JP2001056527A - Heat developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable image recording material which suppresses fogging in storage before development and the increase of fog in development by holding a reducible silver salt, a reducing agent, a binder and a specified compound on one face of a substrate. SOLUTION: The heat developable image recording material has a reducible silver salt, a reducing agent, a binder and at least one compound of the formula on at least one face of the substrate. In the formula, X11 and X12 are each H, alkyl, alkoxy, halogen, alkoxycarbonyl or carbamoyl, R11 and R12 are each H or a group substitutable on the benzene ring, Y11 is -SO2-, -CO-, -COCO- or -P(R)O (R has the same meaning as R13), R13 is alkyl, alkenyl, alkynyl, aryl, a heterocyclic group or the like and each of the alkyl, alkenyl, alkynyl, aryl and heterocyclic group as R13 may be substituted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable image recording material. More specifically, the present invention relates to a heat-developable image recording material in which fog due to storage time before development and fog rise during development are extremely small.

[0002]

2. Description of the Related Art There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technique for forming an image by thermal development is a system that can simplify environmental preservation and image forming means. In recent years, environmental preservation in the photoengraving field,
From the viewpoint of space saving, it is strongly desired to reduce the amount of processing waste liquid. There, you can use a laser scanner or a laser imagesetter to make the exposure more efficient,
There is a need for a technique relating to a photosensitive heat-developable material for photoengraving that can form a sharp black image having high resolution and sharpness. These photosensitive heat-developable materials eliminate the use of solution-based processing chemicals and can provide customers with a simpler heat-development system that does not damage the environment.

A method for forming an image by thermal development is described in, for example, US Pat. Nos. 3,152,904 and 3,457,075 and D.C. Morgan and B.A. Sherry (Sh
ely) "Heat treated silver system (Therm
ally Processed Silver Systems) A "(Imaging
Processings and Materials (Imaging Proce
sses and Materials) Neblette 8th edition, Sturg
e), V. Walworth, A .; Edited by Shepp, page 2, 1969). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

[0004] Fog is a major problem in photothermographic materials. Many studies have been made to reduce fog in silver halide light-sensitive materials for thermography. For example, US Pat. No. 3,589,903 discloses a mercury salt. In addition, U.S. Pat.No. 4,152,160 discloses carboxylic acids such as benzene and phthalic acid, U.S. Pat.
No. 6 describes indane or tetralin carboxylic acid,
U.S. Pat. No. 4,820,617 discloses dicarboxylic acids and U.S. Pat. No. 4,626,500 discloses heteroaromatic carboxylic acids. U.S. Patent Nos. 4,545,075, 4,756,999, 4,452,885, 3,874,946 and 3,955,982 disclose halogenated compounds. U.S. Patent No.
5028523 discloses a halogen molecule or a halogen atom combined with a heteroatom ring. Also, Japanese Patent Publication No. 54-165, European Patent Publication EP-605981A, 631176A, U.S. Pat.No. 4,546,075,
U.S. Pat. No. 4,756,999, U.S. Pat. No. 4,452,885, U.S. Pat. No. 3,874,946 and U.S. Pat. No. 3,955,982 disclose polyhalogenated compounds. U.S. Pat.No. 4,103,312 and GB150
No. 2670 is a palladium compound, U.S. Pat.No. 4,128,428 is a metal of irons, U.S. Pat.
No. 25,430 discloses substituted triazoles, U.S. Pat.
213,784, U.S. Pat.No. 4,245,033 and JP-A-51-26019 disclose sulfur compounds, U.S. Pat.
No. 2,479 discloses thiouracils, and JP-A-50-123331 discloses sulfinic acid.

Further, US Pat. No. 4,125,403, US Pat. No. 4,152,160 and US Pat. No. 4,307,187 disclose metal salts of thiosulfonic acid, JP-A-53-20923 and JP-A-53-193. No. 19825 discloses a combination of a metal salt of thiosulfonic acid and sulfinic acid, and Japanese Patent Publication No. Sho 62-50810, JP-A-7-209797 and JP-A-9-43760 disclose thiosulfonic acid esters. . Further, disulfide compounds are disclosed in JP-A-51-42529 and JP-B-63-37368. But,
These compounds have the drawback that the antifogging effect is low, or the Dmax decreases as the amount added increases, and the image storage stability after processing deteriorates. Was desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a heat-developable image recording material in which fog due to storage time before development and fog increase during development are extremely small.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventor to solve the above-mentioned problems, the present inventors have found that at least one compound represented by the formula (1) defined in the present specification is used. As a result, the present inventors have found that it is possible to provide an excellent heat-developable image recording material in which fog due to storage time before development and fog increase during development are suppressed, and the present invention has been provided.

That is, according to the present invention, (a) a reducible silver salt and (b)
A heat-developable image recording material comprising a reducing agent, (c) a binder, and (d) at least one of the compounds represented by the formula (1) is provided.

Embedded image[In the formula (1), X¹¹And X¹²Is independently hydrogen
Atom, alkyl group, alkoxy group, halogen atom, al
Represents a oxycarbonyl group or a carbamoyl group;¹¹
And R¹²Are each independently placed on a hydrogen atom or a benzene ring
Represents a replaceable group. Y¹¹Is -SO_Two-, -CO-, -C
OCO- or -P (R) O- group (R is R^{1 Three}Synonymous with)
Represent. R¹³Is an alkyl group, alkenyl group, alkynyl
Group, aryl group, heterocyclic group, -OR¹⁴, -N (R^Fifteen) R
¹⁶, Or -SR¹⁷Where R ¹⁴, R^Fifteen, R¹⁶You
And R¹⁷Are each independently a hydrogen atom, an alkyl group, an aryl
A heterocyclic group or a heterocyclic group;¹³To R¹⁷In the definition of
Alkyl, alkenyl, alkynyl, aryl
The group or heterocyclic group may be substituted. ]

Preferably, the photothermographic material of the present invention is a photothermographic material further comprising (e) a photosensitive silver halide on the same surface. Preferably, the heat-developable image recording material of the present invention further has (f) a super-high contrast agent on the same surface. Preferably, the superhigh contrast agent is at least one compound selected from the compounds represented by the formula (2), (3) or (4).

Embedded image [In the formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z, R ² and R ³ ,
R ¹ and R ² , and R ³ and Z may be bonded to each other to form a cyclic structure. In the formula (3), R
⁴ represents a substituent. In the formula (4), X and Y are
A and B each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic group. Represents an amino group. In Formula (4), X and Y, and A and B
May be bonded to each other to form a cyclic structure. ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments and methods of the heat-developable image recording material of the present invention will be described in detail.
The heat-developable image recording material of the present invention is characterized by containing at least one compound represented by the formula (1), whereby fog due to storage time before development and fog increase during development can be reduced. Can be suppressed. First, the compound represented by the formula (1) used as an antifoggant in the present invention will be described in detail. Equation (1) is shown below.

[0011]

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In equation (1), X¹¹And X¹²Are each
Independently hydrogen, alkyl, alkoxy, halogen
Atom, alkoxycarbonyl group or carbamoyl group
Represents, R¹¹And R¹²Are each independently a hydrogen atom or
Represents a group that can be substituted on the zen ring. Y¹¹Is -SO_Two-, -C
O-, -COCO-, or -P (R) O- groups (R is R^{1 Three}
Synonymous with). R¹³Represents an alkyl group, an alkenyl group,
Rukinyl group, aryl group, heterocyclic group, -OR¹⁴, -N
(R^Fifteen) R¹⁶, Or -SR¹⁷Where R ¹⁴,
R^Fifteen, R¹⁶And R¹⁷Are each independently a hydrogen atom, an alkyl
Group, an aryl group or a heterocyclic group,¹³To R¹⁷
Alkyl, alkenyl, alkynyl in the definition of
Group, aryl group or heterocyclic group may be substituted
No.

In the formula (1), X ¹¹ and X ¹² may be the same or different. As the alkyl group for X ¹¹ and X ¹² , a saturated or unsaturated C 1 to C 20 alkyl group
Straight, branched, cyclic or combinations thereof, such as methyl, ethyl, propyl, isopropyl, butyl,
sec-butyl, tert-butyl, hexyl, 2-hexyl,
Cyclohexyl, octyl, tert-octyl, dodecyl, octadecyl and the like can be mentioned. The alkoxy group for X ¹¹ and X ¹² is a saturated or unsaturated, straight-chain, branched, cyclic or combination thereof having 1 to 20 carbon atoms, and examples thereof include methoxy, ethoxy, propoxy, hexyloxy and benzyloxy. Examples of the halogen atom for X ¹¹ and X ¹² include fluorine, chlorine, bromine, and iodine. The alkoxycarbonyl group for X ¹¹ and X ¹² has 1 to 20 carbon atoms and includes, for example, methoxycarbonyl, 2-ethylhexyloxycarbonyl and cyclohexyloxycarbonyl. X
The ¹¹ and carbamoyl group X ^12, those having 1 to 20 carbon atoms, the nitrogen atom is an alkyl group, may be substituted with an aryl group, e.g., N- propylcarbamoyl, N- octylcarbamoyl, N- phenyl Carbamoyl. At least one of X ¹¹ and X ¹² is preferably a group other than a hydrogen atom, and more preferably both are groups other than a hydrogen atom. X ¹¹ and X ¹² are preferably a tertiary alkyl group, an alkoxy group or a chlorine atom, and more preferably a tertiary alkyl group and an alkoxy group. X ¹¹ and X ¹² may be further substituted with groups described below as specific examples of R ¹¹ and R ¹² .

R ¹¹ and R ¹² each independently represent a hydrogen atom or a group which can be substituted on a benzene ring. R ¹¹ and R ¹² may be the same or different. The group that can be substituted on the benzene ring includes a halogen atom, a carbon atom, an oxygen atom,
Examples of the substituent include a substituent bonded to a benzene ring at a nitrogen atom or a sulfur atom. Examples of the substituent bonded at a carbon atom include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group, an oxycarbonyl group, a carbamoyl group, a heterocyclic group, a cyano group, and the like. Examples of the substituent include a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, and the like.Examples of the substituent bonded with a nitrogen atom include, for example, acylamino Group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, imide group, heterocyclic group, etc. Examples of the substituent bonded at the sulfur atom include: In example, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfonyl group, a sulfinyl group.
These substituents may be further substituted with alkyl, alkenyl, alkynyl, aryl, hydroxyl, cyano, halogen or other substituents formed from oxygen, nitrogen, sulfur or carbon atoms. Is also good. R ¹¹ and X ¹¹ or R ¹² and X ¹² may combine to form a 5- to 7-membered ring.

Specific examples of R ¹¹ and R ¹² are described below.
Examples of the halogen atom include a fluorine atom, a chlorine atom,
It is a bromine atom. The alkyl group has 1 to 16 carbon atoms,
Preferably, it is a linear, branched, cyclic, or combination thereof alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, isopropyl, 2-hydroxyethyl, benzyl, 2-methanesulfonamidoethyl, 2-methoxyethyl. , Cyclopentyl, 2-carboxylethyl and the like. The alkenyl group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and includes, for example, vinyl, 1-propenyl, 1-hexenyl, styryl and the like. The alkynyl group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and includes, for example, ethynyl, 1-butynyl, 1-dodecenyl, phenylethynyl and the like. The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl.

The heterocyclic group linked by a carbon atom on the ring may be a 5- or 6-membered saturated or unsaturated monocyclic or monocyclic ring having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms. A condensed ring, for example, 2-pyridyl, 2
-Quinolyl, 1-isoquinolyl, 2-pyrimidinyl, 2
-Pyrazinyl, 3-pyridazinyl, 1-phthalazinyl,
2-triazinyl, 2-furyl, 2-thienyl, 2-pyrrolyl, 2-oxazolyl, 4-thiazolyl, 4-imidazolyl, 2-thiadiazolyl, 2-triazolyl, 5
-Benzimidazolyl. The acyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group includes an alkoxycarbonyl group and an aryloxycarbonyl group, and the alkoxycarbonyl group has 2 to 2 carbon atoms.
18, preferably 2 to 10, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms, and is, for example, phenoxycarbonyl. The carbamoyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, such as carbamoyl, N-ethylcarbamoyl, N-octylcarbamoyl and N-phenylcarbamoyl.

The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, 2-methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, preferably 2 to 12 carbon atoms, such as phenoxy, 4-methoxyphenoxy,
Chlorophenoxy. As the heterocyclic oxy group, an oxygen atom, a nitrogen atom or a sulfur atom having 1 to 5 carbon atoms can be used.
The number of the heteroatoms and the kind of the element which are a 5- or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one ring may be one or more.
Phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy. The acyloxy group has 1 to 16 carbon atoms, preferably 1 to 1 carbon atoms.
Ten acyloxy groups are, for example, acetoxy, benzoyloxy, 4-hydroxybutanoyloxy. As the carbamoyloxy group, a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 16 carbon atoms,
Preferably an acylamino group having 1 to 10 carbon atoms, for example,
Acetamide, 2-methoxypropionamide, and p-chlorobenzoylamide. The alkylamino group is an alkylamino group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as N, N-dimethylamino, N, N
-Diethylamino, N- (2-phenoxyethyl) amino. The arylamino group has 6 to 24 carbon atoms,
Preferred or 6-12 arylamino groups are, for example, anilino, m-nitroanilino, N-methylanilino.
The heterocyclic amino group is a 5- or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, which is a heteroatom constituting the ring. May be one or more in number, for example, 2-oxazolylamino, 2-
Tetrahydropyranylamino and 4-pyridylamino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as ureide, methyl ureide, N, N-diethyl ureide and 2-methanesulfonamidoethyl ureide.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 10 carbon atoms, such as dimethylsulfamoylamino, methylsulfamoylamino, and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropyloxycarbonylamino. The aryloxycarbonylamino group has 7 to 2 carbon atoms.
4, preferably 7 to 12 aryloxycarbonylamino groups, for example, phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, 2,6-dimethoxyphenoxycarbonylamino. As the sulfonamide group, a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methanesulfonamide, p
-Toluenesulfonamide, 2-methoxyethanesulfonamide. The imide group is an imide group having 4 to 16 carbon atoms, such as N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom includes at least one of a carbon atom, an oxygen atom and a sulfur atom.
A 5- to 6-membered heterocycle consisting of a species and a nitrogen atom, for example, pyrrolidino, morpholino, imidazolino.

The alkylthio group has 1 to 16 carbon atoms,
Preferably an alkylthio group having 1 to 10 carbon atoms, for example,
Methylthio, butylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, such as phenylthio, 2-chlorophenylthio, and 4-cyanophenylthio. Examples of the heterocyclic thio group include those having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms.
The number of heteroatoms and the kind of element constituting a saturated or unsaturated heterocyclic thio group of a 6-membered or 6-membered ring are 1
One or more may be 2-benzothiazolylthio, 2-pyridylthio. The sulfamoyl group has 0 to 16 carbon atoms, preferably 0 to 10 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Phenylsulfamoyl. The sulfonyl group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms,
For example, methanesulfonyl and benzenesulfonyl.
The sulfinyl group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, such as methanesulfinyl and benzenesulfinyl. R ¹¹ and R ¹² are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyloxy group, an acylamino group, a ureido group, a sulfonamide group, a heterocyclic group, an alkylthio group, and a heterocyclic thio group. And more preferably a hydrogen atom, a halogen atom, an alkyl group and an alkoxy group, and most preferably a hydrogen atom.

