JPH11242304A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain such a heat developable photosensitive material that a sample after developed causes no increase in the fog with time, to provide a heat developable photosensitive material for a laser imaging device which shows good raw preservability of the photosensitive material, and to provide a heat developable photosensitive material for a output film of an image setter which shows high contrast, high sensitivity, low fog and good raw preservability of the photosensitive material. SOLUTION: This heat developable photosensitive material contains org. silver salts, binder, photosensitive silver halides and at least one kind of compd. expressed by the formula on a supporting body. In the formula, X1 , X2 are each halogen atom, Y is a bivalent connecting group, A is a hydrogen atom, halogen atom or other electron withdrawing groups, (m) is an integer of 1 to 4, Q is a nitrogen-contg. Heterocyclic group having a betaine structure as a partial structure, and (n) is an integer of 0 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material having reduced fog, reduced sensitivity, and improved raw storability without deterioration of image storability.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed in, for example, U.S. Pat.
No. 4, No. 3457075 and D.C. Morgan
an) and B. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials) Neblette
Eighth Edition, Sturge, V.E. Wallworth (Wa
lworth); Edited by Shepp, page 2, 196
9 years).

In such a photothermographic material, a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a reducing agent are usually dispersed in an (organic) binder matrix. It is contained in a state.

A photothermographic material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, oxidation between a silver source (functioning as an oxidizing agent) and a reducing agent which can be reduced. Generates silver through a reduction reaction. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure.
The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which is symmetrical with the unexposed areas, resulting in the formation of an image. An antifoggant for controlling the fogging of the image is used in the photosensitive material as necessary.

[0005] The most effective method as a conventional antifogging technique has been a method using a mercury compound as an antifoggant.

The use of mercury compounds as antifoggants in photosensitive materials is described, for example, in US Pat. No. 358.
No. 9903. However, mercury compounds are environmentally unfavorable, and the development of non-mercury antifoggants has been desired.

As the non-mercury antifoggant, various polyhalogen compounds have been disclosed (for example, US Pat. Nos. 3,874,946, 4,756,999, 5,340,712, EP 605981A1, and 622666A1). 631176A1, No. 5
4-165, JP-A-7-2781).

However, these compounds have problems in that the effect of preventing fogging is low and the color tone of silver is deteriorated.

Further, those having a high anti-fogging effect have problems such as lowering of sensitivity, and need to be improved.

[0010] Further, when exposed and developed after aging under forced conditions of humidification and heating in the form of laminated photosensitive materials, there is a problem that fog in unexposed areas rises. The development of was desired.

As a method for solving these problems, Japanese Patent Application Laid-Open No. 9-16
No. 0164, No. 9-244178, No. 9-258367, No. 9-265150,
JP-A-9-281640 and JP-A-9-319022 disclose polyhalogen compounds in which the above disadvantages are improved.

However, in particular, these photothermographic materials for use in medical laser imagers or photothermographic materials for output of printing imagesetters containing a high contrast agent and having an oscillation wavelength of 600 to 800 nm are used. When the compound is applied, the above-mentioned drawbacks are considerably improved, but there is a drawback that the image-preserved storability of the image is poor such that the developed sample fogs with time.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photothermographic material in which a developed sample does not cause fog to rise over time. To provide a photothermographic material for a laser imager having good raw preservability of a material, and for an image setter output film having high hardness, high sensitivity, low fog, and good raw preservability of a photosensitive material. An object of the present invention is to provide a photothermographic material.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. The first invention is to provide an organic silver salt on a support. And a binder, a photosensitive silver halide, and at least one compound represented by the following general formula 1.

[0015]

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[In the formula, X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. m represents an integer of 1 or more and 4 or less. Q represents a nitrogen-containing heterocyclic group having a betaine structure as a partial structure. n represents an integer of 0 or more and 3 or less. ]

According to a second aspect of the present invention, there is provided a photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula (2). It is.

[0018]

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Wherein X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in formula 1. Q represents a nitrogen-containing heterocyclic group having a quaternary ammonium nitrogen atom in the ring and having a counter anion as another molecule. ]

According to a third aspect of the present invention, there is provided a photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula (3). It is.

[0021]

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Wherein X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in formula 1. Q has two benzene rings
Represents a pyridine ring condensed in one or more and four or less. ]

According to a fourth aspect of the present invention, there is provided a photothermographic material comprising a support and at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula (4). It is.

[0024]

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Wherein X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in formula 1. Q represents an isoquinoline ring. ]

According to a fifth aspect of the present invention, there is provided a photothermographic material comprising a support containing at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula (5). It is.

[0027]

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[Wherein X₁, X_Two, Y, A, m and n are one
It has the same meaning as that described in the general formula 1. Where X ₁, X_Twoas well as
A cannot be a bromine atom at the same time. Q is a quinoline ring
Represents ]

In a preferred embodiment of the first to fifth aspects of the present invention, the photothermographic material contains a hydrazine compound.

Another preferred embodiment of the invention is a photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support. The photosensitive layer contains at least one kind of the compound represented by the general formula 1 according to claim 1, and at least a photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide is provided on a support. In a photothermographic material having one layer, the photosensitive layer contains at least one compound represented by the formula (2) according to claim 2, and an organic silver salt, a binder and a photosensitive halogen are provided on a support. A photothermographic material having at least one photosensitive layer containing silver halide, wherein the photosensitive layer is a photosensitive layer.
And a photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder, and a photosensitive silver halide on a support. Wherein the photosensitive layer comprises at least one of the compounds represented by the general formula 4 according to claim 4.
The photothermographic material according to claim 5, wherein the photothermographic material has at least one photosensitive layer containing an organic silver salt, a binder and photosensitive silver halide on a support. A photothermographic material comprising at least one compound represented by the formula (5):

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by the general formula 1 used in the first invention will be described in detail.

The halogen atom represented by X ₁ and X ₂ is
A fluorine atom, a chlorine atom, a bromine atom and an iodine atom which may be the same or different from each other, preferably a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom and a bromine atom, particularly preferably bromine Is an atom.

