JP2000206641A - Heat-developable photosensitive material and image recording and forming method by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress heat developing fog and fog due to storage and improve the deterioration of image density by including a specific compound and including one kind of compound selected from the other specific compound, an aziridine compound, an epoxy compound and a carboxyimide compound. SOLUTION: The heat-developable photosensitive material contains at least one kind of compound selected from formula I and the like and at least one of compounds selected from ones represented by formula II and the like, and aziridine compounds, epoxy compounds, and carboxyimide compounds. In formula I, each of Hal1 and Hal2 is a halogen atom; X1 is an anion; R1 is a group having a carbonyl group as a partial structure; each of R2 and R3 is an H atom or a group substitutible on an N atom; and (n) is 1 or 2, and in formula II, each of R1-R3 is, independently, an alkyl or aralkyl group or the like; and X- is a counter ion and when a sulfonyl group is present in the molecule, X- is absent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic material, an image recording method using the same, and an image forming method.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical care,
The waste liquid caused by the wet processing of the image forming material has become a problem in terms of workability, and in recent years, it has been strongly desired to reduce the amount of the treated waste liquid from the viewpoint of environmental conservation and space saving. Therefore, in recent years, a technique relating to a photothermographic material capable of efficiently exposing by a laser image setter or a laser imager and forming a high-resolution and clear black image has been particularly required in recent years.

As techniques for this purpose, silver halide photosensitive materials which form a photographic image by heat treatment are known, for example, US Pat. Nos. 3,152,904, 3,457,075 and D. . Morgan
n) and B. "Thermal Proc Silver System" by Shelly
essed Silver Systems), Imaging Processes and Materials (I
Managing Processes and Mate
reals) Neblette 8th edition, Sturge (S
purge), V.T. Walworth
h), A. Shepp Editing, Page 2, 19
It was disclosed in 1969.

[0004] Such a photothermographic material comprises a reducible silver source (eg, a non-photosensitive organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a reducing agent, usually in an organic binder matrix. It is contained in a dispersed state. The photothermographic material is stable at room temperature, but when heated to a high temperature after exposure, metallic silver is generated by a redox reaction between a reducible silver source (acting as an oxidizing agent) and a reducing agent.

[0005] This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and results in the formation of an image. An antifoggant is used to control the fogging of the image, and the most effective method as a conventional antifogging technique is a method using a mercury compound as the antifoggant.

The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 89,903. However, the use of mercury compounds is environmentally unfavorable, and the development of non-mercury antifoggants has been desired. As the non-mercury antifoggant, various polyhalogen compounds have hitherto been used, for example, US Pat. Nos. 3,874,946 and 4,874,946.
756,999, 5,340,712, EP 605,981A1, 622,666A1
No. 631,176A1, No. 54-165
And Japanese Patent Application Laid-Open No. 7-2781. However, the compounds described therein have a low antifogging effect or have a problem of deteriorating the color tone of silver.
Improvement was needed. In addition, when the photothermographic material is stored under forced conditions of humidification and heating, and then exposed and developed, there is a problem that fog in an unexposed portion increases,
The development of an antifoggant free of these problems has been desired.

As a method for solving these problems, for example, a perbromide compound described in JP-A-4-232939 has been proposed. This is considered to suppress fog by oxidatively bleaching the fog nucleus due to the strong oxidizing action of the perbromide compound, but it is difficult to sufficiently suppress fog in thermal development alone and improve the storage stability of the photosensitive material. Was.

Accordingly, as a method for solving these problems, Japanese Patent Application Laid-Open Nos. 9-160164 and 9-244178,
9-258367, 9-265150, 9-
Nos. 281640 and 9-319022 disclose polyhalogen compounds having the above-mentioned disadvantages improved.
However, particularly, it contains a photothermographic material for a laser imager for medical use, or contains a high contrast agent, and
Even when these techniques are applied to a photothermographic material for output of a printing laser imagesetter having an oscillation wavelength of 00 nm, the above disadvantages are considerably improved, but they still have the disadvantage that fog is still large.

Japanese Unexamined Patent Publication (Kokai) No. 6-208193 discloses a photothermographic material having improved fog by containing not only a halogenated antifoggant compound but also a compound having an isocyanate group in combination.
JP-A-6-208192 discloses that a vinyl sulfone compound has a large antifogging effect in a heat development system. However, these cannot be said to have a sufficient effect yet, and a technique for improving fog without the above-mentioned disadvantages has been desired.

[0010]

SUMMARY OF THE INVENTION The present invention relates to a heat-developable photosensitive material in which heat-development fog is suppressed, fog and image density during storage are improved, and an image recording method and an image forming method using the same. To provide.

[0011]

The above object has been attained by the following means.

1. A support comprising at least a) a non-photosensitive organic silver salt; b) silver halide; c) a reducing agent capable of reducing silver ions of the organic silver salt to silver when activated by heat; and a hydrophobic binder. The photothermographic material thus obtained further contains at least one compound selected from the compounds represented by formulas (A) to (C) and is represented by formulas (1) to (6). Compound, aziridine compound,
A photothermographic material comprising at least one compound selected from an epoxy compound and a carbodiimide compound.

[0013]

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In the formula, Hal ₁ and Hal ₂ represent a halogen atom. Hal ₁ and Hal ₂ may be the same or different. X ₁ represents an anion. R ₁ represents a group having a carbonyl group as a partial structure, and R ₂ and R ₃ represent a substituent that can be substituted on a nitrogen atom or a hydrogen atom. R ₁ ~
R ₃ do not bond to each other so as to form a ring structure in which the nitrogen atom becomes an inner ring atom. n represents 1 or 2.

[0015]

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In the formula, Hal ₃ and Hal ₄ represent a halogen atom. Hal ₃ and Hal ₄ may be the same or different. X ₂ represents F ⁻ , CL ⁻ , I ⁻ , a carboxylate anion, a sulfonate anion, or a phosphate anion.
Z ₂ represents an atom group necessary for constructing a 5- to 7-membered nitrogen-containing heterocyclic ring together with an adjacent nitrogen atom. The heterocyclic ring may be condensed with the nitrogen-containing heterocyclic ring, or may be bonded by a bonding group.

[0017]

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In the formula, Z ₃ represents an atomic group necessary for constructing a 5- to 7-membered nitrogen-containing heterocyclic ring together with an adjacent nitrogen atom group. This nitrogen-containing hetero ring is fused with another ring,
Alternatively, they may be bonded by a bonding group.

[0019]

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[0020] In the general formula _{(1), R 1, R} 2, R 3 may be the same or different, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, X ^- is a counter anion, the molecular when the sulfo groups, within the X ^- is absent.

[0021]

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In the general formulas (2) and (3), R ₁ , R ₂ , R
₃ and R ₄ may be the same or different and each represents an alkyl group, an aralkyl group, an alkenyl group, or an aryl group;
Represents a divalent linking group, X ^- is a counter anion R _1, R
_2, if R _3, sulfo groups, the R ₄ is X ^- is absent.

[0023]

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In the general formula (4), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group and a heteroaromatic group which may be the same or different. These groups may be substituted. X is a group capable of leaving when reacted with a nucleophile.

[0025]

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In the general formula (5), when R ₁ and R ₂ are singly, an alkyl group having 1 to 20 carbon atoms, a carbon atom having 6 to 20 carbon atoms,
Selected from an aryl group having 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein when R ₁ is taken together with R ₂ , two nitrogen atoms in the above formula Other than 5 atoms that can contain one nitrogen atom
R ₂ and R ₃ together form a heterocyclic ring having 5 or 6 atoms which can contain 1 or 2 nitrogen atoms in addition to the nitrogen atom to which R ₂ is bonded. Forming the above R
_1, atoms other than the nitrogen of the ring formed by the ring and R _2, R ₃ formed by R ₂ is a carbon, R ₄ is selected from hydrogen or an alkyl group having a carbon atom number of 1 to 20, R ₅ Represents hydrogen or one or more substituents at any of the positions 3 to 6 of the pyridine ring, wherein the substituents have 1 to 20 carbon atoms.
An alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms May include an aryloxy group, a carboxyl group, a halogen atom, a nitro group or a sulfo group, and X ⁻ represents an anion. However when forming an intramolecular salt include sulfo group in the molecule, X ^- it does not exist.

[0027]

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In the general formula (6), R represents a substituent selected from an ethyl group, an n-propyl group and an isopropyl group;
Represents a divalent linking group which may have a substituent.

[0029]

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In the general formula (7), R represents an unsubstituted alkyl group, and L represents a divalent linking group which may have a substituent.

2. A support comprising at least a) a non-photosensitive organic silver salt; b) silver halide; c) a reducing agent capable of reducing silver ions of the organic silver salt to silver when activated by heat; and a hydrophobic binder. The photothermographic material according to claim 1, further comprising at least one compound selected from compounds represented by formula (D);
A photothermographic material comprising at least one compound selected from compounds represented by formulas (1) to (6), an aziridine compound, an epoxy compound and a carbodiimide compound.

[0032]

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In the general formula (D), R ₁ is a hydrogen atom, —O
M ₂ , an alkyl group substituted with at least one group containing at least one hetero atom, or an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group,
Aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyloxy, aryloxycarbonyloxy, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, amino Group, sulfonyl group, sulfinyl group, sulfonyloxy group, ureido group, silyl group, mercapto group, hydroxy group, nitroso group, sulfo group, carboxyl group, phosphate group, heterocyclic group, at least selected from halogenoalkyl group Represents an aryl group substituted by one group, or a heterocyclic group. L
Represents a linking group, and M ₁ and M ₂ represent a hydrogen atom or a cation. m represents an integer of 0 or more and 5 or less, and n represents an integer of 1 or more and 3 or less. However, when m is 0, and when m is 1 and R ₁ is —OH, L is a halogen atom, an acyloxy group, an acylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a formyl group, an aryloxycarbonylamino group. , An alkoxycarbonyloxy group,
Aryloxycarbonyloxy, sulfonylamino, sulfamoyl, amino, sulfonyl, sulfinyl, sulfonyloxy, ureido, silyl, mercapto, hydroxy, nitroso, sulfo, phosphate ester groups It represents a linking group substituted with one or more and three or less groups selected from a telocyclic group.

3. (3) The photothermographic material as described in (2) above, which contains at least one compound selected from formulas (A) to (C).

4. 4. The photothermographic material according to any one of the above items 1 to 3, wherein the photosensitive layer or the non-photosensitive layer on the side of the photosensitive layer viewed from the support contains a compound of the formula [H].

[0036]

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In the formula, A represents an aliphatic group, an aromatic group, a -G ₀ -D ₀ group or a heterocyclic group which may have a substituent,
Represents a blocking group, A ₁ and A ₂ are both hydrogen atoms,
Alternatively, one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. G ₀ is a -CO- group, -COCO
— Group, —CS— group, —C (＝ NG ₁ D ₁ ) — group, —SO—
A —SO ₂ — group or —P (O) (G ₁ D ₁ ) — group, where G ₁ is a mere bond, a —O— group, a —S— group, or a —N
(D ₁ ) — represents a group, D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, Represents an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

5. 5. An image recording method, wherein an exposure is performed by a laser scanning exposing machine in which an angle between an exposure surface of the photothermographic material and the scanning laser beam does not become substantially perpendicular.

