JP2001272751A - Heat developable material and method for developing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable material excellent in the scuffing resistance of the film surface, excellent also in fog reducing properties and properties of preventing printout after development as photographic performances, giving a processed film whose surface is less liable to stain even in development processes repeated many times and not causing the contamination of a heat drum or a heat roller in a processing machine in which heat development is carried out and to provide a method for developing the material. SOLUTION: In the heat developable material with a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder and a protective layer containing a fluorine compound, a matting agent and a binder on the base, the binder in the photosensitive layer or the protective layer is cured in the presence of a compound of formula (1) or (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable material for forming an image by heat development, and more particularly to a heat-developable material which has excellent scratch resistance on the film surface, low fog in photographic performance, and The present invention relates to a heat-developable material which is excellent in printout prevention property and is less likely to cause stains on the processing film surface even in the development processing of a large amount of heat-developable material, and further, a heat drum or a heat roller in a processing machine for developing the heat-developable material The present invention relates to a developing method that does not cause stains on the image.

[0002]

2. Description of the Related Art In recent years, in the fields of medical care and printing, there has been a strong demand for a photosensitive material which is developed by heat without waste liquid, instead of a photosensitive material which is subjected to wet development processing from the viewpoint of environmental protection and workability.
That is, there is a need for a technique relating to a photothermographic material for photographic technology, which can form a high-resolution and clear black image by developing with heat. Since these photosensitive materials are usually developed at a temperature of 80 ° C. or higher, they are called heat developing materials.

In the case of a heat-developable material, it is necessary to increase the strength of the film so as to withstand development at a high temperature, and a material that cures a binder has been used. The material to be cured is
It is selected according to the material used for the binder, for example, an epoxy compound is particularly useful because it increases the film strength.
The curing reaction is slow, and the photographic performance fluctuates as the curing progresses. If the curing is accelerated at a high temperature, fogging occurs, so that it was necessary to cure at a low temperature. Therefore, there is an isocyanate compound disclosed in JP-A-6-208193 as a material that can be rapidly cured at a low temperature. However, if water is present in a coating solution, it is decomposed and loses its curing performance. It had disadvantages such as lack of stability of the prepared coating solution. On the other hand, carboxy active compounds and bisvinylsulfone compounds are useful for binders having carboxyl groups and amino groups, but have no effect on cellulose-based or polyvinyl alcohol-based binders having hydroxyl groups. As another approach, as a method of improving the scratch resistance of the heat developing material, there is a method of improving the slipperiness of the film surface of the outermost layer and a method of reducing the charge amount due to friction. Improving the slipperiness of the film surface has the effect of reducing the unreasonable load from a hard metal or plastic transfer roller, transfer guide, or the like that comes into contact with the film, and suppressing the occurrence of scratches.

[0004]

However, an excessive increase in the slipperiness causes a decrease in the accuracy of the repetition of the cutting dimension at the time of cutting. In addition, reducing the amount of charge means that the thermal developing material may be damaged by sticking or rubbing between the thermally developed materials during transport or handling, and that the attached dust may be caught by the transport rollers or the transport guide and damaged. Although there is an effect of preventing such a problem, the use of an antistatic agent causes a disadvantage that the hardness of the film is lowered and the film is easily damaged.
In addition, the matting agent reduces the adhesion of fingerprints of hands when handling the heat-developable material, prevents slippage during transport for cutting, and improves the accuracy of cutting, or when storing the heat-developable material, It has the effect of preventing sticking of developing materials, but on the other hand, by adding a matting agent,
Since irregularities are formed on the surface of the film, dust is accumulated in the irregularities when the thermal developing material is conveyed, and scratches easily occur. As described above, the heat-developable material is provided with scratch resistance by imparting, for example, curing, slipperiness, charging properties, and matte properties (the formation of uneven portions on the film surface by the addition of a matting agent) of the binder on the film surface of the heat-developable material. On the other hand, conflicting obstacles occurred, and satisfactory effects could not always be obtained. The present invention has been proposed based on the above-mentioned circumstances, and its object is to provide excellent film surface scratch resistance, excellent photographic performance fog reduction, excellent printout prevention after development, and a large number of developments. It is an object of the present invention to provide a heat developing material which is less likely to adhere to a processing film surface during processing. It is still another object of the present invention to provide a developing method that does not cause contamination on a heat drum or a heat roller in a processing machine for performing a development process using the heat development material.

[0005]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
In a heat-developable material having a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support and a protective layer containing a fluorine compound, a matting agent and a binder, the photosensitive layer or the protective layer The binder of the layer is cured in the presence of the compound represented by the general formula (1) or (2) (Binders of both the photosensitive layer and the protective layer may be cured). Or containing a polyhalomethane in the layer adjacent thereto, and further containing an acid anhydride, the fluorine compound contained in the protective layer is an anionic compound having a fluorinated aliphatic group, or fluorinated Is a nonionic compound in which a polyoxyalkylene group is bonded directly or via a bonding group to an aliphatic group obtained, and the matting agent contained in the protective layer has hydroxyl It is accomplished by the heat developable material characterized by having a. Further, the heat development material of the present invention contains iron oxide, and has a surface hardness of 20 to 90 when expressed in durometer A hardness, a surface unevenness difference of 0.5 to 8 μm, Using a heat drum or a heat roller having a surface layer of silicone rubber having a frequency of 10 to 1000 irregularities per 1 mm (both the heat drum and the heat roller may have a surface layer of silicone rubber). This is achieved by a developing method characterized in that development is performed in a temperature range of from 200 to 200 ° C.

Hereinafter, the present invention will be described in detail. <Heat developing material> The heat developing material of the present invention has a photosensitive layer on a support, in which at least photosensitive silver halide, organic silver salt, reducing agent and binder (polymer binding material) The protective layer contains a fluorine compound, a matting agent and a binder, and the binder of the photosensitive layer and / or the protective layer is a compound represented by the general formula (1) or (2) (Also referred to as an agent).
Hereinafter, the materials used for the heat development material of the present invention will be sequentially described. First, the curing agent of the present invention, a binder, a fluorine compound, a matting agent, a photosensitive silver halide, an organic silver salt,
The reducing agent, other additives, and the techniques for using them will be described sequentially.

(Explanation of general formulas (1) and (2))
The atoms forming the ring Z ¹ and the ring Z ² of the general formulas (1) and (2) representing the curing agent of the present invention are preferably selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Has other atoms, such as phosphorus, arsenic, antimony,
It may be selected from tin or selenium. Preferred rings include a pyridine ring, an imidazole ring, a succinimide ring,
Thiazole ring, oxazole ring, thiadiazole ring, oxadiazole ring, triazole ring, tetrazole ring,
Examples thereof include a pyrrolidine ring and a pyrimidine ring, and a pyridine ring, a succinimide ring and an imidazole ring are particularly preferable. As the substituent to be introduced into these rings, any of a group that promotes adsorption to silver halide and a sterically hindered group that suppresses adsorption to silver halide is selected. In addition, the group which is eliminated after performing the curing reaction may volatilize by thermal development and contaminate the environment.In this case, the volatility can be reduced by increasing the molecular weight of the group. Although it is preferable to increase the molecular weight, on the other hand, if the molecular weight is too large, the curing reaction decreases, so that it is preferable to select a practical range. In the case of a quaternary structure containing nitrogen, an inorganic or organic anion is preferred as the counter ion, but a halogen atom is particularly preferred, and a bromine ion is often used. Examples of the substituents on the rings Z ¹ and Z ² include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a hydroxy group, a cyano group, a nitro group, an amino group,
Carboxyl group, sulfonic acid group, phosphoric acid group, carbonic acid group, alkyl group having 1 to 40 carbon atoms (eg, methyl group, ethyl group, octyl group, dodecyl group, etc.), alkenyl group (eg, ethenyl group, butenyl group, octenyl) Group, etc.), aromatic groups (for example, phenyl group, naphthalene group, 2,4-methylphenyl group, 2,4-dimethoxy group, 2,4-diamylphenyl group, 4-acetoxy group, 4-acetyl group,
4-acetamino group, 4-cyanophenyl group, etc.), alkoxy group (methoxy group, ethoxy group, butoxy group, etc.),
Heterocyclic group (for example, pyridine ring, pyrimidine ring, pyrrole ring, pyrrolidine ring, imidazole-ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring,
Thiadiazole ring, oxadiazole ring, etc.). Preferred specific examples are shown below, but are not limited thereto.

