JPS62139551A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a laser tendency for generating a color unevenness and capable of forming a clear image by specifying the film thickness of the non-photosensitive protective layer and by raising a hard ness of the film in the title material which is provided with the heat developing photosensitive layer and the non-photosensitive protective layer on the substrate body. CONSTITUTION:The titled material comprises at least >=1 layer of the heat developable photosensitive layer and at least >=1 layer of the non-photosensitive protective layer on the substrate. The non-photosensitive protective layer is composed of a gelatin, its derivative, a polyvinylpyrrolidone, a polyvinylalcohol and a polyethyloxazoline, etc., and has a film thickness of 0.05-3mum. The hardness of the film of the protective layer makes larger than that of the photoprotective layer. The mat agent such as silicon dioxide is added to the protective layer, thereby making the surface thereof a coarse, and preventing a sticking of said surface with each other. Thus, as the thickness and the hardness of the film are specified, the titled material having a less tendency for generating a density unevenness and capable of forming the transfer image having the high density is obtd.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a heat-developable color photosensitive material, and particularly to a heat-developable color photosensitive material in which a transferred image is formed by transferring a diffusible dye formed by heat development. Regarding.

[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. Patent Nos. 3.531.286 and 3.7.
61゜270 and No. 3.764.328, etc., in which a dye image is formed by reaction of an oxidized product of a vital drug for an aromatic primary amine with a coupler;
Research Disclosure (ResearchQ)
1sclosure) 15108 and 1512
7. A reducing agent that is a sulfonamide phenol or sulfonamide aniline derivative described in U.S. Patent No. 4,021,240 (hereinafter also referred to as a developer or developing agent)
A method of forming a dye image by the reaction of an oxidized form of and a coupler, as disclosed in British Patent No. 1.590.956, using an organic imino silver salt having a dye moiety and subjecting the dye to TtM in a thermal development section. A method of releasing a dye image on a separately provided image-receiving layer is also disclosed in JP-A Nos. 52-105821, 52-105822, 56-50328, and U.S. Pat. No. 4,235,957. A method for obtaining a positive dye image by a silver dye bleaching method, as well as U.S. Pat. No. 3,180,731, U.S. Pat.
Various methods have been proposed, such as a method of obtaining a dye image using an Oico dye, which is disclosed in Japanese Patent Application Laid-Open No. 59-206831.

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 using heat development, Japanese Patent Application Laid-open Nos. 57-179840 and 57-186 have been developed.
No. 744, No. 57-198458, No. 57-2072
No. 50, etc., disclosed a method of obtaining a color image by transferring a diffusible dye released by thermal development.

These methods were further improved to produce diffusible dyes by oxidizing non-diffusible reducing dye-donating substances, such as those disclosed in Japanese Patent Application Laid-open Nos. 58-58543 and 59-168439. A method for releasing , JP-A-58-
No. 79247, No. 59-174834, No. 59-12
No. 431, No. 59-159159, No. 6G-2950
JP-A-58-149046, JP-A-58-149047;
No. 59-124339, No. 59-181345, No. 60-2950, Japanese Patent Application No. 59-181604, No. 5
No. 9-182506, No. 59-182507, No. 59
A system using a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye as disclosed in Japanese Patent Application Laid-Open Nos. 152440-1987 and 124327-1987, , 59-154445@,
Non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes upon oxidation, and conversely non-diffusible dyes that release diffusible dyes upon reduction, as disclosed in No. 59-166954, etc. A method containing a donor substance has been proposed.

The color image υ due to these emitted or formed diffusible pigments
The basic composition of color type photothermographic materials that obtain
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 image receiving element is referred to as an image receiving member.

The above heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto the receiving a 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.

However, in these heat-developable photosensitive materials, the transferred images had large unevenness and were insufficient for obtaining clear images.

It is presumed that the unevenness of the transferred image is mainly caused by film destruction of the photosensitive layer during thermal development, or disturbance of the film due to scratches during exposure, thermal development, transportation, etc. These problems caused by the film strength of the photosensitive layer are generally solved by increasing the hardness of the photosensitive layer or by providing a non-photosensitive layer (m<protective layer) on the top layer of the photosensitive material. However, in heat-developable photosensitive materials, especially dye-transfer-type photothermographic materials, if the degree of hardness of the photosensitive layer is increased in order to increase the film strength of the photosensitive layer, developability tends to decrease. Furthermore, if a compound such as a hot solvent is added to improve the developability, or if the amount of binder is reduced to improve the transferability of the dye, there is a problem that the degree of hardness cannot be sufficiently increased. Furthermore, if a protective layer with sufficient thickness and hardness is provided to prevent film destruction of the photosensitive layer, there is a drawback that the transferability of the dye will be significantly reduced, and the protective layer itself may be damaged or scratched. There were problems such as uneven transfer and staining of the image due to movement of the protective layer itself to the receiving member.

[Object of the Invention] An object of the present invention is to solve the problems of known thermal mass υ photosensitive materials.

That is, a first object of the present invention is to provide a heat-developable color photosensitive material that can provide a clear transferred image without unevenness.

A second object of the present invention is to provide a thermal color photosensitive material capable of obtaining transferred images of high density.

A third object of the present invention is to provide a heat-developable color photosensitive material with high scratch resistance.

[Structure of the Invention] In order to achieve the above object, the inventors of the present invention have conducted extensive research, and as a result, have created a four-layer structure consisting of at least one thermal phenomenon photosensitive layer and at least 1 WJ of non-photosensitive layer on a support. In a heat-developable color photosensitive material having a thermal mass furthest from the support, at least 1W of heat is applied to the side of the image-sensitive layer opposite to the support.
J, the non-photosensitive protective layer has a thickness of 0.05 μIll to 3 μI, and the hardness of the non-photosensitive protective layer is equal to the hardness of the heat-developable photosensitive layer. It has been found that the above objects of the present invention can be achieved with a heat-developable color photosensitive material having a larger size than the above.

[Specific Structure of the Invention] The heat-developable color photosensitive material of the present invention has at least one non-photosensitive protective layer (hereinafter simply referred to as "retainer") on the side opposite to the support of the heat-developable photosensitive layer furthest from the support. ).

As a binder for the protective layer, polyvinyl butyral,
Synthetic or natural polymeric substances such as polyvinyl acetate, ethylcellulose, polymethylmethacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, gelatin, and phthalated gelatin can be used in combination of one or more. can.

Particularly preferred are binders in which gelatin and/or its derivatives are used alone or in combination with hydrophilic polymers that are compatible with gelatin, such as polyvinyl bioxydone, polyvinyl alcohol, and polyethyloxazoline.

Gelatin may be treated with lime, acid, or ion exchange, and may be ossein gelatin, big skin gelatin, hyde gelatin, or modified gelatin made by esterifying, phenylcarbamoylating, etc. good.

When using gelatin and other hydrophilic polymers together,
Preferably 20% or more of the binder, more preferably 3
0% or more is gelatin.