6. 5. An image recording method, wherein an image is recorded on a photothermographic material according to the above item 1 or 4, by using a laser scanning exposure device in which a scanning laser beam is a multi-scan laser beam.

7. 5. An image forming method, wherein the photothermographic material according to the above item 1 or 4 is heated and developed in a state where the photothermographic material contains 40 to 4500 ppm of a solvent.

Hereinafter, the present invention will be described in detail.

The general formulas (A) and (B) of the present invention are compounds having a strong oxidizing property, including the above-mentioned perbromide compounds. These are considered to contribute to fog prevention by oxidizing the fog nucleus immediately after the preparation of the organic silver salt due to its oxidizing property. General formulas (1) to (7) which are one compound of the present invention
And aziridine compounds, epoxy compounds and carbodiimide compounds are all compounds known as hardeners in ordinary silver halide photographic materials. The fact that compounds known as hardeners in these ordinary silver halide photographic light-sensitive materials have an effect of preventing fogging in a heat development system is, for example, an isocyanate compound which exhibits an effect when used in combination with a polyhalogen compound, or And vinyl sulfone compounds. It is unknown what mechanism these compounds perform to prevent fog.However, it is considered that these compounds are more effective for longer-term preservation, although various factors may be considered, such as curing of the film and reaction with the reducing agent. ing. It appears that some action suppresses the reaction leading to fog formation. However, these compounds exhibit an effect in combination with a polyhalogen compound, and it has been known so far that these compounds exhibit a more effective antifoggant effect when used in combination with a bromine compound which is an antifoggant. Had not been.

It is unclear what mechanism these compounds, which are different from each other, effectively exert their effects in cooperation, but the compounds of the general formulas (A) to (C) initially cause fog nuclei. In a system in which fog nuclei are reduced by attacking and oxidative bleaching, a longer-term antifogging effect of the compounds of the general formulas (1) to (7) of the present invention and compounds such as aziridine, epoxy and carbodiimide. Is more effectively exhibited.

Another antifogging technology of the present invention is as follows:
The compound represented by formula (D) was found to be particularly effective in a system containing a sensitizing dye. In general, it is well known that when the adsorption of a photosensitive dye is weak, fog increases and sensitivity decreases particularly in a heat development system. Since these compounds have a great effect when used as a dissolving agent for dyes, when they are present in the thermal development system, they probably affect the adsorption of the dyes and promote the adsorption. The present inventor believes that is likely to decrease. These also prevent the formation of undesirable fog nuclei, thereby enhancing the effects of compounds of general formulas (1) to (6) and aziridine, epoxy, carbodiimide and the like. It was an unexpected result that the compound considered to have the dye adsorption accelerating effect and the compound known as a long-term antifoggant in the heat development system exhibited a better effect when used in combination.

Now, the compounds used in the present invention will be described in detail.

It is considered that the compound represented by the general formula (A) has a large effect as an oxidizing agent and has an action of bleaching fog silver nuclei in a heat development system. Therefore, when it is mixed with an organic silver salt, the effect is immediately exhibited.

In the general formula (A), Hal ₁ and Ha
halogen atom represented by l ₂ may be the the same or different and each independently represents a chlorine atom, a bromine atom, an iodine atom, but represents a fluorine atom, a case is also preferably both bromine atoms. Specific examples of the anion group represented by X ₁ include a halogen anion (chlorine anion, bromine anion, iodine anion, and fluorine anion), a carboxylate anion, a sulfonate anion, and a phosphate anion. And more preferably a bromine anion.

R ₁ represents a group having a carbonyl group as a partial structure, specifically, an acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). And acetyl, benzoyl, formyl, pivaloyl and the like.), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 2 carbon atoms).
12, for example, methoxycarbonyl, ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonyl), and an acylamino group (preferably It has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like.), Alkoxycarbonylamino group (preferably 2 to 20 carbon atoms) 20, more preferably 2 to 16 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 carbon atoms)
To 12, for example, phenyloxycarbonylamino and the like. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl). A ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include ureido, methylureide, and phenylureide. ). Preferably an acyl group,
Particularly preferred is an acetyl group.

R ₂ and R _{3 each} represent a hydrogen atom or a group that can be substituted with a nitrogen atom. Examples of the group that can be substituted with a nitrogen atom include a halogen atom (a chlorine atom, a bromine atom, an iodine atom, A fluorine atom, preferably a bromine atom; an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 1 carbon atoms).
8, for example, methyl, trifluoromethyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 carbon atoms.
-8, for example, vinyl, allyl, 2-butenyl, 3
-Pentenyl and the like. ), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl, 3-
Pentenyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms).
And examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms).
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, for example, phenyloxycarbonyl and the like), an acylamino group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 carbon atoms
-16, particularly preferably 2-10 carbon atoms, such as acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonylamino and the like), an aryloxycarbonyl group (Preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, etc.), a sulfonylamino group (preferably 1 to carbon atoms). 2
It has 0, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino. ),
Sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 0 carbon atoms)
12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl and the like. ),
Carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms)
And examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylsulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylsulfonyl,
Ethyl sulfonyl and the like. ), An arylsulfonyl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, and examples thereof include phenylsulfonyl).
Sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms
And methanesulfinyl, benzenesulfinyl and the like. ), A ureido group (preferably having 1 carbon atom)
-20, more preferably 1-16, particularly preferably 1-12, for example, ureide, methylureide, phenylureide and the like. ), A silyl group (eg, trimethylsilyl group), a nitro group, a hydroxy group, a phosphate group, a heterocyclic group (eg, triazolyl, imidazolyl, pyridyl, furyl, piperidyl,
Morpholinyl and the like. ).
These groups may be further substituted. n is 1 or 2, and more preferably 2.

Next, the compound represented by formula (B) will be described in detail.

The halogen atoms represented by Hal ₃ and Hal ₄ may be the same or different and each independently represents a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom. Is the case.

Z ₂ represents an atomic group necessary for constructing a 5- to 7-membered nitrogen-containing hetero ring together with an adjacent nitrogen atom. The nitrogen-containing hetero ring to be formed is preferably an aromatic nitrogen-containing hetero ring. Heterocycle, specifically, pyrrole, imidazole, pyrazole, pyridine, pyridazine, pyrimidine, triazole, triazine, tetrazine, pentazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline Quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole and the like. Preferably, pyridine, pyrazine, pyrimidine, pyridazine, triazine,
They are quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline and pteridine, more preferably pyridine, quinoline and isoquinoline.

Next, the compound represented by formula (C) will be described in detail.

Z ₃ represents an atomic group necessary for constructing a 5- to 7-membered nitrogen-containing hetero ring together with an adjacent nitrogen atom. The nitrogen-containing hetero ring formed is preferably an aromatic nitrogen-containing hetero ring. The ring is specifically, pyrrole, imidazole, pyrazole, pyridine, pyridazine, pyrimidine, triazole, triazine, tetrazine, pentadine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, Examples include quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, and benzothiazole. Preferably, pyridine, pyrazine, pyrimidine, pyridazine, triazine,
They are quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline and pteridine, more preferably pyridine, quinoline and isoquinoline.

Representative examples of the compounds represented by formulas (A) to (C) are shown below.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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These compounds may be added at any time after the preparation of the organic silver salt and before or after the formation of the silver halide or after the separate preparation, but preferably the coating of the photothermographic layer after the preparation of the organic silver salt is preferred. It is preferably before coating to prepare a liquid, and particularly preferably added after silver halide addition. The addition amount of these polyhalogen compounds is from 5 × 10 ^{−4 to} 0.5 mol, preferably from 5 × 10 ⁻³ to 1 mol per mol of silver.
It is contained at a content of 5 × 10 ^-2 mol.

Next, the compounds of the general formulas (1) to (7) used in combination with these compounds will be described in detail.

In the general formula (1), R ₁ , R ₂ and R ₃ may be the same or different and each represents an alkyl group, an aralkyl group, an alkenyl group or an aryl group; X ⁻ is a counter anion; X is absent if it contains a group.
The alkyl group may be linear or branched, and may be further substituted with a suitable group (eg, a sulfo group, a carboxy group, etc.) or a halogen atom (eg, a chlorine, bromine atom, etc.). . Preferably, it has 1 to 15 carbon atoms, for example, methyl, ethyl, n-propyl, n
-Hexyl, sulfoethyl, sulfopropyl, carboxymethyl and the like. The aralkyl group may be linear or branched, and may further have a suitable group (eg, a sulfo group, a carboxy group, etc.) or a halogen atom (eg, chlorine,
A bromine atom or the like). Preferably, it has 7 to 15 carbon atoms, such as benzyl, phenethyl, phenylpropyl, 2-carboxybenzyl and the like.
The alkenyl group may be linear or branched, and preferably has 2 to 8 carbon atoms, for example,
Vinyl, allyl, butenyl, octenyl, etc., and the aryl group is phenyl, naphthyl, p-tolyl, p-tolyl,
-Chlorophenyl, p-methoxyphenyl and the like. X
Represents a counter anion, preferably a metsulfate or a halogen (chlorine, iodine) ion.

Next, representative examples of the compounds represented by the general formula (1) will be given.

[0073]

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[0074]

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[0075]

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[0076]

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In the compounds represented by the general formulas (2) and (3), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and represent an alkyl group, an aralkyl group, an alkenyl group or an aryl group. A and B represent a divalent linking group, X ⁻ is a counter anion, and X is not present when R ₁ , R ₂ , R ₃ and R ₄ contain a sulfo group. The alkyl group may be linear or branched, and may be further substituted with a suitable group (eg, a sulfo group, a carboxy group, etc.) or a halogen atom (eg, a chlorine, bromine atom, etc.). . Preferably, it has 1 to 15 carbon atoms, for example, methyl, ethyl, n-propyl, n-hexyl, sulfoethyl, sulfopropyl, carboxymethyl and the like. The aralkyl group may be linear or branched and may be further substituted with an appropriate group (eg, a sulfo group, a carboxy group, etc.) or a halogen atom (eg, a chlorine, bromine atom, etc.). good. Preferably, it has 7 to 15 carbon atoms, for example, benzyl, phenethyl, phenylpropyl, 2-phenyl
Carboxybenzyl and the like.

The alkenyl group may be linear or branched and preferably has 2 to 8 carbon atoms, for example, vinyl, allyl, butenyl, octenyl and the like. Phenyl, naphthyl, p
-Tolyl, p-chlorophenyl, p-methoxyphenyl and the like. A and B are an alkylene (preferably having 10 or less carbon atoms), an arylene group (preferably having 12 or less carbon atoms), an aralkylene group (preferably having 20 or less carbon atoms),
Examples of the alkylene group include a divalent group in which a part of carbon atoms and hydrogen atoms is substituted with an oxygen atom, a sulfur atom, and a nitrogen atom.

