JPH061364B2 - Photothermographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photothermographic material capable of forming an image by heat development, and more particularly to a photothermographic color containing a novel inhibitor that suppresses fogging in heat development. Photosensitive material.

[Prior Art] Regarding a photothermographic material capable of performing a development step by heat treatment, there is a description thereof, for example, in Japanese Patent Publication Nos. 43-4921 and 43-4924, and organic silver salts, silver halides and reducing agents are used. Is disclosed.

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, a heat-developable color light-sensitive material for forming a color image by reacting an oxidized product of an aromatic primary amine developing agent with a coupler is disclosed. Is disclosed.

Further, Research Disclosure Nos. 15108 and 15127 disclose a heat-developable color light-sensitive material which forms a color image by reacting an oxidized product of a sulfonamidephenol or sulfonamideaniline derivative developing agent with a coupler. However, in these methods, there is a problem that the image of reduced silver and the color image are simultaneously formed in the exposed portion after the heat development, so that the color image becomes turbid. As a method of solving this problem, there is a method of removing the silver image by liquid treatment or transferring only the dye to another layer, for example, an image receiving sheet having an image receiving layer. There is a problem that it is not easy to transfer only the dye.

In addition, in Research Disclosure No. 16966, an organic imino silver salt having a dye part is used, and the imino group is released in the exposed part by heat development, and a solvent is used to form a color image on the image receiving layer as a transfer paper. A color light-sensitive material is disclosed. However, this method has a problem that it is difficult to suppress the release of the dye in a portion which is not exposed to light, and a clear color image cannot be obtained.

Further, JP-A-52-105821, JP-A-52-105822 and JP-A-56-50328
U.S. Pat. No. 4,235,957, Research Disclosures 14448, 15227 and 18137 disclose heat-developable color light-sensitive materials for forming a positive color image by a heat-sensitive silver dye bleaching method. However, this method requires an extra step such as stacking and heating sheets containing an activator for accelerating the bleaching of the dye and a photographic constituent material, and the color image obtained is stored for a long period of time. In addition, it has a problem that it is gradually reduced and bleached by coexisting free silver.

In addition, U.S. Patent Nos. 3180732, 3985565 and
Nos. 4022617 and Research Disclosure 12533 disclose a heat-developable color light-sensitive material in which a leuco dye is used to form a color image. But,
According to this method, it is difficult to stably incorporate the leuco dye in the photographic light-sensitive material, and there is a problem in that it is gradually colored during storage.

Furthermore, JP-A-57-179840, 57-186744, and 123533.
No. 59-12431, 59-124339, 59-166954,
JP-A Nos. 59-159159, 59-181395 and 59-229556 disclose heat-developable color light-sensitive materials which release or form a diffusible dye by heat development to obtain a transferred color image.

However, in these prior arts, the highest concentration (Dma
If x) is increased, the fog (Dmin) increases, and if an inhibitor used in a conventional conventional photographic light-sensitive material is used to suppress the fog, the inhibitory effect is not exhibited, and the fog is rather adversely affected. Therefore, there is a strong demand for the development of an inhibitor which can be used in a photothermographic material because of its drawbacks such as an increase in Dmax or a decrease in Dmax and sensitivity.

[Object of the Invention]

An object of the present invention is to solve the above-mentioned problems of the photothermographic material.

That is, an object of the present invention is to provide a photothermographic material containing a novel inhibitor.

Another object of the present invention is to provide a photothermographic material capable of obtaining an image with high density and without fog.

Another object of the present invention is to provide a photothermographic material having improved raw storability.

[Structure of Invention]

The present inventors, as a result of earnest research to achieve the above object,
In a photothermographic material having a layer containing a photosensitive silver halide on a support, the above object of the present invention can be achieved by a photothermographic material containing a compound represented by the following general formula (1): I found it.

General formula (1) In the formula, X represents a residue of a photographic inhibitor represented by the following general formulas (2) to (18), and J represents -CONH-, -SO ₂ NH-, -NHCONH-, -COO-, _{-NHCO -, - NHSO 2 -,} - O -, - S-, (R represents a hydrogen atom or an alkyl group) and a bonding group selected from -CO-, B represents a ballast group,
n represents 0 or 1.

General formula (2) R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, and M represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue.

General formula (3) R ¹ represents an alkyl group, an aryl group or a hydrogen atom,
M has the same meaning as M in formula (2).

General formula (4) R ³ is a hydrogen atom, an alkyl group, an aryl group or (M represents 1 or 2), R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group,
It represents an aryl group or a nitro group, and R ⁴ and R ⁵ may combine to form a 5- or 6-membered ring.

General formula (5) R ¹ represents an alkyl group, an aryl group or a hydrogen atom,
R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group, an aryl group or a nitro group, and R ⁴ and R ⁵ may combine to form a 5- or 6-membered ring.

General formula (6) Y represents -N-, -O-, or -S-, R ¹ represents an alkyl group, an aryl group or a hydrogen atom, and M represents a general formula.
It is synonymous with M in (2).

General formula (7) Y ¹ is -O-, -S-, Or R ¹ and R ⁶ each represent an alkyl group, an aryl group or a hydrogen atom, and R ⁴ and R ⁵ each represent a hydrogen atom,
It represents an alkyl group, an aryl group or a nitro group, and R ⁴ and R ⁵ may combine to form a 5- or 6-membered ring.

General formula (8) Y ¹ and ^{Y 1} in the general formula (7), ^{R 4} and ^{R 5} with ^{R 4} and ^{R 5} of the general formula (7), M are each as M in the general formula (2) interchangeably.

General formula (9) R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an aryl group, a nitro group or a halogen atom, and R ⁷ and R ⁸ may be bonded to each other to form a 5- or 6-membered ring.

General formula (10) R ⁹ , R ¹⁰ and R ¹¹ are each an alkyl group, an amino group,
Alkoxy group, thioalkoxy group, -SM (M is a general formula
It is synonymous with M in (2). ), A hydroxyl group or a hydrogen atom.

General formula (11) R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrogen atom, an alkyl group, an aryl group, R ¹ —NH— (R ¹ represents a hydrogen atom, an alkyl group or an aryl group), —SM.
(M has the same meaning as M in formula (2)), an alkylthio group, a hydroxyl group or an alkoxy group.

