JP2003207869A - Photothermographic recording material and thermal development method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photothermographic recording material having low fog, good raw stock preservability and high sensitivity, satisfying a high Dmax (maximum density) and a high color tone, having small temperature dependency in development and optimum for an image for a medical diagnosis. <P>SOLUTION: In the photothermographic recording material comprising at least one photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder on a support, the mean silver iodide content of the photosensitive silver halide is 5-100 mol% and at least one of the compounds represented by the formula (X)<SB>k</SB>-(L)<SB>m</SB>-(A-B)<SB>n</SB>is incorporated. In the formula, X is a silver halide attracting group or a light absorbing group having at least one atom selected from N, S, P, Se and Te; L is a (k+n)-valent linking group having at least one atom selected from C, N, S and O; A is an electron donative group: B is a releasable group or H; and A-B is released or deprotonated after oxidation to generate a radical A. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat-developable image recording material and a heat-development method thereof.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand in the medical field to reduce the amount of processing waste liquid from the viewpoint of environmental protection and space saving.
So, laser imagesetter or laser
What is needed is a technique for photosensitive photothermographic materials for medical diagnostics and photographic applications that can be efficiently exposed by an imager to form a clear black image with high resolution and sharpness. ing. With these photosensitive photothermographic materials, it is possible to supply a customer with a heat development processing system which eliminates the use of solution processing chemicals and is simpler and does not damage the environment.

Although there are similar demands in the field of general image forming materials, since medical images are required to be minutely drawn, high image quality excellent in sharpness and graininess is required, and diagnosis is easy. From a viewpoint, there is a feature that a cold black image is preferred. At present, various hard copy systems using pigments and dyes such as inkjet printers and electrophotography are in circulation as general image forming systems, but none are satisfactory as output systems for medical images.

On the other hand, a thermal image forming system using an organic silver salt is known (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1).

In particular, a heat-developable image recording material generally controls a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent, a reducible silver salt (eg, organic silver salt), and if necessary, the color tone of silver. The resulting toning agent has a photosensitive layer in which a binder matrix is dispersed. The heat-developable image recording material is heated to a high temperature (for example, 80 ° C. or higher) after image exposure, and silver halide or a reducible silver salt (functions as an oxidizing agent)
A black-and-white silver image is formed by a redox reaction between the dye and the reducing agent. The redox reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, a black silver image is formed in the exposed area. US Patent 2910377
Fuji Medical Dry Imager FM as a medical image forming system using a heat-developable image recording material, which is disclosed in many documents including Japanese Patent Publication No. 43-4924.
-DPL has been released.

In the production of a thermal image forming system using an organic silver salt, there are a method of producing by a solvent coating and a method of producing by coating and drying a coating solution containing polymer fine particles as a water dispersion as a main binder. . The latter method does not require steps such as solvent recovery, and thus has simple manufacturing equipment and is advantageous for mass production.

An image forming system using such an organic silver salt does not have a fixing step, so that the image storability after development processing,
In particular, deterioration of printout when exposed to light was a big problem. Formed by converting an organic silver salt as a means to improve this printout
A method using AgI is disclosed in Patent Documents (for example, refer to Patent Documents 3 and 4). However, the method of converting an organic silver salt as disclosed herein with iodine cannot obtain sufficient sensitivity, and it is difficult to construct an actual system. Other photosensitive materials using AgI are described in several patent documents and the like (see, for example, Patent Documents 5 to 9), but none of them can achieve sufficient sensitivity and fog level, and laser exposure It was not suitable for practical use as a sensitive material. The development of a method of utilizing such silver halide having a high silver iodide content has been awaited.

[0008]

[Patent Document 1] US Pat. No. 3,152,904

[Patent Document 2] US Pat. No. 3,457,075

[Patent Document 3] U.S. Patent No. 6143488

[Patent Document 4] European Patent EP0922995

[Patent Document 5] WO97-48014

[Patent Document 6] WO97-48015

[Patent Document 7] US Pat. No. 6,165,705

[Patent Document 8] Japanese Patent Laid-Open No. 8-297345

[Patent Document 9] Japanese Patent No. 2785129

[Non-Patent Document 1] B. Shely, "Thermally Processed Silver
Systems) "(Imaging Processes and
Materials (Imaging Processes and Materials) Neble
tte Eighth Edition, Sturge, V. Wallworth
worth), edited by A. Shepp, page 2, 1996
Year)

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a heat-developable image recording material having high sensitivity and high image quality even though it is a high silver iodide silver halide photosensitive material, and a heat development method using the same. is there.