As specific examples of A and B,-(CH ₂ ) _{3
-, - (CH 2) 4} -, - (CH 2) 6 -, - CH 2 CH 2 O
_{CH 2 CH 2 -, - CH} 2 CH 2 SCH 2 CH 2 -, - CH 2
_{CH 2 SCH 2 CH 2 SCH 2} CH 2 -, - (p-C 6 H 4)
_{-, - (m-C 6} H 4) -, - CH 2 COCH 2 -, - CH
_{2 OCH 2 CH 2 OCH 2 -} , - CH 2 (p-C 6 H 4) CH 2
—, —CH ₂ NHCO (CH ₂ ) ₄ CONHCH ₂ —, and the like. X represents a counter anion, preferably a metsulfate or a halogen (chlorine, iodine) ion.

Next, representative examples of the compounds represented by formulas (2) and (3) will be given.

[0081]

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[0082]

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[0083]

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[0084]

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In the compound represented by the general formula (4), R ₁ and R ₂ may be the same or different from each other and may be a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a heteroaromatic group. Represents a ring group. Those groups may be substituted. X is a group that can be eliminated when the compound represented by the general formula (4) reacts with a nucleophile. More specifically, R ₁ and R ₂ are each a hydrogen atom or, preferably, a linear or branched alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group). Group, a dodecyl group, etc.), a C3-C20 cycloalkyl group (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc.), a C6-C20 aryl group (e.g., phenyl group, naphthyl group, etc.), carbon An aralkyl group of the number 7 to 20 (for example, benzyl group, phenethyl group, etc.),
20 alkenyl groups (for example, a vinyl group and a propenyl group); and a heteroaromatic group having 5 to 20 carbon atoms (for example, a pyridyl group and a quinolyl group). R ₁ and R ₂ may have a substituent, for example, a halogen atom (for example, B
r, Cl, F, etc.), a nitro group, a cyano group, a sulfo group,
Examples include a carbamoyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. In the present invention, unsubstituted ones are preferred. X is a group capable of leaving when the compound represented by the general formula (4) is reacted with a nucleophile, and examples thereof include a halogen atom (eg, chlorine, bromine, iodine, fluorine), a phthalimidyloxy group, and a succinimidyl. Oxy group, glutarimidyloxy group, azolyloxy group (eg, 1-benzotriazolyloxy group, etc.), ammonium group (eg, 1-pyridinio group, 1-quinolinio group, etc.), alkylsulfonyloxy having 1 to 20 carbon atoms Groups (e.g., methylsulfonyloxy group) and arylsulfonyloxy groups having 6 to 20 carbon atoms (e.g., benzenesulfonyloxy group, p-toluenesulfonyloxy group, etc.). X may be substituted, and preferable substituents include a halogen atom, a nitro group, a sulfo group, a carbamoyl group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. X is preferably a halogen atom. Examples of the compound represented by the general formula (4) are shown below.

[0086]

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[0087]

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[0088]

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[0089]

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In the general formula (5), R ₁ represents alkyl, aralkyl, aryl or alkenyl. R
₂ is bonded together with R ₃ to form another nitrogen atom or 2
It forms a five- or six-membered ring that can be individually contained. Other R ₂ -R ₃ ring structures, can R ₁ form a ring structure together with R _2. R ₄ can be hydrogen or alkyl. R ₅ can be hydrogen, alkyl, aryl, aralkyl, alkenyl, alkoxy, aryloxy, carboxy, halogen, be a nitro or sulfo. R ₅ can be a fused ring structure as in quinoline. Preferably, R ₁ is alkyl having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, 2-ethylhexyl or dodecyl), aralkyl having 7 to 20 carbon atoms (eg, benzyl, phenethyl), 6 carbon atoms. ~ 20
(Eg, phenyl, naphthyl) or alkenyl having 2 to 20 carbon atoms (eg, vinyl, propenyl). It is also preferred that R ₁ and R ₂ can combine with each other to form a heterocyclic ring having 5 to 8 atoms. R ₁
-R ₂ ring contains a nitrogen atom to which R ₁ and R ₂ are attached, and can be further containing one additional nitrogen atom. R ₂ and R ₃ combine to form either a 5- or 6-membered ring, wherein the R ₂ -R ₃ ring contains the nitrogen atom to which R ₂ is attached, and It is also possible to contain one or two. Examples of R ₂ -R ₃ rings, pyridine, imidazole, pyrazole and triazole. Preferably, R ₄ can be hydrogen or alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl or isopropyl). R ₅ may be one or more substituents in any position of the 3-6-position hydrogen or a pyridine ring. Examples of such substituents include alkyl having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, 2-ethylhexyl or dodecyl), aryl having 6 to 20 carbon atoms (eg, phenyl, naphthyl), carbon C 7-20 aralkyl (eg, benzyl, phenethyl), C 2-20 alkenyl (eg, vinyl, propenyl), alkoxy (eg, methoxy or ethoxy), aryloxy (eg, phenoxy), carboxy, Halogen (eg, fluoro, chloro or bromo), nitro or sulfo. X ⁻ represents a counter anion or an anionic moiety of the general formula (5) which forms an inner salt (zwitterion). Any anion can be used as long as it forms a salt and does not interfere with the hardening treatment. Preferred anions include sulfonate ions such as methylsulfonate, p-toluenesulfonate, trifluoromethylsulfonate or 1,3-propylenedisulfonate, tetrafluoroborate, pentafluorophosphate and perchlorate. X ⁻ can be the anionic portion of R ₁ of the compound represented by the general formula (5). Preferred anionic substituents that form internal salts include alkyl sulfonates such as sulfatoethyl, sulfatopropyl and sulfatobutyl.

The aforementioned alkyl, aralkyl, aryl,
In addition to alkenyl and ring systems, substituted alkyl, aralkyl, aryl, alkenyl and ring systems are also useful. Useful substituents include halogens, 1-20 carbon atoms.
Alkoxy, aryloxy having 6 to 20 carbon atoms,
Carboxy, sulfo, N, N-disubstituted carbamoyl,
Included are N, N-disubstituted sulfamoyls and other groups well known in the art that do not interfere with the action of the compound of the present invention. Examples of the compound represented by the general formula (5) are shown below.

[0092]

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[0093]

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In the general formula (6), R represents a substituent selected from an ethyl group, an n-propyl group and an isopropyl group, and L represents a divalent linking group which may have a substituent. Examples include, but are not limited to, an alkylene group and an aralkylene group. JP-A-53-11385
No. 6 describes a compound in which R is a methyl group. However, a steric hindrance is small in a methyl group, and in order to realize a preferable effect, a substituent having a greater steric hindrance than an ethyl group is required. Is done. On the other hand, if the substituent is larger than the propyl group, the solubility becomes poor and it is not practical. Representative compounds are exemplified below.

[0095]

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[0096]

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[0097]

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In the general formula (7), R is an unsubstituted alkyl group, and preferably has 6 or less carbon atoms in view of the water solubility of these compounds. For example, methyl, ethyl, propyl, isopropyl, Butyl group, isobutyl group,
It represents a pentyl group, a hexyl group, a cyclohexyl group or the like, but the present invention is not limited thereto. L represents a divalent linking group which may have a substituent, and examples thereof include an alkylene group and an aralkylene group, but are not limited thereto. Representative compounds are exemplified below.

[0099]

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[0100]

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[0101]

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Next, compounds having an aziridine group which can be used in the present invention will be described. In the present invention, any compound having an aziridine group can be used arbitrarily. In the practice of the present invention, the following specific compounds can be preferably used.

[0103]

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Next, the epoxy compounds that can be used in the present invention will be described. As the epoxy-type compound, those containing a hydroxy group or an ether condensation are preferred. Specific examples of the compounds are shown below.

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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The above compounds are almost commercially available,
It can be easily obtained. The method for adding the compound having an epoxy group may be such that the compound is dissolved in an organic solvent such as alcohol, acetone, and toluene or water and added as it is, or a salt of dodecylbenzene sulfonate or nonylphenoxyalkylene oxide. You may add after dispersing using a surfactant.

Preferred carbodiimide compounds that can be used in the present invention are those represented by the following general formula.

[0114]

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Here, A is an aliphatic group such as methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, allyl, crotyl, β
Organic groups such as -hydroxyethyl group, methoxymethyl-β-bromoallyl group, and aromatic groups such as phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl group and iodophenyl group. ,
An alicyclic group represents a group such as a cyclohexyl group, a bornyl group or a menthyl group, and a group such as a heterocyclic group such as a pyridyl group or a quinolyl group. R ₁ and R ₂ are lower alkyl groups, for example, a methyl group, an ethyl group, a propyl group,
B and B ₁ (which may be the same or different) represent alkylene, arylene, or aralkylene groups such as propylene, phenylene, tolylene, propyl Represents a group such as a phenylene group.

These disubstituted carbodiimides can be used to convert N, N'-disubstituted symmetric or asymmetric thioureas having at least one tertiary amino group to Berichte Vo.
l. 71, pp. 1512-21, Vol. 73,467
Pp. 477, 1114 to 1123, Vol. 75,
Pp. 100-5, Annalen, vol. 560,22
2-231 pages, Journal of Organic
As described in Chemistry, vol., Pp. 1024-6, it can be obtained by treating with a desulfurizing agent such as an oxide of a heavy metal such as lead or mercury. The following are representative compounds.

CZ-1: N-isopropyl-N '-(4
-Dimethylaminophenyl) carbodiimide CZ-2: N-phenyl-N '-(4-dimethylaminophenyl) carbodiimide CZ-3: N, N'-di (4-dimethylaminophenyl) carbodiimide CZ-4: N, N '-Di (4-dipropylaminotolyl) carbodiimide CZ-5: N-bornyl-N'-(4-dimethylaminophenyl) carbodiimide CZ-6: N-menthyl-N '-(4-dimethylaminophenyl) carbodiimide CZ-7: N- (β-bromoallyl) -N ′-(γ-dimethylaminophenyl) carbodiimide CZ-8: N- (t-butyl) -N ′-(γ-dimethylaminophenyl) carbodiimide CZ-9: N-cyclohexyl-N '-(4-dimethylaminophenyl) carbodiimide CZ-10: N-isoprop Pill-N '-(γ-dimethylaminopropyl) carbodiimide CZ-11: N-methoxymethyl-N- (γ-dimethylaminopropyl) carbodiimide CZ-12: N, N'-di (γ-pyridyl) carbodiimide N, N'-disubstituted carbodiimides having a tertiary amine can be used directly or in the presence of ethyl acetate, chloroform, benzene, toluene or a mixed solvent thereof with a suitable quaternizing agent such as odorant. Methyl iodide, ethyl bromide, methyl iodide, ethyl iodide, dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate,
By reacting with ethyl p-toluenesulfonate or the like, it can be converted to a quaternary ammonium salt, whereby the solubility can be controlled. It may be added in the form of a quaternary salt.