General formula (12) R ¹² , R ¹³ , R ¹⁴ and R ^{15 are} each R in the general formula (11).
It is synonymous with the ^{12 ~R 16.}

General formula (13) R ¹⁷ and R ¹⁸ each represent an alkyl group or a hydrogen atom, and M has the same meaning as M in formula (2).

General formula (14) R ¹⁹ and R ²⁰ each represent an alkyl group, an aryl group or a hydrogen atom, and R ¹⁹ and R ²⁰ may combine to form a 5-membered or 6-membered ring.

General formula (15) R ¹ , R ¹⁹ and R ²⁰ each represent an alkyl group, an aryl group or a hydrogen atom, and R ¹⁹ and R ²⁰ are bonded to each other to form 5
May form a 6-membered or 6-membered ring. Y ² is -O-, -S
-Or (R ¹⁷ represents a hydrogen atom or an alkyl group).

General formula (16) R ¹ represents each alkyl group, aryl group or hydrogen atom, Y ² represents —O—, —S— or (R ¹⁷ represents a hydrogen atom or an alkyl group). M has the same meaning as M in formula (2).

General formula (17) Y ³ is Or = N- to ^{represent, R 19} and ^{R 20} each represents an alkyl group, an aryl group or a hydrogen ^{atom, R 19} and R
²⁰ may combine to form a 5- or 6-membered ring. R
¹⁷ and R ¹⁷ in formula (16), M has the same meaning as each and M in formula (2).

General formula (18) R ¹ , R ¹⁹ and R ²⁰ each represent an alkyl group, an aryl group or a hydrogen atom, and R ¹⁹ and R ²⁰ may combine to form a 5- or 6-membered ring.

Y Represents a counter anion.

Although the mechanism of action of the compound of the present invention is not clear, a photographic inhibitor used in a conventional photographic light-sensitive material generally causes a remarkable fog-increasing effect or a decrease in sensitivity in a photothermographic material. The effect of the compounds of the present invention in comparison with that of is surprising.

[Specific Structure of the Invention] As the residue of the photographic inhibitor represented by X in the general formula (1), a photographic inhibitor residue represented by the general formula (3) or (8) is particularly preferable.

The ballast group represented by B in the general formula (1) of the present invention may reduce the diffusivity of the compound represented by the general formula (1) of the present invention and its silver salt (or silver complex) during thermal development. An organic ballast group having a size and shape of a molecule to be diffusion-resistant, and a general organic ballast group is X
A long-chain alkyl group bonded directly to a photographic inhibitor residue represented by or through a divalent linking group represented by (J) n, and a carbocyclic nucleus or heterocyclic nucleus of the inhibitor residue Benzene- and naphthalene-based aromatic groups fused directly or indirectly to Effective ballast groups are generally those having at least 8 carbon atoms,
More preferably, it is a substituted or unsubstituted alkyl group having 8 to 40 carbon atoms.

Further, a group having a group substituted with a hydrophilic group such as a sulfo group and a carboxy group, and a group having a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms is also an effective ballast group. .

Preferred specific examples of the ballast group are shown below.

-C ₁₇ H ₃₃ , -C ₁₅ H ₃₁ , -C ₁₀ H ₂₁ , − (CH ₂ ) ₃ O (CH ₂ ) ₇ CH ₃ , Specific examples of the compound of the present invention are shown below.

Specific synthetic examples of the compound of the present invention are shown below.

Synthesis Example-1 Synthesis of Compound (A-1) 1- (p-Aminophenyl) -1,2,3,4-tetrazole-5-thiol 19.3 g and viridine 20 ml were mixed with acenitrile 2
In addition to 00 ml, 33 g of palmitoyl chloride was added dropwise with stirring at room temperature. After dropping, the mixture was heated under reflux for 1 hour and then cooled to precipitate crystals. The crystals were collected by filtration, washed with cold acetonitrile, and then dried to obtain the desired product 31.5 (76%).

Synthesis Example-2 Synthesis of Compound (A-15) 18.2 g of 6-amino-2-mercaptobenzothiazole and 20 ml of pyridine were added to 200 ml of acetonitrile, and 3- (2,4-di- (t) was added at room temperature with stirring. Pentylphenoxy) -butyric acid chloride 35 g acetonitrile (50 ml)
The solution was added dropwise. After the dropping was completed, the mixture was heated under reflux for 1 hour. The reaction solution was poured into water, the crystals were separated by filtration, and the crystals were recrystallized from acetonitrile to obtain 33.8 g of the desired product (yield 88%).

Other inventions can also be synthesized by the same method.

The compounds of the present invention may be used alone or in combination of two or more. The amount used is not limited, depending on the kind of the compound, single use or two or more combined use, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more layers. It may be determined, but it is preferably 0.01 g to 500 g, and more preferably 0.5 g to 50 g per mol of silver halide.

The method of incorporating the compound of the present invention into the photographic constituent layers of the photothermographic material is arbitrary, and examples thereof include low boiling point solvents (methanol, ethanol, ethyl acetate, etc.) or high boiling point solvents (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate). Etc.) and then ultrasonically disperse
Or an alkaline aqueous solution (for example, sodium hydroxide 10
% Aqueous solution) and then neutralized with a mineral acid (for example, hydrochloric acid or nitric acid), or dispersed with a suitable polymer aqueous solution (for example, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill. After allowing it to be used.

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 Japanese Patent Application No. 58-104249.

This binder contains gelatin and a vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer of vinylpyrrolidone and one or more other monomers copolymerizable with vinylpyrrolidone (including a Kraft copolymer). .). These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone,
Preferably the polyvinylpyrrolidone has a molecular weight of 1000-400000
belongs to. Other monomers copolymerizable with vinylpyrrolidone include (meth) acrylic acid esters such as acrylic acid, methacrylic acid and their alkyl esters,
Vinyl alcohols, vinyl imidazoles, (meth)
Examples thereof include vinyl monomers such as acrylamides, vinyl carbinols, and vinyl alkyl ethers, but it is preferable that at least 20% (% by weight, the same applies hereinafter) of the composition ratio is polyvinylpyrrolidone. A preferred example of such a copolymer has a molecular weight of 5,000 to 400,000.

