JPH0685075B2 - Photothermographic material - Google Patents

Description

The present invention relates to a photothermographic material, and more particularly to a photothermographic material having a layer containing a polyoxazoline polymer having excellent compatibility with gelatin and the like. Is.

BACKGROUND OF THE INVENTION In recent years, a photothermographic material capable of performing a developing step by heat treatment has been attracting attention as a photosensitive material.

For such a photothermographic material, for example, Japanese Patent Publication No. 43-4
Nos. 921 and 43-4924 disclose the light-sensitive material comprising an organic silver salt, silver halide, a reducing agent and a binder, which is commercialized by 3M Company as dry silver.

Attempts have been made to improve the photothermographic material and obtain a color image by various methods.

For example, in U.S. Pat. Nos. 3,531,286, 3,761,270 and 3,764,328, etc., a method of forming a dye image by reacting an oxidized product of an aromatic primary amine developing agent with a coupler, Research. Disclosure (Re
search disclosure) 15108 and 15127, US Patent No.
A method of forming a dye image by reacting an oxidant of a reducing agent (hereinafter, also referred to as a developer and a developing agent) which is a sulfonamidephenol or a sulfonamideaniline derivative described in 4,021,240 with a coupler, British Patent No. 1,
As disclosed in Japanese Patent No. 590,956, a method of using an organic imino silver salt having a dye portion to release the dye in the heat developing portion to release the dye image on a separately provided image-receiving point, and JP-A-52
-105821, 52-105822, 56-50328, U.S. Pat. Nos. 4,235,957, and the like, and a method for obtaining a positive dye image by the silver dye bleaching method, and U.S. Pat. No. 3,180,731.
No., No. 3,985,565, No. 4,022,617, No. 4,452,883
Various methods have been proposed, such as a method for obtaining a dye image using the leuco dye disclosed in JP-A-59-206831 and the like.

However, these proposals relating to the above heat-developable color light-sensitive material make it difficult to bleach-fix a black-and-white silver image formed at the same time, and it is difficult to obtain a clear color image, and more complicated It was not yet satisfactory for practical use because it required post-treatment.

In recent years, as a color image forming method by a new type of heat development, JP-A-57-179840, 57-186744 and 57-198 have been proposed.
No. 458, No. 57-207250 and the like, a method of transferring a diffusible dye released by heat development to obtain a color image was disclosed.

Then, by further improving these methods, for example, a non-diffusible reducing dye-providing substance disclosed in JP-A-58-58543, 59-168439, etc. is oxidized to form a diffusible dye. Method of releasing the gas, JP-A-58-79247 and 59-17483
No. 4, No. 59-12431, No. 59-159159, No. 60-2950, a method of releasing a diffusible dye by coupling with an oxidant of a developing agent as disclosed in JP-A- Sho 58
-149046, 58-149047, 59-124339, 59-1813
No. 45, No. 60-2950, Japanese Patent Application No. 59-181604, No. 59-182506
No. 59-182507, No. 59-272335 and the like, a method using a non-diffusible compound which reacts with an oxidized product of a developing agent to form a diffusible dye, and further, JP 59-1
52440, 59-124327, 59-154445, 59-166954
Containing a non-diffusible reducing dye-donor substance that loses its ability to release a diffusible dye by oxidation, and a non-diffusible dye-donor substance that releases a diffusible dye when reduced. A method for doing so has been proposed.

The basic constitution of a color type photothermographic material for obtaining a color image by these released or formed diffusible dyes is as follows.
It consists of a light-sensitive element and an image-receiving element, and the light-sensitive element basically comprises a light-sensitive silver halide, an organic silver salt, a reducing agent, a dye-donor substance,
It consists of a binder. In the present invention, only the photosensitive element is narrowly interpreted as a photothermographic material, and the image receiving element is referred to as an image receiving member.

The photothermographic material is a material for obtaining a dye image by transferring the released or formed diffusible dye onto an image-receiving layer of an image-receiving member provided on the same support or on another independent support. In view of the sharpness and stability of the image, it has been improved in many points as compared with the conventional heat-developable color photosensitive materials.

However, it cannot be said to be sufficient as a whole, and there are the following problems.

Gelatin has hitherto been used as a binder for the photosensitive layer of a heat-developable light-sensitive material, but it has the drawback of poor heat developability because it is not thermoplastic. In particular, when gelatin is used as the binder of the photosensitive layer of the transfer type photothermographic material, the dye permeability is poor. In order to improve this, there is a method in which gelatin is mixed with polyvinyl alcohol, polyvinyl pyrrolidone, or polyvinyl butyral. According to this method, the heat developability and the dye permeability are slightly improved as compared with the case where only gelatin is used, but it is still insufficient, and the compatibility with the above-mentioned polymer mixed with gelatin is poor, so that in the transfer type. Transfer unevenness is likely to occur.

Generally, three layers of full-color light-sensitive materials are layered.
It is common to have an intermediate layer separating the photosensitive layers in addition to the photosensitive layers sensitive to different types of spectral sensitivity regions.
In a normal color light-sensitive material, the same gelatin as that of the emulsion layer is used in consideration of the permeability of an alkaline aqueous solution, the set coatability and the like. However, in the intermediate layer of the transfer type photothermographic material, since the dye is diffused in the film overlaid in the substantially water-free state, a film having good permeability of the released or formed dye is required. .

Even in the intermediate layer, gelatin is advantageous from the viewpoint of high uniformity of the film because simultaneous multi-layer coatability with the photosensitive layer and set coating are possible, but the release of the dry film or the permeability of the formed dye is difficult. Since it is low in the case of gelatin, it has been proposed to use gelatin in combination with other polymers as described in Japanese Patent Application No. 58-223274.

In particular, an attempt has been made to improve the permeability of the dye while maintaining the above advantages of using gelatin by using gelatin in combination with other water-soluble thermoplastic polymer such as polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone. However, it is desired that uniform coating is difficult and that the dye permeability is further improved.

Further, it is generally known to provide a protective film on a photosensitive material. Also in the photothermographic material, a protective film is coated for the purpose of preventing scratches, improving developability, and preventing smoke emission.

Further, it is generally known to provide a protective film on a photosensitive material. Also in the photothermographic material, a protective film is coated for the purpose of preventing scratches, improving developability, and preventing smoke emission. When gelatin, for example, is used as the protective film, it is characterized in that it can be applied uniformly, but it hinders the thermal transfer of the released dye and is not very effective for the stickiness of the film. Further, polyvinyl alcohol and the like have little inhibition of the transferability of the dye and have a considerable performance as a protective film, but are inferior to gelatin in coating property. Gelatin has good coating properties because it has the property of being set-coatable.
In general, gelatin and other water-soluble polymer are mixed and applied.

However, even if gelatin and polyvinyl alcohol are mixed and applied, it is difficult to form a very uniform film and satisfactory performance cannot be obtained.

The present situation is that none of the mixed films of other water-soluble polymers and gelatin can sufficiently achieve the above object.

[Object of the Invention] In view of the above-mentioned conventional drawbacks, the present invention contains a polyoxazoline-based polymer having excellent compatibility with gelatin and the like in a binder of a photosensitive layer, an intermediate layer provided between photosensitive layers, or a protective film. However, it is an object of the present invention to provide a photothermographic material which has good heat developability and dye permeability, has no transfer unevenness, and has excellent coatability during production.

Another object of the present invention is to provide a novel binder composition having good heat developability in a photothermographic material.

[Constitution of Invention] The above object of the present invention has been achieved by a photothermographic material containing a polymer having a repeating unit represented by the following general formula (I).

General formula (I) In the formula, R represents an alkyl group (including a substituted alkyl group) or an aryl group (including a substituted aryl group).

[Specific Structure of the Invention] In the general formula (I), R represents an alkyl group or an aryl group each containing a substituent, and the alkyl group represented by R may be branched or linear.
Examples thereof include a methyl group, an ethyl group, a propyl group, an i-butyl group, and a dodecyl group. Of these, a lower alkyl group is preferable, and an ethyl group is more preferable. R
Examples of the aryl group represented by include a phenyl group and the like.

As the substituent of the substituted alkyl group for R, a halogen atom,
Examples thereof include an alkoxy group, an aryl group, an acyl group, a cyano group and an amino group. Moreover, examples of the substituent of the substituted aryl group of R include an alkyl group, an alkoxy group, and a halogen atom.

Preferred specific examples of the repeating unit represented by formula (I) of the present invention are shown below.

In the present invention, a preferred polymer is a homopolymer consisting of one type of repeating unit represented by the general formula (I), more preferably the general formula (I).
Is a homopolymer in which R is an alkyl group having 1 to 4 carbon atoms. Here, R is more preferably an ethyl group. That is, polyethyloxazoline is preferable.

The polymer of the present invention is preferably a homopolymer, but may be a copolymer. The copolymer is a copolymer containing two or more kinds of repeating units represented by the general formula (I), and examples thereof include a copolymer having the following structure.

These polymers of the present invention, based on generally known 2-alkyl (or aryl) -2-oxazoline monomer compounds, US Pat. Nos. 4,464,438, 4,474,928, and 4,
436,789, West German patent 3,321,891, JP-A-58-67749,
It can be synthesized according to the method described in JP-A-57-153048.

The polymer of the repeating unit represented by the general formula (I) can be obtained by using the 2-alkyl (or aryl) -2-oxazoline as a monomer compound. These monomer compounds are described in U.S. Pat.
It can be synthesized according to the method described in 029, West German Patent 3,224,880 and the like.

In the present invention, two or more polymers of the present invention having different compositions can be used in combination.