R ¹³ is an alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, —OR ¹⁴ , —N (R
¹⁵ ) R ¹⁶ or —SR ¹⁷ , wherein R ¹⁴ , R ¹⁵ ,
R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group in the definition of R ¹³ to R ¹⁷ is substituted. May be. R
Specific examples of R ¹⁷ to ^13, include those similar to the respective groups described in R ¹¹ and R ^12. R ¹³ is preferably an alkyl group, an aryl group, or a heterocyclic group, and more preferably an aryl group or a heterocyclic group. Alkyl group in the definition of R ¹³ to R ^17, alkenyl group, alkynyl group, aryl group or heterocyclic group may be substituted with one or more substituents, specific examples of the substituents R ¹¹ and R ¹² The groups mentioned are mentioned. As a substituent of X ¹¹ , X ¹² , R ¹¹ , R ¹² , and R ¹³ , a ballast group used in a photographic material to reduce diffusivity may be provided, or the substituents may bind to each other. Alternatively, a screw type or a tris type may be formed. Next, specific examples of the antifoggant of the formula (1) used in the present invention are shown, but the compounds used in the present invention are not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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The compound represented by the formula (1) used in the present invention is prepared by reacting the corresponding 4-hydroxythiophenol compound (A) with various acid halides (B, sulfonyl chloride, carbonyl chloride) in the presence of a base (pyridine, triethylamine or the like). , Sulfamoyl chloride, carbamoyl chloride, etc.).

[0030]

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A typical synthesis example is shown below. 1. Synthesis of Exemplified Compound (1-1)

[0032]

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1-1. Synthesis of Intermediate D Literature (SD Pastor, J. Org. Chem.
49 , 5260 (1984)). 25.1 g (0.12 mol) of compound C and 0.22 g (1.2 mmol) of titanium tetrachloride in toluene 80
While cooling the solution in an ice-methanol bath, 8.5 g (0.063 mol) of disulfur dichloride at -6 to 0 ° C.
Was added dropwise over 25 minutes. After further reacting at −6 ° C. for 2.5 hours, the mixture was washed three times with 3N hydrochloric acid, three times with water, and concentrated under reduced pressure. Recrystallization from 100 ml of hexane gave 14.2 g (50%) of compound D. NMR (CDCl ₃ ): δ 1.4 (s, 36H);
3 (s, 2H), 7.3 (s, 4H)

1-2. Synthesis of Intermediate E Literature (SD Pastor et al., Phosphorus)
and Sulfur, 29 , 67 (1986)). 9.48 g of compound D (20 m
M), ethanol 25 ml, toluene 50 ml and 3
23 g of zinc powder was added to a mixture of 190 ml of N-hydrochloric acid over 15 minutes while stirring at room temperature. After further reacting at room temperature for 3 hours, the mixture was filtered while washing with a mixed solution of ethyl acetate and hexane. The filtrate was washed with water containing a small amount of hydrosulfite and dried over anhydrous sodium sulfate. 8. After filtration, the filtrate was concentrated to give compound E as white crystals.
1 g (96%) was obtained. NMR (CDCl ₃ ): δ 1.4 (s, 18H);
35 (s, 1H), 5.15 (s, 1H), 7.15
(S, 2H)

1-3. Synthesis of Compound (1-1) Pyridine 1.7 was added to a solution of 4.8 g (20 mmol) of compound E and 4.0 g (21 mmol) of p-toluenesulfonyl chloride in 50 ml of acetonitrile while stirring under ice-cooling.
g (21 mmol) were added dropwise in 5 minutes. After further reacting for 1 hour while cooling with ice, water was added, and the mixture was extracted and washed with ethyl acetate. After concentrating the ethyl acetate layer, the residue was separated and purified by silica gel column chromatography to obtain 3.8 g (48%) of the target product 1-1 as white crystals. NMR (CDCl ₃ ): δ 1.35 (s, 18H),
2.4 (s, 3H), 5.55 (s, 1H), 7.05
(S, 2H), 7.2 (d, 2H), 7.45 (d, 2
H)

2. Synthesis of Exemplified Compound (1-2) Literature (AJ Bridgewater et al., J. Che)
m. Soc. PerkinTrans. II530 (19
78)). 3. Synthesis of Exemplified Compound (1-25) Literature (E. Mueller et al., Justus Liebi)
gsAnn. Chem. 645 , 79 (1961)). 4. Synthesis of Exemplified Compound (1-37) Literature (A. Rieker, Z. Naturforsc)
h. B Anorg. Chem. Org. Chem. B
iochem. Biophys. Biol. 21 , 64
7 (1966)). 5. Synthesis of Exemplified Compound (1-38) Literature (SD Pastor et al., Phosphorus)
and Sulfur, 29 , 31 (1986)).

The compound represented by the formula (1) used in the present invention may be water or a suitable organic solvent such as an alcohol.
(E.g., methanol, ethanol, propanol, fluorinated alcohols), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and the like. Also, 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, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method.

The compound represented by the formula (1) used in the present invention may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. Is preferably added to the image forming layer or a layer adjacent thereto. In the present invention, only one compound represented by the formula (1) may be used, or two or more compounds may be used in combination.
The amount of the compound represented by the formula (1) used in the present invention is:
The coating amount per m ^{2 of the} image recording material is preferably 1
× 10 ^-6 to 1 × 10 ^-2 mol / m ² , more preferably 1 × 10
^{−5 to} 5 × 10 ⁻³ mol / m ² , particularly preferably 2 × 10 ⁻⁵ to 1
× 10 ⁻³ mol / m ² . These compounds may be used alone or in combination of two or more. In the heat-developable image recording material of the present invention, at least one selected from a substituted alkene derivative, a substituted isoxazole derivative and a specific acetal compound represented by the following formulas (2) to (4) as a super-high contrast agent: It is preferable to contain a compound. Hereinafter, the compounds represented by Formula (2), Formula (3), and Formula (4) will be described.

[0039]

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In the formula (2), R ¹ , R ² and R ³ are
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z,
R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. In the formula (3), R ⁴ represents a substituent. In the formula (4), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a hetero group. Represents a ring oxy group, a heterocyclic thio group or a heterocyclic amino group. In the formula (4), X and Y, and A and B may be bonded to each other to form a cyclic structure.

The compound represented by the formula (2) will be described in detail. In the formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z,
R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (a cycloalkyl group, an active methine group) Etc.), an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including an N-substituted nitrogen-containing heterocyclic group), a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group) ), Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, imino group, imino group substituted with N atom, thiocarbonyl group, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl Group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group Others (including a group containing repeating ethyleneoxy group or propyleneoxy group units) salt thereof, an alkoxy group,
Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide Group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl Or aryl) sulfonyluureido, acylureido, acylsulfamoylamino, nitro, mercapto, (alkyl, aryl or heterocycle) thio, acylthio, (alkyl or aryl) s A honyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphoryl group, a group containing a phosphoric acid amide or a phosphate ester structure, Examples thereof include a silyl group and a stannyl group. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the formula (2) is a substituent whose Hammett's substituent constant σ _p can take a positive value, and specifically includes a cyano group, An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a halogen atom,
A perfluoroalkyl group, a perfluoroalkaneamide group, a sulfonamide group, an acyl group, a formyl group, a phosphoryl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), a heterocyclic group, an alkenyl group, an alkynyl group, Examples include an acyloxy group, an acylthio group, a sulfonyloxy group, and an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is a saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group,
Examples thereof include a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, a hydantoin-1-yl group, a succinimide group, and a phthalimido group.

The electron-withdrawing group represented by Z in the formula (2) may further have a substituent, and the substituent may be R ¹ , R ² , R ^{3 in the} formula (2). Is the same as the substituent which may be present when represents a substituent. In the formula (2), R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. A structure is a non-aromatic carbocycle or a non-aromatic heterocycle.

Next, the preferred range of the compound represented by the formula (2) will be described. The silyl group represented by Z in the formula (2) is preferably a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a trimethylsilyldimethylsilyl group, or the like. . In the formula (2), the electron withdrawing group represented by Z is preferably a group having a total carbon number of 0 to 30 or less, that is, a cyano group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, thiocarbonyl group, imino group, N
An atom substituted imino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acyloxy group, acylthio group, or any electron-withdrawing group Substituted phenyl group, etc., more preferably, cyano group, alkoxycarbonyl group, carbamoyl group, imino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, formyl group, phosphoryl group, trifluoromethyl group Or a phenyl group substituted with an arbitrary electron-withdrawing group, and particularly preferably a cyano group, formyl group, acyl group, alkoxycarbonyl group, imino group or carbamoyl group.

The group represented by Z in the formula (2) is more preferably an electron-withdrawing group. In the formula (2), R ¹ , R ² ,
And the substituent represented by R ³ is preferably a group having a total carbon number of 0 to 30, specifically, a group having the same meaning as the electron-withdrawing group represented by Z in the above formula (2), and Alkyl group, hydroxy group (or salt thereof), mercapto group (or salt thereof), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, aryl Amino group,
Examples include a heterocyclic amino group, a ureido group, an acylamino group, a sulfonamide group, and a substituted or unsubstituted aryl group. Further, in the formula (2), R ¹ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom or a silyl group.

When R ¹ represents an electron-withdrawing group, preferably the following groups having a total carbon number of 0 to 30, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), Or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, a carboxy group (or a salt thereof) Or a saturated or unsaturated heterocyclic group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a saturated or unsaturated heterocyclic group. When R ¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms in total, and examples of the substituent include arbitrary substituents. Is preferred. In formula (2), R ¹ is more preferably a group representing an electron-withdrawing group or an aryl group.

In the formula (2), the substituents represented by R ² and R ³ are preferably, specifically, groups having the same meaning as the electron-withdrawing group represented by Z in the above formula (2), alkyl, Group, hydroxy group (or salt thereof), mercapto group (or salt thereof), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, anilino group , A heterocyclic amino group, an acylamino group, a substituted or unsubstituted phenyl group and the like. In the formula (2), R ² and R ³ are
More preferably, one of them is a hydrogen atom and the other represents a substituent. Preferably as the substituent,
Alkyl group, hydroxy group (or a salt thereof), mercapto group (or a salt thereof), alkoxy group, aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
A heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly a perfluoroalkaneamide group), a sulfonamide group, a substituted or unsubstituted phenyl group, or a heterocyclic group; More preferably, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group, Particularly preferred are a hydroxy group (or a salt thereof), an alkoxy group, and a heterocyclic group.

In the formula (2), it is also preferable that Z and R ¹ , or R ² and R ³ form a cyclic structure.
The cyclic structure formed in this case is a non-aromatic carbon ring or a non-aromatic hetero ring, preferably 5 to 7 members.
Having a total carbon number of 1 to 4 including substituents.
0, more preferably 3 to 30. Among the compounds represented by the formula (2), one of the more preferable ones is that Z is a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group,
Represents an imino group or a carbamoyl group, R ¹ represents an electron-withdrawing group or an aryl group, one of R ^{2 and} R ³ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), a mercapto group ( Or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group,
A compound representing an arylthio group, a heterocyclic thio group, or a heterocyclic group. Furthermore, one of the particularly preferable compounds represented by the formula (2) is that Z and R ^{1 form a} non-aromatic 5- to 7-membered cyclic structure, and R ² or R ³ Is one of a hydrogen atom, the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, Or a compound representing a heterocyclic group. At this time, Z which forms a non-aromatic cyclic structure together with R ¹ is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, and the like, and R ¹ is an acyl group, a carbamoyl group , An oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted by an N atom, an acylamino group, and a carbonylthio group.

Next, the compound represented by the formula (3) will be described. As the substituent represented by R ⁴ in the formula (3), the same substituents as described for the substituents R ^{1 to} R ^{3 in} the formula (2) can be mentioned. In formula (3), the substituent represented by R ⁴ is preferably an electron-withdrawing group or an aryl group. When R ⁴ represents an electron withdrawing group, preferably
The following groups having a total carbon number of 0 to 30, that is, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, alkylsulfonyl group,
Arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group, phosphoryl group, imino group, or a saturated or unsaturated heterocyclic group, further cyano group, acyl group, formyl group, alkoxycarbonyl group, carbamoyl group, Sulfamoyl, alkylsulfonyl, arylsulfonyl, and heterocyclic groups are preferred. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a heterocyclic group. When R ⁴ represents an aryl group, preferably a total carbon number of 0 to 30, a substituted or unsubstituted phenyl group, the substituent group, R ^1, R ² of formula (2),
When R ³ represents a substituent, the same as those described as the substituent can be mentioned. In the formula (3), R ⁴ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group, or a substituted or unsubstituted phenyl group, and most preferably a cyano group, a heterocyclic group, or an alkoxycarbonyl group. Group.

Next, the compound represented by the formula (4) will be described in detail. In the formula (4), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group. X and Y or A and B may be bonded to each other to form a cyclic structure. In the formula (4), substituents represented by X and Y include R ^{1 to} R ^{3 in the} formula (2).
And the same substituents as described above. Specifically, alkyl groups (including perfluoroalkyl groups, trichloromethyl groups, etc.), aryl groups, heterocyclic groups, halogen atoms, cyano groups, nitro groups, alkenyl groups, alkynyl groups, acyl groups, formyl groups, alkoxy groups Carbonyl group, aryloxycarbonyl group, imino group, imino group substituted with an N atom, carbamoyl group, thiocarbonyl group, acyloxy group, acylthio group, acylamino group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphoryl group, carboxy Group (or its salt), sulfo group (or its salt), hydroxy group (or its salt), mercapto group (or its salt), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero group Ring thio group, amino group, alkylami Group, anilino group, heterocyclic amino group, a silyl group, and the like. These groups may further have a substituent. X and Y may be bonded to each other to form a cyclic structure, and the cyclic structure formed in this case may be a non-aromatic carbon ring or a non-aromatic hetero ring. .

The substituent represented by X and Y in the formula (4) is preferably a group having 1 to 40 carbon atoms, more preferably a group having 1 to 30 carbon atoms, and is preferably a cyano group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group , An acylamino group, an acyloxy group, an acylthio group, a heterocyclic group, an alkylthio group, an alkoxy group, or an aryl group. In the formula (4), X and Y are more preferably cyano group, nitro group, alkoxycarbonyl group, carbamoyl group, acyl group, formyl group, acylthio group, acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, aryl A sulfonyl group, an imino group, an imino group substituted with an N atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkyl group Sulfonyl group,
An arylsulfonyl group, an acyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, or a phenyl group substituted with any electron-withdrawing group, etc. It is. X
It is also preferable that Y and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the formed ring structure is preferably a 5- to 7-membered ring,
The total carbon number is preferably 1 to 40, more preferably 3 to 30. X and Y forming a cyclic structure are preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted by an N atom, an acylamino group, a carbonylthio group, and the like.

In the formula (4), A and B are each independent
, An alkoxy group, an alkylthio group, an alkylamino
Group, aryloxy group, arylthio group, anilino group,
A heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic a
Represents amino groups, which combine with each other to form a cyclic structure
It may be. Groups represented by A and B in the formula (4)
Is preferably 1 to 40 carbon atoms in total, more preferably
A group having 1 to 30 carbon atoms, further having a substituent,
Is also good. In equation (4), A and B are
More preferably, they form a ring structure. This
The cyclic structure formed at this time is a 5- to 7-membered non-aromatic
A telocyclic ring is preferable, and its total carbon number is 1 to 40, and furthermore
3 to 30 are preferred. In this case, A and B are connected
When (-AB-) is mentioned, for example, -O- (CH_Two)_Two-O
-, -O- (CH_Two)_Three-O-, -S- (CH_Two)_Two-S
-, -S- (CH_Two)_Three-S-, -S-ph-S-, -N
(CH_Three)-(CH_Two)_Two-O-, -N (CH _Three)-(CH
_Two)_Two-S-, -O- (CH_Two)_Two-S-, -O- (C
H_Two)_Three-S-, -N (CH_Three) -Ph-O-,-N (C
H_Three) -Ph-S-,-N (ph)-(CH_Two)_Two-S-
And so on.