The following are quaternized N, N'-disubstituted carbodiimides.

N-isopropyl-N '-(4-dimethylaminophenyl) carbodiimide ethyl p-toluenesulfonate N-phenyl-N'-(4-dimethylaminophenyl)
Carbodiimide ethyl p-toluenesulfonate N, N'-di (4-dimethylaminophenyl) carbodiimide monoethobromide N, N'-di (4-dipropylaminotolyl) carbodiimide ethyl p-toluenesulfonate N-bornyl -N '-(4-dimethylaminophenyl)
Carbodiimide methosulfate N-menthyl-N '-(4-dimethylaminophenyl)
Carbodiimide ethosulfate N- (β-bromoallyl) -N ′-(γ-dimethylaminophenyl) carbodiimide ethosulfate N- (t-butyl) -N ′-(γ-dimethylaminophenyl) carbodiimideethyl p-toluenesulfonate N-cyclohexyl-N '-(4-dimethylaminophenyl) carbodiimideethyl p-toluenesulfonate N-isopropyl-N'-([gamma] -dimethylaminopropyl) carbodiimide ethobromide N-methoxymethyl-N-([gamma] -dimethylamino Propyl) carbodiimide ethyl p-toluenesulfonate N, N′-di (γ-pyridyl) carbodiimide monomethosulfate Compounds represented by the general formulas (1) to (7) according to the present invention,
The aziridine compound, epoxy compound and carbodiimide compound are used in an amount of 0.002 mol or more per 1 mol of silver. Usually, 0.002 to 2 mol of the above compound per mol of silver, preferably 0.003 to 1 mol of silver.
It is used in the range of ０．３0.3 mol of the above compound.

Next, the compound represented by formula (D) will be described in detail. In the formula, R ₁ is a hydrogen atom, -O
M ₂ , an alkyl group substituted with at least one group containing at least one hetero atom, or an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group,
Aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyloxy, aryloxycarbonyloxy, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, amino Group, sulfonyl group, sulfinyl group, sulfonyloxy group, ureido group, silyl group, mercapto group, hydroxy group, nitroso group, sulfo group, carboxyl group, phosphate group, heterocyclic group, at least selected from halogenoalkyl group Represents an aryl group substituted with one group, or a heterocyclic group,
When R ₁ is —OM ₂ , specific examples of the cation represented by M ₁ and M ₂ include, for example, alkali metal ions (such as lithium ion, sodium ion, potassium ion, and cesium ion), and alkaline earth metal ions (magnesium ion). Ions, calcium ions, etc.), ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium, etc.) pyridinium, imidazolium, phosphonium (tetrabutylphosphonium, etc.) Is mentioned. M ₁ and M ₂ are preferably a hydrogen atom and an alkali metal ion, and more preferably a hydrogen atom.

When R ₁ is an alkyl group substituted with a group containing at least one hetero atom, a specific example of the group containing at least one hetero atom is an amino group (preferably having 0 to 20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), an alkoxy group (preferably carbon 1 to 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy, etc.),
Aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 1 carbon atoms)
2, for example, phenyloxy, 2-naphthyloxy, etc.), and an acyl group (preferably having 1 to 1 carbon atom).
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl,
Formyl, pivaloyl and the like), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl) ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 1 carbon atoms)
6, particularly preferably 7 to 10 carbon atoms, for example, phenyloxycarbonyl and the like), acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 2 carbon atoms) 10, for example, acetoxy, benzoyloxy and the like), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 carbon atoms).
-10, for example, acetylamino, benzoylamino and the like), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 carbon atoms)
To 16, particularly preferably having 2 to 12 carbon atoms, such as, for example, metoquinicarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 2 carbon atoms).
0, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenyloxycarbonylamino and the like, a sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably carbon number) 1 to 1
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably 0 carbon atoms)
-20, more preferably 0-16 carbon atoms, particularly preferably 0-12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (preferably Represents 1 to 20 carbon atoms, more preferably 1 carbon atom
To 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Particularly preferably has 1 to 12 carbon atoms, for example, methylthio, ethylthio, etc.), and arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 carbon atoms)
To 12, for example, phenylthio and the like), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 1 carbon atoms).
12, for example, mesyl, tosyl, etc.), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 carbon atom).
To 12, for example, methanesulfinyl, benzenesulfinyl and the like), a ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureido ,
Methylureide, phenyl, ureide, etc.), a phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atom)
To 12, for example, diethylphosphoramide, phenylphosphoramide, etc.), a hydroxy group, a mercapto group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, Examples include a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, and a heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholinyl, and the like).

When R ₁ is an alkyl group substituted with a group containing at least one hetero atom, the alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 12 carbon atoms, and particularly preferably has 1 to 12 carbon atoms. It has 1 to 8 carbon atoms and includes, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

R ₁ is an alkoxy group, an aryloxy group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, Alkylthio group, arylthio group, amino group, sulfonyl group, sulfinyl group, sulfonyloxy group, ureido group, silyl group, mercapto group, hydroxy group, nitroso group, sulfo group, carboxyl group, phosphate group, heterocyclic group, When it is an aryl group substituted with at least one group selected from a halogenoalkyl group, specific examples of the substituent include an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly Mashiku is 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy),
Aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 1 carbon atoms)
2, for example, phenyloxy, 2-naphthyloxy, etc.), and an acyl group (preferably having 1 to 1 carbon atom).
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl,
Formyl, pivaloyl and the like), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl) ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 1 carbon atoms)
6, particularly preferably 7 to 10 carbon atoms, for example, phenyloxycarbonyl and the like), acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 2 carbon atoms) 10, for example, acetoxy, benzoyloxy and the like), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 carbon atoms).
Acetylamino, benzoylamino and the like), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 12 carbon atoms). , For example, methoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 7 carbon atoms).
20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenyloxycarbonylamino and the like, an alkoxycarbonyloxy group (preferably 2 to 20 carbon atoms, more preferably carbon Number 2 to 16, particularly preferably carbon number 2 to 12,
For example, ethoxycarbonyloxy, etc.),
An aryloxycarbonyloxy group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonyloxy and the like), a sulfonylamino group (preferably Represents 1 to 20 carbon atoms, more preferably 1 carbon atom
To 16 and particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like), sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably Has 0 to 12 carbon atoms, for example, sulfamoyl,
Methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 to 12 carbon atoms. For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, Methylthio, ethylthio, etc.), arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 carbon atoms).
To 12, for example, phenylthio and the like), an amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, Dimethylamino,
Diethylamino, dibenzylamino, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms).
12, for example, mesyl, tosyl and the like), a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 carbon atom.
To 12, for example, methanesulfinyl, benzenesulfinyl and the like), a sulfonyloxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
-16, particularly preferably 1-12 carbon atoms, for example, mesyloxy, tosyloxy, etc.), ureido group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1 carbon atoms) ~ 12,
For example, ureido, methylureide, phenylureide and the like), silyl group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as trimethylsilyl, etc.), a phosphate group (preferably 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and includes, for example, diethyl phosphate, phenyl phosphate and the like, and a heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, Morpholinyl, etc.), halogenoalkyl groups (for example, chloromethyl group, dibromomethyl group, trifluoromethyl group, etc.).

R ₁ is an alkoxy group, an aryloxy group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, Alkylthio group, arylthio group, amino group, sulfonyl group, sulfinyl group, sulfonyloxy group, ureido group, silyl group, mercapto group, hydroxy group, nitroso group, sulfo group, carboxyl group, phosphate group, heterocyclic group, When the aryl group is substituted with at least one group selected from a halogenoalkyl group, the substituted aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.

When R ₁ is a heterocyclic group, preferably, imitazolyl, pyridyl, furyl, piperidyl, morpholinyl and the like are mentioned.

L represents a linking group, preferably an alkylene, arylene, or heterocyclic group.

When m is 0, and when m is 1 and R ₁ is-
In the case of OH, L is a halogen atom, acyloxy group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group, formyl group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfonylamino group, sulfamoyl group One or more selected from carbamoyl, amino, sulfonyl, sulfinyl, sulfonyloxy, ureido, silyl, mercapto, hydroxy, nitroso, sulfo, phosphate, and heterocyclic groups It represents a linking group substituted by three or less groups, and specific examples of the above-mentioned substituent are the same as the above-mentioned substituent when R ₁ is an aryl group. When m is 0, it preferably represents a connecting group substituted with a halogen atom, and more preferably represents an arylene group substituted with a halogen atom.

Specific examples of the compound represented by formula (D) are listed below, but the present invention is not limited thereto.

[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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As the compound represented by formula (D) of the present invention, commercially available compounds can be used. For example, Chem. Pharm. Bulletin, 31
(8), 2632 (1983); Chem. So
c. , Section B Physical 0rg
anic Chemistry, Part 1. PP14
5-148 (1971); Amer. Chem. S
oc. 77, 1909 (1955), 0rg. Pre
p. Proced. Int. 28 (5), 609 (19
96), Chem. Ber. 44, 1236 (191
1). Amer. Chem. Soc. 60,250
2 (1938), Bull. Soc. Khim. Fr.
25 (3) 173 (1901); Chem. Abst
r. 9861 (1960), West German Patent No. 297,018
No. Justus Liebigs Ann. Che
m. 300, 299 (1898) and the like.

The amount of the compound represented by the general formula (D) of the present invention is not particularly limited, but may be from 10 ^-4 mol to 1 mol / l.
Ag mole is preferred, especially 10 ^-3 mole to 0.3 mole / A.
g mol is preferred.

The compound represented by formula (D) of the present invention can be added to a photosensitive layer or a non-photosensitive layer, but is preferably a photosensitive layer. As a typical embodiment, in a photothermographic material having at least one photosensitive layer and a layer adjacent thereto on a support, the photosensitive layer contains a photosensitive silver halide, an organic silver salt, and a binder. ,
Further, an embodiment containing at least one compound represented by the general formula (D), a photosensitive layer containing a photosensitive silver halide, an organic silver salt and a binder, and a compound represented by the general formula (D) in an adjacent layer Wherein the photosensitive layer contains a photosensitive silver halide and a binder, further contains at least one compound represented by the general formula (1), and contains an organic silver salt in an adjacent layer. And an embodiment in which the photosensitive layer contains a photosensitive silver halide and a binder, the adjacent layer contains an organic silver salt, and further contains at least one compound represented by the general formula (D). Preferred in the present invention is the embodiment of

The compound represented by formula (D) of the present invention is preferably added by dissolving it in an organic solvent.
Particularly, it is preferable to add it together with the sensitizing dye.