One way to make the hardness of the protective layer higher than that of the photosensitive layer is to use, for example, a diffusion-resistant hardener. Polymer hardeners are known as diffusion-resistant hardeners. Hardeners described in Japanese Patent Publication No. 58-50528 and the like can be used.

These hardeners are dissolved in water or a solvent and added to the coating solution for the protective layer.

Another way to make the hardness of the protective layer higher than that of the photosensitive layer is to include a diffusive hardener (for example, a vinyl sulfone hardener) only in the protective layer, or to The degree of hardness of the protective layer can be made greater than that of the photosensitive layer by making the layer contain more proviso than the photosensitive layer and rapidly drying after simultaneous multilayer coating.

Of course, the present invention is not limited to the above method. In the art, methods for evaluating the degree of hardening of a hardened layer include the degree of swelling when the hardened layer is soaked in a certain solution at 1Bfl;
Alternatively, evaluation can be made using the time taken until the membrane begins to dissolve when immersed in a solution at a certain temperature.

In the present invention, a 30°C water-ethanol solution (water:
Evaluation was performed using the dissolution time when immersed in ethanol-2=1). In the present invention, the dissolution of am
The dissolution time of the protective layer is preferably 200 to 800 seconds, and the dissolution time of the photosensitive layer is preferably 20 to 200 seconds.

The thickness of the protective layer of the present invention is 0.05 μm to 3 μm,
More preferably, it is 0.1 μm to 1.0 μm.

If the film thickness is larger than 3 μm, the transferability of the dye will be significantly reduced and a high-density transferred image cannot be obtained, while if it is smaller than 0.05 μm, the effect of preservation III is not sufficient and the film adhesion is insufficient. , stains and unevenness occur in the transferred image. Further, the protective layer of the present invention may be a single layer or may be composed of two or more layers.

When the protective layer is composed of two or more layers, the thickness of the protective layer in the present invention is the total thickness of these multiple layers. Further, in the present invention, when the protective layer is composed of two or more layers,
At least the layer farthest from the support among the protective layers has a hardness higher than that of the photosensitive layer.

Various additives used in the photographic field can be used in the protective layer of the present invention. These additives include various matting agents, colloidal silica, slip agents, organic fluoro compounds (especially fluorosurfactants), antistatic agents, ultraviolet absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, and polymers. Examples include 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 an inorganic substance or a paid substance, which is incorporated into a heat-developable photosensitive 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 comonolymer described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341, JP-A-58-145935 A combination of two or more types of fine particle powders with different Mohs hardnesses, a combination of oil droplets and fine particle powders as described in JP-A-58-147734, two types with different average particle sizes as described in JP-A-59-149356 Combination of the above spherical matting agents, JP-A-56-4
Combination of fluorinated surfactant and matting agent described in 4411 @, British Patent No. 1,055,713, Red Seal Patent No. 1,939,213, British Patent No. 2,221,813, British Patent No. 2
．． No. 268.662, No. 2,322,037, No. 2,
No. 378, 005, No. 2.391.181, Note 2,7
No. 01,245, No. 2.992.101, No. 3,0
No. 79,257, No. 3,262,782, No. 3, 4
No. 43,946, No. 3,516,832, No. 3.53
No. 9.344, No. 3,591,379, No. 3,754
, No. 924, No. 3.767゜448, Japanese Unexamined Patent Publication No. 49-1
Organic matting agents described and inscribed in No. 06821, No. 57-14835, etc., West German Patent No. 2.529.321, British Patent No. 760.775 @, No. 1.260.772,
U.S. Patent No. 1,201,905, U.S. Patent No. 2.192,24
1 @, 3, 053.662, 3.062.64
No. 9, No. 3,257,206, No. 3.322.55
No. 5, No. 3,353,958, No. 3,370,951
No. 3.411.907, No. 3,437,484, No. 3.523°022, No. 3,615,554,
Inorganic matting agents described in 3,635,714, 3,769.020, 4,021,245, 4,029.504, etc., or JP-A-46-77
No. 81, No. 49-106821, No. 51-6017, No. 53-116143, No. 53-100226, No. 57-14835, No. 57-82832, No. 5
Matting agents having physical properties such as those described in Japanese Patent Publication No. 3-70426, Japanese Patent Publication No. 59-149357, Japanese Patent Publication No. 57-9053, and EP-107,378 are preferably used.

In the protective layer of the present invention, the amount of matting agent added is 10111 per 1f! J/2. h is preferred, and more preferably 20 mg to 1.0 g. The particle size of the matting agent is 0.
5 to 10 μm is preferable, more preferably 1.0 to 6 μm
It is m.

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

Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, French Patent Nos. 2 and 1
No. 80,465, British Patent No. 955,061, No. 1,
143,118, 1,270.578, 1,3
No. 20゜564, No. 1,320,757, Japanese Unexamined Patent Publication No. 1973
-5017, 51-141623, 54-15
No. 9221, No. 56-81841, Research Disclosure
) 13969, U.S. Patent No. i, 263.72
No. 2, No. 2,588.765, No. 2,739,891
No. 3,018.178, No. 3,042,522, No. 3.080.317, No. 3,082.087,
3,121,060, 3.222.178, 3,295,979, 3.489.567,
Those described in 3,516,832, 3,658,573, 3,679,411, 3,870°521, etc. can be preferably used.

In order to improve film adhesion and brittleness, or to improve slipperiness, the adhesive agent of the present invention contains a high boiling point solvent (for example, U.S. Pat. No. 2,322,027, U.S. Pat. ，
No. 533,514, No. 2,882,157, Special Publication No. 4
No. 6-23233, British Patent No. 958.441, 1
, 222,753, U.S. Patent No. 2.353.262, U.S. Patent No. 3,676.142, U.S. Patent No. 3.700.454,
Esters (e.g. phthalates, phosphoric esters, fatty acid esters, etc.), amides (e.g. fatty acid amides, (sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ) may contain oil droplets in which a water-insoluble oil compound is emulsified and dispersed. Furthermore, these oil droplets may contain additives for various purposes.

The heat-developable photosensitive material of the present invention basically includes one thermal mass a.
Photosensitive β contains (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, (4) binder, and further contains (5) organic silver salt as necessary. It is preferable. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, two heat-developable photosensitive layers may be included.
F! 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.

Further, the heat-developable photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, a high-density layer and a low-density layer, and 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 thermal phenomenon photosensitive layers with different color sensitivities, and each photosensitive layer forms or releases dyes with different hues upon thermal 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 red-sensitive layer and a green-sensitive layer are sequentially formed on a support.

A structure in which a blue-sensitive layer is formed, a structure in which a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer are sequentially formed on a support, or a structure in which a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer are sequentially formed on a support. , a blue-sensitive layer, etc.

The heat-developable photosensitive material of the present invention may be provided with non-photosensitive layers such as an undercoat, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer in addition to the thermal phenomenon photosensitive layer. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

That is, dip method, 0-sea method, reverse roll method, air knife method, doctor player method, spray method,
There are methods and devices for the bead method, extrusion method, stretch flow method, curtain method, etc.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
It 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 I) Aill constant. At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, EIH, DACI, 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. When the width of the distribution is defined by the relational expression, the width of the distribution of the silver halide grains used in the present invention is preferably 15% or less, and more preferably monodispersity of 10% or less. It is.

