JP2002196452A - Photothermal photographic image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photo-thermal photographic image forming material having high antistatic performance and good photographic performance, such as reduced fog, high sensitivity, improved in stability, photo-resistance and silver tone. SOLUTION: The photo-thermal photographic image forming material comprises a photosensitive layer containing photosensitive silver halide particles, an organic silver salt, a reducing agent and a binder on a substrate, a protecting layer on the photosensitive layer and a backing layer on the opposite side of the substrate to the photosensitive layer. This material is specified by including a polythiophene, a polypyrrole or a polyfuran in the layer or forming another layer including any of them.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic image forming material which forms an image by thermal development after exposure, which is provided with an antistatic treatment having a high visible light transmittance, and has a fog, sensitivity, storage property, light resistance and The present invention relates to a photothermographic image forming material which forms an image having an improved silver tone.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand in the medical field for photographic materials which form an image by light or heat treatment which does not generate waste liquid due to wet processing from the viewpoint of environmental protection and workability. Techniques relating to photothermographic image forming materials for photographic technology, which can form a high-resolution and clear black image by development using the same, have been commercialized and rapidly spread.
Since these photothermographic materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic image forming materials, as distinguished from conventional wet photosensitive materials which are liquid-developed in the range of 25 ° C. to 45 ° C.

Conventionally, this type of photothermographic image forming material has a problem in that it tends to be charged with static electricity due to friction or peeling, and all of them tend to form static marks and dust which cause image defects. One solution to this problem is to coat inorganic fine particles such as conductive tin oxide and indium oxide between the support and the photosensitive layer. However, in this method, in order to obtain conductivity, it is necessary to contain the fine particles up to a density at which the fine particles come into contact with each other. Conventionally, these problems have been solved by using a tough binder or a crosslinkable hardener to enhance the film strength, but it has been difficult to obtain satisfactory performance.

In particular, since a photothermographic image forming material contains a reducing agent and an organic silver salt as essential components in addition to photosensitive silver halide, it does not use inorganic fine particles such as conductive tin oxide and indium oxide. There are problems to be improved, such as fogging, difficulty in obtaining high sensitivity, and deterioration of storage stability, light resistance, and silver color tone. Selection of the agent was difficult.

For example, for fog, Japanese Patent Application Laid-Open No.
000643, JP-A-5-341432, JP-A-11-295846 and JP-A-2000-2066642 disclose examples of using disulfide compounds, but they are not sufficient, and sensitivity is not sufficient. The
There is a technique using a hydrazide compound, but the fog tends to be high, which is not satisfactory. As for the silver tone, a derivative of a phthalazine compound or a phthalic acid compound has been developed, but no good one has been found because storage stability is likely to deteriorate.

On the other hand, the use of organic conductive polymers has also been studied. However, there is no suitable solvent for dissolving the polymer, and it is difficult to apply them. There were drawbacks such as easy coloring, and practical application was difficult. As a technique for solving this problem, European Patent 440,
957A3 and 1,031,875A1 disclose the use of a water-dispersible polythiophene compound as a water-soluble dopant. However, when a small amount of a weak doping agent or a doping agent is used, the antistatic effect is weak, and when a large amount of a strong doping agent or a doping agent is used, the antistatic effect is enhanced.However, in a photothermographic image forming material, fog, sensitivity, Photographic performance such as storability, light fastness, and color tone was impaired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve photographic performance, that is, fog is reduced, high sensitivity, storability, light fastness and silver tone are improved, while having high antistatic performance. It is to obtain a photothermographic image forming material.

[0008]

The above object of the present invention is attained by the following constitutions (1) to (8).

1. Photosensitive silver halide grains on a support,
In a photothermographic image-forming material having a photosensitive layer containing an organic silver salt, a reducing agent and a binder and a protective layer on the photosensitive layer, and having a backing layer on the side of the support opposite to the side having the photosensitive layer, polythiophene A photothermographic image forming material characterized in that the layer contains a compound, a polypyrrole compound or a polyfuran compound, or a layer containing a polythiophene compound, a polypyrrole compound or a polyfuran compound is provided separately from the layer.

[0010] 2. 2. The photothermographic image forming material according to the item 1, wherein a polythiophene compound, a polypyrrole compound or a polyfuran compound is represented by the general formula (1).

3. 3. The photothermographic image forming material according to the above 1 or 2, wherein the layer containing a polythiophene compound, a polypyrrole compound or a polyfuran compound contains a fluorine-containing surfactant compound, a perchlorate or a tetrafluoroborate. .

4. 4. The photothermographic image-forming material according to the above item 1, 2 or 3, which contains a thiuronium compound.

5. Item 4. The photothermographic image-forming material according to item 1, 2 or 3, further comprising a hydrazine compound.

6. 6. The photothermographic image-forming material as described in 1, 2, or 3 above, which contains a polyhalomethane compound. 4. The photothermographic image-forming material as described in 1, 2, or 3 above, comprising a disulfide compound.

[8] 4. The photothermographic image-forming material as described in 1, 2, or 3, which contains a phthalazine compound.

9. 4. The photothermographic image-forming material according to the above item 1, 2 or 3, comprising a phthalic acid compound.

Hereinafter, the present invention will be described in detail. The present invention relates to a method for improving the antistatic performance (antistatic effect) of a photothermographic image forming material. In order to enhance the antistatic performance, a conductive polymer compound comprising at least one layer of polythiophene, polypyrrole and polyfuran compound is used. The present invention relates to a photothermographic image forming material having a layer containing the same.

The photothermographic image forming material contains a reducing agent and an organic silver salt as essential components in addition to the photosensitive silver halide,
Since the image formation reaction is based on the principle of dissolution physical development by heating, in the case of using inorganic fine particles such as conductive tin oxide and indium oxide, these act as physical development nuclei, so that silver halide is used. This is considered to cause fog, decrease in sensitivity, deterioration of color tone, and the like. In the present invention, in order to enhance the antistatic performance (antistatic effect) of the photothermographic image forming material, a conductive polymer compound composed of a polythiophene, a polypyrrole, and a polyfuran compound is used in place of the inorganic fine particles. Is improved.