[0010]

The objects of the present invention have been achieved by the following heat-developable image recording material and heat-development method. <1> In a heat-developable image recording material containing at least one layer of a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder on a support, the silver iodide content of the photosensitive silver halide is A heat-developable image recording material comprising 5 to 100 mol% of silver halide and at least one compound represented by the following general formula (I).

[0011]

[Chemical 2]

[In the formula, X represents a silver halide adsorption group or a light absorption group having at least one atom of N, S, P, Se or Te. L represents a (k + n) -valent linking group having at least one atom of C, N, S and O. A represents an electron donating group, B represents a leaving group or a hydrogen atom, and A-
After being oxidized, B is eliminated or deprotonated to generate a radical A. k represents an integer of 0 to 3, m represents 0 or 1, and n represents 1 or 2. However, when k = 0 and n = 1, m = 0. <2> The silver iodide content of the silver halide is 10 to 1
The heat-developable image recording material as described in <1> above, wherein the content is 00 mol%. <3> The silver iodide content of the silver halide is 40 to 1
The heat-developable image recording material as described in <1> above, wherein the content is 00 mol%. <4> The above-mentioned <1>, wherein the silver halide grains have direct transition absorption derived from a high silver iodide crystal structure.
> A heat-developable image recording material according to any one of <3>. <5> A heat developing method, wherein the heat developing image recording material according to any one of the above <1> to <4> has a maximum temperature of 100 to 120 ° C. when heat developing. <6> A heat development method, wherein the heat development image recording material according to any one of the above <1> to <4> has a maximum temperature of 105 to 115 ° C. <7> Heat development is performed by transporting the heat-developable image recording material according to any one of the above <1> to <4> while being brought into contact with the heat-development section including two to six plate-shaped heat development heaters. The heat development method as described in <5> or <6> above. <8> The average grain size of the silver halide is 5 to 7
The heat-developable image recording material described in any one of the above items <1> to <4>, which has a thickness of 0 nm. <9> The average grain size of the silver halide is 5 to 7
The heat-developable image recording material described in any one of the above items <1> to <4>, which has a thickness of 0 nm. <10> A heat development method, wherein the maximum temperature at which the heat development image recording material of <8> or <9> is subjected to heat development is 100 to 120 ° C. <11> A heat development method, wherein the maximum temperature at the time of heat development of the heat development image recording material of <8> or <9> is 105 to 115 ° C. <12> Heat development is carried out by transporting the heat-developable image recording material of <8> or <9> while contacting the heat-development section consisting of two to six plate-shaped heat development heaters. The heat development method according to claim 10 or 11, characterized in that.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
It is important that the photosensitive silver halide used in the present invention is a high silver iodide emulsion containing 5 mol% or more and 100 mol% or less of silver iodide as a halogen composition. Generally, silver halide having a high silver iodide content has low sensitivity and low utility value. Part of the silver halide of the present invention preferably has a phase that absorbs light by direct transition. The exposure wavelength of the present invention is 350 nm to 450 n
It is well known that in m, the direct transition absorption can be realized by having a high silver iodide structure having a hexagonal wurtzite structure or a cubic zinc blend structure. However, silver halide having such an absorption structure is generally low in sensitivity and has low utility value in the photographic industry.

According to the studies of the present inventors, by using the compound of the general formula (I) of the present invention in a heat-developable image recording material having a non-photosensitive organic acid silver salt and a heat developing agent, It was found that high sensitivity and high sharpness can be achieved with various high silver iodide light-sensitive materials. According to the present study, the size of silver halide at this time is preferably 80 nm or less. In the present invention, more preferably, the size of silver halide is 5 nm to 80 nm,
More preferably, it is 5 nm to 70 nm. The effect of the present invention is clearly exhibited particularly in silver halide having such a small grain size.