Also, for example, JP-A-58-111933, JP-A No. 58-1
11934, No. 58-108526, Research Disk No. 22534, etc., each of these crystal planes has two parallel crystal planes, and each of these crystal planes is It is also possible to use a silver halide emulsion consisting of tabular silver halide grains having a larger area than the crystals 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 previously coupled, 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, same 3,761,266@, same
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 patent, for example, by first preparing A901 grains and then adding bromide or a small amount of iodide thereto. A method in which the center core of chemically sensitized silver halide is coated with non-chemically sensitized silver halide, or a method in which chemically sensitized coarse grain emulsion and chemically sensitized Many methods are known, such as a method in which a fine grain emulsion which has not been chemically sensitized is mixed and a fine grain emulsion is deposited on a coarse grain emulsion.

Also, U.S. Patent Nos. 3.271□157 and 3.44
7.927 and 3,531,291, or silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or U.S. Pat.
A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in JP-A-50-8524 and JP-A-50-8524 and JP-A-50-8524;
Silver halide emulsions consisting of grains having a laminated structure as described in No. 38525, etc., and other JP-A-52-15
These include silver halide emulsions described in No. 6614 and JP-A-55-127549.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include
Various methods 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. .01μ■ to about 0°, 5μm.

The photosensitive silver halide emulsion produced by WA as described above can most preferably be applied to the heat-developable photosensitive layer, which is component (2) 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 method 11 is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an N84 group, or a gold m atom, and X represents 011% 13r or l
When n is an MSH atom or an NH group, it is 1, and when M is a metal atom, it is its valence. Metal atoms include lithium, sodium, potassium, ludium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth,
Chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, Odium, palladium,
Examples include osmium, iridium, platinum, and cerium. ), halogen-containing gold i complexes (e.g., K2 PtCj
! s, 2PtSrs, HAuC1+.

(NH Gin) 21r C4! s, (NH4)3 [r
Cj! s.

(Nl-14)2 Ru C1e, (NH4)3 RI
JC4! s.

(NH4)2 Rh Cff1s, (NH4, > 3
Rh 3rs etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methyldeazolium bromide, -trimethylbenzylammonium bromide, quaternary ammonium halides, tetraethylphos) Quaternary phosphonium halides such as phonium bromide, benzylethylmethylsulfonium bromide, 1
-tertiary sulfonium halides such as ethylthiazolium 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-
Chlorophthalazinone, N-bromoacetanilide, N,
'N-dibromobenzenesulfonamide, N-bromo-
N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g. triphenylmedyl chloride, triphenylmethyl bromide, 2-promobutyric acid, 2- bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 (1 to 501 J) per layer per 1f of support.
It is preferable that it is, more preferably 0.1 g to 1
It is 0g.

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 photosensitive layer of the same color can be divided into 21 or more layers (for example, an island-sensitive 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 have 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.It may also be symmetrical or asymmetrical, Further, 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 tl visible light, which is described in the specifications of 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, 1 x 10-mol to i x
i o−+ moles.

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. Long-chain aliphatic carboxylic acids as described in each publication and specifications such as U.S. Patent Nos. 3,330,633, 3,794,496, and 4,105,451 Silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver valmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc.,
No. 5-12700, No. 45-18416, No. 45-2
No. 2185, JP-A-52-137321, JP-A-58
There are silver salts of imino groups described in publications such as No.-118638, No. 58-IH1639, and US Pat. No. 4,123,274.

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 those substituted with an alkyl group of 04 or less, such as methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.), alkylamidobenztriazole silver (preferably substituted with an alkylamide group of 022 or less) silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably alkylsulfamoyl of 022 or less) those substituted with groups, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, silver 4-(N-diethylsulfamoyl)penztriazole,
-octylsulfamoyl)penztriazole silver, 4
-(N-decylsulfamoyl)penztriazole silver, 5-(N-octylsulfamoyl)penztriazole silver, etc.), silver salts of halogen-substituted benztriazoles (such as 5-chlorobenztriazole silver, 5-bromobenztriazole silver), triazole silver, etc.), alkoxybenztriazole silver (preferably substituted with an alkoxy group of 022 or less, more preferably an alkoxy group of C4 or less),
For example, silver 5-methoxybenztriazole, silver 5-ethoxybenztriazole, etc.), silver 5-nitrobenztriazole, silver 5-aminobenztriazole, silver 4-hydroxybenztriazole, silver 5-carboxybenztriazole, silver 4-sulfobenztriazole. silver, 5-
Examples include silver 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, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzoxazole Silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver, 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 4.5-10.0 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-methylpenzotriazole 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 generally preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles, per mole 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, 58-1
No. 49047, No. 59-124339, No. 59-
If it is a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent as disclosed in No. 181345, No. 60-2950, etc., it can be used in the present invention. Examples of the reducing agent required include those described in US Pat. No. 3,531,286 and US Pat. No. 3,761.
No. 270, No. 3.764.328, 8 specifications, and RD No. 12146, No. 3.764.328.

No. 15108, No. 15127, and JP-A No. 15108-
Using p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoramide phenol-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 it. Further, color developing agent precursors described in U.S. Pat. No. 3,342,599, U.S. Pat. I can do it.

As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (1) described in No.

The following is a general formula (1) in which R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R1 and R2 may be ring-closed to form a heterocycle. R3, R4.

R5 and R6 are a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a! ! 1 to 30 carbon atoms (preferably 1 to 30), which may have a group in
4) represents an alkyl group, R3 and R1 and R5 and R
2 may each be ring-closed to form a heterocycle. M represents a compound containing an alkali diabetic atom, an ammonium group, a nitrogen-containing base, or a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming a solid salt, and particularly important organic bases include amine compounds. And as a chain amine compound, the first tI
I & amines, secondary amines, tertiary amines, etc., and typical examples of cyclic amine compounds include lysine, quinoline, piperidine, etc.
Examples include imidazole. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used.

On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a 4Iilli covalent bond.

Next, preferred specific examples of the reducing agent represented by the general formula (1) are not shown below.

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

(R-7) (R-8) (R-9) (R-10) (R-11) (R-12) H CH1 (R-20) (R-21) (R-23) The above general formula The reducing agent represented by (1) can be prepared by a known method,
For example, Louben Peil, Methoden der Organitschen Hemi, Band XI/2 ()louben.
-Weyl, fvlethoden der Qrg
anischen Chemie, Band X
It can be synthesized according to the method described in I/2), pages 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-donating substance used in the present invention is JP-A No. 57-179840, No. 58-58543, No. 5
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. Alternatively, in the case where only a silver image is simply obtained, a developing agent as described below can also be used.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-p-aminephenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dicoO-4-benzenesulfonamidophenol, 2,6-dipromo4-
(p-toluenesulfonamide)phenol, etc.], or polyhydroxybenzenes (e.g., hydroquinone,
tert-7-tyloctahydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxylic hydroquinone, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol) , 4-methoxynaphthol, etc.), hydroxybinaphdyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6.6'-dibromo-2,2'-dihydroxy-1,11-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 and sphenols [e.g. 1.1
-bis(2-hydroxy-3,5-dimethylphenyl)
-3゜5.5-trimethylhexane, 1.1-bis(2
-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5
-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tart-butyl-
5-methylphenyl)-4-methylphenol, α-phenyl-α, α-bis(2-hydroxy-3-tert
-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-
Methylpropane, 1,1,5,5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,2-bis(4-hydroxy-3,5-
dimethylphenyl)propane, 2.2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2.2-bis(4-hydroxy-3,5-
tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These developing agents mentioned above can also be used alone or in combination of two or more.