The polythiophene, the polypyrrole of the present invention,
The layer containing the conductive polymer compound comprising a polyfuran compound may be any layer, but usually, the photothermographic image forming material is provided with at least a photosensitive layer and a protective layer on one surface of a support, and The structure is such that a BC layer or a protective layer of a BC layer is provided on the side of the body opposite to the side having the photosensitive layer. The photosensitive layer contains photosensitive silver halide grains which may be sensitized, an organic silver salt serving as a silver source, and a reducing agent for developing a silver salt to form a silver image. Conductive polymer compounds such as polythiophene compounds, polypyrrole compounds or polyfuran compounds used in the present invention are:
It may be added to any of the above layers, and when added to these layers, it is particularly preferable to add it to the protective layer. In addition, these conductive polymer compounds may be added to an intermediate layer adjacent to the photosensitive layer, an undercoat layer, or the like, separately from these layers, or may be added to a layer via an intermediate layer. I can do it. Further, it can be added to the backing layer, or the antistatic performance of the back surface of the photothermographic image forming material, such as a backing protective layer, can be enhanced.

Preferred conductive high molecular compounds such as polyophene compounds, polypyrrole compounds and polyfuran compounds which can be used in the present invention are represented by the above general formula.

R¹And R^TwoMay be replaced by
Examples of the alkyl group include a methyl group, an ethyl group,
Ropyl, butyl, hexyl, octyl, dodecyl
And the like. Salts of these alkyl groups include salts
Halogen atom such as hydrogen or fluorine, hydroxy group,
Coxy group (methoxy group, ethoxy group, etc.)
Can be. In addition, these R¹And R^TwoGroups represented by
May be linked to ¹, R^TwoIs linked to an ethylene group,
A len group or the like may be formed. X is a sulfur atom, an oxygen atom
And a nitrogen atom, preferably a sulfur atom.

X is a sulfur atom (-S-), a nitrogen atom (-N
(R ³ ) —) or an oxygen atom (—O—), and R ³ represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is preferable. n represents an integer of 4 to 100. However, if it is 100 or more, solubility becomes difficult, and coloring becomes large, so 100 or less is preferable.
Particularly, the range of 4 to 50 is preferable.

These conductive high molecular compounds can be produced by a known method of oxidatively polymerizing a monomer in various solvents in the presence of various oxidizing agents. May be added during the production of an inorganic or organic anionic compound. The organic or inorganic anion has a function of increasing the conductivity of these conductive polymer compounds, including those introduced from the oxidizing agent used during the oxidative polymerization, such as a lithiophene compound, as a doping agent.

When a polythiophene compound or the like is produced in an aqueous medium, for example, sodium polystyrene sulfonate or the like is usually used as an emulsifier, and it seems that these anionic compounds also act as doping agents. is there.

In addition, it is possible to add an activator or the like used as a coating aid after the production without adding an ion as a doping agent at the time of producing these conductive polymer compounds. Can be For example, it is known that a sulfonic acid-based anionic surfactant used as an emulsifier is effective as a doping agent and contributes to the stability of a polythiophene compound.

The conductive polymer compound such as a polyophene compound, polypyrrole compound or polyfuran compound of the present invention is preferably used in a photothermographic image-forming material together with various organic or inorganic anionic compounds as a doping agent. The antistatic performance is enhanced, and excellent photographic characteristics such as low fog are imparted to the photothermographic image forming material.However, these dopants have a weak antistatic effect, but the doping agent enhances the antistatic effect, The photographic performance such as fog, sensitivity, storage stability, light resistance and color tone was at a level requiring further improvement.

In the present invention, among such anionic compounds, a conductive polymer compound such as a polythiophene compound is used by using a fluorine-based surfactant, a perchlorate (perchlorate) or a tetrafluoroborate as a doping agent. It is particularly preferable in view of these points that the photothermographic image-forming material has high antistatic performance and inhibits the effect of each additive relating to the photographic characteristics of the image-forming material. Excellent photographic characteristics without causing an increase in fog, deterioration of color tone and the like.

The addition amount of the polythiophene compound, polypyrrole compound or polyfuran compound is preferably in the range of 1 microgram to 10 grams per unit area of the photothermographic image material, and the thiuronium compound and hydrazine used in the present invention are preferably used. When used in combination with a compound, a polyhalomethane compound, a disulfide compound, a phthalazine compound, and a phthalic acid compound, it is preferable to add 1 × 10 ⁻⁸ g to 1 × 10 ³ g per 1 mol of the compound. Addition methods include water, alcohols (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.), and aromatic organic solvents (eg, toluene,
Dissolved in xylene or the like or dispersed in fine particles. The average particle diameter when the fine particles are dispersed is 1 nm to
A size of 300 nm is preferred. Specific examples of preferred polythiophene compounds, polypyrrole compounds or polyfuran compounds are shown below.

[0029]

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[0030]

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These polythiophene compounds, polypyrrole compounds and polyfuran compounds are described, for example, in European Patent Nos. 440,957 and 1,031,87.
It can be produced by a known production method described in the specification of No. 5, etc., and examples are shown below.

