JP2001005137A - Heat developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable image recording material which does not cause an unevenness in heat processing due to a defective conveyance in the handling of the heat developable photosensitive material by incorporating lubricant dispersed particles comprising a specified lubricant and a specified dispersant into the outermost layer on the image forming layer side of a substrate. SOLUTION: The heat developable image recording material is heat-developed at a temp. of 80-140 deg.C and contains lubricant dispersed particles comprising a lubricant of the formula (R1COO)pL(COOR2)q and a dispersant of the formula (R3)a-G-(D)d in the outermost layer on the image forming layer side of the substrate. In the formulae, R1-R3 are each a 1-60C optionally substituted alkyl or the like, L is a (p+q)-valent hydrocarbon which may contain O or S, (p) and (q) are each an integer of 0-6, 1<=p+q<=6, G is a di- to heptavalent combining group, D is (B)n-E, B is -CH2CH2O- or the like, (n) is an integer of 1-5, E is H, 1-8C optionally substituted alkyl or the like and (a) and (d) are each an integer of 1-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable image recording material, particularly to a heat-developable image recording material used for photolithography, and more particularly to an image recording material for a scanner and an imagesetter. More specifically, the present invention is suitable for a heat-developable image recording material which is free from troubles in film transportability and has no damage due to heat development, and is suitable for a color photographic plate having excellent antistatic properties without deteriorating photographic performance. The present invention relates to a heat-developable image recording material, an X-ray photosensitive material for heat development, and a micro-sensitive material.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic light-sensitive material is to scan an original figure and to expose a silver halide photographic light-sensitive material based on an image signal of the original figure, thereby obtaining a negative image or a positive image corresponding to the image of the original figure. An image forming method based on a so-called scanner method for forming an image is known. Further, there is a demand for a scanner photosensitive material having a super-high contrast characteristic for a case of printing on a printing plate directly after the output from a scanner to a film, without going through a turning process, or a scanner light source having a soft beam profile. A photosensitive material having a photosensitive layer on a support and performing image formation by exposing the image,
Many are known. Among them, a technology for forming an image by thermal development is a system that can simplify environmental protection and image forming means. In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there is a need for a technique relating to a photosensitive heat-developable material for photolithography, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a sharp black image having high resolution and sharpness. It has been. These photosensitive heat-developable materials eliminate the use of solution-based processing chemicals and can provide customers with a simpler heat-development system that does not damage the environment.

[0003] A method of forming an image by thermal development is described in, for example, US Patent Nos. 3,152,904 and 3,457,075, and
Morgan and B.A. "Thermally Processed Silver System" by Shely
Silver Systems ”(Imaging Processes and Mate
rials) Neblette 8th edition, Sturge, V.R. Walworth, A .; Shepp, page 2, 1969). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature,
When heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is generated through a redox reaction between a reducible silver source (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

Conventionally, this type of photothermographic material has been known. However, most of these photothermographic materials use stretched film-formed polyester as a support, and the high temperature (8
(0 ° C. or higher), the thermal deformation of the support (mainly thermal shrinkage) causes the disadvantage that the image is deformed. In addition, the binder of the image forming layer also undergoes dehydration shrinkage and thermal expansion at the same time during thermal development. Can only get. As a technique for preventing dimensional changes and wrinkles due to the thermal development, various heat treatment methods for relaxing internal strain generated when a support is formed into a film by stretching are disclosed.
JP-A-3-24936, JP-A-64-64833,
JP-A-8-211547, JP-A-3-97523,
JP-A-61-154829, JP-A-3-97523
And JP-A-57-109946.

[0005] Color photoengraving includes Y, M, C
Plate and K plate, and these 4
Although it is good if the plate is exposed / heat developed at the same time,
Often, exposure / heat development is performed with a time lag. In such a case, since the elapsed time after the heat development processing of each film is different, the dimensions of each film do not match and often cause color shift. There has been a demand for a technique for providing a photothermographic material having excellent dimensional stability in any handling state. Furthermore, the handling of the film is more severe than ever, because of its simplicity as compared with the conventional wet type. For example, it is scratched during high-speed conveyance, causing jamming during development, wrapping around a conveyance roller, and failure of unevenness. In addition, a failure occurs in which the surface of the photosensitive material and the back surface stick together during storage. In addition, there is dust due to a charging failure due to static electricity, which significantly reduces the commercial value.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve these problems of the prior art. That is, an object of the present invention is to provide a heat-developable image recording material which does not cause heat treatment unevenness due to defective conveyance during handling of the heat-developable photosensitive material. Another object of the present invention is to provide a heat-developable image recording material that is resistant to scratches during handling. The invention further provides
One of the problems to be solved was to provide a heat-developable image recording material free from trouble with dust and electrostatic trouble during handling. The present invention is further intended to solve the problem of providing a heat-developable image recording material which has little dimensional change over time after heat development, has no wrinkles during heat development, and has little dimensional change before and after heat development. One of the issues.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the outermost layer on the image forming layer side has a slipping agent represented by a specific chemical structure and a specific structure. It has been found that by incorporating a slip agent-dispersed particle composed of a dispersant represented by formula (1), an excellent heat-developable image recording material having desired effects can be provided, and the present invention has been provided. That is, according to the present invention, in a heat-developable image recording material having an image forming layer and an outermost layer on at least one of the supports, and being subjected to a heat development treatment at a developing temperature of 80 ° C or more and 140 ° C or less, the outermost layer A heat-developable image recording material is provided which comprises a slip agent-dispersed particle comprising at least one kind of a slip agent represented by the following general formula (1) and at least one kind of a dispersant represented by the general formula (2). Is done. Formula (1) (R ¹ COO) _p L (COOR ² ) _q (wherein R ¹ and R ² are a substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl group having 1 to 60 carbon atoms) And when p or q is 2 or more, a plurality of R ¹ and R ² may be the same or different from each other; L is a p + q-valent carbon atom which may contain an oxygen atom or a sulfur atom. A hydrogen group, and p and q each represent an integer of 0 to 6 and 1 ≦ p + q ≦ 6. General Formula (2) (R ³ ) _a -G- (D) _d (where R ³ is carbon A substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group having 10 to 60; G represents a divalent to hexavalent linking group;
(B) is _n -E, B is _{-CH 2 CH 2 O -, -} CH 2 CH 2 CH 2 O -, - CH
(CH ₃ ) CH ₂ O— or —CH ₂ CH (OH) CH ₂ O—, where n is 1 to 5
It is an integer of 0. Here, E represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, an alkylcarbonyl group or an arylcarbonyl group;
a and d each represent an integer of 1 to 6; a plurality of R ³ , D and E may be the same or different. )

[0008] In one embodiment of the present invention, the slip agent-dispersed particles include:
It is prepared from 25 to 99% by weight of at least one slipping agent represented by the general formula (1) and 1 to 75% by weight of at least one dispersing agent represented by the general formula (2). In one embodiment of the present invention, the slip agent-dispersed particles have an average particle diameter of 0.005.
A dispersion having a size of not less than μm and not more than 0.5 μm is added to the coating solution. In one embodiment of the present invention, the melting point of the slip agent-dispersed particles is 5
It is 0 ° C or more and 200 ° C or less. In one embodiment of the present invention, the slip agent-dispersed particles melt at least one slip agent represented by the general formula (1) and at least one dispersant represented by the general formula (2) at a temperature equal to or higher than the melting point thereof. It is created by mixing and then dispersing in a dispersing step. In one aspect of the present invention, the dynamic friction coefficient of the outermost layer containing the slip agent-dispersed particles is 0.35 or less and 0.05 or more. In one embodiment of the present invention, at least one layer has a fluorinated surfactant. In one embodiment of the present invention, at least one conductive layer is provided on at least one surface of the support, and has a resistance of 10 ¹²
Ω or less.

In one embodiment of the present invention, at least one image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide is provided, and 70 to 99.9% by weight of vinylidene chloride is used as an undercoat layer of the support. Monomer repeating unit and 0.1 to 5
A polymer containing by weight% of repeating units of a carboxyl group-containing vinyl monomer is used. In one embodiment of the present invention, the support is a biaxially stretched polyester, and after applying an undercoat layer containing a vinylidene chloride copolymer,
It is manufactured by performing a heat treatment at a temperature of 30 ° C. or more and 185 ° C. or less.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a heat-developed image recording of the present invention will be described.
A detailed description will be given of material embodiments and implementation methods.
You. The heat-developable image recording material of the present invention has
The outer layer has at least one kind of lubricating material represented by the following general formula (1).
And at least one kind of dispersion represented by the general formula (2)
It is characterized by containing a slip agent dispersed particles consisting of an agent
You. General formula (1) (R¹COO)_pL (COOR^Two)_q (Where R¹And R^TwoIs substituted or substituted having 1 to 60 carbon atoms
Represents an unsubstituted alkyl group, alkenyl group, aralkyl group, etc.
Or p is an aryl group and p or q is 2 or more.
If there is more than one R¹And R^TwoAre the same but different
L includes an oxygen atom or a sulfur atom
A p + q valent hydrocarbon group, wherein p and q are
Represents an integer of 0 to 6 and 1 ≦ p + q ≦ 6) General formula (2) (R^Three) a (G) b- (D) d-E or (R^Three)
a (G) b (DE) d (where R^ThreeIs substituted or unsubstituted having 10 to 60 carbon atoms
Alkyl, alkenyl, aralkyl or ant
G is a divalent to divalent linking group; D is
The general formula is-(BO) n-. Where B is -CH_TwoCH_Two-, -C
H_TwoCH_TwoCH_Two-, -CH (CH _Three) CH_Two-Or-CH_TwoCH (OH) CH_Two-
n is an integer of 1 to 50. Where E is hydrogen, carbon
A substituted or unsubstituted alkyl group or aryl of the formulas 1 to 8
Group, alkylcarbonyl group or arylcarbonyl group
A, b, and d each represent an integer of 1 to 6. )

First, the slip agent represented by the general formula (1) will be described. The total number of carbon atoms in the compound represented by the general formula (1) is not particularly limited, but is generally preferably 20 or more, more preferably 30 or more, for example, 40 to 1
00, more preferably 50 to 100, especially 50 to 80.
Examples of the substituent which the alkyl group, alkenyl group, aralkyl group or aryl group in the definition of R ¹ and R ² may have include a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an aryloxy group and an alkylthio group. Groups, arylthio, alkoxycarbonyl, aryloxycarbonyl, amino, acylamino, sulfonylamino, ureido, carbamoyl, sulfamoyl, acyl, sulfonyl, sulfinyl, aryl, and alkyl groups Can be. These groups may further have a substituent. Preferred substituents include a halogen atom, a hydroxy group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group,
An acylamino group, a sulfonylamino group, an acyl group and an alkyl group. As the halogen atom, a fluorine atom and a chlorine atom are preferable. The alkyl component in the alkoxy group, the alkylthio group and the alkoxycarbonyl group is the same as the alkyl group of R ² described later. The amino group of the acylamino group and the sulfonylamino group may be an N-substituted amino group, and the substituent is preferably an alkyl group. The group bonded to the acylamino group, the carbonyl group of the acyl group and the sulfonyl group of the sulfonylamino group are an alkyl group and an aryl group, and the above-mentioned alkyl group is preferable.

R ¹ and R ^{2 each} have ^{1 to} 60 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 10 to 40 carbon atoms.
A substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group.The alkyl group, alkenyl group, and aralkyl group may be linear, branched, or include a cyclic structure, or a mixture thereof. May be. Examples of preferred R ¹ and R ² are methyl, ethyl, propyl, butyl, octyl, t-octyl, dodecyl, tetradecyl, hexadecyl, 2-hexyl decyl, octadecyl, and _{C n H 2n-1 (n} 20~6
0), eicosyl, docosanyl, mericinyl, octenyl, myristoleyl, oleyl, ersyl, phenyl, naphthyl, benzyl, nonylphenyl, dipentylphenyl, cyclohexyl, and groups having the above substituents.

L is a p + q valent hydrocarbon group which may contain an oxygen atom or a sulfur atom. Although the carbon number of the hydrocarbon group is not particularly limited, it is preferably 1 to 60, more preferably 1 to 40, and still more preferably 10 to 40. “p + q valence” in a p + q valent hydrocarbon group means that p + q hydrogen atoms in the hydrocarbon are removed and p R ¹ COO— groups and q R ² OCO— groups are bonded thereto. Is shown. p and q represent an integer of 0 to 6 and 1 ≦ p + q
≦ 6, preferably 1 ≦ p + q ≦ 4. Also,
It is preferred that either p or q is 0.