Y represents a divalent linking group, specifically, -S
_{O 2 -, -SO-, -CO-,} -N (R 11) -SO 2 -, - N (R 11) -CO-, -
N (R ₁₁ ) -COO-, -COCO-, -COO-, -OCO-, -OCOO-, -S
_{CO-, -SCOO-, -C (Z 1} ) (Z 2) -, represents an alkylene, arylene, a divalent hetero ring or a divalent linking group formed of these in any combination.

Preferred as Y are -SO _2- , -SO- and -C
O- is more preferable, and -SO _2- is more preferable.

R ₁₁ represents a hydrogen atom or an alkyl group,
Preferably it is a hydrogen atom.

Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but Z ₁ and Z ₂ are not hydrogen atoms at the same time.

Preferred as the electron-withdrawing group are those having a Hammett's substituent constant σp value of 0.01 or more;
More preferably, the substituent is 0.1 or more.

With respect to Hammett's substituent constant, see Journa
l of Medicinal Chemistry, 1973, Vol.16, No.11,1207-12
16 mag can be referred to.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σ
p value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl ( σp value: 0.33), trifluoromethyl (σ
p value: 0.54)), cyano group (σp value: 0.66),
Nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (eg, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value) Value: 0.5
0), benzoyl (σp value: 0.43)), ethynyl group (σp value: 0.09), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxy) Carbonyl (σp
Value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57).

Preferred as Z ₁ and Z ₂ are a halogen atom, a cyano group or a nitro group, and among the halogen atoms, preferred are a chlorine atom, a bromine atom and an iodine atom, and more preferred are a chlorine atom, A bromine atom is particularly preferred.

A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. The electron-withdrawing group represented by A is preferably a compound having a Hammett's substituent constant σp value of 0.01.
The above substituents are more preferable, and the σp value is more preferably 0.1.
These are the above substituents.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06) and a chlorine atom (σp value
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.29) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), ethynyl group (σp value
Value: 0.09), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp
Value: 0.45), phenoxycarbonyl (σp value: 0.
45)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57) and the like.

A is preferably an electron-withdrawing group,
More preferred are a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group, and particularly preferred is a halogen atom. Among the halogen atoms, preferred are chlorine atoms,
A bromine atom and an iodine atom are preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is particularly preferable.

The nitrogen-containing heterocyclic group having a betaine structure represented by Q as a partial structure includes an N-oxide structure, an N-imine structure, or an alkyl, aryl, or heterocyclic group having an anionic group. Examples include a nitrogen-containing heterocyclic group having a quaternary nitrogen atom as a partial structure. Preferred are nitrogen-containing heterocyclic groups having an N-oxide structure as a partial structure. Preferred as the nitrogen-containing hetero ring is an aromatic nitrogen-containing hetero ring,
Specifically, pyrrole, imidazole, pyrazole, pyridine, pyrazine, 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. Among them, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline and pteridine are preferable, and pyridine, quinoline and isoquinoline are more preferable.

The nitrogen-containing heterocyclic group having a betaine structure represented by Q as a partial structure may have a substituent or may be condensed with another ring.

M represents an integer of 1 or more and 4 or less, preferably 1 or 2, and more preferably 1. n represents an integer of 0 or more and 3 or less, and is preferably 1.

Next, the compound represented by the general formula 2 used in the second invention will be described in detail. Where X ₁ , X ₂ ,
Y, A, m, and n have the same meanings as those described in Formula 1. Q represents a nitrogen-containing heterocyclic group having a quaternary ammonium nitrogen atom in the ring and having a counter anion as another molecule, and is preferably a quaternary ammonium nitrogen substituted with an alkyl group, an aryl group, or a heterocyclic group. Represents a nitrogen-containing aromatic hetero ring having an atom in the ring.

The counter anion of another molecule is preferably a halogen anion, a carboxylate anion or a sulfonate anion.

Specific examples of the nitrogen-containing aromatic hetero ring include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, tetrazine, pentazine, indole, indazole, purine, thiadiazole, oxadiazole,
Quinoline, isoquinoline, phthalazine, naphthyridine,
Quinoxaline, quinazoline, cinnoline, pteridine,
Examples include acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, and benzothiazole. Among them, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, naphthyridine, quinoxaline, quinazoline, cinnoline and pteridine are preferable, and pyridine, quinoline and isoquinoline are more preferable.

The nitrogen-containing heterocyclic group having a quaternary ammonium nitrogen atom represented by Q in the ring and having a counter anion as another molecule may have a substituent and can be condensed with another ring. It may be.

Next, the compound represented by Formula 3 used in the third invention will be described in detail.

In the formula, X ₁ , X ₂ , Y, A, m, and n have the same meanings as those described in Formula 1. Q represents a pyridine ring in which 2 to 4 benzene rings are condensed, and specifically, acridine, phenanthridine, naphthopyridine,
9b-azaphenalene and the like. Preferably it is phenanthridine. These rings may be substituted with a substituent.

Next, the compound represented by the general formula 4 used in the fourth invention will be described in detail. Wherein X ₁ , X ₂ ,
Y, A, m, and n have the same meanings as those described in Formula 1. Q represents an isoquinoline ring, and may have a substituent on the ring.

Next, the compound represented by the formula 5 used in the fifth invention will be described in detail. Wherein X ₁ , X ₂ ,
Y, A, m, and n have the same meanings as those described in Formula 1. However, X ₁ , X ₂ and A are not simultaneously a bromine atom. In the general formula 5, X ₁ and X ₂ are preferable.
Is a bromine atom, and A is a chlorine atom. Q
Represents a quinoline ring, but may have a substituent on the ring.

In the compounds represented by the above general formulas 1 to 5,
Examples of the substituent which each ring group represented by Q may have include, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 carbon atom.
-8, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n
-Hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms)
2, particularly preferably having 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl), and amino. A group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 10 carbon atoms, particularly preferably having 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, and dibenzylamino); An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, such as methoxy, ethoxy, and butoxy), and an aryloxy group (preferably Has 6 to 2 carbon atoms
It has 0, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl,
Benzoyl, formyl, pivaloyl and the like can be mentioned. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
-20, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms.
2, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), and an alkoxycarbonylamino group. (Preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethyl sulfamoyl 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). An alkylthio group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio and the like. ), An arylthio group (preferably having 6 carbon atoms)
-20, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms, such as phenylthio. ), A sulfinyl group (preferably having 1 to 1 carbon atoms)
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom)
To 16, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), Phosphoric amide group (preferably having 1 to carbon atoms)
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoric acid amide,
And phenylphosphoramide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) )). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

Hereinafter, specific examples of the compounds represented by Formulas 1 to 5 will be shown, but the present invention is not limited thereto.