(Synthesis of PT5 monomer)
In a four-necked flask equipped with a stirrer, a thermometer and a blowing tube in an L autoclave, dry toluene 960 was placed under a nitrogen atmosphere.
thiophene-2,5-dicarbaldehyde in 14 ml
0 g (1.0 mol) and 5 g (0.02
Mol), and an oxidation reaction was carried out at 10 ° C. while blowing air. The precipitated thiophene-2,5-dicarboxylic acid was collected by filtration (155 g), dissolved in 870 ml of methanol, 3.4 g of concentrated sulfuric acid was added dropwise, and the mixture was refluxed for 4 hours.
162 g of precipitated thiophene-2,5-dicarboxylic acid dimethyl ester was collected by filtration, added to 820 ml of a tetrahydrofuran solution, and 144 g of bromine was added.
(1.8 mol) and reacted at 52 ° C. for 3 hours, then 1.3 mol of 2,5-dimethylpyridine and 12 g (0.3 mol) of 3 mol / l sodium hydroxide.
In addition, purification was performed by silica gel chromatography with a solvent of hexane: ethyl acetate = 3: 1. The obtained compound was heated and decarbonated at 260 ° C. under a nitrogen atmosphere, and dissolved in 760 ml of ethyl acetate.
And 166 g of glycidyl chloride were added at 43 ° C.
After reacting for 3 hours, sodium methoxide was further added to 62
g, and reacted for 2 hours, and then purified by silica gel chromatography using a solvent of hexane: ethyl acetate = 3: 1. After drying at 110 ° C for 3 hours under a nitrogen atmosphere,
182 g (0.62 mol) of the desired monomer were obtained.

Identification of PT5 monomer The mass spectrum and elemental analysis value of the obtained PT5 monomer compound were determined. MALDI measurement of mass spectrum
The method and the measuring device were TRIFT-II manufactured by PHI USA, the excitation light source was a nitrogen laser, the matrix was 2,5-dihydroxybenzoic acid, and the solvent was methyl ethyl ketone. A peak value of 380 (molecular weight: 380.364) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 4
4.21%, H = 5.30%, O = 42.06%, S =
The measured values were C = 44.00% and H =
5.30, S = 8.40%.

(Synthesis of PT5 and Evaluation of Conductivity) PT5 monomer (3,4-bis (2,3-dimethoxypropyloxy) thiophene) was dissolved in 1 liter of acetonitrile solution.
38 g (0.1 mol) and 2.7 g of potassium persulfate
(0.01 mol), and the temperature was raised to 55 ° C.
Stirred for minutes. The color changed to pale blue with the progress of the reaction. After the reaction, the mixture was allowed to stand, the supernatant was decanted, and the resulting precipitate was collected by filtration and added to methyl ethyl ketone to obtain 3.7 g (0.1 mol) of lithium boron tetrafluoride.
The solution was added to room temperature, and coated on a plasma-treated polyethylene terephthalate using a wire bar coating machine so as to have a wet thickness of 5 μm (dry thickness of 0.6 μm). Relative humidity 20
% For 8 hours, and the resistance value was measured. The value obtained was 1.6 × 10 ⁶ Ω.

(Synthesis of PT8 monomer)
In a four-necked flask equipped with a stirrer, a thermometer and a blowing tube in an L autoclave, dry toluene 960 was placed under a nitrogen atmosphere.
124 g of furan-2,5-dicarbaldehyde in ml
(1.0 mol) and 5 g (0.02 mol) of ferric sulfate were added, and an oxidation reaction was performed at 10 ° C. while blowing air. The precipitated furan-2,5-dicarboxylic acid was collected by filtration (141 g), dissolved in 870 ml of ethanol, 3.4 g of concentrated sulfuric acid was added dropwise, and the mixture was refluxed for 4 hours. 147 g of 2,5-dicarboxylic acid diethyl ester was taken out, added to 820 ml of a tetrahydrofuran solution, and 288 g of bromine (1.8 g) was added.
Mol), and reacted at 52 ° C. for 3 hours.
1.3 mol of -dimethylpyridine and 12 g (0.3 mol) of 3N sodium hydroxide were added, and the mixture was purified by silica gel chromatography with a solvent of toluene: hexane = 3: 1. The obtained compound was heated and decarbonated at 260 ° C. under a nitrogen atmosphere, added to ethanol, 2.9 g (0.03) mol of concentrated sulfuric acid was added, and the mixture was reacted at 52 ° C. for 3 hours. Purification by silica gel chromatography using a solvent of toluene: hexane = 3: 1. After drying at 110 ° C. for 3 hours under a nitrogen atmosphere, 95 g of the desired monomer
(0.63 mol).

Identification of Monomer The mass spectrum and elemental analysis value of the obtained PT8 monomer compound were determined. MALDI measurement of mass spectrum
The method and the measuring device were TRIFT-II manufactured by PHI USA, the excitation light source was a nitrogen laser, the matrix was 2,5-dihydroxybenzoic acid, and the solvent was methyl ethyl ketone. The peak value 151 (molecular weight 151.141) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 6
3.58%, H = 4.67%, O = 31.75%, whereas the measured values were C = 63.55%, H = 4.70%, O
= 31.69%.

(Synthesis of PT8 and Evaluation of Conductivity) 3,1-Diethoxyfuran 15.1 in 1 liter of toluene solution
g (0.1 mol) and 2.7 g of potassium persulfate (0.
(01 mol), and the mixture was heated to a temperature of 56 ° C. and stirred for 56 minutes. The color changed to pale blue with the progress of the reaction. After the reaction, the mixture was allowed to stand, the supernatant was decanted, and the resulting precipitate was collected by filtration and added to methyl ethyl ketone.
3.7 g (0.1 mol) of lithium boron fluoride was added, the temperature was brought to room temperature, and the mixture was applied to a plasma-treated polyethylene terephthalate by a wire bar coater so as to have a wet thickness of 5 μm (dry thickness of 0.6 μm). It was left in a room with a relative humidity of 20% for 8 hours, and the resistance value was measured. The obtained value was 1.3 × 10 ⁶ Ω.