The compound represented by the general formula (1) may be a synthetic product or a natural product. Natural compounds or synthetic compounds made from natural higher fatty acids or alcohols, even if they are synthetic, include those having different numbers of carbon atoms, straight-chain and branched ones, and mixtures of these. There is nothing wrong with using. From the viewpoint of quality stability of the composition, a synthetic product is preferable. Specific examples of preferred compounds represented by the general formula (1) are shown below.

[0015]

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These compounds are disclosed, for example, in JP-A-58-1983.
No. 90633 is partially described. In addition to the above compounds, montanic acid esters, carnauba wax, oleostock and the like can also be added as examples of natural products.

Next, the dispersant represented by the general formula (2) will be described. In the present invention, R ³ is a substituted or unsubstituted linear, branched or cyclic alkyl group, alkenyl group, aralkyl group or substituted or unsubstituted aryl group having 10 to 60 carbon atoms. Preferred examples of R ³ include C _g
H _{2g + 1} (g represents an integer of 12 to 60), eicosyl,
Docosanil. Furthermore, dodecyl, myristil,
Cetyl, stearyl, oleyl, eicosyl, docosacil, triacontacil, tetracontacil, heptacontacil, dinonylphenyl, didodecylphenyl, tetradecylphenyl, tripentylphenyl, dodecylnaphthyl and the like. D represents a polyoxyalkylene group represented by the general formula-(B) n-E. Where B is -CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH
_{2 O -, - CH (CH} 3) CH 2 O- or _{-CH 2 CH (OH) CH 2} O- and represents, n is the number of 1 to 50. Preferred as B is -CH ₂ CH ₂ O-
Wherein n is preferably an integer of 5 to 30. E is hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,
Represents an aryl group, an alkylcarbonyl group or an arylcarbonyl group. As the alkyl group, methyl, ethyl, propyl, butyl, hexyl and cyclohexyl are preferred, and methyl, ethyl and propyl are particularly preferred. As the alkylcarbonyl group, preferably acetyl, propionyl, butyroyl, pivaloyl,
Cyclohexanecarbonyl is particularly preferred, and acetyl is particularly preferred. Examples of the aryl group include a phenyl group, and examples of the arylcarbonyl group include a benzoyl group. Particularly preferred for E are hydrogen, methyl, methyl, propyl, acetyl, propionyl, benzoyl.

G represents a divalent to heptavalent, preferably divalent to pentavalent, more preferably divalent to tetravalent, still more preferably divalent or trivalent, linking group or single bond, preferably an alkylene group or an arylene. Represents a group or a complex thereof, which may be a divalent substituted or unsubstituted linking group interrupted by a heteroatom such as oxygen, ester group, sulfur, amide group, sulfonyl group or sulfur. Particularly preferred are oxygen, ester group and amide group. a and d are each 1 to 6
Represents an integer. The dispersant represented by the general formula (2) desirably has low solubility in an aqueous system, for example, preferably has a solubility in water of 0.5% by weight or less (25 ° C.), more preferably 0.1% by weight or less. Specific examples of the compound represented by formula (2) are shown below, but it should not be construed that the invention is limited thereto.

[0019]

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[0020]

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In the present invention, in addition to the dispersed particles comprising the slipping agent represented by the general formula (1) and the dispersing agent represented by the general formula (2) (hereinafter, also referred to as the slipping agent dispersed particles used in the present invention), other known slipping agents are used. It can also be used in combination with an agent. Preferred examples of the known slipping agent are similar to the compound represented by the general formula (1), for example, higher aliphatic amides described in U.S. Pat. No. 4,275,146, and U.S. Pat. No. 516, higher fatty acids or metal salts thereof, other higher alcohols and derivatives thereof, polyethylene wax, paraffin wax, microcrystalline wax, polyoxyethylene alkylphenyl ether compound and the like. In addition, natural fats and oils, waxes and oils, such as beeswax, can also be used in combination. Further, as a preferred known slip agent that can be used in combination,
Examples include commercially available or synthetically available silicone compounds. Polyorganosiloxanes are preferred among the silicone compounds. For use in these aqueous solutions, it is preferable to add them in the form of a dispersion.

The slip agent-dispersed particles used in the present invention are added to the slip agent layer in the form of a dispersion, but the solvent is preferably water but is not limited thereto. For example, a usual organic solvent can be appropriately selected and used at the time of dispersion. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), alcohols (lower alcohols having 1 to 8 carbon atoms,
For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc.), glycol derivatives (cellosolve, ethylene glycol diethyl ether,
Propylene glycol monomethyl ether, etc., lower fatty acid esters having 1 to 5 carbon atoms (ethyl acetate, butyl acetate, ethyl propionate, etc.), haloalkanes (methylene dichloride, ethylene dichloride, trichlene, trichloromethane, trichloroethane, carbon tetrachloride, etc.) ), Hydrocarbons (octane, solvent naphtha, turpentine oil, petroleum ether, thinner, petroleum benzine, benzene, toluene, xylene, etc.), phenols (phenol, resorcinol, etc.), ethers (tetrahydrofuran, dioxane, etc.), phosphoric acid Esters (trimethyl phosphate, triethyl phosphate,
Amide-based DMF and other DMSO. Preferred are alcohols, ketones, glycol derivatives, lower fatty acid esters, haloalkanes, and hydrocarbons. In particular, in a solvent system in which water is mixed and used, the solvent is selected from alcohols, ketones, and glycol derivatives that become a uniform solvent with water. , Lower fatty acid esters and haloalkanes are preferred.

With these, the stability of the dispersion of the slipping agent in the coating solution, the coating properties, the smoothness of the resulting coating film, the prevention of adhesion of photosensitive material dust and dust, the improvement of cissing during the development process, and the scratch resistance are improved. It is excellent. The above organic solvents may be used as a mixture of two or more of the same or different types of solvents. In the present invention, the coating solution is supplied as a homogeneous solution of a mixed solvent system of water and an organic solvent or as a fine dispersion of a slipping agent. The fine dispersion can be obtained by a known dispersion technique, for example, dispersion by mechanical shearing force, ultrasonic dispersion, or precipitation by mixing two liquids. The dispersion has an average particle size of 2.0 μm.
m, preferably 1.0 μm or less, more preferably 0.5 μm or less and 0.005 μm or more. In order to make the average particle diameter 0.005 μm or less, it is necessary to use a large amount of a dispersant, but this may adversely affect photographic properties. In the case of a mixed solvent with water, the water content is preferably 50 Vol% or more.

Next, the slip agent-dispersed particles used in the present invention will be described in more detail. In the present invention, the constituent ratio of the two components in the slip agent-dispersed particles comprising the slip agent of the general formula (1) and the dispersant of the general formula (2) is not particularly limited, but 25 to 99% by weight of the slip agent and 1 It is preferred to use slip agent dispersed particles made from ~ 75 wt% dispersant. This is because, as the content of the slipping agent of the general formula (1) increases, the properties of the slipping agent-dispersed particles are exhibited in the outermost layer. Therefore, it is preferable that the content ratio of the dispersant of the general formula (2) in the slip agent-dispersed particles is as small as possible. It is preferable that the slip agent-dispersed particles used in the present invention are mixed at a higher temperature than the compound having a higher melting point before being dispersed in advance, that is, so-called melt mixing. Then, the solvent serving as the dispersion medium is similarly heated to a high temperature,
What is necessary is just to add a molten mixture to this and make it finely dispersed by various dispersion methods. In addition, it is also preferable to add a heated solvent to the molten mixture to disperse and form particles. In addition, after dissolving these in a non-aqueous organic solvent that dissolves the slip agent or dispersant, finely disperse them in water using another water-soluble surfactant, and as it is, as the outermost layer as dispersed particles of the slip agent. , For example, ethyl acetate is preferred as the non-aqueous organic solvent. Further, it is also useful to remove the organic solvent after dispersing and use it as a slip agent particle dispersion.
The advantage in this case is that even when the melting points of the compounds of the general formulas (1) and (2) are 100 ° C. or higher, they can be dissolved and mixed in an organic solvent at a low temperature, and the high melting point lubricant can be dispersed in an aqueous system. The ability to create particles. Here, the melting points of the general formulas (1) and (2) are not particularly limited, but the melting points effective for the scratching property are as follows.
200 ° C. or lower, more preferably 60 ° C. or higher, particularly 80 ° C.
The temperature is preferably not less than 150 ° C and not more than 150 ° C. As the solvent, water is most preferred from the viewpoint of environmental friendliness in preparing the heat-developable image recording material of the present invention. Therefore, when using the slipping agent of the general formula (1) having a melting point of 80 ° C., it is necessary to disperse the water at a temperature of 80 ° C. or higher.

In the present invention, the outermost layer on the image forming layer side contains at least one kind of slip agent-dispersed particles. In this case, two or more kinds of the slip agents represented by the general formula (1), for example, two or more kinds of the compound represented by the general formula (1), or the compound represented by the general formula (1) and the other It can be used in combination with an agent. The coating amount of the slip agent-dispersed particles is in the range of ^{2 to} 200 mg / m ² . Preferably 5 to 10
A 0 mg / m ^2, more preferably in the range of 5 to 50 mg / m ^2. Even when the slip agent-dispersed particles comprising the slip agent of the general formula (1) and the dispersant of the general formula (2) are used in combination with other slip agents, the total coating amount is within the above range. When the compound represented by the general formula (1) is used in combination with another slip agent, the compound represented by the general formula (1) is desirably 50% by weight or more of the entire slip agent. In particular, 70% by weight or more is preferable.

The outermost layer containing the slip agent-dispersed particles used in the present invention may optionally contain a binder. As the binder, known compounds, for example, various gelatins (eg, alkali treatment, acid treatment, enzyme treatment, modification (phthalation, succination, trimellitation, etc.), modification, gelatin having a special molecular weight distribution, etc.), substitution Or it is soluble in hydrophilic binders such as unsubstituted celluloses, natural gum arabic, dextran and other common organic solvents, and is completely or almost insoluble in water, such as a developing solution, and has a film-forming hydrophobic property. Binders, for example, homo- or copolymers such as polystyrene, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, cellulose diacetate, cellulose triacetate, ethylcellulose, cellulose nitrate, hydroxypropylcellulose, cellulose propionate, etc. Loin derivatives, further polyvinyl acetals, polyvinyl benzal, such acetals such as polyvinyl formal and the like. These may be used in combination of two or more.

In the present invention, gelatin or a substituted or unsubstituted cellulose derivative, particularly a substituted alkyl cellulose, is preferably used as the hydrophilic binder, and a cellulose derivative is preferably used as the hydrophobic binder. In particular, use of hydroxyalkyl (alkyl group having 1 to 5 carbon atoms) celluloses and cellulose diacetate is preferred, and use of hydroxyalkyl (2 to 4 carbon atoms) cellulose is preferred. Furthermore, in the present invention, a binder in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium is also preferable as the binder of the outermost layer having the slip agent-dispersed particles. A latex which is a water-based hydrophobic binder is particularly preferred. The latex may be in a dispersed state in which the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially hydrophilic in the polymer molecule and the molecular chain itself is a molecule. Any of those dispersed in a state may be used. Regarding the polymer binder preferably used in the present invention, "Synthetic resin emulsion (Hei Okuda, edited by Hiroshi Inagaki, published by Kobunshi Kankai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara) Edited by the Society of Polymer Publishing (1993)), `` Synthesis of Synthetic Latex (Souichi Muroi,
Published by Kobunshi Kankokai (1970)). The average particle size of the dispersed particles is 1 to 5000 nm, more preferably 5 to 1000 nm.
A range of about nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution. The polymer binder may be a so-called core / shell type polymer latex other than the usual polymer latex having a uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

Glass transition temperature (Tg) of the polymer of the polymer latex used as a binder in the present invention
Has a glass transition temperature of 25 ° C. to 100 ° C. from the viewpoint of film strength and prevention of adhesion failure since it comes into contact with various devices. Minimum film formation temperature (MFT) of polymer latex is -3
0 ° C to 90 ° C, more preferably about 0 ° C to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming assistant is also called a temporary plasticizer and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex. ))"It is described in. Examples of the polymer species used for the polymer latex include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is 50 by weight average molecular weight.
00-1,000,000, preferably 10,000-100
About 000 is preferable. If the molecular weight is too small, the mechanical strength as a binder is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder of the heat-developable image recording material of the present invention include the following. Methyl methacrylate / ethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / Vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer and the like. Such polymers are also commercially available, and the following polymers can be used. For example, as examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,8
57, 857x2 (Nippon Zeon Co., Ltd.), VONCORT R3340,
R3360, R3370, 4280, 2830, 2210 (all manufactured by Dainippon Ink and Chemicals, Inc.), Julimer ET-410, 530, SEK101-SEK30
1, FC30, FC35 (all manufactured by Nippon Pure Chemical Co., Ltd.), Polysol F
Polyester resins such as 410, AM200 and AP50 (all manufactured by Showa Polymer Co., Ltd.) include FINETEX ES650, 611, 675, 8
HYDRAN AP10, 20, 30, 40, VONDIC 1320NS (Dai Nippon Ink Chemical Co., Ltd.), such as 50 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical), etc. L) as rubber-based resin
ACSTAR 7310K, 3307B, 4700H, 7132C, LQ-618-1 (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 410, 430, 43
5, 2507 (Nippon Zeon Co., Ltd.) and other vinyl chloride resins such as Nipol G351 and G576 (Nippon Zeon Co., Ltd.)
For example, vinylidene chloride resins such as L502 and L513 (manufactured by Asahi Kasei Kogyo Co., Ltd.) and Aron D7020, D5040, D5071 (manufactured by Toa Gosei Co., Ltd.). And the like). These polymers may be used alone or as a blend of two or more as necessary.

