JP2001272744A - Heat developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable image recording material with improved dependence of development on processing and image quality. SOLUTION: The heat developable image recording material has (a) a reducible silver salt, (b) a binder, (c) a compound of formula (1) or the formula Q1- NHNH-V6 and (d) a development inhibitor releasing coupler compound of the formula A-(TIME)n-DI on the same face of the base. In the formula (I), A is a coupler residue which releases (TIME)n-DI by a coupling reaction with the oxidized body of the compound of the formula (1) or Q1-NHNH-V6; TIME is a timing group which cleaves (TIME)n-1-DI after release from A by a coupling reaction or a timing group which cleaves (TIME)n-2-DI after release from TIME; (n) is an integer of 0-3, in the case of n>=2, a plurality of symbols TIME may be the same or different; and DI is a group which acts as a development inhibitor after release from A or TIME.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable image recording material, and more particularly, to a heat-developable image recording material which is excellent in processing dependency of development and image quality.

[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 used as a system capable of preserving the environment and simplifying the image forming means. Methods for forming an image by thermal development are described in, for example, U.S. Pat. Nos. 3,152,904 and 3,457,075 and D.C. "Thermally Processed Silver Sys" by D. Klosterboer
tems) A "(Imaging Processes and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, J.M. Sturge, V.S. Walworth, A .; Shepp, Chapter 9, p. 279, 1989). The light-sensitive materials described therein include a non-photosensitive reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, a light-sensitive silver halide), and a silver reducing agent, usually an organic binder. It is contained in a dispersed state in the matrix. 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 by 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 formed by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas becomes black and forms an image because it contrasts with the unexposed areas.

Further, a method has been proposed in which a diffusible dye is released or formed in an image form by thermal development, and the diffusible dye is transferred to an image receiving material. In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-donating compound to be used or the type of silver halide to be used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914, 4,503,137 and 4,55.
9,290, JP-A-58-149046, JP-A-60-133449, and JP-A-59-21844.
No. 3, No. 61-238056, European Patent Publication EP220746A2, and Technical Report 87-619.
9, European Patent Publication EP210660A2 and the like.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, US Pat. No. 4,559,290 describes a so-called Dye
A compound obtained by converting a releasing redox compound (hereinafter also referred to as a DRR compound) into an oxidized form having no dye releasing ability is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is oxidized by thermal development in accordance with the exposure amount of silver halide, A method has been proposed in which a diffusible dye is released by reduction with a reducing agent remaining without being oxidized. In addition, European Patent Publication EP
No. 220746A, published technical report 87-6199 (first
No. 2, No. 22) discloses a compound that releases a diffusible dye by the same mechanism as a compound that releases a diffusible dye by reductive cleavage of an NX bond (X represents an oxygen atom, a nitrogen atom, or a sulfur atom). There is described a heat-developable color light-sensitive material using a compound having the above formula.

On the other hand, as a color image forming method for photographic light-sensitive materials, a method utilizing a coupling reaction between a coupler and an oxidized developing agent is the most common, and a heat-developable color light-sensitive material employing this method is known in the United States. Patent No. 3,761,270
No. 4,021,240, JP-A-5
JP-A-9-231439 and JP-A-60-128438
In these patents, p.
-Sulfonamidophenols are used as developing agents. Photosensitive materials using the coupling method are advantageous in terms of sensitivity compared to the photosensitive materials using color materials as described above, because the coupler does not absorb in the visible region before processing, and not only printing materials but also photographing It is considered that there is an advantage that it can be used as a material. These methods of obtaining a dye image by thermal development are suitable for a photothermographic material of a system in which thermal transfer, diffusion transfer or sublimation thermal transfer from a photosensitive layer to an image receiving layer is performed. However, when a dye image is obtained as a mono-sheet type photothermographic material, it does not necessarily have appropriate characteristics in terms of image forming temperature, image stability, and color tone.

In heat-developable image recording materials, it is important to reduce the temperature, humidity and time dependence of development. There have been few studies on the reduction of the processing dependency and the improvement of the image quality. Certain antifoggants (U.S. Pat. Nos. 4,123,374, 4,129,
Substituted triazoles described in US Pat. Nos. 557 and 4,125,430, US Pat. Nos. 4,125,403, 4,152,160 and 4,3.
No. 07,187, a metal salt of thiosulfonic acid, JP-A-53-20923 and JP-A-53-19825, a combination of a metal salt of thiosulfonic acid and sulfinic acid;
JP-B-62-50810, JP-A-7-20979
Nos. 7 and 9-43760, thiosulfonic acid esters, disulfide compounds disclosed in JP-A-51-42529 and JP-B-63-37368, JP-B-54-165, and European Patent Publication EP60598.
1A1, JP631176A1, U.S. Pat. No. 4,546,075 and 4,756,99.
No. 9, No. 4,452,885, No. 3,8
74,946 and 3,955,982) may be effective. However, these methods have problems such as a decrease in sensitivity because they suppress not only high-density images but also low-density images, and development of alternative materials has been desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-developable image recording material which is excellent in processing dependency of development and image quality.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, by using a specific compound in combination, an excellent heat-developable image recording exhibiting an expected effect is obtained. They have found that a material can be provided, and have completed the present invention.

That is, according to the present invention, (a) a reducible silver salt is provided on at least one same surface of a support;
(B) a binder, (c) a compound represented by the following general formula (1) or (2), and (d) a development inhibitor releasing coupler compound represented by the following general formula (I). Heat-developable image recording material.

Embedded image (In the general formula (1), V ^{1 to} V ⁴ each independently represent a hydrogen atom or a substituent, and V ⁵ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.)

Embedded image (In the general formula (2), Q ¹ is a carbon atom and NHNH-
It represents a 5- to 7-membered unsaturated ring bonded with V ^6, V ⁶ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group. )

Embedded image (In the general formula (I), A represents a coupler residue that releases (TIME) _n -DI by a coupling reaction with an oxidized form of the compound represented by the general formula (1) or (2), and TIME represents A timing group that cleaves _{n- 1-} DI after leaving from A by a coupling reaction, or after leaving from TIME (TIME)
_n-2 represents a timing group for cleaving -DI, where n is 0 to 3
Represents an integer. When n is 2 or more, a plurality of TIMEs
May be the same or different. DI is A or TI
It represents a group that acts as a development inhibitor after leaving from ME. )

Preferably, the heat-developable image recording material of the present invention further comprises (e) photosensitive silver halide on the surface having the above (a), (b), (c) and (d). Preferably, the heat-developable image recording material of the present invention has a surface having the above (a), (b), (c) and (d),
And (f) a reducing agent. Preferably, the heat-developable image recording material of the present invention further comprises (g) a super-high contrast agent on the surface having the above (a), (b), (c) and (d). Preferably, the heat-developable image recording material of the present invention further comprises (h) a polyhalogen compound on the surface having the above (a), (b), (c) and (d). Preferably, the heat-developable image recording material of the present invention comprises the above (a),
The surface having (b), (c) and (d) further has (i) a coupler compound. In addition, in this specification, “to” is a range including numerical values described before and after it as a minimum value and a maximum value.

[0011]

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 may be a heat-developable image recording material having the above-mentioned materials (a) to (d) only on one side of a support, or the above-mentioned material ( A heat-developable image recording material having a) to (d) and having the above materials (a) to (d) on the opposite surface may also be used.

The heat-developable image recording material of the present invention has a shape such as a sheet or a roll, and the support may be transparent or opaque, but is preferably transparent.
Specific examples of the support include a polyester film, an undercoat polyester film, a poly (ethylene terephthalate) film, a polyethylene naphthalate film, a cellulose nitrate film, a cellulose ester film,
Examples thereof include resin materials such as poly (vinyl acetal) film and polycarbonate film, and glass, paper, and metal. Typical supports include paper supports coated with polymers, including flexible substrates, especially partially acetylated and / or barytered alpha-olefin polymers, especially polyethylene, Α-olefin polymers having 2 to 10 carbon atoms such as polypropylene and ethylene-butene copolymer are used. Among them, biaxially stretched polyethylene terephthalate (PET) having a thickness of about 75 to 200 μm is particularly preferable.

When a plastic film is passed through a heat developing machine at a temperature of 80 ° C. or higher, the dimensions of the film generally expand and contract.
When the processed material is used for printing plate making, this expansion and contraction becomes 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, which is designed to reduce internal strain remaining in the film during biaxial stretching and eliminate thermal shrinkage distortion generated during thermal development. For example, polyethylene terephthalate or the like which is heat-treated at a temperature in the range of 100 ° C. to 210 ° C. before applying the coating solution for the image forming layer for thermal development is preferably used. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyarylate, polycarbonate and the like can be used.

The heat-developable image recording material of the present invention has (a) a reducible silver salt on at least one surface of the support. Organic silver salts are used as reducible silver salts.
The organic silver salt used in the present invention is any organic substance containing a source capable of reducing silver ions, is relatively stable to light, and is exposed to a photocatalyst (a latent image of a photosensitive silver halide). Etc.) and in the presence of a reducing agent, form a silver image when heated to 80 ° C. or higher. Specific examples thereof include a silver salt of an organic compound having a carboxyl group, that is, a silver salt of an organic acid. Among them, a silver salt of an aliphatic carboxylic acid is preferable, and has 10 to 30 carbon atoms, and more preferably 15 to 28 carbon atoms. Silver salts of long-chain aliphatic carboxylic acids are more preferred. The ligand is 4.0
Complexes of organic silver salts (which may contain inorganic silver salts) having a complex stability constant in the range of １10.0 to 10.0 are also preferred.

Specific examples 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.
Examples include silver fumarate, silver tartrate, silver linoleate, silver butyrate, silver camphorate, and mixtures thereof. The silver donor can preferably comprise about 5 to 70% by weight of the imaging layer.

As the organic silver salt, 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 a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, Silver salts of thioglycolic acid such as silver salts of-(ethylglycolamide) benzothiazole, silver salts of S-alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithioacetic acid, etc. Silver salt of dithiocarboxylic acid, silver salt of thioamide, 5-carboxyl-
Silver salt of 1-methyl-2-phenyl-4-thiopyridine,
Silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt described in U.S. Pat. No. 4,123,274, for example, silver of 3-amino-5-benzylthio-1,2,4-thiazole 1,2,4- such as salt
Silver salts of mercaptothiazole derivatives, US Pat. No. 3,3
And silver salts of thione compounds such as silver salt of 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione described in JP-A-01,678. 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 US Pat. No. 4,220,709, silver salts of 1,2,4-triazole or 1-H-tetrazole, and silver salts of imidazole and imidazole derivatives. Also, U.S. Pat.
Various silver acetylide compounds described in 1,361, 4,775,613 and the like can also be used.

The organic silver salt can be used in a desired amount, but the silver amount is preferably 0.1 to 5 g / m ² , more preferably 1 to 3 g, expressed in terms of the coating amount per m ^{2 of} the heat-developable image recording material. / M ² .

The heat-developable image recording material of the present invention has (b) a binder. As the binder used in the present invention,
Any one can be selected from well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, 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 polymers are:
It is used in an amount sufficient to retain the ingredients therein. That is, it 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, the ratio of binder to organic silver salt is preferably in the range of 15: 1 to 1: 2, particularly preferably 8: 1 to 1: 1.

As the polymer latex used in the present invention, a so-called core / shell type latex may be used in addition to a polymer latex having an ordinary uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

The polymer used in the polymer latex used in the present invention includes acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or a copolymer thereof. and so on. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is preferably about 5,000 to 1,000,000 in number average molecular weight, more preferably 10,000 to 100,000.
It is about. 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 of the heat-developable image recording material of the present invention include the following. 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, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like. Such polymers are also commercially available,
The following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635,46583,4
601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol
Examples of polyester resins such as Lx811, 814, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.)
FINITEX ES650, 611, 675, 850
(Manufactured by Dainippon Ink and Chemicals, Inc.), WD-size,
Examples of polyurethane resins such as WMS (all manufactured by Eastman Chemical) include HYDRAN AP10, 20, 3
Rubber-based resins such as 0, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) are LACSTAR7310K, 3307
B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 410, 438
C, 2507 (both manufactured by Nippon Zeon Co., Ltd.), vinyl chloride resins such as G351 and G576 (both manufactured by Nippon Zeon Co., Ltd.), and vinylidene chloride resin such as L50
2, L513 (all made by Asahi Kasei Corporation), Aron D7
020, D504, D5071 (Mitsui Toatsu Co., Ltd.
Chemical Pearl S12 as an olefin resin
And SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.). These polymers may be used alone or as a mixture of two or more as necessary. In the present invention, the total amount of the binder in the image forming layer is 0.1.
The range is preferably ^{2 to} 30 g / m ² , more preferably 1 to 15 g / m ² . A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer.

The heat-developable image recording material of the present invention comprises a compound represented by the above general formula (1) or (2) on a support on the same surface as the photosensitive silver halide and the reducible silver salt. Have. The compound represented by the general formula (1) is a developing agent generally called sulfonamidophenol. Where:
V ^{1 to} V ⁴ each independently represent a hydrogen atom or a substituent. Preferred examples of V ^{1 to} V ⁴ include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonamide group,
Alkylsulfonamide, arylsulfonamide, alkoxy, aryloxy, alkylthio, arylthio, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, cyano, sulfamoyl, alkylsulfonyl, arylsulfonyl And acyloxy groups. Among V ¹ ~V ^4, V ² and V ⁴ are preferably hydrogen atoms. When the group represented by V ^{1 to} V ⁴ is a substitutable group, it may further have a substituent, and preferred examples of the substituent are the same as those described as V ^{1 to} V ⁴ .
The sum of Hammett σ _P values of V ^{1 to} V ⁴ is preferably 0 or more, more preferably 0.2 or more. The upper limit is preferably 1.2, and more preferably 0.1.
8

V ⁵ is a substituted or unsubstituted alkyl group,
Represents an aryl group or a heterocyclic group. Among them, V ⁵ is preferably an aryl group, more preferably an aryl group having a substituent. Preferred substituents of the aryl group include a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyl group, and a sulfamoyl group. , Cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
An aryloxycarbonyl group and an acyl group can be mentioned. If these substituents are groups capable of substitution, they may have further substituents, preferred examples of the substituent are the same as those exemplified as V ¹ ~V ^4. Further, these substituents may be bonded to each other to form a ring.

The compound represented by the general formula (1) may have a ballast group. The ballast group as used herein refers to a hydrophobic group and has 8 to 80 carbon atoms, preferably 10 to 40 carbon atoms.
Is a group containing a hydrophobic partial structure of Hereinafter, specific examples of the compound represented by Formula (1) are shown, but the compounds used in the present invention are not limited to these specific examples.

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[0027]

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[0029]

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The compound represented by the general formula (1) can be synthesized by a known method described in JP-A-9-146248 and the like.

The compound represented by the general formula (2) is a developing agent generally called a hydrazine-based developing agent. Where Q
¹ represents a 5- to 7-membered unsaturated ring that binds to NHNH-V ⁶ at a carbon atom, V ⁶ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group. Preferred examples of the 5- to 7-membered unsaturated ring represented by Q ¹ include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring, a 1,3,5- Triazine ring, pyrrole ring, imidazole ring, pyrazole ring,
1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1, 3,4-oxadiazole ring, 1,
A 2,4-oxadiazole ring, a 1,2,5-oxadiazole ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a thiophene ring, etc., and a condensed ring in which these rings are fused to each other Is also preferred.
These rings may have the groups mentioned as preferable substituents of the above-mentioned aryl group, and when they have two or more substituents, those substituents may be the same or different. Is also good.

The carbamoyl group represented by V ⁶ preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. , N-sec-butylcarbamoyl, N-octylcarbamoyl, N-cyclohexylcarbamoyl, Nt
tert-butylcarbamoyl, N-dodecylcarbamoyl, N- (3-dodecyloxypropyl) carbamoyl, N-octadecylcarbamoyl, N- {3- (2,
4-tert-pentylphenoxy) propyl} carbamoyl, N- (2-hexyldecyl) carbamoyl, N
-Phenylcarbamoyl, N- (4-dodecyloxyphenyl) carbamoyl, N- (2-chloro-5-dodecyloxycarbonylphenyl) carbamoyl, N-naphthylcarbamoyl, N-3-pyridylcarbamoyl, N
-Benzylcarbamoyl).