(Synthesis of PT13 monomer) A 4-liter flask equipped with a stirrer, a thermometer and a blowing tube was placed in a 1-liter autoclave purged with nitrogen, and dried toluene 96
Pyrrole-2,5-dicarbaldehyde 138 in 0 ml
g (1.0 mol) and 5 g (0.02 mol) of ferric sulfate were added, and an oxidation reaction was performed at 10 ° C. while blowing air. The precipitated pyrrole-2.5-carboxylic acid was collected by filtration (153 g), dissolved in 870 ml of ethanol, 3.4 g of concentrated sulfuric acid was added dropwise, refluxed for 4 hours, cooled to 5 ° C., and deposited pyrrole-2. 147 g of .5-dicarboxylic acid ethyl ester was taken out, added to 820 ml of a tetrahydrofuran solution, and 288 g of bromine (1.8 g) was added.
Mol) and reacted at 52 ° C. for 3 hours. Then, 12 g (0.3 mol) of sodium hydroxide was added, and the mixture was purified by silica gel chromatography using a 3: 1 toluene / hexane solvent. 260 ° C. under nitrogen atmosphere
The mixture was heated and decarboxylated, added to methanol, 2.9 g (0.03 mol) of concentrated sulfuric acid was added, and the reaction was carried out at 52 ° C. for 3 hours. And purified by silica gel chromatography. After drying at 110 ° C. for 3 hours under a nitrogen atmosphere, 78 g of the desired monomer is obtained.
(0.63 mol).

Identification of Monomer The analysis was performed in the same manner as in the analysis of the PT8 monomer, and the peak value 124 (molecular weight 124.12) of the mass spectrum was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 5
8.06%, H = 4.87%, O = 25.78%, N =
11.28%, measured values C = 58.00%, H = 4.
80%, N = 11.24%.

(Synthesis of PT13 Polymer and Evaluation of Conductivity) 3,4-Dimethoxypyrrole (0.1 mol) and potassium persulfate in 1 liter of acetonitrile solution
7 g (0.01 mol) was added and the temperature was raised to 62 ° C.
Stirred for 48 minutes. The color changed to pale blue with the progress of the reaction. After the reaction, stand still and decant the supernatant,
The resulting precipitate was collected by filtration, added to methyl ethyl ketone, added with 3.7 g (0.1 mol) of lithium boron tetrafluoride, brought to room temperature, and wet on a plasma-treated polyethylene terephthalate using a wire bar coater. 5 μm thick
(Dry thickness 0.5 μm). It was left in a room with a relative humidity of 20% for 8 hours, and the resistance value was measured. The obtained value was 2.4 × 10 ⁶ Ω.

The fluorine-containing surfactant compound preferably used as a doping agent in the present invention is a long-chain or branched alkyl group having 5 to 30 carbon atoms, wherein at least 50% or more of the hydrogen atoms in the group are present. It is an alkali metal salt, alkaline earth metal salt or ammonium salt-based surfactant compound of a sulfonic acid or a carboxylic acid having an alkyl group substituted by a fluorine atom, and examples thereof include the following compounds. (DP1) Perfluorooctane-1-sodium sulfonate (DP2) Lithium perfluorononane-1-sulfonate (DP3) Lithium perfluorohexane-1-benzenesulfonate (DP4) Sodium perfluoropentylbenzenesulfonate (DP5) ) Sodium perfluorooctane-1-carboxylate (DP6) Lithium perfluorononane-1-carboxylate (DP7) Sodium perfluorononylbenzenecarboxylate (DP8) Ammonium perfluorononylbenzenecarboxylate (DP9) Perfluorohexyloxypolyethylene Sodium oxyethanesulfonate (n = 9) Specific examples of perchlorates (perchlorates) and tetrafluoroborate, which are preferable as the doping agent of the present invention, are shown below. (DP10) Lithium perchlorate (DP11) Sodium perchlorate (DL12) Lithium tetrafluoroborate The preferable addition amount of these doping agents is a total of 1 to 10,000 mass% with respect to these conductive polymer compounds. What is necessary is 10-100
0 mass%, more preferably 30 to 300 mass%.

In the present invention, these polythiophene compounds, polypyrrole compounds or polyfuran compounds and the above-mentioned doping agents are incorporated into a photothermographic image forming material.
When used as an antistatic agent (preferably in a protective layer), these effects and an antistatic effect (static electricity) can be effectively achieved without impairing the effects of the following additives used in the photothermographic image forming material. Prevention effect) (that is, the effect of these additives can be effectively exhibited).

As the additives used in the photothermographic image forming material used in combination with the polythiophene compound, polypyrrole compound or polyfuran compound according to the present invention, thiuronium compounds, hydrazine compounds, polyhalomethane compounds, disulfide compounds, phthalazine compounds, phthalic acid compounds These will be described in detail below.

(Tiuronium Compound) The polythiophene compound, polypyrrole compound or polyfuran compound is
When used together with a thiuronium compound which is used in a photothermographic image forming material and has an effect as a supersensitizer or the like, the above effects of the present invention are sufficiently exhibited.

The thiuronium compound used in the present invention is
Those in which an imidazole group, an oxazole group, a thiazole group, a benzoxazole group, a benzothiazole group, a benzimidazole group, or the like is bonded to a sulfur atom of thiourea via an alkylene group (for example, a methylene group, an ethylene group, and a propylene group). preferable. The addition amount is preferably from 1 mg to 10 g, and particularly preferably from 10 mg to 500 mg, per m ^{2 of} the image forming material. Preferred specific examples are shown below, but the present invention is not limited thereto.

[0046]

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(Hydrazine Compound) The polythiophene compound of the present invention can sufficiently exhibit the above-mentioned effects of the present invention when used together with a hydrazine compound used as a nucleating agent or a sensitizer in a photothermographic image forming material.

The hydrazine compound used in the present invention is-
Compounds having an NHNH-CO- bond are preferred. The addition amount is preferably from 1 mg to 10 g, and particularly preferably from 10 mg to 600 mg, per m ^{2 of} the image forming material. The timing of addition may be at the time of chemical sensitization or at any time after chemical sensitization until immediately before coating. Preferred specific examples are shown below, but the present invention is not limited thereto.

[0049]

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(Polyhalomethane Compound) The compound such as polythiophene of the present invention, when used together with a polyhalomethane compound used as an antifoggant or printout inhibitor in a photothermographic image forming material,
The above effects of the present invention are sufficiently exhibited.