As the binder in the polymer latex, an acrylic, styrene, acryl / styrene, vinyl chloride or vinylidene chloride polymer latex is preferably used. Specifically, acrylic resin-based VONCORT R3370, 4280, NipolLx857, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, vinyl chloride resin Nipol G576, and vinylidene chloride resin ARON D5071 are preferably used. . Styrene / butadiene-based polymer latex is preferably used. Specifically, rubber-based resins such as LACSTAR3307B and Nipol Lx43
0 and 435 are preferably used. If necessary, a hydrophilic polymer such as polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose may be added to the binder in an amount of 25% by weight or less of the whole binder. More preferably, the amount of the hydrophilic polymer to be added is not more than 15% by weight of the total binder in the outermost layer.

The total amount of the binder for the outermost layer of the heat-developable image recording material of the present invention is preferably from 0.1 to 10.0 g / m ² , more preferably from 0.2 to 5.0 g / m ² . When using a hydrophilic binder, it is desirable to use a curing agent to make it water-insoluble or hardly soluble. In the case of various gelatins, known hardeners can be used. For these, for example, the compounds described in the aforementioned RD307105, Chapter X, can be used. For hydroxyalkyl celluloses, it is preferable to use a polyfunctional isocyanate compound having two or more isocyanate groups. By using such a curing agent, the molecular weight is increased, the hydrophilicity is reduced, and the film becomes insoluble or hardly soluble in water such as a developing solution, and film forming properties can be imparted. The amount of binder used in the outermost layer is 8 g
/ M ² or less, more preferably 6 g / m ² . Most preferably, it is 5 g / m ² or less and 0.5 g / m ² or more.
A matting agent, a coating aid,
It may contain a wetting agent and the like.

The slip agent-containing layer is applied by a known coating method,
For example, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll,
Coating can be performed using a coating method such as gravure, kiss, cast, spray, dip, bar, and extrusion. The sliding property of the outermost layer containing the slip agent-dispersed particles has a dynamic friction coefficient of preferably 0.35 or less and 0.05 or more, more preferably 0.3 or less, and particularly preferably 0.25 or less. The reason why the dynamic friction coefficient is set to 0.05 or more is that it is difficult to make the dynamic friction coefficient smaller than that in a stable manufacturing process. Here, in evaluating the dynamic friction coefficient, a stainless steel hard sphere having a diameter of 5 mm with a load of 100 g and a speed of 60 mm / sec was subjected to dynamic friction with the surface of the outermost layer containing a slip agent in an environment of 25 ° C. and 60% RH. Is measured. The drying temperature is not particularly limited as long as it does not affect properties such as photographic properties and film quality.
It is carried out in the range of 〜100 ° C. In this case, in the case where the slip agent-dispersed particles having a low melting point are used, they may be once dissolved at a higher drying temperature and solidified again by cooling. This phenomenon is also actively used for the purpose of haze reduction.

In a preferred embodiment of the present invention, the outermost layer contains a fluorine-containing surfactant. Hereinafter, the fluorine-containing surfactant preferably used in the present invention will be described. Fluorosurfactants are preferably used because of their unique properties.Especially, addition of a small amount lowers the surface tension of the coating solution to provide excellent coating performance and good surface condition. Thus, it can be used for antistatic. The fluorine-containing surfactant preferably used in the present invention is represented by the following general formula (3). Formula (3) Rf-AX wherein Rf is a partially or completely fluorinated substituted or unsubstituted alkyl, alkenyl or aryl group containing at least 3, preferably 7 or more, fluorine atoms. Represents a group. A represents a divalent linking group or a single bond, and X represents a water-soluble group. A preferably represents an alkylene group, an arylene group or a composite group thereof, which is a divalent substituted or unsubstituted linking group interrupted by a heteroatom such as oxygen, ester group, amide group, sulfonyl group or sulfur. It may be.

X is a hydrophilic group, for example, of the general formula-(T-
O) j-R ₄₁ polyoxyalkylene group (where T is -CH ₂ C
H ₂ —, —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH (OH) CH ₂ —, j represents the average degree of polymerization of the polyoxyalkylene group, and 1 to 50
Is the number of R ₄₁ represents a substituted or unsubstituted alkyl group or aryl group), a nonionic group represented by a hydrophilic betaine group, for example,-+ N (R ⁵ ) (R ⁶ ) -AIK-COO-and-+ N
(R ⁵ ) (R ⁶ ) -AIK-SO _3- (wherein AIK represents a lower alkylene group having 1 to 5 carbon atoms, for example, methylene, ethylene, propylene and butylene, and R ⁵ and R ⁶ each independently represent hydrogen. Atom, a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aryl group such as a methyl group, an ethyl group, a benzyl group or the like having 1 to 12 carbon atoms and a hydrophilic cation group such as-+ N (R ⁵ ) (R ⁶ ) (R ⁷ ) · Y-(where
R ⁵ , R ⁶ , and R ⁷ have the same meanings as R ⁵ described above, and Y − represents an inorganic or organic anion, and includes a hydroxy group, a halogen group, a sulfate group, a carbonate group, a perchlorate group, and an organic carboxylic acid group. ,
Organic sulfonic acid group, organic sulfate group, etc.), and preferably a hydrophilic anionic group such as -SO ₃ M, -OSO
₃ M, -COOM, -O-PO (OM) ₂ , -PO (OM) ₂ , -O-PO (OM) (OAR
f), -PO (OM) (OA-Rf) and the like. Here, M represents an inorganic or organic cation, preferably a hydrogen atom, an alkali metal (eg, Li ⁺ , Na ⁺ , K ⁺ ), an alkaline earth metal (eg, Mg ²⁺ , Ca ²⁺ ), and a carbon number of 0. ~ 18 ammonium,
And lower alkylamines. A and Rf are as defined above. Specific examples of typical fluorine-containing surfactants that can be used in the present invention are shown below.

[0035]

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[0036]

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[0038]

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[0039]

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[0040]

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[0041] In the present invention, the coating amount of the fluorine-containing surfactant is 1 m ² per 250mg below 0.01mg above. It is preferably 100 mg or less and 0.1 mg or more, more preferably 50 mg or less and 0.5 mg. As the solvent used for the fluorine-containing surfactant, water and the above-mentioned ordinary organic solvents can be appropriately selected and used. Preferred are alcohols, ketones, glycol derivatives, lower fatty acid esters, haloalkanes, and hydrocarbons. Particularly preferably, in a solvent system in which water is mixed and used, a solvent selected from alcohols, ketones, and glycol derivatives which are mixed with water to form a uniform solvent, and as a solvent when water is not used, Alcohols, ketones, lower fatty acid esters, haloalkanes, and hydrocarbons. As the above-mentioned organic solvent, the same or different kinds of solvents may be used as a mixture of two or more kinds. When used as a mixed solvent of water and an organic solvent, the mixing ratio thereof can be arbitrarily determined and is not particularly limited.

The method of applying the outermost layer, which is the layer containing the slip agent-dispersed particles, is described in RD307105, Chapter XV. For example, the air doctor of the application method mentioned above,
Examples include blades, air knives, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, and the like. In the present invention, it is also preferable to use a non-fluorine-containing surfactant in combination with the above-mentioned fluorine-containing surfactant, and it is preferable to use any of a cationic, anionic, betaine-based, and nonionic non-fluorine-containing surfactant. it can. Preferred are cationic, anionic and nonionic types. Combinations of fluorine-containing surfactants and non-fluorine-containing surfactants include three types of fluorine-containing surfactants: anionic, cationic and nonionic, and the same non-fluorine-containing surfactants of cationic, anionic and nonionic types. At least one of the three types can be arbitrarily selected and all of the cases that can be combined in a numerical manner can be used. Preferably, one of the fluorine-containing surfactant and the non-fluorine-containing surfactant is a cationic type. The other is a combination of an anionic surfactant or a combination of a nonionic surfactant and a nonionic surfactant. In particular, the cationic surfactant is a fluorine-containing surfactant and the anionic surfactant is a combination of a non-fluorine-containing surfactant, or a combination of a nonionic fluorine-containing or non-fluorine-containing surfactant. This is because the optimal amount of a fluorine-based surfactant with negative chargeability and a non-fluorine-based surfactant with positive chargeability is used in the charge train to adjust the charge train and improve the power generation with the partner material that comes into contact. By making it smaller, it is preferably used in the present invention. The following are typical examples of non-fluorine-containing surfactants.

[0043]

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[0044]

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[0045]

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[0046]

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The amount of the non-fluorine-containing surfactant used in combination with the fluorine-containing surfactant is not more than 200 mg / m ² . Preferably it is 100 mg or less. Particularly preferably 5
0 mg or less and 1 mg or more. The case where the non-fluorine-containing surfactant is not used at all is included, and the total coating amount is the same as described above. Since the non-fluorine-containing surfactant is used in combination with the fluorine-containing surfactant, the solvent and the like are the same as those of the fluorine-containing surfactant. The molar ratio of the cationic surfactant / anionic surfactant in the above-mentioned combination is in the range of 0.01 to 100. Preferably 0.1 to 1
0. More preferably, it is in the range of 0.2 to 2. Representative specific examples of the ion complex are shown below.

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[0049]

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In the present invention, an antistatic layer comprising a conductive antistatic agent is preferably used. The antistatic agent is not particularly limited, and may be an organic substance or an inorganic compound. In the case of an organic substance, it may be any of an anion, a cation, or a nonion, and may be a low molecular compound or a high molecular compound. In the case of an organic compound, a polymer is preferable. For example, the anionic polymer electrolyte is a polymer containing carboxylic acid and its salt and sulfonate.
No. 6-24159, JP-A-51-30725, JP-A-51-129216 and JP-A-55-95942. Examples of the cationic polymer include those described in JP-A-49-121523, JP-A-48-91165, and JP-B-49-24582. In addition, ionic surfactants as low molecular compounds also have anionic and cationic properties. For example, JP-A-49-85826 and JP-A-49-85826.
No. 33630, U.S. Pat. No. 2,992,108, U.S. Pat. No. 3,206,312, JP-A-48-87826,
JP-B-49-11567, JP-B-49-11568
And compounds described in JP-A-55-70837.

An antistatic layer made of an inorganic conductive material is very useful. Among them, those preferable as an antistatic agent include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ and In _2.
At least one metal oxide selected from O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ or a composite oxide thereof (Sb, P, B, In, S, Si, C), which may be crystalline or sol. Furthermore, conductive carbon particles may be used.
The fine particles of the conductive crystalline or sol-like metal oxide or its composite oxide used in the present invention have a volume resistivity of 10 ⁷ Ω-cm or less, more preferably 10 ⁵ Ω-cm or less. And particularly preferably 10 ² Ω-cm or less. The shape is not particularly limited, and various shapes such as a sphere, a rod, a needle, a scale, and a plate can be used. Further, the material may be hollow, and a material such as carbon nanofiber corresponds thereto. The primary particle size is desirably 0.0005 to 2 μm, particularly preferably 0.001 to 1 μm. In order to provide conductivity more efficiently, the primary fine particles are partially aggregated (2 to 2).
10000 aggregates) to form 0.01 to 0.5
It is preferable to use an aggregate of fine particles or fillers of conductive crystalline or sol oxide or composite oxide thereof having a thickness of μm. The relationship between the crystallite size and the particle size of these conductive particles is not particularly limited. When the crystallinity is high, the ratio between the crystallite size and the particle size is 1 /.
It is 1 and the ratio can be as high as 1/2000 when the crystallinity is low and amorphous. As the conductivity reached when an antistatic layer is produced using these, the electric resistance thereof is preferably 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω or less, particularly preferably 10 ¹⁰ Ω or less, both in raw and after heat development. ^{Has an} electric resistance of 10 ^9.5 Ω or less. The position of the conductive antistatic layer is not particularly limited, and may be at least one layer not only on the back side but also on the emulsion side. Furthermore, it may be the outermost surface or the inside, and is not particularly limited.