The acyl group represented by V ⁶ preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms,
Examples include formyl, acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl, 2-hydroxymethylbenzoyl. The alkoxycarbonyl group represented by V ⁶ preferably has 2 to 50 carbon atoms, more preferably 6 to 40 carbon atoms.
And examples thereof include methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, and benzyloxycarbonyl.

The aryloxycarbonyl group represented by V ⁶ preferably has 6 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, and is, for example, phenoxycarbonyl,
-Octyloxyphenoxycarbonyl, 2-hydroxymethylphenoxycarbonyl, 4-dodecyloxyphenoxycarbonyl. The sulfonyl group represented by V ⁶ preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, for example, methylsulfonyl,
Butylsulfonyl, octylsulfonyl, 2-hexadecylsulfonyl, 3-dodecyloxypropylsulfonyl, 2-octyloxy-5-tert-octylphenylsulfonyl, 4-dodecyloxyphenylsulfonyl.

The sulfamoyl group represented by V ⁶ preferably has 0 to 50 carbon atoms, more preferably 6 to 40 carbon atoms.
For example, unsubstituted sulfamoyl, N-ethylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl, N-decylsulfamoyl, N-hexadecylsulfamoyl, N- {3- (2-ethylhexyl) Oxy) propyl} sulfamoyl, N- (2-chloro-5
-Dodecyloxycarbonylphenyl) sulfamoyl and N- (2-tetradecyloxyphenyl) sulfamoyl. The group represented by V ⁶ may further have, at a substitutable position, the group mentioned as a preferable substituent of the aryl group represented by V ⁵ , and may have two or more substituents In such cases, those substituents may be the same or different.

Among the compounds represented by the general formula (2),
Q ¹ is preferably a 5- or 6-membered unsaturated ring,
More preferably, Q ¹ is a benzene ring, a pyrimidine ring,
1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,3,4-oxadiazole ring, It is a 1,2,4-oxadiazole ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, or a ring in which these rings are fused with a benzene ring or an unsaturated heterocycle. Further, V ⁶ is preferably a carbamoyl group, particularly preferably
V ⁶ is a carbamoyl group having a hydrogen atom on a nitrogen atom. Hereinafter, specific examples of the compound represented by Formula (2) are shown, but the compounds used in the present invention are not limited to these specific examples.

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[0043]

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[0044]

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[0045]

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The synthesis of the compound represented by the general formula (2)
JP-A-9-152702, JP-A-8-286340, JP-A-9-152700, and JP-A-9-152701
Gazette, JP-A-9-152703 and JP-A-9-15
It can be carried out according to the method described in JP-A No. 2704 or the like. The addition amount of the compound represented by the general formula (1) or (2) is wide, but is preferably 0.01 to 100 times by mole, more preferably 0.1 to 10 times by mole based on the coupler compound. It is. The compound represented by the general formula (1) or (2) may be added to the coating solution by any method such as a solution, a powder, a solid fine particle dispersion, an emulsion, and an oil protection dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The heat-developable image recording material of the present invention comprises, on at least one surface of a support, (d) a development inhibitor represented by the above general formula (I) together with the above (a) to (c). It is characterized by having at least one release coupler compound. General formula (I): A- (TIME) _n -DI In general formula (I), A represents general formula (1) or (2)
A coupler residue which releases (TIME) _n -DI by a coupling reaction with an oxidized form of the compound represented by
TIME is a timing group that cleaves (TIME) _{n- 1-} DI after leaving TIME from A by a coupling reaction, or (TIME) _n-2- DI after leaving TIME.
Represents a timing group for cleaving, and n represents an integer of 0 to 3. When n is 2 or more, a plurality of TIMEs may be the same or different. DI represents a group which functions as a development inhibitor after leaving from A or TIME.

The compound represented by formula (I) used in the present invention will be described below in detail. In the general formula (I), A represents a coupler residue, specifically, a yellow image forming coupler residue, a magenta image forming coupler residue,
A cyan image forming coupler residue, a colorless coupler residue, or a dye efflux coupler residue, and is described in detail in Research Disclosure 37038 (Feb. 1995), pp. 80-85, and pp. 87-89. ing. When A represents a yellow image forming coupler residue,
For example, pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolyl acetamide type, malon ester monoamide type, benzoxazolylacetamide type, benzimidazolylacetamide type, benzothia Zolylacetamide type, cycloalkanoylacetamide type, indoline-2-ylacetamide type, quinazolin-4-one-2-ylacetamide type described in U.S. Pat. No. 5,021,332, 5,021,330 Benzo-1,
2,4-Thiadiazine-1,1-dioxide-3-ylacetamide type coupler residues, EP 421221
A. Residues described in US Pat.
The coupler residues described in US Pat. No. 5,149, and the coupler residues described in EP-A-0622673 are exemplified.

When A represents a magenta image forming coupler residue, for example, 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5,1-c] [1,2] , 4] triazole type, 1H-
Pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type, active propene type described in WO93 / 01523, WO93 / 07534 The enamine type described, 1H-imidazo [1,2-b] [1,2,2
4] triazole-type coupler residues, and coupler residues described in U.S. Pat. No. 4,871,652.

When A represents a cyan image forming coupler residue, for example, phenol type, naphthol type, 2,5-diphenylimidazole type described in EP-A-249453, 1H-pyrrolo [1,2- b] [1,
2,4] triazole type, 1H-pyrrolo [2,1-c]
[1,2,4] triazole type, JP-A-4-18813
No. 7, No. 4-190347, pyrrole type described in JP-A-1-315736 and JP-A-1-315736.
-Hydroxypyridine type, U.S. Patent No. 5,164,28
Patent No. 9: pyrrolopyrazole type disclosed in
Pyrrolopimidazole type described in JP-A-174429, pyrazolopyrimidine type described in U.S. Pat. No. 4,950,585, pyrrolotriazine-type coupler residue described in JP-A-4-204730, US A coupler residue described in Japanese Patent No. 4746602;
The coupler residue described in U.S. Pat. No. 5,104,783, the coupler residue described in U.S. Pat. No. 5,162,196, and the coupler residue described in EP 0556700 are used. No.

Further, A may be a coupler residue which does not substantially leave a color image. Examples of this type of coupler residue include coupler residues of indanone type, acetophenone type and the like, EP 443530A and EP 4445.
01A, JP-A-6-138612 and JP-A-6-138612.
Examples thereof include an eluting coupler residue described in JP-A-82995, JP-A-6-82996, or JP-A-6-82998, and an intramolecular ring-closing coupler residue described in EP 950,922A1.

Preferred examples of the coupler residue represented by A in the general formula (I) include the following general formulas (Cp-1) and (Cp-1).
-2), (Cp-3), (Cp-4), (Cp-5),
(Cp-6), (Cp-7), (Cp-8), (Cp-
9), (Cp-10), (Cp-11), or (Cp
This is when the coupler residue is represented by -12). These couplers are preferred because of their high coupling speed.

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In the above formula, derived from the coupling position
Is a free bond represented by-(TIM) in the general formula (I).
E)_n-Represents the bonding position of DI. In the above formula, R⁵¹,
R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, R
⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵Or R⁶⁶Expandable
If it contains a radical, it has a total number of carbon atoms of 8 to 40,
Preferably selected to be 10 to 30,
In other cases, the total number of carbon atoms is preferably 15 or less. Screw
Type, telomer type or polymer type couplers
Any of the above substituents represents a divalent group,
Concatenate the positions. In this case, the range of carbon number is not specified
It may be.

Hereinafter, R ^{51 to} R ⁶⁶ , a, b, d, e, and f will be described in detail. R ^{51 to} R ⁶³ may be further substituted, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a silyl group, a hydroxyl group, a carboxyl group, Nitro group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfa Moyloxy group, alkane sulfonyloxy group, arene sulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, Bonamide group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group , Sulfo group, alkane sulfonyl group, arene sulfonyl group,
Examples include a sulfamoyl group, a phosphonyl group, and a phosphinoylamino group.

The following formulas (Cp-1) to (Cp-1)
The substituents R ^{51 to} R ^{66 in} 2) will be described. General formula (C
In p-1), R ⁵¹ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. a is 0 or 1
Represents R ⁵² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. General formula (Cp-
In 2), R ⁵¹ represents an alkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group. R ⁵² and R ⁵³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and b represents 0 or 1. In the general formula (Cp-3), R ⁵⁴ represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbonamide group, a sulfonamide group, an amino group, an anilino group, an alkylthio group, an arylthio group, an alkoxy group, a cyclo group. Represents an alkyloxy group, an aryloxy group, a ureido group, or an alkoxycarbonylamino group. R ⁵⁵ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

In the general formulas (Cp-4) and (Cp-5), R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbonamido group, a sulfonamido group. , An amino group, an anilino group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a ureido group, an alkoxycarbonylamino group, or a cycloalkyloxycarbonylamino group.

In the general formulas (Cp-6) and (Cp-7), R ⁵⁸ and R ⁶⁰ each represent an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ⁵⁹ represents an alkyl group, Alkyl group, aryl group, heterocyclic group, silyl group, carbonamide group, sulfonamide group,
Amino group, anilino group, alkylthio group, cycloalkylthio group, arylthio type, alkoxy group, cycloalkyloxy group, aryloxy group, ureido group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino group or a halogen atom, d is Represents an integer of 0 to 3. When d is plural, plural R ^59s represent the same substituent or different substituents.

In the general formula (Cp-8), R ⁶¹ represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group,
A cyano group, a sulfamoyl group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a cycloalkyloxycarbonylamino group, an aryloxycarbonylamino group, or a sulfonamido group, and R ⁶² represents an alkyl group, a cycloalkyl group, an aryl group , A heterocyclic group,
Carbonamido group, sulfonamido group, amino group, anilino group, alkylthio group, cycloalkylthio group, arylthio type, alkoxy group, cycloalkyloxy group,
Represents an aryloxy group, a ureido group, an alkoxycarbonylamino group, a cycloalkyloxycarbonylamino group or a halogen atom, and e represents an integer of 0 to 4. If e is more, a plurality of R ⁶² represent the same or different.

Formulas (Cp-9) and (Cp-10)
In the formula, R ⁶³ represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbonamide group, a sulfonamide group, an amino group, an anilino group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkoxy group, a cycloalkyloxy group , An aryloxy group, a ureido group, an alkoxycarbonylamino group, a cycloalkyloxycarbonylamino group, or a halogen atom;
And f represents an integer of 0 to 2.
When e or f is plural, plural R ⁶³ represent the same or different.

Formulas (Cp-11) and (Cp-1)
In 2), R ⁶⁴ and R ⁶⁵ each represents a carbamoyl group, an alkoxycarbonyl group, a cycloalkyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, alkanesulfonyl group, arenesulfonyl group, or a nitro group,, R ⁶⁶ Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The groups represented by R ^{51 to} R ⁶⁶ may further have a substituent.

Next, the group represented by TIME will be described. The group represented by TIME has the general formula (I)
After the bond on the left side of TIME in the above is cleaved, any timing group can be used as long as it can cleave the group bonded on the right side. For example, U.S. Pat.
396, 4,652,516 or 4,698,297, a group utilizing the cleavage reaction of hemiacetal, US Pat. No. 4,248,
962, 4,847,185, 4,857,440, and 5,262,2
No. 91, a timing group for causing a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction, U.S. Pat.
No. 409,323 or 4,421,845
No. 4,546,075, a timing group for causing a cleavage reaction by utilizing an electron transfer reaction described in US Pat.
No. 73, British Patent No. 1,531,927, European Patent Publication No. 057284 or
No. 684512. L binds to the coupling active site of the coupler at a hetero atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom contained therein. In general formula (I), when n is 2 or more, a plurality of TIMEs represent the same or different. As a preferred TIME, the following general formula (T-
1), (T-2) and (T-3).

Formula (T-1) * -W- (Z ¹ = Z ² ) _j -C (R ⁷¹ ) (R ⁷² )-** Formula (T-2) * -W-CO-** Formula (T-3) * -W-LINK-E-** In these formulas, * represents a position bonding to the group on the left side of TIME in Formula (I), and ** represents Formula (I) Represents a position to which the group on the right side of TIME is bonded, W represents an oxygen atom, a sulfur atom or> NR ⁷³ ; Z ¹ and Z ² each represent a substituted or unsubstituted methine or nitrogen atom; Represents 0, 1 or 2, R ⁷¹ and R ⁷² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group; R ⁷³ represents an alkyl group, a cycloalkyl group, an aryl group, an acyl group, Represents an alkane sulfonyl group or an arene sulfonyl group. When Z ¹ and Z ² represent a substituted methine, the substituent is R ⁵¹
It can be exemplified those mentioned as substituents of to R ^66. Here, when Z ¹ and Z ² represent a substituted methine, any two of the substituents, R ⁷¹ , R ⁷² and R ⁷³ , are connected to each other to form a cyclic structure (for example, a benzene ring,
(A pyrazole ring). In the general formula (T-3), E represents an electrophilic group, and LINK represents a linking group that sterically relates W and E so that an intramolecular nucleophilic substitution reaction can occur. When the compound represented by formula (I) is a dye efflux type development inhibitor releasing coupler, n
Represents 1, 2, or 3, and at least one TIME
The group preferably has a diffusion-resistant group having 10 to 40 carbon atoms. The following are specific examples of the TIME represented by the general formula (T-1).

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The following are specific examples of the TIME represented by the general formula (T-2).

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The following are specific examples of the TIME represented by the general formula (T-3).

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Specific examples of (TIME) _n when n is 2 or more in the general formula (I) and examples of other timing groups include the following.

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Next, the development inhibitor group represented by DI in the formula (I) will be described. Examples of the development inhibitor represented by DI include Research Disclosure (R
essearch Disclosure) No. 370
38 (February 1995), pp. 86-88, and development inhibitors which can be released from DIR couplers. 17643 (Jan 1978
February), U.S. Pat. Nos. 4,477,563 and 5,
Nos. 021,332, 5,026,628, 3,227,554, 3,384,6
No. 57, No. 3,615,506, No. 3,
617,291, 3,733,201, 3,933,500, 3,958,9
Nos. 93, 3,961,959, 4,
149,886, 4,259,437, 4,095,984, 4,782,0
12, British Patent No. 1450479, JP-B-63-49216, or U.S. Pat.
And development inhibitors as described in JP-A-34,311. Preferred are a heterocyclic thio group, a heterocyclic seleno group or a triazolyl group (monocyclic or condensed-ring 1,2,3-triazolyl or 1,2,4-tolyazolyl), and particularly preferred is tetrazolylthio,
Tetrazolylseleno, 1,3,4-oxadiazolylthio, 1,3,4-thiadiazolylthio, 1- (or 2
-) Benzotriazolyl, 1,2,4-triazole-
1- (or 4-) yl, 1,2,3-triazole-
1-yl, 2-benzothiazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio and derivatives thereof. Preferred development inhibitors are represented by the following general formulas DI-1 to DI-6.

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In the formula, R ⁹¹ has the same meaning as the substituent described for R ^{51 to} R ⁶³ . R ⁹¹ may further have a substituent, and preferred substituents are the substituents ^exemplified as R ⁹¹ . V is an oxygen atom, a sulfur atom, or —N (R ⁹³ ) —
Wherein R ⁹² and R ⁹³ are each independently an alkyl group,
Represents a cycloalkyl group, an aryl group, or a heterocyclic group. k represents 0 to 4, g represents 0 or 1, and h represents 1 or 2. Specific examples of preferred development inhibitors are shown below, but the invention is not limited thereto.

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Next, the preferred range of the compound represented by formula (I) will be described. Among the compounds represented by the general formula (I), a group represented by A is represented by the general formula (Cp-1),
(Cp-2), (Cp-6), (Cp-7), (Cp-
8) or (Cp-11), n is 1 or 2, and DI is represented by the general formula (DI-1), (DI-2) or (D
I-3) or (DI-6) is preferable,
The group represented by A is represented by the general formula (Cp-1) or (Cp-
8) wherein TIME is -OCO- or a general formula (T-
3) wherein n is 1 or 2 and DI
Is the general formula (DI-1), (DI-2) or (DI-
6) is more preferable. Specific representative examples of the development inhibitor releasing coupler represented by formula (I) used in the invention are shown below, but the invention is not limited thereto.