The weight molecular weight of the polymer of the present invention is preferably 1,000 to 800,000. More preferably, it is 5,000 to 200,000.

In the present invention, the addition amount of the polymer of the present invention is 0.02 part by weight or more, preferably 0.1 part by weight or more, relative to 1 part by weight of the other binder in the layer to be contained. It is also a preferable embodiment when the layer containing the polymer of the present invention contains no other binder. The most preferred embodiment contains gelatin as another binder, and the weight ratio of the polymer of the present invention to gelatin is 0.05 to 20, more preferably 0.1 to 1.
It is 0.

There is no limitation on the method of adding the polymer of the present invention, and there are a method of adding as a solution of water or an organic solvent, a method of pulverizing and adding a ball mill, a sand mill and the like.

The photothermographic material of the invention is preferably provided with a protective layer. Hereinafter, it is referred to as the protective layer of the present invention.

Various additives used in the field of photography can be used in the protective layer of the present invention. Examples of the additive include various matting agents, colloidal silica, sliding agents, organic fluoro compounds (particularly fluorine-based surfactants), antistatic agents, ultraviolet absorbers, high boiling organic solvents, antioxidants, hydroquinone derivatives, polymers. Examples thereof include latex, surfactants (including polymer surfactants), hardeners (including polymer hardeners), organic silver salt particles, non-photosensitive silver halide particles, and the like.

The matting agent used in the protective layer of the present invention is a fine particle of an inorganic substance or an organic substance, which is contained in the photothermographic material to increase the roughness of the surface of the photosensitive material to form a so-called matte. is there. A method of using a matting agent to prevent adhesion that occurs during production, storage, use, etc. of a light-sensitive material, and to prevent charging caused by contact, friction, or peeling between the same or different substances is known in the art. Is well known in. Specific examples of the matting agent include JP-A-50-46316
Silicon dioxide described in JP-A-53-7231 and JP-A-58-66937.
Alkali-soluble matting agents such as alkyl methacrylate / methacrylic acid copolymers described in JP-A No. 60-8894,
An alkali-soluble polymer having an anionic group described in JP-A-58-166341, a combination of two or more kinds of fine particle powders having different Mohs hardness described in JP-A-58-145935, and JP-A-58-147734.
Combination of oil droplets and fine particle powder described in JP-A-59-149356, combination of two or more spherical matting agents described in JP-A-59-149356, and fluorinated surfactant described in JP-A-56-44411. Combined use of matting agents, and British Patent No. 1,055,713, U.S. Patent Nos. 1,939,213, 2,221,873, 2,268,662, 2,3
22,037, 2,376,005, 2,391,181, 2,701,24
No. 5, No. 2,992,101, No. 3,079,257, No. 3,262,782,
No. 3,443,946, No. 3,516,832, No. 3,539,344, No. 3,5
91,379, 3,754,924, 3,767,448, JP-A-49-1
06821, organic matting agents described in 57-14835, West German Patent 2,529,321, British Patent 760,775, 1,
260,772, U.S. Pat.Nos. 1,201,905 and 2,192,241,
3,053,662, 3,062,649, 3,257,206, 3,3
No. 22,555, No. 3,353,958, No. 3,370,951, No. 3,411,90
No. 7, No. 3,437,484, No. 3,523,022, No. 3,615,554,
No. 3,635,714, No. 3,760,020, No. 4,021,245, No. 4,0
Inorganic matting agents described in JP-A-29-504, JP-A-46-7781, JP-A-49-106821, JP-A-51-6017, and JP-A-53-11.
6143, 53-100226, 57-14835, 57-82832
No. 53-70426, No. 59-149357, JP-B No. 57-9053, EP-107,378, and the like, matting agents having physical properties are preferably used.

In the protective layer of the present invention, the amount of the matting agent added is preferably 10 mg / 2.0 g, and more preferably ²⁰ mg to 1.0 g per 1 m ² . The particle size of the matting agent is preferably 0.5 to 10 μm, more preferably 1.0 to 6 μm.

You may use the said matting agent in combination of 2 or more type.

Examples of the sliding agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, and the like, specifically, French Patent No. 2,180,
465, British Patent Nos. 955,061, 1,143,118, 1,27
0,578, 1,320,564, 1,320,757, JP-A-49-50
No. 17, No. 51-141623, No. 54-159221, No. 56-81841,
Research Disclosur
e) 13969, U.S. Pat.Nos. 1,263,722, 2,588,765,
No. 2,739,891, No. 3,018,178, No. 3,042,522, No. 3,0
80,317, 3,082,087, 3,121,060, 3,222,17
No. 8, No. 3,295,979, No. 3,489,567, No. 3,516,832,
Those described in No. 3,658,573, No. 3,679,411, No. 3,870,521 and the like can be preferably used.

The protective layer of the present invention includes a high-boiling organic solvent (e.g., U.S. Pat.Nos. 2,322,027 and 2,533,514) for the purpose of improving film adhesion and brittleness, or improving slip properties.
No. 2,882,157, Japanese Examined Patent Publication No. 46-23233, British Patent No. 95
8,441, 1,222,753, U.S. Pat.No. 2,353,262,
3,676,142, 3,700,454, JP-A-50-82078, 51
-27921, 51-141623 and the like (for example, phthalic acid esters, phosphoric acid esters, fatty acid esters, etc.), amides (for example, fatty acid amides, sulfonic acid amides, etc.), ethers, alcohols And paraffins. ), Which may be emulsified and dispersed with an oily compound insoluble in water. Further, these oil droplets may contain a photographic additive according to various purposes.

Examples of the binder used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethylmethacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, gelatin and phthalated gelatin. The high molecular weight substances can be used alone or in combination of two or more.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecular weight 1,000 to 400,000 is preferable), polyvinyl alcohol (molecular weight 1,000 to 100,000 is preferable)
And a binder in which gelatin is used alone or in combination with gelatin and a hydrophilic polymer having good compatibility with gelatin such as polyvinylpyrrolidone and polyvinyl alcohol described above are particularly preferable. The gelatin may be lime-treated, acid-treated, or ion-exchanged, and may be ossein gelatin, pigskin gelatin, hide gelatin, or modified gelatin obtained by esterification or phenylcarbamoylation thereof.

The thickness of the protective layer of the present invention is also 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, for the purpose of increasing the film strength and preventing the film destruction, it is also preferable to make the hardness of the protective layer larger than that of the photosensitive layer. As a method of increasing the hardness of the protective layer to be larger than that of the photosensitive layer, that is, a method of controlling the hardness of each layer, there is a method of using a diffusion resistant hardener. By using the protective layer, only the hardness of the protective layer can be made higher than that of the photosensitive layer. Polymeric hardeners are known as diffusion-resistant hardeners, for example, U.S. Patent Nos. 3,057,723, 3,396,029, and 4,161,
Hardeners described in JP-A No. 407 and JP-A No. 58-50528 can be used.

As another method of controlling the dura degree for each layer,
A protective layer may be prepared by incorporating a diffusible hardener (for example, a vinyl sulfone-based hardener) only in the protective layer, or by setting the content of the protective layer to be larger than that of the photosensitive layer and performing simultaneous multi-layer coating and rapid drying. The degree of hardness of can be larger than that of the photosensitive layer.

The photothermographic material of the present invention basically comprises (1) a photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, and (4) a binder in one photothermographic layer. Contains,
Further, it is preferable to contain (5) an organic silver salt, if necessary. However, these do not necessarily have to be contained in a single photographic constituent layer. For example, the photothermographic layer is divided into two layers, and the components (1), (2), (4) and (5) are added. If the photothermographic layer on one side contains the dye-donor substance (3) on the layer on the other side adjacent to the photosensitive layer, two or more constituent layers can be formed if they can react with each other. It may be contained separately.

The heat-developable photosensitive layer may be divided into two or more layers such as a high-sensitivity layer and a low-sensitivity layer and a high-concentration layer and a low-concentration layer.

The photothermographic material of the invention has one or more photothermographic layers on a support. In the case of color, it generally has three heat-developable photosensitive layers having different color sensitivities, and in each photosensitive layer, dyes having different hues are formed or released by heat development. Usually, a yellow dye is combined with the blue photosensitive layer, a magenta dye is combined with the green photosensitive layer, and a cyan dye is combined with the red photosensitive layer, but the combination is not limited thereto. It is also possible to combine a near-infrared photosensitive layer.

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

The photothermographic material of the invention may be provided with a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a release layer in addition to the photothermographic layer.
For coating the heat-developable photosensitive layer and these non-photosensitive layers on a support, the same methods as those used for coating and preparing a general silver halide photosensitive material can be applied.

That is, there are methods and devices in the dip method, roller method, reverse, roll method, air knife method, doctor blade method, spray method, bead method, extrusion method, stretch flow method, curtain method and the like.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide. The photosensitive silver halide is
It can be prepared by any method such as a single jet method and a double jet method in the field of photographic technology. For example, by applying the method described in JP-A-54-48521, pA
Monodisperse silver halide grains can be obtained by the double jet method while keeping g constant. At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pH, pAg, temperature and the like. According to a further preferred embodiment, a silver halide emulsion having silver halide grains having a shell can be used. The silver halide grain having a shell can be obtained by using the method described above and using a silver halide grain having good monodispersity as a core and sequentially growing a shell on the silver halide grain.