[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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The compounds represented by the general formulas 1 to 5 of the present invention are described, for example, in JP-A-54-165 and JP-A-6-3406.
Nos. 11, 7-2781, 7-5621, JP-B-7-119953, U.S. Pat. Nos. 5,369,000, 5,374,514, 5,460,938 and 546473.
7, European Patent Nos. 605981 and 631176,
New Laboratory Chemistry Course (Maruzen) 14-IV, Chapter 9, 9-3, 9-
4, U.S. Pat. No. 3,874,946, European Patent Publication No. 605
No. 98, New Laboratory Chemistry Course (Maruzen) 14-IV, Chapter 9 9-
3, 9-4, etc., can be synthesized according to the method described in New Experimental Chemistry Course (Maruzen) 14-I, Chapter 2, etc.

Specific examples of the synthesis of the compounds represented by the general formulas 1 to 5 are shown below.

Synthesis Example 1 Synthesis of Compound 1-3 Synthesis of 2-carboxymethylthiopyridine N-oxide 18.1 g of 2-mercaptopyridine N-oxide (0.1 g)
13 mol), 13.6 g (0.14 mol) of chloroacetic acid and 100 ml of ethanol were stirred at room temperature, and 5.6 g (0.14 mol) of sodium hydroxide / water 3
0 ml of the aqueous solution was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and 5.6 g (0.14 mol) of sodium hydroxide was further added.
An aqueous solution of 30 ml of water / water was slowly added dropwise. 3 at 50 ° C
After stirring for an hour, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added for neutralization. The obtained crystals were collected by filtration and recrystallized from methanol to give 19.7 g of 2-carboxymethylthiopyridine N-oxide.
(0.10 mol). Yield 76% Synthesis of 2-tribromomethylsulfonylpyridine N-oxide (Compound 1-3) Synthesis of sodium hydroxide 16.4 g (0.41 mol) / water 50
While stirring 0 ml at 0-5 ° C., 10.4 ml of bromine was slowly added dropwise. Further, the 2-carboxymethylthiopyridine N obtained by the above reaction
An aqueous solution of 8.5 g (0.043 mol) of sodium oxide, 7.2 g (0.0857 mol) of sodium hydrogencarbonate and 150 ml of water was slowly added dropwise so that the internal temperature did not exceed 5 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and then recrystallized with ethanol to obtain 9.4 g of a white solid (Compound 1-3).
(0.023 mol). 53% yield

Synthesis Example 2 Synthesis of compound 2-1 Synthesis of 2-carboxymethylthiopyridine 22.2 g (0.20 mol) of 2-mercaptopyridine
While stirring 27.0 g (0.22 mol) of chloroacetic acid and 300 ml of ethanol at room temperature, an aqueous solution of 8.8 g (0.22 mol) of sodium hydroxide / 15 ml of water was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and an aqueous solution of 8.8 g (0.22 mol) of sodium hydroxide / 15 ml of water was slowly added dropwise. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture. The obtained crystals are collected by filtration,
By recrystallization from methanol, 25.0 g (0.148 mol) of 2-carboxymethylthiopyridine was obtained. Synthesis of 2-tribromomethylsulfonylpyridine 74% Yield 22.5 g (0.56 mol) of sodium hydroxide / l liter of water were stirred at 0-5 ° C.
7 ml was slowly dropped. Further, 11.9 g of 2-carboxymethylthiopyridine obtained by the above reaction was obtained.
(0.0706 mol), 7.2 g of sodium hydrogen carbonate
(0.0857 mol) and 150 ml of water were slowly added dropwise so that the internal temperature did not exceed 5 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized with ethanol to obtain 12.3 g (0.0312 mol) of 2-tribromomethylsulfonylpyridine as a white solid. 43% yield Synthesis of N-ethyl-2-tribromomethylsulfonylpyridine-p-toluenesulfonate (Compound 2-1) 2-Tribromomethylsulfonylpyridine 1 obtained
2.3 g (0.0312 mol) was dissolved in 300 ml of acetone, and 8.0 g of ethyl p-toluenesulfonate (0.
04 mol) and heated under reflux for 8 hours. The solvent was distilled off, and the residue was recrystallized from ethanol (compound 2-1).
Was obtained 14.8 g. 80% yield

Synthesis Example 3 Synthesis of Compound 3-1 Synthesis of 2-carboxymethylthiophenanthridine 2-mercaptophenanthridine obtained from phenanthridine via phenanthridine N-oxide and 2-chlorophenanthridine according to a known method 2
1.1 g (0.10 mol), 13.5 g of chloroacetic acid
(0.11 mol) and 300 ml of ethanol were stirred at room temperature.
An aqueous solution (11 mol) / water (10 ml) was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C. and further 4.4 g of sodium hydroxide.
An aqueous solution of (0.11 mol) / 10 ml of water was slowly dropped. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture. The obtained crystals were collected by filtration and recrystallized from methanol to obtain 21.5 g (0.08 mol) of 2-carboxymethylthiophenanthridine. Yield 80% Synthesis of 2-tribromomethylsulfonylphenanthridine (Compound 3-1) 22.5 g of sodium hydroxide (0.
13.7 ml of bromine was slowly added dropwise while stirring 1 liter of water (56 mol) / water at 0-5 ° C. Further, 19.9 g (0.0706 mol) of 2-carboxymethylthiophenanthridine obtained in the above reaction,
An aqueous solution of 7.2 g (0.0857 mol) of sodium bicarbonate and 150 ml of water was slowly added dropwise so that the internal temperature did not exceed 5 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized from ethanol to obtain 14.3 g (0.0289 mol) of a white solid (Compound 3-1). Yield 41
%

