JPS62136643A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having adhesion resistance and antistatic property and excellent quality of a transferred image by incorporating a matt agent having a softening point in a prescribed range into a heat developable photosensitive material. CONSTITUTION:The heat meltable matt agent to be used is preferably a high- polymer compd. having >=40 deg.C and <=180 deg.C glass transition point (Tg) which is exemplified by styrene and styrene deriv. such as styrene and o-methyl styrene and olefin such as ethylene and propylene. A copolymer having >=70 deg.C and <=150 deg.C glass transition point is more particularly adequate. The amt. of the heat metable matt agent to be added is 10mg-2.0g, more preferably 20mg-1.0g per 1m<2> photosensitive material. The photosensitive material which has the adhesion resistance and antistatic property during the production and preservation and provides the excellent image quality (density, gloss, transparency, sharpness and granularity etc.) is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-developable photosensitive material, and more particularly to a heat-developable photosensitive material that has adhesion resistance and antistatic properties and has excellent transferred image quality.

[Background of the Invention J] In recent years, heat-developable photosensitive materials in which the developing step is performed by heat treatment have attracted attention as photosensitive materials.

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

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

For example, U.S. Pat. No. 3,531,286, U.S. Pat.
No. 61270 and No. 3,764,328, each of which describes a method for forming a dye image by the reaction of an oxidized product of an aromatic primary amine image agent with a coupler, Research Disclosure (Research Q 1scl).
osure ) 15108 and 15127, U.S. Pat. No. 4,021,240, etc., the oxidized form of a reducing agent (hereinafter also referred to as a developer or developing agent), which is a sulfonamide phenol or sulfonamide aniline derivative, and a coupler. A method of forming a dye image by reaction,
As disclosed in British Patent No. 1,590,956, a method of using an organic imino silver salt having a dye part and releasing the dye in a heat development part to form a dye image on a separately provided image-receiving layer; Also, JP-A No. 52-105821, No. 52
-105822, No. 56-50328, U.S. Patent No. 4,235,957, etc., methods for obtaining positive dyes and images by silver dye bleaching methods, Zarani U.S. Patent No. 3
, No. 180,731, No. 3,985,565, No. 4,022,617, No. 4,452,883, Japanese Patent Application Laid-Open No. 59-206831, etc. Various methods have been proposed, including methods for obtaining dye images using

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
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.

By further improving these methods, for example, the non-diffusible reducible dye-donating substance disclosed in JP-A-58-5F3543 and JP-A-59-168439 is oxidized to produce a diffusible dye. A method for releasing , JP-A-58
-79247, 59-174834, 59-1
No. 2431, No. 59-159159, No. 60-295
A method of releasing a diffusible dye by coupling with an oxidized form of a developing agent as disclosed in No. 0, etc.;
JP-A-58-149046, JP-A No. 58-149047
No. 59-124339, No. 59-181345
No. 60-2950, Japanese Patent Application No. 59-181604, No. 59-182506, No. 59-182507
No. 59-272335, etc., which uses a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye;
No. 52440, No. 59-124327, No. 59-15
Disclosed in No. 4445, No. 59-166954, etc.
Methods have been proposed that include non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and systems that contain non-diffusible dye-donating substances that release diffusible dyes when reduced. ing.

゛The basic composition of a color type heat-developable photosensitive material that produces a color image using these emitted or formed diffusive dyes consists of a photosensitive element and an image-receiving element, and the photosensitive element basically contains photosensitive silver halide, It consists of an R-containing silver salt, a reducing agent, a dye-providing substance, and a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense, and the receiver and element are referred to as an image receiving member.

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

It is also used to prevent scratches on various photosensitive materials and to prevent fogging and desensitization caused by pressure. It is well known to provide a top layer during manufacture or storage.

It is known to provide a protective layer in the case of heat-developable photosensitive materials, for example, it is known to use gelatin as a protective layer, as disclosed in Japanese Patent Publication No. 54-11694, and other patent publications. In 1982-178456, polyvinyl alcohol was used for protection, in JP-A-60-107648, acid-treated gelatin was used, and in JP-A-60-120357, a nonionic water-soluble polymer such as polyacrylic acid amide was used for protection. It is used as a layer. However, when these materials are used as adhesives, the surface of the photosensitive material increases in adhesiveness or tackiness in an atmosphere of high temperature and humidity, and when it comes into contact with other objects, it easily adheres to other objects and can be peeled off. may damage the surface or generate static electricity. In order to provide the desired rough surface, it is known to use solid particles of inorganic material such as silicon dioxide or solid particles of organic material such as cellulose ester, so-called matting agents, in the protective layer. However, by adding these matting agents, it is necessary to have a considerable amount of matting agents present in order to provide a sufficiently rough surface, and therefore the image quality after heat development processing, such as gloss, sharpness, graininess, etc. It has the disadvantage of significantly worsening the condition.

It is also known that the above-mentioned matting agent is added to the protective layer for the same purpose in diffusion transfer type heat-developable color photosensitive materials. In diffusion transfer type heat-developable color photosensitive materials, improvements such as adhesion and antistatic properties can be seen by adding these matting agents, but due to poor adhesion between the photosensitive material and image receiving member during heat development, formation or It has the disadvantage that it inhibits the transferability of the released dye and significantly deteriorates the image quality.

[Objective of the Invention 1 The object of the present invention is to provide a heat-developable photosensitive material that has adhesive resistance and antistatic properties during production and storage, and has excellent image quality (density, gloss, transparency, sharpness, graininess, etc.) The purpose is to provide materials.

[Structure of the Invention] The above object of the present invention has been achieved by incorporating a matting agent with a softening point of 40° C. or more and 180° C. or less into a photothermographic material.

[Specific Structure of the Invention] The matting agent having a softening point of 40° C. or higher and 180° C. or lower used in the present invention will be explained. Here, the softening point refers to, for example, the glass transition point of a polymer compound. Hereinafter, softening A matting agent having a temperature of 40° C. or more and 180° C. or less is called a heat-melting matting agent.

The heat-melting matting agent used in the present invention is preferably a polymer compound having a glass transition point (T(1)) of 40°C or more and 180°C or less. Specific examples of monomers of these polymer compounds include styrene, O-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-butylstyrene, p-tert-butylstyrene, p-hexylstyrene, ρ-octylstyrene, p-
Alkylstyrenes such as nonylstyrene, p-decylstyrene, p-dodecylstyrene, phenylstyrenes such as p-methoxystyrene, arylstyrenes such as p-phenylstyrene, halogenostyrenes such as p-chlorostyrene, 3,4-dichlorostyrene, etc. Styrene and styrene derivatives such as ethylene, propylene, butylene, isobutylene, etc., vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc. vinyl halides: vinyl acetate, vinyl propionate, vinyl benzoyl, vinyl butyrate Vinyl esters such as: methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, dodecyl acrylate, (2-ethyl)hexyl acrylate, phenyl acrylate, α-chloroacrylate Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate,
Octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate,
Acrylic acid or methacrylic acid esters such as methacrylic phenyl, methacrylic dimethylaminoethyl, diethylaminoethyl methacrylate: acrylonitrile,
Methacrylonitrile, acrylic acid or methacrylic M derivatives of acrylamide acid, vinyl ethers such as copinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone;
Examples include N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and vinylnaphthalene.