The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide, the type of organic acid silver salt, and the type of other additives used, but usually is 0.0 for 111 moles of photosensitive halogenide.
In the range of 1 to 1500 mol, preferably 0.1 to 2
00 moles.

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 copolymer 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 it. ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
It is of 0.000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates,
Examples include vinyl monomers such as vinyl imidazoles, (meth)acrylamides, vinyl carbinols, and vinyl alkyl ethers, but at least 20% of the composition ratio (weight is %, the same applies hereinafter) must be polyvinylpyrrolidone. is preferred. Preferred examples of such copolymers are those having a molecular weight of s,ooo to 400,000.

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%, more preferably 20 to 60%, and vinyl and lolidone account for 5 to 90% of the total binder.
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 m s, ooo to 400,0
A mixture of the vinylpyrrolidone copolymer No. 00 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 0.05+7 to 50a per layer per support 1112, preferably 0.05+7 to 50a.
It is 1 g to 10 g.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
~1(l) is preferably used, more preferably 0.2
It is 5 to 4 g.

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

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. Regarding these compounds, for example, U.S. Patent No. 3.347□615, U.S. Pat.
56, Japanese Patent Application No. 59-47787, etc., and those particularly useful in the present invention include urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.). ), amide derivatives (e.g. acetamide, benzamide, etc.),
Examples include polyhydric alcohols (eg, 1.5-bentanediol, 1.6-bentanediol, 1.2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), and polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are more preferably used.

A water-insoluble solid thermal solvent is a compound that is solid at room temperature but becomes liquid at high temperatures (60°C or higher, preferably 100°C or higher, particularly preferably 130°C or higher and 250°C or lower), and is inorganic/organic. Sex ratio (“Organic Conceptual Diagram” Yoshio Koda,
Sankyo Shuppan ■, 1984) is in the range of 0.5 to 3.0, preferably 0.7 to 2.5, particularly preferably 1.0 to 2.0, and the solubility in water at room temperature is 1
Refers to smaller compounds.

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

sun - to sun sato
! ω Toro cQ
Q Chain Many of the 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, a middle @ layer, an image receiving layer of a 4L image receiving member, etc., and are added so as to obtain the respective effects.

The amount of water-insoluble heat solvent added is usually 10% to 500% by weight, preferably 50% to 300% by weight of the binder amount.

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 U.S. Patent No. 3.438.776;
Compounds such as polyalkylene glycols described in US 'R Kitsuki 3.667, No. 959 (7) -CO-1-
The melting point of lactones etc. having 8O2-1-80- group is 20
There are non-aqueous polar organic compounds with temperatures above ℃.

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 sulfamoylamide 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,
No. 49-5020, No. 49-91215, No. 49-
No. 101727, No. 5G-2524, No. 5G-67
No. 132, No. 5G-67641, No. 5G-11421
γ No. 52-33722, No. 52-99813,
53-1020, j5J53-55115, 53-76020, 53-125014, 54
-156523, 54-156524, 54
-156525, 54-156526, 55
-4060, 55-4061, 55-3201
No. 5, as well as West German Patent No. 2,140,406, West German Patent No. 2,141°063, West German Patent No. 2,220,618, US Patent No. 3.847.612, West German Patent No. 3.782.
No. 941, No. 4,201,582 and JP-A-57
-207244, 57-207245, 58-
Each Ming IQ such as No. 189628, No. 5B-193541, etc.
Phthalazinone, phthalimide, bilane, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2.3-dihydro-phthalazinedione, 2.3-dihydro-phthalazinedione, which is a compound described in I.
Dihydro-1,3-oxazine-2,4-sion, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide,
2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazoletotetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazole phthalic acid, naphthalic acid, phthalamic acid, etc. mixtures of one or more imidazole compounds and at least one acid or acid anhydride such as phthalic acid, naphthalic acid, etc.
Examples include mixtures of phthalazine and phthalazine compounds, 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 fatty acids (e.g. behenic acid, stearic acid, etc.) described in Japanese Patent Publication No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983, and N described in Japanese Patent Publication No. 47419/1983.
- halogen compounds (e.g. N-halogenoacetamide,
N-halogenosuccinimide, etc.), U.S. Patent Nos. 3 and 7
00, 457, mercapto compound releasing compound described in JP-A No. 51-50725, JP-A No. 49-125016
Aryl sulfonic acids (e.g. benzenesulfonic acid etc.) described in No. 51-47419, carboxylic acid lithium salts (e.g. lithium laurate) described in No. 51-47419, British Patent No. 1
, 455,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A-50101019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825, JP-A-50101019. 2-thiouracils described in No.-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-81124
Disulfide and polysulfide compounds described in No. 55-93149, rosins or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxamides I described in No. 51-104338. or sulfone M groups, thiazolinthiones described in U.S. Pat. No. 4,138,265, JP-A-54-51821, U.S. Pat.
1.2.4-triazole or 5-mercapto-1.2.4-triazole described in No. 137,079, thiosulfinic acid esters described in No. 55-140833, 1 described in No. 55-142331 .2.3
．． Examples include 4-thiatriazoles, dihalogen compounds or trihalogen compounds described in No. 59-46641, No. 59-57233, and No. 59-57234, and thiol compounds described in No. 59-111636.

In addition, as other antifoggants, special f+
Hydroquinone derivatives described in No. 506 (for example, di-
t-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives and benzotriazole derivatives (e.g., 4-
Sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used in combination.

Silver image stabilizers include U.S. Pat.
Polyhalogenated mFli-forming agents (e.g., natrab0mobutane, tribromoquinaridine, etc.) described in No. 311 Mei 1s, 5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768,071 Mei 1l1g , monohenyl 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-bromomethylsulfonylbenzo), Thiazole, 2,4-bis(tribromomethyl)-
6-methyltriazine, etc.), and JP-A-53-4602
Examples include tribromoethanol described in No. 0. Also, various monohalogenated organic antifoggants for silver halide emulsions as described in JP-A-50-119624 can be used.