[0008]

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[0009]

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The curing agent of the general formula (1) or (2) of the present invention can be synthesized by referring to a known synthesis method. An amine compound having a ring Z ¹ and a ring Z ² or an acid halide thereof is acetonitrile, toluene, dioxane,
Is dissolved in dimethylformamide or dimethyl sulfoxide solvent such as, carbonylating agent or acetylating agent having a linking group L ¹ to, succinic anhydride, by introducing polyethylene glycol, polypropylene glycol or polybutylene glycol, triethylamine as a catalyst, The compounds of the present invention can be easily synthesized using amines such as tributylamine and pyridine. The method of adding the curing agent of the general formula (1) or (2) can be added according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Also, 1μ by sand mill dispersion, jet mill classification dispersion, ultrasonic dispersion and homogenizer dispersion.
m or less and dispersed in water or an organic solvent. Many techniques are disclosed for the fine particle dispersion technique.
It can be added as fine particle dispersion water or organic solvent dispersion of 5 to 10 μm. In order to use fine particles, the value (monodispersity) represented by a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter and multiplying by 100 is preferably 1 to 30, more preferably 1 to 20. The amount added is 1 per gram of binder.
The range is from nanomolar to 50 mmol, preferably from 1 micromolar to 100 mmol. The addition of the curing agent can be added to the layer in which the binder to be cured is present in an in-line manner using a batch type or a static mixer, but added to the coating solution for forming the adjacent layer or the intermediate layer, During the coating and drying, the reaction may be aimed at by diffusing and moving to a layer in which a binder is present, that is, a photosensitive layer or a protective layer.

(Binder) As the binder contained in the photosensitive layer and the protective layer of the heat-developable material of the present invention, it is preferable to use a material which is preferable as a place where the photosensitive silver halide, the organic silver salt and the reducing agent react. it can. For example, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, acetyl cellulose, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, styrene- Maleic anhydride copolymer, polyacrylamide, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene- Butadiene-acrylic copolymer. After drying and forming a film, the coating film preferably has a low equilibrium moisture content. The amount used is
0.4 to 50 g / m ^{2 in} the photosensitive layer, 0.1 to 10 in the protective layer
g / m ² is preferred.

(Fluorine Compound) The fluorine compound contained in the protective layer of the photothermographic material of the present invention is preferably an anionic surfactant having a fluorine-containing aliphatic group (Rf group) or a nonionic surfactant. The aliphatic has 1 to 36 carbon atoms, the anion part is a carboxylic acid group and a sulfonic acid group, and the nonionic group is a polyalkyleneoxy group, preferably having 3 to 60 alkylene units. It is particularly preferable that both ends of the nonionic surfactant be an aliphatic group, and it is particularly preferable to use a fluorine-containing aliphatic nonionic surfactant and a fluorine-containing aliphatic anionic surfactant at both ends. Preferred compounds are shown below as general formula (3).

[0013]

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In the formula, Rf represents a branched or straight-chain aliphatic group containing a fluorine atom having 1 to 36 carbon atoms, G represents a divalent linking group, and A represents a hydrophilic group. p and q represent 0 or 1, and when q is 0, A represents an anionic group. The aliphatic group includes an alkyl group (for example, a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a hexadecyl group, or a docosanyl group) or an alkenyl group (ethenyl group, butenyl group, octenyl group, nonenyl group, or dodecenyl group). Etc.) represents a group in which part or all of the hydrogen of the above (i. The G group may be a sulfonamide group, a carboxamide group, a fluorinated group, a hydroxy group or a substituent of an alkyl group having 1 to 24 carbon atoms (eg, a methyl group, an ethyl group, a hexyl group, or a dodecyl group). Or a polyoxyalkylene group which may have a 1,4-phenylene group (such as a 2-methoxyphenylene group, a 2-hydroxyphenylene group, a 2,5-dimethoxyphenylene group, or a 2,5-diamylphenylene group) A 1,3-phenylene group (such as a 4-methylphenylene group, a 4-methoxyphenylene group, a 4-hydroxyphenylene group or a 4-amylphenylene group), a naphthylene group (a 1,5-naphthylene group or a 1,4-naphthylene group) Etc.), heterocyclic groups (pyridine group, imidazole group, thiazole group, oxazole group, pyrazole group, tetrazo Le group or furan group), when A is q is 0, an acid group such as sulfonic acid or carboxylic acid groups, these acid groups may be sodium, potassium or alkali metal salts such as lithium.
Preferred specific examples are shown below.

[0015]

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[0016]

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[0017]

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The fluorine compound of the present invention can be obtained from a general market or synthesized by a known method, and the fluorine compound can be added to the protective layer according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles having a particle size of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion and added. Many techniques have been disclosed for the fine particle dispersion technique, and a fine particle dispersion having an average particle size of 0.05 to 10 μm can be added according to these techniques. The fluorine compound is preferably added to the protective layer, but can be added to the photosensitive layer or a layer below the photosensitive layer in a smaller amount than the protective layer. In some cases, it may be added more than the protective layer, but it is necessary to adjust the surface tension of the coating solution. The addition amount is in the range of 10 ^-4 mass% to 30 mass%, preferably 10 ^-4 mass%, based on the coating solution.
^-2 % by mass to 10% by mass.

(Photosensitive Silver Halide) The photosensitive silver halide used in the photothermographic material of the present invention can be prepared, for example, by a method known in the field of photographic technology such as a single jet method or a double jet method. It can be prepared by any method such as a method emulsion, a neutral method and an acidic method. Thus, the composition can be prepared in advance and then mixed with the other components of the present invention and introduced into the composition for coating the photosensitive layer. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat.
No. 564, No. 3,706,565, No. 3,71
No. 3,833, 3,748,143, British Patent No. 1,362,970, etc., means using a polymer other than gelatin such as polyvinyl acetal described in each specification, and British Patent No. 1 Means for Enzymatically Degrading the Gelatin of Photosensitive Silver Halide Emulsions as described in U.S. Pat. No. 4,076,53.
As described in the specification of JP-A No. 9, various means such as a method of omitting the use of a protective polymer by preparing a photosensitive silver halide in the presence of a surfactant can be applied.

The photosensitive silver halide functions as an optical sensor, and preferably has a small grain size in order to suppress white turbidity after image formation or to obtain good image quality. 0.1 μm or less in average particle size,
Preferably it is 0.01-0.1 μm, especially 0.02-0.1 μm.
08 μm is preferred. The shape of the photosensitive silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals or non-normal crystals, such as spherical, rod-shaped, and tabular grains. The composition of the photosensitive silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The amount of the photosensitive silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 0.1% by mass, based on the total amount of the silver halide and the organic silver salt described below. It is.

The above-mentioned photosensitive silver halide may also be used, as described in British Patent 1,447,454, to form a halogen component such as halide ion into an organic silver salt when preparing the organic silver salt. By coexisting with the component and injecting silver ions into this, it is possible to generate the organic silver salt almost simultaneously.