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The development inhibitor releasing couplers represented by formula (I) are described in US Pat. Nos. 4,248,962, 4,857,440 and 5,021,322. No. 5,256,523, European Patent Publication No. 0299726, Japanese Patent No. 0348139, Japanese Patent No. 0354532, Japanese Patent No. 0438150, Japanese Patent No. 0499279, European Patent No. 0
Nos. 514896 and 0594256 and 05
23423, 0520496, 057
Nos. 6052, 0576087, 0576
Nos. 088 and 0576089 and 05761
No. 82, JP-B-63-39889, and JP-A-63-38989.
No. 61656, Japanese Patent Publication No. 5-18095, Japanese Patent Application Laid-Open No. 7-133259, and Japanese Patent Application Laid-Open No. 6-1305.
It can be synthesized according to the method described in the specification such as Japanese Patent Publication No. 94-94.

The compounds of formula (I) may be used alone or in combination of two or more. The amount to be used is 1 × 10 ⁻⁶ to 1 × 10 ⁻⁶ as the coating amount per m ² of the heat-developable image recording material.
1 × 10 ⁻² mol / m ² is preferable, and 1 × 10 ⁻² mol / m ² is more preferable.
It is 10 ^{-5 to} 3 × 10 ^-3 mol / m ² , more preferably 5 × 10 ^-5 to 1 × 10 ^-3 mol / m ² . Compounds of general formula (I) may be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone,
Methyl ethyl ketone, methyl isobutyl ketone),
It can be used by dissolving in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also,
Using a known emulsification dispersion method, dissolving using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically preparing and using an emulsified dispersion. Can be. Alternatively, the powder can be dispersed in water using a method known as a solid dispersion method using a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves. The compound represented by the general formula (I) 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 preferable to add it to the layer to be formed.

The heat-developable image recording material of the present invention preferably further comprises (e) photosensitive silver halide on the surface having the above (a) to (d). 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, photosensitive silver halide grains having a core / shell structure can be preferably used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, 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 of forming photosensitive silver halide 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. Can be used. Specifically, a method of converting a part of the silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, a method of converting silver into gelatin or another polymer solution. A method can be used in which photosensitive silver halide grains are prepared by adding a supply compound and a halogen supply compound and mixed with an organic silver salt. 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, preferably 0.20 μm or less, more preferably 0.01 to 0.15 μm, and still more preferably. Is 0.02-
0.12 μm. Here, the grain size means the length of the edge of the photosensitive silver halide grains when the photosensitive silver halide grains are cubic or octahedral so-called normal crystals. In the case where the photosensitive silver halide grains are tabular grains, the diameter refers to the diameter of a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of the photosensitive silver halide grains.

Examples of the shape of the photosensitive silver halide grains include cubic, octahedral, tabular grains, spherical grains, rod-like grains, potato-like grains and the like. In the present invention, cubic grains, tabular grains and tabular grains are particularly preferred. Particles are preferred. When tabular photosensitive silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 5: 1.
0: 1 to 3: 1. Further, grains having rounded corners of photosensitive 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 ratio of the [100] plane, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, is high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more. The ratio of the [100] plane of the Miller index is determined by T.M. using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani; J. Imaging Sci. , 29,16
5 (1985).

The photosensitive silver halide grains used in the present invention may be 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 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver, more preferably in the range of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

The photosensitive silver halide emulsion used in the present invention is preferably chemically sensitized. As a method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, Sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization and the like are preferred.

Reduction sensitization can be used in the photosensitive silver halide emulsion used in the present invention. 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. it can.
When the pH of the photosensitive silver halide emulsion is 7 or more or pAg
Can be reduced and sensitized by keeping at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation. A thiosulfonic acid compound may be added to the photosensitive silver halide emulsion used in the present invention by a method described in European Patent Publication No. 293,917A1. The photosensitive silver halide used in the heat-developable image recording material of the present invention may be of one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, Sensitization conditions).

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, per 1 mol of the organic silver salt. And more preferably 0.03 to 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the photosensitive silver halide particles and organic silver salt which have been prepared are mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill There is a method of mixing with a homogenizer or 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. Is not particularly limited as long as appears sufficiently.

The heat-developable image recording material of the present invention may further comprise (f) a reducing agent for a reducible silver salt (organic silver salt) on the surface having the above (a) to (d). preferable. The reducing agent for the organic silver salt is any substance that reduces silver ions to metallic silver, and is preferably an organic substance. In addition to conventional photographic developers such as phenidone, hydroquinone and catechol, hindered phenol reducing agents can also be mentioned as preferred examples. The reducing agent is
It 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 image forming layer side with respect to the support. 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% based on 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 the photothermographic material utilizing an organic silver salt, a wide range of reducing agents can be used. For example,
JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, JP-A-49-46427, JP-A-49-115540, and JP-A-50-1433.
No. 4, No. 50-36110, No. 50-147
Nos. 711 and 51-32632 and 51-1
Nos. 023721, 51-32324, and 5
1-51933, 52-84727, 55-108654, 56-146133, 57-82828, 57-82829, JP-A-6-3793, U.S.A. Patent No. 3,66
Nos. 7,9586, 3,679,426, 3,751,252 and 3,75
Nos. 1,255, 3,761,270, 3,782,949, 3,832
9,048, 3,928,686, 5,464,738, German Patent 2,
No. 321,328, EP 692,73.
The reducing agent disclosed in Japanese Patent Publication No. 2 and the like can be used.

Specific examples include amide oximes such as phenylamide oxime, 2-thienylamide oxime and p-phenoxyphenylamide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; and 2,2 ' A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid; polyhydroxybenzene, hydroxylamine, reductone and / or
Or a combination of hydrazines (eg, hydroquinone and
Bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine); phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β
-Hydroxamic acids such as alinine hydroxamic acid; combinations of azines and sulfonamidophenols (e.g., phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano-2-
Α-cyanophenylacetic acid derivatives such as methylphenylacetate and ethyl-α-cyanophenylacetate;
2,2′-dihydroxy-1,1′-binaphthyl, 6,
6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl and bis (2-hydroxy-1-naphthyl)
Bis-β-naphthol as exemplified by methane; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (such as 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 3-methyl 5-pyrazolone, such as -1-phenyl-5-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2, Sulfonamide phenol reducing agents such as 6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7-tert-butyl-
Chromanes such as 6-doxocycloman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-tert- Butyl-5-methylphenyl) methane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane, 4,4
-Ethylidenebis (2-tert-butyl-6-methylphenol), 1,1-bis (2-hydroxy-3,5
-Dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate) Aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidones and certain indane-1,3-diones; chromanols (such as tocopherol).

The reducing agent used in the heat-developable image recording material of the present invention may be added by any method such as a solution, a powder and a dispersion of solid fine particles. The solid fine particle dispersion can be obtained by a known means for making fine (for example, a ball mill, a vibrating ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.).
Done in When dispersing the solid fine particles, a dispersing aid may be used.

The heat-developable image recording material of the present invention preferably further comprises (g) a super-high contrast agent on the surface having the above (a) to (d). Although the kind of the super-high contrast agent used in the present invention is not particularly limited, as a preferable super-high contrast agent, formula (H) described in Japanese Patent Application No. 11-87297 is described.
(Specifically, the hydrazine derivatives described in Tables 1 to 4 of the same specification), and JP-A-10-1
0672, JP-A-10-161270, JP-A-10-62898, and JP-A-9-304870
JP, JP-A-9-304872, JP-A-9-3
No. 04871, JP-A-10-31282, US Pat. No. 5,496,695, and all hydrazine derivatives described in European Patent Publication No. 741,320. In addition, Japanese Patent Application No. 11-8729.
No. 7, the substituted alkene derivative represented by the formulas (1) to (3), the substituted isoxazole derivative and a specific acetal compound, more preferably the formula (A) or the formula (B) described in the same specification. ), Specifically, Compounds 1 to 72 described in Chemical Formulas 8 to 12 of the same specification.
Can also be used. Further, a plurality of these super-high contrast agents may be used in combination.

The super-high contrast agent may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), It can be used by dissolving it in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. In addition, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved by a well-known emulsification dispersion method. Then, an emulsified dispersion can be prepared and used mechanically. Alternatively, the powder of the ultra-high contrast agent can be dispersed in a suitable solvent such as water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method. The super-high contrast agent may be added to any layer on the image forming layer side of the support, but is preferably added to the image forming layer or a layer adjacent thereto. The added amount of the super-high contrast agent is preferably 1 × 10 ⁻⁶ to 1 mol per mol of silver,
10 ^{-5 to} 5 × 10 ^-1 mol is more preferred, and 2 × 10 ^-5 to 5 × 10 ^-1
2 × 10 ⁻¹ mole is most preferred.

In addition to the above compounds, US Pat.
545,515, 5,635,339 and 5,654,130, International Publication WO
97/34196, US Pat. No. 5,686,22.
No. 8 or the compound described in JP-A-11-1
19372, 11-133546, 1
Compounds described in 1-119373, 11-109546, 11-95365, 11-95366, and 11-149136 may be used.

In the present invention, in order to form 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. Pat. No. 5,545,505, specifically AM-1 to AM-
5. Hydroxamic acids described in U.S. Pat. No. 5,545,507, specifically HA-1 to HA-11, acrylonitriles described in U.S. Pat. No. 5,545,507, specifically Are CN-1 to CN-13, hydrazine compounds described in U.S. Pat. No. 5,558,983, specifically, CA-1 to CA-6, and JP-A-9-29.
No. 7368, onium salts, specifically A
-1 to A-42, B-1 to B-27, C-1 to C-14
Etc. can be used.

In a heat-developable image recording material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, formic acid or formate is a strong fogging substance. In the present invention, the content of formic acid or formate on the side having the image-forming layer containing the photosensitive silver halide of the heat-developable image recording material may be 5 mmol or less, more preferably 1 mmol or less per mole of silver. preferable. In the heat-developable image recording material of the present invention, an acid or a salt thereof formed by hydration of diphosphorus pentoxide is preferably used in combination with a superhigh contrast agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt),
Triphosphate (salt), tetraphosphate (salt), hexametaphosphate (salt) and the like can be mentioned. Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, and ammonium hexametaphosphate.

The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto from the viewpoint that the desired effect is exhibited in a small amount. . The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide (the amount of coating per m ^{2 of the} image recording material) may be a desired amount according to the performance such as sensitivity and fog, but may be 0.1 to 500 mg. /
m ² is preferable, and 0.5 to 100 mg / m ² is more preferable. The synthesis method, addition method, addition amount, and the like of the above-mentioned super-high contrast agent and these high-contrast accelerators can be performed as described in each of the cited patents. In the heat-developable image recording material of the present invention, it is also preferable to use (e) the photosensitive silver halide and (g) a super-high contrast agent in combination.

The heat-developable image recording material of the present invention further comprises the following general formula (3) on the surface having the above (a) to (d): Q ² -Y ² CZ ¹ Z ² X ² (3) wherein, Q ² represents an aryl group or a heterocyclic group, Y ²
Represents —SO ₂ — or —CO—, Z ¹ and Z ² represent a halogen atom, and X ² represents a hydrogen atom or an electron-withdrawing group. )) (H) a polyhalogen compound. In the general formula (3), Q ² represents an aryl group or a heterocyclic group. Aryl groups include phenyl, naphthyl and the like. As the heterocyclic group, a 5- to 7-membered heterocyclic ring, wherein the heterocyclic ring contains at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur atoms,
Those which are saturated or unsaturated monocyclic or fused rings are preferred. Examples of heterocycles include pyridine, quinoline, isoquinoline, pyrimidine, pyrazine, pyridazine, phthalazine, triazine, furan, thiophene, pyrrole,
Oxazole, thiazole, imidazole, thiadiazole, triazole, benzimidazole and the like can be mentioned. Q ² is preferably an aryl group, a quinolyl group, a thiazolyl group, a thiadiazolyl group, or a triazolyl group, and more preferably a phenyl group, a naphthyl group, a quinolyl group, or a triazolyl group. Q ² may have a substituent, and examples of the substituent include the substituents that A in formula (I) may have. The substituent of Q ² may have a ballast group used in a photographic material to reduce the diffusivity or an adsorptive group to a silver salt. A mold may be formed.

In the general formula (3), Y ² is —SO ₂ — or —CO—, preferably —SO ₂ —. Z ¹
And Z ² each independently represent a halogen atom (eg, fluorine, chlorine, bromine, etc.), but it is most preferred that both Z ¹ and Z ² are bromine atoms. X ² represents a hydrogen atom or an electron withdrawing group. The electron-withdrawing group represented by X ² is a substituent whose Hammett's substituent constant σ _p can take a positive value, specifically, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group. Group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, halogen atom, acyl group, heterocyclic group and the like. X ² is preferably a hydrogen atom or a halogen atom, and most preferably a bromine atom.

The polyhalogen compound of the general formula (3) is a compound known as an antifoggant.
-160164, 10-197988,
JP-A-9-244177, JP-A-9-244178, JP-A-9-160167, JP-A-9-319022, JP-A-9-258367, JP-A-9-265150
JP-A-10-197989, JP-A-10-171
Nos. 063, 10-181459 and 11-
No. 89733, for example. The polyhalogen compound represented by the general formula (3) may be used alone or in combination of two or more. The amount to be used is 1 × 10 ⁻⁶ to 1 as a coating amount per m ² of the heat-developable image recording material.
× 10 ^-2 mol / m ² is preferable, and 1 × 1 is more preferable.
It is 0 ^{-5 to} 5 × 10 ^-3 mol / m ² , more preferably 2 × 10 ^-5 to 1 × 10 ^-3 mol / m ² . The polyhalogen compound represented by the general formula (3) 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 layer on this layer side. Preferably, it is added to an adjacent layer.

The polyhalogen compound represented by the general formula (3) may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). Etc.), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. In addition, by a known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved to prepare an emulsified dispersion mechanically. Can be used. Alternatively, the powder can be dispersed in water using a method known as a solid dispersion method using a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves.

The heat-developable image recording material of the present invention preferably further comprises (i) a coupler compound on the surface having the above (a) to (d). As the coupler compound used in the present invention, two equivalents or four equivalents known in the photographic industry are used.
Equivalent couplers can be used. Among them, the following general formula (4)
It is preferable to use any of the compounds represented by (18).

[0113]

Embedded image

In the general formulas (4) to (18), X ¹ to
X ¹⁵ each independently represents a hydrogen atom or a substituent. In the general formula (4), R ¹ and R ² each independently represent an electron-withdrawing group. In the general formulas (5) to (18),
R ^{3 to} R ²⁸ each independently represent a hydrogen atom or a substituent. m, n, p and q each independently represent an integer of 0 to 4. In the general formulas (4) to (18), X ¹ to
X ¹⁵ each independently represents a hydrogen atom or a substituent. X
^The substituents represented by ^{1 to} X ¹⁵ may be the same or different, and preferred examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom) and an aryl group (preferably having 6 to ¹⁵ carbon atoms). 30, more preferably 6 carbon atoms
-20, more preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl, etc.), an alkoxy group (preferably 1-20 carbon atoms, more preferably 1-12 carbon atoms, more preferably It has 1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms).
For example, phenyloxy, 2-naphthyloxy and the like), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, methylthio, Ethylthio, butylthio, etc.), arylthio group (preferably having 6 to 6 carbon atoms)
20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenylthio, naphthylthio and the like, an acyloxy group (preferably 1 to 2 carbon atoms)
0, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy and the like, an acylamino group (preferably 2 to 16 carbon atoms)
20, more preferably 2 to 16 carbon atoms, further preferably 2 to 10 carbon atoms, for example, N-methylacetylamino, benzoylamino, etc.), sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably Carbon number 1
To 16, more preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like, a carbamoyl group (preferably 1 to 20 carbon atoms,
More preferably 1 to 16 carbon atoms, still more preferably 1 to
12, for example, carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, etc.), an acyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 to 12 carbon atoms). For example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, methoxycarbonyl and the like, a sulfo group, a sulfonyl group (preferably 1 to carbon atoms)
20, more preferably 1 to 16 carbon atoms, further preferably 1 to 12 carbon atoms, for example, mesyl, tosyl and the like, a sulfonyloxy group (preferably 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, methanesulfonyloxy, benzenesulfonyloxy, etc.), azo group, heterocyclic group, heterocyclic mercapto group, cyano group and the like. No. The heterocyclic group referred to herein means a saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group,
Examples include a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, a pyrazolyl group, an imidazolyl group, a benzimidazolyl group, a tetrazolyl group, a hydantoin-1-yl group, a succinimide group, and a phthalimido group. These substituents may be further substituted with other substituents, and the substituent may be any commonly known substituent as long as it does not deteriorate photographic performance.