The monodisperse silver halide emulsion referred to in the present invention means one in which the variation in the size of silver halide grains contained in the emulsion has a grain size distribution of a certain ratio or less with respect to the average grain size as shown below. . The standard deviation is easily found because the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of grains in which the photosensitive silver halide grains have uniform grain morphology and small variation in grain size is almost normal. ,
Relational expression When the breadth of the distribution is defined by, the breadth of the silver halide grains used in the present invention is preferably 15% or less, more preferably 10% or less. .

In addition, for example, JP-A-58-111933, JP-A-58-111934 and JP-A-58-111934.
-108526, Research Disclosure 22534, etc., having two parallel crystal faces,
And, each of these crystal faces is a grain having a larger area than other single crystals of this grain, and its aspect ratio, that is, the ratio of the diameter of the grain to the thickness of the tabular silver halide grain of 5: 1 or more, The silver halide emulsion consisting of

Further, in the present invention, a silver halide emulsion containing an internal latent image type silver halide grain whose surface is not previously fogged can be used. For internal latent image type silver halide in which the surface is not previously fogged, for example, U.S. Pat.
592,250, 3,206,313, 3,317,322, 3,511,6
No. 62, No. 3,447,927, No. 3,761,266, No. 3,703,584
No. 3,736,140, etc., the silver halide has a higher sensitivity inside the grain than at the surface of the grain. The method for producing a silver halide emulsion containing these internal latent image type silver halides is as described in the above-mentioned patent, for example, by first preparing AgCl grains and then adding bromide or a small amount of iodide thereto. Is added to cause halide exchange, or the central nucleus of chemically sensitized silver halide is coated with non-chemically sensitized silver halide, or chemically sensitized coarse grain emulsion and chemical sensitization Mixed or not chemically sensitized fine grain emulsion,
Many methods are known, such as a method of depositing a fine grain emulsion on a coarse grain emulsion. Further, a silver halide emulsion having silver halide grains containing a polyvalent metal ion described in U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291, or described in U.S. Pat.No. 3,761,276. A silver halide emulsion in which the grain surface of a silver halide grain containing a doping agent is weakly chemically sensitized, or has a laminated structure described in JP-A Nos. 50-8524 and 50-38525. Examples thereof include silver halide emulsions composed of grains, and silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549.

The photosensitive silver halide emulsion may be chemically sensitized by any method in the photographic art. As such a sensitizing method,
Various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization and reduction sensitization can be used.

The silver halide in the above light-sensitive emulsion may be coarse particles or fine particles, but the preferable grain size is about 0.001 μm to about 1.5 μm, and more preferably about 0.01 μm to about 0.01 μm. It is about 0.5 μm.

The light-sensitive silver halide emulsion prepared as described above can be most preferably applied to the heat-developable light-sensitive layer which is a constituent layer of the light-sensitive 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 on a part of the organic silver salt. . As the photosensitive silver salt forming component used in this preparation method, an inorganic halide, for example, a halide represented by MXn (wherein M represents an H atom, an NH ₄ group represents a metal atom, X represents Cl, Represents Br or I,
n is 1 when M is a H atom or NH ₄ group, and shows the valence when M is a metal atom. Examples of the metal atom are lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, and magnesium. , Calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium,
Molybdenum, tungsten, manganese, rhenium, iron,
Examples thereof include cobalt, nickel, rhodium, palladium, osmium, iridium, platinum and cerium. ),
Halogen-containing metal complex (eg K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuC
l ₄ , (NH ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ , (NH ₄ ) ₃ R
uCl ₆ , (NH ₄ ) ₂ RhCl ₆ , (NH ₄ ) ₃ RhBr _6, etc.), onium halides (for example, tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, Quaternary ammonium halides such as trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide, etc.), Halogenated hydrocarbons (eg, iodoform, bromoform, carbon tetrabromide,
2-bromo-2-methylpropane, etc., N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazide Non, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-
Bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc., and other halogen-containing compounds (eg triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromo) Ethanol, etc.) and the like.

These photosensitive silver halide and photosensitive silver salt-forming component can be used in combination in various methods, and the amount used is
The amount is preferably 0.001 g to 50 g, and more preferably 0.1 g to 10 g per 1 m ^{2 of the} support.

The photothermographic material of the present invention has a multi-layered structure as each layer having photosensitivity to blue light, green light and red light, that is, a photothermographic blue photosensitive layer, a photothermographic green photosensitive layer and a photothermographic red photosensitive layer. You can also Further, the photosensitive layer of the same color may 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 in each case are obtained by adding various spectral sensitizing dyes to the silver halide emulsion. You can

Representative spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hexianine, oxonol and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferable. Such a nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a condensed 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.

The merocyanine dye has, in addition to the basic nucleus, an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidian nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazoline thione nucleus, a malononitrile nucleus, and a pyrazolone nucleus. Good. 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 derivative,
Azaindene cadmium salt, organic sulfonic acid and the like, for example, supersensitizing additives which do not absorb visible light as described in the specifications of US Pat. Nos. 2,933,390 and 2,937,089 can be used in combination.

The addition amount of these sensitizing dyes is 1 × 10 ⁻⁴ to 1 mol per mol of the photosensitive silver halide or the silver halide-forming component. More preferably, it is 1 × 10 ^-4 mol to 1 × 10 ^-1 mol.

In the photothermographic 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 the organic silver salt used in the photothermographic material of the present invention include JP-B-43-4921, JP-A-49-52626, and JP-A-52-141222.
No. 53-36224, No. 53-37610, etc., and U.S. Pat.Nos. 3,330,633, 3,794,496, and 4,10
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle such as those described in each specification such as 5,451, such as silver laurate, silver myristate, silver palmitate, and stearin. Acid silver, arachidonic acid silver, behenic acid silver, α- (1-phenyltetrazolethio) acetic acid silver, etc., aromatic carboxylic acid silver, for example, silver benzoate, silver latarate, etc., JP-B-44-26582, 45- 12700, 45-18416
No. 45-22185, JP-A-52-137321, JP-A-58-1186
No. 38, No. 58-118639, U.S. Pat. No. 4,123,274 and the like, there are silver salts of imino groups.

Examples of the silver salt of an imino group include benztriazole silver. The benztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, alkyl-substituted benztriazole silver (preferably one substituted with an alkyl group having C ₂₂ or less, more preferably C ₄ or less,
For example, methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.),
Alkylamidobenztriazole silver (preferably C ₂₂
Those substituted with the following alkylamide groups, for example, acetamide benztriazole silver, propionamide benztriazole silver, iso-butylamide benztriazole silver, lauryl amide benztriazole silver, etc.),
Alkylsulfamoylbenztriazole silver (preferably substituted with an alkylsulfamoyl group having a C ₂₂ or less, for example, 4- (N, N-diethylsulfamoyl)
Benztriazole silver, 4- (N-propylsulfamoyl) benztriazole silver, 4- (N-octylsulfamoyl) benztriazole silver, 4- (N-decylsulfamoyl) benztriazole silver, 5- (N -Octylsulfamoyl) benztriazole silver, etc.), silver salts of halogen-substituted benztriazoles (for example, 5-chlorobenztriazole silver, 5-bromobenztriazole silver, etc.), alkoxybenztriazole silver (preferably C ₂₂ or less alkoxy) Groups, more preferably those substituted with a C ₄ or less alkoxy group, for example, 5-methoxybenztriazole silver, 5-ethoxybenztriazole silver, etc.), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4- Hydroxybenztriazole silver, 5-cal Boxybenztriazole silver, 4-
Examples thereof include sulfobenztriazole silver and 5-sulfobenztriazole silver.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1,2,4
-Triazole silver, 1H-tetrazole silver, 3-amino-
Silver salts of other mercapto compounds such as silver 5-benzylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, and silver phthalimide, for example, silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, and silver 2-mercaptobenzothiazole. , 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4
-Triazole silver, 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver and the like can be mentioned.

In addition, a silver complex compound having a stability constant of 4.5 to 10.0 as described in JP-A-52-31728, a silver salt of imidazoline thione as described in U.S. Pat. .

Among the above organic silver salts, silver salts of imino groups are preferable,
Particularly, a silver salt of a benzotriazole derivative, more preferably 5-methylbenzotriazole and its derivative, sulfobenzotriazole and its derivative, N-alkylsulfamoylbenzotriazole and its derivative are preferable.

The organic silver salt used in the present invention may be used alone or in combination of two or more kinds. The silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated product may be dispersed in the binder by a suitable means before use. Examples of the dispersing method include, but are not limited to, a ball mill, a sand mill, a colloid mill and a vibration mill.

Further, the method for preparing the organic silver salt is generally a method in which silver nitrate and a raw material organic compound are dissolved and mixed in water or an organic solvent, but a binder may be added if necessary, or sodium hydroxide or the like may be added. It is also effective to add an alkali to accelerate the dissolution of the organic compound or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is usually preferably 0.01 to 500 mol, and more preferably 0.1 to 1 mol, per 1 mol of the photosensitive silver halide.
~ 100 mol. Further, 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.

Dye-donor substances used in the photothermographic material of the present invention, for example, JP-A-57-186744, 58-79247,
58-149046, 58-149047, 59-124339, 59-
No. 181345, No. 60-2950 and the like, by coupling with an oxidant of a reducing agent as disclosed in, a dye-donating substance that releases or forms a diffusible dye,
Examples of the reducing agent used in the present invention include U.S. Pat.
No. 531,286, No. 3,761,270, No. 3,764,328, each specification, RD No. 12146, No. 15108, No. 15127 and p-phenylenediamine system described in JP-A-56-27132 and A p-aminophenol-based developing agent, a phosphoramidophenol-based developing agent, a sulfonamidephenol-based developing agent, a sulfonamideaniline-based developing agent, and a hydrazone-based color developing agent can be used. Also,
U.S. Pat.Nos. 3,342,599 and 3,719,492, JP-A-53-1
Color developing agent precursors described in 35628, 54-79035 and the like can also be advantageously used.