The photothermographic material of the present invention is particularly preferably from 600 to 8
In the case of a photothermographic material for output of an image setter having an oscillation wavelength of 00 nm, a hydrazine compound is preferably contained in the light-sensitive material. By using the hydrazine compound represented by the general formula [H], a photosensitive material having a high contrast gamma can be obtained, which can be suitable for printing. The general formula [H] will be described in detail.

In the general formula [H], A represents an aliphatic group, an aromatic group, a -G ₀ -D ₀ group or a heterocyclic group which may have a substituent, B represents a blocking group, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group,
Represents a sulfonyl group or an oxalyl group. G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group , An amino group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group.

In the general formula [H], the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly preferably a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A is preferably a monocyclic or condensed ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. As a single ring or fused ring nitrogen, sulfur,
Heterocycles containing at least one heteroatom selected from oxygen atoms are preferred, for example, a pyrrolidine ring, imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring, thiophene ring, furan A ring;
Particularly preferred as ₀ are an aryl group and a heterocyclic group, and the aromatic group and the heterocyclic group represented by A ₀ may have a substituent, and particularly preferably have an acidic group having a pKa of 7 to 11. Specific examples of the substituent include a sulfonamide group, a hydroxyl group, and a mercapto group.

In the general formula [H], -G represented by A
It will be described ₀ -D ₀ group.

G ₀ represents a —CO— group, a —COCO— group, —
CS-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -S
Represents an O ₂ — group or a —P (O) (G ₁ D ₁ ) — group, and preferred G ₀ is a —CO— group or a —COCO— group, and particularly preferably a —COCO— group. G ₁ represents a mere bond, —O— group, —S— group or —N (D ₁ ) — group; D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom; When a plurality of D ₁ are present, they may be the same or different.

D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group,
Represents an alkylthio group or an arylthio group, and is preferably D ₀
Examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group and the like.

In the general formula [H], A preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, a photographically inactive alkyl group having 8 or more carbon atoms, alkenyl group, alkynyl group, alkoxy group Group, phenyl group, phenoxy group, alkylphenoxy group and the like.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

In the general formula [H], B represents a blocking group, preferably -G ₀ -D ₀ ,
It has the same meaning as the G ₀ -D ₀ group, and A and B may be the same or different.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg, acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.) ),
Or an oxalyl group (such as an ethoxalyl group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

As the hydrazine compound used in the present invention, the following compounds can be used in addition to the above.

RESEARCH DISCLOSURE
Item 23516 (November 1983, p. 3)
46) and references cited therein, as well as U.S. Pat. Nos. 4,080,207, 4,269,929, 4,276,364, 4,278,748, and 4,385. No. 4,108,347, No. 4,478,928, No. 4,560,638, No. 4,686,167, No. 4,912,016, No. 4,988,604 Nos. 4,994,365, 5,041,355, 5,104,769, British Patent No. 2,011,391B, and European Patent No. 217,3
No. 10, No. 301,799, No. 356,898, JP-A-60-179834, JP-A-61-170733,
Nos. 61-270744, 62-178246, 62-270948, 63-29751, 63
No. 32538, No. 63-104047, No. 63-1
Nos. 21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
No. 245, No. 63-234246, No. 63-2945
No. 52, No. 63-306438, No. 64-10233
No., JP-A-1-90439, JP-A-1-100530,
No. 1-1055941, No. 1-105943, No. 1-
No. 276128, No. 1-280747, No. 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962
No. 35, No. 2-198440, No. 2-198441
No. 2-198442, No. 2-220042, No. 2-221953, No. 2-221954, No. 2-2
No. 85342, No. 2-285343, No. 2-2898
No. 43, No. 2-302750, No. 2-304550
No. 3-37642, 3-54549, 3-
No. 125134, No. 3-184039, No. 3-240
No. 036, No. 3-240037, No. 3-259240
No. 3-2820038, No. 3-282536, No. 4-51143, No. 4-56842, No. 4-841
No. 34, No. 2-230233, No. 4-96053,
4-216544, 5-45761, 5-4
No. 5762, No. 5-45763, No. 5-45764
No. 5-45765, No. 6-289524, No. 9
-160164 and the like.

Other than these, the compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, the compounds described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by formula (6), specifically, compounds 4-1 to 4-
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same.
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
Compounds represented by Chemical Formula 1 described in No. 13951, specifically, compounds described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in No. 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I) described in JP-A-7-77783.
Compounds represented by I), specifically, pages 10 to 2 of the publication
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
Compounds represented by a), specifically, pages 8 to 15 of the same publication
The compounds described in Compounds H-1 to H-44 on the page can be used.

The hydrazine derivative-added layer is a photosensitive layer and / or a constituent layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of reducing agent, the type of inhibitor, etc., but it is 10 ^-6 per mol of silver halide. Mol ~
The range is preferably about 10 ^-1 mol, particularly preferably 10 ^-5 mol to 10 ^-2 mol.

The hydrazine compound of the present invention can be prepared by using a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

In the present invention, in combination with a hydrazine compound,
It is preferable to use indazoles (for example, nitroindazole) as an antifoggant.

The light-sensitive material of the present invention may contain a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative in combination with the hydrazine compound.

The photosensitive silver halide used in the photothermographic material of the present invention can be produced by any method known in the field of photographic technology such as a single jet method or a double jet method, for example, by an ammonia method emulsion, a neutral method, It can be prepared by any method such as an acidic method. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 as protective polymers for preparing photosensitive silver halide. , 56
No. 5, No. 3,713,833, No. 3,748,1
No. 43, British Patent No. 1,362,970, means for using a polymer other than gelatin such as polyvinyl acetal, and British Patent No. 1,354,18.
Means for enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in US Pat. No. 6,6,086, or photosensitive silver halide grains as described in US Pat. No. 4,076,539. Is prepared in the presence of a surfactant, various means such as omitting the use of the protective polymer can be applied.

The silver halide functions as an optical sensor, and preferably has a small grain size in order to suppress white turbidity after image formation and to obtain good image quality. The average particle size is 0.1 μm or less, preferably 0.1 μm or less.
01 μm to 0.1 μm, especially 0.02 μm to 0.08 μ
m is preferred. 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 silver halide is 50% or less, preferably 25% or less, based on the total amount of silver halide and an organic silver salt described below.
0.1%, more preferably between 15% and 0.1%.

The photosensitive silver halide used in the photothermographic material of the present invention may also be used in preparing an organic silver salt as described in British Patent 1,447,454. Halogen components such as ions coexist with organic silver salt-forming components, and silver ions are implanted into the components to produce organic silver salts almost simultaneously.

As still another method, a silver halide forming component is allowed to act on a previously prepared solution or dispersion of an organic silver salt or a sheet material containing the organic silver salt, so that a part of the organic silver salt is exposed to light. It can also be converted to neutral silver halide.
The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak specific to silver halide. Silver halide-forming components confirmed to be effective by such tests include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Are U.S. Pat. Nos. 4,009,039 and 3,45
7,075, 4,003,749, British Patent 1,498,956 and JP-A-53-270.
Nos. 27 and 53-25420, each of which is described in detail below.

(1) Inorganic halide: For example, a halide represented by MXn (where M represents H, NH ₄ , and a metal atom, n is 1 when M is H and NH ₄ ,
When is a metal atom, it represents its valence. Examples of the metal atom include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, manganese, iron, cobalt, nickel, rhodium, and cerium. ). Further, halogen molecules such as bromine water are also effective.

(2) Onium halides: quaternary ammonium halides such as, for example, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, and quaternary phosphonium halides such as tetraethylphosphonium bromide And tertiary sulfonium halides such as trimethylsulfonium iodide.

(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like.

(4) N-halogen compounds: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazone, N-bromo Oxazolinone, N-chlorophthalazone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide,
N-bromo-N-methylbenzenesulfonamide, 1,
3-dibromo-4,4-dimethylhydantoin, N-bromourazole and the like.

(5) Other halogen-containing compounds: for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is from 0.001 mol to 0.7 mol, preferably from 0.03 mol to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as reaction temperature, reaction time, reaction pressure and the like in the step of converting a part of the organic silver salt to silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. Usually, the reaction temperature is -20 ° C to 70 ° C, the reaction time is 0.1 second to 72 hours,
The reaction pressure is preferably set at atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by weight, preferably 0.1 to 10 parts by weight per 1 part by weight of the organic silver salt.

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 achieved by a chromium compound or a combination thereof. The method and procedure of this chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, JP-A-51-224.
No. 30, No. 51-78319, and No. 51-81124. Also, when a part of the organic silver salt is converted to a photosensitive silver halide by a silver halide forming component, as described in US Pat. No. 3,980,482, sensitization is achieved. A low molecular weight amide compound may coexist.

In addition, these photosensitive silver halides may have an illuminance failure or 10 to 10 groups from the periodic table of the element to control gradation.
Metals belonging to group III, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof, or a complex ion can be contained. It is particularly preferable to add as a complex ion. For example, Ir complex ion such as IrCl ₆ ^2- may be added due to illuminance failure.

In the present invention, the organic silver salt is a reducible silver source, and is preferably a silver salt of an organic acid or a hetero organic acid, particularly a long-chain (10 to 30 carbon atoms, preferably 15 to 2
5) Silver salts of aliphatic carboxylic acids and nitrogen-containing heterocyclic compounds are preferred. Organic or inorganic complexes in which the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions are also preferred. Examples of these suitable silver salts include Res.
ear Disclosure Nos. 17029 and 29996, and include the following.

Silver salts of organic acids, for example, gallic acid, oxalic acid,
Silver salts such as behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, and aldehydes with hydroxy-substituted aromatic carboxylic acids Silver salts or complexes of polymer reaction products, for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted aromatic carboxylic acids (for example, salicylic acid, benzoic acid,
Silver salts or complexes of reaction products of 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes, for example, 3- (2-carboxyethyl) -4
-Hydroxymethyl-4-thiazoline-2-thioene,
And a complex or a silver salt such as 3-carboxymethyl-4-thiazoline-2-thioene, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,2. Complexes or salts of silver and a nitrogen acid selected from 4-triazole and benzotriazole, silver salts such as saccharin and 5-chlorosalicylaldoxime, and silver salts of mercaptides. Among these, preferred silver salts are silver behenate, silver arachidate or silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and includes a normal mixing method, a reverse mixing method, a simultaneous mixing method, and a method disclosed in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After producing sodium behenate, sodium arachidate, etc., silver nitrate or the like is added to the soap to produce crystals of an organic silver salt. At that time, silver halide grains may be mixed. Further, a so-called control double jet method in which the soap and silver nitrate are simultaneously added may be used.

In the present invention, the organic silver salt has an average particle size of 2
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt means that the particles of the organic silver salt are, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of the organic silver salt grains. The average particle size is preferably 0.05 μm to 1.5 μm, particularly 0.05 μm.
m to 1.0 μm is preferred. The term “monodisperse” has the same meaning as in the case of silver halide.
0.