Other image stabilizers include U.S. Pat. No. 3,220;
No. 846, No. 4, 082, 555, No. 4,0
No. 88,496, Japanese Patent Application Laid-open No. 50-22625, Research Disclosure (RD) No. 12021, No. 15168, No. 15567, No. 15732, Research Disclosure (RD) No.
15733, 15734, 15776, etc. Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, galactonamide Compounds such as fludonamide-based compounds, amine imides, 2-carboxycarboxamide, etc., as well as JP-A-56-130745,
A sodium phosphate base generator described in JP-A No. 56-132332, a compound that generates an amine through an intramolecular nucleophilic reaction described in British Patent No. 2,079,480, and a compound that generates an amine through an intramolecular nucleophilic reaction described in JP-A-59-157637. Aldoxime carbamates described in the above, hydroxamic acid carbamates etc. described in the same No. 59-166943, base release agents etc. described in the same No. 59-180537, the same No. 59-174830', the same No. 59-195237, etc. I can list them.

Furthermore, U.S. Patent Nos. 3,301,678 and 3,506
, 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 RD No. 788, RD 12035, RD 18016, etc. may be used for the purpose of stabilizing images. Patent No. 3.669.670, Patent No. 4,012,260,
4.060.420, 4,207,392,
Nitrogen-containing organic bases called activator stabilizers and activator stabilizer precursors described in RD 15109 and RD 17711, such as α-sulfonylacetate or trichloroacetate of 2-aminothiazoline, acylhydrazine compounds, etc., are used to promote development, respectively. It can be used for the purpose of image stabilization.

Also, for example, JP-A-56-130745 and JP-A-59-2
It may be used in the presence of a small amount of water as described in U.S. Pat. .3
12.550, etc., development may be carried out using hot steam, hot air containing moisture, or the like. Compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-2658
Compounds containing water of crystallization as described in No. 2, such as sodium phosphate dodecahydrate, ammonium alum diquadrate, etc., may be included in the photothermographic material.

In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used.

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

The colloidal silica used in the present invention is mainly a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ using water as a separating medium, and the main component is 5i02 (silicon dioxide).
It is. Regarding colloidal lily force, 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 use of colloidal silica is based on the dry weight ratio of O, OS 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 specific fluoro compounds used in the present invention, US Pat. No. 3,589,906, US Pat.
No. 3.754.924, No. 3.775.126, No. 3,850.640, West German Patent Publication No. 1.942
．． No. 665, No. 1.961.638, No. 2,124,
No. 262, British Patent No. 1.330.356, Belgian Patent No. 742,680, and JP-A-46-7781, No. 48-9715, No. 49-46733, No. 49
-133023, 50-99529, 50-1
No. 1322, No. 50-160034, No. 51-431
No. 31, No. 51-129229, No. 51-10641
No. 9, No. 53-84712, No. 54-111330
No. 56-109336, No. 59-30536, No. 59-45441, and compounds described in Japanese Patent Publications No. 47-9303, No. 48-43130, No. 59-5887, etc. 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 the non-photosensitive B (eg, undercoat layer, intermediate layer, protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1
．． 466, 600@, Research Disclosure t -
(Research D 1 closure)
15840, 16258, 16630, U.S. Patent Nos. 2,327,828, 2,861,056, 3°206.312, 3,245,833,
3,428,451, 3,775.126, 3,963°498, 4,025,342, 4
, No. 025,463, No. 4.025,691, No. 4.
Examples include compounds described in No. 025.704 and the like, and these can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
or non-photosensitive WJ (e.g., undercoat layer, intermediate layer, protective m
￥i) Ultraviolet absorber can be used = As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, JP-A-46-2784, U.S. Pat. No. 3,215,530, U.S. Pat. No. 3,698) , 907), butadiene compounds (e.g., those described in U.S. Pat.
, 045,229), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3□314.794M and 3.352,881), with aryl groups!
! converted benzotriazole compounds (for example,
No. 6-10466, No. 41-1687, No. 42-2
No. 6187, No. 44-29620, No. 4B-4157
No. 2, JP-A-54-95233, JP-A No. 57-14297
No. 5, U.S. Patent No. 3,253,921, U.S. Patent No. 3.533
, No. 794, No. 3,754,919, No. 3,79
No. 4,493, No. 4.009,038, No. 4,220
, No. 711, No. 4,323,633, Research Disclosure
e) those described in U.S. Pat.
), cinnamate ester compounds (e.g.
U.S. Patent No. 3,705,805, U.S. Patent No. 3.707.31
No. 5, described in JP-A No. 52-49029). Additionally, U.S. Patent No. 3,499.76
No. 2, and those described in JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α-
naphthol-based cyan dye-forming couplers), ultraviolet-absorbing polymers (for example, JP-A-58-111942, JP-A-178351, JP-A-181041, JP-A-59-19).
No. 945, No. 23344, and those described in the official gazette).

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

Preferred specific examples of the polymer latex used in the present invention include boremethyl acrylate, polyethyl acrylate, poly-herbaceous acrylate, copolymer of ethyl acrylate and acrylic acid, copolymer of vinylidene chloride and butyl acrylate, and copolymer of butyl acrylate and acrylic acid. , a copolymer of vinyl acetate and butyl acrylate, a copolymer of vinyl acetate and ethyl acrylate, a copolymer of ethyl acrylate and 2-'acrylamide, and the like.

The preferred average particle size of the polymer latex is 0.02 μ-
~0.2 μm. The amount of polymer latex used is 0.0 in dry weight ratio to the binder of the added layer.
35-0.5 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 Ml (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, flukylthiphthalenesulfonates, 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 IIIm ester group, or a phosphoric acid ester group are preferable.

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 salt layers containing aliphatic or heterocycles 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 glycol 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. ,
(protective layer, etc.) may contain non-photosensitive 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 relative to the layer to be added.
A range of 02 to 3 ri/l' is preferable.

For the purpose of improving film properties, the heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer, m<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 in the layer preferably has a dry gravity a ratio of 0.05 to 2.0 relative to the binder of the layer to which it is added.

When the thermal mass @photosensitive material of the present invention is a color type, a dye-providing substance is used.

Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on 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 (i.e., one that forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are further classified as follows.

Releases a diffusible dye when oxidized Release type compound　　　Formation type compound Each dye-providing substance will be briefly 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, for example, the following compounds are mentioned.

Below are examples of dye-providing substances in the margin: ■ OCl6H33 (nI U +aMgsLnJ OCI6H33) Other reducing dye-releasing compounds include, for example, the general formula (3).
Examples include compounds represented by:

General formula (3) In the formula, A1 and A2 each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye is Dye represented by general formula (2).
is synonymous with Specific examples of the above compounds are given in JP-A-59-12
This is shown in Japanese Patent No. 4329.

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

General formula (4) % formula % In the formula, CI) 1 is an organic M (so-called coupler residue) that can react with the oxidized form of a reducing agent to release a diffusible dye, and J is a divalent It is a bonding group, and the bond between Cpl and J is cleaved by reaction with the infused form of the reducing agent. nl represents O or 1, and Dye has the same meaning as defined in general formula (2). In addition, C1ot is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms (
more preferably 12 or more) organic groups, or sulfo groups,
It is a hydrophilic group such as a carboxy group, or a group having both 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Another particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (4) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159,
It is described in the specification 59-231540, and includes, for example, the following compounds.