As the substituents represented by X ^{1 to} X ¹⁵ , those known as leaving groups for photographic two-equivalent couplers are preferable. Examples thereof include a heterocyclic group and a heterocyclic mercapto group, and particularly preferably a halogen atom.

In the general formula (4), R ¹ and R ² may be the same or different and represent an electron-withdrawing group. The electron-withdrawing group referred to herein is Hammett's substituent constant σp
Is a substituent that can take a positive value, specifically,
Cyano group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with an N atom, thiocarbonyl group, sulfamoyl group,
Alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom, perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group,
Benzoyl, formyl, phosphoryl, carboxy (or salt thereof), formyl, phosphoryl, carboxy (or salt thereof), sulfo (or salt thereof), heterocyclic, alkenyl, alkynyl, acyloxy Group, an acylthio group, a sulfonyloxy group, or an aryl group substituted with these electron-withdrawing groups. Examples of the heterocyclic group include a saturated or unsaturated heterocyclic group such as a pyridyl group, a quinolyl group, a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, a hydantoin-1-yl group, and succinimide. Group, phthalimido group, indolinyl and the like. R ¹ and R ² may combine with each other to form a saturated or unsaturated carbocyclic or heterocyclic ring. Among them, a substituent having 30 or less carbon atoms is preferable,
More preferably, it has 20 or less carbon atoms. More preferred are a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an acyl group, a benzoyl group, and a heterocyclic group.

In the general formulas (5) to (18), R ³ to
R ²⁸ each independently represents a hydrogen atom or a substituent.
The substituents represented by R ^{3 to} R ²⁸ may be the same or different, and any substituent may be used as long as it does not adversely affect photographic properties. Specific examples include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, More preferably, it has 1 to 13 carbon atoms, for example, methyl,
Ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, tert-octyl, n-amyl, tert-amyl, n-dodecyl, n-tridecyl, cyclohexyl and the like, an alkenyl group (preferably having 2 to 20 carbon atoms) More preferably 2 to 16 carbon atoms, further preferably 2 to 12 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), aryl group (preferably 6 to 30 carbon atoms, more preferably Is carbon number 6
-20, more preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl, etc.), an alkoxy group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, more preferably It has 1 to 12 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy and the like, an aryloxy group (preferably 6 to 3 carbon atoms)
0, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, for example, phenyloxy, 2-
An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, still more preferably having 2 to 12 carbon atoms), for example, acetoxy,
Benzoyloxy, etc.), an amino group (preferably having no carbon
-20, more preferably 1-16 carbon atoms, still more preferably 1-12 carbon atoms, for example, dimethylamino group, diethylamino group, dibutylamino group, anilino group and the like, acylamino group (preferably 2 carbon atoms) 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 carbon atoms
To 13, for example, acetylamino, tridecanoylamino, benzoylamino, etc.) and a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom).
To 16, more preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, etc.), a ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms)
6, more preferably 1 to 12 carbon atoms, for example,
Ureido, methylureide, phenylureide, etc.), carbamate group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, still more preferably having 2 to 12 carbon atoms)
For example, methoxycarbonylamino, phenyloxycarbonylamino, etc.), a carboxyl group, a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, For example, carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl and the like, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 carbon atoms) To 12, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), an acyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 to 1 carbon atoms).
2, for example, acetyl, benzoyl, formyl,
Pivaloyl, etc.), a sulfo group, a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, for example, mesyl,
Tosyl, etc.), a sulfamoyl group (preferably having 0 to 0 carbon atoms)
20, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, hydroxyl Group, mercapto group, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, still more preferably having 1 to 12 carbon atoms, for example, methylthio, butylthio and the like), and a heterocyclic group (preferably Carbon number 2
-20, more preferably 2-16 carbon atoms, even more preferably 2-12 carbon atoms, for example, pyridyl, imidazoyl, pyrrolidyl and the like. These substituents may be further substituted with another substituent. m,
n, p or q is 2 or more, and a plurality of R ¹³ , R ¹⁴ ,
When R ¹⁵ or R ²⁷ are adjacent, two adjacent R ¹³ ,
R ¹⁴ , R ¹⁵ or R ²⁷ may form a ring.

Preferred substituents represented by R ^{3 to} R ²⁸ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an anilino group, an acylamino group, a sulfonylamino group, and a carboxyl group. Carbamoyl, acyl, sulfo, sulfonyl, sulfamoyl, cyano, hydroxyl, mercapto, alkylthio, and heterocyclic groups. In the heat-developable image recording material of the present invention, as the coupler compound, compounds represented by formulas (4) to (18) are preferable, but the compounds represented by formulas (6) to (12) and (1) are preferable.
The compound represented by 6) is more preferable, and the compounds represented by general formulas (6), (7) and (10) are particularly preferable.

Specific examples of the coupler used in the present invention are shown below. Yellow coupler: European Patent Publication EP50
Couplers represented by formulas (I) and (II) in JP-A-2,424A; couplers represented by formulas (1) and (2) in EP-A-513,496A (particularly Y-
28); a coupler represented by formula (I) of claim 1 of EP 568,037A; a general formula (I) of column 1 at line 45 to 55 in U.S. Pat. No. 5,066,576. A coupler represented by the formula:
No. 425, a coupler represented by the general formula (I) in paragraph No. 0008; a coupler described in claim 1 on page 40 of EP 498,381 A1 (especially 18).
P. D-35); European Patent Publication EP 447,969 A1.
JP-A No. 4-page 4 describes a coupler represented by the formula (Y) (especially Y-
1 (page 17), Y-54 (page 41)); and U.S. Pat. No. 4,476,219, column 7 36-5.
Couplers represented by formulas (II) to (IV) on line 8 (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler: JP-A-3-39737
(L-57 (page 11, lower right), L-68 (page 12, lower right),
L-77 (page 13, lower right); European Patent Publication EP 456,2
No. 57, A-4-63 (p. 134), A-4-7
3, -75 (p. 139); European Patent Publication EP 486,9.
No. 65, M-4, -6 (page 26), M-7 (27
M) of EP 571,959A.
45 (p. 19); JP-A-5-204106, (M
-1) (p. 6); and M-22 in paragraph No. 0237 of JP-A-4-362361. Cyan coupler: CX-1, 3, 4, 5,
11, 12, 14, 15 (pages 14 to 16);
43-7, C-7, 10 (p. 35), 34, 3
5 (p. 37), (I-1), (I-17) (42-43)
And a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1 in JP-A-2-44345,
P-5 (page 11).

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent Publication E.
P96,873B and German Patent No. 3,23
Those described in 4,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are represented by the formula (C) described on page 5 of EP 456,257 A1.
Yellow colored cyan couplers represented by I), (CII), (CIII) and (CIV) (especially YC on page 84)
-86), yellow colored magenta coupler ExM-7 (p. 202), EX-1 (249)
EX-7 (p. 251), U.S. Pat.
No. 069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10),
U.S. Pat. No. 4,837,136 (2) (column 8), a colorless masking coupler represented by formula (A) in claim 1 of WO92 / 11575 (especially on pages 36 to 45). Exemplary compounds) are preferred.

The coupler compounds represented by formulas (4) to (18) preferably used in the present invention can be easily synthesized by a method known in the photographic art. The amount of the coupler compound used in the present invention is preferably from 0.2 to 200 mmol, more preferably from 0.3 to 100 mmol, and still more preferably from 0.1 to 100 mmol, per mol of silver.
5 to 30 mmol. One type of coupler compound may be used alone, or two or more types may be used in combination. The coupler compound used in the present invention may be any of water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used after dissolving. Alternatively, according to an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, according to a well-known solid dispersion method, a powder of a coupler compound can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves and used. The coupler compound used in the present invention may be added to any layer on the same surface as the photosensitive silver halide and the reducible silver salt on the support. It is preferable to add it to the layer adjacent thereto.

When the heat-developable image recording material of the present invention contains an additive known as a “toning agent” for improving an image, the optical density may be increased in some cases. Toning agents may also be advantageous in forming black silver images. The toning agent is used in an amount of 0.1 to 5 mol% per mol of silver on the surface having the image forming layer.
It is preferably included, more preferably 0.5 to
20 mol% is contained. 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 color toning agents are disclosed in JP-A-46-6077,
JP 47-10282, JP 49-5019,
JP-A-49-5020, JP-A-49-91215,
JP-A-50-2524, JP-A-50-32927,
Nos. 50-67132, 50-67641, 50-114217, 51-3223, 51-27923, and 52-14788.
JP-A-52-99813, JP-A-53-1020
JP-A-53-76020 and JP-A-54-1565.
Nos. 24, 54-156525 and 61-1
No. 83642, JP-A-4-56848, JP-B-49-10727, JP-A-54-20333, U.S. Pat. Nos. 3,080,254, 3,4
46,648, 3,782,941, 4,123,282, 4,510,2
No. 36, British Patent No. 1380795, Belgian Patent No. 814910, and the like.

Examples of toning agents include phthalimide and N-hydroxyphthalimide; succinimide, pyrazoline-
5-one, and quinazolinone, 3-phenyl-2-
Cyclic imides such as pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (e.g. N-hydroxy-
1,8-naphthalimide); cobalt complex (for example, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl- Mercaptans exemplified by 1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides (for example, (N, N-dimethylaminomethyl) Phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents such as 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 derivatives (for example, 4- (1 -Naphthyl) phthalazinone, 6-chlorophthalazinone, derivatives such as 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione) or metal salts; phthalazinone and phthalic acid derivatives (for example, phthalic acid) Acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; phthalazine, phthalazine derivatives (eg, 4- (1-naphthyl) phthalazine, 6-
Chlorophthalazine, 5,7-dimethoxyphthalazine, 6
Derivatives such as -isobutylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine and 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (for example, phthalic acid) Quinazolinedione, benzoxazine or naphthoxazine derivatives; for the production of photosensitive silver halide in situ as well as color tone modifiers; quinazolinedione, benzoxazine or naphthoxazine derivatives; Rhodium complexes that also function as halide ion sources, such as hexachlororhodium (II
I) ammonium acid, 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-
Benzoxazines such as 2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione
2,4-dione; pyrimidine and asymmetric triazine (for example, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine and the like), azauracil,
And tetraazapentalene derivatives (for example, 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) and the like. In the present invention, the toning agent is a solution,
It may be added by any method such as powder or solid fine particle dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The heat-developable image recording material of the present invention may have a sensitizing dye. As the sensitizing dye used in the present invention, any sensitizing dye may be used as long as it can spectrally sensitize the photosensitive silver halide grains in a desired wavelength region when adsorbed on the photosensitive silver halide grains. Specifically, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RE
SEARCH DISCLOSURE Item 17643 IV-A (197
December 2008 p. 23), Item 1831X (1979)
August, p. 437) or in the literature cited. 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. Examples of spectral sensitization to red light include He-
For so-called red light sources such as Ne lasers, red semiconductor lasers and LEDs, the compounds of I-1 to I-38 described in JP-A-54-18726,
No. 322, I-1 to I-35, JP-A-7-287338, I-1 to I-34, and Dye 1 described in JP-B-55-39818.
To I-20 described in JP-A-62-284343.
Compounds Nos. 1 to I-37 and JP-A-7-287338
The compounds of I-1 to I-34 described in JP-A No. 2000-163, and the like are advantageously selected.

For semiconductor laser light sources in the 750-1400 nm wavelength region, various known dyes, including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes, advantageously spectrally sensitize. Can be done. 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, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus,
Also includes acidic nuclei such as thiazolinone nuclei, malononitrile nuclei and pyrazolone nuclei. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, US Pat.
61,279, 3,719,495, 3,877,943, British Patent 1,4
Nos. 66,201, 1,469,117, 1,422,057, JP-B-3-103
No. 91, 6-52387, JP-A-5-34
It may be appropriately selected from known dyes such as those described in JP-A Nos. 1432, 6-194787 and 6-301141.

Particularly preferred structures of the dyes used in the present invention are cyanine dyes having a thioether bond-containing substituent (for example, JP-A Nos. 62-58239, 3-13838, and 3-138842). JP-A-4-255840, JP-A-5-72659, JP-A-5-72661, JP-A-6-222491, JP-A-2-230506, and JP-A-6-258557.
JP-A-6-317868, JP-A-6-32442
No. 5, JP-T-7-500926, U.S. Pat. No. 5,541,054), a dye having a carboxylic acid group (e.g., JP-A-3-16344).
0, 6-301141, U.S. Pat.
441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524).
JP-A-51-127719, JP-A-52-808
Nos. 29, 54-61517 and 59-21
No. 4846, No. 60-6750, No. 63-1
59841, JP-A-6-35109, 6
-59381, 7-146537, 7
Dyes described in JP-A-146537, JP-T-55-50111, British Patent No. 1,467,638 and U.S. Pat. No. 5,281,515. Further, as a dye forming a J-band,
US Patent Nos. 5,510,236 and 3,87
No. 1,887, the dye described in Example 5;
The dyes described in JP-A-96131 and JP-A-59-48753 can be preferably used in the present invention.

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. In particular, combinations of sensitizing dyes are frequently used for supersensitization. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be used. Useful sensitizing dyes, combinations of supersensitizing dyes and supersensitizing substances are research
Disclosure 176, 17643 (December, 1978), page 23, IV, J, JP-B-49-25500, JP-B-43-4933, JP-A-59-19032
And JP-A-59-192242. The sensitizing dye may be added to the light-sensitive silver halide emulsion by dispersing the sensitizing dye directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2 , 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
A solvent such as N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion.

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid. A method of adding a dispersion to an emulsion, Japanese Patent Publication No. Sho 44
JP-A-23389, JP-A-44-27555 and JP-A-5-27555
As disclosed in JP-A-7-22091, a method in which a dye is dissolved in an acid and this solution is added to an emulsion, or a solution in which an acid or a base is coexistent and added as an aqueous solution to an emulsion, is disclosed in U.S. Pat. 3,822,135, 4,035
JP-A-53-10273, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in JP-A-6,025, etc.
JP-A-51-746, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, as disclosed in JP-A Nos. 3 and 58-105141.
As disclosed in Japanese Patent Publication No. 24, a method in which a dye is dissolved using a compound that causes a red shift, and this solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye may be added to the photosensitive 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 and 3,628,
960, 4,183,756 and 4,225,666, JP-A-58-18414.
As disclosed in JP-A Nos. 2 and 60-196749 and the like, chemical ripening is performed during the step of forming the photosensitive silver halide grains and / or before the desalting, during the desalting step and / or after the desalting. Until the start of the process, JP-A-58-11
As disclosed in the specification such as No. 3920, any time immediately before or during chemical ripening, any time after chemical ripening and before application of the emulsion before coating,
It may be added in the process. U.S. Pat.
No. 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, during the particle forming step and during the chemical ripening step, It may be added separately after chemical ripening or after chemical ripening, or before or during the process, and may be added separately by changing the type of compound to be added and compound combination. May be. The amount of the sensitizing dye used in the present invention may be a desired amount according to the performance such as sensitivity and fog, but is preferably 10 ^-6 to 1 mol per mol of the photosensitive silver halide, and more preferably 10 ^-4.
More preferably, it is 10 to 10 ^-1 mol.

The heat-developable image recording material of the present invention may contain a mercapto compound, a disulfide, or the like to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like. Compounds and thione compounds can be contained. Mercapto compound used in the present invention may be of any structure, those represented by ^{Ar-SM 0, Ar-S} -S-Ar are preferred. 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 ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxyl, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy ( For example, it may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and aryl (which may have a substituent). . Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, and 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 (3
H) -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-
Hydlocyroxy-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 use amount of these mercapto compounds is preferably in the range of 0.0001 to 1 mol per mol of silver in the image forming layer, and more preferably 0.001 to 0.3 mol per mol of silver.

In the image forming layer of the heat-developable image recording material of the present invention, a polyhydric alcohol (for example, glycerin and diol of the kind described in US Pat. No. 2,960,404) may be used as a plasticizer and a lubricant. ), U.S. Pat.
Fatty acids or esters described in 588,765 and 3,121,060, British Patent No. 95
For example, a silicone resin described in Japanese Patent No. 5,061 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. Although any polymer may be used as the binder for the surface protective layer, the binder preferably contains a polymer having a carboxylic acid residue in an amount of 100 mg / m ^{2 to 5} g / m ² . Examples of the polymer having a carboxyl residue include natural polymers (eg, gelatin, alginic acid), modified natural polymers (eg, carboxymethyl cellulose, phthalated gelatin), and synthetic polymers (eg, polymethacrylate, polyacrylate, polyalkyl methacrylate / acrylate). Copolymer, polystyrene / polymethacrylate copolymer, etc.). The content of carboxy residues in such polymers is preferably from 10 mmol to 1.4 mol per 100 g of polymer. 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.