The contents will be described in detail below. (Compound of Formula (I)) First, the compound represented by Formula (I) used in the heat-developable image recording material of the present invention will be described. In the general formula (I), X represents a silver halide adsorption group or a light absorption group having at least one atom of N, S, P, Se or Te. Preferred X is N, S,
It is a silver halide adsorption group having at least one atom of P, Se or Te and having a silver ion ligand structure. Examples of the silver halide adsorbing group having a silver ion ligand structure include groups represented by the following general formula.

[0016] Formula (X-1) -G in ¹ -Z ¹ -Y ¹ formula, G ¹ represents a divalent linking group, a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, an arylene group, It represents a SO ₂ group or a divalent heterocyclic group.
Z ¹ represents an S, Se or Te atom. Y ¹ represents a hydrogen atom or a counter ion necessary when it becomes a dissociation product of Z ¹ , and represents a sodium ion, a potassium ion, a lithium ion and an ammonium ion.

General formulas (X-2a), (X-2b)

[Chemical 3]

The groups represented by the general formulas (X-2a) and (X-2b) have a 5- to 7-membered hetero ring or unsaturated ring. Za represents an O, N, S, Se or Te atom,
n ¹ represents an integer of 0 to 3. Y ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0019] Formula ^{(X-3) -Y 3 -} (Z 2) n in ² -Y ⁴ formula, Z ² is S, Se or Te atom, n ² is 1
Represents an integer of 3. Y ³ is a divalent linking group and represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group or a divalent heterocyclic group. Y ⁴ represents an alkyl group, an aryl group or a heterocyclic group.

General formula (X-4)

[Chemical 4]

In the formula, Y ⁵ and Y ⁶ each independently represent an alkyl group, an alkenyl group, an arylene group or a heterocyclic group.

General formulas (X-5a), (X-5b)

[Chemical 5]

In the formula, Z ³ represents an S, Se or Te atom, E ¹ represents a hydrogen atom, NH ₂ , NHY ¹⁰ , N
It represents (Y ¹⁰ ) ₂ , NHN (Y ¹⁰ ) ₂ , OY ¹⁰ or SY ¹⁰ . E ² is a divalent linking group, and NH, NY ¹⁰ , NHN
Represents Y ¹⁰ , O or S. Y ⁷ , Y ⁸ and Y ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Y ⁸ and Y ⁹ may be bonded to each other to form a ring. Y ¹⁰ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

General formulas (X-6a), (X-6b)

[Chemical 6]

In the formula, Y ¹¹ is a divalent linking group and represents an alkylene group, an alkenylene group, an alkynylene group, an allylene group or a divalent heterocyclic group. G ² and J are each independently COOY ¹² , SO ₂ Y ¹² , COY ¹² , SOY
Represents ¹² , CN, CHO or NO ₂ . Y ¹² represents an alkyl group, an alkenyl group or an aryl group.

The general formula (X-1) will be described in detail. In the formula, the linking group represented by G ¹ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group). , Hexamethylene group, 3-oxapentylene group, 2-hydroxytrimethylene group), and substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene group, cyclopentylene group, cyclohexylene group). , Carbon number 2 to 2
0-substituted or unsubstituted alkenylene group (for example, ethene group, 2-butenylene group), C2-C10 alkynylene group (for example, ethynylene group), C6-C20 substituted or unsubstituted arylene group (for example, And a substituted p-phenylene group and an unsubstituted 2,5-naphthylene group).

In the formula, the SO ₂ group represented by G ¹ is
In addition to the SO ₂ — group, a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkylene group having 3 to 6 carbon atoms or 2 carbon atoms
And a —SO ₂ — group bonded to the alkenylene group of 10 to 10.

In the formula, the divalent heterocyclic group represented by G ¹ is unsubstituted or substituted with an alkylene group, an alkenylene group, an arylene group, a heterocyclic group, a benzo-fused or naphtho-fused group. (For example, 2,3-
Tetrazolediyl group, 1,3-triazolediyl group, 1,2-imidazoldiyl group, 3,5-oxadiazolediyl group, 2,4-thiazoldiyl group, 1,5
-Benzimidazole diyl group, 2,5-benzothiazolediyl group, 2,5-benzoxazolediyl group,
2,5-pyrimidinediyl group, 3-phenyl-2,5-
Tetrazolediyl group, 2,5-pyridinediyl group,
2,4-furandiyl group, 1,3-piperidinediyl group, 2,4-morpholinediyl group).