Synthesis Example 4 Synthesis of Compound 4-1 Synthesis of 1-carboxymethylthioisoquinoline According to a known method. 16.1 g (0.10 g) of 1-mercaptoisoquinoline obtained from isoquinoline via isoquinoline N-oxide and 1-chloroisoquinoline
Mol), 13.5 g (0.11 mol) of chloroacetic acid and 300 ml of ethanol were stirred at room temperature, and 4.4 g (0.11 mol) of sodium hydroxide / 10 ml of water was added.
Was added dropwise. After stirring for 20 minutes, heat to 50 ° C.
Further, 4.4 g (0.22 mol) of sodium hydroxide / water 1
0 ml of the aqueous solution was slowly added dropwise. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture. The obtained crystals were collected by filtration and recrystallized from methanol to obtain 21.5 g (0.098 mol) of 1-carboxymethylthioisoquinoline. Yield 98% Synthesis of 1-tribromomethylsulfonylisoquinoline (compound 4-1) While stirring 22.5 g (0.56 mol) of sodium hydroxide / l liter of water at 0-5 ° C, bromine 13 was added. .
7 ml was slowly dropped. Further, 1-carboxymethylthioisoquinoline obtained by the above reaction.
5 g (0.0706 mol), sodium hydrogen carbonate 7.2
g (0.0857 mol) and 150 ml of water were slowly added dropwise so that the internal temperature did not exceed 5 ° C.
After completion of the dropwise addition, the temperature was raised to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized with ethanol to give 17.9 g (0.04 g) of a white solid (Compound 4-1).
03 mol). 57% yield

Synthesis Example 5 Synthesis of Compound 5-1 Synthesis of 2-carboxymethylthioquinoline 16.1 g (0.10 mol) of 2-mercaptoquinoline,
While stirring 13.5 g (0.11 mol) of chloroacetic acid and 300 ml of ethanol at room temperature, an aqueous solution of 4.4 g (0.11 mol) of sodium hydroxide / 10 ml of water was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and an aqueous solution of 4.4 g (0.22 mol) of sodium hydroxide / 10 ml of water was slowly added dropwise. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture. The obtained crystals are collected by filtration,
By recrystallization from methanol, 19.5 g (0.089 mol) of 2-carboxymethylthioquinoline was obtained. Yield 89% Synthesis of 2-dibromomethylsulfoquinoline 14.0 g (0.35 mol) of sodium hydroxide / 50 of water
8.7 ml of bromine was slowly added dropwise while stirring 0 ml at 0-5 ° C. Furthermore, 2-carboxymethylthioquinoline 1 obtained by the above reaction
An aqueous solution of 5.5 g (0.0706 mol), 7.2 g (0.0857 mol) of sodium hydrogen carbonate and 150 ml of water was slowly added dropwise so that the internal temperature did not exceed 5 ° C. Immediately after completion of the dropping, the temperature was raised to 30 ° C.
Stirred for hours. Then, it was cooled to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized from ethanol to obtain 15.9 g (0.0457 mol) of 2-dibromomethylsulfoquinoline as a white solid. Yield 6
Synthesis of 5% 2-dibromochloromethylsulfonylquinoline (compound 5-1) 10 g of 2-dibromomethylsulfoquinoline (0.028
7 mol) was dissolved in 500 ml of methanol, and 160 ml of a 5% aqueous solution of hypochlorous acid was slowly added dropwise while keeping the internal temperature at about 5 ° C. After 4 hours, the reaction solution was diluted three times with water, and the precipitated crystals were separated by filtration. By recrystallizing with ethanol, 6.9 g (0.01%) of a white solid (Compound 5-1) was obtained.
55 mol). 54% yield

The amount of the compound represented by the general formulas 1 to 5 of the present invention is not particularly limited, but may be from 10 ^-4 mol to 1 mol / l.
The range of Ag mole is preferred, especially 10 ^-3 mole to 0.3 mole.
The mole / Ag mole range is more preferred.

The compounds represented by formulas (1) to (5) of the present invention are preferably added after being dissolved in an organic solvent.

The locations where the compounds represented by formulas 1 to 5 of the present invention are added can be varied depending on the layer constitution of the light-sensitive material, and various embodiments will be described below.

As a typical embodiment, in a photothermographic material having at least one photosensitive layer on a support and a layer adjacent to the photosensitive layer, a photosensitive silver halide,
An embodiment containing an organic silver salt and a binder, and further containing at least one compound represented by the general formulas 1 to 5, wherein the photosensitive layer contains a photosensitive silver halide, an organic silver salt and a binder, and the adjacent layer contains An embodiment containing at least one compound represented by the general formulas 1 to 5, a photosensitive layer containing a photosensitive silver halide and a binder, and further containing at least one compound represented by the general formulas 1 to 5; An embodiment in which an adjacent layer contains an organic silver salt, the photosensitive layer contains a photosensitive silver halide and a binder, the adjacent layer contains an organic silver salt, and at least one of the compounds represented by formulas 1 to 3 Embodiments containing species are included. Preferred in the present invention is
It is an aspect of.

In the present invention, the silver halide grains of the photosensitive silver halide function as an optical sensor.
In order to suppress white turbidity after image formation and obtain good image quality, it is preferable that the average particle size is small, and the preferable average particle size is 0.20 μm or less, more preferably 0.03 μm to 0.15 μm. , Especially 0.03
μm to 0.11 μm is preferred. Here, the average grain size refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide grains are preferably monodisperse grains. The monodisperse particles referred to herein are particles having a degree of monodispersity of 40% or less, more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.
% Or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100

The shape of the silver halide grains is not particularly limited, but it is preferable that the ratio occupied by the Miller index [100] plane is high, and this ratio is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is based on the adsorption dependence of the [111] plane and the [100] plane in the adsorption of the sensitizing dye.
It can be determined by T. Tani, J. Imaging Sci., 29, 165 (1985).

The above-mentioned monodisperse particles have an average particle size of 0.1 μm.
The following is preferable, and more preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm.

Another preferred form of silver halide grains is tabular grains. Here, the tabular grains are:
The aspect ratio (= r / h) is 3 or more when the square root of the projected area of the particle is r μm and the thickness in the vertical direction is h μm. Among them, those having an aspect ratio of 3 or more and 50 or less are preferable.