The polyhalomethane compound used in the present invention is a compound having a polyhalomethyl group, wherein the polyhalomethyl group is an aromatic group (eg, phenyl, naphthyl, chlorophenyl, etc.) or a heterocyclic group (eg, pyridyl, furyl, Those bonded directly or via a linking group to an imidazolyl group and an oxazolyl group are preferred. Preferred linking groups include -CO- group, -SO
₂ -, - NHSO ₂ -, and the like can be given. Examples of the polyhalomethyl group include a trimethylbromo group, a trichloromethyl group, and a dibromomethyl group. The addition amount is preferably from 1 mg to 10 g, and particularly preferably from 10 mg to 400 mg, per m ^{2 of} the image forming material.

[0052]

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(Disulfide Compound) When the compound such as polythiophene of the present invention is used together with a disulfide compound used as an antifoggant in a photothermographic image forming material, the above-mentioned effects of the present invention are sufficiently exhibited.

The disulfide compound used in the present invention is
An alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an octyl group, etc.), an aromatic group (a phenyl group, a chlorophenyl group, a p-methylphenyl group, a naphthyl group, etc.) or a heterocyclic group (e.g., at both ends of a disulfide group) , A pyridyl group, a furyl group, an imidazolyl group, an oxazolyl group, and a triazole group). The amount of addition is from 1 mg / m ^{2 of} image forming material.
10 g is preferable, and particularly preferably 10 mg to 500 mg.

[0055]

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(Phthalazine) When the compound such as polythiophene of the present invention is used together with a phthalazine compound used as a toning agent in a photothermographic image forming material, the above-mentioned effects of the present invention are sufficiently exhibited.

The phthalazine compound used in the present invention may have substituents at positions 3, 4, 5, 6, 7 and 8 of phthalazine. Preferred substituents include an alkyl group (for example, a methyl group, an ethyl group, a propyl group and an octyl group), an aromatic group (a phenyl group, a chlorophenyl group, a p-
A methylphenyl group and a naphthyl group) or a heterocyclic group (for example, a pyridyl group, a furyl group, an imidazolyl group,
Oxazolyl group and triazole group) are preferred. The addition amount is preferably from 1 mg to 10 g, particularly preferably from 10 mg to 500 mg per m ^{2 of} the image forming material.
Is preferred.

[0058]

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(Phthalic acid compound) When the compound such as polythiophene of the present invention is used together with a phthalic acid compound used as a color tone agent in a photothermographic image forming material, the above-mentioned effects of the present invention are sufficiently exhibited.

The phthalic acid compound used in the present invention preferably has a substituent at the 3, 4 and 5 positions of orthophthalic acid. Preferred substituents include a halogen atom (for example, a fluorine atom and a chlorine atom), an alkyl group (for example,
Methyl group, ethyl group, propyl group, octyl group, etc.), aromatic group (phenyl group, chlorophenyl group, p-
A methylphenyl group and a naphthyl group) or a heterocyclic group (for example, a pyridyl group, a furyl group, an imidazolyl group,
Oxazolyl group and triazole group) are preferred. The addition amount is preferably from 1 mg to 10 g, particularly preferably from 10 mg to 500 mg per m ^{2 of} the image forming material.
Is preferred. Preferred specific examples are shown below.

[0061]

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(Photosensitive Silver Halide Particles) The photosensitive silver halide contained in the photosensitive layer of the photothermographic image forming material of the present invention may be any known one in the field of photographic technology such as a single jet or double jet method. Can be prepared in advance by any method such as an ammonia method emulsion, a neutral method, and an acid method. The photosensitive silver halide preferably has a small grain size in order to suppress white turbidity after image formation and to obtain good image quality. 0.1 μm or less in average particle size, preferably 0.01 to 0.1 μm
m, particularly preferably 0.02 to 0.08 μm. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, or non-normal crystals, such as spherical, rod-shaped, or tabular grains. The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

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

The silver halide of the present invention is also disclosed in US Pat. Nos. 4,009,039, 3,457,075, 4,003,749 and British Patent 1,498,95.
No. 6, each specification and JP-A-53-27027, 53-
No. 25420, inorganic halogen compounds, onium halides, halogenated hydrocarbons, N
-It can be produced by converting a part of the organic silver salt into silver halide using a silver halide forming component such as a halogen compound or another halogen-containing compound. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting into silver halide can be appropriately set according to the purpose of production, but usually the reaction temperature is -23 ° C to 74 ° C, and the reaction time Is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be performed by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, and the like.
No. 22430, No. 51-78319, No. 51-811
No. 24 and the like.

The silver halide used in the present invention can be sensitized with a spectral sensitizing dye if necessary. For example, JP-A-63-159814, JP-A-60-140335, and JP-A-6-140335
Nos. 3-231437, 63-259651 and 63
-304242, 63-15245, etc.,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
Sensitizing dyes described in each specification such as 175 and 4,835,096 can be used. Useful sensitizing dyes for use in the present invention include, for example, Research D
issue Item 17643 IV-A (1
December 978, p. 23) and Item 18431X (August 1978, p. 437). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, compounds described in JP-A-9-34078, JP-A-9-54409 and JP-A-9-80679 are preferably used.

(Organic Silver Salt) The organic silver salt contained in the photothermographic image forming material of the present invention is a reducible silver source, and an organic acid, heteroorganic acid and acid polymer containing a reducible silver ion source. Silver salts of the like are used. Also, the ligand is
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of organic silver salts include Research Disclosure No. 17
029 and 29996, and salts of organic acids (for example, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid and the like) and the like are preferable.
The organic silver salt is prepared by mixing the alkali metal salt of the organic acid and silver nitrate, and may be added by a controlled double jet method at the time of mixing, or may be added at a different timing. The silver salt may be added all at once or in several stages at any stage to form a silver salt.