Particularly preferred reducing agents include reducing agents represented by the following general formula (1) described in JP-A-56-146133.

General formula (1) In the formula, R ¹ and R ² represent a hydrogen atom or an optionally substituted alkyl group having 1 to 30 carbon atoms (preferably 1 to 4), and R ¹ and R ² are ring-closed. A heterocycle may be formed. R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group or the number of carbon atoms which may have a substituent. It represents an alkyl group of 1 to 30 (preferably 1 to 4), and R ³ and R ¹ and R ⁵ and R ² may each be ring-closed to form a heterocycle. M represents a compound containing an alkali metal atom, an ammonium group, a nitrogen-containing organic base or a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (1) is an organic compound containing an inorganic salt and a nitrogen atom showing basicity capable of forming a salt, and an amine compound is mentioned as a particularly important organic base. Primary amines, secondary amines, tertiary amines, and the like are used as chain amine compounds, and pyridine, quinoline, and piperidine, which are prominent examples of typical heterocyclic organic bases, are used as cyclic amine compounds. , Imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine and amidine are also useful as chain amines. As the salt of the nitrogen-containing organic base, the inorganic acid salt of the above-mentioned organic base (for example, hydrochloride, sulfate, nitrate, etc.) is preferably used.

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

Next, preferable specific examples of the reducing agent represented by the general formula (1) are shown below.

Next, preferable specific examples of the reducing agent represented by the general formula (1) are shown below.

The reducing agent represented by the general formula (1) can be obtained by a known method,
For example, Houben Bale, Mesodden del Organischen Chemie, band XI / 2 (Houben-Weyl, Methoden
der Organischen Chemie, Band XI / 2) pg. 645-703.

Furthermore, even if two or more reducing agents are used at the same time, it is also possible to use the black-and-white developing agents described below together for the purpose of improving the developability.

Further, the dye-donor substances used in the present invention include JP-A-57-179840, JP-A-58-58543, JP-A-59-152440, and JP-A-59-1.
In the case of compounds that release dyes by oxidation as shown in 54445, compounds that lose dye releasing ability by oxidation, compounds that release dyes by reduction (or simply obtain only silver image) In the case), a developing agent as described below can also be used.

For example, phenols (for example, p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [for example, 4-benzene Sulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4- (p-toluenesulfonamido) phenol, etc.], or polyhydroxybenzenes (eg, Hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc., naphthols (for example, α-naphthol, B-naphthol, 4-aminonaphthol, 4-methoxynaphtho). Etc.), hydroxybinaphthyls and methylenebisnaphthols [eg,
1,1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,
6-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, 4,4'-dimethoxy-1,1'-dihydroxy-2,2 '
-Binaphthyl, bis (2-hydroxy-1-naphthyl)
Methane, etc.], methylenebisphenols [eg 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl) -3,
5,5-trimethylhexane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,
1-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-
3-tert-butyl-5-methylphenyl) -4-methylphenol, α-phenyl-α, α-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,1-bis ( 2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis (2
-Hydroxy-3,5-dimethylphenyl) -2,4-ethylpentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3)
-Methyl-5-tert-butylphenyl) propane, 2,2
-Bis (4-hydroxy-3,5-di-tert-butylphenyl) propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, paraphenylenediamine, and the like.

These developing agents may be used alone or in combination of two or more.

The amount of the reducing agent used in the photothermographic material of the invention depends on the type of the photosensitive silver halide used, the type of the organic acid silver salt, the type of other additives, etc. Is 0.01 to 15 per mol of photosensitive silver halide.
The amount is in the range of 00 mol, preferably 0.1 to 200 mol.

As the binder used in the photothermographic material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, phthalated gelatin, etc. One or a combination of two or more molecular substances can be used. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binders described in JP-A-59-229556.

This binder contains gelatin and a vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) with one or more other monomers copolymerizable with vinylpyrrolidone. ) May be sufficient. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, preferred polyvinylpyrrolidone having a molecular weight of 1,000 to 400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth) acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates, vinyl imidazoles, (meth) acrylamides, Examples thereof include vinyl-based monomers such as vinyl carbinols and vinyl alkyl ethers, but it is preferable that at least 20% (% by weight, hereinafter the same) of the composition ratio is polyvinylpyrrolidone. A preferred example of such a copolymer has a molecular weight of 5,
It is from 000 to 400,000.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, pigskin gelatin, hide gelatin or modified gelatin obtained by esterification or phenylcarbamoylation thereof.

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

The binder may contain other polymeric substances,
Mixture of gelatin and polyvinylpyrrolidone having a molecular weight of 1,000 to 400,000 with one or more other polymeric substances, and mixture of gelatin and vinylpyrrolidone copolymer having a molecular weight of 5,000 to 400,000 with one or more other polymeric substances. Is preferred. Other polymer substances used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol,
Examples thereof include proteins such as polyethylene glycol ester and cellulose derivatives, and natural substances such as polysaccharides such as starch and gum arabic. These are 0-85
%, Preferably 0-70%.

The vinylpyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable that the vinylpyrrolidone polymer is coated on the support and then crosslinked (including the case where the crosslinking reaction is allowed to stand by itself).

The amount of the binder used is usually 0.05 g to 50 g, and preferably 0.1 g to 10 g per 1 m ^{2 of the} support.

Further, the binder is 0.1 to 10 g per 1 g of the dye-donor substance.
It is preferably used, and more preferably 0.25 to 4 g.

The support used in the photothermographic material of the present invention includes
For example, polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, paper for baryta paper and resin-coated paper, and electronic materials on these supports. Examples thereof include a support coated with and cured by a linear curable resin composition.

When the photothermographic material of the present invention, and further when the photosensitive material is a transfer type and an image receiving member is used, it is preferable to add various thermal solvents 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. For these compounds, for example, U.S. Patent Nos. 3,347,675 and 3,667,9.
No. 59, Research Disclosure No.17643 (XI
I), organic compounds having polarity as described in JP-A-59-229556, Japanese Patent Application No. 59-47787 and the like, and particularly useful in the present invention include, for example, urea derivatives (for example, dimethyl ester). Urea, diethylurea, phenylurea, etc.), amide derivatives (eg, acetamide, benzamide, etc.), polyhydric alcohols (eg, 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, penta Erythritol, trimethylolethane, etc.) or polyethylene glycols.

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

The water-insoluble solid thermal solvent is a solid at room temperature, but at a high temperature (60 ° C or higher, preferably 100 ° C or higher, particularly preferably 130 ° C or higher).
It is a compound that turns into a liquid at temperatures between ℃ and 250 ℃, and has an inorganic / organic ratio of 0.5 to 3.0, preferably 0.7 to 2.5, especially "organic conceptual diagram" Yoshio Koda, Sankyo Publishing Co., Ltd., 1984. It is preferably a compound in the range of 1.0 to 2.0 and has a solubility in water at room temperature of less than 1.

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

Many of the compounds used as the water-insoluble solid hot solvent are commercially available and can be easily synthesized by those skilled in the art.

The addition method of the water-insoluble hot solvent is not particularly limited, but a method of pulverizing and dispersing with a ball mill, a sand mill or the like,
There are a method of dissolving in a suitable solvent and adding, a method of dissolving in a high boiling point solvent and adding as an oil-in-water dispersion, and the like.
It is preferable to pulverize and disperse with a ball mill, a sand mill or the like, and add while maintaining the shape of the solid particles.

As the layer to which the water-insoluble solid thermal solvent is added, it is added so as to obtain the respective effects of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member and the like.

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

Even when the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the thermal development temperature, since it is added to the binder, the melting point is lowered, so that it can be effectively used as a thermal solvent.

The photothermographic material of the present invention may contain various additives, if necessary, in addition to the above components.

For example, acetamide described in U.S. Pat.No. 3,438,776, melt formers such as succinimide, U.S. Pat.
No. 477, compounds such as polyalkylene glycols described in JP-A-51-19525, -C described in U.S. Pat.
_{O -, - SO 2 -,} - SO- melting point of the lactone or the like 20 having a group
There are non-aqueous polar organic compounds having a temperature of ℃ or more.

Further, benzophenone derivatives described in JP-A-49-115540, phenol derivatives described in JP-A-53-24829 and JP-A-53-60223, carboxylic acids described in JP-A-58-118640, and The polyhydric alcohols described in JP-A-58-198038 and the sulfamoylamide compounds described in JP-A-59-84236 are also included.

What is known as a toning agent in the photothermographic material may be added to the photothermographic material of the present invention as a development accelerator. As the color tone adjusting agent, for example, JP-A-46-4928 is used.
No. 46, No. 46-6077, No. 49-5019, No. 49-5020, No. 49-91
No. 215, No. 49-107727, No. 50-2524, No. 50-67132,
50-67641, 50-114217, 52-33722, 52-99
813, 53-1020, 53-55115, 53-76020, and
53-125014, 54-156523, 54-156524, 54-15
6525, 54-156526, 55-4060, 55-4061,
55-32015, etc. and West German Patent No. 2,140,406
No. 2,141,063, No. 2,220,618, US Patent No.
3,847,612, 3,782,941, 4,201,582 and JP-A-57-207244, 57-207245, 58-189628.
No. 58-193541 and the like, which are the compounds described in each specification, such as phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazino, naphthoxazinedione, 2,3-dihydro-
Phthalazinedione, 2,3-dihydro-1,3-oxazine-
2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-
(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, aminomercaptotriazole, acylaminomercaptotriazoles, phthalic acid, naphthalic acid, phthalamic acid, etc., and one or more of these and imidazole A mixture with a compound, a mixture of at least one acid or acid anhydride such as phthalic acid and naphthalic acid, and a phthalazine compound, and a combination of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid and the like. be able to.