The compounds represented by the formulas (2) to (4) used in the present invention may have incorporated therein an adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio, arylthio, thiourea,
U.S. Pat. Nos. 4,385,108 and 4,459, such as a thioamide group, a mercapto heterocyclic group and a triazole group;
59,347, JP-A-59-195233, JP-A-59-200231, and JP-A-59-20104.
No. 5, No. 59-201046, No. 59-20
Nos. 1047, 59-201048, 59
JP-201049-A, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, and 63-234424
5 and JP-A-63-234246. The adsorbing groups to these silver halides are
It may be a precursor. Examples of such a precursor include groups described in JP-A-2-285344. The compounds represented by formulas (2) to (4) used in the present invention may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. . Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties. You can choose from. As a polymer,
For example, those described in JP-A-1-100530 can be mentioned.

The compounds represented by the formulas (2) to (4) used in the present invention contain a cationic group (specifically, a group containing a quaternary ammonium group, or a quaternized group). A nitrogen-containing heterocyclic group containing a nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group,
Alternatively, it may contain a dissociable group that can be dissociated by a base (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.). Particularly, a group containing a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group or a group containing an (alkyl, aryl, or heterocyclic) thio group is one of preferred examples of the present invention. Specific examples of these groups include, for example, JP-A-7-234471 and JP-A-5-3334.
No. 66, JP-A-6-19032, JP-A-6-19032.
19031, JP-A-5-45761, US Pat. No. 4,994,365, US Pat. No. 4,988,604, JP-A-3-259240, JP-A-7-5
610, JP-A-7-244348, German Patent 4006032 and the like. Hereinafter, specific examples of the compounds represented by Formulas (2) to (4) used in the present invention are shown below. However, the compounds used in the present invention are not limited to the following compounds.

[0055]

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[0056]

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[0057]

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[0058]

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The compounds represented by the formulas (2) to (4) used in the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol,
It can be used by dissolving it in fluorinated alcohol, etc., ketones (acetone, methyl ethyl ketone, etc.), dimethylformamide, dimethyl sulfoxide, methylcellosolve and the like. Also, 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, the powder of the compound represented by Formula (2) to Formula (4) is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic wave by a method known as a solid dispersion method, and used. Can be. The compounds represented by the formulas (2) to (4) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. It is preferably added to the forming layer or a layer adjacent thereto.

The addition amount of the compounds represented by the formulas (2) to (4) is preferably 1 × 10 ^-6 to 1 mol per 1 mol of silver, and 1 × 10 ^{-5 to} 5 × 10 ^-1 mol. Is more preferable, and 2 ×
Most preferably, it is 10 ^{-5 to} 2 × 10 ^-1 mol. The compounds represented by the formulas (2) to (4) can be easily synthesized by a known method, and for example, US Pat. No. 5,554,551.
5, U.S. Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, International Publication No.
No. 34196, Japanese Patent Application No. 9-354107, Japanese Patent Application No. 9-309813, Japanese Patent Application No.
The compound can be synthesized with reference to the method described in 272002. The compounds represented by the formulas (2) to (4) used in the present invention may be used alone or in combination of two or more. Also, in addition to the above, US Pat.
No. 5,515, U.S. Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, International Patent W
O97 / 34196, U.S. Pat. No. 5,686,228.
Or the compound described in JP-A No. 11-1
19372, Japanese Patent Application No. 9-228881, and
Japanese Patent Application No. 9-273935, Japanese Patent Application No. 9-3541
07, Japanese Patent Application No. 9-309813, Japanese Patent Application No. 9-296174, Japanese Patent Application No. 9-282564.
Specification, JP-A-11-95365, JP-A-11-95365
-95366 and Japanese Patent Application No. 9-332388 may be used in combination.

Further, in the present invention, Japanese Patent Application Laid-Open No. 10-3
39932, Japanese Patent Application No. 9-240511,
The hydrazine derivatives described in JP-A-10-161270 can be used in combination. Further, the following hydrazine derivatives can be used in combination. That is, a compound represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, a compound described on pages 3 and 4 of the same publication. It is a compound represented by the general formula (I) described in JP-B-6-93082.
Compounds 1-38 on pages 18-18. JP-A-6-23
No. 0497, compounds represented by formulas (4), (5) and (6), specifically compounds 4-1 to 4-1 described on pages 25 and 26 of the same publication. 4-1
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7. Compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1-1 described on pages 5 to 7 of the publication. 1
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 6
Compounds represented by (Chemical Formula 1) described in JP-A-313951, specifically, compounds described on pages 3 to 5 of the same publication. Compounds represented by the general formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-10 described on pages 10 to 27 of the same publication
2. Compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H- described on pages 8 to 15 of the same publication.
44. A compound described in EP 713131A, which has an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. Formula (B), Formula (C), Formula (D), Formula (E),
Compounds represented by formula (F), specifically, compounds N-1 to N-30 described in the same publication. European Patent 713131
A compound represented by the general formula (1) described in A publication, specifically, compounds D-1 to D-55 described in the publication. Further, various hydrazine derivatives described on pages 25 to 34 of "Known Techniques (pages 1 to 207)" (Aztec) published on March 22, 1991. JP-A-62-86354 (pages 6 to 7)
Compounds D-2 and D-39.

These hydrazine derivatives are dissolved in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve, etc. Can be used. Also, 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, by a method known as a solid dispersion method, a powder of a hydrazine derivative is put into water using a ball mill, a colloid mill,
Alternatively, it can be dispersed and used by ultrasonic waves.

These hydrazine derivatives may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side, but may be added to the image forming layer or a layer adjacent thereto. It is preferable to add. The amount of the hydrazine derivative to be added is 1 × 10 ⁻⁶ to 1 mol of silver.
1 mol is preferable, 1 * 10 < ^-5 > to 5 * 10 <^-1> mol is more preferable, and 2 * 10 < ^-5 > to 2 * 10 <^-1> mol is most preferable. Also, acrylonitriles described in U.S. Pat. No. 5,545,515, specifically, CN-1 to CN-13 and the like can be used as a super-high contrast agent.

Further, the present invention provides a method for forming a super-high contrast image.
A high contrast accelerator can be used in combination with the above-mentioned super-high contrast agent. For example, the amine compounds described in U.S. Patent No. 5,545,505, specifically, AM-1 to AM-5,
Hydroxamic acids described in the specification of 5,507, specifically, HA-1 to HA-11, hydrazine compounds described in the specification of 5,558,983, specifically, CA-1 to CA-6, JP-A-9-2
Onium salts described in JP-A-97368, specifically, A-1 to A-42, B-1 to B-27, and C-1 to C-14 can be used. The method for synthesizing, adding, and adding amounts of the above-mentioned super-high contrast agent and these high-contrast accelerators can be carried out as described in each of the cited references.

The heat-developable image recording material of the present invention contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable photographic material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
No. 47-33621, No. 49-46427, No. 49-1
No. 15540, No. 50-14334, No. 50-36110,
No. 50-147711, No. 51-32632, No. 51-1023721
JP-A-51-32324, JP-A-51-51933 and JP-A-52-8
No. 4727, No. 55-108654, No. 56-146133,
Nos. 57-82828, 57-82829, JP-A-6-3793, U.S. Pat.No. 3,667,9586, 3,679,426, 3,751,252, 3,751,255,
3,761,270, 3,782,949, 3,839,
No. 048, 3,928,686, 5,464,738, German Patent No. 2321328, European Patent No. 692732 and the like. For example, phenylamide oxime,
Amidoximes such as 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2′-bis (hydroxymethyl) propionyl-β-
A combination of an aliphatic carboxylic acid aryl hydrazide such as a combination of phenylhydrazine and ascorbic acid with ascorbic acid; a combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis (ethoxyethyl) hydroxyl Amines, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; azine and sulfonamide phenol Combinations (e.g., phenothiazine and 2,6-dichloro-4-
Benzenesulfonamidophenol); ethyl-α-
Α-cyanophenylacetic acid derivatives such as cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′- Dihydroxy-1,1'-binaphthyl and bis (2
Bis-β-naphthol as exemplified by -hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxy Acetophenone); 5-pyrazolone, such as 3-methyl-1-phenyl-5-pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone. Reductones as exemplified; sulfonamidophenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2- Chromanes such as dimethyl-7-t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydrogen 1,4-dihydropyridines such as pyridine; bisphenols (eg, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4 2,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2- Screw
(3,5-dimethyl-4-hydroxyphenyl) propane, etc.);
Ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones, such as benzyl and biacetyl; 3-pyrazolidones and certain indan-1,3-diones; chromanols, such as tocopherols; is there. The reducing agent used in the present invention may be added by any method such as a solution, a powder, and a solid fine particle dispersion. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The photothermographic material of the present invention is preferably a photothermographic material containing a photosensitive silver halide. Hereinafter, the photosensitive silver halide used in the present invention will be described in detail. The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride,
Silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously. Further, silver halide grains having a core / shell structure can be preferably used. The structure is preferably a two- to five-fold structure, more preferably a two- to four-fold core /
Shell particles can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods for forming the photosensitive silver halide used in the present invention are well known in the art, and are described, for example, in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. A method can be used. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method in which a silver supply compound and a halogen supply compound are added to another polymer solution to prepare photosensitive silver halide grains and mixed with an organic silver salt can be used. In the present invention, the latter method can be preferably used.
The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less.
The thickness is more preferably 0.02 μm or more and 0.12 μm or less. The grain size as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. If other than normal crystals, for example, spherical particles, rod-like particles, etc.,
It refers to the diameter of a sphere equivalent to the volume of silver halide grains.

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

The light-sensitive silver halide grains used in the present invention are selected from the group VII or VIII (groups 7 to 7) of the periodic table.
It preferably contains a metal of Group 10) or a metal complex. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 10 ^-9 mol to 10 ^-2 mol, preferably 10 ^-8 mol to 10 ^-4 mol, per mol of silver. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

As the rhodium compound preferably used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalate, etc., for example, hexachlororhodium (III) complex salt, pentachloroacolodium (III) complex salt,
Tetrachlorodiachodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium (II)
I) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, fluoride, etc.) Hydrogen acid, etc.) or alkali halides (eg KCl, NaC
l, KBr, NaBr, etc.). Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain doped with rhodium in the preparation of silver halide.

The amount of these rhodium compounds added is
1 × 10 per mole of silver halide^-8Mol ~ 5 x 10^-6Mole of
The range is preferably, particularly preferably 5 × 10^-8Mol ~ 1x
10 ^-6Is a mole. The addition of these compounds is
Each stage during the production of silver halide emulsion grains and before coating the emulsion
Can be suitably performed, but in particular,
And preferably incorporated into silver halide grains.
No. Rhenium and ruthenium preferably used in the present invention
And osmium are disclosed in JP-A-63-2042 and JP-A-1-285941.
No. 2, No. 2-20852, No. 2-20855, etc.
It is added in the form of a water-soluble complex salt. Especially preferred
And a six-coordinate complex represented by the following formula. [ML₆]^n- Here, M represents Ru, Re, or Os, and L represents a ligand.
And n represents 0, 1, 2, 3 or 4. This place
If the counterion is not important, ammonium or
Alkali metal ions are used.

Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands and the like.
Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto. [ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O) ₂ ( CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^- [RuCl ₅ (H ₂ O)] ^2- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] _{^{2- [Ru (CO) 3 Cl}} 3] 2- [Ru (CO) Cl 5] 2- [Ru (CO) Br 5] 2- [OsCl 6] 3- [OsCl 5 (NO)] 2- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (O) ₂ (CN) ₄ ] ^4-

The amount of these compounds added was 1
It is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol per mol, particularly preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. . In order to add these compounds during silver halide grain formation and incorporate them into silver halide grains, a metal complex powder or an aqueous solution dissolved together with NaCl and KCl is dissolved in a water-soluble salt or a water-soluble salt during grain formation. A method in which silver halide grains are added to a neutral halide solution, or a third solution is added when a silver salt and a halide solution are simultaneously mixed, and silver halide grains are prepared by a three-solution simultaneous mixing method, or a grain formation method. There is a method in which a required amount of an aqueous solution of a metal complex is charged into a reaction vessel. In particular, a method of adding a powder or an aqueous solution dissolved together with NaCl and KCl to a water-soluble halide solution is preferable. For the addition to the particle surface, a required amount of an aqueous solution of a metal complex 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.

Various compounds can be used as the iridium compound preferably used in the present invention, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, and pentachloronitrosyliridium. These iridium compounds are used after being dissolved in water or an appropriate solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl, NaCl, KBr, NaBr, etc.)
Can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain doped with iridium in advance during the preparation of silver halide.

The silver halide grains used in the present invention may further include cobalt, iron, nickel, chromium, palladium,
It may contain metal atoms such as platinum, gold, thallium, copper and lead. For compounds of cobalt, iron, chromium and ruthenium, hexacyano metal complexes can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion,
Examples include, but are not limited to, hexacyanochromate ions and hexacyanoruthenate ions. The metal complex in the silver halide may be contained uniformly, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration, and there is no particular limitation. The metal is 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
^0-4 moles are preferred. Further, in order to contain the above-mentioned metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added at the time of preparing particles. The photosensitive silver halide grains can be desalted by washing with a method known in the art, such as a noodle method or flocculation method, but in the present invention, it may or may not be desalted.

The silver halide emulsion used in the present invention is chemically enhanced.
It is preferably felt. As a method of chemical sensitization, sulfuric acid
Yellow sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization
Known methods such as
Are used in combination. When used in combination
For example, sulfur sensitization and gold sensitization,
Len sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization method and gold
Sensitization method, sulfur sensitization method, selenium sensitization method, tellurium sensitization method, and gold
A sensitization method is preferred. Sulfur sensitization used in the present invention
Is usually added at a high temperature of 40 ° C or more by adding a sulfur sensitizer.
This is performed by stirring the emulsion for a certain period of time. Sulfur sensitization
As the agent, a known compound can be used.
For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds
Yellow compounds such as thiosulfates, thioureas, thiazoles
, Rhodanines and the like can be used. Preferred sulfur
Yellow compounds are thiosulfates and thiourea compounds. sulfur
The amount of sensitizer to be added depends on the pH, temperature,
It changes under various conditions such as the size of silver halide particles,
10 per mole of silver halide ^-7-10^-2Mole,
More preferably 10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, JP-A-4-25
The compounds described in JP-A-832, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, JP-A-4-324855
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in the publication. The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion can be tested by the method described in JP-A-5-313284. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di
Use of (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, etc. Can be. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031 and 3,772,031
UK Patent Nos. 235,211; 1,121,496; 1,295,462
No. 1,396,696; Canadian Patent No. 800,958;
No. 204640, JP-A-4-271341, JP-A-4-3
JP-A-33043, JP-A-5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (198)
0), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S.
The Chemistry of Organic Serenium and Telluniu, edited by S. Patai, The Chemistry of Organic Serenium and Telluniu
m Compounds), Vol. 1 (1986) and the compounds described in Vol. 2 (1987) can be used. Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening.

In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also, when the pH of the emulsion is 7 or more or p
Reduction sensitization can be achieved by aging while keeping Ag at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation. To the silver halide emulsion used in the present invention, a thiosulfonic acid compound may be added by the method described in European Patent Publication No. EP293,917.

The silver halide emulsion in the heat-developable image recording material of the present invention may be only one kind or two or more kinds (for example,
Those with different average grain sizes, different halogen compositions, different crystal habits, different chemical sensitization conditions)
You may use together. The amount of the photosensitive silver halide used in the present invention is preferably from 0.01 mol to 0.5 mol, more preferably from 0.02 mol to 0.3 mol, more preferably from 0.03 mol to 0.25 mol, per mol of the organic silver salt. The following are particularly preferred. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, and a homogenizer. And the like, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt. There is no particular limitation as long as it appears in.