In the following margin, exemplified dye-providing substance 0CsaHss(n) As a coupling dye-forming compound, general formula (5) is used.
Examples include compounds represented by:

General formula (5) % formula %) In the formula, CI)2 is a compound capable of reacting (coupling reaction) with an oxidized form of a reducing agent to form a diffusible dye.
[(so-called coupler residue M), where E represents a divalent bonding group and B represents a ballast group.

The coupler residue represented by CE12 preferably has a molecular layer of 700 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 monobase represented by general formula (6).

General formula (6) % formula %) In the formula, CI)2 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 represents O or 1 and Z is 2
1 [i represents an organic group, and 1 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. 60-295
No. 0, Japanese Patent Application No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
Each town of No. 7 is described in Book 1, etc., and examples include the following compounds.

The following margins illustrate dye-providing substance polymer M-4 P2N2-5 PM-7 CHl x: 50% by weight y: 50% by weight PM-8 H x: 50% by weight y: 50% by weight Kamijtun's -L2 formula In (4), (5) and (6),
More specifically, the coupler residue defined by Crl+ or CI)2 is preferably a group represented by the following formula -C2.

General formula (7) General formula (8) General formula (9)
General formula (10) General formula (11)
General formula (12) R'R' General formula (13) General formula (14) General formula (
15) In the blank formula below in general formula (16), R', R8, R9, and Rto are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyllkylsulfonyl group, and an arylsulfonyl group. group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, cyano group, alkylsulfonyl group, arylsulfonyl group, ureido group,
It represents an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, which further includes a hydroxyl group,
Carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group,
It may be substituted with an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like.

These substituents are selected depending on the purpose of Ctl+ and CD2, and as mentioned above, in <CD+, one of the substituents is preferably a ballast group, and in CI)2, it is preferable to improve the diffusivity of the dye formed. The molecular weight is 700 to increase it.
Hereinafter, the number of substituents is preferably selected to be 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),
R represents an alkyl group or a hydrogen atom, R13 represents an oxygen atom, or I2 represents -N-. ) or -802-, r is O
or 1, and Dye has the same meaning as defined in general formula (2). A specific example of this compound is JP-A-59-1
It is described in specifications such as No. 66954 and No. 59-154445, and includes, for example, the following compounds.

In the following margin, exemplified dye-donor substance Zan H3 [Phase] Another positive dye-donor substance is represented by the following general formula (18).
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 group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R1
1, r, E, and Dye have the same meanings as defined in general formula (17). A specific example of this compound is JP-A-59
It is described in specifications such as No. 124327 and No. 59-152440, and includes, for example, the following compounds.

The following is an example of a dye-providing substance in the margin.
Examples include compounds represented by 19).

General formula (19) In the above formula, W2, R''% Dye are the 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 margin shows illustrative dye-providing substances; The following margin shows the general formulas (2), (3), (4), (17)
) and (19), the residue of the diffusible dye represented by Dye will be explained in further detail. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less, for the sake of the diffusibility of the dye;
Examples include residues of azomethine dyes, anthraquinone dyes, naphthoquinone dyes, soudyryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dye residues may also be used in the form of shorter wavelengths.Furthermore, these dye residues are used for the purpose of increasing the light resistance of images, for example, as disclosed in Japanese Patent Application Laid-Open No. 59
The chelatable dye residues described in Japanese Patent No. 48765 and Japanese Patent No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. The use a is not limited, and the type of dye-providing substance, whether it is used for ψ or a combination of two or more types, or the photographic constituent layers of the light-sensitive material of the present invention! 11 layers or 2
The decision can be made depending on whether it is a multilayer of seeds or more, but for example, the usage is Q, 005g to 50'; J per 1v.
, preferably 0.1 g to 10 (J).

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 is usually 80°C to 2°C after imagewise exposure.
00°C, preferably in the temperature range of 100°C to 110°C,
It is developed by simply heating for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with thermal agglomeration by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during thermal development, or by bringing the image-receiving member into close contact with the image-receiving member after thermal development. Transfer may be performed by heating, or by supplying water and then applying heat if necessary. Also, before exposure, heat at 100°C to 70°C.
Preheating may be performed in the temperature range of °C. Also, JP-A-6
As described in Japanese Patent Application No. 0-143338 and Japanese Patent Application No. 60-3644, the photosensitive material and the image receiving member are preheated at a temperature of 80° C. to 250° C. immediately before thermal development transfer to improve mutual adhesion. It's okay.

Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for ordinary 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, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or heated drum, or passing through an atmosphere at temperature a. 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 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 preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The image receiving layer of the receiver and member that can be effectively used in the present invention includes:
It is sufficient that the dye in the heat-developable photosensitive layer released or formed by a thermal phenomenon has the ability to accept, for example, a polymer containing a tertiary amine or a quaternary ammonium salt, as disclosed in US Pat.
Those described in No. 5.709.690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene-N,N,N-tri-0-hexyl-N-vinyl-benzylammonium chloride is 1:4 to 4:1, preferably 1:1. be.

Examples of polymers containing tertiary amines include polyvinylpyridine. A typical receiving layer for diffusion transfer is obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support.

Another useful dye-receiving material is JP-A-57-2072.
The glass transition temperature described in No. 50 etc. is 40°C or higher, 2
Examples include those formed of organic polymeric substances that are heat resistant to 50° C. or lower.

These polymers may be supported on a support as a passive layer, or may themselves be used as a support.

An example of the heat-resistant organic polymer substance is the molecule fi 2
,000-85,000 polystyrene, carbon number 4
Polystyrene derivatives with the following substituents, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyvinyl Fluoroethylene chloride, polyacrylonitrile, poly N, N-dimethylallylamide, polyacrylate with p-cyanophenyl group, pentachlorinyl group and 2,4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyiso10 pyl methacrylate, polyisobutyl methacrylate, polyter
t-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate,
Examples include polyesters such as poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook Second Edition (edited by G.A. Brandrup and E.A.I. Inmargat) John Willy and Son 1 (polymer) - 1an
dbook 2nd ed.

LJ, 3randruO, E, H, Immer
gut III) John W 1ley&5ons
) Synthetic polymers with glass transition temperatures below 40° C. that are described in publications are also useful. These polymeric substances may be used alone or in a blend of two or more thereof, or may be used in combination of two or more to form a copolymer.

Useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as hexamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, and diethylene glycol. Examples include polyester, polyethylene terephthalate, and polycarbonate made of a combination of bis-p-carboxyphenoxybutane, ethylene glycol, and diphenylcarbonate.

These polymers may be modified. For example, cyclohexane dimetatool, isophthalic acid,
Polyethylene terephthalate using methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, or the like as a modifier is also effective.

A particularly preferable a-receptive layer is JP-A-59-22342
Layer made of polyvinyl chloride described in No. 5 and JP-A-60
A layer consisting of polycarbonate and a plasticizer as described in No. 19138 may be mentioned.

These polymers can also be used as a support and an image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or from multiple layers. .

As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used. supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments, cloth, glass, aluminum, etc. Metals, etc., supports on which an electron beam curable resin composition containing a pigment is coated and cured, and supports on which a coating layer containing a pigment is provided. etc.