The average particle diameter of the tabular grains is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm.
μm is more preferred. These are disclosed in U.S. Pat.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained. In the present invention, when these tabular grains are used, the sharpness of an image is further improved.

The composition of silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is Chimie et Physique Photographiq by P. Glafkides.
ue (Paul Montel, 1967), Photograph by GFDuffin
ic Emulsion Chemistry (The Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be prepared by the method described in Emulsion (The Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used. In order to form a solution by reacting a soluble silver salt and a soluble halide, a one-sided mixing method, a double-sided mixing method, a combination thereof and the like are used. Either may be used.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source.

The silver halide may be prepared by converting part or all of the silver in the organic silver salt to silver halide by reacting the organic silver salt with a halogen ion,
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

In general, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the weight of the organic silver salt.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to VIB, VIIB, VIII or IB belonging to a transition metal of the periodic table. Examples of the above-mentioned metals include Cr and W (the above-mentioned VIB group):
Re (VIIB group): Fe, Co, Ni, Ru, Rh, P
d, Os, Ir, Pt (more than VIII group): Cu and Au (more than IB group) are preferable. Among them, when they are used for a photosensitive material for printing plate making, they are selected from Rh, Re, Ru, Ir, and Os. preferable.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from Group VIB, VIIB, VIII and IB of the Periodic Table of the Elements, L is a bridging ligand, m is 0,-
Represents 1, -2 or -3.

Specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and alcohols. Each ligand of
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re) and osmium (Os).

The following are specific examples of the transition metal coordination complex.

[0096] _{^{1: [RhCl 6] 3- 2}} : [RuCl 6] 3- 3: [ReCl 6] 3- 4: [RuBr 6] 3- 5: [OsCl 6] 3- 6: [CrCl 6] 4 _{^{- 7: [Ru (NO)}} Cl 5] 2- 8: [RuBr 4 (H 2 O)] 2- 9: [Ru (NO) (H 2 O) Cl 4] - 10: [RhCl 5 (H 2 _{^{O)] 2- 11: [Re}} (NO) Cl 5] 2- 12: [Re (NO) CN 5] 2- 13: [Re (NO) ClCN 4] 2- 14: [Rh (NO) 2 Cl _{^{4] - 15: [Rh (}} NO) (H 2 O) Cl 4] - 16: [Ru (NO) CN 5] 2- 17: [Fe (CN) 6] 3- 18: [Rh (NS) Cl _{^{5] 2- 19: [Os (}} NO) Cl 5] 2- 20: [Cr (NO) Cl 5] 2- _{^{1: [Re (NO) Cl}} 5] - 22: [Os (NS) Cl 4 (TeCN)] 2- 23: [Ru (NS) Cl 5] 2- 24: [Re (NS) Cl 4 (SeCN) _{^{] 2- 25: [Os (NS}} ) Cl (SCN) 4] 2- 26: [Ir (NO) Cl 5] 2-

These metal ions or complex ions may be used alone or in combination of two or more of the same and different metals.

The content of these metal ions or complex ions is generally in the range of 1 to 1 mol per mol of silver halide.
^X10-9 to ^1x10-2 mol is appropriate, and preferably ^1x10-8 to ^1x10-4 mol.

The compound providing these metal ions or complex ions is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening,
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation and placed, or a silver salt solution and a halide solution are used. When mixed simultaneously, a third aqueous solution is added to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The organic silver salt used in the present invention is a reducible silver source. Silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (preferably having 10 to 30 carbon atoms). , An aliphatic carboxylic acid having 15 to 25 carbon atoms, and a nitrogen-containing heterocyclic ring are more preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts include Research Disclosure No. 170
29 and 29996, and include: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver (For example, 1
-(3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.);
Silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) , 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (e.g., 3
-(2-carboxyethyl) -4-hydroxymethyl-
4- (thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio- Complexes or salts of silver and a nitrogen acid selected from 1,2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. The preferred silver source is silver behenate.

The addition amount of the organic silver salt was 3 g / m
^The content is preferably ² or less, more preferably 2 g / m ² or less.

The organic silver salt can be obtained by mixing a water-soluble silver compound and a compound that forms a complex with silver. The organic silver salt is described in Japanese Patent Application Laid-Open No. 9-127643, a forward mixing method, a reverse mixing method, and a simultaneous mixing method. The controlled double jet method is preferably used.

In the present invention, the organic silver salt preferably has an average particle size of 1 μm or less and is 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 0.01 μm to 0.8 μm, particularly 0.05 μm.
m to 0.5 μm is preferred. The term “monodisperse” has the same meaning as in the case of silver halide grains, and the preferred monodispersity is 1%.
３０30%. In the present invention, the organic silver salt is more preferably monodisperse particles having an average particle size of 1 μm or less,
By setting it in this range, an image with high density can be obtained.

In the present invention, in order to obtain a predetermined optical transmission density, the total amount of silver halide and organic silver salt is preferably from 0.3 g to 1.5 g per m ² in terms of silver. preferable. By setting it in this range, a high-contrast image can be obtained.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research D
No. 17029 and 29996, and include the following:

Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (eg, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

The hindered phenols include compounds represented by the following general formula (A).

[0110]

Embedded image

In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group _(e.g., -C ₄ H _9, 2,4,4-
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, t-
Butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0113]

Embedded image

[0114]

Embedded image

The amount of the reducing agent such as the compound represented by the formula (A) is preferably 1 × per mole of silver.
10 ⁻² to 10 mol, particularly preferably 1 × 10 ⁻² to
1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic,
Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly ( Ester), poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). These may be hydrophilic or non-hydrophilic.