Examples of the antifoggants include higher fatty acids (for example, behenic acid, stearic acid, etc.) described in US Pat. No. 3,645,739, mercuric salts described in JP-B-47-11113, JP-A-51-47419. N-halogen compounds described in (for example, N
-Halogenoacetamide, N-halogenosuccinimide, etc.), mercapto compound-releasing compounds described in U.S. Pat. Acid, etc.), carboxylic acid lithium salts described in JP-A-51-47419 (for example, lithium laurate), British Patent No. 1,455,271,
Oxidizing agents described in JP-A-50-101019 (for example, perchlorates, inorganic peroxides, persulfates, etc.), sulfinic acids or thiosulfonic acids described in 53-19825, 51-322
2-thiouracils described in No. 3, sulfur alone described in No. 51-26019, No. 51-42529, No. 51-81124, No. 55-931
Disulfide and polysulfide compounds described in No. 49, rosins or diterpenes described in No. 51-57435 (for example, abietic acid, pimaric acid, etc.), free carboxy group or sulfonic acid group described in No. 51-104338 Polymeric acid, thiazoline thione described in U.S. Pat. No. 4,138,265, JP-A-54-51821, U.S. Pat. No. 4,137,079
1,2,4-triazole or 5-mercapto-1,2,4-triazole described in No. 55-140833, thiosulfinic acid esters described in No. 55-142331 1,2,
3,4-thiatriazoles, 59-46641, 59-57233
No. 59-57234, and dihalogen compounds or trihalogen compounds, and the thiol compounds described in No. 59-111636.

Other antifoggants include hydroquinone derivatives described in Japanese Patent Application No. 59-56506 (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives described in Japanese Patent Application No. 59-66380. And a benzotriazole derivative (for example, 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used in combination.

Examples of the silver image stabilizer include polyhalogenated organic oxidants described in U.S. Pat.No. 3,707,377 (e.g., tetrabromobutane, tribromoquinaridine, etc.), and Belgian patent No. 768,071. Methoxycarbonylthio-1-phenyltetrazole, monohalo compounds described in JP-A-50-119624 (for example, 2-bromo-2-tolylsulfonylacetamide, etc.), bromine compounds described in JP-A-50-120328 (for example, , 2-bromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine, etc.), and JP-A-53-46020.
And tribromoethanol, etc. Various monohalogenated organic antifoggants for silver halide emulsions described in JP-A-50-119624 can be used.

Other image stabilizers include US Pat.
No. 4,082,555, No. 4,088,496, JP-A-50-22625
Research Disclosure (RD) 12021, 151
No. 68, No. 15567, No. 15732, No. 15733, No. 15734,
A compound called activator precursor described in JP-A-15776, which releases a basic substance by heat,
For example, compounds such as guanidinium trichloroacetate which decarboxylate by heat to release a base, aldonamide compounds such as galactonamide, amine imides, compounds such as 2-carboxycarboxamide, and JP-A-56-130745.
No. 56-132332, sodium phosphate base generators, compounds generating an amine by an intramolecular nucleophilic reaction described in British Patent 2,079,480, JP-A-59-157637.
Aldoxime carbamates described in No. 59-16694
Examples thereof include hydroxamic acid carbamates described in No. 3, and base releasing agents described in Nos. 59-180537, 59-174830, 59-195237 and the like.

Furthermore, U.S. Pat.Nos. 3,301,678, 3,506,444 and 3,82
No. 4,103, No. 3,844,788, RD12035, No. 18016, and other irithiuronium compounds, s-carbomoyl derivatives of mercapto-containing compounds and nitrogen-containing heterocyclic compounds may be used for the purpose of stabilizing an image. , Further U.S. Pat.Nos. 3,669,670, 4,012,260, 4,060,420,
No. 4,207,392, RD15109, and RD17711 described nitrogen activator stabilizer and activator stabilizer precursor nitrogen-containing organic base, for example, α-sulfonylacetic acid salt or trichloroacetic acid salt of 2-aminothiazoline, acyl hydrazine compound etc. It can be used for the purpose of accelerating the image or for stabilizing the image.

Further, for example, the development may be carried out in the presence of a small amount of water as described in JP-A-56-130745 and 59-218443, or a small amount of water may be sprayed before heating or a fixed amount. May be applied to supply water, or as described in U.S. Pat. No. 3,312,550, development may be performed with hot steam or hot air containing moisture. Further, a compound that releases water into the photothermographic material, for example, a compound containing water of crystallization as described in JP-B-44-26582, such as sodium phosphate 12-hydrate, ammonium alum 24-hydrate, etc. is thermally developed. It may be contained in the light-sensitive material.

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

In the photothermographic material of the present invention, colloidal silica is used in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. it can.

The colloidal silica used in the present invention is a colloidal solution of anhydrous silicic acid having an average particle diameter of 3 to 120 mμ, which mainly contains water as a dispersion medium, and its main component is SiO ₂ (silicon dioxide).
Regarding colloidal silica, for example, JP-A-56-10933
6, No. 53-123916, No. 53-112732, No. 53-100226, etc. The amount of colloidal silica used is 0.05 by dry weight ratio to the binder of the layer to be mixed and applied.
The range of to 2.0 is preferable.

In the photothermographic material of the present invention, an organic fluoro compound is used in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. You can

Regarding the organic fluoro compound used in the present invention, U.S. Pat. Nos. 3,589,906, 3,666,478 and 3,754,924 are cited.
, 3,775,126, 3,850,640, West German Patent Publication No. 1,
942,665, 1,961,638, 2,124,262, British patent 1,330,356, Belgian patents 742,680 and JP-A-46-7781, 48-9715, 49-46733, 49-13302.
No. 3, No. 50-99529, No. 50-11322, No. 50-160034, No.
51-43131, 51-129229, 51-106419, 53-847
No. 12, No. 54-111330, No. 56-109336, No. 59-30536,
59-45441 and Japanese Patent Publications 47-9303, 48-43130,
The compounds described in No. 59-5887 and the like can be mentioned, and these compounds can be preferably used.

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, an antistatic agent can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1,
466,600, Research Disclosure (Research
Disclosure) 15840, 16258, 16630, U.S. Patents 2,327,828, 2,861,056, 3,206,312,
3,245,833, 3,428,451, 3,775,126, 3,96
3,498, 4,025,342, 4,025,463, 4,025,691
No. 4,025,704 and the like, and these can be preferably used.

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, an ultraviolet absorber can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the ultraviolet absorber used in the present invention include benzophenone compounds (for example, JP-A-46-2784 and US Pat.
5,530, 3,698,907), butadiene compounds (e.g., those described in U.S. Pat.No. 4,045,229), 4-thiazolidone compounds (e.g., U.S. Pat.
Nos. 314,794 and 3,352,681), benzotriazole compounds substituted with an aryl group [eg, Japanese Patent Publication No.
36-10466, 41-1687, 42-26187, 44-29620
No. 48-41572, JP-A-54-95233, 57-142975.
U.S. Pat.Nos. 3,253,921, 3,533,794 and 3,754,
919, 3,794,493, 4,009,038, 4,220,711
No. 4,323,633, Research Disclosure (R
esearch Disclosure) 22519], benzooxide compounds (for example, those described in U.S. Pat. No. 3,700,455), cinnamic acid ester compounds (for example, U.S. Pat. Nos. 3,705,805, 3,707,375, JP-A-52-52). 49029
Those described in No.). Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used. UV-absorbing couplers (for example, α-naphthol type cyan dye forming couplers),
UV absorber polymers (see, for example, JP-A-58-111942)
No. 178351, No. 181041, No. 59-19945, No. 23344
No., those described in the gazette).

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, a hardener can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the hardener used in the present invention include aldehyde-based and aziridine-based (for example, PB Report 19,921, US Pat.
950,197, 2,964,404, 2,983,611, and
Each specification of 3,271,175, JP-B-46-40898, JP-A-50-
91315), isoxazole-based (e.g., those described in U.S. Pat.No. 331,609), epoxy-based (e.g., U.S. Pat.No. 3,047,394, West German patent 1,085,663, British patent 1,033,518). Nos. 4 to 35495), vinyl sulfone type (for example, PB Report 19,920, West German Patent No. 1,10).
0,942, 2,337,412, 2,545,722, 2,635,518
No. 2,742,308, No. 2,749,260, British Patent No. 1,251,
091, Japanese Patent Application Nos. 45-54236 and 48-110996, U.S. Patent No.
3,539,644, those described in each specification of the same 3,490,911), acryloyl type (for example, Japanese Patent Application No. 48-27949, U.S. Pat.No. 3,640,720 described in each specification), carbodiimide type (for example, U.S. Patent Nos. 2,938,892 and 4,0
43,818 and 4,061,499 specifications, Japanese Patent Publication No. 46-38715
Japanese Patent Application Publication No. 49-15095), triazines (for example, West German Patent Nos. 2,410,973 and 2,553,9).
No. 15, U.S. Pat.No. 3,325,287, JP-A-52-12
No. 722) and other maleimide-based, 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. 2,447,587
No. 2,505,746, No. 2,514,245, U.S. Pat.No. 4,047,
No. 957, No. 3,832,181, each specification of the same 3,840,370, JP-A-48-43319, 50-63062, 52-127329, the combination described in JP-B 48-32364. To be

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, a polymer hardener can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the polymer hardener used in the present invention include, for example, polymers having an aldehyde group described in US Pat. No. 3,396,029 (for example, acrolein copolymers),
362,827, Research Disclosure 17333 (19
78) and the like, polymers having dichlorotriazine groups, US Pat. No. 3,623,878, epoxy group-containing polymers, Research Disc Closure 16725 (1978), US Pat. No. 4,161,407, JP-A-54-65033.
No. 56-142524 and the like, and polymers having an active vinyl group or a group capable of being a precursor thereof, and polymers having an active ester group described in JP-A-56-66841.