A preferable heat-melting matting agent in the present invention is a copolymerization of two or more of these monomers and has a glass transition point of 40°C or higher.
It is a copolymer with a temperature of 80°C or less. More preferably, it is a copolymer having a glass transition point of 70°C to 150°C.

Specific examples of these copolymers (Tg is calculated using the formula for Tg of random copolymers) include styrene:butyl acrylate = 90:10 (vt%) (T (783°C
), Nibutyl acrylate-80:20 (w
t%) (T!I+ 71°C), methyl methacrylate:
Methacrylic acid = 50:50 (wt%) (79157°C
), methyl methacrylate: methacrylic (T (1177°C), methacrylonitrile: methacrylic acid - 80:20 (wt%) (T! 140°C), more preferable examples include styrene: methacrylic acid = 8
0:20 (wt%) (T! 120°C), vinyl chloride: methacrylic acid = 60:40 (wt%) (T! 129°C),
Poly °C-butyl acrylate acrylamide = 60
: 40 (wt96) (TlJ 129°C), styrene:acrylamide-50: 50 (wt%) (
T (1130°C), vinyl alcohol: methacrylic acid =
55:451t%) (Tl3138°C).

Another preferable heat-melting matting agent in the present invention is a polymer having a glass transition point of 4.
It is a homopolymer with a temperature of 0°C or more and 180°C or less. More preferably, it is a homopolymer having a glass transition point of 70°C or higher and 150°C or lower. Specific examples of these homopolymers include poly-4-bromostyrene (TC118°C), poly-
term-butylstyrene (Tg 130°C), poly-4
-Carboxystyrene (Tgll, 3°C), poly-2-
Hydroxymethylstyrene (TO160℃), poly-2
-Phenoxycarbonylstyrene cyclohexylethylene (random polymerization T! 1120℃
), poly-Nt-butylacrylamide (128°C)
, poly tert-butyl acrylate (7973°C)
, poly tert-butyl methacrylate (random,
Tg118℃), polyphenyl methacrylate (Tg1
10℃), polymethylchloroacrylate (70140
℃), poly tert-7 toxyethylene ("[88℃
), poly-4-tert-butylbenzoylethylene (
T (1104°C), polymethachloronitrile (To12
0°C), polytert-butoxycarbonylaminoethylene (Tl11120°C>, etc.).More preferable specific examples include polyvinyl alcohol (T(120°C)).
85°C), polyacrylic I (Tgioe°C), poly-
Examples include 4-acetylstyrene (T (1116°C)), polymethyl methacrylate (Tl 11105°C), polyvinyl chloride (Tl 181°C), polystyrene (Tg 100°C), and the like.

In the present invention, the addition amount of the heat-melting matting agent is 1 for the photosensitive material.
10IIIQ to 2.09 per 12, preferably 20f
fllll~1.0g.

The average particle size of the heat-melting matting agent in the present invention is 0.5μ
-10μ, preferably 1.0μ-6μ.

The average particle size here refers to the diameter in the case of spherical particles, and in the case of particles with shapes other than cubic or spherical, the average value of the diameter when the projected image is converted into a circular image of the same area. , the individual particle size is ri, and the number is ni, defined by the following formula.

As a specific measuring method, the method described in Japanese Unexamined Patent Publication No. 59-29243 can be used.

In the present invention, two or more types of heat-melting matting agents may be used in combination.

The heat-melting matting agent in the present invention is contained in the heat-developable photosensitive material, and is particularly preferably contained in the protective layer. Protection III here refers to the outermost layer during coating in the manufacturing process and the outermost layer of the completed photosensitive material, especially by incorporating a heat-melting matting agent into the protective layer.
11. A heat-developable photosensitive material can be obtained which has good adhesion resistance and antistatic properties during manufacturing and storage, and has excellent image quality after heat development. Furthermore, in the case of a diffusion transfer type heat-developable color photosensitive material,
Due to the reduction in the matt properties of the surface of the photosensitive material during heat development,
It is an object of the present invention to provide a diffusion transfer type heat-developable color photosensitive material that has excellent transfer image quality due to improved adhesion to an image receiving member. Another effect of the peel-off method is that the peelability between the photosensitive material and the image-receiving member after heat development is improved.

In addition, in the present invention, various conventionally used matting agents other than the present invention can be used within a range that does not impair the effects of the present invention.

Various additives used in the photographic field can be used in the protective layer of the present invention. The additives include slip agents, organic fluoro compounds (especially fluorosurfactants),
Antistatic agents, ultraviolet absorbers, high-boiling organic solvents, antioxidants, hydroquinone derivatives, polymer latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), organic Examples include silver salt particles and non-photosensitive silver halide particles.

Examples of the slippery agent used in the protective BF2 of the present invention include solid paraffin, oil, surfactant, natural wax, synthetic wax, etc. Specifically, French Patent No. 2,
180,485, British Patent No. 955,061, 1
, No. 143,118, No. 1,270,578, No. 1,
No. 320.564, No. 1,320,757, JP-A-4
No. 9-5017, No. 51-141623, No. 54-1
No. 59221, No. 56-81841, Research Disclosure
e) 13969, U.S. Patent No. 1,263,72
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
@, No. 3,121,060, No. 3,222,17
No. 8, No. 3,275,779, No. 3,489,567
No. 3,516,832, No. 3,658,573, No. 3,679,411, No. 3,870.521Q, etc. can be preferably used.

Preservation [5] of the present invention includes a high boiling point R solvent (for example, U.S. Pat. No. 2,322,027, U.S. Patent No. 2,322,027, 2,
No. 533,514, No. 2,882,157, Special Publication No. 4
No. 6-23233, British Patent No. 958,441, No. 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 photographic additives for various purposes.

Binders used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyl oxazoline, polyacrylamide,
One or a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin can be used.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecule i preferably 1,000 to 400,000), polyvinyl alcohol (molecule m 1,000 to 400,000),
100,000 (preferably 100,000) and polyoxazoline (preferably 1,000 to 800,000 molecular weight) alone or in combination of two or more of these binders are preferred, and gelatin alone or gelatin and the above polyvinylpyrrolidone, polyvinyl alcohol and poly Particularly preferred is a binder containing a hydrophilic polymer having good compatibility with gelatin, such as oxazoline. Gelatin is produced by lime treatment;
The gelatin may be subjected to acid treatment or ion exchange treatment, or may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatin.

The thickness of the a-retaining layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers.

Further, in order to increase film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using it in the protective layer, only the hardness of VTM can be made higher than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners, such as those disclosed in U.S. Pat. Nos. 3,057,723 and 3,396.
, No. 029, No. 4,161,407, JP-A-58-5
Hardeners described in No. 0528 and the like can be used. , Another way to control the degree of hardness for each layer is to
By containing a diffusible hardener (for example, a vinyl sulfone hardener) only in the protective layer, or by making the protective layer contain more than the photosensitive layer and rapidly drying after simultaneous multilayer coating, the protective layer can be hardened. The degree of hardness of the photosensitive layer can be made greater than that of the photosensitive layer.

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

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, or the like.

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, there are generally three heat-developable photosensitive materials with different color sensitivities, and each photosensitive material forms or releases dyes with different hues upon heat development.