In the present invention, the tabular grains of the organic silver salt preferably have at least 60% of the total organic silver.
In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystal is obtained by dispersing and pulverizing a binder, a surfactant, and the like with a ball mill or the like. Can be Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic materials of the present invention include, 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, U.S. Patent Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175,
Sensitizing dyes described in the above-mentioned 4,835,096 can be used. Useful sensitizing dyes for use in the present invention include, for example, R
search Disclosure Item 1
7643 IV-A (December 1978, p. 23). 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, Japanese Patent Application Laid-Open No. 60-16224 discloses an argon ion laser light source.
7, U.S. Pat. No. 2,486,635, U.S. Pat.
No. 1,331, West German Patent No. 936,071, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-open No. Sho 50-6 / 1991 discloses simple merocyanines and helium neon laser light sources described in
No. 2425, No. 54-18726, No. 59-1022
Trinuclear cyanine dyes described in JP-A No. 29-29, JP-A-7-28
No. 48-42 describes merocyanines, LED light sources and infrared semiconductor laser light sources described in US Pat.
Nos. 172, 51-9609 and 55-39818
JP-A-62-284343, JP-A-2-1051
JP-A-59-191332 discloses thiacarbocyanines and infrared semiconductor laser light sources described in No. 35;
Tricarbocyanines described in JP-A-60-80841, JP-A-59-192242, JP-A-3-67.
No. 242 described in general formulas (IIIa) and (IIIb).
Dicarbocyanines containing a quinoline nucleus are advantageously selected. Further, the wavelength of the infrared laser light source is 750 nm.
More preferably, when the wavelength is 800 nm or more.
No. 2639, No. 5-341432, Tokuhei 6-523
Nos. 87 and 3-10931; U.S. Pat.
Sensitizing dyes described in JP-A-866-866 and JP-A-7-13295 are preferably used.

These sensitizing dyes may be used alone.
In particular, combinations of sensitizing dyes are often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The photothermographic material of the present invention is exposed by an argon ion laser (488 nm), a He—Ne laser (633 nm), a red semiconductor laser (670 nm),
An infrared semiconductor laser (780 nm, 820 nm) or the like is preferably used, but an infrared semiconductor laser is more preferably used from the viewpoint that the laser power is high and the photosensitive material can be made transparent.

The photothermographic material of the present invention preferably contains a mercapto compound, a disulfide compound, and a thione compound in order to improve the spectral sensitizing efficiency. When a mercapto compound is used in the present invention, any structure may be used, but a compound represented by Ar-SM ₁ or Ar-SS-Ar is preferable. In the formula, M ₁ is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having at least one nitrogen, sulfur, oxygen, selenium or tellurium atom. Preferably, the heteroaromatic ring is benzimidazole, benzothiazole, naphthothiazole, benzoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine. , Quinoline or quinazolinone. The heteroaromatic ring may have, for example, one selected from a substituent group consisting of halogen, hydroxy, amino, carboxy, alkyl and alkoxy.

Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzodithiazole, 2-mercapto-5-methylbenzimidazole, and 6-ethoxy-2-mercapto. Benzothiazole,
2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8
-Mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto- 1,2,
Examples include 4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, and the like, but the invention is not limited thereto. The amount added is preferably in the range of 0.001 to 1.0 mol per mol of silver in the photosensitive layer, and more preferably in the range of 0.01 to 0.3 mol per mol of silver.

Examples of the reducing agent used in the photothermographic material of the present invention include generally known reducing agents, such as phenols, polyphenols having two or more phenol groups, naphthols and bisnaphthols. , 2
Polyhydroxybenzenes having at least two hydroxyl groups, 2
Polyhydroxynaphthalenes having at least two hydroxyl groups,
Ascorbic acids, 3-pyrazolidones, pyrazoline-
5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone monoethers,
Hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas, and the like. More specifically, for example, U.S. Patent Nos. 3,615,533 and 3,67.
9,426, 3,672,904, 3,7
No. 51,252, No. 3,782,949, No. 3,
Nos. 801,321, 3,794,488, 3,893,863, 3,887,376, 3,770,448, 3,819,382,
No. 3,773,512 and No. 3,839,048
No. 3,887,378, No. 4,009,03
9, No. 4,021,240, British Patent No. 1,48
No. 6,148 or Belgian Patent No. 786,086 and JP-A-50-36143, 50-36.
No. 110, No. 50-116023, No. 50-9971
No. 9, No. 50-140113, No. 51-51933
Nos. 51-23721, 52-84727 and JP-B-51-35851, and the present invention is appropriately selected from such known reducing agents. Can be used. As a selection method, the simplest method is to actually prepare a photothermographic material and evaluate the photographic performance of the photothermographic material to determine the superiority of the reducing agent used.

Among the above reducing agents, when an aliphatic silver carboxylate is used as the organic silver salt, preferred reducing agents include polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur. In particular, an alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) is provided at at least one of the positions adjacent to the hydroxy substitution position of the phenol group. Are polyphenols in which two or more of the phenol groups substituted by an alkylene group or sulfur, for example, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
5-trimethylhexane, 1,1-bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane,
1,1-bis (2-hydroxy-3,5-di-t-butylphenyl) methane, 2-hydroxy-3-t-butyl-5-methylphenyl)-(2-hydroxy-5-methylphenyl) methane 6,6'-benzylidene-bis (2,4-di-t-butylphenol), 6,6'-benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene-bis (2,4-dimethylphenol), 1,1-bis (2-hydroxy-
3,5-dimethylphenyl) -2-methylpropane,
1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5
U.S. Pat. Nos. 3,589,903 and 4,021,249 or British Patent 1,486,148 and JP-A-51-51933. No. 50-36110, No. 50
Polyphenol compounds described in JP-A-116023, JP-A-52-84727 or JP-B-51-35727), and bisnaphthols described in U.S. Pat. No. 3,672,904, for example, 2,2 '-Dihydroxy-1,1'-binaphthyl,6,6'-dibromo-
2,2'-dihydroxy-1,1'-binaphthyl, 6,
6'-dinitro-2,2'-dihydroxy-1,1'-
Binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl and the like, and further US Pat. No. 3,80
Sulfonamidophenols or sulfonamidonaphthols as described in US Pat. No. 1,321, for example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4
-Benzenesulfonamidophenol, 4-benzenesulfonamidonaphthol and the like.

The amount of the reducing agent used in the photothermographic material of the present invention varies depending on the type of the organic silver salt, the reducing agent, and other additives. The suitable amount is from 05 mol to 10 mol, preferably from 0.1 mol to 3 mol. Further, within this range, two or more of the above-mentioned reducing agents may be used in combination.

The photothermographic materials of the present invention include, for example, US Pat. Nos. 3,874,946 and 4,756,999.
No. 5,340,712 and European Patent No. 605,98.
No. 1A1, No. 622, 666A1, No. 631,176
A1, JP-B-54-165, JP-A-7-2781
JP-A-9-160164 and JP-A-9-244178
, 9-258367, 9-265150, 9-281640, and 9-319022 can be preferably used.

The polyhalogen compound used in the present invention is used in an amount of 5 × 10 ^{−4 to} 0.5 mol, preferably 5 × 10 ⁻⁴ mol, per mol of silver.
It is contained at a content of × 10 ^{-3 to} 5 × 10 ^-2 mol.

In the photothermographic material of the present invention, it is desirable to use an additive (hereinafter referred to as a "toning agent") called a toning agent, a toning agent or an activator toner together with the above-mentioned components. The color tone agent participates in the oxidation-reduction reaction between the organic silver salt and the reducing agent, and has a function of making the resulting silver image dark, particularly black. Examples of suitable toning agents for use in the present invention are Research Disclosure No. 1702
No. 9 and the following.

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles (eg, N, N′-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), isothiuronium (isothiuronium)
m) Combinations of derivatives and certain photobleaches (eg, combinations of 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole ); Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g., 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1, 4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone and sodium benzenesulfinate or 8-methylphthalazinone and sodium p-trisulfonate); a combination of phthalazine and phthalic acid; Phthalazine (including phthalazine adducts) and maleic Anhydride, and phthalic acid, 2,3
Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinedione , Benzoxazine, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg,
2,4-dihydroxypyrimidine); tetraazapentalene derivatives (for example, 3,6-dimercapto-1,4-
Diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The hydrophobic binder suitable for the photothermographic material of the present invention is transparent or translucent and generally colorless, and includes natural polymers, synthetic polymers and copolymers, and other film-forming media such as cellulose acetate and cellulose acetate. Butyrate, polymethyl methacrylate, polyvinyl chloride, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), polyvinylacetals, for example, polyvinylformal, polyvinylbutyral, polyesters, polyurethane , Phenoxy resin, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetates, cellulose esters, polyamides and the like. However, among these binders, particularly preferred are cellulose acetate, cellulose acetate butyrate and polyvinyl butyral, and among them, polyvinyl butyral is particularly preferred.

In the present invention, the binder amount of the photosensitive layer is preferably from 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and it is preferable to provide a matting agent on the surface of the photosensitive material in order to prevent damage to the image after thermal development. It is preferred that the agent be contained in an amount of 0.5 to 30% by weight based on all binders on the photosensitive layer side.

When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent, so that the slipping property and the adhesion of fingerprints of the photosensitive material can be improved. For prevention, it is preferable to provide a matting agent on the surface of the photosensitive material, and the matting agent is used in a weight ratio of 0.5 to 4 with respect to all binders in the layer on the side opposite to the photosensitive layer side.
It is preferable to contain 0%.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent preferably has a variation coefficient of the particle size distribution of 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) ×
100 The matting agent according to the present invention can be contained in any constituent layer. However, in order to achieve the object of the present invention, the matting agent is preferably a constituent layer other than the photosensitive layer, more preferably from the viewpoint of the support. This is the outermost layer and is usually included in the protective film.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and coating the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to high temperature after exposure. The heating temperature is preferably from 80 ° C. to 200 ° C., and more preferably from 100 ° C. to 150 ° C. If the heating temperature is lower than 80 ° C., a sufficient image density cannot be obtained in a short time, and if the heating temperature is higher than 200 ° C., the binder is melted and adversely affects not only the image itself but also transportability such as transfer to a roller and a developing machine. Effect. By heating, a silver image is generated by an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This reaction process proceeds without supply of a processing liquid such as water from the outside. The above-mentioned development is preferably performed by heating from the protective layer side, so that uniform heating can be performed as compared with the case of heating through a base, and image unevenness due to uneven heating can be prevented. For this reason, the polymer used for the protective layer is preferably one having a high softening point, and among the above-mentioned polymers, cellulose acetate, cellulose acetate butyrate and the like are preferable. Polymers such as gelatin can also be used.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer as a protective layer on the photosensitive layer. Also, a back coat layer may be provided on the opposite side of the support to prevent curling and improve sharpness, and the same side as the photosensitive layer to control the amount or wavelength distribution of light transmitted to the photosensitive layer. Alternatively, a filter layer may be formed on the opposite side, or a dye or pigment may be contained in the photosensitive layer. As the dye, compounds described in JP-A-8-201959 are preferred. The photosensitive layer may be composed of a plurality of layers, or a high-sensitivity layer and a low-sensitivity layer may be provided for adjusting the gradation and may be combined. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

The method of coating the photosensitive layer of the present invention with the necessary layers such as the above-mentioned photosensitive layer, protective layer and back coat layer is not particularly limited. Methods such as dip coating, bar coating, curtain coating, and hopper coating can be used. Further, two or more of these layers may be applied simultaneously. As a solvent for the coating solution, an organic solvent such as methyl ethyl ketone (MEK), ethyl acetate, and toluene is preferable, and when a water-soluble polymer such as gelatin is used for the protective layer or the back coat layer, a water solvent is preferable.