In particular, conductive antimony-containing tin oxide fine powder is useful as the conductive material used in the present invention, and these are readily available as commercial products, and include spherical and needle-like materials.
Particularly, the acicular conductive antimony-containing tin oxide powder useful therein is described in detail. This means that at least one of the needles has a short axis average particle diameter of 0.005 to 1 μm, a long axis average particle diameter of 0.05 to 10 μm, an aspect ratio of 3 or more, and a specific resistance of 1 kΩ · cm or less. It is characterized in that it has a layer of a conductive antimony-containing tin oxide powder and is described in detail below. Here, the needle shape is a fiber shape, a column shape, a rod shape,
Scaly and other similar substances are also included. Needle-like conductive antimony-containing tin oxide fine powder used in the present invention,
It can be obtained by depositing hydrated antimony on the surface of acicular tin oxide as the base particles and then firing. Alternatively, it can be prepared by adding antimony oxide at the stage of preparing tin oxide in advance. The method for preparing the acicular conductive antimony-containing tin oxide fine powder used in the present invention is not particularly limited, and these methods are described in, for example, JP-A-9-12314, JP-A-8-231222, and JP-A-8-231222.
Nos. 217445 and 8-217444, US-55
No. 75957, EP-719730, JP-A-56-1
No. 20519 and No. 62-158199.

Needle-like conductors preferably used in the present invention
At least one of the conductive antimony-containing tin oxide fine powder is
Short axis average particle diameter is 0.005 to 1 μm and long axis average particle
Particle size is 0.05-10 μm and aspect ratio is 3 or less
And the specific resistance is 1 kΩ · cm or less, preferably
Has a short axis average particle diameter of 0.005 to 0.5 μm,
It is preferably 0.005 to 0.2 μm, and the long axis average grain
The diameter is 0.05 to 10 μm, more preferably 0.1 to 5 μm.
μm, particularly preferably 0.1 to 3. Short axis average
The aspect ratio between the particle diameter and the major axis average particle diameter is 3 or more
However, it is preferably 5 or more, particularly preferably 7 or more.
In addition, the specific resistance of tin oxide fine powder containing acicular conductive antimony
Is 1 kΩ · cm or less, preferably 500 Ω · cm
It is particularly preferably 100 Ω · cm or less. More effective
In order to give conductivity efficiently, primary particles are partially aggregated.
Needle-shaped conductive antimony made 0.05-1.0 μm
It is preferable to use an aggregate in the form of a fine powder containing tin oxide.
In addition, it has reached the point where an antistatic layer is produced using these.
Preferably, the conductive material has an electric resistance of 10 ¹²
Ω or less, more preferably 10^TenΩ or less, especially preferred
What is new is that the electrical resistance is 10^9.5Ω or less.

Next, a binder in which a conductive material is preferably used will be described. The binder used in the present invention is a known thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural material which is conventionally used as various binders. Combinations (proteins, cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin preferably has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 0.1.
It is 20,000 to 1,000,000, preferably 50,000 to 300,000.
As the thermoplastic resin, vinyl copolymers, nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, cellulose derivatives such as cellulose dodecanoate resin, acrylic Resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone And fluorinated resins.

The binders listed above may be used alone or in a mixture of several kinds. Known binders of chlorocyanuric acid type, vinyl sulfone type, epoxy type, aziridine type, isocyanate type, and / or radiation curable vinyl type monomers may be used. It can be added and cured. The isocyanate-based crosslinking agent is a polyisocyanate compound having two or more isocyanate groups, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine Isocyanates such as diisocyanate, isophorone diisocyanate and triphenylmethane diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, 3 mol of tolylene diisocyanate and 1 m of trimethylolpropane
ol reaction products) and polyisocyanates formed by condensation of these isocyanates. Examples of the epoxy type include neopentyl alcohol triglycidyl, pentaerythritol tetraglycidyl, dipentaerythritol hexaglycidyl, and glycerin triglycidyl.

Further, a hydrophilic binder can be used in the layer having the conductive compound. As the hydrophilic binder to be used, Research Disclosure No. 17643,
26, and Nos. 18716, 651, which illustrate water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, and the like. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer.Examples of cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. And so on. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers,
Acrylic ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers and the like. Among them, gelatin is most preferred, and examples thereof include alkali-treated and acid-treated gelatin. Salts remaining therein are not particularly limited, but preferably calcium is 3000
ppm or less, more preferably 2000 ppm or less,
In particular, it is preferably 1000 ppm, more preferably 500 ppm or less.

The method of dispersing the conductive antimony-containing tin oxide fine powder in the binder is described in, for example,
Various known means other than -35092 are possible,
A kneader, a pin type mill, an annular type mill and the like are preferable, and a combination of a kneader and a pin type mill, or a combination of a kneader and an annular type mill is also preferable. Kneaders include open type (open), closed type, continuous type, etc.
A kneader such as a roll mill and a lab plast mill is also used. Further, at the time of dispersion, a dispersant described in JP-A-5-088283 or other known dispersants can be used. The content of the electrically conductive antistatic agent is preferably 5 to 500 mg / m ^2, particularly preferably 10 to 350 mg / m ^2. Also,
The amount of the binder is preferably from 1-500 mg / m ^2, in particular 5 to 300 mg / m ² is preferred. The ratio of the amount of the conductive crystalline or fine particles of the sol oxide or the composite oxide thereof to the binder is preferably from 1/300 to 100/1,
More preferably, it is 1/100 to 100/5. The conductive layer is provided on at least one surface of the image material, and can be provided on the entire surface or in a stripe by coating or printing. Methods for applying the conductive layer include air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, dip coat, bar coat, and extend. For example, a coating method can be used, and other methods are also available. Specific descriptions of these methods can be found in “Coating Engineering” published by Asakura Shoten, pages 253 to 277 (Showa 4).
6.3.20. Issuance).

Next, the vinylidene chloride undercoating layer preferably used in the present invention will be described. The heat-developable image-recording material of the present invention forms an image by a heat-development process, and its developing temperature is from 80 ° C to 140 ° C. The heating in the thermal development in this case includes not only heating for image formation, but also preliminary heating for the purpose of suppressing processing unevenness and the like. Therefore, the development may be performed at a constant temperature, or may be multi-stage heating in which heating is performed at a constant temperature followed by heating at a higher temperature. In such a heat-developable image recording material, a support having both surfaces coated with an undercoat layer containing a vinylidene chloride copolymer and having a thickness of 0.3 μm or more (total thickness per one surface) is used. Can be prevented from changing over time. And, it is possible to eliminate the generation of wrinkles that are likely to occur during thermal development,
Further, since it is possible to suppress a dimensional change due to thermal development, it is also a great advantage that the dimensional change due to the aging after the thermal development becomes extremely small. In particular, in the present invention, a biaxially stretched polyester support is preferably used. In such a support, preferably, a heat treatment is performed after an undercoat layer is provided, so that a dimensional change due to heating of the support itself or a beco Is suppressed. Therefore, when the polyester support after the heat treatment is used, no wrinkles are generated during the heat development of the heat-developable image recording material, and the dimensional change before and after the heat development is reduced. To this end, the polyester support preferably used in the present invention is subjected to a heat treatment, preferably a heat treatment at a temperature of 130 ° C. or more and 185 ° C. or less after providing an undercoat layer containing vinylidene chloride.

On the other hand, unlike the present invention, when only a polymer other than the vinylidene chloride copolymer (for example, a styrene-butadiene copolymer) is used for the undercoat layer covering both sides of the support, the thermal development The dimensional change due to aging cannot be suppressed. Further, even if the thickness (total thickness per one side) of the undercoat layer of the vinylidene chloride copolymer is less than 0.3 μm, the dimensional change due to aging after thermal development cannot be suppressed. The vinylidene chloride copolymer used in the present invention is 70%.
９９99.9% by weight, more preferably 85-99% by weight of vinylidene chloride monomer and 0.1-5% by weight, more preferably 0.2-3% by weight of a carboxyl group-containing vinyl monomer. Preferably, the copolymer is: The vinylidene chloride copolymer composition used in the present invention will be described in detail. The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer is a vinyl monomer having one or more carboxyl groups in a molecule, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, and citraconic acid. Can be mentioned. The vinylidene chloride copolymer used in the present invention may contain, in addition to the vinylidene chloride monomer and the carboxyl group-containing monomer, a repeating unit of a monomer copolymerizable therewith. Specific examples of these copolymerizable monomers include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene. These copolymerizable monomers may be used alone or in combination of two or more.

The weight average molecular weight of the vinylidene chloride copolymer used in the present invention is 45,000 or less, and more preferably 10,000
It is preferably at least 45,000. When the molecular weight is large, the adhesiveness between the vinylidene chloride copolymer layer and the support layer such as polyester is deteriorated. When used in the present invention, the vinylidene chloride copolymer may be in the form of being dissolved in an organic solvent or in the form of an aqueous dispersion of latex, but the form of an aqueous dispersion of latex is preferred. In this case, a latex of polymer particles having a uniform structure or a latex of polymer particles having a so-called core-shell structure having different compositions in the core portion and the shell portion may be used. The particle size and the like of the polymer particles in the latex are the same as those used for the binder of the image forming layer and the protective layer described later. The arrangement of the monomer units of the vinylidene chloride copolymer is not limited, and may be any of periodic, random, block, and the like. Specific examples of the vinylidene chloride copolymer include the following. However, the numbers in parentheses indicate weight ratios. The average molecular weight represents a weight average molecular weight.

V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1) (average molecular weight: 42,000) V-2: Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (8
7: 4: 4: 4: 1) latex (average molecular weight 40,000) V-3 Vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90: 6: 2: 2)
Latex (average molecular weight 38000) V-4 Vinylidene chloride: ethyl methacrylate: 2-
Hydroxyethyl methacrylate: acrylic acid (90:
8: 1.5: 0.5) latex (average molecular weight 44000) V-5 Core-shell type latex (core 90% by weight, shell 10% by weight) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: Acrylic acid (93:
3: 3: 0.9: 0.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (8
8: 3: 3: 3: 3) (Average molecular weight 38000) V-6 Core-shell type latex (core 70% by weight, shell 30% by weight) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (9
2.5: 3: 3: 1: 0.5) Shell part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (average molecular weight 20,000)

The vinylidene chloride copolymer may be used alone or in combination of two or more. The vinylidene chloride copolymer layer as the undercoat layer may be any of the undercoat layers and is not particularly limited. Above all, however, it is preferable to provide as an undercoat layer first layer directly provided on the support. Usually, one layer is provided on each side, but in some cases, two or more layers may be provided. When a multi-layer structure of two or more layers is used, the amount of the vinylidene chloride copolymer may be in the range specified in the present specification in total. The thickness of the vinylidene chloride copolymer layer is preferably 0.3 μm or more and 4 μm or less, more preferably 0.6 μm or more and 3 μm or less, and still more preferably 1.0 μm or more and 2 μm. The range is as follows.

The heat-developable image recording material of the present invention is preferably prepared by coating an organic silver salt, a reducing agent and a photosensitive silver halide on a polyester support coated on both sides with an undercoat layer containing a vinylidene chloride copolymer. And at least one protective layer is provided on the image forming layer. Further, the heat-developable image recording material of the present invention preferably has at least one back layer on the side opposite to the image forming layer with respect to the support, and has an image forming layer, a protective layer, and a back layer. Is a binder for the back layer,
Synthetic or natural polymers are used, which may be hydrophobic or hydrophilic. Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer.

Various supports can be used in the heat-developable image recording material of the present invention. Typical supports are polyethylene terephthalate, polyethylene naphthalate,
Such as polyester, cellulose nitrate, cellulose ester, polyvinyl acetal, and polycarbonate. Among them, biaxially stretched polyester, especially polyethylene terephthalate (PET) has strength, dimensional stability,
It is preferable from the viewpoint of chemical resistance and the like. The thickness of the support is preferably 60 to 200 μm as a base thickness excluding the undercoat layer. The support used in the heat-developable image recording material of the present invention is used for reducing the internal strain remaining in the film during biaxial stretching and eliminating the heat shrinkage distortion generated during the heat development.
Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of 30 to 185 ° C is preferably used. Such a thermal relaxation treatment may be performed at a constant temperature within the temperature range, or may be performed while increasing the temperature.