Typically, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer.

The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. layer, a green-sensitive layer, a red-sensitive layer, or sequentially on a support,
There are configurations such as a green photosensitive layer, a red photosensitive layer, and a blue photosensitive layer.

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

Namely, dip method, roller method, reverse roll method, air knife method, doctor blade 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, l) A! Monodisperse silver halide grains can be obtained by the double jet method while keeping 11 constant. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc. According to a further preferred embodiment, silver halide emulsions having 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, more preferably monodispersity of 10% or less. It is.

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

Further, in the present invention, a silver halide emulsion containing internal latent silver halide grains whose surfaces have not been fogged in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592,250, No. 3,206.313, No. 3
, No. 317, 322, No. 3,511,662, No. 3
．． No. 447,927, No. 3,761,266, No. 447,927, No. 3,761,266, No.
As described in Nos. 3,703,584 and 3,736,140, silver halide grains have higher sensitivity inside the grains than on the surface thereof. 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 ALJC1 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 No. M3,277.757, i 3,44
7,927 and 3,531,291, or silver halide emulsions having silver halide grains containing multivalent ions, or U.S. Pat.
Silver halide emulsions whose grain surfaces are weakly chemically sensitized containing silver halide grains containing dopants as described in 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 N sensitization, gold-sulfur sensitization, and reduction m sensitization.

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

The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the clear silver salt. can. The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an N84 group, or a metal atom, and X represents Cf1.Br or I is represented by n, and when M is an H atom, and when LM is a metal atom, it represents the atomic plane.Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper,
Gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium,
Examples include germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, Odium, palladium, osmium, iridium, platinum, and cerium. )
, halogen-containing metal complexes (e.g., K2 Pt Cff1
s, K2 Pt Brs, HALI CJ! +
.

(NH4)2 1r C1s , (NH4)a Jr
cp,.

(NH4)2 Ru Cfs , (NH4)3 R
LI Cff14゜(NH4)2 Rh Cff1s
. , quaternary phosphonium halides such as tetraethylphosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g., iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinic acid) imide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N+, bromo N-methylbenzenesulfonamide, 1,3-dibromo-4,4- dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic 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 50 g) per layer per support 112.
It is preferable that it is, more preferably 0.1 (1 to
10 (l.

The heat-developable photosensitive material of the present invention may have 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 photosensitive material, and a heat-developable red-sensitive layer. can. Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer).

In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, can be obtained by adding various spectral sensitizing dyes to the halogenated misemulsion. 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, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent.

In addition to the above-mentioned basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbyl nucleus, thiazolinthione nucleus, 70 nonitrile nucleus, and pyrazolone nucleus. Good too.

These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination.

Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,3
A supersensitizing additive that does not absorb visible light, such as those described in Mei III, No. 90 and No. 2,937,089, can be used in combination.

The amount of these sensitizing dyes to be added is from 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide forming component. More preferably, 1X10-4 mol to 1X1
0" mole.

In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include 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 the specifications of U.S. Patent Nos. 3,330,633, 3,794,496, 4,105,451, etc. Tfi salts and silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolethio)acetate etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582,
No. 45-12700, No. 45-18416@, No. 45
-22185, JP-A-52-137321, JP-A-58-118638, JP-A-58-118639, and U.S. Patent No. 4,123,274, silver salts of imino groups are be.

Examples of silver salts of imino groups include silver benztriazole. The penztriazole silver may be substituted or unsubstituted. Typical examples of substituted benztriazole silver include, for example, alkyl substituted benztriazole silver (preferably substituted with a C22C1 or lower alkyl group, more preferably a 04 or lower alkyl group, such as methylbenztriazole silver, silver ethylbenztriazole, silver n-octylbenztriazole, etc.), silver alkylamidobenztriazole (preferably substituted with an alkylamide group of 022 or less,
For example, silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably substituted with an alkylsulfamoyl group of 022 or less), such as 4-(N,N-diethylsulf?moyl)penztriazole silver, 4-(N-
propylsulfamoyl)penztriazole silver, 4-
Silver salts of halogen-substituted benztriazoles (For example, 5-tribenztriazole silver, 5-triazole silver,
bromobenztriazole silver, etc.), alkoxybenztriazole silver (preferably a C22 or less alkoxy group,
More preferably, those substituted with an alkoxy group of 04 or less, such as 5-methoxybenztriazole silver, 5-
silver ethoxybenztriazole, etc.), silver 5-nitrobenztriazole, silver 5-aminobenztriazole, 4
-Human Oxybenztriazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver, 5-sulfobenztriazole silver and the like.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, urazole silver, urazol silver, 1.2
．． 4-Triazole silver, 1-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., and other mercapto compounds l! , for example 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole capto-4-phenyl-1.2.44 lyazole silver, 4
-hydroxy-6-methyl-1.3.3a,7-chitrazaindene silver and 5-methyl-7-hydroxy-1.
2.3.4.6-pentazaindene silver and the like.

Other silver complex compounds having a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, and imidase as described in U.S. Pat. No. 4,168,980. A silver salt of lynchion or the like is used.

Among the above organic silver salts, imino group silver salts are preferred,
Particularly preferred are silver salts of benzo and triazole derivatives, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives.

The Sil-containing 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 general method for preparing silver salts is to dissolve silver nitrate and raw organic compounds in water or an organic solvent and mix them, but if necessary, binders may be added, sodium hydroxide, etc. It is also effective to add an alkali to promote dissolution of organic compounds, or to use an ammoniacal silver 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;
-19241, 58-149046, 58
-149047, 59-124339, 5
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent such as those disclosed in No. 9-181345 and No. 60-2950, the present invention Examples of reducing agents used in
No. 61,270, No. 3,764.328, each town book, and R D No. 12146, No. 1
No. 5108, No. 15127 and JP-A-56-2
p-phenylenediamine type and p-7 minophenol type developing agents, phosphoramide phenol type, sulfonamide phenol type developing agents, sulfonamide aniline type developing agents, hydrazone type color developing agents, etc. described in Publication No. 1132 are used. I can do things. Also, U.S. Patent No. 3,342,599, U.S. Patent No. 3,749,492,
Color developing agent precursors described in JP-A-53-135628 and JP-A-54-79035 can also be advantageously used.

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

General formula (1) In the formula, R' and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R' and R2 are The ring may be closed to form a heterocycle. R', R'.

R and R are hydrogen atoms, halogen atoms, hydroxy groups,
represents an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R3 and R' and - 1 and R2 may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming a salt with an inorganic salt, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines; examples of cyclic amine compounds include lysine, quinoline, Examples include piperidine and imidazole. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. In addition, the salts of nitrogen-containing organic bases include the above-mentioned non-81M salts (for example, salt M salts, sulfates,
nitrates, etc.) are preferably used.

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

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

(R-5) (R-8) (R-9) (R-10) (R-11) (R-12') H CH.

C,H,NHCOCHl (R-17) C.F.