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

In the above binder, gelatin is preferably 10 to 90%, more preferably 20 to 60%, and the polymer of the present invention is preferably 5 to 90%, more preferably 10 to 80%. .

The binder may contain other polymeric substances,
Mixture of gelatin and polyvinylpyrrolidone having a molecular weight of 1000-400000 with one or more other polymer substances, and mixture of gelatin and vinylpyrrolidone copolymer having a molecular weight of 5000-400000 with one or more other polymer substances Is preferred.

Other polymer substances used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These may be contained in 0 to 85%, preferably 0 to 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 0.005 g per 1 m ^{2 of the} support.
It is 100 g, and preferably 0.01 g to 40 g.

The support used in the photothermographic material of the present invention includes
Examples thereof include polyethylene films, cellulose acetate films and polyethylene terephthalate films, synthetic plastic films such as polyvinyl chloride, and paper supports such as photographic base paper, printing paper, baryta paper and resin-coated paper.

In particular, it is preferable to add various thermal solvents to the photothermographic material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and / or thermal transfer, and is preferably a substance that is solid, semi-solid or liquid at room temperature and dissolves or dissolves in a binder when heated. And preferably a urea derivative (eg dimethylurea,
Diethylurea, phenylurea, etc.), amide derivatives,
(Eg, acetamide, benzamide, etc.), polyhydric alcohols (eg, 1,5-pentanediol, 1.6
-Pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.) or polyethylene glycols. A detailed specific example is described in Japanese Patent Application No. 58-104249. These hot solvents may be used alone or in combination of two or more.

Various additives may be added to the photothermographic material of the present invention, if necessary, in addition to the above components.

For example, as the development accelerator, U.S. Pat. Nos. 3,220,840, 3,531,285, 4012260, 4060420, and 408.
No. 8496, No. 4207392, each specification, RD No. 15833, No. 15
No. 734, No. 15776, JP-A-56-130745, 56-132332
Urea, guanidinium trichloroacetate and other alkali releasing agents, organic acids described in JP-B-45-12700, -CO-, -SO described in U.S. Pat. No. 3,667,959.
₂ -, - SO- non-aqueous polar solvent a compound having a group, U.S. Patent No. 3,438,776 No. described melt formers, U.S. Patent No. 3
666477 and polyalkylene glycols described in JP-A-51-19525.

Further, as a color tone agent, for example, JP-A-46-4928 and 46-60
77, 49-5019, 49-5020, 49-91215, 49
-107727, 50-2524, 50-67132, 50-67641
No. 50, No. 50-114217, No. 52-33722, No. 52-99813, No. 5
3-1020, 53-55115, 53-76020, 53-125014
No. 54, No. 54-156523, No. 54-156524, No. 54-156525,
54-156526, 55-4060, 55-4061, 55-3201
Publications such as No. 5 and West German Patent Nos. 2140406 and 214706
No. 3, 2220618, U.S. Pat.No. 3,080,254, No. 3847612
No. 3782941, No. 3994732, No. 4123282,
Phthalazinones, phthalimides, pyrazolones, quinazolinones, N-hydroxynaphthalimides, benzoxazines, naphthoxazinediones, 2,3-dihydro-phthalazinediones, which are compounds described in the respective specifications such as No. 4201582 and the like, 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, phthalic acid, naphthalic acid, phthalamic acid, etc.
A mixture of one or more imidazole compounds,
Further, a mixture of at least one of an 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 can be mentioned.

Further, 3-amino-5-mercapto-1,2,4-triazoles, 3-acylamino-5-mercapto-1,2, described in JP-A Nos. 58-189628 and 58-193460 are disclosed. 4-
Triazoles are also effective.

Examples of the antifoggant include hydroquinone derivatives described in Japanese Patent Application No. 59-56506 (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) and Japanese Patent Application No. 59-56506.
-66380 and benzotriazole derivatives (for example, 4-sulfobenzotriazole,
5-carboxybenzotriazole etc.) can be preferably used in combination.

In addition, a printout preventing agent after treatment may be used as a stabilizer at the same time, and examples thereof include JP-A-48-45228 and JP-A-50-1
No. 19624, No. 50-120328, No. 53-46020 and the like halogenated hydrocarbons, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo- 2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine and the like can be mentioned.

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Laid-Open Nos. 50-54329, 50-77033.
Post-treatment may be carried out using a sulfur-containing compound as described in each publication.

Furthermore, U.S. Pat.Nos. 3,301,678, 3,506,444, and
No. 3824103, No. 3844788, isothiuronium-based stabilizer precursors described in the respective specifications, and US Pat.
The activator stabilizer precursor described in the specifications of 3669670, 4012260, 4060420 and the like may be contained.

Further, a water-releasing agent such as sucrose or NH ₄ Fe (SO ₄ ) ₂ · 12H ₂ O may be used, and further, as in JP-A-56-132332, water is supplied to carry out heat development. Good.

In addition to the above components, the photothermographic material of the present invention may further contain various agents such as spectral sensitizing dyes, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreaders. Additives, coating aids, etc. are added.

The photothermographic material of the present invention basically comprises (1) in the same layer.
It preferably contains a photosensitive silver halide, (2) a reducing agent, (3) the polymer of the present invention, (4) an organic silver salt and (5) a binder. Further, it is preferable to contain (6) a dye-providing substance, if necessary.

The photothermographic material of the present invention basically comprises (1) in the same layer.
It preferably contains a photosensitive silver halide, (2) a reducing agent, (3) the polymer of the present invention, (4) an organic silver salt and (5) a binder. Further, it is preferable to contain (6) a dye-providing substance, if necessary.

However, these do not necessarily have to be contained in a single photographic constituent layer, and the components (1), (2), (3), (4) and (5) may be contained in one photosensitive layer. If it is in a state where they can react with each other such as containing (6) and (5) in another layer adjacent to this photosensitive layer, they may be contained separately in two or more photographic constituent layers.

The inhibitor of the present invention is of course also effective for a photothermographic material (dry silver) which forms an image only with silver.

Further, the photosensitive layer may be divided into two or more layers such as a high-sensitivity layer and a low-sensitivity layer, and further has one or two or more photosensitive layers for controlling other color sensitivity. It may have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer.