As still another method, a silver halide forming component is allowed to act on a previously prepared solution or dispersion of an organic silver salt described later or a sheet material containing the organic silver salt,
Part of the organic silver salt can also be converted to photosensitive silver halide. The photosensitive silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. be able to. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak peculiar to the photosensitive silver halide. Silver halide-forming components confirmed to be effective by such tests include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. U.S. Pat. No. 4,009,
No. 039, No. 3,457,075, No. 4,00
3,749, British Patent No. 1,498,956, etc. and JP-A-53-27027 and JP-A-53-254.
Each publication such as No. 20 can be referred to.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is 0.001 to 0.7 mol, preferably 0.03 to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt to the photosensitive silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of the production. Usually, the reaction temperature is -23 to 74.
C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is preferably 0.01 to 100 per 1 part by mass of the organic silver salt.
It is 0.1 part by mass, more preferably 0.1 part by mass.

(Organic silver salt) The organic silver salt contained in the photosensitive layer of the heat-developable material of the present invention is a silver salt of an organic acid or a heteroorganic acid, and especially a long-chain (10 to 30 carbon atoms, preferably 15-25) Silver salts of aliphatic carboxylic acids and nitrogen-containing heterocyclic compounds are preferred. Organic or inorganic complexes in which the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions are also preferred. Examples of these suitable silver salts include Research Disclosure No. 17
029 and 29996, and include the following.

Examples of the silver salt of an organic acid include silver salts such as gallic acid, oxalic acid, behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid. Carboxyalkylthiourea salts of silver, for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,
Silver salts such as 3-dimethylthiourea, silver salts and complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids, for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (for example, salicylic acid) Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes, for example, 3- (2-carboxyethyl) -4 Silver salts or complexes such as -hydroxymethyl-4-thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene, imidazole, pyrazole, urazole,
1,2,4-thiazole and 1H-tetrazole, 3-
Complexes or salts of silver with a nitrogen acid selected from amino-5-benzylthio-1,2,4-triazole and benzotriazole, silver salts such as saccharin and 5-chlorosalicylaldoxime, and silver salts of mercaptides Is mentioned. Among them, preferred silver salts are silver behenate, silver arachidate or silver stearate. The organic silver salt compound is obtained by mixing a water-soluble silver compound and a compound that forms a complex with silver, and is described in Japanese Patent Application Laid-Open No. 9-127643, a forward mixing method, a reverse mixing method, a simultaneous mixing method. Controlled double jet method or the like is preferably used. For example, after preparing an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.) by adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid,
By the control double jet, the soap and silver nitrate are added to produce organic silver salt crystals. At that time, photosensitive silver halide grains may be mixed. In the present invention, the organic silver salt preferably has an average particle size of 2 μm or less and is monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.05
To 1.5 μm, particularly preferably 0.05 to 1.0 μm.
The monodispersion has the same meaning as in the case of photosensitive silver halide, and preferably has a monodispersity of 1 to 30. In the present invention, the organic silver salt has a tabular grain of 60% of the total organic silver.
% Or more. In the present invention, the term "tabular grains" refers to the ratio of the average particle diameter to the thickness, that is, the so-called aspect ratio (A).
R) is 3 or more. In order to form the organic silver salt into these shapes, the organic silver salt can be obtained by dispersing and pulverizing the organic silver crystal with a ball mill or the like. Within this range, a photosensitive material having a high density and excellent image storability can be obtained. The total amount of the photosensitive silver halide and the organic silver salt is preferably from 0.5 to 2.2 g per m ² in terms of silver amount. With this range, a high-contrast image can be obtained. The amount of silver halide based on the total amount of silver is 50% by mass or less, preferably 25% by mass or less, and more preferably 0.1 to 15% by mass.

(Reducing Agent) As the reducing agent contained in the photosensitive layer of the heat-developable material of the present invention, a reducing agent for reducing silver halide can be used as a reducing agent for the organic silver salt, or can be used independently. . For example, bisphenol (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis ( 2
-T-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl)-
3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and benzyl And aldehydes and ketones such as biacetyl; 3-pyrazolidone and certain indane-1,3-
There are dione and tocopherol. Amide oximes such as phenylamide oxime, 2-thienylamide oxime and p-phenoxyphenylamide oxime;
Azines such as hydroxy-3,5-dimethoxybenzaldehyde azine; combinations of an aliphatic carboxylic acid aryl hydrazide such as a combination of 2,2-bis (hydroxymethyl) propionyl-β-phenylhydrazine with ascorbic acid and ascorbic acid; A combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (such as a combination of hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); phenylhydroxam Acids, hydroxamic acids such as p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6
-Dichloro-4-benzenesulfonamidophenol and the like); α- such as ethyl-α-cyano-2-methylphenyl acetate and ethyl-α-cyanophenyl acetate.
Cyanophenylacetic acid derivative; 2,2-dihydroxy-
Bis-β as exemplified by 1,1-binaphthyl, 6,6-dibromo-2,2-dihydroxy-1,1-binaphthyl and bis (2-hydroxy-1-naphthyl) methane
-Naphthol; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 3-methyl-1-phenyl-5-pyrazolone, etc. 2,6-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-
Sulfonamidophenol reducing agents such as dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3
-Dione and the like; 2,2-dimethyl-7-t-butyl-6-
Chromanes such as hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine Particularly preferred reducing agents are bisphenols. The addition amount may be an amount sufficient to sufficiently reduce the silver halide salt and the organic silver salt used, and may be selected from the range of 0.01 to 10 mol per mol of silver. Particularly preferred addition amount is 0.1 to
It is in the range of 3 moles. The layer to be added is mainly a photosensitive layer, but it can be partially added to a protective layer or a layer below the photosensitive layer.

(Matting Agent) The matting agent contained in the protective layer of the heat-developable material of the present invention may be either an organic substance or an inorganic substance. As the inorganic substance, for example, Swiss Patent No. 330,
No. 158, silica, French Patent 1,29
No. 6,995, British Patent 1,
173, 181 can be used as a matting agent. Examples of the organic substance include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, etc .; -3643, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, polyacrylonitrile described in U.S. Patent No. 3,079,257, and U.S. Patent No. 3,022. An organic matting agent such as polycarbonate described in the specification of JP-A-169 / 169 can be used. A particularly preferred inorganic substance is silica, and an organic substance is polymethacrylate. More preferred matting agent is one that is processed so that the outer surface has a hydroxyl group, for example,
Those obtained by copolymerizing hydroxyethyl methacrylate, 4-hydroxycyclohexyl methacrylate, 2,3-propyl methacrylate, or the like at the time of polymerization of methyl methacrylate, or those obtained by copolymerizing glycidyl methacrylate and opening the epoxy ring by hydrolysis. And those obtained by copolymerizing a monomer having a hydroxy group and the like.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle size of the matting agent indicates the diameter converted into the spherical shape. The matting agent used in the present invention has an average particle size of 0.5
To 10 μm, more preferably 1.
0 to 8.0 μm. In addition, a matting agent having a particle monodispersity of preferably 50 or less, more preferably 40 or less, and particularly preferably 20 or less. Here, the monodispersity of the particles is represented by a number obtained by dividing the standard deviation of the particle size by the average value of the particle size and multiplying by 100. The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed in advance and applied, or a method in which the matting agent is sprayed before the drying is completed after applying the coating liquid. You may. When a plurality of types of matting agents are added, both methods may be used in combination. The amount of the matting agent can be added in the range of 1 μg to 1 g per 1 g of the binder, but is in the range of 0.001 to 0.1 g from the viewpoint of transparency, film strength, friction coefficient, sticking during storage of the film, and the like. Is appropriate.