(R-20) (R-21) (R-23) The reducing agent represented by the above general formula (1) can be prepared by a known method,
For example, Houben Peil, Methoden der Organitsien Hemi, Band XI/2 (Houben
-Weyl, Methoden der Qrgan
ischen Chemie, Band X ■
/2) It can be synthesized according to the method described on 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 59-454445, 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-aminophenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2.6-dipromo 4-
(p-toluenesulfonamide) phenol, or polyhydroxybenzenes (e.g. hydroquinone,
tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-hydroxylhydroquinone, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxy naphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2
．． 2'-dihydroxy-1,1'-binaphthyl, 4.4
'-dimethoxy-1,1'-dihydroxy-2,2'-
binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylenebisphenols [e.g. 1.1-
Bis(2-hydroxy-3,5-dimethylphenyl)-
3゜5.5-1-limethylhexane, 1,1-bis(2
-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5
-di-tert-butylphenyl)methane, 2,6-methylenebis<2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol, α-7
enyl 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-ethylbencune, 2.2-bis(4-hydroxy-3,5-
dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)
propane, 2,2-bis(4-hydroxy-3,5-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

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

The usage of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide used, the type of ionic acid silver salt, the type of other additives, etc. Usually 0.01 per mole of photosensitive silver halide
-1500 mol, preferably 0.1-20
It is 0 mole.

Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-59-229556.

This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) of vinylpyrrolidone and one or more other monomers copolymerizable with vinylpyrrolidone. ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
0,000. Other polymers that can be copolymerized with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates,
Examples include vinyl thread additives such as vinyl imidazole, (meth)acrylamides, vinyl carbinols, and vinyl alkyl ethers, but at least 20% of the composition ratio (type mouth %, the same hereinafter) is polyvinylpyrrolidone. It is preferable. Preferred examples of such copolymers are those whose molecular size is from 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% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a molecular m s of 1,000 to 400,000, ooo to 400.0
A mixture of the 00 vinyl-rolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycomul 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.

The vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to spread it on a support and then crosslink it (including the case where the crosslinking reaction progresses by leaving it to stand).

The amount of binder used is usually 0.059 to 50 g per layer per support 112, preferably 0.1 g.
~10g.

In addition, the binder is 0.1% per dye-providing substance.
It is preferable to use ~10g, 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, US Pat. No. 3,347,675, US Pat.
229556, Japanese Patent Application No. 59-47787, etc., and those particularly useful in the present invention include, for example, urea derivatives (e.g., dimethylurea, ditechylurea, phenylurea). etc.), amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1.5-bentanediol, 1.6-bentanediol, 1,2-cyclohexanediol, penquerythritol, trimethylolethane, etc.) , or polyethylene glycols.

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

A water-insoluble solid thermal solvent is a compound that is solid in MffFA, but becomes liquid at high temperatures (60'C or higher, preferably ioo''C or higher, particularly preferably 130°C or higher and 250°C or lower), and is an inorganic/ Organic ratio (“Conceptual diagram of state”)
Zenkichi Koda, Sankyo Publishing, 1984) is 0.5-3.0,
Preferably 0.7-2.5, particularly preferably 1.0-2
．． It is a compound in the range of 0, and the solubility in water at room temperature is less than 1.

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

Exemplary Water-Insoluble Solid Thermal Solvent Melting Point (''C) Inorganic/Organic C (CfL)3CONH214f' 1.44
ecONH2128° 1.54 HO+C0NHz 161' 2.25CH
3+CONH2160° 1.34cH3o(/nN
HCOCH3130' 1.31B r+NHCOC
H3168° 1.02σNHCOCH3113 1
15° 1.34 melting point (C) Inorganic/organic CH300cONH2164-16Ashi 147 melting point (°
C) Inorganic/organic CH3!0zNHC2H4NH8OzeCH3168'
1.59 Many compounds used as water-insoluble solid heat solvents are commercially available, and can be easily synthesized by those skilled in the art.

The method of adding the water-insoluble hot solvent is not particularly limited, but it may be added by grinding and dispersing it using a ball mill, sand mill, etc.
There are methods such as adding it by dissolving it in an appropriate solvent, and adding it as an oil-in-water dispersion by dissolving it in a high boiling point solvent.
It is preferable to pulverize and disperse the solid particles using a ball mill, sand mill, etc. and add them while maintaining the solid particle shape.

Layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image-receiving layer of an image-receiving member, and the like, so that the respective effects can be obtained.

The addition port of the water-insoluble hot solvent is usually 10% to 500% by weight, preferably 50% to 300% by weight of the binder.

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 thermal phenomenon photosensitive 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. Pat. No. 3,438,776; polyalkylene glycols described in U.S. Pat. No. 3,666.477 and JP-A-5'1-19525; -CO-1-502 described in U.S. Pat. No. 3,667.959
There are non-aqueous polar organic compounds having a melting point of 20'C or higher, such as lactones having -1-80- groups.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829 and JP-A-53-24829;
Phenol derivatives described in No. 60223, JP-A-5
Carboxylic acids described in No. 8-118640, polyalcohols described in JP-A-58-198038,
Also included are sulnoamoylamide compounds described in JP-A-59-84236.

Further, a color toning agent known in heat-developable photosensitive materials may be added to the heat-developable photosensitive material of the present invention as a phenomenon accelerator.

As a color toning agent, for example, JP-A-46-4928, JP-A-46-4928;
No. 6-6077, No. 49-5019, No. 49-5
No. 020, No. 49-91215, No. 49-1077
No. 27, No. 50-2524, No. 50-67132, No. 50-67641, No. 50-114217,
No. 52-33722, No. 52-99813, No. 5
No. 3-1020, No. 53-55115, No. 53-76
No. 020, No. 53-125014, No. 54-15
No. 6523, No. 54-156524, No. 54i5
No. 6525, No. 54-156526, No. 55-40
No. 60, No. 55-4061, No. 55-32015, West German Patent No. 2,140,406, West German Patent No. 2,141,063, West German Patent No. 2,220,618, U.S. Patent No. 3, No. 847.61'2, No. 3,782,9
No. 41, No. 4.201,582 and JP-A No. 1983-
No. 207244, No. 57-207245, No. 58~
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dividrophthalazine, which are compounds described in the specifications of No. 189628 and No. 58-193541, etc. Dione, 2,3-
Dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl 2H-1,3-benzothiazine-2,4- (3H) dione, benzotriazine, mercapto triacy) and
Dimercabutotetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazole amino acid, etc., mixtures of one or more of these with imidazole compounds, and acids or acid anhydrides such as phthalic acid and naphthalic acid. Examples include mixtures of at least one of these and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

Antifoggants include, for example, U.S. Pat. No. 3,645;
Higher aliphatic compounds (e.g. behenic acid, stearic acid, etc.) described in No. 739, mercuric salts described in Japanese Patent Publication No. 47-11,113, N- as described in Japanese Patent Publication No. 51-47,419 Halogen compounds (e.g. N-halogenoacetamide, N-halogenosuccinimide, etc.), U.S. Pat.
700,457, 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, non-orange peroxides, persulfates, etc.) described in JP-A-50-101019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825. , 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-8112
No. 4, disulfide and polysulfide compounds described in No. 55-93149, rosin or diterpenes (e.g. abietic acid,
pimaric acid, etc.), a polymeric acid having a free carboxy group or sulfonic acid group described in No. 51-104338,
Thiazolinthione described in U.S. Patent No. 4,138,265, JP-A-54-51821, U.S. Patent No. 4,13
1,2,4-triazole or 5-mercapto-1,2,4-triazole described in No. 7,079, No. 55
Thiosulfinate esters described in No.-140833, 1.2.3.4-thiatriazoles described in old issue of No. 551423, No. 59-46641, No. 59-572
33, 59-5, the dihalogen compounds or trihalogen compounds described in 7234, and 59-11.
Examples include thiol compounds described in No. 1636.