(Reducing Agent) Examples of preferred reducing agents contained in the photothermographic image-forming material of the present invention are described in US Pat.
70,448, 3,773,512, 3,59
No. 3,863, etc., and Research D
No. 17029 and 29996, including the following: (K1) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (K2) bis (2-hydroxy-3-t-butyl-5)
-Methylphenyl) methane (K3) 2,2-bis (4-hydroxy-3-methylphenyl) propane (K4) 4,4-ethylidene-bis (2-t-butyl-6-methylphenol) (K5) 2 , 2-Bis (3,5-dimethyl-4-hydroxyphenyl) propane The compound shown above is used by dispersing in water or dissolving in an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be arbitrarily selected. The amount of the reducing agent to be used is 1 × 10 ^-2 to 10 mol, preferably 1 × 10 ^-2 to 1 mol per mol of silver.
5 moles.

(Binder) The polymer binder used in the photosensitive layer or the non-photosensitive layer of the photothermographic image forming material of the present invention includes polyvinyl butyral, polyacrylamide, polystyrene, polyvinyl acetate, polyurethane, polyacrylic ester Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-acryl copolymer, and the like. After drying and forming a film,
Those having a low equilibrium water content of the coating film are preferred, and examples of those having a particularly low water content include, for example, organic solvent-based cellulose acetate, cellulose acetate butyrate and polyacetal. Preferred polyacetals for the present invention include polybutyral acetalized with butyraldehyde and polyacetal acetalized with acetaldehyde (polyacetal in a narrow sense). The degree of acetalization theoretically exists from 1% to 100%, but practically preferably from 20% to 95%. If the degree of acetalization is low, the number of hydroxyl groups is increased, and the photographic performance is weak against humidity. If the degree of acetalization is high, the reaction temperature and time are severe, and the cost and productivity are reduced. The degree of polymerization of the polymer can be freely selected from about 10 to about 10,000, but 100 to 6000 is preferable from the viewpoint of applicability and productivity in synthesis.

(Crosslinking agent) The binder alone can maintain the adhesion to the lower layer and the upper layer and obtain a film strength that is hardly damaged by forming a film alone. Film adhesion and film strength can be increased. However, when the crosslinking reaction is slow, the photographic performance is not stable and the storage stability is deteriorated. As a quick-acting and preferred crosslinking agent used in the present invention, a polyfunctional crosslinking agent having at least two isocyanate groups can be exemplified. Preferred crosslinking agents are shown below. (H1) hexamethylene diisocyanate (H2) trimer of hexamethylene diisocyanate (H3) tolylene diisocyanate (H4) phenylene isocyanate (H5) xylylene diisocyanate The crosslinking agent is water, alcohols , Ketones or non-polar organic solvents, or may be added as a solid in the coating solution. The addition amount is preferably equivalent to the group to be crosslinked of the binder, but may be increased up to 10 times,
The weight may be reduced to 1/0 or less. If the amount is too small, the crosslinking reaction does not proceed. If the amount is too large, the unreacted crosslinking agent deteriorates photographic properties, which is not preferable.

(Dye optionally used in AH layer or BC layer) The photothermographic image forming material of the present invention may contain, if necessary, an AH layer or a BC layer for preventing halation or preventing halation of the photothermographic image forming material. Is provided.
The dye used in the AH layer or the BC layer may be any dye that absorbs light used for image exposure. Preferred examples thereof include JP-A-2-216140 and JP-A-7-13295.
No. 7,114,432, US Pat. No. 5,380,38.
And dyes described in JP-A-0,635 and the like.

(Support) The support is preferably a support such as polyethylene terephthalate, polyethylene naphthalate or syndiotactic polystyrene.
A film having a thickness of 50 μm to 400 μm, which is axially stretched and heat-fixed, has high optical isotropy, and has good dimensional stability is preferred.

(Image Exposure) The exposure method is described in
JP-A-304869, JP-A-9-311403 and JP-A-2
000-10230 can be used for laser exposure. In the exposure of the photothermographic image forming material of the present invention, it is desirable to use a light source appropriate for the color sensitivity imparted to the image forming material. For example, when the image forming material is made to be able to feel infrared light,
Although it can be applied to any light source in the infrared light range, an infrared semiconductor laser (780) can be used because the laser power is high and the image forming material can be made transparent.
nm, 820 nm) are more preferably used.

(Thermal Developing Apparatus) An apparatus for developing a photothermographic image forming material is disclosed in JP-A-11-65067 and JP-A-11-7.
The apparatuses described in the specifications of JP-A-2897 and JP-A-84619 can be used.

[0075]

EXAMPLES Examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Subbed Support> A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 12 W / m ² · min on both sides, and the following coating solution a- 1
Is applied to a dry film thickness of 0.6 μm and dried to form an undercoat layer A-1.
-1 was applied to a dry film thickness of 0.6 μm and dried to form an undercoat layer B-1.

<< Undercoating Coating Solution a-1 >> Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Styrene (25% by mass) 2-hydroxyethyl acrylate (25% by mass) copolymer latex liquid (30% solids) is diluted 15-fold.

<< Undercoat Coating Solution b-1 >> A copolymer latex liquid (solid content 30%) of butyl acrylate (40% by weight) styrene (20% by weight) glycidyl acrylate (40% by weight) is diluted 15 times. .

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A 12 W / m ² · min corona discharge is applied to the upper surface of the undercoating layer A-1. The undercoat layer B-1 (for the BC layer) was provided by applying and drying the following undercoat upper layer coating solution b-2 on the undercoat layer B-1.

<< Undercoat upper layer coating solution a-2 >> 1: 2 copolymer of styrene and butadiene 0.4 g / m ² butyl acrylate (30 mass%) t-butyl acrylate (20 mass%) styrene (25 mass% ) 2-Hydroxyethyl acrylate (20% by mass) Methacrylic acid (5% by mass) copolymer latex liquid (solid content 30%) 0.3 g / m ² Cross-linking agent (hexamethylene diisocyanate) 0.1 g / m ² << Undercoat upper layer coating solution b-2 >> 1: 2 copolymer of styrene and butadiene 0.4 g / m ² butyl acrylate (30 mass%) t-butyl acrylate (20 mass%) styrene (25 mass%) 2 - hydroxyethyl acrylate (20 weight%) copolymer latex liquid methacrylic acid (5 weight%) (solid content 30%) 0.3 g / m ² crosslinking agent (hexamethylene Nji isocyanate) 0.1 g / m ² First, the silver halide was prepared prior to the coating, and then to prepare an organic silver salt using a silver halide prepared.