In the heat developing material of the present invention, a polyhalomethane compound is used as a compound that inactivates a reducing agent during storage and suppresses the reducing agent from reducing an organic silver salt to silver.

(Sulfur Sensitizer etc.) The photosensitive silver halide in the photosensitive layer of the heat-developable material of the present invention may be, for example, a sulfur-containing compound,
Chemical sensitization can be performed by using a gold compound, a platinum compound, a palladium compound, or a combination thereof. The method and procedure of this chemical sensitization are described, for example, in U.S. Pat. No. 4,036,650 and British Patent 1,518,850.
And Japanese Patent Application Laid-Open Nos. 51-22430 and 51-224.
Nos. 78319 and 51-81124. Further, when a part of the organic silver salt is converted into a photosensitive silver halide by a silver halide forming component, as described in US Pat. No. 3,980,482,
In order to achieve sensitization, a low molecular weight amide compound may coexist. In addition, these photosensitive silver halides may have an illuminance failure, and may be selected from Group 6 of the Periodic Table of the Elements to control gradation.
Metals belonging to Group 0, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof, or a complex ion can be contained. It is particularly preferable to contain ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. These metals can be introduced into the photosensitive silver halide in the form of a complex (transition metal complex).

(Transition Metal Complex) The transition metal complex to be introduced into the photosensitive silver halide is preferably a hexacoordinate complex represented by the formula (ML ₆ ) ^{m in} which the ligand is bonded.

In the formula, M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a hardening ligand, and m is 0, 1
Represents-, 2- or 3-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate,
Examples include ligands of selenocyanate, tellurocyanate, azide and aquo, nitrosyl, thionitrosyl and the like, and preferably aquo, nitrosyl and thionitrosyl and the like. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different, and particularly preferable specific examples of M include rhodium (Rh), ruthenium (Ru), rhenium (Re), and osmium (Os). The content of metal ions or complex ions is generally from 1 × 10 ^-9 to 1 × 10 ^-2 mol, preferably from 1 × 10 ^-8 to 1 mol, per mol of photosensitive silver halide. × 10 ^-4 mol. It is preferable that a compound providing an ion or a complex ion of these metals is added during the formation of the photosensitive silver halide grains and incorporated into the grains, thereby preparing the photosensitive silver halide grains, that is, nucleation and growth. , Physical ripening, may be added at any stage before and after chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth, and physical ripening, and more preferably at the stage of nucleation and growth. Preferably, most preferably, it is added at the stage of nucleation. Upon addition, the compound may be added in several divided portions, and may be uniformly contained in the photosensitive silver halide grains.
29603, JP-A-2-306236, 3-16
No. 7545, No. 4-76534, No. 6-110146
As described in JP-A Nos. 5-273683 and 5-273683, they can be contained in the particles with distribution.
Preferably, a distribution can be provided inside the photosensitive silver halide grains. The transition metal complex can be added by dissolving it in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). Or an aqueous solution in which a transition metal complex and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or the silver salt solution and the halide solution are simultaneously A method of preparing photosensitive silver halide grains by a method of simultaneous mixing of three liquids, adding a required amount of an aqueous solution of a transition metal complex to a reaction vessel during grain formation, Alternatively, there is a method in which another photosensitive silver halide grain doped with a transition metal complex ion in advance during the preparation of the photosensitive silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a transition metal complex powder or an aqueous solution in which the transition metal complex is dissolved together with NaCl and KCl to the water-soluble halide solution is preferable. When adding to the surface of the photosensitive silver halide grains, a required amount of an aqueous solution of a transition metal complex can be charged into the reaction vessel immediately after grain formation, during or during physical ripening, or at the time of chemical ripening.

(Sensitizing Dye) The photosensitive silver halide in the photosensitive layer of the heat-developable material of the present invention is described in, for example, JP-A-63-15 / 1988.
No. 9841, No. 60-140335, No. 63-231
No. 437, No. 63-259651, No. 63-3042
No. 42, No. 63-15245, U.S. Pat.
9,414, 4,740,455, 4,7
No. 41,966, No. 4,751,175, No. 4,
Sensitizing dyes described in 835,096 can be used.
Useful sensitizing dyes for use in the present invention include, for example,
rcDisclosure Item17643IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in section 1X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078
And compounds described in JP-A Nos. 9-54409 and 9-80679 are preferably used.

(Polyhalomethane Compound) The polyhalomethane compound which may be contained in the photosensitive layer of the heat-developable material of the present invention or an adjacent layer thereof is a compound capable of releasing a halogen atom as an active species, and many compounds are already known. However, as a compound preferably used in the present invention, there is a polyhalomethane compound represented by the general formula (4).

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In the general formula (4), Q represents an aryl group or a heterocyclic group, and X ¹ , X ² and X ³ represent a hydrogen atom, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group. , An aryl group, at least one of which is a halogen atom. Y is -C
(= O) -, - SO- or -SO ₂ - represents, n represents 0 or 1.

The aryl group represented by Q may be monocyclic or condensed, and is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.). Preferably a phenyl group, a naphthyl group,
More preferably, it is a phenyl group. The heterocyclic group represented by Q is a group containing at least one atom of N, O or S
It is a 10- to 10-membered saturated or unsaturated heterocyclic group, which may be a single ring, or may form a condensed ring with another ring. The heterocyclic group is preferably a 5- to 6-membered unsaturated heterocyclic group which may have a condensed ring,
More preferably, it is a 5- to 6-membered aromatic heterocyclic group which may have a condensed ring. More preferably, it is a 5- to 6-membered aromatic heterocyclic group which may have a condensed ring containing a nitrogen atom, and particularly preferably it may have a condensed ring containing 1 to 4 nitrogen atoms. A 6-membered aromatic heterocyclic group. As the heterocycle in such a heterocyclic group, preferably, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline , Cinnoline, pteridine, acridine, phenanthroline, phenazine,
Tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole,
Oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, Triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole and benzthiazole, particularly preferably pyridine, thiadiazole, quinoline and benzthiazole. Aryl group and heterocyclic group represented by Q is ^{-Y-C (X 1) (} X 2)
It may have a substituent other than (X ³ ), and the substituent is preferably an alkyl group, an alkenyl group, an aryl group,
Alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl Group, ureido group, phosphoric amide group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group,
A nitro group, a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group, It is a heterocyclic group, particularly preferably an alkyl group, an aryl group or a halogen atom. X ¹ , X ² and X ³ are preferably a halogen atom, a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a heterocyclic group, more preferably a halogen atom, It is a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a sulfonyl group, more preferably a halogen atom or a trihalomethyl group, and particularly preferably a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred. Y is -O-, -S-,-
C (= O) -, - SO -, - SO 2 -, - CH 2 = CH 2
_{-, - CF 2 = CF 2} - represents preferably -SO ₂ - is.

Specific examples of these compounds are shown below.

[0040]

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[0041]

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[0042]

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(Acid Anhydride) As the acid anhydride preferably contained in the photosensitive layer of the heat-developable material of the present invention or in the layer adjacent thereto, two molecules of monocarboxylic acid are dehydrated and condensed to form A-CO-O
It includes those having a -CO-B structure in the molecule, and includes a linear molecular structure in which the substituents A and B are linear, and a cyclic anhydride in which A and B are partially bonded. A linear one is formed by dehydration of two molecules of an aliphatic monocarboxylic acid. Examples include acetic anhydride, propanoic anhydride, butanoic anhydride, amylic anhydride, caproic anhydride, lauric anhydride, stearic anhydride, sebacic anhydride, arachidic anhydride, and behenic anhydride. The aliphatic carboxylic acid preferably has 1 to 30 carbon atoms. As aromatic carboxylic acids, there are benzoic anhydride, pyridinecarboxylic anhydride and derivatives thereof. A preferred compound having a cyclic structure is represented by the following general formula (5).