[0117] In the present invention, the binder of the photosensitive layer is preferably 1.5~6g / ^{m 2,} more preferably from 1.7~5g / ^{m 2.} 1.5g / m
^If it is less than ² , the density of the unexposed portion is significantly increased, and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to improve the dimensional repeatability of the present invention, a polymer matting agent or an inorganic matting agent is added to all binders on the emulsion layer side. , 0.5 to 10 by weight
%. 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, Swiss Patent No. 330,1
No. 58, etc., French Patent No. 1,296,99
Glass powder described in No. 5, etc., British Patent No. 1,173,18
Alkaline earth metals or carbonates such as cadmium and zinc described in No. 1 and the like can be used as a matting agent.
Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol as described,
Polystyrene or polymethacrylate described in Swiss Patent No. 330,158 and the like, US Pat. No. 3,079,
Organic matting agents such as polyacrylonitrile described in US Pat. No. 257 and the like and polycarbonate described in US Pat. No. 3,022,169 and 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 has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the coefficient of variation 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, but is preferably used in order to achieve the object of the present invention. Is a constituent layer other than the photosensitive layer, and is more preferably the outermost layer as viewed from the support.

The method for adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying 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.

In the present invention, when the photothermographic material is a photothermographic material for output of a printing imagesetter having an oscillation wavelength of 600 to 800 nm, the hydrazine compound may be contained in the photothermographic material. preferable.

The preferred hydrazine compound used in the present invention is a compound represented by the following general formula [H].

[0126]

Embedded image

[In the formula, A ₀ represents an aliphatic group, an aromatic group, a -G ₀ -D ₀ group or a heterocyclic group which may have a substituent, B ₀ represents a blocking group, and A ₁ , a ₂ are both hydrogen atoms, or one is 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— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) -group, wherein G ₁ is a mere bond, -O- group, -S
— Or a —N (D ₁ ) — group, wherein 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 or a heterocyclic group. Represents an amino group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. ]

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl group, cyclohexyl group, benzyl group, which are further substituted with suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, Ureido group).

In the general formula [H], the aromatic group represented by A ₀ 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. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, A quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring; particularly preferred as A ₀ are an aryl group and a heterocyclic group; and the aromatic and heterocyclic groups of A ₀ have a substituent. And particularly preferred groups include pKa7 to
Examples of the substituent having an acidic group of 11 include a sulfonamide group, a hydroxyl group, and a mercapto group.

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

G ₀ represents a -CO- group, a -COCO- group,-
CS- group, -C (= NG ₁ D ₁ )-group, -SO- group,-
Represents an SO ₂ — group or a —P (O) (G ₁ D ₁ ) — group, and preferable 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 ₀ preferably contains at least one diffusion-resistant group or 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 accelerating group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, and special groups. 64-9
No. 0439.

[0135] In formula (H), _{B 0} represents a blocking group, preferably a _-G 0 -D _0, is synonymous with _-G 0 -D ₀ group in _{A 0, A 0} and _{B 0} are It 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 formula [H] are shown below, but the present invention is not limited thereto.

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

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

RESEARCHDISCLOSURE Item 23516 (11/1983
, P. 346) and the references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,269,929,
4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4,560,638, and 4 No. 4,686,167, 4,912,016, 4,988,604, 4,994,365, 5,041,355, 5,104,769, British Patent No. 2 , 011,391B, EP 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, compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, 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 (I) 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 7
Compounds represented by general formula (H) and general formula (Ha) described in JP-A-104426, specifically, from page 8 to
Compounds described in Compounds H-1 to H-44 on page 15 can be used.

The layer to which the hydrazine derivative is added is a photosensitive layer and / or a constituent layer adjacent to the photosensitive layer. The particle size of the added amount of silver halide grains, the halogen composition, the degree of chemical sensitization, kind of the reducing agent, although the optimum amount is not uniform such as type of inhibitor per mole of silver halide ^10-6 It is preferably in the range of about 10 mol to 10 ^-1 mol, particularly 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 light-sensitive material of the present invention, a nucleation promoting agent such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative can be added in combination with the hydrazine compound.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated on the photosensitive silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support, and only the photosensitive layer may be formed on the support. It is preferable to form at least one non-photosensitive layer. A filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. . As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred.
The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

It is preferable to add a color tone agent to the photothermographic material of the present invention. An example of a suitable toning agent is Resea
rc Disclosure No. 17029, which includes:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2 , 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, isothiuronium (isoth
uronium) derivatives and certain photobleaching combinations (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 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 + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used. Useful sensitizing dyes for use in the present invention are, for example, RESEARCH DISCLO
SURE Item 17643 IV-A (1978
December, p. 23), Item 1831X (1)
August 978, p. 437) or in the literature cited. 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, A) Japanese Patent Application Laid-Open No. 60-162247 and Japanese Patent Application Laid-Open No. 2-486
No. 53, U.S. Pat. No. 2,161,331, West German Patent 93
No. 6,071, and simple merocyanines described in Japanese Patent Application No. 3-189532, and B) helium-neon laser light sources are disclosed in JP-A-50-62425 and JP-A-54-18.
No. 726, No. 59-102229, trinuclear cyanine dyes, merocyanines described in Japanese Patent Application No. 6-103272, C) LED light source and red semiconductor laser are disclosed in JP-B-48-42172. Id. 51-9609
And JP-A-55-39818.
Thiacarbocyanines described in JP-A-2-105135, and D) Tricarbocyanines described in JP-A-59-19032 and JP-A-60-80841 for an infrared semiconductor laser light source. Kind, JP-A-59-19
2242 and JP-A-3-67242.
a), dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIb) and the like are advantageously selected. Further, the wavelength of the infrared laser light source is 750 nm or more,
More preferably, in the case where the wavelength is 800 nm or more, in order to cope with a laser in such a wavelength range, Japanese Patent Laid-Open No.
182639, 5-341432, Tokuhei 6-523
Sensitizing dyes described in US Pat. Nos. 87, 3-10931, US Pat. No. 5,441,866 and JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly 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.

Exposure of the photothermographic material of the present invention is performed using an Ar laser (488 nm) and a He-Ne laser (633 n).
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 830 nm) and the like.