The heat-developable image recording material of the present invention contains a reducible silver salt. The organic silver salt which can be used as a reducible silver salt in the present invention is relatively stable to light, but is exposed to an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. Is a silver salt that forms a silver image when heated to 80 ° C. or higher. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially silver salts of long-chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver supplier is
Preferably it can comprise about 5 to 70% by weight of the image forming layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate.
Silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

A silver salt of a compound containing a mercapto group or a thione group and derivatives thereof can also be used.
Preferred examples of these compounds include 3-mercapto-4
-Phenyl-1,2,4-triazole silver salt, 2-mercaptobenzimidazole silver salt, 2-mercapto-5-aminothiadiazole silver salt, 2- (ethylglycolamide) benzothiazole silver salt, S- Silver salts of thioglycolic acid such as silver salts of alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithiocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamides, 5 -Carboxyl-1-methyl-2-phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, silver salts described in U.S. Pat.No. 4,123,274, such as 3-amino Silver salts of 1,2,4-mercaptothiazole derivatives such as -5-benzylthio-1,2,4-thiazole silver salt, 3- (3-carboxyethyl) -4 described in U.S. Pat. -Methyl-4-thiazoline-2-thione silver salt, etc. Including a silver salt of thione compounds. Further, compounds containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole,
And silver salts of 1,2,4-triazole or 1-H-tetrazole, as described in U.S. Pat. No. 4,220,709, and silver salts of imidazole and imidazole derivatives. For example, U.S. Patent Nos. 4,761,361 and 4,775,613
Various silver acetylide compounds as described in the above specification can also be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. In the present invention, the minor axis is 0.01 μm or more and 0.2 μm or more.
The length is preferably 0 μm or less, the major axis is 0.10 μm or more and 5.0 μm or less, the minor axis is 0.01 μm or more and 0.15 μm or less, and the major axis is 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by the minor axis and major axis, respectively, is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, the percentage of the value divided by the volume-weighted average diameter (coefficient of variation) is preferably 100% or less, more Preferably 80% or less,
More preferably, it is 50% or less. As a measuring method, for example, the particle size (volume weighted average diameter) obtained by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained. Can be. The organic silver salt that can be used in the present invention is preferably desalted. The desalting method is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used.

In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, an organic silver salt which is an image forming medium and a photosensitive silver salt are substantially contained. It is preferable to use a dispersion method in which a water dispersion liquid which is not included in the liquid is converted into a high-speed stream and then the pressure is reduced. Then, after passing through such a process, the mixture is mixed with a photosensitive silver salt aqueous solution to produce a photosensitive image forming medium coating solution. When a heat-developable photographic material is prepared by using such a coating solution, a heat-developable photographic material having low haze, low fog and high sensitivity can be obtained. On the other hand, when the photosensitive silver salt is coexistent when the light is converted into a high-pressure and high-speed flow and dispersed, the fog increases and the sensitivity is liable to decrease remarkably. When an organic solvent is used instead of water as a dispersion medium, haze increases, fog increases, and sensitivity tends to decrease. On the other hand, when a conversion method for converting a part of the organic silver salt in the dispersion liquid to the photosensitive silver salt is used instead of the method of mixing the aqueous solution of the photosensitive silver salt, the sensitivity tends to be lowered. In the above, the high-pressure, high-speed aqueous dispersion to be dispersed is substantially free of a photosensitive silver salt, the content is 0.
The content is 1 mol% or less, and the photosensitive silver salt is not positively added.

In the present invention, the solid dispersion apparatus and the technique used for carrying out the dispersion method as described above are described in, for example, “Dispersion Rheology and Dispersion Technology” (Toshio Kajiuchi and Hiroki Usui, 1991, Shinzansha Publishing Co., Ltd., p357
-P403), "Progress of Chemical Engineering Vol.24" (edited by the Society of Chemical Engineers, Tokai Branch, 1990, Maki Shoten, p184-p185),
Although detailed in the dispersing method of the present invention, the aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and sent into a pipe, and then passed through a narrow slit provided in the pipe, Thereafter, the dispersion is finely dispersed by causing an abrupt pressure drop in the dispersion. Regarding the high-pressure homogenizer to which the present invention relates, generally, (a) `` shearing force '' generated when the dispersoid passes through a narrow gap at a high pressure, at a high speed, (b) the dispersoid is released from a high pressure to a normal pressure. It is considered that the particles are dispersed into fine particles by a dispersing force such as “cavitation force” generated when the particles are dispersed. An example of this type of dispersing device is a Gaulin homogenizer.In this device, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on the cylindrical surface, and the force is applied to the surrounding wall by the force. The particles collide and are emulsified and dispersed by the impact force. Operating pressure is generally 100~600kg / cm ^2, the number is the flow velocity m~3
It is in the range of 0 m / sec, and in order to increase the dispersion efficiency, a device in which the high flow velocity portion is saw-toothed and the number of collisions is increased has been devised. On the other hand, in recent years, apparatuses capable of dispersing at higher pressure and higher flow rate have been developed, and typical examples thereof include a microfluidizer (Microfluidex International Corporation) and a nanomizer (specialized machine). Industrial Co., Ltd.).

The dispersion apparatus suitable for the present invention includes a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation.
(With G10Z interaction chamber), M-
110Y (with H10Z interaction chamber), M-140K (with G10Z interaction chamber), HC-5000 (L30Z or H23
0Z interaction chamber), HC-80
00 (with an E230Z or L30Z interaction chamber) and the like. Using these devices,
After the aqueous dispersion containing at least the organic silver salt is pressurized by a high-pressure pump or the like and sent into the pipe, a desired pressure is applied by passing through a narrow slit provided in the pipe, and thereafter, the inside of the pipe is It is possible to obtain an organic silver salt dispersion optimal for the present invention by causing a rapid pressure drop in the dispersion by, for example, rapidly returning the pressure to the atmospheric pressure.

In the dispersion of the organic silver salt in the present invention,
It is possible to disperse to the desired particle size by adjusting the flow rate, the differential pressure at the time of pressure drop, and the number of treatments.However, from the viewpoint of photographic characteristics and particle size, the flow rate is 200 m / sec to 600 m / sec, the differential pressure is preferably in the range of 900~3000kg / cm ^2, the flow rate is 300 meters / sec ～600M / sec, the pressure difference at the pressure drop 1500-3000
More preferably, it is in the range of kg / cm ² . The number of times of the dispersion processing can be selected as needed. Usually, the number of times of processing is 1 to 10 times, but from the viewpoint of productivity, the number of times of processing is about 1 to 3 times. Elevating such an aqueous dispersion under high pressure is not preferable from the viewpoint of dispersibility and photographic properties,
At a high temperature exceeding ℃, the particle size tends to increase and fog tends to increase. Therefore,
In the present invention, the high pressure, the step before converting to a high flow rate, the step after reducing the pressure, or both of these steps include a cooling step, the temperature of such water dispersion is 5 to 90 by the cooling step C. It is preferably maintained in the range of 5 ° C., more preferably in the range of 5 to 80 ° C., particularly preferably in the range of 5 to 65 ° C. Especially, 1500-3000kg / c
It is effective to provide the above cooling step at the time of high-pressure dispersion in the m ² range. As the cooler, a double tube, a double tube using a static mixer, a multi-tube heat exchanger, a coiled tube heat exchanger, or the like can be appropriately selected according to the required heat exchange amount. In addition, in order to increase the efficiency of heat exchange, it is only necessary to select a suitable one such as the thickness, wall thickness and material of the pipe in consideration of the working pressure. The refrigerant used for the cooler should be 20 ° C well water, 5-10 ° C cold water treated by a refrigerator, and, if necessary, -30 ° C ethylene glycol / water refrigerant, etc. You can also.

In the dispersion operation in the present invention, it is preferable to disperse the organic silver salt in the presence of an aqueous solvent-soluble dispersant (dispersion aid). As the dispersing aid, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer,
Synthetic anionic polymers such as maleic acid monoester copolymer, acrylomethylpropanesulfonic acid copolymer,
Carboxymethyl starch, semi-synthetic anionic polymers such as carboxymethyl cellulose, alginic acid, anionic polymers such as pectic acid, the compounds described in JP-A-7-350753, or known anionic, nonionic, cationic surfactants and the like Other polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, a known polymer such as hydroxypropylmethylcellulose, or a polymer compound existing in nature such as gelatin can be appropriately selected and used, but polyvinyl alcohols, Water-soluble cellulose derivatives are particularly preferred. The dispersing aid is
It is a common method to mix with an organic silver salt powder or an organic silver salt in a wet cake state before dispersion and send it to a dispersing machine as a slurry, but it is a heat treatment or a solvent mixed with the organic silver salt in advance. The treatment may be performed to obtain an organic silver salt powder or a wet cake. The pH may be controlled with a suitable pH adjuster before, during or after dispersion.

Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation. The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of fine particles during storage, or stored in a highly viscous state by a hydrophilic colloid (for example, in a jelly state using gelatin). You can also. Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage. The organic silver salt in the present invention can be used in a desired amount, show a coating amount per image recording material 1 m ^2, preferably 0.1-5 g / m ² as silver amount, more preferably 1 to 3 g /
a m ^2.

When an additive known as a "toning agent" for improving the image is included in the heat-developable image recording material, the optical density may increase. Toning agents may also be advantageous in forming black silver images. The toning agent is preferably contained in an amount of 0.1 to 50% (mole) per mole of silver on the surface having the image forming layer, and more preferably 0.5 to 20% (mole). Further, the color tone agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable photographic material using an organic silver salt, a wide range of toning agents are disclosed in JP-A-46-6077 and JP-A-47-1028.
No. 2, No. 49-5019, No. 49-5020, No. 49-91
No. 215, No. 49-91215, No. 50-2524, No. 50
JP-32927, JP-A-50-67132, JP-A-50-67641,
No. 50-114217, No. 51-3223, No. 51-27923, No. 52-14788, No. 52-99813, No. 53-1020
No. 53-76020, No. 54-156524, No. 54-
156525, 61-183642, JP-A-4-56848, JP-B-49-10727, 54-20333, U.S. Pat.No. 3,080,254, 3,446,648, and 3 , 78
Nos. 2,941, 4,123,282, 4,510,236, British Patent 1380795, Belgian Patent 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4 -Dimercaptopyrimidine, 3-mercapto-4,5-
Mercaptans exemplified by diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N
-(Aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N,
N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N'-
Hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl- (benzothiazole)); And 3-ethyl
-5 [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivative (eg, 4- (1-naphthyl)
Derivatives such as phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione) or metal salts; phthalazinone and phthalic acid derivatives (for example, phthalic acid, Combinations with 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; phthalazine, phthalazine derivatives (eg, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine,
5,7-dimethoxyphthalazine, 6-iso-butylphthalazine,
6-tert-butylphthalazine, 5,7-dimethylphthalazine,
And derivatives such as 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives
(Eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; silver halide in situ as well as color tone modifier Rhodium complex that also functions as a source of halide ions for formation, such as hexachlororhodium
(III) ammonium, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine- 2,4-
Benzoxazine-2,4-diones such as dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric -Triazines (e.g., 2,4-dihydroxypyrimidine,
2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (e.g., 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6
-Dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene). The toning agent used in the present invention may be added by any method such as a solution, a powder, and a solid fine particle dispersion. Solid fine particle dispersion is known micronization means (for example, ball mill, vibrating ball mill, sand mill, colloid mill,
Jet mill, roller mill, etc.). Also,
When dispersing the solid fine particles, a dispersing aid may be used.

The heat-developable image recording material of the present invention contains a binder. As the binder for the image forming layer (photosensitive layer, emulsion layer) of the heat-developable image recording material of the present invention, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, and cellulose acetate , Polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral,
Butyl ethyl cellulose, methacrylate copolymer,
Maleic anhydride copolymer, polystyrene and butadiene-styrene copolymer. If necessary, two or more of these polymers can be used in combination. Such a polymer is used in an amount sufficient to hold the components therein. That is,
Used in an effective range to function as a binder. The effective range can be appropriately determined by those skilled in the art. As a guide when at least the organic silver salt is retained, the ratio of the binder to the organic silver salt is preferably 15: 1 to 1: 2, particularly preferably 8: 1 to 1: 1.

At least one of the image forming layers of the heat-developable image recording material of the present invention is preferably an image forming layer containing the polymer latex described below in an amount of 50% by weight or more of the total binder. (Hereinafter, this image forming layer is referred to as “the image forming layer in the present invention”, and the polymer latex used for the binder is referred to as “the polymer latex used in the present invention.”) The polymer latex is not only an image forming layer but also a protective layer. It may be used for the back layer. In particular, when the heat-developable image recording material of the present invention is used for printing in which dimensional change is a problem, it is necessary to use a polymer latex for the protective layer and the back layer. However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. As a dispersion state, a polymer is emulsified in a dispersion medium,
Emulsion polymerization, micellar dispersion, or a polymer having a partially hydrophilic structure in a polymer molecule and molecular chains themselves molecularly dispersed may be used. As for the polymer latex used in the present invention, `` Synthetic resin emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (19
78))), `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, published by Polymer Publishing Association (199)
3)) "," Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably about 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

The polymer latex used in the present invention may be a so-called core / shell type latex other than a polymer latex having a normal uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell. The preferable range of the glass transition temperature (Tg) of the polymer of the polymer latex used as a binder in the heat-developable image recording material of the present invention differs between the protective layer, the back layer and the image forming layer. In the image forming layer, the temperature is preferably 40 ° C. or lower, more preferably -30 to 40 ° C., in order to promote diffusion of the photographically useful material during thermal development. When used for the protective layer or the back layer, a glass transition temperature of 25 to 70 ° C. is preferable for contacting various devices.

The minimum film forming temperature (MFT) of the polymer latex used in the present invention is -30 ° C to 90 ° C, more preferably 0 ° C to 70 ° C.
C. is preferred. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex, also called a plasticizer. ) "
It is described in. Examples of the polymer species used in the polymer latex used in the present invention include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The polymer has a number average molecular weight of 5000 to 100000, preferably 10,000 to 1000
About 00 is preferable. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the image forming layer in the present invention are as follows. A latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer,
Latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer And latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer. Such polymers are also commercially available, and the following polymers can be used. For example, as an example of acrylic resin,
Polyester resins such as Sebian A-4635,46583,4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,857 (manufactured by Nippon Zeon Co., Ltd.)
HYDRAN AP10, 20, such as INETEX ES650, 611, 675, 850 (manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, WMS (manufactured by Eastman Chemical)
LACSTAR 7310K, 3307B, 4700H, 7132C (both manufactured by Dainippon Ink and Chemicals), Nipol Lx416, 410 and 438, such as 30, 40 (both manufactured by Dainippon Ink and Chemicals)
C, 2507 (Nippon Zeon Co., Ltd.) and the like, and vinyl chloride resins such as G351 and G576 (Nippon Zeon Co., Ltd.), etc.
As vinylidene chloride resins, L502, L513 (manufactured by Asahi Kasei Corporation), Aron D7020, D504, D5071 (manufactured by Mitsui Toatsu
Chemlipar S12 as olefin resin
0, SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone,
If necessary, two or more kinds may be blended and used.

In the image forming layer in the present invention, the above polymer latex is preferably used in an amount of 50% by weight or more of the total binder, and more preferably in an amount of 70% by weight or more. In the image forming layer in the present invention, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, or hydroxypropyl methyl cellulose may be added as needed in the range of 50% by weight or less of the whole binder. . The addition amount of these hydrophilic polymers is 30% of the total binder of the image forming layer.
% By weight, more preferably 15% by weight or less.