[0044]

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Where W¹And W^TwoMay have a substituent
Represents a group of atoms necessary to form a 5- or 6-membered ring,
L⁵¹Is ring W¹And W^TwoRepresents a divalent linking group,
m and n represent 0 or an integer of 1 to 4, and r represents 0 or 1. W
¹And W^TwoThe above substituent R⁵¹And R ⁵²Are each replaced
Good alkoxy groups (methoxy, ethoxy, propyl
Roxy, butoxy, octoxy, dodecanoxy
Group, docosanoxy group, 2-ethylhexanoxy group), c
Logenated alkoxy group (trifluoromethoxy group, perfume
Lolooctanoxy group), cycloalkoxy group (cyclo
Xanoxy group, cyclooctanoxy group, cyclopentano
Xy group), aromatic group (phenoxy group, naphthenoxy group)
Etc.), heterocyclic groups (pyridyl group, furyl group, thiophene
Group, piperazyl group, imidazolyl group, triazole
Group, tetrazole group, etc.), alkylamino group (methyl
Mino group, propylamino group, octylamino group, tetra
Decyl group), dialkylamino group (dimethylamino group,
Diethylamino group, dioctylamino group), alkylthio
O group (methylthio group, ethylthio group, butylthio group,
Octylthio group), and the alkyl group portion has a carbon number of 1 to
25 is preferred. The above substituent R⁵¹And R⁵²Is that m and n are
In the case of two or more, adjacent substituents may form a ring,
In the case of benzene ring, imidazole ring, tri
Azole ring, tetrazole ring, pyridine ring, furyl ring,
Examples include a thiophene ring and a piperazine ring.

L ⁵¹ as the linking group is a —SO ₂ — group,
-SO- _{group, -S-SO 2 -, -} S -, - O -, - CON
_{H -, - SO 2 NH -} , - CONH- group or their aliphatic group, an aromatic Shokumoto, and a combination of such a heterocyclic group.

Preferred examples of the compounds are shown below.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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As the acid anhydride of the present invention, a compound having a carboxylic acid group can be synthesized by ordinary dehydration condensation, or a commercially available product can be obtained. When it is added to the heat-developable material, it can be added according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles having a particle size of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion and added. Many techniques have been disclosed for the fine particle dispersion technique, and a fine particle dispersion having an average particle size of 0.05 to 10 μm can be added according to these techniques. The addition amount is in the range of 10 ^-7 to 10 ^-1 mol, preferably 10 ^-5 , based on the total amount of the photosensitive silver halide and the organic silver.
10 to 10 ^-2 mol.

(Support) As a support of the heat-developable material of the present invention, polyester such as polyethylene terephthalate,
A support such as a plastic film such as polycarbonate or polypropylene can be used, and a composite sheet in which these are combined may be used arbitrarily.

<Developing Method> The photothermographic material of the present invention comprises:
As described above, the photosensitive layer includes a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent, and a binder, and a protective layer containing a fluorine compound, a matting agent, and a binder. A photothermographic material comprising a binder cured by the curing agent of the present invention, and a hydrazine compound, an acid anhydride, a polyhalomethane, a color tone agent and the like in the photosensitive layer and / or the adjacent layer, if necessary. The photothermographic material is stable at room temperature, but is developed by heating to a high temperature (for example, 80 to 200 ° C.) after exposure. Heating includes a one-step method in which heating is performed at a constant temperature for a predetermined time and a method in which heating is performed stepwise such as preheating, main heating, or post-heating, and the heating method can be appropriately selected. By heating, silver is generated through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated on the photosensitive silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

In the present invention, the exposure is preferably performed by laser scanning exposure. However, it is preferable to use a laser scanning exposure machine in which the angle between the exposed surface of the heat-developable material and the scanning laser beam does not become substantially perpendicular. preferable. here,
"Never be substantially perpendicular" means that the angle is most perpendicular to the surface during laser scanning, preferably 55 degrees or more and 88 degrees or more.
Degrees or less, more preferably 60 degrees or more and 86 degrees or less, still more preferably 65 degrees or more and 84 degrees or less, and most preferably 70 degrees or more and 82 degrees or less. The beam spot diameter on the exposed surface of the photothermographic material when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. Note that the lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of unevenness like interference fringes. The exposure in the present invention is also preferably performed using a laser scanning exposure device that emits a scanning laser beam that is a vertical multi. Image quality deterioration such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode. To achieve vertical multiplication,
A method of using return light, applying high frequency superimposition, or the like is preferable. Note that the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

In the developing method of the present invention, development is preferably carried out at a temperature in the range of 80 to 200 ° C.
It is more preferred to develop at ~ 130 ° C and then cool to room temperature. FIG. 1 shows a developing section of the heat developing machine. After being exposed, the heat development material to be developed is sent to the heat drum 4 by the insertion roller 5, travels while being heated between the heat roller group 2 arranged on the outer periphery of the heat drum 4 and the heat drum 4, and is discharged. It is discharged by the roller 6. The heat drum or the heat roller contains iron oxide, and has a surface hardness of 20 to 90 when expressed in durometer A hardness, a surface unevenness difference of 0.5 to 8 μm, and a frequency of surface unevenness. Is developed using a heat roller and / or a heat drum made of silicone rubber with 10 to 1000 pieces per mm. By performing development using such a developing method, the generation of stains on the heat-developable material and the generation of stains on the heat drum or the heat roller are prevented. In addition, 7 is an insertion portion of the heat development material,
Reference numeral 8 denotes a discharge portion for the heat development material.

The surface of the heat-developable material of the present invention in contact with the heat drum may be either an emulsion surface or a BC surface. It is preferable that the heat drum and the heat roller rotate in synchronization with each other. The heat source 3 can use an infrared heater, a nichrome wire, or the like. The adiabatic shield 1 of the heat drum can control the development temperature by attaching a cold mirror that reflects heat rays.

The heat drum or heat roller employed in the heat development section of the processor for developing the heat development material of the present invention is coated with silicone rubber (organopolysiloxane) having the above-mentioned surface properties, and has heat resistance and chemical resistance. The silicone rubber is adjusted in thermal conductivity, color tone, hardness, friction coefficient and the like by adding various additives as needed. As typical additives, silica, carbon black and black red iron oxide are known. Above all, in the present invention, black veneer is effective. A preferred organopolysiloxane compounding example is (A) a part of a silicon atom having 1 to 3 carbon atoms.
100 parts by mass of an organopolysiloxane which may be substituted with 0 different atoms, (B) 1 to 50% by mass of a metal oxide,
(C) It is a curing agent.

In the preparation of the silicone rubber which is particularly preferred for the present invention, the silicon atom of the organopolysiloxane of the component (A) has different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and alkyl groups, alkenyl groups Examples thereof include a group and an aryl group, and a monovalent group selected from a methyl group, a vinyl group and a phenyl group is particularly preferable. The alkenyl group has a content of 0.1.
It is preferably contained in an amount of 01 to 5 mol%, particularly preferably 0.02 to 0.5 mol%. Examples of the substituted hydrocarbon group include an alkyl group, an alkenyl group, and a hydrogen atom bonded to a carbon atom of an unsubstituted hydrocarbon group such as an aryl group. 3
A trifluoropropyl group, a 2-cyanoethyl group and the like, and a 3,3,3-trifluoropropyl group is particularly preferred. Examples of the molecular chain terminal groups include a hydroxy group, a trimethylsilyl group, a dimethylvinylsilyl group, and a trivinylsilyl group, but are not particularly limited thereto.