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

Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, poly-n-butyl acrylate, copolymers of ethyl acrylate and acrylic acid, copolymers of vinylidene chloride and butyl acrylate, and butyl acrylate and acrylic acid. Examples thereof include a copolymer, a copolymer of vinyl acetate and butyl acrylate, a copolymer of vinyl acetate and ethyl acrylate, and a copolymer of ethyl acrylate and 2-acrylamide.

The preferred average particle size of the polymer latex is 0.02 μm to 0.
It is 2 μm. The amount of the polymer latex used is preferably 0.03 to 0.5 as a dry weight ratio with respect to the binder of the layer to be added.

The photothermographic material of the present invention has various surface-active properties in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer) for the purpose of improving coatability. Agents can be used.

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

Examples of the anionic surfactant include alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N
A carboxy group, a sulfo group, such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a phospho group, a sulfuric acid ester group and a phosphoric acid ester group are preferred.

Examples of the cationic surfactant include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocycle are preferable.

As the amphoteric surfactant, for example, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides and the like are preferable.

Examples of nonionic surfactants include saponins (steroidal), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene). Glycol sorbitan esters,
Polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like are preferable.

The heat-developable photosensitive material of the present invention contains a heat-developable photosensitive layer and / or a non-photosensitive layer (for example, an undercoat layer or an intermediate layer) for the purpose of improving developability, improving transferability of image dye, improving optical physical properties and the like. ,
The non-photosensitive silver halide grains may be contained in the protective layer).

The non-photosensitive silver halide grains used in the present invention have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. Can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
It is 3 μm or less. Further, the addition amount is preferably in the range of 0.02 to 3 g / m ^{2 in} terms of silver amount with respect to the layer to be added.

In the photothermographic material of the present invention, for the purpose of improving the physical properties of the film, the photothermographic layer and / or the non-photosensitive layer (undercoat layer, intermediate layer, protective layer, etc.) may be, for example, disclosed in JP-A-51-104338. The vinyl polymer having a carboxyl group or a sulfo group described in the above publication can be contained.

The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in dry weight ratio with respect to the binder of the layer to be added.

When the photothermographic material of the invention is of the color type, a dye-donor substance is used.

Hereinafter, the dye-providing substance that can be used in the present invention will be described. The dye-donating substance may be any one as long as it can participate in the reduction reaction of the photosensitive silver halide and / or the organic silver salt optionally used and can form or release a diffusible dye as a function of the reaction, Depending on the reaction form, a negative-working dye-donor that acts on a positive function (that is, it forms a negative dye image when using a negative-working silver halide) and a positive-working that works on a negative function. Dye-donor substances (ie, a positive dye image is formed when a negative-working silver halide is used). Negative type dye-donor substances are further classified as follows.

Each dye-donor will be further described.

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

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

Specific examples of the above reducing dye-releasing compound include those disclosed in JP-A-
57-179840, 58-116537, 59-60434, 59-658
39, 59-71046, 59-87450, 59-88730, 59
59-123837, 59-165054, 59-165055 and the like, and examples thereof include the following compounds.

As another reducing dye-releasing compound, for example, general formula (3)
The compound shown by is mentioned.

General formula (3) In the formula, A ₁ and A ₂ each represent a hydrogen atom, a hydroxy group or an amino group, and Dye has the same meaning as Dye represented by the general formula (2). Specific examples of the above compounds are shown in JP-A-59-124329.

As the coupling dye-releasing compound, a compound represented by the general formula (4)
The compound shown by is mentioned.

General formula (4) Cp ₁ J _n1 Dye In the formula, Cp ₁ is an organic group capable of releasing a diffusible dye by reacting with an oxidant of a reducing agent (so-called coupler residue).
And J is a divalent linking group, and the bond between Cp ₁ and J is cleaved by the reaction with the oxidized form of the reducing agent. n ₁ is O or 1
And Dye has the same meaning as defined by the general formula (2). Further, Cp ₁ is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible. The ballast group has 8 or more carbon atoms depending on the form of the photosensitive material used. (More preferably 12
Or more) organic groups, or hydrophilic groups such as sulfo groups and carboxy groups, or groups having both 8 or more (more preferably 12 or more) carbon atoms and hydrophilic groups such as sulfo groups and carboxy groups. is there. Another particularly preferred ballast group may include a polymer chain.

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

Examples of the coupling dye-forming compound include those represented by the general formula (5)
The compound shown by is mentioned.

In the general formula (5) Cp ₂ FB), Cp ₂ is an organic group (so-called coupler residue) capable of forming a diffusible dye by reacting with an oxidant of a reducing agent (coupling reaction), F represents a divalent linking group, and B represents a ballast group.

The coupler residue represented by Cp ₂ has a molecular weight of preferably 700 or less, more preferably 500 or less because of the diffusibility of the dye formed.

Further, the ballast group is preferably the same ballast group as the ballast group defined by the general formula (4), particularly 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. A group having both groups is preferable, and a polymer chain is more preferable.

As the coupling dye-forming compound having the polymer chain, a polymer having a repeating unit derived from the monomer represented by the general formula (6) is preferable.

General formula (6) Cp ₂ FY ₁ ZL) In the formula, Cp ₂ and F have the same meanings as defined in the general formula (5), Y represents an alkylene group, an arylene group or an aralkylene group, and l is 0. Or 1 represents, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compounds represented by the general formulas (5) and (6) include JP-A-59-124339,
59-181345, 60-2950, Japanese Patent Application No. 59-179657, 5
No. 9-181604, No. 59-182506, No. 59-182507, and the like, and examples thereof include the following compounds.

Exemplified dye donor polymer In the above general formulas (4), (5) and (6), Cp ₁
Further, the coupler residue defined by Cp ₂ will be described in more detail, and a group represented by the following general formula is preferred.

In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
Acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, cyano group, alkylsulfonyl group, arylsulfonyl group Represents a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group or a heterocyclic residue,
These are further substituted with hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. It may have been done.

These substituents are selected according to the purpose of Cp ₁ and Cp ₂ ,
As described above, in Cp ₁ , _one of the substituents is preferably a ballast group, and in Cp ₂ , it is substituted so that the molecular weight is 700 or less, more preferably 500 or less in order to enhance the diffusibility of the dye formed. It is preferred that a group is selected.

As the positive type dye-donating substance, for example, the following general formula (1
There are oxidizing dye-releasing compounds represented by 7).

General formula (17) In the formula, W ₁ represents a group of atoms necessary for forming a quinone ring (which may have a substituent on this ring), and R 1
¹¹ represents an alkyl group or a hydrogen atom, and E is (In the formula, R ¹² represents an alkyl group or a hydrogen atom, and R ¹³ represents an oxygen atom or Represents ) Or —SO ₂ —, r represents 0 or 1, and Dye has the same meaning as defined in formula (2). Specific examples of this compound are disclosed in JP-A Nos. 59-166954 and 59-15.
It is described in the specification such as No. 4445, and there are the following compounds, for example.

Exemplified dye donor Another positive dye-donor substance is a compound represented by the following general formula (18), which loses its dye releasing ability when oxidized.

General formula (18) In the formula, W ₂ represents a group of atoms necessary for forming a benzene ring (which may have a substituent on the ring),
R ¹¹ , r, E and Dye have the same meaning as defined in the general formula (17). Specific examples of this compound are described in JP-A-59-124327 and JP-A-5-124327.
It is described in the specification such as 9-152440 and there are the following compounds, for example.

Exemplified dye donor Still another positive type dye-donor substance includes compounds represented by the following general formula (19).

General formula (19) In the above formula, W ₂ , R ¹¹ and Dye have the same meaning as defined in the general formula (18). Specific examples of this compound are described in JP-A-59-154445 and the like, for example, the following compounds.

Exemplified dye donor The residue of the diffusible dye represented by Dye in the above general formulas (2), (3), (4), (17), (18) and (19) will be described in more detail. The residue of the diffusible dye has a molecular weight of 800 or less, more preferably 600 because of the diffusibility of the dye.
The following are preferred, and examples thereof include residues of azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes and the like. These dye residues may be in the form of a temporary short-wave that allows multiple colors during heat development or transfer. Further, these dye residues are used for the purpose of improving the light resistance of an image, for example, JP-A-59-48765 and 59-1.
The chelatable dye residue described in 24337 is also a preferred form.

These dye-donor substances may be used alone or in combination of two or more. The amount used is not limited, depending on the type of the dye-donating substance, a single use or a combination use of two or more kinds, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more kinds of multilayers. It may be determined depending on the case, but for example, the amount used may be 0.005 g to 50 g, preferably 0.1 g to 10 g per 1 m ² .