In the above formula, an alkylene group represented by G ¹ ,
Alkenylene group, alkynylene group, arylene group, SO
_The divalent or divalent heterocyclic group may have a substituent. The substituents that can be used are described below, but in the present specification, the substituents described below are referred to as “substituent Y”.
Examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, isopropyl group, n-propyl group, t
ert-butyl group), alkenyl group (eg allyl group,
2-butenyl group), alkynyl group (eg propargyl group), aralkyl group (eg benzyl group), aryl group (eg phenyl group, naphthyl group, 4-methylphenyl group), heterocyclic group (eg pyridyl group, furyl group, Imidazolyl group, piperidinyl group, morpholyl group), alkoxy group (eg methoxy group, ethoxy group, butoxy group,
2-ethylhexyloxy group, ethoxyethoxy group, methoxyethoxy group), aryloxy group (for example, phenoxy group, 2-naphthyloxy group), amino group (for example, unsubstituted amino group, dimethylamino group, diethylamino group,
Dipropylamino group, dibutylamino group, ethylamino group, anilino group), acylamino group (eg acetylamino group, benzoylamino group), ureido group (eg unsubstituted ureido group, N-methylureido group), urethane group (eg Methoxycarbonylamino group, phenoxycarbonylamino group), sulfonylamino group (for example, methylsulfonylamino group, phenylsulfonylamino group),
A sulfamoyl group (for example, an unsubstituted sulfamoyl group,
N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group), carbamoyl group (eg unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group), sulfonyl group (eg mesyl group, Tosyl group), sulfinyl group (eg methylsulfinyl group, phenylsulfinyl group), alkyloxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), acyl group (eg acetyl group, Benzoyl group, formyl group, pivaloyl group), acyloxy group (eg acetoxy group, benzoyloxy group), phosphoric acid amide group (eg N, N-diethylphosphoric acid amide group), cyano group, sulfo group, thiosulfonic acid group,
Examples thereof include sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonio group, phosphonio group, hydrazino group and thiazolino group. In addition, the substituent is 2
When there are two or more, they may be the same or different,
The substituent may further have a substituent.

Preferred examples of the general formula (X-1) are shown below. In the preferable general formula (X-1), G ¹ has 6 to ¹ carbon atoms.
5 to 7-membered heterocyclic groups bonded to 0 or a substituted or unsubstituted arylene group, an unsubstituted or alkylene group or an arylene group, or benzo-fused or naphtho-fused. Examples of Z ¹ include S and Se, and examples of Y ¹ include a hydrogen atom, sodium ion, and potassium ion. More preferably, G ¹ is
A substituted or unsubstituted arylene group having 6 to 8 carbon atoms, 5 bonded to an arylene group, or benzo-fused
It is a 6-membered heterocyclic group, most preferably a 5- or 6-membered heterocyclic group bonded to an arylene group or benzo-fused. More desirable Z ¹ is S, and Y ¹
Are hydrogen atoms and sodium ions.

The general formulas (X-2a) and (X-2b) will be described in detail. In the formula, the alkyl group, alkenyl group, and alkynyl group represented by Y ^{2 have} 1 to 1 carbon atoms.
10 substituted or unsubstituted linear or branched alkyl groups (eg, methyl group, ethyl group, isopropyl group, n-
Propyl group, n-butyl group, tert-butyl group, 2-
Pentyl group, n-hexyl group, n-octyl group, ter
t-octyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, diethylaminoethyl group, n-butoxypropyl group, methoxymethyl group), substituted or unsubstituted cyclic alkyl having 3 to 6 carbon atoms Group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group), alkenyl group having 2 to 10 carbon atoms (for example, allyl group, 2-butenyl group, 3-pentenyl group),
Examples thereof include an alkynyl group having 2 to 10 carbon atoms (eg, propargyl group, 3-pentynyl group), an aralkyl group having 6 to 12 carbon atoms (eg, benzyl group) and the like. Examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, a hydroxyphenyl group, a 4-methylhydroxyphenyl group) and the like. The above Y ² may further have a substituent Y or the like.