The organopolysiloxane of the component (A) is
In order to obtain sufficient mechanical strength, the degree of polymerization is at least 2,700, preferably from 3,000 to 20,000, and particularly preferably from 4,800 to 10,000. As the organopolysiloxane of the component (A), two or more kinds having different structures and degrees of polymerization can be used in combination.

The component (B) is preferably a suitable compound, and particularly preferably a metal oxide, in order to give the silicone rubber an appropriate hardness and to improve the mechanical strength such as the tensile strength. The amount of the component (B) is from 10 to 100 parts by mass, preferably from 20 to 50 parts by mass, per 100 parts by mass of the organopolysiloxane of the component (A). If the compounding amount is out of this range, the processability of the silicone rubber composition may deteriorate or sufficient mechanical strength may not be obtained.

The curing agent of the component (C) cures the composition of the present invention to form a silicone rubber, and generally uses an organic peroxide. When the organopolysiloxane of the component (A) contains two or more alkenyl groups in the molecule, a combination of an organohydrogenpolysiloxane and a platinum-based catalyst can be used as a curing agent. The amount of the curing agent may be an amount sufficient to cure the composition of the present invention as described below. Examples of the organic peroxide that can be used in the present invention include dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy). ) Hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, benzoylper oxide,
Examples thereof include 2,4-dichlorobenzoyl peroxide and 4-chlorobenzoyl peroxide. The compounding amount of these organic peroxides is set to a sufficient amount to cure the composition of the present invention, and to 0.1 parts by mass based on 100 parts by mass of the component (A).
It is in the range of 1 to 10 parts by mass.

When the organopolysiloxane of the component (A) contains two or more alkenyl groups in the molecule, the organohydrogenpolysiloxane usable as a curing agent includes methylhydrogenpolysiloxane having a trimethylsiloxy group at both terminals. Examples thereof include siloxane, a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends terminated with a trimethylsiloxy group, and a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends terminated with a methylhydrogensiloxy group. On the other hand, examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of chloroplatinic acid and divinyltetramethylsiloxane. The amount of the above-mentioned organohydrogenpolysiloxane is generally such that the ratio of the number of moles of hydrogen atoms bonded to silicon atoms contained in the organohydrogenpolysiloxane to the number of moles of alkenyl groups in the component (A) is ( 0.5: 1) to (20: 1), and the amount of the platinum-based catalyst is generally about 0.1 to 3,000 ppm in terms of platinum based on the mass of the component (A). When a platinum compound is used as the heat-resistant agent, it can be used in common.
The silicone rubber composition may contain, in addition to the components (A) to (C), various rubber compounding agents, for example, diphenylsilanediol, which are appropriately compounded in the silicone rubber in an amount which does not impair the object of the present invention. Dispersants such as silicone oil with low polymerization degree, hydroxyl group terminal hydroxyl group, hexamethyldisilazane, and alkoxysilane, pulverized silica, diatomaceous earth, zinc oxide, titanium oxide, carbon black, barium oxide, calcium carbonate, magnesium carbonate, and carbonic acid Zinc, asbestos, glass wool, fine mica, fused silica powder and the like may be added and blended. Further, if necessary, an antioxidant, an antioxidant, an antistatic agent, a thermal conductivity improver such as boron nitride and aluminum oxide may be blended.

The method for producing the silicone rubber composition is not particularly limited, but the components (A) and (B)
Into a kneading device such as a kneader and blended at room temperature.
A method in which heat treatment is performed at a temperature of 80 ° C. to 200 ° C. for 30 minutes to 5 hours, and then the component (C) is added and kneaded with a roller mill, a Banbury mixer, or the like can be employed. The silicone rubber thus obtained can provide good heat resistance and developability of the heat-developable material. Silicone rubber can form an uneven surface by adding inorganic fine particles or by the surface shape of a molding die. The uneven surface is adjusted for uniform development of the heat developing material and reduction of scratches and stains. In the present invention, the average uneven surface difference is 0.5 to 8 μm, and the frequency of unevenness is 10
Preferably, the number is up to 1,000.

[0066]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Subbed Support> A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 8 W / m ² · min on both sides, and the following coating solution a- 1 was applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1.
Was applied to a dry film thickness of 0.8 μm and dried to obtain an undercoat layer B-1.

(Undercoat Coating Solution a-1) Co-weight of butyl acrylate (30% by mass), t-butyl acrylate (20% by mass), styrene (25% by mass), and 2-hydroxyethyl acrylate (25% by mass) Combined latex liquid (solid content 30% by mass) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 L with water.

(Undercoat Coating Solution b-1) Copolymer Latex Solution of Butyl Acrylate (40% by Mass), Styrene (20% by Mass), and Glycidyl Acrylate (40% by Mass) (Solid Content 30% by Mass) 270 g Hexamethylene -1,6-Bis (ethylene urea) 0.8g Finish to 1L with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 W / m ² .min. Is applied to the upper surface of the undercoating layer A, and the undercoating upper layer coating solution a-2 shown below is applied on the undercoating layer A-1 to a dry film thickness of 0.1 μm. To provide an undercoat layer A-2,
An undercoating layer B-2 having an antistatic function was provided on the undercoating layer B-1 by applying the following undercoating layer coating solution b-2 to a dry film thickness of 0.8 μm.

(Undercoat upper layer coating solution a-2) Gelatin Mass of 0.4 g / m ² Silica particles (average particle size 3 μm) 0.1 g Finished to 1 L with water.

(Lower Coating Upper Layer Coating Solution b-2) Styrene butadiene copolymer latex solution (solid content: 20% by mass) 80 g Polyethylene glycol (weight average molecular weight: 600) 6 g Finished to 1 L with water.

<Preparation of silver halide grain emulsion A>
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 0 mL and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 mL of an aqueous solution containing 74 g of silver nitrate and (98 /
An aqueous solution containing potassium bromide and potassium iodide in the molar ratio of 2) was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8
%, And a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
After adjusting the pAg to 5.9 and pAg 7.5, a silver halide grain emulsion A was obtained.

<Preparation of Water-Dispersed Organic Silver Salt> 111.4 g of behenic acid and 83.8 of arachidic acid were added to 4720 mL of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, 540.2 mL of a 1.5 mol aqueous sodium hydroxide solution was added, 6.9 mL of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the above-mentioned organic acid sodium solution at 55 ° C., the above-mentioned silver halide emulsion (containing 0.038 mol of silver)
And 450 mL of pure water were added and stirred for 5 minutes. Next, 760.6 mL of a 1 mol silver nitrate solution was added over 2 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration.
Thereafter, washing with deionized water and filtration were repeated until the conductivity of the filtrate became 2 μs / cm, and water was added to a predetermined concentration to finish.

<Coating on photosensitive layer surface side> AH layer (first layer) Binder: polyvinyl butyral (PVB-1) 0.3 g / m ² Dye: C 8 mg / m ² photosensitive layer (second layer) Preparation of photosensitive layer An aqueous dispersion of the following composition was added to water to prepare a coating solution. The coating solution was kept at a temperature close to 35 ° C. and a silver electrometer formed from a silver electrode and a reference electrode consisting of a Ag / AgCl electrode in a 3 molar solution via a salt bridge consisting of a 10% KNO ₃ salt solution was used. After the measurement of the silver potential, coating and drying were performed so that the following amounts were obtained.

A preparation solution of silver halide and an organic silver salt in an amount of 1.4 g / m ² in terms of silver was mixed with a polymer binder. The silver halide was added so as to be 1/10 equivalent to the organic silver salt.

