Module 277, 3M Co., Ltd.). After heat development was carried out at different temperatures and times using a commercially available product (manufactured by M. Co., Ltd.), the photosensitive material and the 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 ■), and the film of the photosensitive material after processing was measured. The degree of collapse was 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 collapse was observed.

B: When observed under a microscope at 100 times magnification, some or slight membrane deformation is observed.

C: Significant film deterioration is observed when observed under a microscope at 100 times magnification.

Margin Table 3 below As is clear from Table 3, the photosensitive material (I) that does not use any hardening agent has severe film deterioration, and the photosensitive material that uses the comparative hardening agent (H-1) Material (I[), (III)
In , film collapse occurs during thermal development regardless of the addition position, and Owin is also higher than in [) IaX.

In contrast, the photosensitive material (V
) to (■), it can be seen that the occurrence of film deterioration is improved, fog (Dmin> is low, [) wax is high, and color turbidity is also improved. This improvement effect is particularly remarkable in the photosensitive material (■), and no film deterioration is observed even at high processing temperatures.

Example '2 Illustrative dye donor
After dissolving in 460 iR 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, water was added, and 5
A yellow dye-providing substance dispersion (2) of 00d was prepared. Exemplary dye-providing substance (■) and Exemplary dye-providing substance - (O)
A magenta dye-providing substance dispersion (2) and a cyan dye-providing substance dispersion (2) were also prepared using the same formulation.
) was prepared.

Furthermore, 30.0 g of the following color clouding prevention agent (SC-2) and 15.0 g of tricresyl phosphate. OIJ, ethyl acetate 901Q
Dissolved in ζalkanol XC 5% by weight aqueous solution 50112
The mixture was mixed with 560 d of an aqueous solution containing gelatin 2G and OQ, dispersed using an ultrasonic homogenizer, and ethyl acetate was distilled off to prepare 600 d of color clouding prevention agent dispersion (2).

Color clouding prevention agent (SC-2) H Using these and the same silver halide emulsion and 5-methylbenzotriazole silver dispersion as used in Example 1,
Photothermographic materials (■) to (Xr
V) was created. At this time, a hardening agent shown in Table 5 was also included.

An image receiving member (2) was then prepared by sequentially applying the following layers onto a 200 μm thick polyethylene coated paper support.

(1) Neutralizing layer made of polyacrylic acid (7, OMf).

(2) Timing layer made of cellulose acetate (4-OQ/f ).

(3) Styrene and N-benzyl-N, N-dimethyl-N
- Cough consisting of a 1=1 copolymer of (3-maleimidopropyl) ammonium chloride (3, OQ/12) and acid-treated gelatin (3,0 g/f).

(4) Urea (4.0g/12) and polyvinyl alcohol (saponification degree 98%) (3.0<1/l”)
A layer consisting of.

However, each layer also contains a black surfactant and a hardening agent in addition to these.

The heat-developable photosensitive materials (■) to (X IV) were exposed to 1,600 CMS through a step wedge, combined with the image-receiving member (2), and then placed in a heat developing machine at different temperatures and R. After thermal development, 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 image receiving member was measured using a densitometer (PDA-65, manufactured by Konishiroku Photo Industry ■), and the degree of film deterioration of the photosensitive material after processing was measured. was observed, and Table 6 was obtained using the same display as in Example 1.
Shown below.

Margin Table 6 below As is clear from Table 6, photosensitive materials using hardeners other than those of the present invention suffer from film deterioration, which causes image deterioration, and also have fogging (Dmin) compared to Dfila×. ), whereas the present invention achieves a high Q while keeping fog low without causing any film deterioration during thermal development.
It turned out that it is possible to achieve max. Moreover, color turbidity was also improved.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (shoulder) February 25, 1985 Patent application No. 281501 2, Title of invention Heat-developable color photosensitive material 3, Person making the amendment Relationship to the case Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Ide 4, Agent 102 Address 1-1 Kudankita 4-chome, Chiyoda-ku, Tokyo (Delivery date) February 258, 1985 6. Purification of the full text of the specification subject to amendment! ! (No change in content) 7. Procedure for amendment content? ill i:E t@ (spontaneous) December 8, 1986 Gourd

Claims (4)

[Claims] (1) On a support, at least two heat-developable photosensitive layers and at least one non-photosensitive layer are provided, in which the color sensitivity of the photosensitive silver halide and the hue of the dye formed from the dye-providing substance are different from each other. 1. A heat-developable color photosensitive material having a photographic constituent layer consisting of a photosensitive layer, characterized in that at least one of the photographic constituent layers contains a polymer hardener. (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 polymer hardener is contained in at least one of the non-photosensitive layers.
) The heat-developable color photosensitive material described in item 2. (4) The heat-developable color photosensitive material according to claim (3), wherein the heat-developable color photosensitive material further contains a heat solvent.