Preferred examples of the general formulas (X-2a) and (X-2b) are shown below. In the formula, preferably Y ² is a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms,
Za is O, N or S, and n ¹ is ¹ to 3. More preferably, Y ² is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Za is N or S, and n ¹ is 2
Or it is 3.

Next, the general formula (X-3) will be described in detail. In the formula, the linking group represented by Y ³ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene group, ethylene group, trimethylene group, isopropylene group, tetramethylene group). Group, hexamethylene group, 3-oxapentylene group, 2-hydroxytrimethylene group), substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene group, cyclopentynylene group, cyclohexylene group) ), A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (e.g., ethene group, 2-butenylene group), and 2 to 1 carbon atoms.
0 alkynylene group (eg ethynylene group), 6 carbon atoms
To 20 substituted or unsubstituted arylene groups (eg, unsubstituted p-phenylene group, unsubstituted 2,5-naphthylene group)
As the heterocyclic group, an unsubstituted or alkylene group, an alkenylene group, an arylene group, and a heterocyclic group further substituted (for example, 2,5-pyridinediyl group, 3-phenyl-2,5- Pyridinediyl group, 1,3-piperidinediyl group, 2,4-morpholinediyl group).

In the formula, the alkyl group represented by Y ⁴ is a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, n-propyl group). Group, n-butyl group, tert
-Butyl group, 2-pentyl group, n-hexyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, diethylaminoethyl group, dibutylaminoethyl group, n-butoxymethyl group, methoxymethyl group), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group), and the aryl group has 6 to 6 carbon atoms. 1
And a substituted or unsubstituted aryl group of 2 (for example, an unsubstituted phenyl group and a 2-methylphenyl group). Examples of the heterocyclic group include an unsubstituted or alkyl group, an alkenyl group, an aryl group, and a group in which a heterocyclic group is further substituted (for example, a pyridyl group, a 3-phenylpyridyl group, a piperidyl group, a morpholyl group). The Y ⁴ may further have a substituent Y or the like.

Preferred examples of the general formula (X-3) are shown below. In the formula, preferably Y ³ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and Y ⁴ is a substituted or unsubstituted C 1 to 6 or Unsubstituted alkyl group or C6 to C1
0 is a substituted or unsubstituted aryl group, and Z ² is S
Alternatively, it is Se and n ² is 1-2. More preferably, Y ³ is an alkylene group having 1 to ⁴ carbon atoms, Y ⁴ is an alkyl group having 1 to ⁴ carbon atoms, Z ² is S, and n ²
Is 1.

Next, the general formula (X-4) will be described in detail. In the formula, the alkyl group and the alkenyl group represented by Y ⁵ and Y ⁶ are a substituted or unsubstituted straight chain or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group,
Ethyl group, isopropyl group, n-propyl group, n-butyl group, tert-butyl group, 2-pentyl group, n-hexyl group, n-octyl group, tert-octyl group, 2-
Ethylhexyl group, hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, diethylaminoethyl group, dibutylaminoethyl group, n-butoxymethyl group, n-butoxypropyl group, methoxymethyl group),
Substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg cyclopropyl group, cyclopentyl group, cyclohexyl group), alkenyl group having 2 to 10 carbon atoms (eg allyl group, 2-butenyl group, 3-pentenyl group) Is mentioned. As the aryl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, an unsubstituted phenyl group,
4-methylphenyl group), as the heterocyclic group, unsubstituted or alkylene group, alkenylene group, arylene group, and further substituted heterocyclic group (for example, pyridyl group, 3-phenylpyridyl group, furyl group) ,
And piperidyl group and morpholyl group). In the above formula, Y ⁵ and Y ⁶ may further have a substituent Y or the like.

Preferred examples of the general formula (X-4) are shown below. In the formula, preferably Y ⁵ and Y ⁶ are a substituted or unsubstituted alkyl group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. More preferably, Y ⁵ and Y ⁶ are aryl groups having 6 to 8 carbon atoms.