The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. In the case where the transfer is carried out in the form of a web, the transfer tension of the support during the heat treatment is preferably relatively low, and specifically, 7 kg /
cm ² or less, particularly preferably to 4.2 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is about 0.5 kg / cm ² . Such a heat treatment is preferably performed after a treatment for improving the adhesiveness of the image forming layer and the back layer to the support, an undercoating layer containing a vinylidene chloride copolymer, and the like are applied. The heat shrinkage of the support after heating at 120 ° C. for 30 seconds is preferably −0.03% to + 0.01% in the machine direction (MD) and 0 to 0.04% in the transverse direction (TD). . The support may include a vinylidene chloride copolymer layer if necessary,
An undercoat layer using BR, polyester, gelatin or the like as a binder may be applied. These undercoat layers may have a multilayer structure, or may be provided on one side or both sides of the support. At least one of these undercoat layers can be a conductive layer. The general thickness (per layer) of the undercoat layer is 0.01 to 5 μm, more preferably 0.05 to 1 μm.
μm, and the thickness when forming a conductive layer is 0.01
１1 μm, more preferably 0.03 to 0.8 μm.

Next, binders such as an image forming layer, an intermediate layer, a back layer, and a back protective layer will be described. The polymer binder preferably used for the binder used in the present invention is one in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. The average particle size of the dispersed particles is 1
The range is preferably about 5000 nm, more preferably about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles,
Those having a wide particle size distribution or those having a monodispersed particle size distribution may be used. The polymer binder may be a so-called core / shell type polymer latex other than the usual polymer latex having a uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

Glass transition temperature (Tg) of polymer of polymer latex used as a binder in the present invention
The preferred temperature range differs between the protective layer, the back layer and the image forming layer. Since the protective layer and the back layer are in contact with various devices, from the viewpoint of film strength and prevention of adhesion failure, 25 ° C to 100 ° C.
The glass transition temperature of -30 ° C. to 70 ° C. is particularly preferable in order to promote the diffusion of the photographically useful material during thermal development and to obtain good photographic properties such as high Dmax and low fog. The glass transition temperature is particularly preferably 0 ° C to 50 ° C. The minimum film forming temperature (MFT) of the polymer latex is -30C to 90C, more preferably 0C to 7C.
About 0 ° C. is preferable. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid is also called a temporary plasticizer and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex.For example, the aforementioned `` Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Kankokai (19
70))).

The polymer used in the polymer latex in the present invention includes acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. There is. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The polymer has a weight average molecular weight of 5,000 to 1,000,000, preferably 1
About 0000 to 100000 is preferable. If the molecular weight is too small, the mechanical strength as a binder is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the heat-developable image recording material of the present invention include the following. Methyl methacrylate / ethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / Vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer and the like. Such polymers are also commercially available, and the following polymers can be used. For example, as examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,8
57, 857x2 (Nippon Zeon Co., Ltd.), VONCORT R3340,
R3360, R3370, 4280, 2830, 2210 (all manufactured by Dainippon Ink and Chemicals, Inc.), Julimer ET-410, 530, SEK101-SEK30
1, FC30, FC35 (all manufactured by Nippon Pure Chemical Co., Ltd.), Polysol F
Polyester resins such as 410, AM200 and AP50 (all manufactured by Showa Polymer Co., Ltd.) include FINETEX ES650, 611, 675, 8
HYDRAN AP10, 20, 30, 40, VONDIC 1320NS (Dai Nippon Ink Chemical Co., Ltd.), such as 50 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical), etc. L) as rubber-based resin
ACSTAR 7310K, 3307B, 4700H, 7132C, LQ-618-1 (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 410, 430, 43
5, 2507 (Nippon Zeon Co., Ltd.) and other vinyl chloride resins such as Nipol G351 and G576 (Nippon Zeon Co., Ltd.)
For example, vinylidene chloride resins such as L502 and L513 (manufactured by Asahi Kasei Kogyo Co., Ltd.) and Aron D7020, D5040, D5071 (manufactured by Toa Gosei Co., Ltd.). And the like). These polymers may be used alone or as a blend of two or more as necessary.

As the binder for the intermediate layer and the protective layer in the polymer latex, acrylic, styrene, acryl / styrene, vinyl chloride and vinylidene chloride polymer latexes are preferably used. Specifically, acrylic resin VONCORTR 3370, 4280, Nipol Lx85
7, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene /
Acrylic acid copolymer, vinyl chloride resin Nipol G576,
Alon D5071 of vinylidene chloride resin is preferably used. In addition, styrene /
Butadiene-based polymer latex is preferably used. Specifically, rubber-based resins LACSTAR3307B, Nipol Lx43
0 and 435 are preferably used. As a binder for the back layer, an acrylic, olefin, or vinylidene chloride-based polymer latex is used. Chemipearl S120, vinylidene chloride-based L502, Aron D7020 and the like are preferred.
If necessary, a hydrophilic polymer such as polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose may be added to the binder used in the present invention in a range of 20% by weight or less of the total binder. The addition amount of these hydrophilic polymers is preferably 10% by weight or less of the total binder in the protective layer and the image forming layer.

The photographic constituent layer in the heat-developable image recording material of the present invention is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 60% by weight or more of the solvent (dispersion medium) of the coating liquid is water. Components other than water of the solvent of the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxyethyl A water-miscible organic solvent such as phenyl ether can be used. The total amount of the binder for the protective layer is preferably in the range of 0.1 to 10.0 g / m ² , more preferably 0.2 to 5.0 g / m ² . The total amount of the binder for the image forming layer is preferably in the range of 0.2 to 30 g / m ² , more preferably 1.0 to 15 g / m ² . Total amount of binder for the back layer is 0.01~15g / m ^2, more preferably in the range of 0.05-5 g / m ^2. A cross-linking agent for cross-linking, a surfactant for improving coating properties, and the like may be added to each layer. Each of these layers may be provided in two or more layers. When the image forming layer has two or more layers, it is preferable to mainly use a polymer latex as a binder for all the layers. The protective layer is a layer provided on the image forming layer and refers to a layer which is not the outermost layer when two or more layers are present, and is preferably at least one layer. The back layer is provided above the undercoat layer on the back surface of the support, and there may be two or more layers. However, it is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.

The Beck smoothness in the present invention can be determined by the Japanese Industrial Standards (JIS) P8119 “Smoothness test method for paper and paperboard using Beck tester” and TAPPI standard method T4.
79 can be easily obtained. The Beck smoothness of at least one of the surface having the image forming layer and the surface of the outermost layer opposite to the surface having the image forming layer of the heat-developable image recording material of the present invention is preferably 2000 seconds or less, and more preferably 1 second or less.
0 second to 2000 seconds. The Beck smoothness of the surface of the outermost layer having the image forming layer of the heat-developable image recording material and the surface of the outermost layer opposite to the surface are determined by the average particle diameter of fine particles called a matting agent to be contained in the layers on both sides and addition. It can be controlled by varying the amount.
The matting agent is preferably contained in the protective layer that is the outermost layer farthest from the support on the surface having the image forming layer, and is preferably contained in the outermost layer or the back layer that is not the outermost layer on the opposite side. .

In the present invention, the average particle size of the matting agent is preferably in the range of 0.5 to 20 μm, and more preferably 1 to 10 μm. In the present invention, a preferable addition amount of the matting agent is in the range of 5 to 400 mg / m ² , particularly 5 to 100 mg / m ² . The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic properties. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, silicates of calcium and aluminum, and examples of organic matting agents include cellulose. Mention may be made of organic polymeric matting agents such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof. In the present invention, JP-A-3-109542
JP-A-4-127142, page 3, upper right column, line 7 to page 5, lower right column, line 4 describes the porous matting agent described in page 2, lower left column, line 8 to page 3, upper right column, line 4. The matting agent surface-modified with the described alkali, paragraph No. "0" of JP-A-6-118542.
It is more preferable to use an organic polymer matting agent described in “005” to “0026”. Further, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an amorphous matting agent and a spherical matting agent, mats having different average particle sizes. (For example, when the average particle size described in JP-A-6-118542 is 1.
A matting agent having a particle size of 5 μm or more and a matting agent having an average particle size of 1 μm or less). The layer containing the matting agent may be the outermost layer, or the lower layer or the image forming layer. Regarding the surface roughness formed by the matting agent, the average height of the projections from the surface is 0.2 μm or more and 10 μm or less, more preferably 0.5 μm or more and 7 μm or less.

The heat-developable image recording material of the present invention preferably contains a photosensitive silver halide. The photosensitive silver halide used in the present invention may be any of silver chloride, silver chlorobromide, and silver iodochlorobromide. Further, the distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously. The method of forming the photosensitive silver halide in the present invention is well known in the art, and for example, the methods described in Research Disclosure No. 17029, June 1978, and U.S. Pat.No. 3,700,458 can be used. . Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method in which a silver supply compound and a halogen supply compound are added to another polymer solution to prepare photosensitive silver halide grains and mixed with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation to be low.
20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less,
More preferably, the thickness is 0.02 μm or more and 0.12 μm or less. The grain size as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical particles, rod-shaped particles, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited, but the spectral sensitizing efficiency when a spectral sensitizing dye is adsorbed is high.
The proportion occupied by the [100] plane is preferably high. The ratio is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. The ratio of the Miller index [100] plane was determined by T. Tani; J. Imaging Sci., 29, 165 (1985) using the dependence of the adsorption of sensitizing dye on the [111] and [100] planes. It can be determined by the method described.

The photosensitive silver halide grains are the same as those of the periodic table.
It preferably contains a metal or a metal complex of Group VII or Group VIII (Groups 7 to 10). Of the periodic table
Rhodium, rhenium, ruthenium, preferably as the central metal of the Group VII or Group VIII metal or metal complex
Osnium and iridium. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is 1n per mole of silver.
Mol to 10 mmol, preferably 10 nmol to 100 μm.
A molar range is more preferred. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used. The silver halide emulsion is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, Sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization and the like are preferred. Sulfur sensitization used in the present invention,
Usually, a sulfur sensitizer is added and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably from 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As a method for preparing silver halide, a so-called halide method in which a part of silver of an organic silver salt is halogenated with an organic or inorganic halide is also preferably used. The organic halide used herein may be any compound as long as it is a compound that reacts with an organic silver salt to generate a silver halide, and includes N-halogenimide (N-bromosuccinimide, etc.), quaternary nitrogen halide (e.g. Tetrabutylammonium bromide), an association of a quaternary nitrogen halide and a halogen molecule (pyridinium bromide perbromide), and the like. As the inorganic halogen compound, any compound may be used as long as it is a compound which reacts with an organic silver salt to generate silver halide, and includes an alkali metal or ammonium halide (such as sodium chloride, lithium bromide, potassium iodide, and ammonium bromide). ), Alkali earth metal halides (calcium bromide, magnesium chloride, etc.), transition metal halides (ferric chloride, cupric bromide, etc.), metal complexes with halogen ligands (sodium iridium bromide) , Ammonium rhodate, etc.), halogen molecules (bromine, chlorine, iodine)
and so on. Further, a desired organic / inorganic halide may be used in combination.

The amount of the halide to be added at the time of the hiding is preferably 1 to 500 mmol, more preferably 10 to 250 mmol, as a halogen atom per 1 mol of the organic silver salt. The organic silver salt that can be used in the present invention is relatively stable to light, but at 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated as described above. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids,
Particularly, a silver salt of a long-chain fatty carboxylic acid (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) is preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor is preferably present in about 5-7 of the imaging layer.
0% by weight can be constituted. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate,
Silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. In the present invention, the minor axis is 0.01 μm or more and 0.2 μm or more.
The length is preferably 0 μm or less, the major axis is 0.10 μm or more and 5.0 μm or less, the minor axis is 0.01 μm or more and 0.15 μm or less, and the major axis is 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by the minor axis and major axis, respectively, is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. The organic silver salt that can be used in the present invention is preferably desalted. The desalting method is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used. For the purpose of obtaining fine particles having a small particle size and no aggregation, a method of preparing a solid fine particle dispersion using a dispersant is used for the organic silver salt that can be used in the present invention. The method of dispersing the organic silver salt into solid fine particles is carried out by using a known fine-granulating means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill, high-pressure homogenizer) in the presence of a dispersing aid. Used and can be dispersed mechanically. When the organic silver salt is formed into solid fine particles using a dispersant, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, a maleic acid monoester copolymer, and acryloylmethylpropanesulfonic acid Synthetic anionic polymers such as copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, and the anions described in JP-A-52-92716 and WO88 / 04794. Surfactant, JP-A-9-17924
No. 3 or known anionic, nonionic, cationic surfactants and other known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, or gelatin. A polymer compound existing in nature can be appropriately selected and used.