In particular, a support that is coated with an electron beam curable resin composition containing a pigment on paper and cured, or a support that has a pigment coating layer directly on the paper or an electron beam curable resin composition on the pigment coating layer. The support coated with the composition and cured can be used as an image-receiving member as it is because the resin layer itself can be used as an image-receiving layer.

When the present invention is applied to a heat-developable color light-sensitive material, the various polymers mentioned above can be used as a mordant for a dye image and as an image-receiving layer. It may be an image-receiving element or the image-receiving layer may be a single layer that is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, such layer providing a desired degree of radiation e.g. Used to reflect light. The opacifying layer (reflection layer) can contain various reagents that provide the necessary reflection, such as titanium dioxide.

The receiving a 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 the imagewise exposure of the heat-developable color photosensitive material, a uniform heating phenomenon can be carried out by superimposing the receiver Q5 on the heat-developable photosensitive layer. Further, after imagewise exposure and uniform heat development of the heat-developable color light-sensitive material, an image-receiving layer can be superimposed and heated at a temperature lower than the development temperature to transfer the pigment released or formed from the dye-providing substance.

[Examples] Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these embodiments.

Example-1 Preparation of organic silver salt dispersion> 5-methylbenzotriazole 128. obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent. BQ and poly(N-vinylpyrrolidone>16.0g were dispersed in an alumina ball mill, and p
It was set to H5.5 and 200 vQ.

<Preparation of dye-providing substance dispersion> Exemplary dye-providing substance (PM-7> 35.5 g, and the following hydroquinone compound 5.
00d, alkanol XC (manufactured by DuPont) 5
Overlay % aqueous solution 124d, phenylcarbamoylated gelatin (Rouslow, type 17819P C) 30.5!
After mixing with 720vQ of gelatin aqueous solution containing II and dispersing with an ultrasonic homogenizer, and distilling off the ethyl acetate,
p)l was changed to 5.5 and designated as 7951Q.

Hydroquinone compound [Preparation of silver iodobromide emulsion] At 50°C, JP-A-57-92523M;
Potassium iodide 11.6 (l
and 500 i of an aqueous solution containing 130 g of potassium bromide.
Solution B of Q, an aqueous solution containing 1 mol of silver nitrate and ammonia, and solution C of 2 at the same time 1) AO and pH
was added while keeping it constant. Furthermore, by controlling the addition speed of Solution B and Solution C, a core emulsion containing 711% silver iodide, having regular hexahedral grains, and having an average grain size of 0.25 μm was prepared.

Next, in the same manner as described above, by coating a silver halide shell with a silver iodide content of 1 mol %, regular hexahedral grains with an average diameter of 0.3 μm (shell thickness 0.05 μm) were formed. A core/shell type silver halide emulsion was prepared. (The monodispersity was 8%.) The above emulsion was washed with water, desalted, and collected in a can of 700
I got a crane.

Preparation of reducing agent dispersion> Exemplary reducing agent (R-11) 23.3(+, poly(N-
(vinylpyrrolidone) 14.6g and 050g of the following fluorine-based surfactant were dissolved in water, and the pl-15.5 was adjusted to 2.
5(he)

Surfactant Na03S CHC00CHz (CFzCF2)qJ
4CHz-COOCHtCCFzCF2), rLH (war, and = 2JR is 3) <Preparation of heat-developable photosensitive material> Organic silver salt dispersion 12.5i12, silver halide emulsion e,
oo, 1. After mixing 39.8 d of dye-donor dispersion and 12.5 d of reducing agent dispersion, and adding 3.80 Q of polyethylene glycol 300 (Kanto Kagaku) as a heat solvent, subbing was performed. thickness ? 1.76 silver on 80um photographic polyethylene terephthalate film
(A photosensitive material 4(1) was prepared by coating the film at a ratio of 1/f.

Separately, when preparing the above photosensitive material, the following hardener solution (2.5 d
) was added to increase the hardness, but the same photosensitive material (2) as photosensitive material (1) was produced.

Photosensitive material in which a 5% gelatin solution is applied to the upper layer of the photosensitive material (1) so that the dry film thickness is 0.8 μm and 3.5 μm (3), (4), 5% gelatin solution and 5% polyvinylpyrrolidone A photosensitive material (5) was prepared by coating a mixed solution (fA ratio: 6:4) of (molecules, 130,000) to a dry film thickness of 0.8 μm. Separately, the above photosensitive material (3),
By adding 3.0 d of the hardening agent solution below to the coating solution 50112 of (5) and quickly drying it after coating,
Photosensitive material $1 with a higher degree of hardness than the photosensitive layer
(6) and (7) were produced.

Hardening agent solution Tetra (vinylsulfonylmethyl)methane and taurine are reacted at a ratio of 1:1 (fffffi ratio), and dissolved in a 1% gelatin aqueous solution, so that the tetra(vinylsulfonylmethyl)methane is triple base%. What I did.

Preparation of image receiving member-1> Polyvinyl chloride (n=1.100
, Wako txt'y;p> was applied in tetrahydrofuran so that the polyvinyl chloride ratio was 120/u'.

The heat-developable photosensitive material was exposed to 1,600 C, M, S through a step wedge, and together with the image-receiving member-1, it was heated to 150° C. in a heat developing machine (Developer Module 277.3M). After thermal development for a minute, the photosensitive material and image receiving member were separated, and a magenta step-quench negative image was obtained on the polyvinyl chloride surface of the image receiving member.

The reflection density of the obtained stroke was measured using a densitometer (PDA-65, manufactured by Konishiroku Photo Industry (Fj7J)) at arbitrary 10 points of maximum density, and the average value and its standard deviation (σn-1) were calculated. (A larger value of σn-1 does not indicate greater density unevenness.) The results are shown in Table 1.

In addition, the protective layer and photosensitive layer of the photosensitive material were immersed in a water-ethanol solution (water:ethanol = 2 = 1) at 30°C, and the time required for each to begin to dissolve was measured to evaluate the degree of hardness. did. The results are shown in Table 1.

Below is a blank table-1 Example-2 Preparation of dye-donor dispersion-2> Exemplary dye-donor substance @30. OQ as tricresyl phosphate 3
Gelatin aqueous solution 4 containing the same surfactant as in Example-1 and dissolved in 0, og and ethyl acetate 90.0tj2
60. After mixing with Q and dispersing with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to make 500 ml.

Made by U4, a heat-developable photosensitive material> Silver halide emulsion 40.0, organic silver salt dispersion 25
．． 0d, 50.0d of dye-providing substance dispersion were mixed, and 4.201J of polyethylene glycol 300 (Kanto Kagaku) was added as a heat solvent, 10fflfft% methanol V! of 1-phenyl-4,4'-dimethyl-3-pyrazolidone. t1. hN, VI! Membrane agent solution (tetra(vinylsulfonylmethyl)methane and taurine 1:1 (ff
im ratio) and dissolved in a 1% gelatin aqueous solution so that the content of tetra(vinylsulfonylmethyl)methane was 3 mm%) 1. 10% wt water-alcohol solution of OOd and guanidine trichloroacetic acid 20.0 mQ
2.50 μm of silver m
A photosensitive material (8) was prepared by applying the film at a ratio of 0/f.