Next, general formulas (X-5a) and (X-5)
The b) will be described in detail. In the formula, E¹Group represented by
As NH₂, NHCH₃, NHC₂H_Five, NHPh, N
(CH₃)₂, N (Ph)₂, NHNHC₃H₇, NHNH
Ph, OC_FourH₉, OPh, SCH ₃Etc., E²When
Then NH, NCH₃, NC₂H_Five, NPh, NHNC₃
H ₇, NHNPh and the like. In addition, in this specification
And "Ph" represents a phenyl group. General formula (X-5a)
And (X-5b), Y⁷, Y⁸And Y⁹Represented by
The alkyl group and the alkenyl group have 1 to 10 carbon atoms.
Substituted or unsubstituted linear or branched alkyl group
(For example, methyl group, ethyl group, isopropyl group, n-
Propyl group, n-butyl group, tert-butyl group, 2-
Pentyl group, n-hexyl group, n-octyl group, ter
t-octyl group, 2-ethylhexyl group, hydroxy
Cyl group, 2-hydroxyethyl group, 1-hydroxyethyl group
Group, diethylaminoethyl group, dibutylaminoethyl group
Group, n-butoxymethyl group, n-butoxypropyl group,
Methoxymethyl group), substituted or non-substituted with 3 to 6 carbon atoms
A substituted cyclic alkyl group (eg, cyclopropyl group, cyclo
Ropentyl group, cyclohexyl group), having 2 to 10 carbon atoms
Alkenyl group (eg, allyl group, 2-butenyl group, 3
-Pentenyl group). As an aryl group,
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg,
Examples include unsubstituted phenyl group and 4-methylphenyl group).
Gera, the heterocyclic group is unsubstituted or alkylene
Groups, alkenylene groups, arylene groups, and further
Those substituted with a ring group (for example, pyridyl group, 3-
Phenylpyridyl group, furyl group, piperidyl group, morpho
Ryl group). Y⁷, Y⁸And Y⁹Is further
It may have a substituent Y or the like.

Preferred examples of formulas (X-5a) and (X-5b) are shown below. In the formula, preferably E ¹ is an alkyl-substituted or unsubstituted amino group or an alkoxy group, E ² is an alkyl-substituted or unsubstituted amino linking group, and Y ⁷ , Y ⁸ and Y ⁹ are each a carbon number of 1 to 1. A substituted or unsubstituted alkyl group having 6 or 6 or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and Z ³ is S or Se. More preferably, E ¹ is an alkyl-substituted or unsubstituted amino group, E ² is an alkyl-substituted or unsubstituted amino linking group, and Y ⁷ , Y ⁸ and Y
⁹ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Z ³ is S.

Next, general formulas (X-6a) and (X-6
The b) will be described in detail. In the formula, the groups represented by G ² and J include COOCH ₃ , COOC ₃ H ₇ , and COO.
_{C 6 H 13, COOPh, SO} 2 CH 3, SO 2 C 4 H 9, CO
C ₂ H ₅ , COPh, SOCH ₃ , SOPh, CN, CH
O, NO _2, etc. may be mentioned. In the formula, the linking group represented by Y ¹¹ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group). , Hexamethylene group, 3-oxapentylene group, 2-hydroxytrimethylene group), carbon number 3 to 1
8 substituted or unsubstituted cyclic alkylene group (eg, cyclopropylene group, cyclopentylene group, cyclohexylene group), substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, ethene group, 2-butenylene group) , An alkynylene group having 2 to 10 carbon atoms (eg, ethynylene group), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg, unsubstituted p-phenylene group, unsubstituted 2,5-
Naphthylene group). In the formula, 2 represented by Y ¹¹
The valent heterocyclic group is unsubstituted or substituted with an alkylene group, an alkenylene group, an arylene group, or a heterocyclic group (for example, 2,5-pyridinediyl group, 3-phenyl-2,5-pyridine). Diyl group,
2,4-furandiyl group, 1,3-piperidinediyl group, 2,4-morpholinediyl group). In the formula, Y ¹¹ may further have a substituent Y or the like.

Preferred examples of the general formulas (X-6a) and (X-6b) are shown below. In the formula, preferably G ² and J are carboxylic acid esters having 2 to 6 carbon atoms and carbonyls, and Y ¹¹ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substituted carbon atom having 6 to 10 carbon atoms. Alternatively, it is an unsubstituted arylene group. More preferably, G ² and J are carboxylic acid esters having 2 to 4 carbon atoms, and Y ¹¹
Is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms or a substituted or unsubstituted arylene group having 6 to 8 carbon atoms.