The image forming layer in the present invention is preferably prepared by applying an aqueous coating solution and then drying it. However, the `` water-based '' here is 60% by weight of the solvent (dispersion medium) of the coating liquid.
It means that the above is water. As components other than water of the coating solution, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following in addition to water. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 9
0/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent% by weight.) The total binder amount of the image forming layer in the present invention is 0.2 to 30 g.
/ M ² , more preferably in the range of 1 to 15 g / m ² . A crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added to the image forming layer in the invention.

A sensitizing dye can be used in the heat-developable image recording material of the present invention. As the sensitizing dye used in the present invention, any dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH D
ISCLOSURE Item17643 IV-A (p.23, December 1978), Item1
It is described in the literature described or cited in section 831X (p. 437, August 1979). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate making cameras can be advantageously selected.

As an example of spectral sensitization to red light, He-Ne
For a so-called red light source such as a laser, a red semiconductor laser or an LED, the I-1 described in JP-A-54-18726 is used.
To I-38, I-1 described in JP-A-6-75322.
To I-35 and the compounds of I-1 to I-34 described in JP-A-7-287338, the dyes 1 to 20 described in JP-B-55-39818, and JP-A-62-284343. I-1 described in
To I-37 and the compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected. 750
For semiconductor laser light sources in the wavelength range of ~ 1400 nm,
A variety of known dyes, including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol, and xanthene dyes, can be spectrally sensitized favorably. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective.
For example, U.S. Pat.Nos. 3,761,279, 3,719,495, 3,877,943, British Patent 1,466,201
No. 1,469,117, No. 1,422,057, Japanese Patent Publication No. 3-10391, No. 6-52387, Japanese Unexamined Patent Publication No. 5-341432, No. 6-1
It may be appropriately selected from known dyes as described in JP-A-94781 and JP-A-6-301141.

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, JP-A Nos. 62-58239 and 3-1).
No. 38638, 3-138642, 4-255840,
No. 5-72659, No. 5-72661, No. 6-222491, No. 2-230506, No. 6-258757, No. 6-317868
JP-A-6-324425, JP-T-Hei 7-500926, the dye described in U.S. Patent No. 5,541,054), a dye having a carboxylic acid group (for example, JP-A-3-163440) No. 6-301141, dyes described in U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329,
No. 49-105524, No. 51-127719, No. 52-80829, No. 54-61517, No. 59-214846, No. 60-6750
No. 63-159841, JP-A-6-35109,
No. 6-59381, No. 7-146537, No. 7-146537, Japanese Patent Publication No. 55-50111, British Patent No. 1,467,638,
Dyes described in U.S. Pat. No. 5,281,515).

Further, as the dye forming a J-band, the dye described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131, JP-A-59-48753
No. 6,019,036, which can be preferably used in the present invention. These sensitizing dyes may be used alone,
It may be used in combination of more than one kind. In particular, combinations of sensitizing dyes are frequently 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are
Research Disclosure Volume 176, 17643 (December 1978) No. 23
Paragraph J on page IV, or JP-B-49-25500, 43-4933
And JP-A-59-19032 and JP-A-59-192242.

The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2, 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy
It may be added to the emulsion by dissolving it in a solvent such as 1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, alone or in a mixed solvent. Further, as disclosed in U.S. Pat.No. 3,469,987, a dye is dissolved in a volatile organic solvent, this solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to the emulsion. Japanese Patent Publication No. 44-23389,
As disclosed in 44-27555 and 57-22091, a dye is dissolved in an acid, and this solution is added to the emulsion, or an acid or base is allowed to coexist to form an aqueous solution into the emulsion. Addition method, U.S. Pat.No. 3,822,135, U.S. Pat.
A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in JP-A-6,025, etc.
A method of directly dispersing a dye in a hydrophilic colloid as disclosed in Japanese Patent No. 105141, and adding the dispersion to an emulsion, as disclosed in JP-A-51-74624,
It is also possible to use a method in which a dye is dissolved using a compound that causes a red shift, and this solution is added to the emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye may be added to the silver halide emulsion at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat.Nos. 2,735,766, 3,628,960, and 4,183,
No. 756, 4,225,666, JP-A-58-184142
As disclosed in the specifications such as JP-A Nos. 60-196749 and 60-1966749, chemical ripening is performed during the step before silver halide grain formation and / or before desalination, during and / or after desalination. Before the start of the process, as disclosed in the specification of Japanese Patent Application Laid-Open No. 58-113920, etc., immediately before or during the chemical ripening, during the process, after the chemical ripening, the emulsion was coated before the coating. May be added at any time before the process. Further, as disclosed in U.S. Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, to form particles. Compounds and compounds to be dividedly added may be added separately during the process and during the chemical ripening process or after the completion of the chemical ripening, or before the chemical ripening or during the process and after the completion. May be added by changing the type of combination. The amount of the sensitizing dye used in the present invention may be a desired amount in accordance with performance such as sensitivity and fog, but is preferably 10 ^-6 to 1 mol, more preferably 10 ^-4 to 1 mol per mol of silver halide in the photosensitive layer. 10 ^-1 mol is more preferred.

In the heat-developable image recording material of the present invention, a mercapto compound or a disulfide compound is used for suppressing or accelerating the development to control the development, for improving the spectral sensitization efficiency, for improving the storage stability before and after the development, and the like. , A thione compound. When a mercapto compound is used in the present invention, it may have any structure, but is preferably a compound represented by Ar-SM ⁰ or Ar-SS-Ar. In the formula, M ⁰ is a hydrogen atom or an alkali metal atom, and Ar is an aromatic or fused aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic rings in these groups are benzimidazole, naphthimidazole, benzothiazole,
Naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is
For example, halogen (e.g., Br or Cl), hydroxy,
Amino, carboxy, alkyl (e.g., having one or more carbon atoms, preferably having 1-4 carbon atoms), alkoxy (e.g., one or more carbon atoms, preferably
It may have a substituent selected from the group consisting of those having 4 carbon atoms) and aryl (which may have a substituent). As mercapto-substituted heteroaromatic compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-
Ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl- 2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4 -Pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto
-1,2,4-Triazole, 4-Hydrocyr-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5 -Phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, 3
-(5-Mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N '-[3- (5-mercaptotetrazolyl)
[Phenyl] urea, 2-mercapto-4-phenyloxazole, and the like, but the present invention is not limited thereto. The addition amount of these mercapto compounds is preferably in the range of 0.0001 to 1 mol per mol of silver in the emulsion layer (image forming layer), and more preferably 0.01 to 1 mol per mol of silver.
It is in the amount of 01-0.3 mol.

In the image forming layer (photosensitive layer) in the present invention, a polyhydric alcohol (for example, glycerin and diol of the type described in US Pat. No. 2,960,404) as a plasticizer and a lubricant, and US Pat. Fatty acids or esters described in 2,588,765 and 3,121,060, and silicone resins described in British Patent No. 955,061 can be used. The heat-developable image recording material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer. As the binder for the surface protective layer in the present invention, any polymer may be used, but it is preferable that the polymer having a carboxylic acid residue is contained in an amount of 100 mg / m ^{2 to} 5 g / m ² . Examples of the polymer having a carboxyl residue include natural polymers (gelatin, alginic acid, etc.), modified natural polymers (carboxymethylcellulose, phthalated gelatin, etc.), and synthetic polymers (polymethacrylate, polyacrylate, polyalkylmethacrylate / acrylate). Copolymer, polystyrene / polymethacrylate copolymer, etc.). The content of carboxy residues in such a polymer is 100 g of polymer
It is preferably 10 mmol or more and 1.4 mol or less per unit. Further, the carboxylic acid residue may form a salt with an alkali metal ion, an alkaline earth metal ion, an organic cation, or the like.

As the surface protective layer in the present invention, any adhesion preventing material may be used. Examples of anti-adhesion materials include wax, silica particles, styrene-containing elastomeric block copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and the like. And mixtures. Further, a crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the surface protective layer. U.S. Pat.Nos. 3,253,921, 2,274,782, and
Light absorbing substances and filter dyes such as those described in 2,527,583 and 2,956,879 can be used. Also, for example, U.S. Pat.
The dye can be mordanted as described in US Pat. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3, and particularly preferably 0.2 to 1.5.

Various dyes and pigments can be used in the photosensitive layer of the present invention from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer in the present invention may be any, for example, pigments and dyes described in the color index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, Examples thereof include carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments including phthalocyanine, and inorganic pigments. Preferred dyes used in the present invention are anthraquinone dyes
(E.g., compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147)
Azomethine dyes (e.g., compounds 17 to 47 described in JP-A-5-341441) and indoaniline dyes (e.g., JP-A-5-341441).
Compounds 11 to 19 described in 289227, Compound 47 described in JP-A-5-341441, Compound described in JP-A-5-165147
2-10 to 11) and azo dyes (compounds 10 to 16 described in JP-A-5-341441). As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds used is determined depending on the desired absorption amount, but it is generally preferable to use them in an amount of 1 μg or more and 1 g or less per 1 m ² of the image recording material.

The heat-developable image recording material of the present invention has at least one photosensitive layer (image forming layer) containing a silver halide emulsion on one side of a support, and has a back layer on the other side. It is preferably a so-called single-sided photosensitive material. In the present invention, the back layer has a maximum absorption in a desired range of about
It is preferably from 0.3 to 2.0. The desired range is 75
When it is 0 to 1400 nm, the optical density at 750 to 360 nm is preferably 0.005 or more and less than 0.5, and more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3. Desired range is 750n
m or less, the maximum absorption in the desired range before image formation is 0.3 or more and 2.0 or less, and 360 to 7 after image formation.
It is preferable that the antihalation layer has an optical density at 50 nm of 0.005 or more and less than 0.3. There is no particular limitation on the method of reducing the optical density after image formation to the above range, for example, a method of reducing the density by dyeing by heating to reduce the density by heating as described in Belgian Patent No. 733,706,
JP-A-54-17833 discloses a method of reducing the density by decoloring by light irradiation.

When antihalation dyes are used in the present invention, such dyes have the desired absorption in the desired range,
Any compound may be used as long as it has a sufficiently low absorption in the visible region after the treatment and a preferable absorbance spectrum of the back layer is obtained. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458, JP-A-2-216140
No. 7-13295, No. 7-11432, U.S. Pat.No.5,380,635, JP-A-2-688539, page 13, lower left column
From line 1 to page 9, lower left column, line 9, line 3-24539, No. 14
From the lower left column of the page to the right lower column of page 16, there are compounds described in JP-A-52-139136, as dyes which can be decolorized by the treatment.
No. 132334, No. 56-501480, No. 57-16060, No. 57-68831, No. 57-101835, No. 59-1824
No. 36, JP-A-7-36145, JP-A-7-199409,
JP-B-48-33692, JP-B-50-16648, JP-B-2-41
No. 734, U.S. Pat.No. 4,088,497, U.S. Pat.
No. 7, 4,548,896, and 5,187,049.

In the present invention, suitable binders for the back layer 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, and 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 (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal)).
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

When the heat-developable image recording material of the present invention is a single-sided photosensitive material, a surface protective layer of a photosensitive emulsion layer (image forming layer) and / or a surface protective layer of a back layer or a back layer for improving transportability. May be added with a matting agent. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used,
For example, U.S. Patent Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782,
3,539,344, the organic matting agent described in each specification such as 3,767,448, etc., 1,260,772, 2,19
No. 2,241, No. 3,257,206, No. 3,370,951, No. 3,523,022, No. 3,769,020 Use those well-known in the art such as inorganic matting agents described in each specification such as No. 3,769,020. be able to. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of a water-dispersible vinyl polymer, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer,
Polystyrene, styrene-divinylbenzene copolymer,
Examples of cellulose derivatives such as polyvinyl acetate, polyethylene carbonate, and polytetrafluoroethylene, such as methylcellulose, cellulose acetate, and cellulose acetate propionate; examples of starch derivatives such as carboxy starch, carboxynitrophenyl starch, and urea-formaldehyde-starch reactant For example, gelatin hardened with a known hardener and hardened gelatin obtained by coacervate hardening into fine capsule hollow particles can be preferably used. Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. The above matting agents can be used by mixing different types of substances as necessary.
The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In carrying out the present invention
It is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the photosensitive material and the surface gloss, the particle size, shape, and particle size distribution can be adjusted as needed during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, it is a preferred embodiment to add a matting agent to the backing layer. The matting degree of the backing layer is preferably Beck smoothness of 1200 seconds or less and 10 seconds or more, more preferably 700 seconds or less and 50 seconds or more. It is. In the present invention, the matting agent is preferably contained in the layer functioning as the outermost surface layer or the outermost surface layer of the light-sensitive material, or a layer close to the outer surface, and is contained in a layer acting as a so-called protective layer. Is preferred. The matte degree of the emulsion surface protective layer may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably from 500 seconds to 10,000 seconds, and particularly preferably from 500 seconds to 2,000 seconds.

The heat-developable photographic emulsion used in the present invention comprises one or more layers on a support. One layer construction must include optional additional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is that the first emulsion layer (usually the layer adjacent to the support) contains an organic silver salt and silver halide, and the second layer or both layers do not contain some other components. No. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, and may include all components in a single layer as described in U.S. Pat.No. 4,708,928. You may go out. In the case of a multi-dye, multi-color photosensitive heat-developable photographic material, each emulsion layer is generally functionalized or non-functional between each emulsion layer (photosensitive layer) as described in U.S. Pat. No. 4,460,681. By using a functional barrier layer,
They are kept distinct from each other. Backside resistive heating layer as shown in U.S. Pat.Nos. 4,460,681 and 4,374,921
Can be used in a photosensitive heat-developable photographic image system.

In the heat-developable image recording material of the present invention, a hardener may be used for each layer such as an image forming layer (photosensitive layer), a protective layer and a back layer. Examples of hardeners include U.S. Pat.
No. 4,281,060, polyisocyanates described in JP-A-6-208193 and the like, U.S. Pat.
Epoxy compounds described in the specification of No. 2, etc., vinyl sulfone compounds described in JP-A No. 62-89048 and the like are used. In the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate.
Specifically, JP-A-62-170950, U.S. Pat.
No. 0,644, a fluorine-containing polymer surfactant described in JP-A-60-244945, a fluorine-containing surfactant described in JP-A-63-188135, U.S. Pat.
And polyalkylene oxides and anionic surfactants described in JP-A-6-301140.

The heat-developable photographic emulsion of the present invention can be generally coated on various supports. Typical supports include polyester films, primed polyester films, poly (ethylene terephthalate) films, polyethylene naphthalate films, cellulose nitrate films, cellulose ester films, poly (vinyl acetal) films, polycarbonate films and related or resinous Materials, as well as glass,
Including paper, metal, etc. Flexible substrates, especially coated with baryta and / or partially acetylated α-olefin polymers, especially polymers of C 2-10 α-olefins such as polyethylene, polypropylene, ethylene-butene copolymer A paper support is typically used. Such a support may be transparent or opaque, but is preferably transparent. Among them, biaxially stretched polyethylene terephthalate (PET) of about 75 to 200 μm is particularly preferred.