Binder: Polyvinyl butyral (PVB-1) 5.6 g / m ² Curing agent changed to 6 types as shown in Table 1 0.21 mmol / m ² Sensitizing dye: Dye A 8 mg / m ² Antifoggant -1: 2-mercaptobenzimidazole 0.3 mg / m ² antifoggant -2: isothiazolone 1.2 mg / m ² reducing agent: 1,1-bis (2-hydroxy-3,5-dimethylphenyl) - 3, 5,5-trimethylhexane 3.3 mmol / m ² surface protective layer (third layer) Binder: cellulose having a carboxyacetylation degree of 15% 1.2 g / m ² 4-methylphthalic acid 0.7 g / m ² tetrachlorophthalate Acid 0.2 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Fluorine compound changed to 7 types as shown in Table 1 0.26 g / m ² Polymethyl methacrylate matting agent (Average particle size: 5 μm) 0.05 g / m ² 1,2-bis (vinylsulfone acetamide) ethane 0.3 g / m ² Curing agent was changed to 8 types as shown in Table 1 0.16 mmol / m ² <Back Surface-side coating> A back layer and a back layer protective layer were prepared by adding an aqueous solution or an aqueous dispersion of the following composition to water. Sample (sample numbers 101 to 109)
I got

Back layer (first layer) Inert gelatin 1.1 g / m ² Dye: C 12 mg / m ² Colloidal silica 12 mg / m ² Sodium dodecylbenzenesulfonate 13 mg / m ² Back layer protective film (second layer) Inert Gelatin 0.8 g / m ² Matting agent (PMMA: average particle size 3 μm) 0.02 g / m ² Activator: N-propyloctylsulfonamidoacetic acid 0.02 g / m ² Hardener: 1,2-bis (vinyl) Sulfonamide) ethane 0.02 g / m ^{2 The} above composition was dissolved in MEK solvent, and the above-mentioned amount was applied simultaneously with an extrusion coating machine at a coating speed of 600 m / min and dried at 48 ° C. for 56 seconds.

[0079]

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<Evaluation of photographic performance> Nine kinds of tests were performed using the nine kinds of prepared samples as follows, and the results were evaluated. That is, the above nine types of samples are exposed with a semiconductor laser sensitometer, and then have the same configuration as the heat drum 4 in the developing section of FIG. 1, but provided with a surface layer (also called a coating layer) of the following silicone rubber on the surface. Using a heat drum for test (contact of the heat drum with the photosensitive layer) at 120 ° C. for 6 seconds, a sensitometric measurement was performed. The fog and sensitivity of the obtained image were measured with a densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the amount of exposure that gives a density 0.3 higher than the fog density, and expressed as a relative sensitivity based on Sample No. 101. The surface of the silicone rubber coating layer of the test heat drum is made of silica particles having an average particle size of 8.6 μm.
Fine irregularities are present, the average irregularity difference is 4.2 μm, the frequency of irregularities is 280 times / mm on average, and the hardness at that time is the durometer hardness (JIS A type A of K7215) and the value of HDA80. Set to. Next, using the above-mentioned heat drum for the test, development processing was performed under the condition of 5 ° C. higher than the development temperature for sensitometry and the development time was doubled to evaluate the scratch resistance. The scratch resistance was evaluated by visually observing the degree of scratch on each sample. The evaluation is based on a five-rank system, with 5 being the best level, 1 being the worst level, and 3 being the middle. Stain was evaluated by treating each sample with 200 m ² using a developing machine for evaluating scratch resistance, and then visually checking the film for stains.
It was rated on a scale. Here, similarly, in the 5-rank system, 5 represents the best level, 1 represents the worst level, 3 represents the middle level, and the evaluation results are shown in Table 1.

[0081]

[Table 1]

Table 1 shows that the sample for the present invention (sample No. 103)
To 109) are comparative samples (sample numbers 101 and 102).
It can be seen that the scratch resistance is excellent and the photographic performance of the obtained image is also excellent.

Example 2 A polyhalomethane compound was added to the protective layer in an amount of 0.01 mmol per 8 types as shown in Table 2, and a polyhalomethane compound was added to the photosensitive layer in an amount of 0.09 as shown in Table 2.
Nine kinds of samples (sample Nos. 201 to 209) were prepared in the same manner as in Example 1 except that 5 mmol was added, and nine kinds of tests using these were performed. In addition to scratch resistance and photographic performance, printout was performed. The evaluation was performed in the same manner as in Example 1 except that resistance was added, and the results are shown in Table 2. The printout resistance was evaluated by developing a non-exposed sample and irradiating the unexposed sample with 300 lux for 9 hours under a UV-cut fluorescent lamp for 9 hours. The smaller the difference in fog increase, the better the printout resistance.

[0084]

[Table 2]

Table 2 shows that the sample for the present invention (sample No. 201)
To 209) are excellent in scratch resistance and excellent in photographic performance and printout resistance of the obtained image, but the samples containing the polyhalomethane compound in the photosensitive layer or the protective layer (Sample Nos. 202 to 209) are photosensitive. It can be seen that the printout resistance is superior to the sample (Sample No. 201) which does not contain any of the layer and the protective layer.

Example 3 A polyhalomethane compound was added to the protective layer in the form of eight kinds as shown in Table 3 in an amount of 0.01 mmol, and a polyhalomethane compound was added to the photosensitive layer in the form of nine kinds as shown in Table 3.
5 mmol each was added, and the acid anhydride was further added to the protective layer.
As shown in Table 3, the amount of acid anhydride was changed to 8 and added to the photosensitive layer.
07 mmol each and adding 10 mmol in the same manner as in Example 1.
Various kinds of samples (sample numbers 301 to 310) were prepared, and ten kinds of tests using these were performed. The scratch resistance and the photographic performance were evaluated in the same manner as in Example 1, and the results are shown in Table 3. .

[0087]

[Table 3]

Table 3 shows that the sample for the present invention (sample No. 301)
To 310) are excellent in scratch resistance and excellent in photographic performance of the obtained image, but the samples containing an acid anhydride in the photosensitive layer or the protective layer (Sample Nos. 304 to 310) are the photosensitive layer and the protective layer. A sample not contained in any of the layers (sample No. 30
1 to 303), the fogging is small and the photographic performance is excellent.

Example 4 The sample of Example 1 (Sample No. 109) using polymethyl methacrylate as a matting agent was designated as Sample No. 401, and the following seven types having hydroxyl groups on the surface in place of the polymethyl methacrylate were used. (Sample Nos. 402 to 408) using the matting agents (M1 to M7) were prepared, and eight kinds of sample stains were tested using these samples, and evaluated as follows. The results are shown in FIG.

Preparation of matting agent (M1): 3 L of ion-exchanged water, 16 g of lauryl sulfonaminodoethanesulfonic acid, 8 g of polyoxyethylene hexylphenoxy ether and 4 g of gelatin were added to a three-necked flask, and the temperature was raised to 66 ° C. After that, 30 g of methyl methacrylate and 27 g of potassium persulfate were added and reacted for 3 minutes. Then 30
0 g of methyl methacrylate was added dropwise over 1 hour, and 6 g of hydroxyethyl methacrylate was added over 1 minute. The average particle size was 5.2 μm.

Preparation of matting agent (M2): 3 L of ion-exchanged water, 16 g of lauryl sulfonaminodoethanesulfonic acid, 8 g of polyoxyethylene hexylphenoxy ether and 2 g of gelatin were added to a three-necked flask, and the temperature was raised to 58 ° C. After. 30 g of methyl methacrylate and 27 g of potassium persulfate were added and reacted for 3 minutes. Then 30
0 g of methyl methacrylate was added dropwise over 1 hour, and 12 g of glycidyl methacrylate was added over 1 minute. After continuing the reaction for 3 hours, the temperature was increased to 90 ° C.
Set the pH to 12 with sodium hydroxide and add 1
After reacting for an hour, the mixture was neutralized with sulfuric acid. After the completion of the reaction, desalting was performed using an anion exchange membrane and a cation exchange membrane. The average particle size was 5.2 μm.