In addition, other antifogging agents and stones are available in Japanese Patent Application No. 59-565.
Hydroquinone derivatives described in No. 06 (for example, G.C.
-octylhydroquinone, dodecanylhydroquinone, etc.) or the 14 hydroquinones described in Japanese Patent Application No. 59-66380, and benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) are preferably used in combination. I can do it.

Silver image stabilizers include U.S. Pat. No. 3,707,377.
The polyhalogenated organic oxidizing agent described in No. ms (for example,
tetrabromobutane, tribromoquinaridine, etc.), 5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768,071, monohalo compounds described in JP-A-50-119624 (e.g. 2 -bromo-2-tolylsulfonylacetamide, etc.)
, bromine compounds described in JP-A-50-120328 (e.g., 2-bromomethylsulfonylbenzothiazole,
2,4-bis(tribromomethyl)-6-methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, JP-A-50-1
Various monohalogenated organic antifoggants for silver halide emulsions, such as those described in No. 19624, can be used.

Other image stabilizers include U.S. Pat. No. 3,220;
No. 846, No. 4,082,555, No. 4,088
, No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, same.
15168, 15567, 15732, 15733, 15734, 15776, etc. Compounds that release basic substances by heat, called activator precursors, such as compounds that release basic substances by heat decarboxylation. Compounds such as guanidinium trichloroacetate, aldnamide compounds such as galactonamide, amine imides, 2-carboxycarboxamide, etc., which are released, as well as JP-A-56-130745 and JP-A-56-130745. Sodium phosphate base generator described in British Patent No. 2,079,
Compounds that generate amines through intramolecular nucleophilic reactions as described in No. 480, aldoxime carbamates as described in JP-A No. 59-157637, hydroxamic acid carbamates as described in JP-A No. 59-166943, etc.
No. 9-180537, No. 59-174830, No. 5
Examples include base release agents described in No. 9-195237 and the like.

Furthermore, U.S. Patent No. 3,3ot, sys@, 3,506
, No. 444, No. 3,824,103, No. 3,844
, No. 788, No. RD 12035, No. 18016, etc., irrithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds may be used for the purpose of stabilizing images. U.S. Patent No. 3,669,670, U.S. Patent No. 4,012,260,
No. 4,060,420, No. 4,207,392,
Nitrogen-containing organic bases called activator stabilizers and activator stabilizer precursors described in RD 15109, RD 17711, etc., such as the α-sulfonylacetic acid group of 2-aminothiazoline or trichloroacetic acid and acylhydrazine compounds, are used to accelerate development, respectively. It can be used for any purpose or for the purpose of stabilizing an image.

Also, for example, JP-A-56-130745 and JP-A-59-2
Developing may be done in the presence of a small amount of water as described in U.S. Pat.
, No. 550, etc., development may be carried out using hot steam, hot air containing moisture, or the like. In addition, compounds that release water into the heat-developable light-sensitive material, such as compounds containing crystal water such as those described in Japanese Patent Publication No. 44-26582, such as sodium phosphate decahydrate, ammonium alum diquadrate, etc., are added to the heat-developable photosensitive material. It may be included in the material.

In addition, various additives such as antihalation dyes, fluorescent whitening agents, 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 a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main component is SiO2 (silicon dioxide).
It is. Colloidal silica is described in, for example, Japanese Patent Application Laid-open Nos. 56-109336, 53-123916, 53-112732, and 53-100226. The amount of colloidal silica used is 0.00% by dry weight relative to the binder of the layer to be mixed and coated.
A range of 0.05 to 2.0 is preferable. .

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

Regarding the organic fluoro compounds used in the present invention, please refer to U.S. Patent No. 3,589,906, U.S. Pat.
Same 3. ．． No. 850,640, West German Patent Publication No. 1,942
, No. 665, Id. +, No. 961,638, Id. 2.124
No. 262, British Patent No. 1,330,356, Belbar Patent No. 742,680, and JP-A-46-7781.
No. 48-9715, No. 49-46733, No. 4
No. 9-133023, No. 50-99529, No. 50-
No. 11322, No. 50-160034, No. 51-43
No. 131, No. 51-129229, No. 51-1064
No. 19, No. 53-84712, No. 54-11133
No. 0, No. 56-109336, No. 59-30536
No. 59-45441 and Special Publication No. 47-9303
No. 48-43130, No. 59-5587, etc., and these compounds can be preferably used.

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

As the antistatic agent used in the present invention, British Patent No. 1
, No. 466.600, Research Disclosure t-
(Research 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, etc., and these can be preferably used.

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

As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, those described in JP-A-46-2784, U.S. Pat. No. 3,215,530, and U.S. Pat. No. 3,698,907), butadiene compounds (for example, , U.S. Patent No. 4
, 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794 and U.S. Pat. No. 3,352,681), benzotriazole compounds substituted with an aryl group (For example, Tokko Showa 3rd floor
No. 3-10466, No. 41-1687, No. 42-2
No. 6187, No. 44-29620, No. 48-4157
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. 4,22
No. 0,711, No. 4,323,633, Research
Disclosure (Research[) isclo
22519), benzoxidol compounds (e.g., those described in U.S. Pat. No. 3,700.455), cinnamate ester compounds (e.g., those described in U.S. Pat. No. 3,705,805, U.S. Pat. 3.707
．． No. 375, as described in JP-A No. 52-49029)
can be mentioned. Additionally, U.S. Patent No. 3,499
, 762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (e.g., α-naphthol cyan dye-forming couplers) and ultraviolet absorbing polymers (e.g., JP-A-58-1119
No. 42, No. 178351, No. 181041, No. 59
- No. 19945, No. 23344, those described in the gazette)
etc. can be mentioned.

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

Hardening agents used in the present invention include aldehyde-based and aziridine-based hardeners (for example, Pa Report, 19.921, U.S. Pat. No. 2,950,197, U.S. Pat. No. 2,964,40).
No. 4, No. 2,983,611, No. 3,271,1
75, Japanese Patent Publication No. 46-40898, and Japanese Patent Publication No. 50-91315), isoxazole series (for example, those described in U.S. Patent No. 331,609-M. ), epoxy-based (e.g. U.S. Patent No. 3)
, 047,394, the specifications of West German Patent No. 1,085,663, British Patent No. 1,033. Report 19,920, West German Patent No. 1,100,942, West German Patent No. 2,337.412, West German Patent No. 2,545,722, West German Patent No. 2,635,518,
No. 2.742,308, No. 2,749,260, British Patent No. 1,251.091, Patent Application No. 1974-5423
No. 6, No. 48-11099.6, U.S. Patent No. 3,5
No. 39,644 and No. 3,490,911>, acryloyl type (for example, those described in the specifications of JfI No. 1987-27949 and U.S. Patent No. 3,640,720); (described in US Pat. No. 2,938,892, US Pat. No. 4,043,8
No. 18, Specifications of No. 4,061,499, Special Publication No. 4
6-38715, Japanese Patent Application No. 4915095), triazine type (for example, West German Patent No. 2
, 410,973, 2,553,915, U.S. Patent No. 3,325,287, and JP-A-1988-1
2722), other maleimides,
Acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardeners can be used alone or in combination. As a useful combination technique, for example, West German Patent No. 2,
No. 447,587, No. 2,505,746, No. 2,5
No. 14,245, U.S. Patent No. 4,047,957, U.S. Pat. No. 3,832,181, U.S. Pat.
No. 62, No. 52-127329, Special Publication Sho 4g-323
Examples include combinations described in each publication of No. 64.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a polymeric hardener can be used in the non-photosensitive layer (eg, lower layer II, intermediate layer, protective layer, etc.).