On the other hand, when the plastic film is passed through a heat developing machine at a temperature of 80 ° C. or more, the dimensions of the film generally expand and contract. If the processed material is used for printing plate making,
This expansion and contraction is a serious problem when performing precision multicolor printing.
Therefore, in the present invention, it is preferable to use a film having a small dimensional change, in which internal strain remaining in the film at the time of biaxial stretching is alleviated and heat shrinkage distortion generated during thermal development is devised. For example, polyethylene terephthalate which is heat-treated at a temperature of 100 ° C. to 210 ° C. before applying the photographic emulsion for thermal development is preferably used. Those having a high glass transition temperature are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyethersulfone, polyarylate, polycarbonate and the like can be used. The heat-developable image recording material of the present invention is, for antistatic,
For example, soluble salts (eg, chlorides, nitrates, etc.), deposited metal layers, U.S. Pat. Nos. 2,861,056 and 3,20
6,312, an ionic polymer or an insoluble inorganic salt as described in U.S. Pat.No. 3,428,451, and the oxidation described in JP-A-60-252349 and JP-A-57-104931. It may have a layer containing tin fine particles and the like.

As a method for obtaining a color image using the heat-developable image recording material of the present invention, there is a method described in JP-A-7-13295, page 10, left column, line 43 to 11 left column, line 40. Also,
British Patent No. 1,326,889 as stabilizer for color dye images
And U.S. Pat. Nos. 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337 and 4,042,394. The photothermographic emulsions of the present invention can be coated by various coating operations including dip coating, air knife coating, flow coating or extrusion coating using a hopper of the type described in U.S. Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761,791 and GB 837,095. Additional layers in the heat-developable image recording material of the present invention are known in the photothermographic art, for example, a dye-receiving layer for receiving a migrating dye image, an opacifying layer if reflective printing is desired, a protective topcoat layer. And the like. The image recording material of the present invention is preferably capable of forming an image with only one image recording material, and it is preferable that a functional layer such as an image receiving layer required for image formation does not form another image recording.

The image recording material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source. As laser light according to the present invention, gas lasers,
YAG lasers, dye lasers, semiconductor lasers and the like are preferred. Further, a semiconductor laser and a second harmonic generation element can be used. The image recording material of the present invention has a low haze at the time of exposure and tends to cause interference fringes.
As the interference fringe prevention technology, a technology for obliquely entering a laser beam into an image recording material, such as disclosed in Japanese Patent Application Laid-Open No. 5-113548, and disclosed in International Publication WO95 / 31754, etc. Known methods using a multi-mode laser are known, and it is preferable to use these techniques. To expose the image recording material of the present invention, SPIE v
ol.169 Laser Printing 116-128 (1979), JP-A-4-510
No. 43, International Publication No. WO95 / 31754, etc., it is preferable to expose the laser beams so that they overlap each other so that the scanning lines are not visible.

In the heat development step of the image forming method using the heat-developable image recording material of the present invention, any method may be used for development. Usually, the image recording material exposed imagewise is heated and developed. As a preferred embodiment of the heat developing machine to be used, a heat developing image recording material is brought into contact with a heat source such as a heat roller or a heat drum.
-56499, Patent Publication No. 684453,
JP-A-9-292695, JP-A-9-29738
No. 5 and International Publication No. WO95 / 30934, a non-contact type heat developing machine disclosed in
No. 13,294, WO 97/28489, WO 97/28488 and WO 97/284.
No. 87 has a heat developing machine. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C, more preferably 10 to 250 ° C.
0-140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds. As a method of preventing processing unevenness due to a dimensional change during the heat development of the heat-developable image recording material of the present invention, after heating at a temperature of 80 ° C. or more and less than 115 ° C. for 5 seconds or more to prevent an image from appearing,
A method of forming an image by thermal development at a temperature of from 140 ° C. to 140 ° C. (a so-called multi-stage heating method) is effective.

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

The surface material of the roller 13 and the smooth surface 14
Is a high-temperature durable, heat-developable image recording material 10
Any material may be used as long as it does not hinder the conveyance of the roller. However, the material of the roller surface is preferably silicon rubber, and the member having a smooth surface is preferably a nonwoven fabric made of aromatic polyamide or Teflon (PTFE). It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely. The preheating section upstream of the heat development processing section has a temperature and time lower than the heat development temperature (for example, about 10 to 30 ° C. lower) and sufficient for evaporating the amount of water in the heat development image recording material. It is desirable to set the temperature so as to avoid development unevenness at a temperature higher than the glass transition temperature (Tg) of the support of the heat-developable image recording material 10. Further, a guide plate 16 is provided downstream of the thermal development processing section, and a slow cooling section is further provided. The guide plate is preferably made of a material having a low thermal conductivity, and is preferably cooled gradually to prevent deformation of the heat-developable image recording material.

Although the above has been described with reference to the illustrated examples, the present invention is not limited to this. For example, the thermal developing machine used in the present invention, such as that described in JP-A-7-13294, may have various structures. . In the case of the multi-stage heating method preferably used in the present invention, in the above-described apparatus, two or more heat sources having different heating temperatures may be provided, and heating may be performed continuously at different temperatures. The heat-developable image recording material of the present invention forms a black-and-white image by a silver image, and is used for medical diagnosis, a photothermographic material for industrial photography, a photothermographic material for printing, and a photothermographic material for COM. It is preferably used as In these uses, a duplication film MI-Du manufactured by Fuji Photo Film Co., Ltd. is used for medical diagnosis based on the formed black and white image.
p-101 and PDO-1 for return printing films manufactured by Fuji Photo Film Co., Ltd.
Needless to say, it can be used as a mask for forming an image on 00 or an offset printing plate. The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples.

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EXAMPLES Example 1 The compounds used in Example 1 are shown below.

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(Preparation of PET support) Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV =
0.66 (phenol / tetrachloroethane = 6/4
(Measured at 25 ° C. in (weight ratio)). This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and quenched to prepare an unstretched film having a thickness of 175 μm after heat setting. This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively.
After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck part of the tenter, knurling is performed on both ends, and 4 kg / c
It was wound up at m ² to obtain a roll having a thickness of 175 μm.

(Surface Corona Treatment) Using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, 0.375 kV was applied to the support.
-It turned out that the processing of A * minute / m < ² > was performed.
The processing frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

(Preparation of Undercoating Support) (1) Preparation of Undercoating Layer Coating Formulation (1) (for Undercoating Layer on Photosensitive Layer Side) Pesresin A-515GB manufactured by Takamatsu Oil Co., Ltd. (30 wt% solution) 234 g Polyethylene glycol Monononylphenyl ether (average ethylene oxide number = 8.5) 10 wt% solution 21.5 g Soken Chemical Co., Ltd. MP-1000 (polymer fine particles, average particle diameter 0.4 μm) 0.91 g distilled water 744 ml

Formulation (2) (for the backside first layer) Butadiene-styrene copolymer latex 158 g (solid content 40 wt%, butadiene / styrene weight ratio = 32/68) 2,4-dichloro-6-hydroxy-S -Triazine sodium salt 8wt% aqueous solution 20g 1wt% aqueous solution of sodium laurylbenzenesulfonate 10ml distilled water 854ml

Formulation (3) (for back surface side second layer) SnO ₂ / SbO (9/1 weight ratio, average particle size 0.038 μm, 17 wt% dispersion) 84 g Gelatin (10% aqueous solution) 89.2 g Shin-Etsu 8.6 g Metrolose TC-5 (2% aqueous solution) manufactured by Chemical Co., Ltd. MP-1000 (polymer fine particles) manufactured by Soken Chemical Co., Ltd. 0.01 g 1 wt% aqueous solution of sodium dodecylbenzenesulfonate 10 ml NaOH (1%) 6 ml Proxel (Manufactured by ICI) 1ml distilled water 805ml

(Preparation of Undercoating Support) Thickness of 175 μm
m, on both sides of the biaxially stretched polyethylene terephthalate support, the above-mentioned corona discharge treatment was applied, and then an undercoating coating solution formulation (1) was applied on one side (photosensitive layer side) with a wire bar at a wet application amount of 6.6 ml / m. ² (per side) and dried at 180 ° C. for 5 minutes. Then, the undercoating coating liquid formulation (2) was applied to the back surface (back surface) with a wire bar to a wet application amount of 5.7 ml / m ² . And dried at 180 ° C. for 5 minutes. Further, the undercoating coating liquid formulation (3) was further applied to the back surface (back surface) with a wire bar so that the wet application amount was 7.7 ml / m ² , and 18
After drying at 0 ° C. for 6 minutes, an undercoat support was prepared.

(Preparation of Back Surface Coating Solution) (Preparation of Solid Particle Dispersion (a) of Base Precursor)
64 g of the base precursor compound 11, 28 g of diphenyl sulfone, and a surfactant Demol N manufactured by Kao Corporation
10 g was mixed with 220 ml of distilled water, and the mixed solution was dispersed in beads using a sand mill (1/4 Gallon sand grinder mill, manufactured by Imex Co., Ltd.) to obtain a solid fine particle dispersion of a base precursor compound having an average particle diameter of 0.2 μm. (A) was obtained. (Preparation of Dye Solid Fine Particle Dispersion) Cyanine Dye Compound 1
Of No. 3 and 5.8 g of sodium P-dodecylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixture was dispersed using a sand mill (1/4 Gallon sand grinder mill, manufactured by Imex Co., Ltd.) and dispersed in beads. A dispersion of solid dye fine particles having a particle diameter of 0.2 μm was obtained. (Preparation of antihalation layer coating solution) Gelatin 17 g,
9.6 g of polyacrylamide, 70 g of the above-mentioned base precursor solid fine particle dispersion (a), 56 g of the above-mentioned dye solid fine particle dispersion, 1.5 g of polymethyl methacrylate fine particles (average particle size 6.5 μm), and 0.03 g of benzoisothiazolinone 1. Sodium polyethylene sulfonate
2 g, blue dye compound 14 0.2 g, water 844 ml
The mixture was mixed to prepare an antihalation layer coating solution.

(Preparation of Back Surface Protective Layer Coating Solution)
Incubate at 0 ° C., gelatin 50 g, polystyrene sodium sulfonate 0.2 g, N, N-ethylenebis (vinylsulfone acetamide) 2.4 g, sodium t-octylphenoxyethoxy ethanesulfonate 1 g, benzoisothiazolinone 30 mg, N -Perfluorooctylsulfonyl-N-propylalanine potassium salt 37m
g, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl)
Ether [average degree of polymerization of ethylene oxide 15] 0.1
5 g, 32 mg of C ₈ F ₁₇ SO ₃ K, C ₈ F ₁₇ SO ₂ N (C
_{3 H 7) (CH 2 CH} 2 O) 4 and _{(CH 2) 4 -SO 3 Na} 64
mg, acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) 8.8 g, aerosol OT (manufactured by American Cyanamid Co.) 0.6 g, liquid paraffin emulsion 1.8 g as liquid paraffin, 950 ml of water
The mixture was mixed to give a back surface protective layer coating solution.

<< Preparation of Silver Halide Emulsion 1 >> Distilled Water 14
8.0cc of a 1 wt% potassium bromide solution is added to 2cc,
Further, 8.2 cc of 1N nitric acid and 20 g of phthalated gelatin
While stirring the solution to which the solution was added in a titanium-coated stainless steel reaction bottle, the solution temperature was maintained at 37 ° C., and silver nitrate was 37.0.
Distilled water was added to 4 g, and a solution A diluted to 159 cc and a solution B prepared by diluting potassium bromide to a volume of 200 cc with distilled water were prepared, and the pAg was maintained at 8.1 by the control double jet method. The whole amount of the solution A was added at a constant flow rate over 1 minute. Solution B was added by a controlled double jet method. Thereafter, 30 cc of a 3.5 wt% aqueous hydrogen peroxide solution was added, and 36 cc of a 3 wt% aqueous solution of benzimidazole was further added. Thereafter, the solution A2 was again diluted with distilled water to 317.5 cc, and the solution B was mixed with a solution of the solution 6 and a solution of the potassium salt of tripotassium hexachloridate so that the final concentration would be 1 × 10 ^-4 mol per mol of silver. The solution A2 was dissolved and the solution A2 was diluted with distilled water to 400 cc twice the volume of the solution B, and the solution A2 was maintained at a constant flow rate by the controlled double jet method while maintaining the pAg at 8.1. The whole amount was added over 10 minutes. Solution B2 was added by a controlled double jet method. Thereafter, 50 cc of a 0.5 wt% methanol solution of 5-methyl-2-mercaptobenzimidazole was added, and the pAg was increased to 7.5 with silver nitrate.
The pH was adjusted to 3.8 with sulfuric acid, the stirring was stopped, the precipitation / desalting / water washing steps were performed, 3.5 g of deionized gelatin was added, 1N sodium hydroxide was added, and the pH was adjusted to 6.0.
The dispersion was adjusted to 0 and pA8.2 to prepare a silver halide dispersion.

The grains in the completed silver halide emulsion were pure silver bromide grains having an average equivalent sphere diameter of 0.053 μm and a variation coefficient of equivalent sphere diameter of 18%. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The {100} plane ratio of the particles was determined to be 85% using the Kubelka-Munk method. The above emulsion was maintained at 38 ° C. with stirring, and 0.035 g of benzoisothiazolinone was added.
(Added with a 3.5 wt% methanol solution), and after 40 minutes, a solid dispersion of the spectral sensitizing dye A (aqueous gelatin solution) was added at 5 × 10 ⁻³ mol per mol of silver, and after 1 minute, the temperature was raised to 47 ° C. , 3 × 10 ^-5 mol was added after 20 minutes sodium benzenethiosulfonate per mole of silver, further, a tellurium sensitizer B was aged 5 × 10 ^-5 mol addition 90 min per mol of silver after 2 minutes . Immediately before the completion of ripening, 5 cc of a 0.5 wt% methanol solution of N, N′-dihydroxy-N ″ -diethylmelamine was added, the temperature was lowered to 31 ° C., 5 cc of a 3.5 wt% methanol solution of phenoxyethanol,
5-methyl-2-mercaptobenzimidazole is converted to silver 1
The halogenation is carried out by adding 7 × 10 ^-3 mol and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole per mol of 6.4 × 10 ^-3 mol per mol of silver. Silver emulsion 1 was prepared.

<< Preparation of Silver Halide Emulsion 2 >> In the preparation of silver halide emulsion 1, a liquid temperature of 37 ° C. during grain formation was adjusted to 5 ° C.
Average sphere equivalent diameter 0.08 in the same manner except that the temperature was changed to 0 ° C.
A pure silver bromide cubic grain emulsion having a diameter of μm and a coefficient of variation of sphere equivalent diameter of 15% was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1. Further, spectral sensitization, chemical sensitization and 5-methyl-sensitization were carried out in the same manner as in Emulsion 1, except that the amount of the spectral sensitizing dye A was changed to 4.5 × 10 ^-3 mol per mol of silver.
2-mercaptobenzimidazole, 1-phenyl-2
-Heptyl-5-mercapto-1,3,4-triazole was added to obtain a silver halide emulsion 2.

<< Preparation of Silver Halide Emulsion 3 >> Halogenation
In the preparation of silver emulsion 1, the liquid temperature at the time of grain formation was 37 ° C.
The average sphere equivalent diameter is 0.03 in the same manner except that the temperature is changed to 7 ° C.
Pure silver bromide cubic grains having a diameter of 8 μm and a coefficient of variation of equivalent sphere diameter of 20%
An emulsion was prepared. Precipitation as in silver halide emulsion 1 /
Desalting / water washing / dispersion was performed. Further addition of spectral sensitizing dye A
The amount is 6 × 10 per mole of silver. ^-3Emulsion except changed to mole
Spectral sensitization, chemical sensitization and 5-methyl-2
-Mercaptobenzimidazole, 1-phenyl-2-
Heptyl-5-mercapto-1,3,4-triazole
Was added to obtain a silver halide emulsion 3.