The photothermographic layer of the light-sensitive material of the present invention can be provided and optionally. Protective layer, intermediate layer, undercoat layer, back layer,
For other photographic constituent layers, the respective coating solutions are prepared, and the dipping method, air knife method, curtain coating method or US patent
A photosensitive material can be prepared by coating by various coating methods such as the hopper coating method described in No. 3681294.

Furthermore, if desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761,791 and British Patent No. 837095.

The above components used in the photographic constituent layers of the photothermographic material of the invention are coated on a support, and the thickness of coating is preferably 1 to 1000 μm after drying, more preferably 3 to 20 μm.

The photothermographic material of the present invention is exposed imagewise as it is,
Usually, color development is carried out only by heating in the temperature range of 80 ° C. to 200 ° C., preferably 120 ° C. to 170 ° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. If necessary, a water-impermeable material may be brought into close contact with the surface for development, or preheating may be carried out before exposure in the temperature range of 70 ° C to 180 ° 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 or a CRT beam can be used as a 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 in a high temperature atmosphere. Alternatively, high frequency heating may be used, or a conductive layer may be provided in the light-sensitive material of the present invention or in the image transfer layer (element) for thermal transfer, and Joule heat generated by energization or a strong magnetic field may be used. The heating pattern is not particularly limited, and includes a method of preheating (preheating) in advance and then heating again, at a high temperature for a short time, or at a low temperature for a long time, continuously rising, lowering or repeating, and further discontinuous. Heating is also possible, but a simple pattern is preferred. Further, it may be a system in which exposure and heating proceed simultaneously.

The photosensitive silver halide of the present invention will be described. The photothermographic material of the present invention contains a photosensitive silver halide together with the dye-donor polymer of the present invention.

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 and the like. The photosensitive silver halide is
Although it can be adjusted by any method such as a single jet method and a double jet method in the field of photographic technology, in the present invention, a photosensitive silver halide emulsion prepared according to a usual method for preparing a silver halide gelatin emulsion is used. Gives good results.

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

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

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below to form photosensitive silver halide on a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents H base paper, NH ₄ group or metal atom, and X represents Cl, Br. Or I, where n is 1 when M is a H atom, NH ₄ group, and its valence when M is a metal atom.
Sodium, potassium, rubidium, cesium, copper,
Gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium,
Germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium,
Examples thereof include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum and cerium. ), A halogen-containing metal complex (for example, K ₂ PtCl ₆ , K ₂ PtBr
₆ , HAu Cl ₄ , (NH ₄ ) ₂ , IrCl ₆ , (NH ₄ ) ₃ Ir Cl ₆ , (NH ₄ ) ₂ Ru C
l ₆ , (NH ₄ ) ₃ Ru Cl ₆ , (NH ₄ ) ₃ Rh Cl ₆ , (NH ₄ ) ₃ RhBr ₆ etc.), onium halides (for example, tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethyl) Ammonium bromide, 3
-Quaternary ammonium halides such as methylthiazolium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide Tertiary sulfonium halides, 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-bromophthalazinone, 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-bromoethanol, 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 per layer is preferably 0.01 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 same color photosensitive layer can be divided into two or more layers (for example, a high sensitivity layer and a low sensitivity layer).

In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion used in each case are obtained by adding various spectral sensitizing dyes to the silver halide emulsion. You can

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holoboler cyanine, styryl,
Examples include hemicyanine and oxonol. 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 has 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. Good. 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 may have an acidic nucleus such as a thiohydantoin nucleus, a rhodanin nucleus, an oxazolidine nucleus, a barbituric acid nucleus, a thiazoline thione nucleus, a malononitrile nucleus and a pyrazolone nucleus, in addition to the basic nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamino group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivative, azaindene cadmium salt,
Organic sulfonic acids, etc., such as US Pat.
A supersensitizing additive which does not absorb visible light as described in the specification of 937089 and the like can be used in combination.

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

In the present invention, it is preferable to add an organic silver salt.

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 with the photothermographic material of the present invention include JP-B Nos. 43-4921, 44-26582, and 45-18416.
No. 45-12700, No. 45-22185, JP-A-49-52626,
52-31728, 52-137321, 52-141222, 53-3
6224 and 53-37610 and U.S. patents
No. 3330633, No. 3794496, No. 4105451, No. 41232
No. 74, No. 4168980 and the like silver salts of aliphatic carboxylic acids as described in each specification, for example silver laurate,
Aromatic carboxylate silver, such as silver myristate, silver palmitate, silver stearate, silver arachidonic acid, silver behenate, and α- (1-phenyltetrazolethio) acetic acid, for example, silver benzoate, silver phthalate, etc. Kosho 44-26582, 45
-12700, 45-18416, 45-22185, JP-A-52-317
No. 28, No. 52-137321, JP-A No. 58-118638, No. 58-11863.
No. 9, etc., silver salts of imino groups, for example, benzotriazole silver, 5-acetamidobenzotriazole silver, 5-nitrobenzotriazole silver, 5-chlorobenzotriazole silver, 5-methoxybenzotriazole. Silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-methylsulfobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole Silver, silver pyrazole, silver urazole, 1,2,4
-Triazole silver, 1H-tetrazole silver, 3-amino-5-bezylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, and others 2
-Mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2
-Mercaptobenzimidazole silver, 3-mercapto-
4-Phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4, 6-Ventaza indene silver and the like.

Among the above organic silver salts, silver salts of imino groups are preferable,
In particular, a silver salt of a bentriazole derivative, more preferably a silver salt of a sulfobenzotriazole derivative is preferable.

The organic silver salt used in the present invention may be used singly or in combination of two or more kinds, and the isolated salt may be dispersed in a binder by a suitable means before use. The silver salt may be prepared in a different binder and used as it is without isolation.

The amount of the organic silver salt used is 1 mol of photosensitive silver halide.
It is preferably 0.1 to 5 mol, more preferably 0.3.
Mol to 3 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. For example, U.S. Pat.Nos. 3531286, 3761270, and
No. 3764328, Research Disclosure No. 12146, No. 15108, No. 15127, and JP-A-56-2
Examples thereof include p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based and sulfonamidephenol-based developing agents, and hydrazone-based developing agents described in JP-A-7132.

In addition, U.S. Pat.
-135628, 54-79035, etc. Color developing agent precursors and the like can also be used advantageously.