When the light-sensitive material of the present invention is thermally developed, the light-sensitive material preferably contains a small amount of a solvent, whereby high sensitivity and low fog can be obtained.

In the present invention, examples of these solvents include ketones such as acetone, isophorone, ethyl amyl ketone, methyl ethyl ketone, and methyl isobutyl ketone. Methyl alcohol, ethyl alcohol, n-propyl alcohol as alcohols,
Isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, cyclohexanol, benzyl alcohol and the like. As glycols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Hexylene glycol and the like can be mentioned. Ethylene glycol monomethyl ether as ether alcohols,
And diethylene glycol monoethyl ether. Examples of ethers include ethyl ether, dioxane, and isopropyl ether. Examples of the esters include ethyl acetate, butyl acetate, amyl acetate, and isopropyl acetate. N-pentane, n as hydrocarbons
-Hexane, n-heptane, cyclohexane, benzene, toluene, xylene and the like. Examples of chlorides include methyl chloride, methylene chloride, chloroform, dichlorobenzene and the like. Examples of the amines include monomethylamine, dimethylamine, triethanolamine, ethylenediamine, and triethylamine. Other examples include water, formamide, dimethylformamide, nitromethane, pyridine, toluidine, tetrahydrofuran, acetic acid and the like. However, it is not limited to these. These solvents can be used alone or in combination of several kinds.

The content of the solvent in the light-sensitive material can be adjusted by changing conditions such as temperature conditions in a drying step after the coating step. The content of the solvent can be measured by gas chromatography under conditions suitable for detecting the contained solvent.

The amount of the solvent contained in the light-sensitive material according to the present invention is 40 to 4500 pp in total amount (based on weight).
m, preferably 100 to 4000 ppm (calculated based on the weight of the light-sensitive material components other than the support).

When the content is within the above range, a photothermographic material having high fog and low fog density can be obtained.

In the present invention, the exposure is preferably performed by laser scanning exposure. However, it is preferable to use a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular. Is preferred.

Here, "not substantially vertical" means that the angle is closest to vertical during laser scanning, preferably 55 to 88 degrees, more preferably 60 to 86 degrees, and still more preferably. 65 degrees or more and 84 degrees or less,
Most preferably, it is 70 degrees or more and 82 degrees or less.

The beam spot diameter on the exposed surface of the photosensitive material when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. Incidentally, the adjustment of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of interference fringe-like unevenness.

The exposure in the present invention is also preferably performed using a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi. Image quality deterioration such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode.

In order to form the vertical multi-path, it is preferable to use a method of combining, using return light, or superimposing a high frequency. still,
The vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

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

[0224]

EXAMPLES Example 1 (Preparation of Support) Concentration 0.170 (densitometer PDA-65 manufactured by Konica Corp.) was colored blue and had a thickness of 175.
A corona discharge treatment of 8 W / m ² · min was applied to both sides of a μm PET film.

(Preparation of Photosensitive Silver Halide Emulsion A) Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate, potassium bromide and potassium iodide in a molar ratio of (98/2) were equimolar to silver nitrate, and iridium chloride was converted to silver 1
370 ml of an aqueous solution containing 1 × 10 ^-4 mol per mol was added to p
Ag was added over 10 minutes by a controlled double jet method while keeping the Ag at 7.7. Then 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene
After adding 3 g and adjusting the pH to 5 with NaOH, the average particle size was 0.06 μm, the variation coefficient of the particle size was 12%, and [1
00] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then 0.1 g of phenoxyethanol was added thereto.
Ag was adjusted to 7.5 to obtain photosensitive silver halide emulsion A.

(Preparation of Powdered Organic Silver Salt A) 111.4 g of behenic acid and 83.8 of arachidic acid were added to 4720 ml of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 M aqueous sodium hydroxide solution was added. Next, after adding 6.9 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While keeping the temperature of the organic acid sodium solution at 55 ° C., the silver halide emulsion A (containing 0.038 mol of silver) and 450 ml of pure water were added, and the mixture was stirred for 5 minutes. Then 1
760.6 ml of M silver nitrate solution is added over 2 minutes,
The mixture was further stirred for 20 minutes, and the water-soluble salts were removed by filtration. Thereafter, washing with deionized water and filtration are repeated until the conductivity of the filtrate becomes 2 μS / cm, centrifugal dehydration is performed, and then hot air drying is performed at 37 ° C. until the weight is no longer reduced. I got

(Preparation of photosensitive emulsion dispersion) Polyvinyl butyral powder (Butvar B manufactured by Monsanto)
-79) with 14.57 g of methyl ethyl ketone (hereinafter ME
K) (1457 g), and 500 g of powdered organic silver salt A was gradually added thereto with stirring with a dissolver-type homogenizer, followed by thorough mixing. Thereafter, a media type disperser (Get) filled with 80% of 1 mm Zr beads (manufactured by Toray)
(manufactured by tzmann) at a peripheral speed of 13 m and a residence time in the mill of 0.5 minute to prepare a photosensitive emulsion dispersion.

<Preparation of infrared sensitizing dye liquid> Infrared sensitizing dye 1
350 mg, 13.96 g of 2-chlorobenzoic acid and 5-methyl-2-mercaptobenzimidazole.
14 g was dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

<Preparation of Stabilizer Liquid> 1.0 g of Stabilizer 1 was prepared.
0.5 g of potassium acetate was dissolved in 8.5 g of methanol to prepare a stabilizer solution.

<Preparation of developer solution> Developer (1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3-
17.74 g of methylpropane) was dissolved in MEK, and 1
Finished to 00 ml to make a developer solution.

<Preparation of Antifoggant Solution> Antifoggant 2
Is dissolved in MEK and finished to 100 ml.
An antifoggant solution was used.

[0232]

Embedded image

(Preparation of Coating Solution for Photosensitive Layer) The above-mentioned photosensitive emulsion dispersion (50 g) and 15.11 g of MEK were kept at 21 ° C. with stirring to obtain the compound of the present invention (general formula (A) to (11)).
(C) was added in a 10% methanol solution to the amount shown in Table 1 and stirred for 1 hour. Further, 889 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes.

Next, 1.416 ml of the infrared sensitizing dye solution and 667 μl of the stabilizer solution were added, and the mixture was stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes.

While keeping the temperature at 13 ° C., polyvinyl butyral (Monvarto Butvar B-79) was used.
After adding 13.31 g and stirring for 30 minutes, the following additives were added at intervals of 15 minutes while stirring was continued.

Phthalazine: 305 mg Tetrachlorophthalic acid: 102 mg 4-Methylphthalic acid: 137 mg Infrared dye 1: 37 mg After adding the above and stirring for 15 minutes, antifoggant solution: 5.47 ml Developer solution: 14.06 ml Inventive compound (shown in Table 1) 10% MEK solution: 1.60 ml (selected from general formulas (1) to (7), an aziridine compound, an epoxy compound, and a carbodiimide compound) are sequentially added, and the mixture is stirred, followed by application to the photosensitive layer. A liquid was obtained.

[0237]

Embedded image

Next, the following layers were sequentially formed on a support to prepare a light-sensitive material. The drying was performed at 75 ° C. for 5 minutes.

<Back side coating> Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² Matting agent: 30 mg / m ² (monodispersity 15% average particle size 10 μm monodisperse silica) <Photosensitive layer side coating> Photosensitive layer : The solution having the above composition was applied so that the applied silver amount was 2 g / m ² .

Surface protective layer: A solution having the following composition was applied on the photosensitive layer.

Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Matting agent: 70 mg / m ² (monodispersity 10% average particle size 4 μm monodisperse silica) << Exposure and development treatment >> Photosensitivity prepared as described above From the emulsion side of the material, a wavelength of 800 nm to 820
Exposure was performed by laser scanning using an exposure machine using a semiconductor laser having a vertical multi-mode of nm as an exposure source.
At this time, the angle between the exposure surface of the photosensitive material and the exposure laser beam was set to 75 degrees.

Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum so that the protective layer of the photosensitive material was in contact with the drum surface. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. The obtained image was evaluated using a densitometer. The results of the measurement were evaluated by sensitivity (the reciprocal of the ratio of the exposure amount giving a density higher than that of the unexposed portion by 1.0) and fog, and the sensitivity of the photosensitive material was indicated by a relative value. Table 1 shows the results.

(Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.)

[0244]

[Table 1]

Example 2 In the same manner as in Example 1, a support was prepared, and a photosensitive silver halide emulsion and a powdered organic silver salt were prepared to prepare a photosensitive emulsion dispersion.

<Preparation of infrared sensitizing dye liquid> Infrared sensitizing dye 1
And the amount of the compound of the present invention (compound represented by the general formula (D)) shown in Table 2 in place of chlorobenzoic acid, and 5-methyl-2-mercaptobenzimidazole 2.1
4 g was dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

<Preparation of stabilizer solution> Same as in Example 1 <Preparation of developer solution> Same as in Example 1 <Preparation of antifoggant solution> Same as in Example 1 (Preparation of photosensitive layer coating solution) Example 1 The same photosensitive emulsion dispersion (50 g) and 15.11 g of MEK were kept at 21 ° C. while stirring, and 390 μl of the present compound A1 in a 10% methanol solution was added, followed by stirring for 1 hour. Further, 889 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes.

Next, 1.416 ml of the infrared sensitizing dye solution and 667 μl of the stabilizer solution were added, and the mixture was stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. 13 ℃
While keeping the temperature in the polyvinyl butyral (Monsan
13.31 g of Tovar Butvar B-79) was added and stirred for 30 minutes, and then the following additives were added at 15-minute intervals while stirring was continued.

Phthalazine: 305 mg Tetrachlorophthalic acid: 102 mg 4-Methylphthalic acid: 137 mg Infrared dye 1: 37 mg After adding the above and stirring for 15 minutes, antifoggant solution: 5.47 ml Developer solution: 14.06 ml Inventive compound (shown in Table 2) 10% MEK solution: 1.60 ml (selected from general formulas (1) to (7), aziridine compound, epoxy compound and carbodiimide compound) sequentially added and stirred, followed by stirring the photosensitive layer A coating solution was obtained.