Examples of the polymeric hardener used in the present invention include polymers having aldehyde groups (e.g., acrolein copolymers, etc.) described in U.S. Pat. No. 3,396,029.
, U.S. Pat. No. 3,362,827, Research Disclosure No. 17333 (197B>, etc.), and U.S. Pat. No. 3,623.
, No. 878, Research Disclosure p-16725 (1978)
, U.S. Pat. No. 4,161. lN7, JP-A-54-6
Polymers having an active vinyl group or a group that can be a precursor thereof, as described in JP-A No. 5033 and JP-A No. 56-442524, and polymers having an active ester group, as described in JP-A-56-6684-1, etc. It will be done.

In the thermal phenomenon 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 layer, 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 polymethyl acrylate, polyethyl acrylate, polylobyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of vinylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. , 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 μm
~0.2 μm. The polymer latex used has a dry weight ratio of 0.0 to the binder of the layer to which it is added.
3 to 0.5 is preferred.

In the heat-developable photosensitive material of the present invention, various interfaces are added to the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving coating properties. Activators can be used.

The surfactant used in the present invention may be any of anionic, cationic, amphoteric and nonionic surfactants.

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N
- Carboxy groups, sulfur groups, phosphor groups, sulfuric acid esters such as acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphoric acid esters, etc. Those containing an acidic group such as a group or a phosphoric acid ester group are preferable.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Preferred are heterocyclic quaternary ammonium salts such as gerridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.

Examples of amphoteric surfactants include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or fAi
! i2 esters, alkyl betaines, amine oxides, etc. are preferred.

Examples of nonionic surfactants include saponin (steroids), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl 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.

In addition, it is necessary to add 0.0% to the layer to be added using a silver recess.
The range of 02 to 3 (1/i' is preferable).

In the heat-developable photosensitive material of the present invention, for the purpose of improving film properties, the heat-developable photosensitive F a3 and/or non-photosensitive layers (undercoat layer, intermediate layer, protective layer, etc.) are added with, for example, JP-A-51-1-1. 10
Vinyl polymers having carboxyl or sulfo groups as described in No. 4338 can be included.

The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in terms of dry ml ratio to the binder of the layer to which it is added.

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

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 (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are further classified as follows.

Coupling dye Coupling dye-releasing compound
The dye-providing substances in each of the forming compounds will be further explained.

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

General formula (2) % formula % In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of the photosensitive silver halide and/or the organic silver salt used as necessary. , Dy
e is a diffusible dye residue.

As a specific example of the above-mentioned reducible dye-releasing compound, JP-A No. 5
No. 7-179840, No. 58-116537, No. 59
-6134, 59-65839, 59-710
No. 46, 59-874! No. 59-88730,
59-123837, 59-16!54, 5
No. 9-165055, the following compounds are listed, for example.

Below is a blank space, Exemplary dye-donor substance O QC, 6H3! ('I (Ju16[, [n) 0C16H33 ■ e [phase] ■ O As another reducing dye-releasing compound, for example, general formula (3)
Examples include compounds represented by:

In the formula, AI and A2 each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye represents Dy represented by the general formula (2).
It is synonymous with e. Specific examples of the above compounds are given in JP-A-59-1
This is shown in Japanese Patent No. 24329.

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

General formula (4) % Formula % In the formula, CI]+ is a 11 (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a 2flli bond. The bond between Cp+ and J is cleaved by reaction with the oxidized form of the reducing agent. nl represents O or 1, and Dye represents general formula (2)
It has the same meaning as defined in . In addition, CD+ 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), or a hydrophilic group such as a sulfo group or a carboxy group, or 8 or more (more preferably 12 or more) carbon atoms and a sulfo group,
It is a group that also has a hydrophilic group such as a carboxy group. Another particularly preferred ballast group can include polymer chains.

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

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

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

The molecular weight of the coupler residue represented by C1]2 is preferably 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 the same group are preferred, and polymer chains are more preferred.

As a coupled dye-forming compound having this polymer chain, mono6c, aHu(
n) Polymers having repeating units derived from one monomer are preferred.

General formula (6) % formula %) In the formula, C1)2. F has the same meaning as defined in general formula (5), Y represents an alkylene group, arylene group, or aralkylene group, 2 represents O or 1, and Z represents 2
filli, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupled dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-1243
No. 39, 59-181345 @, 60-2950
No., Patent Application No. 59-179657, No. 59-1f316
No. 04, No. 59-1132506, No. 59-1825
It is described in each specification of No. 07, and examples thereof include the following compounds.

Margin below Exemplary dye-donor substances OCRC14H20 " OOH [phase] polymer PM-1 CH2COOH PM-3CH3 M-4 CH.

M-5 H x: 60% by weight y: 40% by weight M-6 0Hy・50% by weight M-7 CH3 M-8 NHCOCH2 H In the above general formulas (4), (5) and (6), Cp
More specifically, the coupler residue defined by + or Cp2 is preferably a group represented by the following general formula.

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

These substituents are selected depending on the purpose of CD+ and Cp2, and as mentioned above, in Cpl, one of the substituents is preferably a ballast group, and in C1)2, it is preferable to increase the diffusibility of the dye formed. Preferably, the substituents are selected so that the molecular weight is 700 or less, more preferably 500 or less.

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

General formula (17) In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring),
R represents an alkyl group or a hydrogen atom, and represents -N-. ) or -3O2-, "represents O or 1, Dye
is the same as that defined by the general formula (2).Specific examples of this compound are given in JP-A-59-166954 and JP-A-59-166954.
It is described in specifications such as No. 154445, and includes, for example, the following compounds.

Below are examples of dyes/donors in the margin ■ CHl ■ 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
/, fill, E, DyeG; are synonymous with those defined in general formula (17). Specific examples of this compound are described in the specifications of JP-A-59-124327 and JP-A-59-152440, and include the following compounds.

Below is an example of a dye-providing substance in the margin.
Examples include compounds represented by (1).

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

Specific examples of this compound are described in JP-A-59154445 and the like, 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 such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes.

These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in
Chelatable dye residues described in No. 48765 and No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. The use m is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination of two or more, whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more types, etc. It may be determined accordingly, but for example, the number of times of use is 0.005Q to 50g per bottle, preferably 0.
．． 1+] to 10 g can be used.

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 a suitable polymer (eg, gelatin, polyvinyl butyral, polyvinyl and lolidone, etc.).