For the surface protective layer, any anti-adhesion material may be used. Examples of anti-adhesion materials include waxes, silica particles, styrene-containing elastomeric block copolymers (eg, 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. The image forming layer or the protective layer of the image forming layer of the heat-developable image recording material of the present invention is described in U.S. Pat. Nos. 3,253,921 and 2,274,7.
Light absorbing substances and filter dyes such as those described in U.S. Pat. Nos. 82, 2,527,583 and 2,956,879 can be used. Also, dyes can be mordant, for example, as described in US Pat. No. 3,282,699. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3, particularly preferably 0.2 to 1.5.

Image forming layer of heat-developable image recording material of the present invention
In order to improve color tone and prevent irradiation,
Dyes and pigments can be used. Dyes and pigments yes
May be acceptable, but for example, color index
Pigments and dyes, specifically pyrazoloazole dyeing
Pigment, anthraquinone dye, azo dye, azomethine dye,
Oxonol dye, carbocyanine dye, styryl dye
Dyes, triphenylmethane dyes, indoaniline dyes,
Yes, including phenol dyes and phthalocyanines
Mechanical pigments and inorganic pigments. Used in the present invention
More preferred dyes include anthraquinone dyes (eg,
Compounds 1 to 9 described in JP-A-5-341441,
Compounds 3-6 to 6 described in JP-A-5-165147
18 and 3-23 to 38), azomethine dyes (particularly
Compounds 17 to 47 described in JP-A-5-341441
Etc.), indoaniline dyes (for example, JP-A-5-289)
No. 227, Compounds 11 to 19, JP-A-5-3
Compound 47 described in JP-A No. 41441, JP-A-5-16
No. 5147, compounds 2-10 to 11) and the like.
And azo dyes (described in JP-A-5-341441)
Compounds 10 to 16). Addition of these dyes
Additives include solutions, emulsions, solid fine particle dispersions,
Any method may be used, such as a state in which a mordant is mordanted.
The amount of these compounds used depends on the desired absorption.
However, in general, the heat-developable image recording material 1 m ^Two1μ per
It is preferably used in the range of g to 1 g.

The heat-developable image recording material of the present invention has an image recording layer containing at least one photosensitive silver halide emulsion on one side of a support and a back layer on the other side.
It is preferably a so-called one-sided photosensitive material. In the present invention, the backing layer has a maximum absorption in the desired range of about 0.5.
It is preferably from 3 to 2.0. Desired range is 750
When it is from 1 to 400 nm, the optical density at 750 to 360 nm is preferably from 0.005 to less than 0.5, more preferably from 0.001 to 0.3.
It is preferable that the antihalation layer has an optical density of less than. When the desired range is 750 nm or less, the maximum absorption in the desired range before image formation is 0.3 or more.
0 or less, and 360 to 750 nm after image formation.
Is preferably an antihalation layer having an optical density of 0.005 or more and less than 0.3. There is no particular limitation on the method for lowering the optical density after image formation to the above range. Japanese Patent Application Laid-Open No. 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, JP-A-7-13295,
No. 7-11432, US Pat. No. 5,380,63
No. 5, JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9, 3-2453
No. 9, page 14, lower left column to page 16, lower right column. Dyes which can be decolorized by the treatment include JP-A Nos. 52-139136 and 53-132334.
JP-A-56-501480, JP-A-57-160
Nos. 60, 57-68831 and 57-10
1835, 59-182436, JP-A-7-36145, 7-199409, JP-B-48-33692, JP-B-50-16648, JP-B2-41734, U.S.A. Patent No. 4,08
8,497, 4,283,487,
4,548,896 and 5,187,049
And the dyes described in the specification.

In the present invention, binders suitable 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 (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)),
Poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. 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 matting agent is added to the surface protective layer of the image forming layer and / or the back layer or the surface protective layer of the back layer in order to improve transportability. You may. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, US Pat. Nos. 1,939,213, 2,701,245, 2,322,037, and 3,26.
2,782, 3,539,344,
Organic matting agents described in 3,767,448 and the like, U.S. Pat. Nos. 1,260,772 and 2,1
Nos. 92,241, 3,257,206, 3,370,951, 3,523,0
Those well-known in the art, such as inorganic matting agents described in JP-A No. 22 and 3,769,020 and the like can be used. Specifically, examples of the organic compound that can be used as a matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile as examples of a water-dispersible vinyl polymer.
α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate,
Polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, etc. Gelatin hardened with a hardener and hardened gelatin coacervated to form microcapsule hollow particles can be preferably used. Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by known methods,
Similarly, silver bromide, glass, diatomaceous earth and the like can be mentioned. 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 practicing 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 and surface gloss of the image recording material, the particle size, shape, and particle size distribution should be adjusted as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. Is preferred. In the present invention, it is a preferable embodiment to add a matting agent to the back layer, and the matting degree of the back layer is preferably a Beck smoothness of 10 to 1200 seconds, more preferably 50 to 700 seconds. 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 heat-developable image recording material, or in a layer close to the outer surface. It is preferable to be contained. The matte degree of the protective layer on the image forming layer side may be any value as long as stardust failure does not occur,
The Beck smoothness is preferably from 500 to 10,000 seconds, particularly preferably from 500 to 2,000 seconds.

The heat-developable image recording material of the present invention has one or more layers on a support. In the case of one layer, a reducible silver salt (organic silver salt), a reducing agent (developer),
Binder, photosensitive silver halide, and, if desired,
Toning agents, coating aids and other auxiliaries must be included. In the case of a two-layer structure, the first layer (usually the layer adjacent to the support) contains an organic silver salt and a light-sensitive silver halide, and the second layer or both layers contain some other components. Must be included. Further, the first layer may include all components, and the second layer may include a protective topcoat.
Multicolor light-sensitive heat-developable image recording materials may include a combination of these two layers for each color, and US Pat.
As described in U.S. Pat. No. 708,928, all components may be contained in a single layer. In the case of a multi-dye, multi-color photosensitive heat-developable image recording material, US Pat. No. 4,460,68
As described in the specification, generally, each image forming layer (photosensitive layer) is kept distinct from each other by using a functional or non-functional barrier layer therebetween.

A backside resistive heating layer as shown in US Pat. Nos. 4,460,681 and 4,374,921.
Can be used in a photosensitive heat-developable photographic image system. An image forming layer (photosensitive layer) of the heat-developable image recording material of the present invention,
A hardener may be used for each layer such as the protective layer and the back layer. Examples of hardeners include U.S. Pat. No. 4,281,06.
No. 0, JP-A-6-208193, and the like, US Pat.
Epoxy compounds described in 1,042, etc., vinylsulfone compounds described in JP-A-62-89048, and the like are used.

In the heat-developable image recording material of the present invention, a surfactant may be used for the purpose of improving coatability and chargeability. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine is appropriately used. Specifically, fluorine-containing polymer surfactants described in JP-A-62-170950, U.S. Pat. No. 5,380,644, etc., and JP-A-60-244945.
JP-A-6-188135, fluorinated surfactants described in U.S. Pat. No. 3,885,965, etc .;
Examples include polyalkylene oxides and anionic surfactants described in JP-A-01140. If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose may be added to the image forming layer of the heat-developable image recording material of the present invention. The amount of the hydrophilic polymer to be added is 50% by mass or less, preferably 30% by mass or less, more preferably 1% by mass, based on the total binder of the image forming layer.
5% by mass or less.

The heat-developable image recording material of the present invention may be prepared, for example, by adding a soluble salt (for example, chloride or nitrate), a vapor deposited metal layer, US Pat. No. 206,312, etc., or US Pat. No. 3,428,451.
Insoluble inorganic salts described in JP-A No. 60-252
It may have a layer containing fine particles of tin oxide described in JP-A-349-57, JP-A-57-104931, and the like. The heat-developable image recording material of the present invention may comprise additional layers, such as a dye-receiving layer for receiving a migrating dye image, an opaque layer if reflective printing is desired, a protective topcoat layer, a primer known in the photothermographic art. Layers and the like. In the heat-developable image recording material of the present invention, it is preferable that an image can be formed with only one sheet of the material, and it is preferable that a functional layer required for image formation such as an image receiving layer does not become another material.

The image forming layer of the heat-developable image recording material of the present invention is preferably prepared by applying an aqueous coating solution and then drying. Here, "aqueous" means that 60% by mass or more of the solvent (dispersion medium) of the coating liquid is water. Components other than water of the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve,
Water-miscible organic solvents such as 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 = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80 / 15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent mass%.)
In the present invention, a coating solution such as an image forming layer is coated with various coating operations such as dip coating, air knife coating, flow coating, and extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. Can be coated. If desired, the method described in U.S. Pat. No. 2,761,791 and GB 837,095
One or more layers can be coated simultaneously.

As a method for obtaining a color image using the heat-developable image recording material of the present invention, the method described in JP-A-7-13295, page 43, left column, line 43 to 11 left column, line 40 can be mentioned. Can be Also, color dye image stabilizers are
British Patent Nos. 1,326,889, U.S. Pat. Nos. 3,432,300, 3,698,909, 3,574,627 and 3,57
This is exemplified in 3,050, 3,764,337 and 4,042,394.
The heat-developable image-recording material of the present invention may be developed by any method, but is usually developed by elevating the temperature of an image-wise exposed image-recording material. As a preferred embodiment of the heat developing machine used, as a type in which the heat-developable image recording material is brought into contact with a heat source such as a heat roller or a heat drum,
Japanese Patent Publication No. 5-56499, Patent Publication No. 684453
JP-A-9-292695 and JP-A-9-29738.
No. 5 and International Publication No. WO95 / 30934.
No. 13,294, International Publication WO97 / 28489, International Publication WO97 / 28488 and International Publication WO97 / 2
No. 8487. A particularly preferred embodiment is a non-contact type thermal developing machine. Development temperature is 8
0 to 250 ° C. is preferable, and 100 to 1 is more preferable.
40 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

In the heat-developable image recording material of the present invention, as a method for preventing processing unevenness due to a dimensional change during heat development, an image is not formed at a temperature of 80 ° C. or more and less than 115 ° C. (preferably 113 ° C. or less). After heating for 5 seconds or more, a method of forming an image by thermal development at 110 ° C. or more and 140 ° C. or less (preferably 130 ° C. or less) (so-called multi-stage heating method) is effective. The heat-developable 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 the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a semiconductor laser and a second harmonic generation element can be used.
The heat-developable image recording material of the present invention has a low haze at the time of exposure and tends to generate interference fringes. Examples of the technology for preventing the occurrence of interference fringes include a technology disclosed in Japanese Patent Application Laid-Open No. 5-113548, in which a laser beam is obliquely incident on a heat-developable image recording material, and a technology disclosed in International Publication WO 95/317.
A method utilizing a multi-mode laser disclosed in, for example, Japanese Patent No. 54-54 is known, and it is preferable to use these techniques. To expose the heat-developable image recording material of the present invention, SPIE vol. 169 Laser Printing 1
As disclosed in pages 16-128 (1979), JP-A-4-51043, and International Publication WO95 / 31754, laser beams are exposed so as to overlap each other so that scanning lines are not visible. preferable.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process 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 includes a carry-in roller pair 11 (a lower roller is a heat roller) for carrying the heat-developable image recording material 10 into a heating section while correcting and preheating the heat-developable image recording material 10 in a planar shape, and after heat development after heat development. It has a carry-out roller pair 12 that carries out the heat-developable image recording material 10 from the heating unit while correcting it into a planar 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. The transport means for transporting the heat-developable image recording material 10 during the thermal development includes a plurality of rollers 13 on the side where the surface having the image forming layer contacts, and the non-woven fabric on the opposite side where the back surface contacts. A smooth surface 14 on which, for example, polyphenylene sulfite or Teflon (registered trademark) is bonded 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. Heating means is provided on the upper portion of the roller 13 and the lower portion of the smooth surface 14 such that the heating device 1 is heated from both sides of the heat-developable image recording material 10.
5 is installed. 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.

Material of Roller 13 Surface and Smooth Surface 1
The member No. 4 is durable at high temperature and is a heat-developable image recording material 1
Any material may be used as long as it does not hinder the conveyance of 0, but the material of the roller surface is preferably silicon rubber, and the member of the 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 heating unit has a preheating unit upstream of the heat development processing unit that has a temperature lower than the heat development temperature (for example, about 10 to 30 ° C. lower) and has a temperature and a temperature sufficient to evaporate the water content in the heat development image recording material. The time is desirably set, and it is preferable to set the temperature at a temperature higher than the glass transition temperature (Tg) of the support of the heat-developable image recording material 10 so that development unevenness does not occur. A guide plate 16 is provided downstream of the thermal development processing section, and a slow cooling section C
Is installed. 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 example, the 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 be of various configurations. . In the case of the multi-stage heating method preferably used in the present invention, in the above-described apparatus, two or more heat sources having different heating temperatures may be provided, and heating may be performed continuously at different temperatures. Hereinafter, the present invention will be described more specifically with reference to Examples. The materials, usage amounts, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[0150]

EXAMPLES Example 1 The structure of the compound used in Example 1 is shown below.

[0151]

Embedded image

[0152]

Embedded image

<< Preparation of polyethylene terephthalate (PET) support having undercoat layer >> (1) Preparation of PET support Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 (phenol- Polyethylene terephthalate (PET) was obtained at a temperature of 25 ° C. in 6/4 (weight ratio). After pelletizing this, it is 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. did. This was performed at 110 ° C. using rolls having different peripheral speeds.
The film was longitudinally stretched three times and then transversely stretched 4.5 times at 130 ° C. using a tenter. Thereafter, after heat-setting at 240 ° C. for 20 seconds, it was relaxed by 4% in the lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling is performed on both ends, the film is wound at 4.8 kg / cm ² , and the thickness is 175 mm.
A μm-roll PET support was obtained.

(2) Surface Corona Treatment Both sides of the PET support obtained in the above (1) were treated at room temperature at 20 m / min using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., Ltd. From the current and voltage readings at this time, 0.375 kV · A ·
It was found that the processing of 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.

(3) Preparation of Undercoat Layer Coating Solution (Formulation 1) For undercoat layer on the side of organic acid silver layer Pesresin A-515GB (30% by mass solution) manufactured by Takamatsu Oil & Fat Co., Ltd. 234 g polyethylene glycol monononyl phenyl ether (average ethylene oxide Number = 8.5) 10% by mass solution 21.5 g Soken Chemical Co., Ltd. MP-1000 0.91 g (polymer fine particles, average particle diameter 0.4 μm) Distilled water 744 ml

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

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

(4) Preparation of PET support having undercoat layer
Composition Piece of PET support subjected to corona discharge obtained in (2) above
The undercoat layer coating liquid formulation 1 obtained in (3) above was
Yar bar, wet application amount 6.6ml / m ^Twobecome
And dried at 180 ° C. for 5 minutes. Then this back
On the side (back side), apply the undercoat layer coating liquid formulation 2 with a wire
5.7ml / m wet coating amount with bar ^TwoTo be
Apply and dry at 180 ° C for 5 minutes.
Surface), apply undercoat coating liquid formulation 3 with a wire bar.
7.7ml / m^TwoApply so that it becomes 18
PET support having an undercoat layer, dried at 0 ° C. for 6 minutes
It was created.

<< Preparation of Coating Solution for Back Surface >><< Preparation of Coating Solution for Anti-Halation Layer >> (1) Preparation of Solid Precursor Dispersion of Base Precursor 64 g of base precursor compound 11, 28 g of diphenyl sulfone, and interface manufactured by Kao Corporation Activator Demol N (10 g) was mixed with distilled water (220 ml), and the mixture was dispersed in beads using a sand mill (1/4 Gallon sand grinder mill, manufactured by Imex Co., Ltd.) to give a base precursor having an average particle diameter of 0.2 μm. Was obtained.