The following layers were sequentially formed on a support to prepare a light-sensitive material. In addition, each drying was performed at 75 ° C. for 5 minutes.

<Back side coating> Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² Matting agent: 30 mg / m ² (monodispersity 15% average particle size 10 μm monodisperse silica) <Photosensitive layer side coating> Photosensitive layer 1-4: The solution having the above composition was applied so that the applied silver amount was 2 g / m ² .

Surface protective layer: A solution having the following composition was applied on the photosensitive layer.

Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Matting agent: 70 mg / m ² (monodispersity 10% average particle size 4 μm monodisperse silica) << Exposure and development treatment >> Photosensitivity prepared as described above From the emulsion side of the material, a wavelength of 800 nm to 820
Exposure was performed by laser scanning using an exposure machine using a semiconductor laser having a vertical multi-mode of nm as an exposure source.
At this time, the angle between the exposure surface of the photosensitive material and the exposure laser beam was set to 75 degrees.

Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum so that the protective layer of the photosensitive material was in contact with the drum surface. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. The obtained image was evaluated using a densitometer. The results of the measurement were evaluated by sensitivity (the reciprocal of the ratio of the exposure amount giving a density higher than that of the unexposed portion by 1.0) and fog, and the sensitivity of the photosensitive material was indicated by a relative value. Table 2 shows the results. (Note that
Also in this case, an image having less unevenness and unexpectedly good sharpness and the like was obtained as compared with the case where the angle was set to 90 degrees. << Evaluation of preservability of sample before exposure >> Further, the photosensitive material prepared as described above was sealed in a light-shielded bag on which aluminum was vapor-deposited at a humidity of 20% RH, placed in a thermostat at 30 ° C., and after one day, 3
After 7 days, 7 days, 14 days, 30 days, and 60 days, the samples immediately after coating were exposed to an exposure amount giving a density of 2.0, developed, and evaluated for density fluctuation. Table 2 also shows the results.

[0255]

[Table 2]

Example 3 In the same manner as in Example 1, a photosensitive silver halide emulsion and a powdered organic silver salt were prepared to prepare a photosensitive emulsion dispersion. However, the preparation of the coating solution, etc. also in the preparation of the photosensitive layer coating solution,
After addition of 4-methylphthalic acid, the compound of the general formula [H] is shown in Table 3.
The procedure was performed in the same manner as in Example 1 except that the amounts shown in (1) and (2) were added. or,
Level No. A1 (10% methanol solution) as a compound represented by general formulas (A) to (C) other than 390
μl, EP-1 was used in the same amount as in Example 1 as a compound selected from the compounds represented by the general formulas (1) to (7), aziridine compounds, epoxy compounds and carbodiimide compounds.

(Level No. 1 does not contain general formulas (A) to (C) and general formulas (1) to (7), an aziridine compound, an epoxy compound, and a carbodiimide compound.) The support is biaxially stretched. A 100 μm-thick polyethylene terephthalate film was used.

<< Exposure and Development Processing >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning with an exposure machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, the angle between the exposure surface of the photosensitive material and the exposure laser beam was set to 75 degrees.

Thereafter, heat development was carried out at 120 ° C. for 20 seconds using an automatic developing machine having an oven zone with a heater. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. The obtained image was evaluated using a densitometer. The results of the measurement were evaluated by sensitivity (the reciprocal of the ratio of the exposure amount giving a density higher than that of the unexposed portion by 1.0) and fog, and the sensitivity of the photosensitive material was indicated by relative sensitivity. The results are shown in Table 3.

(Note that when the angle between the exposure surface of the photosensitive material and the exposure laser beam was set to 75 degrees, an image having less unevenness and unexpectedly good sharpness and the like was obtained than when the angle was set to 90 degrees.) Was done.)

[0261]

[Table 3]

[0262]

According to the present invention, heat development fog of a photothermographic material can be suppressed, and the preservability of the photothermographic material, in particular, fog and image density reduction due to storage can be improved. It is suitable as a material or a photothermographic material for output of laser imagesetter for printing.

Claims (7)

[Claims] 1. A support comprising at least a) a non-photosensitive organic silver salt; b) silver halide; c) a reducing agent capable of reducing silver ions of the organic silver salt to silver when activated by heat; The photothermographic material containing a hydrophobic binder further contains at least one compound selected from the compounds represented by formulas (A) to (C), and further contains at least one compound represented by formulas (1) to (6). ), An aziridine compound,
A photothermographic material comprising at least one compound selected from an epoxy compound and a carbodiimide compound. Embedded image [In the formula, Hal ₁ and Hal ₂ represent a halogen atom. H
al ₁ and Hal ₂ may be the same or different. X ₁ represents an anion. R ₁ represents a group having a carbonyl group as a partial structure, and R ₂ and R ₃ represent a substituent that can be substituted on a nitrogen atom or a hydrogen atom. R _{1 to} R ₃ do not bond to each other so as to form a ring structure in which the nitrogen atom becomes an inner ring atom. n represents 1 or 2. [Chemical formula 2] [In the formula, Hal ₃ and Hal ₄ represent a halogen atom. H
al ₃ and Hal ₄ may be the same or different. X ₂ represents F ⁻ , CL ⁻ , I ⁻ , a carboxylate anion, a sulfonate anion, or a phosphate anion. Z ₂ represents an atom group necessary for constructing a 5- to 7-membered nitrogen-containing heterocyclic ring together with an adjacent nitrogen atom. The heterocyclic ring may be condensed with the nitrogen-containing heterocyclic ring, or may be bonded by a bonding group. [Chemical formula 3] [Wherein, Z ₃ represents an atom group necessary for constructing a 5- to 7-membered nitrogen-containing heterocyclic ring together with an adjacent nitrogen atom group. This nitrogen-containing hetero ring may be condensed with another ring, or may be bonded by a bonding group. [Formula 4] [In the general formula (1), R ₁ , R ₂ , and R ₃ may be the same or different and represent an alkyl group, an aralkyl group, an alkenyl group, or an aryl group; X ⁻ is a counter anion; X ^- is not present when a sulfo group is included. [Chemical formula 5] [In the general formulas (2) and (3), R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different, and may be an alkyl group, an aralkyl group,
A and B represent a divalent linking group; X ⁻ represents a counter anion; and R ₁ , R ₂ , R ₃ , R
_{When 4} contains a sulfo group, X ^- is not present. [Formula 6] [In the general formula (4), R ₁ and R ₂ may be the same or different and may be a hydrogen atom, an alkyl group, an aryl group,
Represents an aralkyl group, an alkenyl group or a heteroaromatic ring group. These groups may be substituted. X is a group capable of leaving when reacted with a nucleophile. [Formula 7] [In the general formula (5), when R ₁ and R ₂ are each independently, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or carbon atom Selected from alkenyl groups having 2 to 20 atoms, and R ₁ , when taken together with R ₂ , has 5 to 8 atoms which can contain one nitrogen atom in addition to the two nitrogen atoms in the above formula. R ₂ and R ₃ together form a heterocyclic ring having 5 or 6 atoms which can contain one or two nitrogen atoms in addition to the nitrogen atom to which R ₂ is bonded. The atoms other than nitrogen in the ring formed by R ₁ and R ₂ and the ring formed by R ₂ and R ₃ are carbon, and R ₄ is hydrogen or an alkyl group having 1 to 20 carbon atoms. R ₅ is hydrogen or 3 to 3 of the pyridine ring
Represents one or more substituents at any of the 6-positions, and the substituents include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a
20 aralkyl groups, alkenyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 6 carbon atoms
20 aryloxy group, a carboxyl group, a halogen atom, it is possible to include a nitro group or a sulfo group, and X ^- represents an anion. However when forming an intramolecular salt include sulfo group in the molecule, X ^- it does not exist. Embedded image [In the general formula (6), R represents a substituent selected from an ethyl group, an n-propyl group, and an isopropyl group, and L represents a divalent linking group which may have a substituent. Embedded image [In the general formula (7), R represents an unsubstituted alkyl group, and L represents a divalent linking group which may have a substituent. ] 2. A support comprising at least a) a non-photosensitive organic silver salt; b) silver halide; c) a reducing agent capable of reducing silver ions of said organic silver salt to silver when activated by heat; The photothermographic material containing a hydrophobic binder further contains at least one compound selected from the compounds represented by formula (D), and the compound represented by formula (1)
A photothermographic material comprising at least one compound selected from compounds represented by formulas (1) to (6), an aziridine compound, an epoxy compound and a carbodiimide compound. Embedded image [In the general formula (D), R ₁ represents an alkyl group substituted with at least one hydrogen atom, —OM ₂ , or a group containing at least one hetero atom, or an alkoxy group, an aryloxy group, an acyl group, or an alkoxy group. Carbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio Group, amino group, sulfonyl group, sulfinyl group, sulfonyloxy group, ureido group, silyl group, mercapto group, hydroxy group, nitroso group, sulfo group, carboxyl group, phosphate group, heterocyclic group, halogenoalkyl group Choice That at least one of an aryl group substituted group, or to represent a heterocyclic group. L represents a linking group, and M ₁ and M ₂ represent a hydrogen atom or a cation. m is 0
Represents an integer of 5 or more, and n represents an integer of 1 or more and 3 or less. However, when m is 0, and when m is 1 and R ₁ is -O
In the case of H, L is a halogen atom, acyloxy group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group, formyl group, aryloxycarbonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfonylamino group, sulfamoyl group , Amino group, sulfonyl group, sulfinyl group,
Represents a linking group substituted with one or more and three or less groups selected from a sulfonyloxy group, a ureido group, a silyl group, a mercapto group, a hydroxy group, a nitroso group, a sulfo group, a phosphate group, and a heterocyclic group. . ] 3. The photothermographic material according to claim 2, wherein the photothermographic material contains at least one compound selected from formulas (A) to (C). 4. The photothermographic material according to claim 1, wherein the photosensitive layer or the non-photosensitive layer on the side of the photosensitive layer viewed from the support contains a compound of the formula [H]. . Embedded image [In the formula, A is an aliphatic group which may have a substituent,
Aromatic group, a -G ₀ -D ₀ group or heterocyclic group, B represents a blocking group, A _1, A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group Represents G ₀ is a -CO- group, a -COCO- group, -C
S-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -SO
₂ - group or _{-P (O) (G 1 D} 1) - represents a group, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group, D ₁ Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. Represents a group. ] 5. A method according to claim 1, wherein the exposure is performed by a laser scanning exposing machine in which the angle between the exposed surface of the photothermographic material and the scanning laser beam does not become substantially perpendicular. Image recording method. 6. An image recording method, wherein an image is recorded on a photothermographic material according to claim 1 or 4 by using a laser scanning exposing device in which a scanning laser beam is a vertical multi-scan laser beam. 7. An image forming method, wherein the photothermographic material according to claim 1 or 4 is heat-developed in a state containing 40 to 4500 ppm of a solvent.