Particularly preferred reducing agents include reducing agents represented by the following general formula (19) described in JP-A-56-146133.

General formula (19) In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 30 (preferably 1 to 4) carbon atoms which may have a substituent, and R ¹ and R ² are ring-closed. A heterocycle may be formed. R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms,
Halogen atom, hydroxy group, amino group, alkoxy group, acylamide group, sulfonamide group, alkylsulfonamide group or carbon atom which may have a substituent
To 30 (preferably 1 to 4) alkyl group, R ³
And R ¹ and R ⁵ and R ² may be 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 (19) is an organic compound containing a nitrogen atom showing basicity capable of forming a salt with an inorganic acid, 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 a quaternary nitrogen in the above general formula (19) include salts or hydroxides of substituted compounds having a tetravalent covalent bond.

Next, preferable specific examples of the reducing agent represented by the general formula (19) are shown below.

The reducing agent represented by the general formula (19) is a known method, for example, Houben-weyl, Methoden der Organischen Chemie, Bard.
XI / 2, can be synthesized according to the method described on pages 645-703.

Other reducing agents such as those described below can also be used.

For example, phenols (eg p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [eg 4-benzene Sulfonamide phenol, 2-benzenesulfonamide phenol, 2,6-dichloro-4-benzenesulfonamide phenol, 2,6-dibromo-4- (p-
Toluenesulfonamide) phenol, etc.] or polyhydroxybenzenes (eg hydroquinone, tert-
Butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (eg α-naphthol, β-naphthol, 4
-Aminonaphthol, 4-methoxynaphthol, 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-3,5-di-tert-butylphenyl) methane, 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, ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines.

These reducing agents may be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of the photosensitive silver halide used, the type of the organic acid silver salt and the type of other additives, but is usually 0.05 per mol of the photosensitive silver halide. The amount is in the range of -10 mol, preferably 0.1-5 mol.

In the photothermographic material of the invention, it is preferable to add a dye-donor substance, and it is a preferred embodiment to obtain a color image by this addition.

As the dye-providing substance of the present invention, those forming a diffusible dye are particularly preferable.

The dye-providing substance that can be preferably used in the present invention will be described. The dye-providing substance may be any one that can participate in the reduction reaction of silver halide and / or organic silver salt and can form a diffusible dye as a function of the reaction, and a positive function depending on the reaction form. Negative-working dye-donors (ie, forming a negative dye image when negative-working silver halide is used) and positive-working dye-donors (ie, negative-working dyes) A positive dye image is formed when 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 following general formula (20).

General formula (20) Car-NHSO ₂ -Dye In the formula, Car is a reducing substrate (so-called carrier) which releases an oxidized feed upon reduction of silver halide and / or organic silver salt, and Dye is a diffusible substance. It is a sex dye residue.

Specific examples of the above reducing dye-releasing compounds include JP-A-57
-179840, 58-116537, 59-60434, 59-65839
Issue 59-71046, Issue 59-87450, Issue 59-88730, Issue 59
-123837, 59-165054, 59-165055, and the like, and examples thereof include the following compounds.

Exemplified dye donor As another reducing dye releasing compound, for example, a compound represented by the general formula (21) can be mentioned.

General formula (21) In the formula, A ₁ and A ₂ each represent a hydrogen atom, a hydroxyl group or an amino group, and Dye is represented by the general formula (20) and has the same meaning as Dye. Specific examples of the compound represented by the general formula (21) are shown in JP-A-59-124329.

As the coupling dye-releasing compound, the following general formula (2
Examples thereof include compounds represented by 2).

General formula (22) In the formula, Cp 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 represents 0 or 1, and Dye has the same meaning as defined in the general formula (20). Further, Cp ₁ is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible, and has 8 or more carbon atoms (depending on the form of the light-sensitive material used as the ballast group ( More preferably 12
Or more) organic groups, or hydrophilic groups such as sulfo groups and carboxyl groups, or 8 or more (more preferably 12 or more)
Is a group having both the carbon atom and a hydrophilic group such as a sulfo group and a carboxyl group. Another particularly preferred ballast group may include a polymer chain.

Specific examples of the compound represented by the above general formula (22),
JP-A-57-186744, 57-122596, 57-160698,
Examples thereof include those described in JP-A-59-174834, JP-A-57-224883, JP-A-59-159159 and JP-A-59-104901, and examples thereof include the following compounds.

Exemplified dye donor The coupling dye-forming compound, the following general formula (23)
The compound shown by is mentioned.

General formula (23) In the formula, Cp ₂ is an organic group (so-called coupler residue) capable of reacting with an oxidized form of a reducing agent (coupling reaction) to form a diffusible dye, and X represents a divalent linking group. , Q represents a ballast group.

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

The ballast group of Q is preferably the same ballast group as the ballast group defined by the general formula (22), and particularly 8 or more (more preferably 12 or more) carbon atoms and hydrophilicity such as sulfo group and carboxyl group. A group having both groups is preferable, and a polymer chain is more preferable.

As the coupling dye forming compound having this polymer chain, a polymer having a repeating unit derived from a monomer represented by the following general formula (24) is preferable.

General formula (24) In the formula, Cp ₂ and X have the same meanings as defined in the general formula (23), Y represents an alkylene group, an arylene group or an aralkylene group, Z represents a divalent organic group, and L represents ethylene. Represents a group having an unsaturated unsaturated group or an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compound represented by the general formulas (23) and (24) include JP-A-59-124339 and 59-1813.
No. 45, Japanese Patent Application No. 58-109293, No. 59-179657, No. 59-18160
4, No. 59-182506, and No. 59-182507, and examples thereof include the following compounds.

Exemplified dye donor In the above general formulas (22), (23) and (24), Cp ₁ or Cp
When the coupler residue defined by p ₂ is described in further detail, a group represented by the following general formula is preferable.

In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, aryl. Sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, cyano group, ureido group, alkylthio group, arylthio group,
Represents a carboxyl group, a sulfo group or a heterocyclic residue, which further includes a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, and sulfamoyl. It may be substituted with a group, a carbamoyl group, an imide group, a halogen atom or the like. These substituents are Cp
₁ and Cp ₂ are selected according to the purpose, and as described above, Cp ₁
In one of the above, one of the substituents is preferably a ballast group, and in Cp ₂ , the substituent is selected so that the molecular weight is 700 or less, more preferably 500 or less in order to enhance the diffusibility of the dye formed. Is preferred.