[0156]

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

Example 1 (Preparation of silver halide grains) In 900 ml of pure water, 7.5 g of gelatin and 10 mg of potassium bromide were dissolved, and the temperature was adjusted to 3
After adjusting the pH to 5 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and a controlled double jet while maintaining an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) at pAg 7.7. The method was added over 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added, and N
The pH was adjusted to 5 with aOH and the average particle size was 0.06.
Cubic silver iodobromide grains having a diameter of .mu.m, a coefficient of variation in projected diameter area of 8%, and a {100} face ratio of 86% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Thereafter, sensitizing dyes SD-1 and SD-2 were added in an amount of 5 × 10 −5 mol per mol of silver halide.
Thereafter, the temperature was raised to 60 ° C., 2 mg of sodium thiosulfate was added, the mixture was aged for 100 minutes, and then cooled to 38 ° C. to complete the chemical sensitization to obtain silver halide grains.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
10.6 g of behenic acid was put therein, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was sufficiently stirred.
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared beforehand were added with stirring while heating at 40 ° C. so that the silver content was 10 mol% with respect to behenic acid. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes,
The mixture was left for 1 hour with stirring. Polyvinyl butyral dissolved in ethyl acetate was added to this emulsion, stirred sufficiently, and allowed to stand to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (spherical) manufactured by Tosoh Corporation and 22 cc of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 cc of isopropyl alcohol were added, and the mixture was sufficiently stirred at a high speed at 35 ° C. and dispersed to complete the preparation of the organic fatty acid silver emulsion.

(Composition of photosensitive layer) A coating solution for a photosensitive layer was prepared as follows. As the solvent, methyl ethyl ketone, acetone, and methanol were appropriately used. Organic fatty acid silver emulsion 1.75 g (in silver) / m ² Pyridinium hydrobromide perbromide 1.5 × 10 ⁻⁴ mol / m ² Calcium bromide 1.8 × 10 ⁻⁴ mol / m ² 2- (4-chloro Benzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² Sensitizing dye-1 4.2 × 10 ⁻⁶ mol / m ² 2-mercaptobenzimidazole 3.2 × 10 ⁻³ mol / m ² General formula 1 To 5 compounds, comparative compound (Table 1) 6.0 × 10 ⁻⁴ mol / m ²

[0160]

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[0161]

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(Surface Protective Layer Composition) A surface protective layer coating solution was prepared as follows. Solvents include methyl ethyl ketone,
Acetone and methanol were used as appropriate. Cellulose acetate 4 g / m ² 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 4.8 × 10 ⁻³ mol / m ² Phthalazine 3.2 × 10 ⁻³ mol / m ² 4-methylphthalic acid 1.6 × 10 ⁻³ mol / m ² Tetrachlorophthalic acid 7.9 × 10 ⁻⁴ mol / m ² Tetrachlorophthalic anhydride 9.1 × 10 ⁻⁴ mol / m ² silicon dioxide (particle size 2 μm) 0.22 g / m ²

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows. Cellulose acetate 4 g / m ² Antihalation dye Dye D-2 0.06 g / m ² Dye D-3 0.018 g / m ² Polymethyl methacrylate (particle size 10 μm) 0.02 g / m ²

[0164]

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The coating solution having the above composition was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm and dried to obtain a coated sample.

[Evaluation of Sensitometry] The photothermographic material prepared above was processed into a half-cut size, and a 830 nm laser diode was exposed to a beam inclined by 13 ° from the vertical plane. Thereafter, using a heat drum, 120 ° C x 15
Second heat development processing. The fog value at that time was measured. Further, the sensitivity (reciprocal of the ratio of the exposure amount giving a density higher than fog by 1.0) was measured. Sample N in Table 1
o. When the sensitivity of 1 was set to 100, the sensitivity of each sample was evaluated by a relative value. Table 1 shows the results.

[Evaluation of Raw Storage Property]
After putting three coated samples in a closed container maintained at 5%, 5
Aged at 0 ° C. for 7 days (forced aging). The second sample in this and a sample for comparison with time (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for the evaluation of sensitometry, and the concentration of the fog portion was measured. Table 1 shows the results. (Increase in fog 1) = (fog during forced aging) − (fog during aging for comparison)

"Evaluation of Image Preservation" Two samples subjected to the same processing as in the sensitometry evaluation were subjected to the same processing at 25.degree.
% At 7% at 25 ° C and 55% for 7 days.
After exposure to natural light for one day, the density of both fog portions was measured. Table 1 shows the results. (Fog increase 2) = (Fog when exposed to natural light)
-(Fog when stored in shade)

[0169]

[Table 1]

From Table 1, it can be seen that the sample of the present invention has sufficient sensitivity, low fog, and good raw storage stability and image storage stability of the light-sensitive material.

Example 2 [Preparation of Subbed Photographic Support] <Preparation of PET Subbed Photographic Support> A commercially available biaxially stretched, heat-fixed PET film having a thickness of 100 μm and 8 w / m on both sides. Apply a corona discharge treatment for ² minutes, apply the following undercoating coating solution a-1 on one surface so as to have a dry film thickness of 0.8 μm, and dry to form an undercoating layer A-1. Was coated with the following undercoating coating solution b-1 so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

<< Undercoat Coating Solution b-1 >> Copolymer latex liquid of butyl acrylate (40% by weight) styrene (20% by weight) glycidyl acrylate (40% by weight) (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Make up to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 w / m ² · min is applied to the upper surface of the lower layer, and the lower layer upper layer coating solution a-2 described below is coated on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. Sublayer B as Layer A-2
-1 is coated with the following undercoating layer coating solution b-2 having a dry film thickness of 0.
Coating was performed as a subbing upper layer B-2 having an antistatic function so as to have a thickness of 8 μm.

<< Coating Solution for Subbing Upper Layer a-2 >> Gelatin 0.4 g / m^Two (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles (average particle size 3 μm) 0.1 g Finished to 1 liter with water.

<< Lower Coating Upper Layer Coating Solution b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol ( (Weight average molecular weight: 600) 6 g Finished to 1 liter with water.

[0177]

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[0178]

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(Preparation of Emulsion A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0.
g of the aqueous solution containing potassium bromide and potassium iodide at a molar ratio of (98/2) and rhodium chloride in an amount of 1 × 10 −4 mol per mol of silver and pAg of 7.7.
, And added over 10 minutes by a controlled double jet method. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the average particle size was 0.0.
Cubic silver iodobromide grains having a size of 6 μm, a variation coefficient of the projected diameter area of 8%, and a [100] face 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 to the emulsion to give a pH of 5.9 and a pAg of 7.5.
To obtain a silver halide emulsion. JP-A-9-12
No. 7643 According to the method of Example 1, silver behenate was prepared in the following manner.