<< Preparation of Mixed Emulsion A for Coating Solution >> A silver halide emulsion 1 was dissolved in 70% by weight, a silver halide emulsion 2 was dissolved in 15% by weight, and a silver halide emulsion 3 was dissolved in 15% by weight. 7 × 10 ^-3 mol per mol of silver was added as a 1 wt% aqueous solution.

<< Preparation of silver salt of flaky fatty acid >> Behenic acid (product name: Edenor C22-85R) 8 manufactured by Henkel
7.6 g, distilled water 423 ml, 5N-NaOH aqueous solution 4
9.2 ml and tert-butanol (120 ml) were mixed, and reacted by stirring at 75 ° C. for 1 hour to obtain a sodium behenate solution. Separately, an aqueous solution of 40.4 g of silver nitrate 20
6.2 ml (pH 4.0) was prepared and kept at 10 ° C. A reaction vessel containing 635 ml of distilled water and 30 ml of tert-butanol was kept at 30 ° C., and while stirring, the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes, 10 seconds and 60 minutes, respectively. And added. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the addition of the silver sulfate aqueous solution was started, and then the sodium behenate solution was started to be added. After the addition of the silver nitrate aqueous solution was completed, the sodium behenate solution was added for 9 minutes and 30 seconds. Only to be added. At this time, the temperature inside the reaction vessel was set at 30 ° C., and the external temperature was controlled so that the liquid temperature became constant. The piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the steam opening was adjusted so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted so as not to contact the reaction solution.

After the completion of the addition of the sodium behenate solution, the mixture was allowed to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water became 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying. When the morphology of the obtained silver behenate particles was evaluated by electron microscopy,
A = 0.14 μm, b = 0.4 μm, c = 0.
6 μm, average aspect ratio 5.2, average sphere equivalent diameter 0.5
It was a scaly crystal having a diameter of 2 μm and a coefficient of variation of the sphere equivalent diameter of 15%. (The silver salt of the organic acid was observed with an electron microscope, and the shape of the silver salt of the organic acid was approximated to a rectangular parallelepiped, and the sides of the rectangular parallelepiped were defined as a, b, and c from the shortest side.) For a considerable wet cake, 7.4 g of polyvinyl alcohol (trade name: PVA-217)
And water were added to make the total amount 385 g, and the mixture was pre-dispersed with a homomixer. Next, the pre-dispersed stock solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-
EH, Microfluidics International
The pressure of the G10Z interaction chamber manufactured by Corporation was adjusted to 1750 kg / cm ² ,
After three treatments, a silver behenate dispersion was obtained. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the dispersion temperature was set at 18 ° C. by adjusting the temperature of the refrigerant.

<< Preparation of 25 wt% Dispersion of Reducing Agent >>
10 kg of 1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP
16 kg of water was added to 10 kg of the 20 wt% aqueous solution of 203) and mixed well to form a slurry. This slurry was sent by a diaphragm pump, and a horizontal sand mill filled with zirconia beads having an average diameter of 0.5 mm (UVM-
2: 3 hours and 30 minutes by the use of IMEX Co., Ltd., and then 0.2 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the reducing agent to 25 wt%. I got The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.42 μm and a maximum particle diameter of 2.0 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 10 wt% dispersion of mercapto compound >> 1-phenyl-2-heptyl-5-mercapto-
5 kg of 1,3,4-triazole and 20 parts of modified polyvinyl alcohol (POPAL MP203 manufactured by Kuraray Co., Ltd.)
8.3 kg of water was added to 5 kg of a wt% aqueous solution and mixed well to form a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 6 hours, and then water was added thereto to obtain a concentration of the mercapto compound. Is adjusted to 10 wt%.
A mercapto dispersion was obtained. The mercapto compound particles contained in the mercapto compound dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 2.0 μm or less. The resulting mercapto compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored. Immediately before use, the hole diameter is 10
The mixture was filtered through a μm polypropylene filter.

<< Preparation of 20 wt% Dispersion-1 of Organic Polyhalogen Compound >> 5 kg of tribromomethylnaphthyl sulfone (polyhalogen compound 5-2) and modified polyvinyl alcohol (Popearl MP203 manufactured by Kuraray Co., Ltd.)
2.5 kg of 0 wt% aqueous solution and 213 g of 20 wt% aqueous solution of sodium triisopropylnaphthalenesulfonate
And 10 g of water, and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then sodium benzoisothiazolinone sodium salt was added. 2 g and water were added to adjust the concentration of the organic polyhalogen compound to 20% by weight to obtain an organic polyhalogen compound dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.36 μm and a maximum particle diameter of 2.0 μm or less. The resulting organic polyhalogen compound dispersion had a pore size of 3.0 μm.
And filtered to remove foreign matter such as dust, and stored.

<< Preparation of 25 wt% Dispersion-2 of Organic Polyhalogen Compound >> 20 wt% of Organic Polyhalogen Compound
Same as Dispersion-1, except that 5 kg of tribromomethylnaphthyl sulfone was used instead of tribromomethyl (4-
5 kg of (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone (polyhalogen compound 5-3) was dispersed and 25% by weight of the organic polyhalogen compound was used.
And filtered. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained have a median diameter of 0.38 μm and a maximum particle diameter of 2.
It was 0 μm or less. The obtained organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 30 wt% Dispersion-3 of Organic Polyhalogen Compound >> 20 wt% of Organic Polyhalogen Compound
Similar to Dispersion-1, except that 5 kg of tribromomethylphenylsulfone (polyhalogen compound 5-1) was used instead of 5 kg of tribromomethylnaphthyl sulfone.
5 kg of a 0 wt% MP203 aqueous solution was dispersed, diluted to 30 wt% of this organic polyhalogen compound, and filtered. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained had a median diameter of 0.41 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion has a pore size of 3.
Filtered with a 0 μm polypropylene filter,
Foreign matter such as dust was removed and stored. After storage, it was stored at 10 ° C. or lower until use. Other formulas (1) for the present invention
And a comparative compound were prepared in the same manner as in Dispersion-1.

<< Preparation of 10 wt% methanol solution of phthalazine compound >> 10 g of 6-isopropylphthalazine was dissolved in 90 g of methanol and used.

<< Preparation of 20 wt% dispersion of pigment >>
I. Pigment Blue 60 and 6.4 g of Demol N manufactured by Kao Corporation were added to 250 g of water and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm was prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours to obtain a pigment dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

<< Preparation of SBR Latex 40 wt% >> Ultrafiltration (UF) purified SBR latex was obtained as follows. The following SBR latex diluted 10-fold with distilled water was used for UF-purification module FS03-FC-
Using FUY03Al (Daisen Membrane System Co., Ltd.), the product was diluted and purified until the ionic conductivity reached 1.5 mS / cm, and Sandyot-BL manufactured by Sanyo Chemical Industries, Ltd.
Was added to be 0.22 wt%. Further NaOH
Na ⁺ ion: NH ₄ ⁺ ion = 1: using NH ₄ OH and NH ₄ OH
The mixture was added to 2.3 (molar ratio) and adjusted to pH 8.4. The latex concentration at this time was 40% by weight. (SBR latex: -St (68) -Bu (29) -AA
(Stex: latex) (St: styrene, Bu: butadiene, AA: acrylic acid) Average particle size 0.1 μm, concentration 45%, 25 ° C. 60% R
3. Equilibrium water content in H 0.6 wt%, ionic conductivity 4.
2 mS / cm (Measurement of ionic conductivity is performed using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd. at 25 ° C. for a latex stock solution (40%)), pH 8.2

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution >> 1.1 g of a 20 wt% aqueous dispersion of the pigment obtained above, 103 g of a silver salt of an organic acid, polyvinyl alcohol PVA-205
5 g of a 20 wt% aqueous solution (produced by Kuraray Co., Ltd.)
25% by weight of a reducing agent dispersion and an organic polyhalogen compound dispersion-1, 2, 3 in a weight ratio of 5: 1: 3 (total weight: 13)
g, the type and amount of the compound dispersion represented by the formula (1) or the comparative compound dispersion described in Table 1 and the mercapto compound 10
% Dispersion of 6.2 g, ultrafiltration (UF) purified and pH-adjusted SBR latex 40 wt%, 106 g, and a phthalazine compound 10 wt% methanol solution 16 ml were added thereto.
10 g of the mixed silver halide emulsion A was mixed well to prepare a coating solution for the emulsion layer.
/ M ² and applied. The viscosity of the above emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki Co., Ltd.
(No. 1 rotor, 60 rpm) at 85 [mPa
s]. 25 using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd.
The viscosity of the coating solution at 0 ° C. is such that the shear rate is 0.1, 1, 10, 1
1500 at 00 and 1000 [1 / sec], respectively.
220, 70, 40, and 20 [mPa · s].

<< Preparation of Emulsion Surface Intermediate Layer Coating Solution >> 10 w of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.)
772 g of t% aqueous solution, 20 wt% dispersion of pigment 5.3
g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20/5/2) latex 27.5 wt% liquid and aerosol OT (American cyanamide) 2m of 5wt% aqueous solution
1, 20 wt% aqueous solution of diammonium phthalate
Water was added so that the total amount became 0.5 ml, and the total amount was 880 g, to give a coating solution for the intermediate layer, and the solution was fed to the coating die so as to be 10 ml / m ² . The viscosity after application is B-type viscometer 40 ° C
(No. 1 rotor, 60 rpm) at 21 [mPa ·
s].

<< Preparation of Coating Solution for First Layer of Emulsion Surface Protective Layer >> Inert gelatin (64 g) was dissolved in water, and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio: 6)
4/9/20/5/2) 27.5 wt% latex liquid 8
0 g, phthalic acid 10 wt% methanol solution 64 m
1, 74 ml of a 10 wt% aqueous solution of 4-methylphthalic acid,
28 ml of 1N sulfuric acid, 5 ml of a 5 wt% aqueous solution of aerosol OT (manufactured by American Cyanamid Co.), 0.5 g of phenoxyethanol, 0.5 g of benzoisothiazolinone.
1 g was added thereto, and water was added to make a total amount of 750 g to obtain a coating liquid, and 18.6 ml of a mixture obtained by mixing 26 ml of 4 wt% chrome alum with a static mixer immediately before coating was used.
/ M ² to the coating die. The viscosity of the coating solution was 40 ° C. using a B-type viscometer (No. 1 rotor, 60
rpm) was 17 [mPa · s].

<< Preparation of Coating Solution for Second Layer of Emulsion Surface Protective Layer >> 80 g of inert gelatin was dissolved in water, and a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio: 6)
4/9/20/5/2) 27.5wt% liquid latex 1
02g, N-perfluorooctylsulfonyl-N-
3.2 m of a 5 wt% solution of propylalanine potassium salt
1, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl)
2w of ether [average degree of polymerization of ethylene oxide = 15]
32 ml of a t% aqueous solution, 23 ml of a 5 wt% solution of aerosol OT (manufactured by American Cyanamid Co.), and polymethyl methacrylate fine particles (average particle diameter 0.7 μm) 4
g, polymethyl methacrylate fine particles (average particle size 6.4)
μm) 21 g, 1.6 g of 4-methylphthalic acid, 8.1 g of phthalic acid, 44 ml of 1N sulfuric acid, and water were added to 10 mg of benzoisothiazolinone to a total amount of 650 g,
Immediately before coating, 445 ml of an aqueous solution containing 4 wt% of chromium alum and 0.67 wt% of phthalic acid was mixed with a static mixer to obtain a coating solution for the surface protective layer.
The solution was sent to the coating die at 3 ml / m ² . The viscosity of the coating solution was 9 mPa · s using a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).

<< Preparation of Photothermographic Material >> On the back side of the undercoating support, a coating solution for the antihalation layer was applied so that the coating amount of the solid fine particle dye was 0.04 g / m ^2. When the coating amount of the protective layer is 1.
7 g / m ² was applied at the same time as multi-layer coating, followed by drying to form an antihalation back layer. On the side opposite to the back side, from the undercoat side to the emulsion layer (a silver halide coating amount of 0.1
4 g / m ² ), the intermediate layer, the protective layer first layer, and the protective layer second layer were simultaneously coated in multiple layers by a slide bead coating method to prepare a photothermographic material sample. Application speed 160
m / min, and the distance between the coating die tip and the support was adjusted to 0.14 to 0.28 mm, and the coating width was adjusted to 0.5 mm for both the left and right sides of the coating liquid discharge slit width. , The pressure in the decompression chamber is 39
It was set lower by 2 Pa. At that time, the handling and the temperature and humidity were controlled so that the support was not charged, and the charge was removed by ion wind immediately before coating. In the subsequent chilling zone, a wind having a drying temperature of 18 ° C. and a wet bulb temperature of 12 ° C. was blown for 30 seconds to cool the coating liquid, and then the drying temperature was 30 ° C. in a helical floating type drying zone. After spraying a dry air having a wet-bulb temperature of 18 ° C. for 200 seconds, passing a dry-bulb zone of 70 ° C. for 20 seconds, passing a dry zone of 90 ° C. for 10 seconds, and then cooling to 25 ° C. The solvent was volatilized. The average wind speed of the wind blowing on the coating liquid film surface in the chilling zone and the drying zone was 7 m / sec.

(Evaluation of photographic performance) After exposing the photosensitive material with a laser sensitometer (details described below), the photosensitive material was heated to 118 ° C.
For 5 seconds and then at 122 ° C. for 16 seconds (heat development)
The obtained image was evaluated using a densitometer. Laser sensitometer: Two 660 nm diode lasers with 35 mW output are combined. Single mode Gaussian beam spot 1 / e ² is sent in the sub-scanning direction at a pitch of 100 μm 25 μm. One pixel is written four times. The measurement results are Dmax, fog ( Dmin), sensitivity (Dmin)
(The reciprocal of the ratio of the exposure amount giving a density higher than 1.5). The sensitivity was 10 for the sensitivity of the photothermographic material 101 in Table 1.
It was shown as a relative value as 0. The results obtained are shown in Table 1 below.

[0157]

[Table 1]

(Results) From the results shown in Table 1, it is clear that the photosensitive material of the present invention exhibits excellent performance as compared with the photosensitive material of the comparative example.

Example 2 The compounds used in Example 2 are shown below.

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

1. Preparation of silver halide emulsion (Emulsion A) In 700 ml of water, 11 g of alkali-treated gelatin (2700 ppm or less as calcium content), 30 mg of potassium bromide, 10 m of sodium benzenethiosulfonate
g, and the pH was adjusted to 5.0 at a temperature of 40 ° C., 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 mol / l of potassium bromide, and (NH ₄ ) ₂ RhCl ₅ (H ₂
O) is 5 × 10 ⁻⁵ mol / l and K ₃ IrCl ₆ is 2
A solution containing × 10 ⁻⁵ mol / liter was added over 6 minutes and 30 seconds by a control double jet method while maintaining the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / l of potassium bromide and K
A halogen salt aqueous solution containing ₃ IrCl ₆ at 2 × 10 ⁻⁵ mol / l was added by a control double jet method over 28 minutes and 30 seconds while keeping the pAg at 7.7. Thereafter, the pH was lowered and subjected to a desalting treatment by flocculation and sedimentation, and 0.17 g of compound A and 51.1 g of low molecular weight gelatin having an average molecular weight of 15,000 (calcium content of 20 ppm or less) were obtained.
In addition, pH was adjusted to 5.9 and pAg to 8.0. The obtained particles had an average particle size of 0.08 μm and a projection area variation number of 9
%, (100) cubic grains having a 90% face ratio. The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and after 3 minutes, 71 μmol of triethylthiourea was added, and the mixture was aged for 100 minutes. After adding 5 × 10 ⁻⁴ mol of hydroxy-6-methyl-1,3,3a-7-tetrazaindene, the temperature was lowered to 40 ° C. Thereafter, the temperature was maintained at 40 ° C., and 12.8 × 10
^-4 mol of sensitizing dye A and 6.4 × 10 ^-3 mol of compound B were added with stirring, and after 20 minutes, the mixture was rapidly cooled to 30 ° C. to complete the preparation of silver halide emulsion A.