As a positive type dye-donor, for example, the following general formula (25)
There is an oxidative dye-releasing compound represented by.

General formula (25) In the formula, W ¹ represents an atomic group necessary for forming a quinone ring (which may have a substituent on the ring), R ⁵ represents an alkyl group or a hydrogen atom, and B represents (In the formula, R ⁶ represents an alkyl group or a hydrogen atom, and R ⁷ represents an oxygen atom or Represents ) Or —SO ₂ —, r represents 0 or 1, and Dye has the same meaning as defined in formula (20). Specific examples of this compound are described in the specifications such as JP-A-59-166954 and JP-A-59-154445, and examples thereof include the following compounds.

Exemplified dye donor Another positive type dye-donor substance is a compound represented by the following general formula (26), which loses its dye releasing ability when oxidized.

General formula (26) In the formula, W ² represents an atomic group necessary for forming a benzene ring (which may have a substituent on the ring), R ⁵ , B,
r and Dye have the same meaning as defined in formula (25). Specific examples of this compound are disclosed in JP-A-59-124329 and JP-A-59-15.
No. 4445 and the like, for example, there are the following compounds.

Exemplified dye donor Still another positive dye-donating substance is represented by the following general formula (2
Examples thereof include compounds represented by 7).

General formula (27) In the above formula, W ² , R ⁵ and Dye have the same meanings as defined in the general formula (26). Specific examples of this compound are described in JP-A-59-154445 and the like, for example, the following compounds.

Exemplified dye donor In the above general formulas (20), (21), (25), (26) and (27), D
The residue of the diffusion dye represented by ye will be described in more detail. The residue of the diffusible dye has a molecular weight of 800 or less, more preferably 600 or less for the diffusibility of the dye, preferably an azo dye, an azomethine dye, an anthraquinone dye, a naphthoquinone dye, a styryl dye, a nitro dye,
Examples thereof include residues of 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.
For the purpose of improving the light resistance of the image, these dye residues are also preferable forms of the chelatable dye residues described in JP-A-59-48765 and JP-A-50-124337.

These dye-donor substances may be used alone or in combination of two or more. The amount used is not limited, and depends on the kind of the dye-donating substance, single use or two or more combined use, or photographic constituent layer or single layer or two or more multi-layers of the light-sensitive material of the present invention. It may be determined, 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 of incorporating the dye-donor compound of the present invention into the photographic constituent layer of the photothermographic material is arbitrary, and examples include low-boiling point solvents (methanol, ethanol, ethyl acetate, etc.) or high-boiling point solvents (dibutyl phthalate, dioctyl phthalate,
After being dissolved in triclendiphosphate, etc., ultrasonically dispersed or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide aqueous solution) and then neutralized with a mineral acid (eg, hydrochloric acid or nitric acid). It can be used after being dispersed by using a ball mill together with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyrate, polyvinylpyrrolidone, etc.).

When the photothermographic material of the invention contains a dye-donor that releases or forms a diffusible dye, it is necessary to use an image-receiving layer.

In the present invention, as the image-receiving layer which receives the diffusible dye imagewise formed by imagewise exposure of the photographic constituent layer and thermal development, those commonly used in this field can be used, and for example, paper, Although cloth, plastic, or the like can be used, a support having an image-receiving layer containing a mordant or a compound having a dye-receiving ability is preferably used. Particularly preferred image-receiving layers are layers made of polyvinyl chloride described in Japanese Patent Application No. 58-97907 and Japanese Patent Application No. 58-12860.
Examples of the layer include the polycarbonate described in No. 0 and a plasticizer.

The image-receiving layer may be provided on the same support as the photographic constituent layer, in which case it may be peeled off from the photographic constituent layer after the dye is transferred, or may be provided on a separate support. The formation is not particularly limited, and any technique can be used.

[Examples] Examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

Example-1 [Preparation of 5-methylbenzotriazole silver] 2-methylbenzotriazole silver was reacted with silver nitrate in a water / ethanol mixed solvent to obtain 28.8 g of 5-methylbenzotriazole silver and poly-N-vinylpyrrolidone 150 ml of water containing 16 g of (molecular weight 30.000) was dispersed by an alumina ball mill, and the pH of this dispersion was adjusted to 5.5, and then 200 ml was finished.

[Dye donor dispersion]

35.5 g of the following dye-providing substance (cpm-I), 5.0 g of the following hydroquinone compound and the compound (A-1) of the present invention were dissolved in 200 ml of ethyl acetate, and alkanol XC (manufactured by DuPont)
Mix with 124 ml of 5 wt% aqueous solution and 720 ml of gelatin aqueous solution containing 30.5 g of phenylcarbamoylated gelatin (Type 17819PC, Haslow Co.), disperse with an ultrasonic homogenizer, distill off ethyl acetate, and then adjust to pH 5.5 to 800 ml. It was

[Developer solution] 23.3 g of the following developer, 1.10 g of the following development accelerator, poly (N-vinylpyrrolidone) (molecular weight 30,000) and 0.5 g of the following fluorochemical surfactant are dissolved in water to pH 5.5 and 250 ml. Finished.

<Preparation of Photothermographic Material> 12.5 ml of the organic silver salt dispersion, 4 of the dye-providing substance dispersion
0.0 ml, the developer 12.5 ml, polyethylene glycol 2.0
g, 3-methylpentane-1,3,5-triol 2.0 g and 6 ml of a silver halide emulsion having an average particle size of 0.13 μm (containing 7.5 × 10 ⁻³ mol of silver halide in terms of silver) are mixed. , And a hardening agent solution [tetra (vinylsulfonylmethyl) methane and taurine were reacted at a ratio of 1: 1 (weight ratio) and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin to obtain 3% by weight of tetra (vinylsulfonylmethyl) methane. %)] After adding 2.5 ml, it was coated on a 180 μm-thick photographic polyethylene terephthalate film with a thickness of 2.64 g / m ^2, and further on it. A protective layer made of a mixture of the phenylcarbomoylated gelatin and poly (N-vinylpyrrolidone) (molecular weight 30.000) was provided to prepare Photosensitive Material No. 1.