In the present invention, the organic silver salt can be used in a desired amount, but is preferably 0.1 to 5 g / m ² , more preferably 1 to 3 g, as an amount per 1 m ^{2 of} the heat-developable image recording material. a / m ^2. The heat-developable image recording material of the present invention preferably contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Phenidone,
Conventional photographic developers such as hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50% (mole) based on 1 mol of silver on the surface having the image forming layer, and 10 to 40%.
(Mol) is more preferable. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When added to layers other than the image forming layer, 10
It is preferable to use a relatively large amount of about 50% (mol). Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development. In a photothermographic material using an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, and JP-A-49-5.
No. 020, No. 49-91215, No. 49-91215, No. 50-2524, Same
No. 50-32927, No. 50-67132, No. 50-67641, No. 50-11421
No. 7, No. 51-3223, No. 51-27923, No. 52-14788, No. 52
-99813, 53-1020, 53-76020, 54-156524
No. 54-156525, No. 61-183642, JP-A-4-56848
No., JP-B-49-10727, JP-B-54-20333, U.S. Pat.
No. 254, No. 3,446,648, No. 3,782,941, No. 4,123,282
No. 4,510,236, UK Patent 1380795, Belgium Patent
No. 841910 and the like.

The heat-developable image recording material of the present invention preferably contains an ultrahigh contrast agent (also referred to as a nucleating agent) in the image forming layer and / or an adjacent layer in order to obtain a high contrast image. Further, in the present invention, for forming a super-high contrast image, a high contrast accelerator can be used in combination with the above super-high contrast agent. For example, amine compounds described in U.S. Patent No. 5,545,505, specifically AM-1 to AM-5, hydroxamic acids described in 5,545,507, specifically HA-1 to HA-11,
Acrylonitrile described in JP-A-5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in JP-A-5,558,983, specifically CA-1 to CA-6, JP-A-9-297
No. 368, specifically, A-1 to A
-42, B-1 to B-27, C-1 to C-14 and the like can be used. As the sensitizing dye in the present invention, any dye can be used as long as it can spectrally sensitize the silver halide grains in a desired wavelength region when adsorbed on the silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used.

As an example of spectral sensitization to red light, He-Ne
For lasers, so-called red light sources such as red semiconductor lasers and LEDs, I-1 to I-1 described in JP-A-54-18726.
-38, the compound of I-1 to I-35 described in JP-A-6-75322 and the compound of I-1 to I-34 described in JP-A-7-287338, JP-B-55-39818 Dyes 1 to 20 described, compounds of I-1 to I-37 described in JP-A-62-284343 and compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected. Is done. For a semiconductor laser light source in the wavelength region of 750 to 1400 nm, various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes can be spectrally advantageously sensitized. it can. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Pat.
3,719,495 and 3,877,943, UK Patent 1,466,201
No. 1,469,117, No. 1,422,057, Tokuhei 3-10391
No., 6-52387, JP-A-5-341432, 6-94781,
The dye may be appropriately selected from known dyes as described in JP-A-6-301141.

Further, dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887 as dyes forming a J-band,
JP-A-2-96131 and JP-A-59-48753 are disclosed and can be preferably used in the present invention. The silver halide emulsions and / or organic silver salts of the present invention are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and have a reduced sensitivity during storage in inventory. Can be stabilized. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are described in U.S. Pat.
No. 8,694,716, azaindene described in U.S. Pat.Nos. 2,886,437 and 2,444,605, mercury salt described in U.S. Pat.
Urazole described in U.S. Pat.No. 3,287,135, sulfocatechol described in U.S. Pat.
No. 23,448, oximes, nitrones, nitroindazoles, polyvalent metal salts described in U.S. Pat.No. 2,839,405, thyuronium salts described in U.S. Pat. Palladium, platinum and gold salts, U.S. Pat.No. 4,108,665
No. 4,442,202 and halogen-substituted organic compounds described in U.S. Pat.Nos. 4,128,557 and 4,137,079,
No. 4,138,365 and No. 4,459,350, and the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The antifoggant used in the present invention may be added by any method such as a solution, a powder or a solid fine particle dispersion. Solid fine particle dispersion is known micronization means (for example, ball mill, vibrating ball mill, sand mill, colloid mill,
Jet mill, roller mill, etc.). Also,
When dispersing the solid fine particles, a dispersing aid may be used. The heat-developable image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The heat-developable image recording material of the present invention controls the development by suppressing or accelerating the development, improving the spectral sensitization efficiency, and improving the storage stability before and after the development, such as a mercapto compound, a disulfide compound, and a thione compound. Can be contained. The heat-developable image recording material in the invention has an image forming layer such as a photosensitive layer containing at least one silver halide emulsion on one side of a support, and a back layer (backing layer) on the other side. It is preferably a so-called single-sided image recording material having In the present invention, the back layer has a maximum absorption in a desired wavelength range of preferably 0.3 or more and 2 or less, more preferably an absorption of 0.5 or more and 2 or less, and an absorption in a visible region after the treatment of 0.001 or more.
It is preferably less than 0.5, more preferably 0.001
The layer preferably has an optical density of at least 0.3 and less than 0.3. Examples of the antihalation dye used in the back layer are the same as those of the antihalation layer described above. U.S. Pat.Nos. 4,460,681 and 4,374,921 show a backside resistive heating layer.
layer) can also be used in a photothermographic imaging system. Image forming layer in the heat-developable image recording material of the present invention,
A hardener may be used for each layer such as the protective layer and the back layer.
Examples of hardeners, U.S. Pat.No. 4,281,060, JP-A-6-2
Polyisocyanates described in 08193 No.
Epoxy compounds described in US Pat. No. 4,791,042 and the like, vinylsulfone compounds described in JP-A-62-89048 and the like are used.

In the present invention, the exposure apparatus used for imagewise exposure may be any apparatus capable of performing exposure with an exposure time of less than 10 ^-7 seconds.
D), an exposure apparatus using a Light Emitting Diode (LED) as a light source is preferably used. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, for LD,
Dye lasers, gas lasers, solid-state lasers, semiconductor lasers, and the like can be used. The exposure is performed by overlapping the light beams of the light source, and the overlap means that the sub-scanning pitch width is smaller than the beam diameter. For example, the overlap can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient) when the beam diameter is represented by a half width of beam intensity (FWHM). In the present invention, the overlap coefficient is preferably 0.2 or more. The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. The channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface type, a multi-channel is preferably used.

The heat-developable image recording material of the present invention has a low haze at the time of exposure and tends to cause interference fringes. Examples of the interference fringe prevention technology include a technology disclosed in Japanese Patent Application Laid-Open No. HEI 5-113548 and the like, in which a laser beam is obliquely incident on a photosensitive material, and a technology disclosed in International Publication WO95 / 31754 and the like. Methods using a mode laser are known, and it is preferable to use these techniques. In the heat development step of the image forming method, development may be performed by any method, but usually development is performed by raising the temperature of the photosensitive material exposed imagewise. As a preferred embodiment of the thermal developing machine used, JP-B 5-56499 as a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum,
Patent Publication No. 684453, JP-A-9-292695, JP-A-9-2973
No. 85 and the thermal developing machine described in International Publication WO95 / 30934,
Japanese Patent Application Laid-Open No. 7-13294, International Publication W as a non-contact type
There are thermal developing machines described in O97 / 28489, 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. A preferred development temperature is 80 to 250
° C, more preferably 100-140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 5 to 90 seconds. As a method for preventing processing unevenness due to dimensional change during thermal development of the photothermographic material of the present invention, after heating at 80 ° C. or more and less than 115 ° C. for 3 seconds or more to prevent an image from appearing, A method in which an image is formed by heat development at a temperature of not more than ° C (a so-called multi-stage heating method) is effective.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the heat-developable image recording material of the present invention. FIG. 1 is a side view of the heat developing machine. The thermal developing machine shown in FIG. 1 includes a pair of carry-in rollers 11 (the lower roller is a heat roller) for carrying the heat-developable photosensitive material 10 into a heating section while correcting and preheating the photosensitive material 10 into a planar shape, and thermal development after thermal development after thermal development. It has a pair of unloading rollers 12 that unloads the photosensitive material 10 from the heating unit while correcting the photosensitive material 10 into a planar shape. The photothermographic material 10 is thermally developed while being transported from the carry-in roller pair 11 to the carry-out roller pair 12. In the conveying means for conveying the photothermographic material 10 during the heat development, a plurality of rollers 13 are provided on the side where the surface having the image forming layer contacts, and the non-woven fabric (for example, A smooth surface 14 on which polyphenylene sulphite or Teflon is adhered is installed. The back surface of the photothermographic material 10 is conveyed by sliding on the smooth surface 14 by driving a plurality of rollers 13 that come into contact with the surface having the image forming layer. As the heating means, a heater 15 is provided at an upper portion of the roller 13 and a lower portion of the smooth surface 14 so as to be heated from both sides of the photothermographic material 10. As a heating means in this case, a plate heater or the like can be used. The clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, but is appropriately adjusted to a clearance that allows the photothermographic material 10 to be transported. Preferably it is 0 to 1 mm.

The material of the surface of the roller 13 and the smooth surface 14
May be any material as long as it has high-temperature durability and does not hinder conveyance of the photothermographic material 10, but the material of the roller surface is silicon rubber, and the material of the smooth surface is a nonwoven fabric made of aromatic polyamide or Teflon (PTFE). Is preferred. It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely. The preliminary heating section upstream of the thermal development processing section is lower than the thermal development temperature (for example, 1
It is desirable to set the temperature and the time sufficient to evaporate the amount of water in the photothermographic material, and to set the temperature and the glass transition temperature (Tg) of the support of the photothermographic material 10 below. It is preferable to set the temperature so that the development unevenness does not occur at a high temperature. Further, a guide plate 16 is provided downstream of the thermal development processing section, and a slow cooling section is further provided. The guide plate is preferably made of a material having low thermal conductivity, and is preferably cooled gradually. Although the above has been described with reference to the illustrated examples, the invention is not limited thereto. For example, the thermal developing machine used in the present invention, such as that described in JP-A-7-13294, may have various configurations. In the case of the multi-stage heating method preferably used in the present invention, in the above-described apparatus, two or more heat sources having different heating temperatures may be provided, and heating may be performed continuously at different temperatures.

[0089]

The present invention will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. <Example 1> 1. Preparation of silver halide emulsion (1-1) Emulsion A 11 g of alkali-treated gelatin (2700 ppm or less as calcium content), 30 mg of potassium bromide, and 10 mg of sodium benzenethiosulfonate were dissolved in 700 ml of water, and pH was adjusted at 40 ° C. After adjusting to 5.0, 159m of aqueous solution containing 18.6g of silver nitrate
l and potassium bromide at 1 mol / l (NH ₄ ) ₂ RhCl ₅
(H ₂ O) at 5 × 10 ⁻⁶ mol / L and K ₃ IrCl ₆
An aqueous solution containing 2 × 10 ⁻⁵ mol / l was added over 6 minutes and 30 seconds by the control double jet method while maintaining the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / l of potassium bromide and 2 × 10 ₃ of K ₃ IrCl ₆ were added.
^An aqueous solution of a halogen salt containing ^-5 mol / l was added over 28 minutes and 30 seconds by a control double jet method while maintaining the pAg at 7.7. Thereafter, the pH was lowered to cause coagulation and sedimentation, followed by desalting treatment. 0.17 g of compound A, low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) 51.
The solution was adjusted to pH 5.9 and pAg 8.0 by adding 1 g. The obtained particles were cubic particles having an average particle size of 0.08 μm, a projected area variation coefficient of 9%, and a (100) plane ratio of 90%. The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and 3 minutes later, 71 μmol of triethylthiourea was added, followed by aging for 100 minutes.
After adding 5 × 10 ⁻⁴ mol of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, the temperature was lowered to 40 ° C.
Thereafter, the temperature was maintained at 40 ° C., and 12.8 × 10 ⁻⁴ mol of the following sensitizing dye A and 6.4 × 10 ⁻³ mol of compound B were added to 1 mol of silver halide with stirring. The mixture was rapidly cooled to ℃ to complete the preparation of silver halide emulsion A.

[0090]

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(1-2) Preparation of Organic Acid Silver Dispersion <Organic Acid Silver A> Behenic acid manufactured by Henkel (product name Eden)
or C22-85R) 87.6 g, distilled water 423 ml, 5N-NaOH aqueous solution 49.
2 ml, tert-butyl alcohol 120 ml mixed, at 75 ℃
The mixture was stirred and reacted for 1 hour to obtain a sodium behenate solution. Separately, prepare 206.2 ml of an aqueous solution of 40.4 g of silver nitrate,
Was kept warm. The reaction vessel containing 635 ml of distilled water and 30 ml of tert-butyl alcohol was kept at 30 ° C., and while stirring, the entire amount of the sodium behenate solution and the entire amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes 10 seconds and 60 minutes, respectively. Added over minutes. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the start of the silver nitrate aqueous solution addition, and then the sodium behenate solution was started to be added.
For 9 minutes and 30 seconds, only the sodium behenate solution was added. At this time, the temperature in the reaction vessel was 30 ° C,
The liquid temperature was controlled so as not to rise. In addition, the piping of the addition system for the sodium behenate solution was kept warm by steam tracing, and the liquid temperature at the outlet of the addition nozzle tip was 75%.
The steam amount was controlled so as to reach ℃. Also,
The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. When the morphology of the obtained silver behenate particles was evaluated by electron micrographing, the average projected area diameter was 0.52 μm,
It was a flaky crystal having an average particle thickness of 0.14 μm and a variation coefficient of the average equivalent sphere diameter of 15%.