The heat-developable photosensitive material of the present invention usually has a temperature of 80°C to 20°C after imagewise exposure.
1 at a temperature range of 0°C, preferably 100°C to 170°C.
It is developed by simply heating for 1.5 seconds to 120 seconds, preferably 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development and heating. Alternatively, the transfer may be performed by supplying water, bringing the film into close contact with the film, and further heating if necessary. Also, before exposure, 70℃~18℃
Preheating may be performed in a temperature range of 0°C. In addition, as described in Japanese Patent Application Laid-open No. 60-143338 and Japanese Patent Application No. 60-3644, in order to improve mutual adhesion, the photosensitive material and image receiving member are heated at 80°C to 250°C immediately before thermal development transfer. Each may be preheated at different temperatures.

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. In general, light sources used in 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 drum, passing through a high-temperature atmosphere, etc. Alternatively, high-frequency heating may be used, or furthermore, a conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or on the image receiving member for thermal transfer, and Joule heat generated by energization may be utilized. You can also do it. There are no particular restrictions on the heating pattern, and preheating is required.
Although methods such as heating again after heating, continuously rising, falling, or repeating heating at a high temperature for a short time or at a low temperature for a long time, and even discontinuous heating are possible, a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The image-receiving layer of the image-receiving member that can be effectively used in the present invention includes:
It is sufficient that the polymer has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, for example, a polymer containing a tertiary amine or a quaternary ammonium salt, as described in US Pat.
．． Those described in No. 709,690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polyacrylate-N,N,N-)-ly-n-hexyl-N-gonyl-benzylammonium chloride is 1:4 to 4:1, preferably 1. :1.

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

Another useful dye-receiving material is JP-A-57-2072.
The glass transition temperature described in No. 50 etc. is 40'C1:1
．． Above, those formed of heat-resistant organic polymeric substances of 250° C. or less can be mentioned.

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

As an example of the heat-resistant organic polymer substance, one molecule is 92.0
00 to 85,000 polystyrene, polystyrene derivatives having substituents having 4 or less carbon atoms, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral. , polyvinyl chloride, chlorinated polyethylene, dichlorobutylene, polyacrylonitrile, polyN, IN-dimethylacrylamide, polyacrylate with p-cyanophenyl, pentachlorophenyl and 2,4-dichlorophenyl groups, polyacrylchloro Acrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl 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 7t'tates. In addition, Polymer Handboo Second Edition (edited by G.I. Brandrup E.H. Inmargate), John Wiley & Sons, (Polymer Handboo
k 2nd ed, (J.

Also useful are synthetic polymers with glass transition temperatures of 40° C. or lower, as described in John Wiley & John Brandrup, E. H., Immergut (Eds.), John Wiley & John Wiley & Sons (eds.). These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types as a copolymer.

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

A particularly preferable image-receiving layer is JP-A-59-22342
The layer made of polyvinyl chloride described in No. 5 and JP-A No. 6
The layer consisting of polycarbonate and a plasticizer described in Japanese Patent No. 0-19138 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 electron beam curable resin compositions containing pigments are coated and cured, supports on which coating layers containing pigments are provided, etc. can be mentioned.

In particular, an electron beam curable resin composition containing a pigment was applied onto paper and cured. If the support has a pigment coating layer directly on the support or paper, and an electron beam curable resin composition is applied and cured on the pigment coating layer, the resin layer itself can be used as an image receiving layer. It can be used as is as an image receiving member.

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

The image-receiving layer of the image-receiving member can also be formed into a type that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. Further, after imagewise exposure and uniform heat development of a heat-developable color light-sensitive material, a dye image released from or formed from a dye-providing substance can be transferred by overlapping a layer and heating at a temperature lower than the development temperature.

[Examples] Specific examples will be described below, but the present invention is not limited thereto.

Example-1 <Preparation of organic silver salt dispersion> 28.80% of 5-methylbenzotriazole silver obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent and poly(N- vinylpyrrolidone) 16. Disperse O(] with an alumina ball mill,
The pH was set to 200t12.

[Preparation of silver iodobromide emulsion] At 50°C, JP-A-57-92523;
B of aqueous solution 500112 containing 11.6 g of potassium iodide and potassium bromide 1309 in solution A prepared by dissolving 20 g of ossein gelatin and distilled water 10001Q and ammonia using the mixing and stirring method shown in the specification of No. 92524.
Aqueous solution containing liquid, 1 mole of silver nitrate, and ammonia 5
Solution C of 0 (hR) was added at the same time while keeping AIJ and pH constant. Furthermore, by controlling the addition speeds of Solution B and Solution C, a core emulsion with a silver iodide content of 7 mol %, regular hexahedral grains, and an average grain size of 0.25 μm was prepared. Next, in the same manner as above, a shell of silver halide containing 1 mol % of silver iodide was coated to form a regular hexahedral grain with an average grain size of 0.
A core/shell silver halide emulsion of 3 μm (shell thickness 0.05 μm) was prepared. (The monodispersity was 8%.) The above emulsion was washed with water and desalted to give a yield of 700. I got Q.

Furthermore, the silver iodobromide emulsion prepared above was treated as follows.
A red-sensitive silver halide emulsion was prepared.

a) Pre-adjustment of red-sensitive silver iodobromide emulsion Filled silver iodobromide emulsion 700 d4-hydroxy-6-methyl-1°3.3a,7tetrazaindene 0.4g gelatin
3.2g Sodium thiosulfate 10mg Sensitizing dye below Methanol 1
% solution 01g Distilled water 1200iN Sensitizing dye (a) b) Preparation of green-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700m+24-
Human Ooxy-6-methyl-1゜3.3a,7-titrazainde', /0,4i;1
Gelatin 32g Sodium thiosulfate 10mg Sensitizing dye shown below Methanol 1% Liquid distilled water 1200d Sensitizing dye (b) C) Preparation of blue-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700iQ4-human Oxy-6-methyl- 1゜3.3a, 7-tet, lazainde: / 0.4Q Gelatin 320 Sodium thiosulfate 10mg The following sensitizing dyes 1% methanol solution 80.12 Distilled water 1200d Sensitizing dye (C) ]3 Dye-donor dispersion > Exemplary polymeric dye-donor substance (PM-7) 35.5a
, and 5.00 g of the following hydroquinone compound were dissolved in ethyl acetate 20Qi12, and Alkanol
, 5Q was mixed with gelatin aqueous solution 720i12 and dispersed with an ultrasonic homogenizer, and after distilling off vinegar and ethyl, the solution was adjusted to DH5.5 to obtain 795M1'.

Hydroquinone compound H <Reducing agent dispersion> The reducing agent (R-11) 23.3Q, the following development accelerator 1.10 g 1 poly(N-vinylpyrrolidone)> 14.
h, Dissolve the following fluorine-based surfactant o, sog in water,
The pH was set to 5.5 and the pH was set to 250.

Surfactant (thermally developable photosensitive material-1) 12.5 ml of organic silver salt dispersion, red-sensitive silver iodobromide emulsion 6.
00I, 39.8 uf of dye-donor dispersion and 12.5 uf of reducing agent dispersion were mixed, and then a hardening agent solution (tetra(vinylsulfonylmethyl)methane and taurine were reacted in a ratio of 1:1 (weight ratio)). and phenylcarbamoylated gelatin 1
% aqueous solution to give 3% tetra(vinylsulfonylmethyl)methane. ) 2,5
0iJ2, polyethylene glycol 300 as heat solvent
(Kanto Chemical) 3.80! 1] was added, and then coated on a photographic polyethylene terephthalate film with a thickness of 180 μm that had been undercoated so that the silver opening was 1.76 LJ/12.