(2) Preparation of Dye Solid Fine Particle Dispersion Solution 9.6 g of cyanine dye compound 13 and 5.8 g of sodium P-dodecylbenzenesulfonate were added to 30 parts of distilled water.
5 ml and mix the mixture with a sand mill (1 / 4Gall
on sand grinder mill, manufactured by Imex Co., Ltd.)
To obtain a dispersion of solid dye fine particles having an average particle diameter of 0.2 μm.

(3) Preparation of Coating Solution for Antihalation Layer 17 g of gelatin, 9.6 g of polyacrylamide, 70 g of solid fine particle dispersion of base precursor obtained in (1-1), and dye obtained in (1-2) Solid fine particle dispersion 5
6 g, polymethyl methacrylate fine particles (average particle size 6.5 μm) 1.5 g, benzoisothiazolinone 0.
03 g, 2.2 g of sodium polyethylene sulfonate,
0.2 g of the blue dye compound 14, 3.9 g of the yellow dye compound 15 and 844 ml of water were mixed to prepare an antihalation layer coating solution.

<< Preparation of Back Surface Protective Layer Coating Solution >>
The mixture was kept at 0 ° C., and gelatin 50 g, polystyrene sodium sulfonate 0.2 g, N, N-ethylenebis (vinylsulfone acetamide) 2.4 g, tert-octylphenoxyethoxyethaneethane sodium 1 g,
Benzoisothiazolinone 30 mg, N-perfluorooctylsulfonyl-N-propylalanine potassium salt 3
7 mg, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide 15]
0.15 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 (CH 2) 4 -SO 3 Na
8.8 g of an acrylic acid / ethyl acrylate copolymer (copolymer weight ratio 5/95), aerosol OT
0.6 g of American Cyanamid Co., 1.8 g of liquid paraffin emulsion as liquid paraffin, and 950 ml of water were mixed to prepare a back surface protective layer coating solution.

<< Preparation of Image Forming Layer Coating Solution >> << Preparation of Silver Halide Mixed Emulsion A >> (1) Preparation of Silver Halide Emulsion 1 A 1% by weight potassium bromide solution in 1,421 ml of distilled water.
1 ml, and the concentration is 1 mol / m^Three3.5m of sulfuric acid
1 and 31.7 g of phthalated gelatin were added. Get
The mixed solution in a titanium-coated stainless steel reaction pot.
While stirring, the liquid temperature was maintained at 34 ° C. Silver nitrate 22.2
Solution A obtained by diluting 2 g to 95.4 ml with distilled water, and bromide
A solution obtained by diluting 26.3 g of potassium to 161 ml with distilled water.
Liquid B was added at a constant flow rate over 45 seconds. So
After that, 10 ml of 3.5 mass% aqueous hydrogen peroxide solution is added.
And a 10% by weight aqueous solution of benzimidazole was added to 1
0.8 ml was added. Further, 51.86 g of silver nitrate was steamed.
Solution C diluted to 317.5 ml with distilled water and potassium bromide
45.8 g diluted with distilled water to 400 ml
, The total amount of solution C was added at a constant flow rate over 20 minutes,
D controls double while maintaining pAg at 8.1
It was added by the jet method. 1 × 10 per mole of silver ^-FourMole
Dissolve potassium hexachloride iridate (III)
10 minutes after adding liquid C and solution D, the total amount
Was added. Five seconds after the completion of the addition of the solution C,
An aqueous solution of potassium iron (II) iodide was added in an amount of 3 × 10^-Four
All moles were added. Concentration 1 mol / m^ThreeP with sulfuric acid
Adjust H to 3.8, stop stirring, settle / desalinate / wash
Went through the process. Concentration 1 mol / m^ThreeUsing sodium hydroxide
Adjusted to pH 5.9, and a silver halide having a pAg of 8.0.
A dispersion was made.

While stirring the above silver halide dispersion, 3
The mixture was maintained at 8 ° C., and 5 ml of a 0.34 mass% 1,2-benzisothiazolinone-3-one methanol solution was added.
Forty minutes later, a methanol solution of the spectral sensitizing dye A was added at 1 × 10 ⁻³ mol per mol of silver, and the temperature was raised to 47 ° C. one minute later. Twenty minutes after the temperature was raised, a methanol solution of sodium benzenethiosulfonate was added to 7.6 × 10 ⁻⁵ per mole of silver.
After 5 minutes, 1.9 × 10 ^-4 mol of a methanol solution of tellurium sensitizer B was added per 1 mol of silver, and the mixture was aged for 91 minutes. 1.3 ml of a 0.8% by weight methanol solution of N, N′-dihydroxy-N ″ -diethylmelamine was added, and 4 minutes later, a methanol solution of 5-methyl-2-mercaptobenzimidazole was added in an amount of 3.
7 × 10 ⁻³ mol, and 1-phenyl-2-heptyl-
Silver halide emulsion 1 was prepared by adding 4.9 × 10 ⁻³ mol of a methanol solution of 5-mercapto-1,3,4-triazole to 1 mol of silver. The grains in the obtained silver halide emulsion were pure silver bromide grains having an average sphere equivalent diameter of 0.046 μm and a variation coefficient of the sphere equivalent diameter of 20%. 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 80% using the Kubelka-Munk method.

(2) Preparation of Silver Halide Emulsion 2
Change the liquid temperature at the time of formation from 34 ° C to 49 ° C, and add the solution C
30 minutes to remove potassium hexacyanoferrate (II)
Except for the above, a silver halide emulsion 2 was prepared.
Precipitation / desalting / washing / dispersion was performed in the same manner as (1). Further
The amount of spectral sensitizing dye A added was 7.5 × 1 per mole of silver.
0^-FourMoles of tellurium sensitizer B per mole of silver
1.1 × 10 ^-FourMolar and 1-phenyl-2-hep
Addition of tyl-5-mercapto-1,3,4-triazole
The addition amount was 3.3 × 10 per mol of silver.^-3Except for the mole
Is the same as (1) for spectral sensitization, chemical sensitization, and 5
-Methyl-2-mercaptobenzimidazole, 1-f
Enyl-2-heptyl-5-mercapto-1,3,4-
Triazole was added to obtain silver halide emulsion 2.
Was. The emulsion grains of the silver halide emulsion 2 have an average sphere equivalent diameter.
Pure silver bromide with 0.080 μm and coefficient of variation of equivalent sphere diameter of 20%
Particles.

(3) Preparation of silver halide emulsion 3 In the preparation of silver halide emulsion 1 in (1) above, except that the liquid temperature during grain formation was changed from 34 ° C. to 27 ° C. Emulsion 3 was prepared. Precipitation / desalting / washing / dispersion was performed in the same manner as (1). Further, spectral sensitizing dye A
Except that the addition amount of the solid dispersion (aqueous gelatin solution) was changed to 6 × 10 ⁻³ mol per mol of silver and the addition amount of tellurium sensitizer B was changed to 5.2 × 10 ⁻⁴ mol per mol of silver. In the same manner as in (1), silver halide emulsion 3 was obtained. The silver halide emulsion 3 had an average sphere equivalent diameter of 0.038.
It was a pure silver bromide particle having a μm and a coefficient of variation of an equivalent sphere diameter of 20%. (4) Preparation of silver halide mixed emulsion A 70% by weight of silver halide emulsion 1 obtained above, 15% by weight of silver halide emulsion 2 and 15% by weight of silver halide emulsion 3 were mixed. A 1% by weight aqueous solution of benzothiazolium iodide was added in an amount of ^{7.times.10.sup.-3} mol per mol of silver to obtain a silver halide mixed emulsion A.

<< Preparation of Organic Acid Silver Dispersion >> 87.6 kg of behenic acid (product name: Edenor C22-85R) manufactured by Henkel Co., Ltd.
423 liters of distilled water, 49.2 of 5N NaOH aqueous solution
Liter and 120 liter of tert-butanol were mixed and reacted by stirring at 75 ° C. for 1 hour to obtain a sodium behenate solution. Separately, 206.2 liters (pH 4.0) of an aqueous solution of 40.4 kg of silver nitrate were prepared, and 10
It was kept at ° C. A reaction vessel containing 635 liters of distilled water and 30 liters of tert-butanol was kept at 30 ° C., and while stirring, the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution were respectively reduced for 62 min.
Added over 0 seconds and 60 minutes. At this time, only the aqueous silver nitrate solution was added for 7 minutes and 20 seconds from the start of the addition of the aqueous silver nitrate solution, and then the addition of the sodium behenate solution was started. 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 addition of the sodium behenate solution was completed, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the 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
The particles were scaly crystals having a sphere equivalent diameter of 2 μm and a coefficient of variation of sphere equivalent diameter of 15%. A, b, c from the shortest one).

To a wet cake having a dry solid content of 100 g, polyvinyl alcohol (trade name: PVA-21)
7) 7.4 g 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, manufactured by Microfluidics International Corporation, using G10Z interaction chamber) at a pressure of 1750 kg / cm ²
And treated three times to obtain a silver behenate dispersion as a silver salt of an organic acid. 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% by mass dispersion of reducing agent (f) >> 10 kg of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane
And 10 kg of a 20% by mass aqueous solution of denatured polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203),
kg was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and has an average diameter of 0.5 m.
horizontal sand mill filled with zirconia beads (UV
M-2: manufactured by Imex Co., Ltd.) for 3 hours and 30 minutes. There benzoisothiazolinone sodium salt 0.1.
2 g and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a 25% by mass dispersion of the reducing agent (f). The reducing agent particles contained in this reducing agent dispersion 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 with a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 25% by Mass Dispersion of Compound Represented by General Formula (1) or (2) >> 80 g of Compound (Type shown in Table 1) Represented by General Formula (1) or (2) And 176 g of water were added to 64 g of a 20% aqueous solution of modified Poval MP203 manufactured by Kuraray Co., Ltd. and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm was prepared and put into a vessel together with the slurry, and the dispersion machine (1
/ 4G Sand Grinder Mill: IMEX Co., Ltd.
For 5 hours to obtain a 25% by mass dispersion of the compound represented by formula (1) or (2). The particles contained in the dispersion thus obtained had an average particle size of 0.72 μm.

<< Preparation of a 22% by mass dispersion of triphenylphosphine oxide (Compound G) >>
And 10 kg of a 20% by mass aqueous solution of denatured polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203),
kg was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and has an average diameter of 0.5 m.
horizontal sand mill filled with zirconia beads (UV
M-2: manufactured by IMEX Co., Ltd.) for 3 hours 30 minutes, and then 0.2 g of benzoisothiazolinone sodium salt
And water were added to adjust the concentration of compound G to 22% by mass to obtain a dispersion. The particles of compound G contained in the dispersion thus obtained had a median diameter of 0.55 μm and a maximum particle diameter of 2.0 μm or less. The resulting dispersion has a pore size of 10.
The mixture was filtered through a 0 μm polypropylene filter to remove foreign substances such as dust, and stored.

<< Preparation of 20% by Mass Dispersion of Coupler Compound >> Compound of general formula (I) (development inhibitor releasing coupler)
And / or 10 kg of the coupler (i) of the general formulas (4) to (18) (the kind shown in Table 1) and 20 of the modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
16 kg of water was added to 10 kg of a mass% 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 3 hours and 30 minutes. 0.2 g and water were added to adjust the concentration of the coupler compound to 20% by mass to obtain a dispersion. The particles of the coupler compound contained in the dispersion thus obtained have a median diameter of 0.55 μm and a maximum particle diameter of 2.0.
μm or less. The resulting dispersion has a pore size of 10.0 μm.
And filtered to remove foreign substances such as dust, and stored.

<< Preparation of 10% by Mass Dispersion of Mercapto Compound >> 1-phenyl-2-heptyl-5-mercapto-
8.3 kg of water was added to 5 kg of 1,3,4-triazole and 5 kg of a 20% by mass aqueous solution of a modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), and mixed well to form a slurry. The slurry was fed 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. Water was added thereto to adjust the concentration of the mercapto compound to 10% by mass to obtain a 10% by mass dispersion of the mercapto compound. The mercapto compound particles contained in this mercapto compound dispersion have a median diameter of 0.40 μm and a maximum particle diameter of 2.0 μm.
It was below. The resulting mercapto compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm,
Foreign matter such as dust was removed and stored. Immediately before use, the mixture was filtered again with a polypropylene filter having a pore size of 10 μm.

<< Preparation of Polyhalogen Compound Dispersion-1 >>
Tribromomethyl-2-naphthyl sulfone (compound 5-
2) 5 kg, modified polyvinyl alcohol (Kuraray Co., Ltd.)
2.5% of a 20% by weight aqueous solution of Poval MP203)
g, 213 g of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate, and 10 kg of water were mixed well to form a slurry. The slurry was fed by a diaphragm pump, and dispersed by 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. Thereto was added 0.2 g of benzoisothiazolinone sodium salt and water, and the concentration of the polyhalogen compound was adjusted to 20% by mass to obtain a dispersion of the polyhalogen compound (compound 5-2). The polyhalogen compound particles contained in this dispersion had a median diameter of 0.36 μm and a maximum particle diameter of 2.0 μm or less.
The resulting 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 Polyhalogen Compound Dispersion-2 >>
In the preparation of the above polyhalogen compound dispersion-1,
Tribromomethyl-2-naphthyl sulfone (compound 5-
2) 5 kg of tribromomethylphenylsulfone (compound 5-1) was used instead of 5 kg, and 20% by mass of MP20
3 The same operation was carried out except that the aqueous solution was changed to 5 kg, and the polyhalogen compound (compound 5-1) was diluted so as to have a concentration of 25% by mass, filtered and dispersed to disperse the polyhalogen compound (compound 5-1). I got something. The polyhalogen compound particles contained in this dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 2.0 μm or less. The resulting polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored. After storage, it was stored at 10 ° C. or less until use.

<< Preparation of Polyhalogen Compound Dispersion-3 >>
In the preparation of the above polyhalogen compound dispersion-1,
Tribromomethyl-2-naphthyl sulfone (compound 5-
2) Instead of 5 kg, tribromomethyl (3-N-butylcarbamoylphenyl) sulfone (compound 5-3) 5
The same operation as above was carried out except that the weight of the polyhalogen compound (compound 5-3) was 25% by mass, and the mixture was filtered to obtain a dispersion of the polyhalogen compound (compound 5-3). Obtained. The polyhalogen compound particles contained in this dispersion had a median diameter of 0.45 μm and a maximum particle diameter of 2.
It was 0 μm or less. The resulting polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 5% by mass solution of phthalazine compound >> 8 kg of denatured polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) was dissolved in 174.57 kg of water.
Then, 3.15 kg of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28 kg of a 70% by mass aqueous solution of 6-isopropylphthalazine were added to prepare a 5% by mass solution of 6-isopropylphthalazine.

<< Preparation of 5% by Mass 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 is prepared, put into a vessel together with the slurry, dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours, and water is added thereto to prepare a pigment. Dilute so that the concentration becomes 5% by mass, and add 5% by mass of the pigment.
A dispersion was obtained. The pigment particles contained in this dispersion had an average particle size of 0.21 μm.

<< Preparation of SBR Latex 40% by Mass Dispersion >> Ultrafiltration (UF) -purified SBR latex was obtained as follows. The following SBR latex was diluted 10-fold with distilled water, and the UF-purified module FS was used.
03-FC-FUY03A1 (Daisen Membrane
Ion conductivity of 1.5 mS /
cm and purified by adding Sandet-BL manufactured by Sanyo Kasei Co., Ltd. to a concentration of 0.22% by mass. Further with NaOH and NH ₄ OH Na ⁺ ion: NH ₄ ⁺ ion = 1: 2.3 was added to a (molar ratio), pH
Adjusted to 8.4. The latex concentration at this time was 40% by mass. (SBR latex: -St (68) -Bu (2
9) -AA (3)-latex) (St: styrene, B
u: butadiene, AA: acrylic acid) average particle size 0.1 μ
m, concentration 45%, equilibrium water content at 25 ° C. and relative humidity 60% 0.6 mass%, ionic conductivity 4.2 mS / cm (Ion conductivity is measured by a conductivity meter CM manufactured by Toa Denpa Kogyo KK)
Using -30S, a latex stock solution (40%) was measured at 25 ° C), pH 8.2.