Next, a dispersion of silver behenate was prepared by the following method. To a wet cake having a dry solid content of 100 g, 7.4 g of polyvinyl alcohol (trade name: PVA-217, average degree of polymerization: about 1700) and water are added, and the total amount is 385 g.
And then predispersed with a homomixer. Next, the pressure of the predispersed stock solution was adjusted to 1750 kg / cm ² by adjusting the pressure of a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber). This was repeated to obtain a silver behenate dispersion. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. The silver behenate particles contained in the silver behenate dispersion thus obtained have a volume-weighted average diameter of 0.52 μm.
m, particles having a variation coefficient of 15%. Measurement of particle size
Performed with MasterSizerX manufactured by Malvern Instruments Ltd.
When evaluated by electron microscopy, the ratio of the long side to the short side was 1.5, the grain thickness was 0.14 μm, and the average aspect ratio (the ratio of the circle equivalent diameter of the projected area of the grain to the grain thickness) was 5.1.

(1-3) Preparation of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane: Reducing Agent Solid Fine Particle Dispersion -Hydroxy-3,5-dimethylphenyl) -3,5,5-
To 25 g of trimethylhexane, 25 g of a 20% aqueous solution of MP-203 manufactured by Kuraray Co., Ltd., 0.1 g of Safinol 104E manufactured by Nissin Chemical Co., Ltd., 2 g of methanol and 48 ml of water were added and stirred well. The slurry was left for 3 hours. Then 1
360 g of zirconia beads having a diameter of 360 mm were prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 3 hours to prepare a dispersion of solid fine particles of a reducing agent. The particle size is 80% by weight of the particles
It was 0.3 μm or more and 1.0 μm or less.

(1-4) Preparation of solid fine particle dispersion of polyhalogen compound For 30 g of polyhalogen compound-A, 4 g of MP-203, an MP polymer manufactured by Kuraray Co., Ltd., 0.25 g of compound C, and 66 g of water Was added and stirred well, then 200 g of 0.5 mm zirconia silicate beads were prepared and placed in a vessel together with the slurry, and dispersed for 5 hours with a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) A solid particulate dispersion was prepared. Particle size, 80% by weight of the particles 0.3μm or more 1.0μ
m or less. For polyhalogen compound-B, a solid fine particle dispersion was prepared in the same manner as for polyhalogen compound-A, and had the same particle diameter.

(1-5) Preparation of dispersion of solid fine particles of nucleating agent To 10 g of nucleating agent (compound AA), 2.5 g of polyvinyl alcohol (PVA-217 manufactured by Kuraray) and 87.5 g of water were added and stirred well. And left as a slurry for 3 hours. Thereafter, 240 g of 0.5 mm zirconia beads were prepared, put into a vessel together with the slurry, and dispersed for 10 hours with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) to prepare a solid fine particle dispersion. . The particle diameter was such that 80% by weight of the particles were 0.1 μm or more and 1.0 μm or less and the average particle diameter was 0.5 μm.

(1-6) Preparation of Solid Fine Particle Dispersion of Compound Z To 30 g of Compound Z, 3 g of MP-203 (manufactured by Kuraray Co., Ltd.) and 87 ml of water were added, and the mixture was thoroughly stirred. Left for 3 hours. Thereafter, a solid fine particle dispersion of the compound Z was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. The particle diameter is 80 wt% of the particles 0.3 μm or more 1.
It was 0 μm or less.

(1-7) Preparation of Emulsion Layer Coating Solution The following binder, material and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above. Water was added to obtain an emulsion layer coating solution. The viscosity was 20-70 cp (25 ° C.) and the pH was 7.4.・ Binder; Luckstar 3307B 397 g as solid content (manufactured by Dainippon Ink and Chemicals, Inc .; glass transition temperature of 17 ° C. with SBR latex) ・ 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3 , 5,5-Trimethylhexane 149g as solid content ・ Polyhalogen compound-A 34.8g as solid content ・ Polyhalogen compound-B as solid content 9.0g ・ Sodium ethylthiosulfonate 0.30g ・ Benzotriazole 1.04g ・ Polyvinyl alcohol ( 10.8g ・ 6-iso-propylphthalazine 15.0g ・ Sodium dihydrogen orthophosphate dihydrate 0.37g ・ Compound Z 9.7g as solid content ・ Nucleating agent (compound AA) 5.0 g ・ Dye A Amount of coating at which the optical density of 783 nm becomes 0.3 (0.37 g as a guide) ・ Silver halide emulsion A Ag amount of 0.06 mol

[0098]

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[0099] 2. Preparation of Coating Solution for Lower Emulsion Surface Protective Layer Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt%) polymer latex solution (copolymer glass transition temperature 57 ° C., 21.5% as a solid content concentration of H ₂ O was added to 15 wt% containing) 956G compound D with respect to the solid content of the latex as coalescent, compound E-1 0.81 compound E -0.81 g, 1.62 g of compound S, 1.98 g of matting agent (polystyrene particles, average particle diameter 7 μm) and 23.6 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235), and further H ₂ O was added. Thus, a coating solution was prepared. The viscosity is 20-70 cp (25
° C) and the pH was 5.4.

[0100] 3. Preparation of Coating Solution for Emulsion Surface Upper Layer Protective Layer First, slip agent-dispersed particles were prepared by the following method. Compound LB-7 (60 g) and compound WA-2 (40 g)
The mixture was added to a 1 liter stainless disperser, heated to 100 ° C. and mixed to obtain a uniform and viscous mixture. 800 g of hot water at 95 ° C. was added to the molten mixture, and the mixture was dispersed at a high speed with a homogenizer (10,000 rotations, 10 minutes). While the stirring was continued, the disperser was cooled to gradually lower the internal temperature. When the average particle diameter of the thus obtained dispersed particles of the slip agent was evaluated by an optical diffraction method, it was 0.09 μm, which was an excellent dispersion. Then, methyl methacrylate / styrene / 2-
Ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (wt.
630 g of a polymer latex solution (containing a copolymer having a glass transition temperature of 54 ° C., a solid content of 21.5%, and a compound D as a film-forming aid in an amount of 15 wt% based on the solid content of the latex).
Of H ₂ O was added to the amount of addition of slip agent dispersed particles 10 wt% solution prepared above equivalent weight, the compound E-1, 0.36 g, Compound E-2 0.36 g Compound F 7.95 g Compound S 0,
72 g, matting agent (polystyrene particles, average particle size 7 μm)
1.18 g and polyvinyl alcohol (Kuraray Co., Ltd., PVA
-235) 8.30 g was added, and further H ₂ O was added to prepare a coating solution. Viscosity is 20-70 cp (25 ° C), pH
Was 2.9.

[0101]

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[0102] 4. PET support with backing / priming layer
Preparation of (4-1) Support PET of IV (intrinsic viscosity) = 0.66 (measured at 25 ° C. in phenol / tetrachloroethane = 6/4 (weight ratio)) using terephthalic acid and ethylene glycol according to a conventional method. I got After pelletizing this, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and quenched,
An unstretched film having a thickness of 120 μm after heat setting was prepared. Using rolls with different peripheral speeds,
The film was longitudinally stretched 3.3 times and then stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the lateral direction at the same temperature. Then, after slitting the chuck part of the tenter, knurling is performed on both ends, and 4.8 kg / cm ²
Rolled up. In this way, width 2.4m, length 3500m,
A roll having a thickness of 120 μm was obtained.

(4-2) Undercoat layer (a) Polymer latex (1) (core-shell type latex having a core of 90% by weight and a shell of 10% by weight, core: vinylidene chloride / methyl acrylate / methyl methacrylate) / Acrylonitrile / acrylic acid = 93/3/3 / 0.9 / 0.1 (wt%), shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (wt%) ) consisting essentially of the weight average polymer latex having a molecular weight 38000) solid content as 3.0g / m ² · 2,4- dichloro-6-hydroxy -s- triazine 23 mg / m ² · matting agent (polystyrene, mean particle size 2.4 [mu] m) 1.5 mg / m ²

(4-3) Undercoat layer (b) Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly strength 230 g 50 mg / m ²

(4-4) Conductive layer ・ Julima ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ²・ Alkali-treated gelatin (molecular weight about 10,000, Ca ²⁺ content 30 ppm) 42 mg / m ²・ Deionized Processed gelatin (Ca ²⁺ content 0.6 ppm) 8 mg / m ² · Compound-A 0.2 mg / m ² · Polyoxyethylene phenyl ether 10 mg / m ² · Sumitex Resin M-3 (Water-soluble melamine compound, Sumitomo Chemical ( Co., Ltd.) 18 mg / m ² · Dye A Coating amount at which the optical density of 783 nm becomes 1.2 · SnO2 / Sb (9/1 weight ratio, acicular fine particles, major axis / minor axis = 20-30, Ishihara Sangyo Co., Ltd.) )) 160mg / m ² · Matting agent (polymethyl methacrylate, average particle size 5μm) 7mg / m ²

(4-5) Back protective layer Polymer latex- (2) (Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (% by weight) Copolymer of the following)) Solid content: 1000 mg / m ² · polystyrene sulfonate (molecular weight: 1,000 to 5,000) 2.6 mg / m ² · sodium cetyl sulfate 10 mg / m ² · cellosol 524 (Carnauba wax, Chukyo Yushi Co., Ltd.) ) 15 mg / m ² · Sumitex Resin M-3 (water-soluble melamine compound, manufactured by Sumitomo Chemical Co., Ltd.) 218 mg / m ²

(4-6) PE with back / undercoat layer
Preparation of T support An undercoat layer (a) and an undercoat layer (b) were sequentially applied to both sides of the support (base), and each was dried at 180 ° C for 4 minutes. Next, the undercoat layer (a) and the undercoat layer (b) were applied, and a conductive layer and a protective layer were sequentially applied to one surface on one side.
After drying for minutes, a PET support with a back / subbing layer was prepared. The dry thickness of the undercoat layer (a) was 2.0 μm.

[0108] 5. Transport Heat Treatment (5-1) Heat Treatment The prepared PET support with the back / undercoat layer was placed in a heat treatment zone having a total length of 200 m set at 160 ° C., and was transported at a tension of 3 kg / cm ² and a transport speed of 20 m / min. (5-2) Post-heat treatment After the heat treatment, post-heat treatment was performed by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time is 10
kg / cm ² .

[0109]

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[0110] 6. Preparation of photothermographic material The above-mentioned undercoat layer (a) and the undercoat layer on the side of the PET support coated with the undercoat layer (b) were coated with the emulsion layer coating solution described above in an amount of 1.7 g of silver.
/ m ² . Further, the emulsion layer lower layer protective layer coating solution was coated simultaneously with the emulsion coating solution so that the solid content of the polymer latex was 1.31 g / m ² . Thereafter, the above-mentioned coating solution for the upper protective layer on the emulsion surface was applied thereon so that the applied amount of the solid content of the polymer latex was 3.02 g / m ² , thereby producing a photothermographic material. The film surface pH on the image forming side of the obtained photothermographic material was 4.9 and the Beck smoothness was 660 seconds. The film surface pH on the opposite side was 5.9 and the Beck smoothness was 560.

[0111] 7. Thermal development (7-1) Exposure treatment The resulting photothermographic material was irradiated with a beam having a beam diameter (1/1 of beam intensity).
2 FWHM) 12.56μm, laser output 50mW, output wavelength
Using a laser exposure apparatus of single channel cylindrical inner surface type provided with a semiconductor laser of 783 nm, the exposure time by changing the rotational speed of the mirror, adjusting dose by changing the output value, 2 × 10 ^-8 Exposure in seconds. The overlap coefficient at this time was set to 0.449. (7-2) Thermal development processing The exposed photothermographic material is exposed using the thermal developing machine shown in FIG.
The roller surface material of the heat development processing part is silicon rubber, the smooth surface is Teflon nonwoven fabric, preheating part 90 ~ 100 ℃ 5 seconds,
Thermal development processing was performed at 120 ° C. for 20 seconds. The temperature accuracy in the width direction was ± 1 ° C.