Furthermore, a gelatin protective layer containing a small amount of a surfactant and a hardening agent was provided thereon, and a heat solvent catalytic matting agent as shown in Table 1 was contained in the protective layer.

However, the gelatin content of the protective layer was 0.42 g/i'.

The average particle diameter of the above heat-melting matting agent is 1.0μ in the following margins.
And each additive mother is 60 m! ]/v'.

The evaluation of durable adhesiveness was carried out as follows.
A degree 30℃. In an atmosphere with a relative humidity of 70%, the emulsion surfaces of two sheets of each sample were left for one hour, and then the emulsion surfaces of the same type were brought into contact with each other, pressurized to 500 g/C1 for 10 seconds, and then isolated. The evaluation criteria were as follows.

Evaluation Evaluation criteria O→Can be isolated very easily without viscosity.

△→Although accompanied by viscosity, it can be easily isolated without causing film destruction on the emulsion surface.

×→ Adhesion occurs, and when the emulsion is peeled off, the film on the emulsion surface is destroyed, and one emulsion film is peeled off and becomes adhered to the other emulsion film.

The chargeability was evaluated by thermally developing a rapidly transported sample in an atmosphere with a temperature of 23° C. and a relative humidity of 20%, overlapping it with a receiver paper, and checking the amount of stitch marks that appeared on the receiver paper.

Evaluation Evaluation Criteria ○ Almost no stitch marks were generated △ Stitch marks were generated X Stitch marks were generated on the entire surface Next, the following image receiving member was prepared.

Image receiving member> Polyvinyl chloride (n=1.10
0, Wako Pure M) by applying a tetrahydrofuran solution,
The ratio of polyvinyl chloride was set to 12 (1/n2).

Samples A to G of the heat-developable photosensitive materials obtained were exposed to red light at 1,600C, M, and S through a step wedge, and then placed together with the image-receiving member in a heat development oven (Developer Module 277.3M). 150℃1
After carrying out thermal development transfer for a few minutes, the photosensitive material and image receiving member were quickly peeled off, and a magenta step wedge negative image was obtained on the polyvinyl chloride surface of the image receiving member.

By quantifying the transfer dye factor and the amount of residual dye in the same area of the image receiving member and photosensitive material for the portion where the maximum density of this image was obtained, the transferred color wood composition with respect to the total amount of dye produced was determined. The ratio was taken as the transfer rate.

Table 2 shows the evaluation results of the adhesive resistance, antistatic property, and transferability of Samples A to G.

Table 2 Comparative Sample 11 F had poor adhesion resistance and antistatic properties, so it was not possible to measure the transfer rate. On the other hand, Comparative Sample G has good adhesion resistance and antistatic properties, but has a low dye transfer rate due to poor adhesion to the image receiving element during thermal phenomena.

Sample A and BS using the heat-melting matting agent in the present invention
C, D, and E have excellent adhesion resistance and antistatic properties, and also have a high dye transfer rate. In this way, it was possible to improve both durable adhesiveness, antistatic properties, and transferability.

Example 2 A multilayer photosensitive material having the structure shown in Table 3 was prepared. Further, a gelatin protective layer was provided on this light-sensitive material, and a heat-melting matting agent as shown in Table 4 was contained therein. However, the gelatin of the protective layer was 0.42 g/f.

The following margin color anti-smudge agent 5C-1 (weight ratio) Filter dye Y F -,1 Heat solvent S-1 polyethylene glycol (average molecular weight 300) The same procedure was carried out except that the red light exposure in Example 1 was not changed to white light exposure. Table 5 shows the results of the evaluation of adhesion resistance, antistatic property, and transferability in exactly the same manner as in Example 1.

Similar to the results of Example 1, Samples H, I, and J using the heat-melting matting agent of the present invention had adhesion resistance, antistatic properties,
A heat-developable photosensitive material with improved transferability could be obtained.

Below is a margin table-5 Example-3 <Preparation of dye-donor dispersion liquid-2> Exemplary dye-donor substance <cD> 30. og to tricresyl phosphate 30. It was dissolved in Og and ethyl acetate 90.01Rt2, mixed with the same surfactant-containing gelatin aqueous solution 460- as in Example-1, dispersed with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added. 500TI
It was set as I2.

<Preparation of heat-developable photosensitive material-2> Red-sensitive silver iodobromide emulsion 40.01j2, organic silver salt dispersion 25.0112, dye-providing substance dispersion-2 50.0
Fuji, and then polyethylene glycol 300 (Kanto Kagaku) 4,20i) as a heat solvent, 1.5 mQ of a 10% by weight methanol solution of 1-phenyl-4゜4'-dimethyl-3-pyrazolidone, Example- Hardener 3 same as 1
．． 0Otff and 20.0 mL of a 10% water-alcohol solution of guanidine trichloroacetic acid were added onto a subbed photographic polyethylene terephthalate film with a thickness of 180 μm so that the amount of silver was 2.50Q/112. It was applied to.

Furthermore, a gelatin protective layer containing a small amount of hardening agent was provided thereon, and the organic fluoro compound and nonionic water-soluble polymer as shown in Table 5 were contained in the protective layer as in Example 2. . However, the gelatin of the protective layer is 0.
It was set to 42 g/f.

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

(1) Layer made of polyacrylic acid.

(7,00!+/f) (2) A layer consisting of cellulose acetate.

(4,00 liters/f) (3) Styrene and N-benzyl-N,N-dimethyl-N
- a layer consisting of a 1=1 copolymer of (3-maleimidopropyl)ammonium chloride and gelatin. (Copolymer 3.00!+/v', gelatin 3.00i1/
v' ) (4) Urea and polyvinyl alcohol (saponification degree 98%
). (Urea 4.0g/v', polyvinyl alcohol 3.OQ/f) The photothermographic material-2 was exposed to 3,200C, M, S through a step wedge, combined with the image receiving member-2, After heating at 150° C. for 1 minute in the same manner as in Example-1, the image receiving member was immediately peeled off. A yellow transparent image was obtained on the surface of the image receiving member.

Table 7 shows the results of adhesion resistance, antistatic property, and transfer rate measured in exactly the same manner as in Example 1.

Table 7 [↓ Similar to the results of Example 1, samples M, N, ○, P, and Q using the heat-melting matting agent of the present invention had improved durability, antistatic properties, and transferability. A heat-developable photosensitive material could be obtained.

Procedural formalities <Method> March 12, 1985 Patent Application No. 277771 2, Name of the invention Heat-developable photosensitive material 3, Relationship with the person making the amendment Patent applicant's address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Onegin 4, Agent 102 Address 4-1-1 Kudankita, Chiyoda-ku, Tokyo (Shipping date) February 25, 1986 61. Engraving of the entire statement of the specification subject to amendment (no change in content) 7. Contents of amendment

Claims (1)

[Claims] A photothermographic material characterized by containing a matting agent having a softening point of 40°C or more and 180°C or less.