<< Preparation of Image Forming Layer Coating Solution >> 2.8 g of a 5% by mass aqueous dispersion of the pigment obtained above, 103 g of the organic acid silver dispersion obtained above, and polyvinyl alcohol PVA-205
5 g of a 20% by mass aqueous solution of Kuraray Co., Ltd., 11.7 g of a 25% by mass dispersion of the reducing agent (f) obtained above, and a triphenylphosphine oxide dispersion equimolar to the reducing agent, obtained above. 1.0 g of polyhalogen compound dispersion-1;
2.2 g of the polyhalogen compound dispersion-2 and 6.5 g of the polyhalogen compound-3, 2.2 g of the 10% by mass dispersion of the mercapto compound obtained above, and 120 g of the 40% by mass dispersion of the SBR latex obtained above , And 18 ml of the 5% by mass solution of the phthalazine compound obtained above, and 10 g of the silver halide mixed emulsion A obtained above were mixed well to prepare a coating solution for the image forming layer. ^The solution was fed so as to be ² . The viscosity of the coating solution for the image forming layer was 85 ° C. at 40 ° C. (No. 1 rotor, 60 rpm) as measured with a B-type viscometer of Tokyo Keiki.
[mPa · s]. The viscosity of the coating solution at 25 ° C. using an RFS Fluid Spectrometer manufactured by Rheometrics Far East Co., Ltd. was such that the shear rate was 0.1%.
1500, 220, 70, 40, 20 [mPa · s] at 1, 1, 10, 100, and 1000 [1 / sec]
Met.

<< Preparation of Coating Solution for Intermediate Layer on Image Forming Layer >> 772 g of a 10% by weight aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), pigment (same as the pigment described in paragraph [0179] of the present specification) 5.3 g of a 20% by weight dispersion of) and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate /
Acrylic acid copolymer (copolymerization weight ratio 64/9/20/5)
/ 2) 5% by mass of aerosol OT (manufactured by American Cyanamid Co.) in 226 g of 27.5% by mass of latex
2 ml of aqueous solution and 20 ammonium phthalate
10.5 ml of a 1% by mass aqueous solution was added, and water was further added to make a total amount of 880 g, thereby obtaining an intermediate layer coating liquid. 10ml of this
/ M ² to the coating die. The viscosity of the coating solution was measured using a B-type viscometer at 40 ° C (No. 1 rotor, 60r
pm) was 21 [mPa · s].

<< Preparation of Coating Solution for Image Forming Layer Surface Protective Layer >><< Preparation of Coating Solution for First Protective Layer >> 64 g of inert gelatin
Dissolved in water, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20/5 /
2) 80 g of a 27.5% by mass latex solution, 1 of phthalic acid
23 ml of 0% by mass methanol solution, 23 ml of 10% by mass aqueous solution of 4-methylphthalic acid, 28 ml of 1N sulfuric acid, 5 ml of 5% by mass aqueous solution of Aerosol OT (manufactured by American Cyanamid Co.), 0.5 g of phenoxyethanol, and benzoisothiazo 0.1 g of linone was added, and water was further added to make a total amount of 750 g to obtain a coating liquid for the first protective layer. Immediately before the coating, 26 ml of 4% by mass chromium alum was mixed with a static mixer, and the mixture was fed to a coating die at 18.6 ml / m ² . The viscosity of this coating solution is 40 ° C. using a B-type viscometer (No. 1 rotor, 60 rpm).
Was 17 [mPa · s].

<< Preparation of Coating Solution for Protective Layer Second Layer >> Inert gelatin (80 g) was dissolved in water, and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio: 64/9)
/ 20/5/2) Latex 27.5% by mass liquid 102
g, 3.2 ml of a 5% by mass solution of potassium salt of N-perfluorooctylsulfonyl-N-propylalanine, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether
32 ml of a 2% by mass aqueous solution of [ethylene oxide average polymerization degree = 15], 23 ml of a 5% by mass solution of aerosol OT (manufactured by American Cyanamid Co.), 4 g of polymethyl methacrylate fine particles (average particle size 0.7 μm), 4 g of polystyrene Methyl methacrylate fine particles (average particle size: 6.4 μm) 21
g, 4-methylphthalic acid 1.6 g, phthalic acid 4.8 g,
44 ml of 1N sulfuric acid and benzoisothiazolinone 1
0 mg was added, and water was further added to make a total amount of 650 g.
445 ml of an aqueous solution containing 4% by mass of chromium alum and 0.67% by mass of phthalic acid were mixed with a static mixer immediately before coating, and the second layer of the protective layer (surface protective layer)
It was used as a coating solution and sent to a coating die at 8.3 ml / m ² . The viscosity of this coating solution was measured using a B-type viscometer 40.
C. (No. 1 rotor, 60 rpm) was 9 [mPa · s].

<< Preparation of heat-developable image recording material >> On the back surface of the PET support having an undercoat layer prepared above, the coating solution for anti-halation layer obtained above was coated with a solid fine particle dye having a solid content of 0. Further, the back surface protective layer coating solution obtained above was simultaneously and multi-layer-coated so that the coating amount of gelatin was 1.7 g / m ² so as to be 0.4 g / m ² , followed by drying.
An antihalation back layer was formed. On the undercoat layer opposite to the back surface, on the undercoat layer, the coating solution for the image forming layer obtained above (a coating amount of photosensitive silver halide of 0.14 g / m ² ), the coating solution for the intermediate layer, and the first layer for the protective layer The solution and the coating solution for the second layer of the protective layer were simultaneously coated in this order by a slide bead coating method to prepare a heat-developable image recording material.

The coating was performed at a speed of 160 m / min. The distance between the tip of the coating die and the support was 0.14 to 0.2
The width of the coating was adjusted to be 8 mm, and the width of the coating was widened by 0.5 mm on both the left and right sides with respect to the width of the slit for discharging the coating solution. 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, the coating solution is cooled by blowing a wind having a dry bulb temperature of 18 ° C. and a wet bulb temperature of 12 ° C. for 30 seconds, and then, in a helical floating type drying zone, a dry bulb temperature of 30 ° C. , A dry air having a wet bulb temperature of 18 ° C was blown for 200 seconds, passed through a drying zone at 70 ° C for 20 seconds, passed through a drying zone at 90 ° C for 10 seconds, and then cooled to 25 ° C to obtain a solvent in the coating solution. Was volatilized. The average wind speed of the air blown to the coating liquid film surface in the chilling zone and the drying zone is 7 m
/ Sec. The matte degree of the prepared heat-developable image recording material is Beck smoothness, and the surface having the image forming layer
The back surface was 130 seconds. To the comparative sample 101 prepared as described above, the general formula (1) or (2), the general formula (I) and the coupler were added as shown in Table 1, and otherwise the same as the sample 101 Operate,
Samples 102 to 115 were prepared.

{Evaluation of Photographic Performance} The heat-developable image recording material prepared above was adjusted to [temperature 20 ° C., humidity 20%] and [temperature 30 ° C., humidity 75%] and aged for 15 hours. After exposing with a laser sensitometer,
After that, the film was processed (heat development) at 122 ° C. for 16 seconds, and the obtained image was evaluated with a densitometer. Laser sensitometer: Two 660 nm diode lasers with 35 mW output are multiplexed. Single mode Gaussian beam spot 1 / e ² is sent in the sub-scanning direction at a pitch of 100 μm and 25 μm, and one pixel is written four times. ), Fog (Dmi
n), and sensitivity (reciprocal of the ratio of the exposure amount giving a density 1.5 higher than Dmin). The sensitivity was shown as a relative value with the sensitivity of the heat-developable image recording material 101 in Table 1 as 100.
Table 1 shows the evaluation results.

[0188]

[Table 1]

From Table 1, it is clear that the heat-developable image recording material of the present invention exhibits excellent performance as compared with Comparative Examples.

Example 2 << Preparation of Silver Halide Emulsion A >> Alkali-treated gelatin (calcium content: 2700 pp
m), 11 g, potassium bromide 30 mg, and sodium 4-methylbenzenesulfonate 1.3 g were dissolved, and the pH was adjusted to 6.5 at 40 ° C. 159 ml of an aqueous solution containing 18.6 g of silver nitrate, 1 mol / l of potassium bromide, and (NH ₄ ) ₂ RhCl
₅ (H ₂ O) at 5 × 10 ⁻⁶ mol / l and K ₃ I
an aqueous solution containing 2 × 10 ⁻⁵ mol / l of rCl ₆ ,
While maintaining the pAg at 7.7, it was added over 6 minutes and 30 seconds by the control double jet method. Then, silver nitrate 55.
476 ml of an aqueous solution containing 5 g and a halogen salt aqueous solution containing 1 mol / l of potassium bromide and 2 × 10 ^-5 mol / l of K ₃ IrCl ₆ by a control double jet method for 28 minutes and 30 seconds while keeping the pAg at 7.7. And added. Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, and 51.1 g of low molecular weight gelatin having an average molecular weight of 15,000 (calculated as 20 ppm or less) was added to adjust the pH to 5.9 and the pAg to 8.0. The obtained particles had an average particle size of 0.08 μm and a projected area variation coefficient of 9
%, (100) cubic grains having a 90% face ratio.

The silver halide grains thus obtained were mixed with 60
° C, 76 µmol of sodium benzenethiosulfonate per mole of silver was added, and 3 minutes later, 71 µmol of triethylthiourea was added.
After adding 5 × 10 ^-4 mol of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 0.17 g of compound A, the mixture was cooled to 40 ° C. Thereafter, the temperature was kept at 40 ° C., and 4.7 × 10 ⁻² mol of potassium bromide (added as an aqueous solution) per 1 mol of silver halide, 12.8 × 10 ² mol
^-4 mol of the following sensitizing dye A (added as an ethanol solution) and 6.4 × 10 ^-3 mol of compound B (added as a methanol solution) were added with stirring, and after 20 minutes, 30 ° C.
Then, the preparation of silver halide emulsion A was completed.

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<< Preparation of Silver Behenate Dispersion A >> Behenic acid (Edenor C22-85R, manufactured by Henkel)
6 kg, 423 liters of distilled water, 49.2 liters of a 5N aqueous solution of NaOH, and 120 liters of tert-butyl alcohol were mixed and reacted by stirring at 75 ° C. for 1 hour to obtain a sodium behenate solution. Aside from this,
206.2 liters of an aqueous solution of 40.4 kg of silver nitrate was prepared and kept at 10 ° C. 635 liters of distilled water and ter
The reaction vessel containing 30 liters of t-butyl alcohol was kept at 30 ° C., and while stirring, the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution were each reduced to 62: 1.
It was added at a constant rate over 0 seconds and 60 minutes. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the start of the silver nitrate aqueous solution addition, and after 7 minutes and 20 seconds, the addition of the sodium behenate solution was started.
For 30 minutes, only the sodium behenate solution was added. At this time, the temperature in the reaction vessel was set at 30 ° C., and the temperature was controlled so as not to rise. Also,
The piping of the addition system of the sodium behenate solution is kept warm by steam tracing, and the liquid temperature at the outlet of the addition nozzle tip is 7
The steam amount was controlled so as to be 5 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After the addition of the sodium behenate solution was completed, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. The morphology of the obtained silver behenate grains was evaluated by electron microscopy. Was.

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 1,700) 7.4 g and water were added to make the total amount 385 g, and the mixture was predispersed with a homomixer. Next, the predispersed undiluted solution is dispersed in a dispersing machine (Microfluidizer M-110S manufactured by Microfluidics International Corporation).
-EH, G10Z interaction chamber) pressure was adjusted to 1750 kg / cm ² and treated three times,
A silver behenate dispersion A was obtained. As a cooling means, coiled heat exchangers were installed before and after the interaction chamber, respectively, and the desired dispersion temperature was set by adjusting the temperature of the refrigerant. The silver behenate particles contained in the silver behenate dispersion A thus obtained have a volume-weighted average diameter of 0.52 μm.
m, particles having a variation coefficient of 15%. Particle size measurements are available from Malvern Instruments Ltd.
d. The measurement was performed with MasterSizerX manufactured by KK. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.
5, the grain thickness was 0.14 μm, and the average aspect ratio (the ratio of the circle equivalent diameter of the projected area of the grain to the grain thickness) was 5.1.

<< Preparation of Solid Fine Particle Dispersion of Reducing Agent (f) >> As a reducing agent, 1,1-bis (2-hydroxy-3,
10 kg of 5-dimethylphenyl) -3,5,5-trimethylhexane and a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
16 kg of water was added to 0 kg and mixed well to form a slurry. This slurry was fed by a diaphragm pump, and a horizontal sand mill filled with zirconia beads having an average diameter of 0.5 mm (UVM-2, manufactured by Imex Co., Ltd.)
After dispersion for 3 hours and 30 minutes, 4 g of sodium benzoisothiazolinone and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the dispersion thus obtained have a median diameter of 0.44 μm, a maximum particle diameter of 2.0 μm or less,
The coefficient of variation of the average particle diameter was 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 25% by mass dispersion of compound represented by formula (1) or (2) >> 80 g of compound represented by formula (1) or (2) (type shown in Table 2) And 176 g of water were added to 64 g of a 20% aqueous solution of modified Poval MP203 manufactured by Kuraray Co., Ltd. and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm was prepared and put into a vessel together with the slurry, and the dispersion machine (1
/ 4G Sand Grinder Mill: IMEX Co., Ltd.
For 5 hours to obtain a 25% by mass dispersion of the compound represented by formula (1) or (2). The particles contained in the dispersion thus obtained had an average particle size of 0.72 μm.

<< Preparation of 20% by Mass Dispersion of Coupler Compound >> Development inhibitor releasing coupler of the general formula (I) and / or (i) coupler of the general formulas (4) to (18) (types described in Table 2) ) 10 kg and 16 kg of water were added to 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203), and mixed well to form a slurry. This slurry is fed by a diaphragm pump, and a horizontal sand mill (UVM-2: IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm.
For 3 hours and 30 minutes, and 0.2 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the coupler compound to 20% by mass to obtain a dispersion. The particles of the coupler compound contained in the dispersion thus obtained had a median diameter of 0.55 μm and a maximum particle diameter of 2.0 μm or less. The obtained dispersion was filtered with a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound A >> Organic polyhalogen compound A [tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone] 10 kg, modified polyvinyl alcohol ( 10 kg of a 20% by weight aqueous solution of Kuraray Co., Ltd., Poval MP203), 639 g of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate,
Surfynol 104E (Nissin Chemical Co., Ltd.) 400
g, 640 g of methanol and 16 kg of water were added 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 5 hours, and then water was added to the organic polyhalogen compound. The concentration of A was adjusted to 25% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound A. The organic polyhalogen compound particles contained in the dispersion thus obtained had a median diameter of 0.36 μm.
m, the maximum particle diameter was 2.0 μm or less, and the variation coefficient of the average particle diameter was 18%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound B >> 5 kg of organic polyhalogen compound B [tribromomethylnaphthyl sulfone], 20 parts of modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.)
A 2.5% by mass aqueous solution, 213 g of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate, and 10 kg of water were added 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 benzoisothiazolinone sodium salt was added. 5 g and water were added to adjust the concentration of the organic polyhalogen compound B to 20% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound B. The organic polyhalogen compound particles contained in the dispersion thus obtained had a median diameter of 0.38 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of the average particle diameter of 20%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Compound Z >> A modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.) was added to 3.5 kg of R-054 manufactured by Sanko Co., Ltd. containing 85 mass% of compound Z. ) 1kg and 15kg of water
Was added and mixed well to obtain a slurry. This slurry is fed by a diaphragm pump and has an average diameter of 0.5 mm.
Was dispersed in a horizontal sand mill filled with zirconia beads (UVM-2, manufactured by Imex Co., Ltd.) for 7 hours, and then water was added to adjust the concentration of compound-Z to 10% by mass. Was obtained. The particles of compound-Z contained in the dispersion thus obtained had a median diameter of 0.45 μm, a maximum particle diameter of 4.0 μm or less, and a variation coefficient of the particle diameter of 17%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Dispersion of 6-Isopropylphthalazine Compound >> A modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP) was stirred at room temperature with 87.9 g of water.
203) 2.0 g was added so as not to form a lump, and stirred and mixed for 10 minutes. Thereafter, the mixture was heated to raise the internal temperature to 50 ° C., and then stirred for 1 hour to be uniformly dissolved. 4 internal temperature
The temperature was lowered to 0 ° C. or lower, 3.0 g of a 20% aqueous solution of sodium tripropylnaphthalenesulfonate and 7.14 g of 6-isopropylphthalazine (70% aqueous solution) were added, and the mixture was stirred for 30 minutes to obtain a transparent dispersion. Was. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored as a dispersion of a 6-isopropylphthalazine compound.