The general formula of the silver halide adsorbing group represented by X is (X-1), (X-2a) and (X-2) in the order of preference.
b), (X-3), (X-5a), (X-5b), (X
-4), (X-6a), and (X-6b).

Next, the light absorbing group represented by X in the general formula (I) will be described in detail. In the general formula (I), examples of the light absorbing group represented by X include groups represented by the following general formula.

General formula (X-7)

[Chemical 7]

In the formula, Z ⁴ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and L ² , L ³ , L
⁴ and L ⁵ represent a methine group. p ¹ represents O or 1 and n ³ represents 0 to 3. M ¹ represents a charge-balancing counterion, m ² represents 0 to 10 necessary for neutralizing the charge of the molecule.
Represents the number of.

In the formula, the 5- or 6-membered nitrogen-containing heterocycle represented by Z ⁴ includes a thiazolidine nucleus, a thiazole nucleus,
Benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine nucleus), imidazoline nucleus, imidazole nucleus Nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole Examples thereof include a nucleus, a thiadiazole nucleus, a tetrazole nucleus and a pyrimidine nucleus. The 5- or 6-membered nitrogen-containing heterocycle represented by Z ⁴ may have the aforementioned substituent Y.

Where L², L³, L^FourAnd L^FiveEach is independent
Represents a methine group. L², L³, L ^FourAnd L^FiveRepresented by
The methine group may have a substituent,
Is, for example, a substituted or unsubstituted C1-C15 al
Kill group (eg, methyl group, ethyl group, 2-carboxy group
Chill group), a substituted or unsubstituted ant having 6 to 20 carbon atoms
Group (eg phenyl group, o-carboxyphenyl
Group), a substituted or unsubstituted heterocyclic ring having 3 to 20 carbon atoms
Group (for example, N, N-diethylbarbituric acid group), halo
Gen atom (eg chlorine atom, bromine atom, fluorine atom, iodine
Elementary atom), an alkoxy group having 1 to 15 carbon atoms (for example, meth
Xy group, ethoxy group), alkylthio having 1 to 15 carbon atoms
Group (for example, methylthio group, ethylthio group), carbon number 6 to
20 arylthio groups (eg phenylthio groups), carbon
An amino group of the number 0 to 15 (for example, N, N-diphenylamido)
Group, N-methyl-N-phenylamino group, N-methyl
Piperazine group) and the like. Also, with other methine groups
You may form a ring. Or form a ring with other parts
It can also be done.

In the formula, M ¹ is included in the formula to indicate the presence of a cation or an anion as necessary to neutralize the ionic charge of the light absorbing group. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ) and alkali metal ions (eg, sodium ion, potassium ion, lithium ion), ammonium ion (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion). , Ethylpyridinium ion) and the like. The anion may be either an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p -Chlorobenzene sulfonate ion), an aryl disulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picric acid Ions, acetate ions, and trifluoromethanesulfonate ions. Further, an ionic polymer or a light absorbing group having an opposite charge may be used.
In the present specification, for example, a sulfo group is represented by SO ₃ ⁻ and a carboxy group is represented by CO ₂ ⁻ , but when the counter ion is a hydrogen ion, they can be represented by SO ₃ H and CO ₂ H, respectively.
Where m ² represents the number required to balance the charge,
It is 0 when a salt is formed in the molecule.

Preferred examples of the general formula (X-7) are shown below. As preferable general formula (X-7), Z ⁴ is a benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus or quinoline nucleus, and L ² , L ³ , L ⁴ and L ⁵ are unsubstituted methine groups. , P ¹ is O and n ³ is 1 or 2. More preferably, Z ⁴ is a benzoxazole nucleus or a benzothiazole nucleus, and n ³ is 1.
A particularly preferred Z ⁴ is a benzothiazole nucleus.

In the general formula (I), k is preferably 0 or 1, and more preferably 1. Specific examples of X in the general formula (I) are shown below, but X that can be employed in the present invention is not limited to these.