[0165] 2. Preparation of Organic Acid Silver Dispersion (Silver Organic Acid A) Behenic Acid (Product Name Edenor C22-)
85R) 87.6 g, distilled water 423 ml, 5N-NaO
H aqueous solution 49.2 ml, tert-butyl alcohol 1
20 ml were mixed and reacted by stirring at 75 ° C. for 1 hour,
A sodium behenate solution was obtained. Separately, silver nitrate 40.4
g of an aqueous solution (206.2 ml) was prepared and kept at 10 ° C. A reaction vessel containing 635 ml of distilled water and 30 ml of tert-butyl alcohol was kept at 30 ° C., and while stirring, the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes 10 seconds and 60 minutes, respectively. Added over minutes. At this time, 7 minutes after the start of the addition of the aqueous silver nitrate solution 2
Only the aqueous solution of silver nitrate was added for 0 seconds, and then the addition of the sodium behenate solution was started. After the addition of the aqueous solution of silver nitrate was completed, only the sodium behenate solution was added for 9 minutes and 30 seconds. At this time, the temperature in the reaction vessel was set to 30 ° C., and the temperature was controlled so as not to rise. Further, the piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the amount of steam was controlled so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. Also, the piping for the addition system of the silver nitrate aqueous solution is 2
The temperature was maintained by circulating cold water outside the heavy pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were symmetrical pipes around the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After the completion of the addition of the sodium behenate solution, the mixture was allowed to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Then, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. When the morphology of the obtained silver behenate grains was evaluated by electron micrographing, the average projected area diameter was 0.52 μm, and the average grain thickness was 0.1.
It was a flaky crystal having a diameter of 4 μm and a coefficient of variation of the average equivalent spherical diameter of 15%.

Next, a dispersion of silver behenate was prepared by the following method. For a wet cake having a dry solid content of 100 g, polyvinyl alcohol (trade name: PVA-21)
7, average degree of polymerization: about 1700) and water were added to make the total amount 385 g, and the mixture was predispersed with a homomixer. Next, the pre-dispersed undiluted solution is dispersed in a disperser (trade name:
The pressure of a microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber) was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain a silver behenate dispersion. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. The silver behenate particles contained in the silver behenate dispersion thus obtained were particles having a volume-weighted average diameter of 0.52 μm and a coefficient of variation of 15%. Particle size measurements are available from Malvern In
instruments Ltd. Master Si
Performed on zer X. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.5, and the particle thickness was 0.14 μm.
m, and the average aspect ratio (ratio of the circle equivalent diameter of the projected area of the particle to the particle thickness) was 5.1.

[0167] 3. 1,1-bis (2-hydroxyloxy-
3,5-dimethylphenyl) -3,5,5-trimethyl
Hexane: Preparation of dispersion of solid fine particle of reducing agent MP- of MP polymer manufactured by Kuraray Co., Ltd. was added to 25 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane. 203 20w
25% t% aqueous solution, Safinol 1 manufactured by Nissin Chemical Co., Ltd.
After adding 0.1 g of 04E, 2 g of methanol and 48 ml of water, the mixture was stirred well and left as a slurry for 3 hours. After that, 360 g of 1 mm zirconia beads were prepared, put into a vessel together with the slurry, and dispersed for 3 hours with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) to prepare a dispersion of solid fine particles of a reducing agent. . As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

[0168] 4. Solid fine particle dispersion of polyhalogen compound
Preparation of product 30 g of polyhalogen compound-A to Kuraray Co., Ltd.
4 g of MP-203, an MP polymer produced, compound C0.2
5 g and 66 g of water were added and stirred well.
m of zirconia silicate beads prepared in a vessel together with the slurry and placed in a vessel (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.).
The mixture was dispersed for a time to prepare a solid fine particle dispersion. The particle size is
80 wt% of the particles were 0.3 μm or more and 1.0 μm or less. Regarding polyhalogen compound-B, a solid dispersion was prepared in the same manner as polyhalogen compound-A, and had the same particle diameter. Further, solid dispersions of the compound represented by the formula (1) and the comparative compound for the present invention were prepared in the same manner as in the polyhalogen compound-A.

[0169] 5. Preparation of solid fine particle dispersion of ultra-high contrast agent To ultra-high contrast agent (nucleating agent) 62 (10 g), 2.5 g of polyvinyl alcohol (Kuraray PVA-217),
87.5 g of water was added, and the mixture was stirred well and left as a slurry for 3 hours. Thereafter, 240 g of 0.5 mm zirconia beads were prepared, put into a vessel together with the slurry, and dispersed for 10 hours with a disperser (I / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) to prepare a solid fine particle dispersion. . As for the particle diameter, 80 wt% of the particles were 0.1 μm or more and 1.0 μm or less, and the average particle diameter was 0.5 μm.

[0170] 6. Preparation of Solid Fine Particle Dispersion of Compound Z To 30 g of Compound Z, MP-203 of MP Polymer manufactured by Kuraray Co., Ltd. and 87 ml of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the compound Z was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. The particle size is 80 wt.
% Was from 0.3 μm to 1.0 μm.

[0171] 7. Preparation of Emulsion Layer Coating Solution The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Liquid. Binder; Luckstar 3307B 470 g as solids (manufactured by Dainippon Ink and Chemicals, Ltd .; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5 , 5-trimethylhexane 166 g as solid content Polyhalogen compound-A 0.05 mol as solid content Solid dispersion of ultrahigh contrast agent 62 17.1 g as solid content Polyhalogen compound-B 0.02 mol as solid content thiosulfone Acid compound 2.2 mmol 5-Methylbenzotriazole 1.36 g Polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 12.1 g 6-iso-propylphthalazine 16.5 g Sodium dihydrogen orthophosphate dihydrate 0.37 g Compound Z 10.5 g as solid content Dye A 783 nm Coating amount at which the optical density becomes 0.3 (approximately 0.50 g) Compound of formula (1) or comparative compound Kind and amount described in Table 1 Silver halide emulsion A 0.05 mol as Ag amount

[0182] 8. Preparation of Coating Solution for Protective Layer Under Emulsion Surface Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Wt%) Polymer latex solution having a particle size of 120 nm (copolymer having a glass transition temperature of 57 ° C, a solid content of 21.5 wt%, and a compound D as a film-forming aid containing 15 wt% based on the solid content of the latex. ) 956g in H ₂ O
And 1.62 g of compound E and 3.15 of compound S were added.
g, matting agent (polystyrene particles, average particle size 7 μm)
1.98 g and polyvinyl alcohol (Kuraray Co., Ltd.)
Ltd., a PVA-235) 23.6 g was added, further H ₂ O
Was added to prepare a coating solution.

[0173] 9. Preparation of Coating Solution for Emulsion Surface Upper Layer Protection Layer Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Wt%) polymer latex solution having a particle diameter of 70 nm (copolymer having a glass transition temperature of 54 ° C, a solid content of 21.5 wt%, and a compound D as a film-forming aid containing 15 wt% based on the solid content of the latex. 630 g), H ₂ O was added thereto, and 6.30 g of a 30 wt% solution of carnava wax (manufactured by Chukyo Yushi Co., Ltd., Cersol 524), 0.72 g of compound E, 7.95 g of compound F, and 0.95 g of compound S were added.
0 g, matting agent (polystyrene particles, average particle size 7 μm)
1.18 g and polyvinyl alcohol (Kuraray Co., Ltd.)
Ltd., a PVA-235) 8.30 g was added, further H ₂ O
Was added to prepare a coating solution.

[0174] 10. PET support with back / undercoat layer
Preparation of support (1) Support Using terephthalic acid and ethylene glycol, 1V (intrinsic viscosity) = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) according to a conventional method. P
I got ET. This is pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, quenched, and made into an unstretched film having a thickness of 120 μm after heat setting. did. This was longitudinally stretched 3.3 times using mails having different peripheral speeds, and then horizontally stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck part of the tenter,
Both ends were knurled and wound at 4.8 kg / cm ² . In this way, the width 2.4 m, the length 3500 m,
A roll having a thickness of 120 μm was obtained.

(2) Undercoat layer (a) Polymer latex- (1) (core-shell type latex having a core of 90 wt% and a shell of 10 wt%, core: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic) Acid = 93/3/3 / 0.9 / 0.1 (wt%), shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (wt%) (A polymer latex having a weight average molecular weight of 38000) consisting of 3.0 g / m ² 2,4-dichloro-6-hydroxy-s-triazine 23 mg / m ² matting agent (polystyrene, average particle diameter 2.4 μm) 5 mg / m ²

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

(4) Conductive Layer Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 42 mg / m ² deionized gelatin (Ca ^{2 +} content 0.6 ppm) 8 mg / m ² compound G 0.2 mg / m ² polyoxyethylene phenyl ether 10 mg / m ² Sumitex resin M-3 (water-soluble melamine compound, Sumitomo chemical Co., Ltd.) 18 mg / m ² Dye A Coating amount at which the optical density of 783 nm becomes 1.2 SnO ₂ / Sb (9/1 weight ratio, needle-like fine particles, major axis / minor axis = 20 to 30, manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² Matting agent (polymethyl methacrylate, average particle size 5 μm) 7 mg / m ²

(5) Protective Layer Polymer Latex- (2) (Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (% by weight) polymer)) 1000 mg / m ² polystyrenesulfonate solid basis (molecular weight 1000~5000) 2.6mg / m ² Cellosol 524 (Chukyo Yushi (Co.)) 25mg / m ² Sumitex resin M-3 (water-soluble melamine Compound, manufactured by Sumitomo Chemical Co., Ltd.) 218 mg / m ²

(6) Preparation of PET support having back / undercoat layer An undercoat layer (a) and an undercoat layer (b) were sequentially applied to both sides of the support (base) and dried at 180 ° C. for 4 minutes, respectively. . Then, a conductive layer and a protective layer are sequentially applied to one side of the upper surface after the undercoat layer (a) and the undercoat layer (b) are applied, and dried at 180 ° C. for 4 minutes, respectively. A PET support was prepared. The dry thickness of the undercoat layer (a) was 2.0 μm.

(7) Heat treatment for transport (7-1) Heat treatment PE thus prepared with a back / undercoat layer
The T support was placed in a heat treatment zone with a total length of 200 m set at 160 ° C., and transported at a tension of 3 kg / cm ² and a transport speed of 20 m / min. (7-2) Post-heat treatment After the above heat treatment, post-heat treatment was performed by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time was 10 kg / cm ² .

[0181] 11. Preparation of photothermographic material P on the side where the undercoat layer (a) and the undercoat layer (b) were applied
The above emulsion layer coating solution was coated on the undercoat layer of the ET support so that the coated silver amount was 1.6 g / m ² . Further, the emulsion layer lower protective layer coating solution was simultaneously coated with the emulsion coating solution so that the coating amount of the solid content of the polymer latex was 1.31 g / m ² . Thereafter, the above-mentioned coating solution for the upper protective layer on the emulsion surface was applied thereon so that the coating amount of the solid content of the polymer latex was 3.02 g / m ² , thereby producing a photothermographic material. The film surface pH on the image forming side of the obtained photothermographic material is 4.9, the Beck smoothness is 660 seconds, and the film surface pH on the opposite side is 5.9 and the Beck smoothness is 560.
Met.

12. Evaluation of photographic performance (exposure processing) The obtained photothermographic material was placed on the inner surface of a single-channel cylinder equipped with a semiconductor laser having a beam diameter (FWHM of ビ ー ム of beam intensity) of 12.56 μm, a laser output of 50 mW, and an output wavelength of 783 nm. Using a laser exposure system, the exposure time is adjusted by changing the number of rotations of the mirror, and the exposure is adjusted by changing the output value.
Exposure was at 2 × 10 ⁻⁸ seconds. At this time, the overlap coefficient was set to 0.449. (Heat development treatment) The exposed heat-developable photosensitive material was subjected to the thermal development machine shown in FIG. 1, the surface of the roller in the heat-development processing section was made of silicon rubber, the smooth surface was made of Teflon nonwoven fabric, and the linear velocity of conveyance was 20 mm / sec 15 seconds at 90-110 ° C in the preheating section (the driving systems of the preheating section and the heat development processing section are independent,
(The speed difference from the heat development section was set to -0.5% to -1%), and the heat development processing was performed at 120 ° C for 20 seconds and the slow cooling section for 15 seconds. The temperature accuracy in the width direction was ± 1 ° C. (Evaluation of photographic performance) Macbeth TD
The measurement was performed using a 904 densitometer (visible density). The measurement results were Dmax, fog (Dmin), and sensitivity (1.5 minutes from Dmin).
(The reciprocal of the ratio of the exposure amount giving a high density). The sensitivity was shown as a relative value with the sensitivity of the heat-developable photographic material 201 in Table 2 as 100. Table 2 shows the obtained results.

[0183]

[Table 2]

(Results) From the results shown in Table 2, it is clear that the photosensitive material of the present invention exhibits excellent performance as compared with the photosensitive material of the comparative example. Results were obtained.

[0185]

According to the present invention, it has become possible to provide a heat-developable image recording material in which fog due to storage time before development and fog rise during development are extremely small.

[Brief description of the drawings]

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

[Description of Signs] 10 Heat-developable image recording material 11 Carry-in roller pair 12 Carry-out roller pair 13 Roller 14 Smooth surface 15 Heater 16 Guide plate A Preheating unit B Heat development processing unit C Slow cooling unit

Claims (4)

[Claims] 1. At least one surface of a support,
(A) a reducible silver salt; (b) a reducing agent;
And (d) a small amount of the compound represented by the formula (1).
A heat-developable image recording material comprising at least one kind.
Fees. Embedded image[In the formula (1), X¹¹And X¹²Is independently hydrogen
Atom, alkyl group, alkoxy group, halogen atom, al
Represents a oxycarbonyl group or a carbamoyl group;¹¹
And R¹²Are each independently placed on a hydrogen atom or a benzene ring
Represents a replaceable group. Y¹¹Is -SO_Two-, -CO-, -C
OCO- or -P (R) O- group (R is R^{1 Three}Synonymous with)
Represent. R¹³Is an alkyl group, alkenyl group, alkynyl
Group, aryl group, heterocyclic group, -OR¹⁴, -N (R^Fifteen) R
¹⁶, Or -SR¹⁷Where R ¹⁴, R^Fifteen, R¹⁶You
And R¹⁷Are each independently a hydrogen atom, an alkyl group, an aryl
A heterocyclic group or a heterocyclic group;¹³To R¹⁷In the definition of
Alkyl, alkenyl, alkynyl, aryl
The group or heterocyclic group may be substituted. ] 2. The heat-developable image recording material according to claim 1, which is a photothermographic material further comprising (e) photosensitive silver halide on the same surface. 3. The heat-developable image recording material according to claim 1, further comprising (f) a super-high contrast agent on the same surface. 4. The ultra-high contrast agent comprises at least one compound selected from the compounds represented by formula (2), formula (3) or formula (4).
The heat-developable image recording material according to claim 3, which is a compound of a kind. Embedded image [In the formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the formula (2), R ¹ and Z, R ² and R ³ ,
R ¹ and R ² , and R ³ and Z may be bonded to each other to form a cyclic structure. In the formula (3), R
⁴ represents a substituent. In the formula (4), X and Y are
A and B each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic group. Represents an amino group. In Formula (4), X and Y, and A and B
May be bonded to each other to form a cyclic structure. ]