The method for incorporating the dye-donor substance used in the present invention into the photographic constituent layer of the photothermographic material is arbitrary and includes, for example, a low-boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high-boiling point solvent (dibutyl phthalate, dioctyl phthalate, tritium). Cresyl phosphate, etc.) and then ultrasonically dispersed or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide solution), and then neutralized with a mineral acid (eg, hydrochloric acid or nitric acid). It can be used after being used or after being dispersed with a suitable polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.

The photothermographic material of the present invention usually has a temperature of 80 to 200 after imagewise exposure.
℃, preferably in the temperature range of 100 ℃ ~ 170 ℃ 1 second ~ 18
It is developed by heating for 0 seconds, preferably 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with the 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 the heat-development. Alternatively, the transfer may be performed by supplying water and then closely contacting the same and then heating it if necessary. Moreover, you may perform a pre-heating in the temperature range of 70 degreeC-180 degreeC before exposure. Also, JP-A-60-143338 and Japanese Patent Application No. 60-36
As described in No. 44, the photosensitive material and the image receiving member are heated to 80 ° C. to 250 ° C. immediately before heat development transfer in order to enhance mutual adhesion.
Each may be preheated at a temperature of ° C.

Various exposing means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation containing visible light. Generally, a light source used for ordinary color printing, for example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam or the like can be used as the light source.

As the heating means, all methods applicable to ordinary photothermographic materials can be used, for example, contact with a heated block or plate, contact with a heat roller or a heat drum, or passage through a high temperature atmosphere. Alternatively, high-frequency heating is used, or further, a conductive layer containing a conductive substance such as carbon black is provided on the back surface of the photosensitive material of the present invention or the back surface of the image transfer member for thermal transfer, and Joule heat generated by energization is used. You can also The heating pattern is not particularly limited, and it includes a method of preheating (preheating) in advance and then heating again, rising at a high temperature for a short time or at a low temperature for a long time, continuously rising, descending or repeating, and further discontinuous. It can be heated,
A simple pattern is preferred. Further, it may be a system in which exposure and heating proceed simultaneously.

The image receiving layer of the image receiving member effectively used in the present invention,
It suffices that it has a function of receiving the dye in the photothermographic layer which is released or formed by the heat development, and is, for example, a polymer containing a tertiary amine or a quaternary ammonium salt, and is described in US Pat.
Those described in No. 709,690 are preferably used. For example, as a polymer containing an ammonium salt, a ratio of polystyrene-co-N, N, N-tri-n-hexyl-N-vinyl-benzylammonium chloride is 1: 4 to.
It is 4: 1 and preferably 1: 1. Examples of polymers containing tertiary amines include polyvinyl pyridine and the like. A typical image-receiving layer for diffusion transfer can be obtained by mixing a polymer containing an ammonium salt, a tertiary amine or the like with gelatin, polyvinyl alcohol or the like and coating the mixture on a support. Another useful dye image receiving substance is JP-A-57-207250.
And the like, which are formed of a heat-resistant organic polymer substance having a glass transition temperature of 40 ° C. or higher and 250 ° C. or lower.

These polymers may be carried on a support as an image receiving layer, or may be used as a support itself.

An example of the heat-resistant organic polymer substance has a molecular weight of 2,000.
~ 85,000 polystyrene, polystyrene derivatives having substituents with 4 or less carbon atoms, polyvinyl cyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyacetals, poly Vinyl chloride,
Chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N, N-dimethylallylamide, polyacrylate having p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, Polyester such as polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, poly-tert-butylmethacrylate, polycyclohexylmethacrylate, polyethyleneglycoldimethacrylate, poly-2-cyano-ethylmethacrylate, polyethyleneterephthalate , Polysulfones, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides And cellulose acetates. Also, Polymer, Handbook, Second Edition (J Brand Wrap, E
H. Inmargat) John Willie and
Sands {Polymer Handbook 2nd ed. (J, Brandrup, EHI
mmergut ed.) John Wiley & Sons} synthetic polymers having a glass transition temperature of 40 ° C. or lower described in the publication are also useful.
These polymeric substances may be used alone or as a mixture of two or more kinds, or may be used as a copolymer by combining two or more kinds.

Useful polymers include cellulose acetates such as triacetate and diacetate, heptamethylenediamine and terephthalic acid, fluorenedipropylpropylamine and adipic acid, hexamethylenediamine and diphenic acid, polyamides in combination with hexamethylenediamine and isophthalic acid, and diethylene glycol. And polyester, polyethylene terephthalate, and polycarbonate obtained by combining diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, and the like. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid as a modifier is also effective.

Particularly preferred image-receiving layers include the layer made of polyvinyl chloride described in JP-A-59-223425 and the layer made of polycarbonate and a plasticizer described in JP-A-60-19138.

These polymers can also be used as a support and an image receiving layer (image receiving member). At that time, the support may be formed of a single layer or a plurality of layers. .

As the support for the image receiving member, any support such as a transparent support or an opaque support may be used. For example, a film of polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, etc. Supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, talc, baryta paper, RC paper laminated with a thermoplastic resin containing pigment on paper, cloth, glass, aluminum, etc. Metals, etc., or a support obtained by coating and curing an electron beam curable resin composition containing a pigment on these supports, and a support provided with a coating layer containing a pigment on these supports. Etc.

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

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

The image-receiving layer of the image-receiving member can be formed in a mold which is peeled off from the photothermographic layer. For example, after the imagewise exposure of the heat-developable color light-sensitive material, the image-receiving layer may be superposed on the heat-developable light-sensitive layer to cause uniform heating. It is also possible to transfer the dye image released or formed from the dye-donor substance by superimposing image-receiving layers after imagewise exposure of the heat-developable color light-sensitive material and uniform heat development, and heating at a temperature lower than the development temperature.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 22.7 g of benzotriazole silver and 400 ml of methyl alcohol,
Add polyvinyl alcohol (PVA) and 500 ml of 8% aqueous solution of each water-soluble polymer shown in Table 1, 18
It was decomposed by a ball mill for an hour. Next, 84 ml of silver iodobromide emulsion (5 mol% of silver iodide, cubic grains containing 60 g of gelatin and 0.353 mol of silver in 1 kg of emulsion and having an average particle size of 0.05 μm) chemically sensitized while stirring this dispersion liquid Was added. (Including about 5.4 g of gelatin) Furthermore, 9 ml of a 2% solution of 3-amino-4-allyl-5-mercaptotriazole in methinol, 8.9 g of ascorbic acid.
And 10 ml of 10% gelatin aqueous solution were mixed, 30 g of D-xylitol was further added, and the mixture was stirred well. The coating liquid thus prepared was applied onto baryta paper and dried to prepare samples 1 to 8.

Then, each sample was uniformly heated in a heat block at 130 ° C. for 20 seconds and thermally developed. Maximum concentration of each sample (Dm
ax) and minimum density (Dmin) are shown below.

From the results shown in Table 1, in the sample using the polymer containing the repeating unit of the present invention, the maximum concentration can be increased without an increase in the minimum concentration as compared with the comparative sample, and the present invention has good heat developability. It can be seen that it has various characteristics.

Example-2 [Preparation of silver iodobromide emulsion] At 50 ° C., 20 g of ossein gelatin was mixed using the mixing and stirring described in JP-A Nos. 57-92523 and 57-92524.
Aqueous solution containing 11.6 g of potassium iodide and 130 g of potassium bromide in solution A containing 1000 ml of distilled water and ammonia 5
00 ml of the solution B and 500 ml of an aqueous solution containing 1 mol of silver nitrate and ammonia were simultaneously added while keeping pAg and pH constant. Further, by controlling the addition rates of the solutions B and C, a core emulsion having a silver iodide content of 7 mol%, a regular hexahedron and an average grain size of 0.25 μm was prepared. Then, in the same manner as described above, a shell of silver halide having a silver iodide content of 1 mol% was coated to form a regular hexahedron with a core having an average grain size of 0.3 μm (shell thickness of 0.05 μm). A shell type silver halide emulsion was prepared. (The monodispersity was 8%.) The above emulsion was washed with water and desalted to obtain a yield of 700 ml. Furthermore, three kinds of photosensitive silver halide emulsions were prepared by using the silver halide prepared above in the following composition.

a) Preparation of red-sensitive silver iodobromide emulsion 700 ml of the aforementioned silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg a) Methanol 1% liquid 80 ml Distilled water 1200 ml b) Preparation of green-sensitive silver iodobromide emulsion 700 ml of the above silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye ( b) Methanol 1% solution 80 ml Distilled water 1200 ml c) Preparation of blue-sensitive silver iodobromide emulsion 700 ml of the above silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye ( c) Methanol 1% solution 80 ml Distilled water 1200 ml <Preparation of Organic Silver Salt Dispersion> 28.8 g of 5-methylbenzotriazole silver obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent, and poly (N-vinylpyrrolidone) 1
Disperse 6.0 g with alumina ball mill, adjust to pH 5.5 and 200 ml
And

<Preparation of Dye Donor Dispersion-1> 35.5 g of Exemplified Polymer Dye Donor (PM-4) and 5.00 g of the following hydroquinone compound are dissolved in 200 ml of ethyl acetate to prepare an alkanol XC (Dupont) 5% by weight aqueous solution. 12
4 ml, phenylcarbamoylated gelatin (Russlaw,
Type 17819PC) was mixed with 720 ml of gelatin aqueous solution containing 30.5 g and dispersed with an ultrasonic homogenizer, and ethyl acetate was distilled off to adjust the pH to 5.5 to 795 ml.