After drying the obtained light-sensitive material, a white exposure of 8000 CMS was given through a step wedge.

Then, separately, the image receiving layer surface of the image receiving sheet coated with polyvinyl chloride (12 g / m ² ) as the image receiving layer material on the baryta paper and the coated surface of the exposed photosensitive material are overlaid at 150 ° C.
Thermal development was performed for 1 minute, the image receiving sheet was peeled off, and a magenta transferred image was obtained on the image receiving sheet. The maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image are shown in Table-1.
Shown in.

Example-2 Photosensitive materials No. 2 to No. 25 were prepared in the same manner as in Example-1 except that the kinds and addition amounts of the compound of the present invention and the inhibitor for comparison were changed as shown in Table-1. The same exposure and heat development as in Example-1 were performed and the results shown in Table-1 were obtained.

Comparative Example-1 The following comparative inhibitor was used in place of the compound of the present invention of Example-1.
The same light-sensitive material as in Example-1 was prepared except that (A, B, C, D) was added, and the same exposure and heat development as in Example-1 were carried out.
The results shown in are obtained.

From the above Examples and Comparative Examples, it is understood that the photothermographic material containing the compound of the present invention has a markedly improved Dmin as compared with those containing no inhibitor and those containing a known inhibitor. .

Example-3 A light-sensitive material was prepared in the same manner as in Example-1 except that the following compounds (cpm-II and cpm-III) were used instead of the dye-donor substance in Example-1, and the same exposure as in Example-1 was performed. Photothermal development was performed and the results shown in Table 2 were obtained.

Table 2 shows that the present invention is effective for various dye-donor substances.

Example 4 A light-sensitive material having the following constitution was prepared from the lower layer on a photographic polyethylene terephthalate film having a thickness of 180 μm and subjected to undercoating.

First photosensitive layer: A photosensitive layer having the same composition as that of Example-1 except that the silver halide of Example-1 was changed to a silver halide having a green sensitivity and an average grain size of 0.13 .mu.m (however, the addition amount is Example- 2/5 of 1).

Intermediate layer: An intermediate layer containing 0.5 g of gelatin, 0.5 g of polyvinylpyrrolidone, 0.5 g of polyethylene glycol, 0.4 g of 3-methylpentane-1,3,5-triol, and 0.4 g of the following compound (CD ′ scavenger) per 1 m ^{2 of the} support.

Second photosensitive layer: A photosensitive layer having the same composition as the first photosensitive layer except that the silver halide having red sensitivity was changed to a silver halide having a red sensitivity and the dye-donor substance cpm-II was used.
1/3).

Intermediate layer: An intermediate layer further having the following yellow filter dye (0.4 g) in the intermediate layer.

Third photosensitive layer: A photosensitive layer having the same composition as the second photosensitive layer except that the silver halide is changed to a silver halide having blue sensitivity and the dye-donor substance is changed to cpm-III.

Protective layer: The same protective layer as the protective layer described in Example-1.

This photosensitive material was exposed to 8000 CMS of red light, green light, and blue light, respectively, and subjected to the same thermal development as in Example-1,
The transfer densities (Dmax and fog) of cyan, magenta and yellow dyes were measured, respectively. The results are shown in Table-3.

Comparative Example-3 A photosensitive material in which the compound of the present invention was removed from each photosensitive layer of Example-4 and a photosensitive material in which the compound of the present invention was changed to the above-mentioned comparative inhibitor (A) was prepared. The same exposure and heat development were performed.

The results are shown in Table-3.

From Example-4 and Comparative Example-3, the present invention provides Dmin when applied to a multilayer type photothermographic material which gives a color image.
Is significantly improved.

Example-5 Photosensitive materials 1,2,3,4,1 of Examples-1 and -2 and Comparative example-1
For 5 and 24, high temperature (50 ℃) and high humidity (relative temperature 80
%), The same heat development as in Example-1 is performed, and Dmax, Dmin and the desensitization rate due to standing [(1-sensitivity after standing / sensitivity before standing) × 100%] are obtained. I asked. The results are shown in Table-4.

From these results, the photothermographic material of the present invention has a sensitivity Dmax and a sensitivity when stored under high temperature and high humidity as compared with the photothermographic material containing no compound of the present invention or containing a comparative inhibitor. It can be seen that the change in Dmin is small and the raw preserved raw material is improved.

Example-6 A light-sensitive material and an image-receiving material having the following constitutions were prepared, exposed from the support side of the light-sensitive material with 8000 CMS in the same manner as in Example-4, and brought into close contact with the image-receiving material and heat-developed at 150 ° C. for 1 minute, The results shown in Table-5 were obtained.

Photosensitive material (listed in order from upper layer to lower layer. The amount of each component is the amount per 1 m ^2. ) Protective layer: 0.42 g of gelatin, 0.36 g of SiO ₂ , 1.0 g of saffron.

Red-sensitive layer: methylbenzotriazole silver 1.6 g, reducing agent (R-11) 0.57 g, cpm-II 0.8 g, red-sensitive silver halide (see note 1 below) 0.58 g in silver, hydroquinone of Example-1 Compound 60 mg, gelatin 0.75 g, phthalated gelatin 0.75 g, polyvinylpyrrolidone 0.5 g, 3-methylpentane-1,3,5-triol 0.38 g, polyethylene glycol 1.1 g, AIK-XC (see Note 3) 80 mg, the present invention 0.52 g of the compound (A-1) and 60 mg of a hardening agent.

Intermediate layer: 0.5 g of gelatin, 0.4 g of the CD 'scavenger of Example-4, 1.2 of methylbenzotriazole silver.
g, hardener 20 mg. Green-sensitive layer: cpm-I 1.3 g, green-sensitive silver halide (see Note 2) 0.76 g in terms of silver, methylbenzotriazole silver 2.7 g, reducing agent (R-11) 0.76 g, hydroquinone compound 90 mg, gelatin 1 g , 1 g of phthalated gelatin,
Polyvinylpyrrolidone 0.66 g, 3-methylpentane-1,
3,5-triol 0.5g, polyethylene glycol 1.5g,
AIK-XC 0.11 g, compound (A-1) 0.68 of the present invention
g, hardener 80 mg.