<Preparation of silver halide grain emulsion A>
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 0 ml and adjusting the temperature to 28 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (98 /
370 ml of an aqueous solution containing equimolar amounts of potassium bromide and potassium iodide in the molar ratio of 2) was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Synchronously with the addition of silver nitrate, the sodium salt of hexachloroiridium was added at 1 × 10 ^-6 mol / mol of silver. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added to 0.3 g, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average particle size of 0.036 μm, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87% Silver particles were obtained. The particles are coagulated and settled using a gelatin coagulant and desalted.
l.

<Preparation of water-dispersed organic silver salt> Behenic acid (111.4 g) and arachidic acid (83.8) were added to 3980 ml of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 mol aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the organic acid sodium acid solution at 55 ° C., the silver halide grain emulsion A (containing 0.038 mol of silver) and 420 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of a 1 mol silver nitrate solution was added over 2 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, the filtrate was repeatedly washed with deionized water and filtered until the conductivity of the filtrate reached 2 μS / cm, and finally dried after centrifugal dehydration.

<Coating of Photosensitive Layer and BC Layer> On the surface having the undercoating upper layer B-2 of the undercoated support, the following layers on the back surface side, and then the undercoating upper layer A-2 were formed. An AH layer, a photosensitive layer and a surface protective layer having the following compositions were simultaneously coated on the surface having the composition. The drying was performed at 45 ° C. for 1 minute on both the BC side and the photosensitive layer side.

<< Coating on Back Side >> On the back side, a coating solution having the following composition (indicated by the amount added) was simultaneously applied in multiple layers and dried to form a BC layer.

(Coating of BC Layer) Binder (PVB-1) 1.8 g / m ² Glycidyltrimethoxysilane 1 × 10 ⁻⁴ mol / m ² Dye (C1) 2.2 × 10 ⁻⁵ mol / m ²

[0086]

Embedded image

(Coating of BC protective layer) Binder (cellulose acetate butyrate) 1.1 g / m ² Crosslinker (hexamethylene diisocyanate) 1 × 10 ⁻⁴ mol / m ^{2 <<} Coating on photosensitive layer side >> (AH Layer Coating) Binder (PVB-1) 0.4 g / m ² Dye (C1) 1.3 × 10 ⁻⁵ mol / m ² (Coating of photosensitive layer) Coating solution of the following composition for forming the photosensitive layer Was prepared and applied and dried so that the following amounts were obtained.
However, a preparation of the organic silver salt in an amount of 1.36 g / m ² in terms of silver was mixed with the polymer binder.

Binder (PVB-1) 2.6 g / m ² Crosslinker (hexamethylene diisocyanate) 2 × 10 ⁻³ mol / m ² Spectral sensitizing dye (A1) 2 × 10 ⁻⁵ mol / m ² Antifoggant (pyridinium hydrobromide perbromide) 0.3 mg / m ² Antifoggant (isothiazolone) 1.2 mg / m ² Reducing agent (K1) 3 × 10 ^-4 mol / m ²

[0089]

Embedded image

(Surface Protective Layer) A coating solution prepared by adding the following composition was applied onto the photosensitive layer so as to have the following coating amount and dried to form a surface protective layer.

Binder (cellulose acetate butyrate) 1.2 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Conductive polymer 0.1 g / m ² Doping agent 0.07 g / m ² Conductivity The polymer compound is a polythiophene compound, a polypyrrole compound, a polyfuran compound, or the like. Was added. The doping agents used are shown in Table 1.

Incidentally, PVB-1 used as a binder was polyvinyl butyral, and was used after being dissolved in methyl ethyl ketone (MEK). PVB-1 has a degree of polymerization of 5
After 98% saponification of polyvinyl acetate of 98%, 8
6% is butyralized. PVB-1 is BC
It was also used as a binder in the layer.

Samples 101 to 108 were prepared by changing the conductive high molecular compound and the doping agent as shown in Table 1.

(Evaluation of photographic performance)
After storing for 3 days in an atmosphere of 48% relative humidity at
Exposure was performed with a 10 nm semiconductor laser exposure sensitometer, and after exposure, heating was performed at 120 ° C. for 8 seconds, and the fog and sensitivity of the obtained sample were determined. Fog is the density value of the unexposed area itself,
In addition, the sensitivity was expressed as a relative sensitivity when the conductive polymer compound of the present invention and a comparative sample containing no doping agent were each set to 100. The laser exposure was set in a double mode with an incident angle of 76 degrees.

(Evaluation of storage stability)
After storing for 7 days in an atmosphere of 80% relative humidity,
Exposure was performed using a 0 nm semiconductor laser exposure sensitometer, and after exposure, heating was performed at 120 ° C. for 8 seconds, and fog of the obtained sample was determined. Laser exposure was set to a double mode with an incident angle of 76 degrees.

(Evaluation of antistatic effect) After leaving the unexposed sample in a room at a relative humidity of 20% for 18 hours, the sample was rubbed five times with a synthetic fiber cloth (60% nylon, 40% polyester), The beads were held over 100 beads (average particle diameter: 3 mm) (approach distance: 15 mm) to evaluate the degree of adsorption of the beads. The level without adsorption is 5 ~ 3 ~
4 for 8 adsorptions, 3 for 9 to 15 adsorptions, 2 from 16
The level of adsorption of 5 pieces was set to 2, and the level of adsorption of 25 pieces or more was set to 1.

[0097]

[Table 1]

Table 1 shows that the use of the conductive polymer compound and the doping agent of the present invention provides an antistatic effect, reduces fog, increases sensitivity, and is excellent in storage stability.