Hydroquinone compound <Preparation of Reducing Agent Dispersion Liquid> Exemplary reducing agent (R-11) 23.3 g, the following development accelerator 1.10 g, poly (N-vinylpyrrolidone) 14.6 g, and the following surfactant 0.5.
0 g was dissolved in water and adjusted to pH 5.5 to make 250 ml.

Development accelerator Surfactant <Preparation of Photothermographic Material-1> 12.5 ml of the organic silver salt dispersion liquid prepared above, 6.00 ml of a blue-sensitive silver iodobromide emulsion, 39.8 ml of the dye-donor dispersion liquid-1 and 12.5 ml of the reducing agent dispersion liquid were prepared. Mix and further react the hardener solution {tetra (vinylsulfonylmethyl) methane with taurine 1: 1 (weight ratio) to give 1% phenylcarbamoylated gelatin.
Dissolved in aqueous solution, tetra (vinylsulfonylmethyl)
Methane is adjusted to 3% by weight. } 2.50 ml,
Polyethylene glycol 300 as a heat solvent (Kanto Chemical)
After adding 3.80 g, the amount of silver on the undercoated 180 μm thick polyethylene terephthalate film for photography
1.76 g / m ² was applied, and alkali-processed gelatin and poly (N-vinylpyrrolidone) were mixed in 1: 1.
Protective layer consisting of a mixture (weight ratio) (dry film thickness 1.0μ
m) is provided.

The obtained coated sample was designated as Sample-8.

Instead of the emulsion layer of Sample-8, the emulsion layers shown below were used to prepare Samples 9 to 15.

<Emulsion Layers of Samples 9 to 15> In Sample-8, instead of poly (N-vinylpyrrolidone) in the organic silver salt dispersion liquid and the reducing agent dispersion liquid, the same amount of other species as shown in Table 2 was used. An emulsion layer similar to that of Sample-8 was prepared except that the coalescence was used.

<Preparation of Image Receiving Member-1> A tetrahydrofuran solution of polyvinyl chloride (n = 1,100, Wako Pure Chemical Industries, Ltd.) was applied on photographic baryta paper so that the polyvinyl chloride would be 12 g / m ² .

Through the step wedge for the photothermographic material
The exposure of 1,600 CMS is applied, and together with the image receiving member, it is 150 in a heat developing machine (developer module 277, 3M company).
After heat development at 1 ° C. for 1 minute, the photosensitive material and the image receiving member were quickly peeled off, and a negative image of a magenta step wedge was obtained on the polyvinyl chloride surface of the image receiving member.

The reflection density of the obtained negative image was measured with a densitometer (PDA-65, manufactured by Konishi Roku Photo Co., Ltd.), and the maximum density (Dmax) and the minimum density (Dmin) are shown in Table 2 below.

As is clear from Table 2, the photothermographic material having the emulsion layer containing the polyoxazoline-based polymer having the repeating unit of the present invention has a higher maximum density than the comparative sample.

Example-3 <Preparation of Dye Donor Dispersion Liquid-2> The same dye as in Example-2 was dissolved in 30.0 g of Exemplified dye-donor substance in 30.0 g of tricresyl phosphate and 90.0 ml of ethyl acetate, and gelatin containing a surfactant was used. After mixing with 460 ml of an aqueous solution and dispersing with an ultrasonic homogenizer, the ethyl acetate was distilled off,
Water was added to make 500 ml.

<Preparation of Photothermographic Material-2> 40.0 ml of the silver halide emulsion and 25.0 ml of an organic silver salt dispersion liquid.
(The above is the one prepared in Example-2), 50.0 ml of the dye-donor dispersion liquid-2 is mixed, and polyethylene glycol 300 (Kanto Kagaku) 4.20 g, 1-phenyl-4,4 is further used as a heat solvent. 1.5% of 10% by weight methanol solution of ′ -dimethyl-3-pyrazolidone, 3.00 ml of the same hardening agent as in Example-2
And a guanidine trichloroacetic acid 10% by weight water-alcohol solution (20.0 ml) were added to give an undercoat thickness of 180 μm.
Was coated on the photographic polyethylene terephthalate film in such a manner that the amount of silver was 2.50 g / m ² and the amount of gelatin was 5.3 g / m ² .

Further thereon, a protective layer (dry film thickness 0.5 μm) made of a mixture of alkali-treated gelatin and poly (N-vinylpyrrolidone) in a ratio of 1: 1 (weight ratio) was provided.

The obtained coated sample was designated as Sample-16.

Instead of the emulsion layer of Sample-16, the following emulsion layers were used to prepare Samples 17 to 22.

<Emulsion Layers of Samples 17 to 22> In Sample-16, except that poly (N-vinylpyrrolidone) in the organic silver salt dispersion was replaced with the same amount of another polymer as shown in Table 3. An emulsion layer similar to that of Sample-16 was prepared.

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

(1) Polyacrylic acid layer (7.00 g / m ² ) (2) Cellulose acetate layer (4.00 g / m ² ) (3) Styrene and N-benzyl-N, N-dimethyl-N-
Of (3-maleimidopropyl) ammonium chloride
Layer consisting of 1: 1 copolymer and gelatin (Copolymer 3.0
0g / m ² , gelatin 3.00g / m ² ) (4) Urea and polyvinyl alcohol (saponification degree 98%)
Layer consisting of (urea 4.0 g / m ² , polyvinyl alcohol 3.0 g /
m ² ) The heat-developable photosensitive material-2 is exposed to 1,600 CMS through a step wedge, superposed on the image-receiving member-2 and thermally developed at 150 ° C. for 1 minute, and then the image-receiving member- I quickly peeled off 2. The transmission density of the yellow transparent image obtained on the surface of the image receiving member was measured with a densitometer (PDA-65, manufactured by Konishi Rokusha Kogyo Co., Ltd.), and the maximum density (Dmax)
The minimum concentration (Dmin) is shown in Table 3 below.

As is apparent from Table 3, even in the photothermographic material containing the reducing dye-donating compound, the photothermographic material having an emulsion layer containing the polyoxazoline-based polymer having the repeating unit of the present invention is It can be seen that the maximum concentration is higher than that of the comparative sample.

Example-4 Samples 23 to 28 were prepared by changing the formulation of the coating liquid for the protective layer in Sample-8 of Example-2 as follows. The protective layer was coated so that the gelatin coverage was 0.55 g / m ² .

<Coating liquid for protective layer of Sample-23> 30 ml of 10% by weight aqueous solution of alkali-treated gelatin and poly (N
-Vinylpyrrolidone) 10% by weight aqueous solution 30 ml,
As an activator, 1 ml of a 1% by weight aqueous solution of the following compound-A was added to make 100 ml of water to obtain a coating solution.

Compound-A <Coating Liquid for Protective Layer of Samples 24-28> Sample-23 except that the same amount of another polymer as shown in Table 4 was used instead of poly (N-vinylpyrrolidone) in Sample-23. 100 ml of each coating solution for protective layer similar to the above was prepared.

For the light-sensitive materials of Samples 23 to 28, in the same manner as in Example-2,
It was exposed to 1,600 CMS, brought into close contact with the image receiving member used in Example-2, and heat-developed at 150 ° C. for 1 minute, and the results shown in Table 4 were obtained.

As is apparent from Table 4, the photothermographic material having the protective layer containing the polyoxazoline polymer having the repeating unit of the present invention has a higher maximum density than the comparative sample and has no transfer unevenness. It can be seen that a good image can be obtained.

Example-5 A multilayered light-sensitive material having the constitution shown in Table-5 was prepared. This overlay sample is referred to as Sample-29.

In Sample-29, two intermediate layers (a first intermediate layer and a second intermediate layer) are used.
Sample-30 was prepared using the same amount of polyethylene oxazoline (polymerization degree 50,000) instead of all the polyvinylpyrrolidone (polymerization degree 40,000) contained in the intermediate layer).

In Sample-29, instead of all the polyvinylpyrrolidone (polymerization degree 40,000) contained in the three emulsion layers (blue-sensitive layer, green-sensitive layer and red-sensitive layer), the same amount of polyethyleneoxazoline (polymerization degree 50,000) was used. Was used to prepare Sample-31.

Sample-32 was prepared by using the same amount of polyethyleneoxazoline (polymerization degree 50,000) instead of polyvinylpyrrolidone (polymerization degree 40,000) contained in the protective layer in sample-29.

In Sample-29, the same amount of polyethyloxazoline (degree of polymerization: 50,000) was used in each layer instead of all the polyvinylpyrrolidone contained in all layers of the photosensitive element.
33 created.

However, the anti-coloring agent (SC-1), the filter dye (F-1) and the thermal solvent (S-1) used in Table 5 are as follows.

Anti-coloring agent Y-filter dye Thermal solvent (S-1) Polyethylene glycol (average molecular weight 300) With respect to the photothermographic material, 1,600 as in Example-2.
It was exposed by CMS, brought into close contact with the image receiving member used in Example-2, and heat-developed at 150 ° C. for 1 minute, and the results shown in Table 6 were obtained.

As is apparent from Table-6, even in the case of a multilayer photothermographic material, a photothermographic material having a constituent layer (emulsion layer, intermediate layer or protective layer) containing the polyoxazoline polymer of the present invention is compared. It can be seen that the maximum concentration is higher than that of the sample. Further, it can be seen that the photothermographic material containing the polyoxazoline-based polymer of the present invention in the protective layer has improved transfer unevenness.

Claims (1)

[Claims] 1. A photothermographic material comprising a polymer having a repeating unit represented by the following general formula (I). General formula (I) In the formula, R represents an alkyl group (including a substituted alkyl group) or an aryl group (including a substituted aryl group).