Preparation of matting agent (M3): Prepared in the same manner as for M1, except that 4-hydroxycyclohexyl methacrylate was used instead of hydroxyethyl methacrylate. The average particle size was 5.3 μm.

Preparation of matting agent (M4): Preparation was conducted in the same manner as for M1, except that 2,3-dihydroxypropyl methacrylate was used instead of hydroxyethyl methacrylate. The average particle size was 5.2 μm.

Preparation of matting agent (M5): 3 L of ion-exchanged water, 16 g of lauryl sulfonaminodoethanesulfonic acid, 8 g of polyoxyethylene hexylphenoxy ether and 3 g of gelatin were added to a three-necked flask, and the temperature was raised to 66 ° C. After. 30 g of methyl methacrylate and 27 g of potassium persulfate were added and reacted for 3 minutes. Then 30
0 g of methyl methacrylate was added dropwise over 1 hour,
6 g of 3,4-dihydroxybutyl methacrylate
Added over minutes. The average particle size was 5.2 μm.

Preparation of matting agent (M6): Prepared in the same manner as for M1, except that tri (oxyethylene) methacrylate was used instead of hydroxyethyl methacrylate. The average particle size was 5.2 μm.

Preparation of matting agent (M7): Prepared in the same manner as for M1, except that dodeca (oxyethylene) methacrylate was used instead of hydroxyethyl methacrylate. The average particle size was 5.2 μm.

A sample was prepared in the same manner as the sample of Example 1 (Sample No. 109) using seven kinds of matting agents containing a hydroxyl group on the surface prepared as described above. The addition amount of the matting agent was 0.05 g / m ² .

The evaluation of the contamination of the film was performed by developing 100 test samples having a width of 10 cm and a length of 40 cm at a temperature of 125 ° C., which was 5 ° C. higher than the developing conditions for sensitometry, and processed 100 times. Was wiped with a white polyester cloth while applying a load of 5 kPa to the photosensitive surface of the film, and the stain level of the wiped cloth was visually evaluated. The results are shown in Table 4. The evaluation level was 5 for the best level and 1 for the worst level. 3 is an intermediate level that is practically acceptable.

[0099]

[Table 4]

From Table 4, the heat-developable material using a matting agent containing a hydroxyl group on the surface (Sample Nos. 402 to 408) is compared with the heat-developing material using a matting agent without a hydroxyl group on the surface (Sample No. 401). Thus, it can be seen that there is little generation of stains on the heat-developable material when the heat-development process is performed, which is excellent.

Example 5 Eight types were selected from the samples prepared in Examples 1 to 4 as shown in Table 5, and 16 types of development tests were performed. In the development test, the material of the silicone rubber coating layer covering the outer periphery of the heat drum and the outer periphery of the heat roller of the heat developing machine was changed as follows. The preparation of the silicone rubber is shown below.

Preparation of silicone rubber (S1): 260 g of polymethylsiloxane containing 6 mol% of ethylene groups, 38 g of methylhydrogenpolysiloxane capped with trimethylsiloxy groups at both ends, 3 g of butoxy peroxide as a polymerization initiator, chloroauric acid 36 μg, average particle diameter 6 μ
Add 56 g of silica and mix with a kneader.
The reaction was performed at 80 ° C. for 3 hours. Durometer hardness A is 60
The average difference between the irregularities on the surface is 2.7 μm, and the irregularity frequency is 2
It was 30 pieces / mm.

Preparation of silicone rubber (S2): Prepared in the same manner as in S1, except that silica was used instead of silica.
μm carbon black was used. Durometer hardness A is 48, surface unevenness difference is 2.5 μm,
The unevenness frequency was 246 / mm.

Preparation of silicone rubber (S3): A sample was prepared in the same manner as in S1, except that iron oxide (black bengara) having an average particle diameter of 6 μm was used instead of silica. The durometer hardness A was 68, the unevenness difference was 2.9 μm, and the unevenness frequency was 233 / mm.

Preparation of silicone rubber (S4): A sample was prepared in the same manner as in S3, except that the amount of chloroauric acid was increased to 67 μg and the reaction was carried out at a reaction temperature of 190 ° C. to obtain a durometer hard A72 rubber. The unevenness difference and the unevenness frequency were almost equal to S3.

Preparation of silicone rubber (S5): A sample was prepared in the same manner as in S3, except that iron oxide was increased to 78 g.

The produced silicone rubber was heated with a stainless steel (SUS304) heat drum having a diameter of 20 cm and a diameter of 3 cm.
Stainless steel (SUS304) heat roller with a thickness of 5 mm. After coating, 100 test samples having a width of 10 cm and a length of 40 cm were prepared, and the test samples were processed under developing conditions in which the temperature was higher by 5 ° C. than the sensitometric measurement conditions and the processing time was set to 20 seconds. The stain on the heat drum was wiped with a white polyester cloth while applying a load of 200 kPa to each surface, and the level of stain on the wipe was visually evaluated. The best level was 5, and the worst level was 1.
3 is an intermediate level that is practically acceptable. Table 5 shows the results of the above test.

[0108]

[Table 5]

As shown in Table 5, when the heat development material of the present invention was used and the heat development treatment was performed using a heat dryer provided with a coating layer of silicone rubber (S3), (S4) and (S5), the silicone rubber ( It can be seen that the heat drum is less contaminated than when heat development is performed using the heat drum provided with the coating layers of S1) and (S2).

[0110]

According to the heat developing material and the developing method of the present invention, as demonstrated by the examples, the film surface of the heat developing material has excellent scratch resistance, reduces fog in photographic performance and prints after development. Excellent effect such as excellent prevention of out, little adhesion of dirt on the processed film surface even in many times of development processing, and little adhesion of dirt to the heat drum or heat roller in the processing machine that performs thermal development processing Having.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a developing unit of a heat developing machine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Insulated shield 2 Heat roller group 3 Heat source 4 Heat drum 5 Insertion roller 6 Discharge roller 7 Insertion part of thermal developing material 8 Discharge part of thermal developing material

Claims (6)

[Claims] 1. A heat-developable material having a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder, and a protective layer containing a fluorine compound, a matting agent and a binder on a support, A heat-developable material, wherein the binder of the photosensitive layer or the protective layer is cured in the presence of a compound represented by the following general formula (1) or (2). Embedded image [In the formula, Z ¹ and Z ² each represent an atomic group necessary for forming a 5- or 6-membered ring which may have a substituent, and L ₁ represents rings Z ¹ and Z
It represents a divalent linking group that binds ^2, m is 1 or 0, when m is 1, n is 0 or 1. Ring Z ¹ and Ring Z ²
May be the same or different. ] 2. The heat-developable material according to claim 1, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a polyhalomethane compound. 3. The photosensitive layer or a layer adjacent to the photosensitive layer contains an acid anhydride.
2. The heat-developable material according to item 1. 4. The fluorine compound contained in the protective layer,
It is an anionic compound having a fluorinated aliphatic group, or a nonionic compound in which a polyoxyalkylene group is bonded to the fluorinated aliphatic group directly or via a bonding group. The heat-developable material according to any one of claims 1 to 3. 5. The heat-developable material according to claim 1, wherein the matting agent contained in the protective layer has a hydroxyl group on its surface. 6. The heat-developable material according to any one of claims 1 to 5, wherein the heat-developable material contains iron oxide, and has a surface hardness of 20 to 90 when represented by a durometer A hardness. The unevenness difference is 0.5 to 8 μm, and the frequency of surface unevenness is 1 m
80-20 using a hot drum or hot roller having a surface layer of silicone rubber 10-1000 per m.
A development method, wherein development is performed in a temperature range of 0 ° C.