[0112] 8. Evaluation (8-1) Evaluation of unevenness in thermal development Using the thermal developing machine shown in FIG.
Was subjected to a heat development process, and the sample was visually observed for wrinkles during processing. Note that the drum type heat developing machine of FIG. 1 optimizes the light distribution of the lamp, and has a temperature accuracy of ± 1 in the width direction.
C. was performed. Further, the ambient temperature was adjusted so that the temperature of the heat-developable image recording material in the vicinity of the correction guide plate 7 did not become 90 ° C. or less. The evaluation was classified as follows. A: No unevenness in thermal development is observed. B: Heat development unevenness is slightly observed. C: Thermal development unevenness is considerably recognized.

(8-2) Scratches A sample (size: 60 cm × 75 cm) was developed using the heat developing machine shown in FIG. 1 under a developing condition of a developing temperature of 120 ° C. and a developing time of 30 seconds.
Was subjected to a heat development treatment, and the level of occurrence of scratches on the image surface side after the treatment was visually observed. In the drum type heat developing machine of FIG. 1, the light distribution of the lamp was optimized, and the temperature accuracy in the width direction was set at ± 1 ° C. Further, the ambient temperature was adjusted so that the temperature of the heat-developable image recording material in the vicinity of the correction guide plate 7 did not become 90 ° C. or less. The evaluation was classified as follows. A: Almost no damage is observed after thermal development, and there is no actual harm on the print. B: Slight damage after thermal development is observed, and it appears on the print. C: Damage after thermal development is considerably recognized, and irreparable harm occurs on the print.

(8-3) Trace of adhesion The obtained raw sample was conditioned at 25 ° C and 70% RH for 2 hours, the back surface and the emulsion surface were overlapped, and a load of 100 g /
The mixture was allowed to stand for 3 days at cm ² , and the degree of adhesion of the emulsion surface was visually observed. A: No adhesion trace is observed. B: Some adhesion marks are observed. C: Significant adhesion marks are observed.

(8-4) Surface condition The surface condition of the image surface of the obtained raw sample 50 m ² was visually observed. The following evaluation was carried out based on the occurrence level and frequency of cissing and butterbur. A: No cissing or bumps are observed. B: Repelling and butting are slightly recognized. C: Repelling and bumps are considerably recognized.

(8-5) Surface condition after aging of the solution The coating solution for the protective layer on the image side was rotated at 25 ° C. at a rotation speed of 100 rpm.
While stirring for 48 hours. Using this liquid,
Coating was performed on the emulsion layer and the protective layer below the emulsion surface prepared in advance. The surface state of the image surface of the obtained raw sample 50 m ² was visually observed. The following evaluation was carried out based on the occurrence level and frequency of cissing and butterbur. A: No cissing or bumps are observed. B: Repelling and butting are slightly recognized. C: Repelling and bumps are considerably recognized.

(8-6) Evaluation with Dust The obtained sample was heat-treated at 120 ° C. for 25 seconds in the entire exposed state to obtain a blackened sample. This sample was placed at 25 ° C, 10
The humidity was adjusted for 2 hours under the condition of% RH, and the back surface and the emulsion surface were overlapped and rubbed 10 times under a load of 1 kg / cm ² . Pulverized polystyrene pieces were scattered on the emulsion surface, and the degree of adhesion was visually observed. A: No adhesion of polystyrene pieces was observed. B: Some adhesion of polystyrene pieces was observed. C: Adhesion of polystyrene pieces is considerably recognized.

(8-7) Conductivity The obtained raw sample was conditioned at 25 ° C. and 10% RH for 2 hours, silver paint was applied to the side surface, and the electrical resistance (Ω) of the sample was measured. did. (8-8) Measuring method of dimensional change rate due to heat development processing Two holes having a diameter of 8 mm were made at intervals of 200 mm in a sample (size 5 cm × 25 cm) which had been exposed to light over the entire surface, and 1
The distance between the two holes was accurately measured using a pin gauge with a precision of / 1000 mm. The dimension at this time is defined as X (unit: mm). Then, using the heat developing machine shown in FIG.
After the heat development processing under the developing condition of second, the dimensions 120 minutes later were measured with a pin gauge. The dimension at this time is Y (unit: m
m). The dimensional change rate (%) = [(Y−X) / 200] × 100. This is an evaluation value in the horizontal direction of the base.

(8-9) Evaluation Results The characteristics of the obtained samples 01 to 16 were evaluated. As is clear from Table 1, Samples 04 to 14 of the present invention had a small dynamic friction coefficient, and satisfied all of the unevenness in thermal development, damage, adhesion marks and surface condition. The rate of dimensional change due to heat development was small, the rate of dimensional change over time at 75% RH was small, and an excellent heat-developable image material free of dust. Further, the conductivity was excellent at a resistance of the order of 10 8 (Ω). The dimensional stability was also excellent. On the other hand, Comparative Material 01 containing no slip agent used in the present invention had an extremely large kinetic friction coefficient and good surface condition, but was significantly inferior in heat development unevenness, scratches and adhesion marks. Further, Comparative Sample 02 consisting of only the compound of the general formula (1) has a large particle size of the lubricant-dispersed particles, and the photosensitive material in the case where the coating solution does not age has good heat development unevenness, scratches, adhesion marks, and surface condition. However, when the coating solution for the upper protective layer on the emulsion surface was aged, the surface condition was significantly deteriorated. Furthermore, Comparative Sample 03 comprising only the compound of the general formula (2) had good surface conditions, but had poor heat development unevenness, scratches, and poor adhesion marks, which was a problem in practical use. In addition, Comparative Samples 14 and 1 prepared using a comparative slip agent other than the present invention.
Sample No. 5 had a large particle size and a slight decrease in the coefficient of dynamic friction was observed, but it was not possible to satisfy all of the unevenness in heat development, damage, adhesion traces, and surface conditions. Further, the photothermographic material of the present invention had no photographic defects and was excellent as an image. From the above, the heat-developable image recording material of the present invention,
It is clear that the recording material is superior to the recording material for comparison.

[0120]

[Table 1]

<Example 2> Sample 06 of the present invention of Example 1
Sample 26 was prepared in the same manner as in Example 1 except that the dispersion time for dispersing the slip agent-dispersed particles added to the outermost layer on the image layer side was shortened (standard 10 minutes was completed in 3 minutes).
I got These samples were evaluated in exactly the same manner as in Example 1. As a result, the particle size was increased to 0.36 μm, and the dynamic friction coefficient was also 0.26. In the property evaluation, there was no actual harm, but the surface state was between A and B ranks, and the influence of the particle size of the slip agent-dispersed particles was slightly observed. From this result, it is understood that the smaller the particle size of the slip agent-dispersed particles is, the better.

<Example 3> Sample 06 of the present invention of Example 1
A sample 36 was obtained in exactly the same manner as in Example 1 except that the fluorine-based surfactant added to the outermost layer on the side of the image forming layer was removed. These samples were evaluated in exactly the same manner as in Example 1. As a result, there is no actual harm, but when applying the extrusion coater, the application speed is set to 150 m.
The first application was slightly unstable when increased to / min. On the other hand, Sample 0, which is a preferred embodiment of the present invention,
The coating liquid of No. 6 formed a stable ghee bead even at a high speed coating, and the coating was stable. From these results, it can be seen that the addition of the fluorine-based surfactant is excellent in exhibiting the effects of the present invention.

Example 4 Sample 06 of the present invention of Example 1
Example 1 was the same as Example 1 except that the acicular conductive antimony-containing tin oxide fine powder of the conductive layer on the back side of the image layer was removed.
A sample 36 was obtained in exactly the same manner as described above. While the conductivity of the sample 06 is 10 ^8.2, the conductivity of the sample 46 10 ¹⁵
Ω, and the conductivity was deactivated. For these samples,
Evaluation was performed in exactly the same manner as in Example 1. As a result, it was found that there was no actual harm, but when observed in detail by reflection, unevenness with a weak surface was generated. On the other hand, the coating liquid of Sample 06, which is a preferred embodiment of the present invention, did not show any of these unevenness and could obtain an excellent image. From these results, it can be seen that providing the conductive layer is excellent in exhibiting the effects of the present invention.

<Example 5> Sample 06 of the present invention of Example 1
SBR with vinylidene chloride material for undercoat layer of support
Sample 56 was obtained in exactly the same manner as in Example 1 except that the compound was changed. These samples were evaluated exactly as in Example 1. As a result, a comparative sample 55 undercoated with SBR latex instead of the vinylidene chloride undercoat layer was obtained.
Although the dimensional change caused by thermal development and the dimensional change caused by aging at 75% RH were slightly deteriorated, there was no practical problem. From the above, it was found that a particularly excellent heat-developable recording material was obtained when a vinylidene chloride undercoat layer was provided.

[0125]

According to the present invention, it has become possible to provide a heat-developable image recording material in which unevenness, scratches, adhesion marks and surface condition during heat development have been greatly improved. Further, according to the present invention, it has become possible to produce an excellent heat-developable image recording material with little dimensional change over time after heat development and no dust.

[Brief description of the drawings]

FIG. 1 is a side view illustrating a configuration example of a heat developing machine.

[Explanation of symbols]

 DESCRIPTION OF REFERENCE NUMERALS 10 photothermographic material 11 carry-in roller pair 12 carry-out roller pair 13 roller 14 smooth surface 15 heating heater 16 guide plate A preheating section B heat development processing section C slow cooling section

Claims (10)

[Claims] 1. A heat-developable image recording material having an image-forming layer and an outermost layer on at least one of the supports and subjected to a heat-development process at a developing temperature of 80 ° C. or more and 140 ° C. or less. A heat-developable image-recording material comprising a slip agent-dispersed particle comprising at least one slip agent represented by (1) and at least one dispersant represented by formula (2). Formula (1) (R ¹ COO) _p L (COOR ² ) _q (wherein R ¹ and R ² are a substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl group having 1 to 60 carbon atoms) And when p or q is 2 or more, a plurality of R ¹ and R ² may be the same or different from each other; L is a p + q-valent carbon atom which may contain an oxygen atom or a sulfur atom. A hydrogen group, and p and q each represent an integer of 0 to 6 and 1 ≦ p + q ≦ 6. General Formula (2) (R ³ ) _a -G- (D) _d (where R ³ is carbon A substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group having 10 to 60; G represents a divalent to hexavalent linking group;
(B) is _n -E, B is _{-CH 2 CH 2 O -, -} CH 2 CH 2 CH 2 O -, - CH
(CH ₃ ) CH ₂ O— or —CH ₂ CH (OH) CH ₂ O—, where n is 1 to 5
It is an integer of 0. Here, E represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, an alkylcarbonyl group or an arylcarbonyl group;
a and d each represent an integer of 1 to 6; a plurality of R ³ , D and E may be the same or different. ) 2. The method of claim 1, wherein the dispersion of the slipping agent comprises 25 to 99% by weight of at least one slipping agent represented by the formula (1).
The heat-developable image recording material according to claim 1, wherein the heat-developable image recording material is prepared from at least one dispersant represented by the general formula (2) in an amount of from 75 to 75% by weight. 3. The slip agent-dispersed particles have an average particle size of 0.00.
The heat-developable image-recording material according to claim 1, wherein the heat-developable image-recording material is added to a coating solution as a dispersion having a size of 5 μm or more and 0.5 μm or less. 4. The melting point of the slip agent-dispersed particles is 50 ° C. or more and 20 ° C.
The heat-developable image recording material according to claim 1, wherein the temperature is 0 ° C. or lower. 5. A slip agent-dispersed particle obtained by melt-mixing at least one kind of a slip agent represented by the general formula (1) and at least one kind of a dispersant represented by the general formula (2) at a temperature not lower than its melting point. 5. The heat-developable image recording material according to claim 1, wherein the heat-developable image recording material is prepared by dispersing in a dispersing step. 6. The heat-developable image recording material according to claim 1, wherein the outermost layer containing the slip agent-dispersed particles has a dynamic friction coefficient of 0.35 or less and 0.05 or more. 7. The heat-developable image recording material according to claim 1, further comprising a fluorine-containing surfactant in at least one layer. 8. The heat-developable image recording according to claim 1, wherein the support has at least one conductive layer on at least one surface thereof, and has a resistance of 10 ¹² Ω or less. material. 9. A support having at least one image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide on a support, and 70 to 99.9% by weight of vinylidene chloride as an undercoat layer of the support. 0.1 to 5% by weight of monomer repeating unit
10. A polymer containing a repeating unit of a carboxyl group-containing vinyl monomer of claim 1.
The heat-developable image recording material according to any one of the above. 10. The support is a biaxially stretched polyester, which is produced by applying an undercoat layer containing a vinylidene chloride copolymer and then performing a heat treatment at a temperature of 130 ° C. or more and 185 ° C. or less. The heat-developable image recording material according to any one of claims 1 to 9, wherein