Example 2 A sample was prepared in the same manner as in Example 1, except that the
86 m of the conductive polymer compound of the present invention per ²
g, and the conductive polymer compound and the doping agent were changed as shown in Table 2;
Samples 201 to 208 were prepared by adding a coating solution of 6 mg / m ² to prepare a coating solution for the protective layer. The thyuronium compound was added after the conductive polymer compound.
The samples 201 to 208 thus produced were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0100]

[Table 2]

From Table 2, it can be seen that even when a thyuronium compound is added to the conductive polymer compound and the doping agent of the present invention, an antistatic effect is obtained, and low fog, high sensitivity and good storage stability are obtained.

Example 3 A sample was prepared in the same manner as in Example 1, except that the
86 m of the conductive polymer compound of the present invention per ²
g, and a hydrazine compound was added so as to be coated in an amount of 86 mg to prepare a coating solution for the protective layer.
308 was produced. The hydrazine compound was added after the conductive polymer compound. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[0103]

[Table 3]

Table 3 shows that even when a hydrazine compound was added to the conductive polymer compound and the doping agent of the present invention, an antistatic effect was obtained, and low fog, high sensitivity and good storage stability were obtained. .

Example 4 A sample was prepared in the same manner as in Example 1, except that the conductive polymer compound of the present invention was 68 mg / m ² and the polyhalomethane compound was 68 mg / m ^2.
m ² coated well was added to the protective layer as is was prepared EXAMPLE 1 Preparation of protective layer coating solution in the same manner as with sample 401 to 408. The polyhalomethane compound was added next to the conductive polymer compound of the present invention. The photographic performance and the antistatic effect were evaluated in the same manner as in Example 1. In the light resistance test, fog was measured when the sample after development was allowed to stand on a 1000 lux shark casten for 10 hours. Table 4 shows the results.

[0106]

[Table 4]

From Table 4, it can be seen that an excellent antistatic effect can be obtained even when a polythiophene compound and a polyhalomethane compound are added and used in combination, and low fog, high sensitivity and good light fastness are obtained.

Example 5 A sample was prepared in the same manner as in Example 1, except that the
^In addition to 78 mg of the conductive polymer compound of the present invention per ² , 78 mg of each disulfide compound was added to prepare a coating solution for the protective layer, and samples 501 to 508 were produced. The disulfide compound was added after the conductive polymer compound of the present invention. The same evaluation as in Example 1 was performed.
Table 5 shows the results.

[0109]

[Table 5]

Table 5 shows that even when a disulfide compound is added or used in addition to the conductive polymer compound and the doping agent of the present invention, an excellent antistatic effect can be obtained, and low fog, high sensitivity and storage stability can be obtained. Is also good.

Example 6 A sample was prepared in the same manner as in Example 1, except that the
56 m of the conductive polymer compound of the present invention per ²
g, and phthalazine was further added to 56 mg /
The coating solution was added so as to obtain m ^2, and a coating solution for the protective layer was prepared to prepare samples 601 to 608. Phthalazine was added next to the conductive polymer compound of the present invention. The photographic performance and antistatic effect were evaluated in the same manner as in Example 1, and other colors were evaluated. For the evaluation of the color tone, the sample after the heat development was placed on a Schaukasten, and the silver color tone was visually evaluated. The black silver image was evaluated as rank 5, the slightly brown silver image was evaluated as rank 4, the slightly brown silver image was evaluated as rank 3, and the strong brown silver image was evaluated as 1. Table 6 shows the results.

[0112]

[Table 6]

From Table 6, it can be seen that, even when a phthalazine compound is added or used in addition to the conductive polymer compound and the doping agent of the present invention, the antistatic effect is excellent, and low fog, high sensitivity and good color tone are obtained. .

Example 7 A sample was prepared in the same manner as in Example 6, except that the
73 mg of the conductive polymer compound of the present invention per ² ,
Further, 73 mg of phthalic acid was added instead of phthalazine to prepare a coating solution for the protective layer, and samples 701 to 708 were produced. Phthalic acid was added next to the conductive polymer compound of the present invention. The same evaluation as in Example 6 was performed, and the results are shown in Table 7.

[0115]

[Table 7]

From Table 7, it can be seen that excellent antistatic effect can be obtained by adding and using phthalic acid in addition to the conductive polymer compound and the doping agent of the present invention, and also low fog, high sensitivity and good color tone. You can see that.

[0117]

According to the present invention, a photothermographic image-forming material which is provided with an antistatic treatment having a high visible light transmittance and which forms an image with improved fog, sensitivity, storability, light fastness and silver tone can be obtained.

Claims (9)

[Claims] 1. A photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, a protective layer on the photosensitive layer, and a side of the support having the photosensitive layer. In the photothermographic image forming material having a backing layer on the opposite side, the layer contains a polythiophene compound, a polypyrrole compound or a polyfuran compound, or separately from the layer, a layer containing a polythiophene compound, a polypyrrole compound or a polyfuran compound. A photothermographic image-forming material characterized by being produced. 2. The photothermographic image forming material according to claim 1, wherein the polythiophene compound, polypyrrole compound or polyfuran compound is represented by the following general formula (1). Embedded image (Wherein, R ¹ and R ² represent an alkyl group having 1 to 12 carbon atoms which may be substituted, and X represents a sulfur atom (—S—), a nitrogen atom (—N (R ³ ) —), or oxygen Represents an atom (—O—), R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 4 to 100.) 3. The method according to claim 1, wherein the layer containing the polythiophene compound, the polypyrrole compound or the polyfuran compound contains a fluorine-containing surfactant compound, a perchlorate or a tetrafluoroborate. Photothermographic image forming material. 4. The photothermographic image forming material according to claim 1, wherein the material contains a thyuronium compound. 5. The photothermographic image forming material according to claim 1, which comprises a hydrazine compound. 6. The photothermographic image-forming material according to claim 1, wherein the material contains a polyhalomethane compound. 7. The photothermographic image forming material according to claim 1, wherein the material contains a disulfide compound. 8. The photothermographic image forming material according to claim 1, which contains a phthalazine compound. 9. The photothermographic image forming material according to claim 1, which contains a phthalic acid compound.