Furthermore, a photosensitive material (9) was produced which was the same as the photosensitive material (8) except that the hardness of the photosensitive material (8) was further increased.

The dry film thickness of the above photosensitive material (8) is 08 μm and 3
．． 5% gelatin solution (the above photosensitive material (
Same VJ as 7)! Photosensitive material (including film agent) coated with 0 cloth (1
0) (11) and photosensitive material (8) with 596 gelatin solution and 5% polyvinylpyrrolidone (molecular ffl 30.0
A photosensitive material (12) was prepared by applying a mixed solution of 0(1) (containing the same hardening agent as the photosensitive material (7) above) (mixing ratio 7:3) to a dry film thickness of 0.8 μm. .

Separately, photosensitive materials (13) and (14) (the present invention) were prepared in which the degree of hardness of the protective layer of the above photosensitive materials (10) and (12) was increased in the same manner as described in Example-1. .

Preparation of Image Receiving Member-2> The following layers were sequentially coated on a transparent polyethylene terephthalate film having a thickness of 100 μm.

(1) Mouth made of polyacrylic acid. (7,0Q(1/T
I') (2) Layer consisting of cellulose acetate. <4. O
Og/v') (3) Styrene and N-benzyl-N,N
- A layer consisting of a 1=1 copolymer of Dimeblue N-(3-maleimidopropyl)ammonium chloride and gelatin.

(copolymer 3.00 (1/v', gelatin 3.0
Og/v') (4) Layer consisting of urea and polyvinyl alcohol (saponification degree 98%). (Urea 4.h
The heat-developable photosensitive material was exposed to 1,600 C, M, S through a step wedge, and combined with the image-receiving member-2 in a hot block@machine. After thermal development at 150° C. for 1 minute, the image receiving member was immediately peeled off. The transmission density of the maximum density of the yellow transparent image obtained on the surface of the image receiving member was measured at arbitrary 10 points using a densitometer (PDA-65゜ manufactured by Konishiroku Photo Industry Co., Ltd.), and the average value and standard deviation of the maximum density ( σn-1) was calculated.

Table 2 shows the dissolution of the film measured in the same manner as in Example 1.
Shown below.

Margin Table 2 Below, as shown in Examples 1 and 2, the photosensitive material of the present invention has good transferability and has no density unevenness, so a clear image with high density can be obtained.However, the hardness of the protective layer is a small photosensitive material (
In Comparative Example), it was not possible to obtain a good transferred image due to extremely uneven transfer, and the density unevenness became less noticeable if the thickness of the retention ff1Fffi was increased or the degree of hardness of the photosensitive layer was increased, but in both cases the density was It has the disadvantage of being low.

Example 3 A photosensitive material and a receiving member having the following configurations were prepared and exposed to red light, green light, blue light, and white light of 1,600 C, M, S from the support side of the photosensitive material to receive an image. Heat development was performed at 150° C. for 1 minute while in close contact with the member, and the results shown in Table 3 were obtained.

Protective layer gelatin (0.42 g), hardening agent described in Example-1 (2.0 meq/100 g of gelatin>, S i 0
2 (0,36 (]), Safon (0,1 g), red-sensitive layer medylbenztriazole silver (1,6 g), m base agent (R
-11) 0.57 g, Exemplary Dye-Providing Substance PM-5 (
0.8(1), contains red-sensitive silver halide (*1),
Silver equivalent (0,58(+), the hydroquinone compound (60+no), gelatin (0,75o), phthalate (
Hipiratin (0.75g), polyvinylpyrrolidone (
0,5o), 3-methylpencune-1,3,5-triol (0,38!J), polyethylene glycol (1
10), AeK-XC (*3) (80mq), intermediate layer gelatin (0,5+2), CD' scavenger (*
4) Contains (0,4(1), methylbenztriazole silver (1,2g), green-sensitive layer exemplary dye-donor substance PM4 (1-3g), green-sensitive silver halide (*2), silver equivalent (0) ,76(+>
, methylbenztriazole silver (2,U), 3o base agent (
R-11) (0,76(1), the hydroquinone compound (90+11(J), gelatin (1,0g)
, phthalated gelatin (1,Oa), polyvinylpyrrolidone (0,66(1), 3-methylpentane-
1,3,5-triol (0,5[+), polyethylene glycol (1,5(+>, AffiK-XC
(*3) (0,11(]) Intermediate layer Y-filter dye (*5) (0,Aa), CD
'Scavenger (*4) (0,4g>, methylbenztriazole silver (1,2(+), gelatin (0,5!;l) Blue-sensitive layer exemplary dye-donor PM-1 (1,4(1) , blue-sensitive silver halide (silver equivalent: 0.970), methylbenztriazole silver (2,7a), reducing agent (R-11) 0,
97g, the above hydroquinone compound (90mo), gelatin (1,26(1), phthalated gelatin (1,26
o) Polyvinylpyrrolidone (0,84(]) , ]3-
Methylpentane-1.3.54-liol (0,63(
1), polyethylene glycol (1,9(] >, A
l1K-XC (*3) (0,14(1) Gelatin layer Gelatin (2,5o) Support 180 μm polyethylene terephthalate film with latex subbing (sweet taste per 1f of support) Image receiving member image receiving layer Polycarbonate io g .

0.5 g of the following compound (1), 0.5 g of the following compound (2)! + Support Baryta paper (sweet taste per support 1112) Compound (1) OCe HI9 Compound (2) *1) Sensitizing dye *2) Sensitizing dye (CH, ), 5osH *3) / IK-XC (Weight Ratio) Table 3 From the results of Example 3, good high-density image quality without density unevenness was obtained even in the full-color photosensitive material with a multilayer structure.

Patent Applicant: Konishiroku Photo Industry Co., Ltd. Procedural Amendment Gate (January 23, 1988) Commissioner of the Special Correction Agency: Michibe Uga 1, Indication of the Case 1985 Patent Application No. 280826 2, Name of the Invention Thermal bulk cropping color photosensitive material 3, relationship with the amendment person case Patent applicant address 26-22 Nishi-Shinjuku 1-chome, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. Representative Director
Keio Benko 4, Agent 102 Address: Kudan-Kita 4-1-1 De Kudan-Rosaka Building, Chiyoda-ku, Tokyo Tel: 263-9524 Engraving of the entire specification (no changes to the content) 6. Contents of amendments

Claims (1)

[Claims] In a heat-developable color photosensitive material having a photographic constituent layer consisting of at least one heat-developable photosensitive layer and at least one non-photosensitive layer on the support, the support of the heat-developable photosensitive layer furthest from the support. has at least one non-photosensitive protective layer on the opposite side, the thickness of the non-photosensitive protective layer is 0.05 μm to 3 μm, and the hardness of the non-photosensitive protective layer is A heat-developable color photosensitive material characterized by a hardness greater than that of the developable photosensitive layer.