Intermediate layer: 0.4 g of the Y-filter dye of Example-4, 0.4 g of the above CD 'scavenger, 1.2 g of methylbenzotriazole silver, 0.5 g of gelatin, 20 mg of a hardening agent. Blue feeling layer: cpm
-III 1.4g, blue sensitive silver halide (0.97g in terms of silver),
Methylbenzotriazole 2.7 g, reducing agent 0.97 g, the hydroquinone compound 90 mg, gelatin 1.26 g, phthalated gelatin 1.26 g, polyvinylpyrrolidone 0.84 g, 3-methylpentane-1,3,5-triol 0.63 g, polyethylene glycol 1.9 g , AIK-XC 0.14 g, the compound of the present invention (A
-1) 0.87 g, a hardener 0.1 g.

Gelatin layer: Gelatin 2.5 g Support: Polyethylene phthalate film with a thickness of 180 μm and latex-subbed.

Image Receiving Material Image Receiving Layer: Polycarbonate 10g, Compound (1) 0.5g,
0.5 g of the following compound (2).

Support: Baryta paper EFFECT OF THE INVENTION The photothermographic material according to the present invention gives an image having a high density and improved fog, and has an improved raw preservation quality (sensitivity D).
(at max and Dmin).

Claims (1)

[Claims] 1. A photosensitive silver halide is contained on a support.
In the photothermographic material having a layer, the following general formula (1)
Thermal development sensation characterized by containing a compound represented
Light material. General formula (1) X- (J)_n-(B) [where X is for photography represented by the following general formulas (2) to (18)
Represents the residue of the inhibitor, J is -CONH-, -SO₂NH-, -NHCONH-, -COO-, -NHCO-, -NHSO₂-, -O-, -S-,(R represents a hydrogen atom or an alkyl group) and -CO-
Represents a bonding group selected from the group, B represents a ballast group,
n represents 0 or 1. ] General formula (2)[R¹And R^TwoAre each a hydrogen atom, an alkyl group or an ari.
Represents a hydrogen atom group, M is a hydrogen atom, an alkali metal atom,
Represents an ammonium group or an organic amine residue. ] General formula (3)[R¹Represents an alkyl group, an aryl group or a hydrogen atom
However, M has the same meaning as M in formula (2). ] General formula (4)[R^ThreeIs a hydrogen atom, an alkyl group, an aryl group or(M represents 1 or 2) and R^FourAnd R⁵Are hydrogen atom, alkyl group,
Represents an aryl group or a nitro group, R^FourAnd R⁵Combined
May form a 5- or 6-membered ring. ] General formula (5)[R¹Represents an alkyl group, an aryl group or a hydrogen atom
And R^FourAnd R⁵Are hydrogen atom, alkyl group, and aryl, respectively.
R or nitro, R^FourAnd R⁵Are joined by 5 members
Alternatively, a 6-membered ring may be formed. ] General formula (6)[Y represents -N-, -O-, or -S-, and R¹A
Represents a alkyl group, an aryl group or a hydrogen atom, and M is generally
It is synonymous with M in formula (2). ] General formula (7)[Y¹Is -O-, -S-,OrAnd R¹And R⁶Are alkyl and aryl groups, respectively
Or represents a hydrogen atom, and R^FourAnd R⁵Are hydrogen atoms,
R represents an alkyl group, an aryl group or a nitro group, and R^FourWhen
R⁵May combine to form a 5- or 6-membered ring. ] General formula (8)[Y¹Is Y in the general formula (7)¹And R^FourAnd R⁵Is the general formula (7)
R^FourAnd R⁵And M are synonymous with M in the general formula (2), respectively.
Is. ] General formula (9)[R⁷And R⁸Is a hydrogen atom, an alkyl group, an aryl group,
Represents a nitro group or a halogen atom, R⁷And R⁸Is joined
To form a 5- or 6-membered ring. ] General formula (10)[R⁹, R¹⁰And R¹¹Are alkyl group and amino
Group, alkoxy group, thioalkoxy group, -SM (M is general
It is synonymous with M in formula (2). ), Hydroxyl group or hydrogen
Represents an atom. ] General formula (11)[R¹², R^Thirteen, R¹⁴, R¹⁵And R¹⁶Each is water
Elementary atom, alkyl group, aryl group, R¹-NH- (R¹Is
It represents a hydrogen atom, an alkyl group or an aryl group. ),-
SM (M has the same meaning as M in formula (2)), alkyl group
Represents a hydroxy group, a hydroxyl group or an alkoxy group. ] General formula (12)[R¹², R^Thirteen, R¹⁴And R¹⁵Each of the general formula (11)
R¹²~ R¹⁶Is synonymous with. ] General formula (13)[R¹⁷And R¹⁸Each represents an alkyl group or a hydrogen atom.
Here, M has the same meaning as M in the general formula (2). ] General formula (14)[R¹⁹And R²⁰Is an alkyl group, an aryl group, or
Represents a hydrogen atom, R¹⁹And R²⁰Are joined by 5 members
May form a 6-membered ring. ] General formula (15)[R¹, R¹⁹And R²⁰Are alkyl and aryl
Represents a hydrogen atom or a hydrogen atom, R¹⁹And R²⁰Combined with
A 5- or 6-membered ring may be formed. Y^TwoIs -O-,-
S-or(R¹⁷Represents a hydrogen atom or an alkyl group. )
You ] General formula (16)[R¹Represents each alkyl group, aryl group or hydrogen atom
Then Y^TwoIs -O-, -S- or(R¹⁷Represents a hydrogen atom or an alkyl group. ) Table
Forget M has the same meaning as M in formula (2). ] General formula (17)[Y^ThreeIsOr = N-, R¹⁹And R²⁰Are each Archi
Represents an alkyl group, an aryl group or a hydrogen atom, and R¹⁹And R
²⁰May combine to form a 5- or 6-membered ring.
R¹⁷Is R in the general formula (16)¹⁷And M is M in the general formula (2)
They are synonymous. ] General formula (18)[R¹, R¹⁹And R²⁰Is an alkyl group or aryl
Represents a group or a hydrogen atom, R¹⁹And R²⁰Combined with 5
May form a 6-membered or 6-membered ring. Y Represents a counter anion. ]