<< Preparation of solid fine particle dispersion of ultrahigh contrast agent >>
4 kg of ultra-high contrast agent (compound AA) is added to modified polyvinyl alcohol (Kuraray Co., Ltd., Poval PVA-2)
17) 1 kg and 36 kg of water were added and mixed well to form a slurry. This slurry was fed by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm in a horizontal sand mill (manufactured by Imex Co., Ltd., UVM-
After dispersion for 12 hours in 2), 4 g of benzoisothiazolinone sodium salt and water were added to the mixture to adjust the concentration of the ultra-high contrast agent to 10%.
It was adjusted so as to be mass% to obtain a solid fine particle dispersion of a super-high contrast agent. The particles of the ultrahigh contrast agent contained in the dispersion thus obtained have a median diameter of 0.34 μm and a maximum particle diameter of 3.
It was 0 μm or less, and the coefficient of variation of the particle diameter was 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Image Forming Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of silver behenate dispersion A prepared above.
Water was added to obtain an image forming layer coating solution. After completion, degassing under reduced pressure was performed at -350 mmHg for 60 minutes. Coating solution pH
Was 7.7 and the viscosity at 25 ° C. was 45 mPa · s.

Binder 397 g as solid content (Lackstar 3307B, manufactured by Dainippon Ink and Chemicals, Inc., glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl)- 3,5,5-Trimethylhexane 90 g as solid content Organic polyhalogen compound A 43.5 g as solid content Organic polyhalogen compound B 13.5 g as solid content Sodium ethylthiosulfonate 0.30 g Benzotriazole 1.04 g polyvinyl Alcohol (manufactured by Kuraray Co., Ltd., PVA-235) 10.8 g 6-isopropylphthalazine 12.8 g as solid content Sodium dihydrogen orthophosphate dihydrate 0.37 g Compound Z 9.7 g as solid content Agent (Compound AA) 0.03 mol as solid content Dye (Added as a mixture with low-molecular-weight gelatin having an average molecular weight of 15,000) Coating amount at which optical density at 783 nm becomes 0.3 (0.37 g as a guide) Silver halide emulsion A Ag amount 0.06 mol Compound C 2.0 g Compound A as preservative 40 ppm in coating solution (2.5 mg / m ² as coating amount) Methanol 2% by mass as total solvent amount in coating solution Ethanol 1% by mass as total solvent amount in coating solution ( The glass transition temperature of the film was 17 ° C.)

[0205]

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<< Preparation of Coating Solution for Lower Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid =
58.9 / 8.6 / 25.4 / 5.1 / 2 (% by mass) of a polymer latex solution (copolymer having a glass transition temperature of 4
6 ° C. (calculated value), solid content concentration 21.5%, compound A 1
Water was added to 943 g of a coating solution containing 15 ppm by mass of the compound D as a film-forming aid based on the solid content of the latex, and water was added to 943 g of the coating solution.
g, matting agent (polystyrene particles, average particle diameter 7 μm, variation coefficient of average particle diameter 8%) 1.98 g, and polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 29.4.
g, and water was further added to prepare a coating solution (containing 2% by mass of a methanol solvent). After preparing the coating liquid, deaeration under reduced pressure was performed at -400 mmHg for 60 minutes. The coating solution had a pH of 5.5 and a viscosity of 40 mPa · s at 25 ° C.

<< Preparation of Coating Solution for Upper Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid =
58.9 / 8.6 / 25.4 / 5.1 / 2 (% by mass) of a polymer latex solution (copolymer having a glass transition temperature of 4
6 ° C. (calculated value), solid content concentration 21.5%, compound A 1
Water was added to 649 g containing 00 ppm, compound D as a film-forming aid, 15% by mass based on the solid content of the latex, and the glass transition temperature of the coating solution was 24 ° C.). Carnauba wax (manufactured by Chukyo Yushi Co., Ltd. 524: less than 5 ppm as silicone content) 6.30 g of a 30% by weight solution,
0.23 g of compound C, 7.95 g of compound F, 0.93 g of compound G, 1.8 g of compound H, and a matting agent (polystyrene particles, average particle diameter 7 μm, coefficient of variation of average particle diameter 8)
%) And 12.1 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235), and water was further added to prepare a coating solution (containing 1.5% by mass of a methanol solvent). After coating solution preparation, degas under reduced pressure -400 m
Performed at mHg for 60 minutes. The coating solution had a pH of 2.8 and a viscosity of 30 mPa · s at 25 ° C.

[0208]

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<< Preparation of Polyethylene Terephthalate (PET) Support Having Back / Undercoat Layer >> (1) Preparation of PET Support According to a conventional method using terephthalic acid and ethylene glycol, the intrinsic viscosity is 0.66 (phenol / tetrachloroform). (Measured at 25 ° C. in ethane = 6/4 (weight ratio)). After pelletizing this, 13
After drying at 0 ° C. for 4 hours, the mixture was melted at 300 ° C., extruded from a T-die, rapidly cooled, and heat-fixed to a thickness of 120 μm.
An unstretched film having a thickness such that This was longitudinally stretched 3.3 times at 110 ° C. using rolls having different peripheral speeds, and then horizontally stretched 4.5 times at 130 ° C. using a tenter. Thereafter, after heat-setting at 240 ° C. for 20 seconds, it was relaxed by 4% in the lateral direction at the same temperature. After this, after slitting the chuck part of the tenter, knurling is performed on both ends,
The film was wound at 4.8 kg / cm ² . Thus, a roll-shaped PET support having a width of 2.4 m, a length of 3,500 m, and a thickness of 120 μm was obtained.

(2) Formation of Undercoat Layer and Back Layer (2-1) Undercoat First Layer A coating solution having the following composition was applied onto a support so as to have a concentration of 6.2 ml / m ² , 30 seconds, 30 minutes at 150 ° C
And dried at 185 ° C. for 30 seconds. Latex-A 280 g KOH 0.5 g Polystyrene fine particles (average particle size: 2 μm, coefficient of variation of average particle size 7%) 0.03 g 2,4-dichloro-6-hydroxy-s-triazine 1.8 g Distilled water Total 1, 000g

(2-2) Second layer of undercoat A coating solution having the composition shown below was applied on the first layer of undercoat so as to have a concentration of 5.5 ml / m ^2, and was applied at 125 ° C. for 30 seconds for 150 seconds.
It dried at 30 degreeC for 30 second and 170 degreeC for 30 second. Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) 10 g Acetic acid (20% aqueous solution) 10 g Compound-Bc-A 0.04 g Methylcellulose (2% aqueous solution) 25 g Polyethyleneoxy compound 0.3 g Distilled water Total 1 2,000g

(2-3) Back first layer: 0.375 kV · V on the surface opposite to the surface coated with the undercoat layer.
A · min / m ² of corona discharge treatment is applied, and a coating liquid having the following composition is applied to the surface so as to have a concentration of 13.8 ml / m ^2. Dry at 30 ° C. for 30 seconds. Julimer ET410 (30% aqueous dispersion, manufactured by Nippon Pure Chemical Co., Ltd.) 23 g Alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 4.44 g Deionized gelatin (Ca ²⁺ content: 0.6 ppm) 84g Compound-Bc-A 0.02g Dye-Bc-A (adjusted to an optical density of 1.33 to 1.4 at 783 nm) As a guide 0.88g Polyoxyethylene phenyl ether 1.7g Water soluble melamine compound (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3 (8% aqueous solution)) 15 g Sb-doped SnO ₂ needle dispersion 24 g (Ishihara Sangyo Co., Ltd., FS-10D) Polystyrene fine particles 0 0.03 g (Average particle size: 2 μm, Coefficient of variation of average particle size: 7%) Distilled water Total amount of 1,000 g

(2-4) Back second layer A coating solution having the following composition was applied on the back first layer so as to have a concentration of 5.5 ml / m ^2, and was applied at 125 ° C. for 30 seconds at 150 ° C.
For 30 seconds and 170 ° C. for 30 seconds. Julimer ET410 (30% aqueous dispersion, manufactured by Nippon Pure Chemical Co., Ltd.) 57.5 g Polyoxyethylene phenyl ether 1.7 g Water-soluble melamine compound (manufactured by Sumitomo Chemical Co., Ltd., Sumitex Resin M-3 (8%) Aqueous solution)) 15 g cellosol 524 (30% aqueous solution, manufactured by Chukyo Yushi Co., Ltd.) 6.6 g distilled water A total amount of 1,000 g

(2-5) Back third layer A coating liquid having the same composition as the coating liquid for the first layer of the undercoat was used.
Apply ² ml / m ² on back second layer to 12 ml / m ²
Drying was performed at 5 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 185 ° C. for 30 seconds.

(2-6) Fourth Back Layer A coating solution having the composition shown below was applied on the third back layer so as to have a concentration of 13.8 ml / m ^2.
It dried at 30 degreeC for 30 second and 170 degreeC for 30 second. Latex-B 286 g Compound-Bc-B 2.7 g Compound-Bc-C 0.6 g Compound-Bc-D 0.5 g 2,4 dichloro-6-hydroxy-s-triazine 2.5 g Polymethyl methacrylate (10% water (Dispersion, average particle diameter 5 μm, coefficient of variation of average particle 7%) 7.7 g distilled water A total amount of 1,000 g

[0216]

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Latex-A: Core-shell type latex core having 90% by weight of core and 10% by weight of shell: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93/3
/3/0.9/0.1 (% by mass) Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3/3
(Mass%) weight average molecular weight 38000 latex-B: methyl methacrylate / styrene / 2
-Ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1
(% By mass of copolymer)

(3) Heat treatment for transportation (3-1) Heat treatment The PET support having the back / undercoat layer prepared was
It was placed in a heat treatment zone having a total length of 200 m set at 60 ° C. and transported at a tension of 2 kg / cm ² and a transport speed of 20 m / min. (3-2) Post-heat treatment After the heat treatment, post-heat treatment was performed by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time was 10 kg / cm ² .

<< Preparation of Photothermographic Material >> A slide beat coating method as shown in FIG.
The above-mentioned image forming layer coating solution was applied so that the coated silver amount was 1.5 g / m ² . The lower protective layer coating solution was further coated with a solid content of 1.31 g of the polymer latex.
/ M ² with the coating solution for the image forming layer. Thereafter, the coating liquid for the upper protective layer was coated on the lower protective layer with a solid content of 3.02 g / polymer latex.
m ² to prepare a photothermographic material.
Table 2 summarizes the general formula (1) or (2), the general formula (I), and the type and amount of the coupler added in the same manner as in Example 1. Drying at the time of coating is carried out at a constant bulb process and a deceleration process at a dry bulb temperature of 70 to 75 ° C and a dew point of 8 to 25.
C. and a liquid film surface temperature of 35 to 40.degree. C. in a horizontal drying zone (at an angle of 1.5 to 3 degrees with respect to the horizontal direction of the coating machine). Winding after drying was carried out under the conditions of 25 ± 5 ° C. and 45 ± 10% relative humidity, and the winding shape was adjusted to the subsequent processing form (image forming layer surface side outer winding), with the image forming layer surface side out. The relative humidity of the photothermographic material is 20 to
At 40% (measured at 25 ° C.), the film surface pH on the image forming side of the obtained photothermographic material was 5.0, the Beck smoothness was 850 seconds, and the film surface pH on the opposite side was 5.9. Smoothness is 5
60 seconds.

[0220]

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<< Evaluation of photographic performance >> (Exposure treatment)
C., humidity 20%) and (temperature 30 ° C., humidity 75%) and aged for 15 hours.
FWHM) /2.56 μm, laser output 50 m
W, using a single-channel cylindrical inner surface type laser exposure device equipped with a semiconductor laser with an output wavelength of 783 nm,
The exposure time was adjusted by changing the number of rotations of the mirror, and the exposure amount was adjusted by changing the output value, and exposure was performed at 2 × 10 ⁻⁸ seconds. At this time, the overlap coefficient was set to 0.449.

(Heat Developing Process) The exposed heat developing image recording material was subjected to a heat developing process using the heat developing machine shown in FIG. The roller surface material of the thermal development processing section is made of silicone rubber, and the smooth surface is made of Teflon non-woven fabric.
1.2 mm / sec at 14.4 seconds for the pre-heating unit (the drive systems for the pre-heating unit and the heat development processing unit are independent, and the speed difference with the heat development unit is set to -0.5% to -1% 1. The temperature setting of the metal roller of each preheating section, the time is the first roller temperature 67 ° C.
4 seconds, second roller temperature 82 ° C., 2.4 seconds, third roller temperature 98 ° C., 2.4 seconds, fourth roller temperature 107
° C, 2.4 seconds, fifth roller temperature 115 ° C, 2.4 seconds,
The sixth roller temperature was set to 120 ° C. and 2.4 seconds), and the heat-development processing section was set to 20 ° C. (heat-developable image recording material surface temperature).
3 seconds, slow cooling section 16 seconds (continuous 1 to 120 ° C to 60 ° C)
The cooling rate was lowered over 6 seconds, and the cooling rate was -3.75 ° C /
Sec.). The temperature accuracy in the width direction was ± 0.5 ° C. The temperature of each roller was set to be 5 cm longer on both sides than the width of the heat-developable image recording material (for example, 61 cm in width), and the temperature was applied to that portion so that the temperature accuracy was improved. Since the temperature at both ends of each roller is drastically lowered, the portion 5 cm longer than the width of the heat-developable image recording material is 1 mm longer than the center of the roller.
The temperature was set to be higher by 3 ° C., and attention was paid so that the image density of the heat-developable image recording material (for example, in a width of 61 cm) was uniform.

(Evaluation of Photographic Performance) The obtained images were evaluated using a Macbeth TD904 densitometer (visible density).
The results of the measurement were evaluated based on Dmin (fog), Dmax (maximum density) and sensitivity (relative value of the reciprocal of the ratio of the exposure amount giving a density 1.5 times higher than Dmin). 201 was set to 100). Table 2 shows the results.

[0224]

[Table 2]

From Table 2, it is clear that the heat-developable image-recording material of the present invention exhibits excellent performance as compared with Comparative Examples.
The same excellent results as in Example 1 were obtained with a heat-developable image recording material having a super-high contrast.

[0226]

As described above, according to the present invention, it is possible to provide a heat-developable black / white image recording material having extremely low temperature / humidity dependency before development.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration example of a heat developing machine used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 heat-developed image recording material 11 carry-in roller pair 12 carry-out roller pair 13 roller 14 smooth surface 15 heating heater 16 guide plate A preheating section B heat development processing section C slow cooling section

Claims (6)

[Claims] 1. At least one surface of a support,
(A) a reducible silver salt, (b) a binder, (c) a compound represented by the following general formula (1) or (2), and (d) a development inhibitor represented by the following general formula (I) A heat-developable image recording material comprising a release coupler compound. Embedded image (In the general formula (1), V ^{1 to} V ⁴ each independently represent a hydrogen atom or a substituent, and V ⁵ represents a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group.) (In the general formula (2), Q ¹ is a carbon atom and NHNH-
It represents a 5- to 7-membered unsaturated ring bonded with V ^6, V ⁶ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group. ) (In the general formula (I), A represents a coupler residue that releases (TIME) _n -DI by a coupling reaction with an oxidized form of the compound represented by the general formula (1) or (2), and TIME represents A timing group that cleaves _{n- 1-} DI after leaving from A by a coupling reaction, or after leaving from TIME (TIME)
_n-2 represents a timing group for cleaving -DI, where n is 0 to 3
Represents an integer. When n is 2 or more, a plurality of TIMEs
May be the same or different. DI is A or TI
It represents a group that acts as a development inhibitor after leaving from ME. ) 2. The method according to claim 1, further comprising (e) photosensitive silver halide on the surface having (a), (b), (c) and (d). Heat developed image recording material. 3. The heat according to claim 1, further comprising (f) a reducing agent on the surface having (a), (b), (c) and (d). Developed image recording material. 4. The method according to claim 1, further comprising (g) a super-high contrast agent on the surface having (a), (b), (c) and (d). A heat-developable image recording material as described in Crab. 5. The method according to claim 1, further comprising (h) a polyhalogen compound on the surface having (a), (b), (c) and (d). 2. The heat-developable image recording material according to item 1. 6. The method according to claim 1, further comprising (i) a coupler compound on the surface having (a), (b), (c) and (d). The heat-developable image recording material according to the above.