Preparation of Na Behenate Solution 34 g of behenic acid was added to 340 ml of isopropanol for 65 days.
Dissolved at ° C. Next, while stirring, a 0.25N aqueous sodium hydroxide solution was added so as to have a pH of 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required.
Next, the aqueous sodium behenate solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

Preparation of silver behenate A 2.94M silver nitrate solution was added to a solution of 30 g of ossein gelatin dissolved in 750 ml of distilled water, and the silver potential was adjusted to 4%.
00 mV. To this, 374 ml of the above sodium behenate solution was added at a speed of 44.6 ml / min at a temperature of 78 ° C. by using a controlled double jet method, and simultaneously a 2.94 M silver nitrate aqueous solution was supplied with a silver potential of 400 mV.
It was added so that it became. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.
Mole. After the addition was completed, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration.

Preparation of Photosensitive Emulsion To this silver behenate dispersion, 0.01 mol of each of the above silver halide emulsions was added, and 100 g of a solution of polyvinyl acetate in n-butyl acetate (1.2 wt%) was gradually added with stirring. To form a floc of the dispersion, remove the water,
After two further water washes and removal of water, polyvinyl butyral (average molecular weight 3000) was used as a binder.
5wt% butyl acetate and isopropyl alcohol 1:
(2) After adding 60 g of the mixed solution with stirring, polyvinyl butyral (average molecular weight of 40) was added as a binder to the gel-like mixture of behenic acid and silver halide thus obtained.
00) and isopropyl alcohol.

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

Coating on back side: A liquid having the following composition was applied to a wet thickness of 80 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0186]

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Photosensitive layer surface side coating Photosensitive layer: A solution having the following composition was applied.
m ² , polyvinyl butyral as a binder.
It was applied so as to be ² g / m ² .

Emulsion A Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% DMF solution) 2 mg General formulas 1 to 3 and comparative compounds (Table 2) (2% acetone solution) 3 ml Phthalazone (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 13 ml Hardener H (1% methanol / DMF = 4: 1 solution) 2 ml

[0189]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied on each photosensitive layer so as to have a thickness of 00 μm.

Acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5 g monodisperse having an average particle size of 4 μm 1% (W / W) based on silica binder

"Evaluation of Sensitometry" The photothermographic material prepared above was exposed to xenon flash light having a light emission time of ^10-3 seconds through an interference filter having a peak at 633 nm. Then, using a heat drum 115
The film was subjected to a heat development treatment at 150 ° C. for 15 seconds. The reciprocal of the exposure amount giving a density of 3.0 was defined as the sensitivity, The relative sensitivity was shown with the sensitivity of 11 as 100. In the characteristic curves, the concentrations 0.1 and 1.
The gradient of the straight line connecting the points of No. 5 and the gradation (γ
₀₁₁₅ ). Table 2 shows the results.

[Evaluation of Raw Storage Property]
After putting three coated samples in a closed container maintained at 5%, 5
Aged at 0 ° C. for 7 days (forced aging). The second sample in this and a sample for comparison with time (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for the evaluation of sensitometry, and the concentration of the fog portion was measured. Table 2 shows the results. (Increase in fog 1) = (fog during forced aging) − (fog during aging for comparison)

"Evaluation of Image Preservation" Two samples subjected to the same processing as in the sensitometric evaluation were subjected to the measurement at 25.degree.
% At 7% at 25 ° C and 55% for 7 days.
After exposure to natural light for one day, the density of both fog portions was measured. Table 2 shows the results. (Fog increase 2) = (Fog when exposed to natural light)
-(Fog when stored in shade)

[0195]

[Table 2]

From Table 2, it can be seen that the sample of the present invention has sufficient sensitivity, high gamma, good contrast, low fog, and good raw storage stability and image storage of the photographic material. I understand.

[0197]

According to the present invention, it is possible to provide a photothermographic material which does not cause fogging of a developed sample over time, and has high sensitivity, low fog, and raw preservability of the photosensitive material. Providing a good photothermographic material for laser imagers, and providing a photothermographic material for an imagesetter output film with high contrast, high sensitivity, low fog, and good raw preservability of the photosensitive material can do.

Claims (11)

[Claims] 1. A photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula 1. Embedded image [Wherein X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. m represents an integer of 1 or more and 4 or less. Q represents a nitrogen-containing heterocyclic group having a betaine structure as a partial structure. n represents an integer of 0 or more and 3 or less. ] 2. A photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula 2. Embedded image [Wherein, X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in Formula 1. Q represents a nitrogen-containing heterocyclic group having a quaternary ammonium nitrogen atom in the ring and having a counter anion as another molecule. ] 3. A photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula 3. Embedded image [Wherein, X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in Formula 1. Q represents a pyridine ring in which two to four benzene rings are condensed. ] 4. A photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following general formula 4. Embedded image [Wherein, X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in Formula 1. Q represents an isoquinoline ring. ] 5. A photothermographic material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide and a compound represented by the following formula (5). Embedded image [Wherein, X ₁ , X ₂ , Y, A, m and n have the same meanings as those described in Formula 1. However, X ₁ , X ₂ and A are not bromine atoms at the same time. Q represents a quinoline ring. ] 6. The photothermographic material according to claim 1, further comprising a hydrazine compound. 7. A photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder and photosensitive silver halide on a support, wherein the photosensitive layer is a compound represented by the general formula of claim 1. A photothermographic material comprising at least one compound represented by formula (1). 8. A photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder and photosensitive silver halide on a support, wherein the photosensitive layer is formed of a photosensitive layer.
A photothermographic material comprising at least one compound represented by the general formula 2 described in (1). 9. A photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder and photosensitive silver halide on a support, wherein the photosensitive layer is formed of a photosensitive layer.
A photothermographic material comprising at least one compound represented by the general formula 3 described in (1). 10. A support comprising at least one photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support.
A photothermographic material having a layer, wherein the photosensitive layer contains at least one compound represented by the formula (4) according to claim 4. 11. A support comprising at least one photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support.
A photothermographic material having a layer, wherein the photosensitive layer contains at least one compound represented by the formula (5) according to claim 5.