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical 12]

[0056]

[Chemical 13]

Next, the linking group represented by L in formula (I) will be described in detail. In the general formula (I), the linking group represented by L is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example,
Methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, 3-oxapentylene group, 2-hydroxytrimethylene group), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms ( For example, a cyclopropylene group, a cyclopentylene group,
A cyclohexylene group), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (e.g., ethene group, 2-butenylene group), an alkynylene group having 2 to 10 carbon atoms (e.g., ethynylene group), 6 to carbon atoms. 20 substituted or unsubstituted arylene group (eg, unsubstituted p-phenylene group, unsubstituted 2,5-naphthylene group), heterocyclic linking group (eg, 2,6-pyridinediyl group), carbonyl group, thiocarbonyl Examples thereof include groups, imide groups, sulfonyl groups, sulfonyloxy groups, ester groups, thioester groups, amide groups, ether groups, thioether groups, amino groups, ureido groups, thioureido groups and thiosulfonyl groups. Further, these linking groups may be linked to each other to form a new linking group. L may further have the above-mentioned substituent Y and the like.

The preferred linking group L has 1 to 1 carbon atoms.
Examples thereof include an unsubstituted alkylene group having 0 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms and an amino group, an amide group, a thioether group, a ureido group or a sulfonyl group. 1 carbon atoms linked to amino group, amino group, amide group or thioether group
~ 6 alkylene groups. In the general formula (I), m is preferably 0 or 1, and more preferably 1.

Next, the electron donating group A will be described in detail. The reaction process in which the AB portion is oxidized and fragmented to generate an electron to generate a radical A., and the radical A. is oxidized to generate an electron to increase the sensitivity is shown below.

[0060]

[Chemical 14]

Since A is an electron-donating group, it is preferable that the substituents on the aromatic group in any structure be selected so that A is in the state of having an excess of electrons. For example, when the aromatic ring is not electron-rich, an electron-donating group is introduced. Conversely, when the aromatic ring is extremely electron-rich, an electron-withdrawing group is introduced to adjust the oxidation potential of each. It is preferably adjusted. Preferred A groups are those having the general formula: General formula (A-1), (A-2), (A-3)

[0062]

[Chemical 15]

In the general formulas (A-1) and (A-2), Y
¹², Y¹²’, Y¹³And Y¹³′ Are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group, aryl group, alkyl group
Represents a len group and an arylene group, Y¹⁴And Y¹⁴’Is
Each independently an alkyl group, COOH, halogen atom, N
(Y¹⁵)₂, OY¹⁵, SY¹⁵, CHO, COY¹⁵, CO
OY¹⁵, CONHY¹⁵, CON (Y¹⁵)₂, SO₃Y¹⁵,
SO₂NHY¹⁵, SO₂NY¹⁵, SO₂Y¹⁵, SOY¹⁵,
CSY¹⁵Represents Ar¹And Ar¹’Are ants independently
And a heterocyclic group. Y¹²And Y¹³, Y¹²And A
r¹, Y¹²’And Y¹³’And Y¹²’And Ar¹'Is that
They may combine with each other to form a ring. Q²And Q²’Is
Each independently represents O, S, Se, Te, m³And m^FourIs
N independently represents 0 or 1,^FourRepresents 1 to 3.
L²Represents NR, N-Ar, O, S, Se, and 5 to 7
Even if it has a heterocyclic ring or an unsaturated ring
Good. Y ¹⁵Is a hydrogen atom, an alkyl group or an aryl group
Represent The cyclic structure of the general formula (A-3) has no substitution or substitution.
It represents a substituted 5- to 7-membered unsaturated ring or heterocyclic group.

General formulas (A-1), (A-2) and (A
-3) will be described in detail. In the formula, Y ¹² , Y ¹² ',
Examples of the alkyl group represented by Y ¹³ and Y ¹³ 'include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, tert-butyl group, 2-pentyl group, n-hexyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, 2
-Hydroxyethyl group, 1-hydroxyethyl group, diethylaminoethyl group, dibutylaminoethyl group, n-butoxymethyl group, methoxymethyl group), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl group) , A cyclopentyl group, a cyclohexyl group), and examples of the aryl group include a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, an unsubstituted phenyl group,
2-methylphenyl group). As the alkylene group, a substituted or unsubstituted straight chain having 1 to 10 carbon atoms,
Alternatively, a branched alkylene group (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a methoxyethylene group) can be mentioned, and an arylene group has 6 carbon atoms.
To 12 substituted or unsubstituted arylene groups (eg, unsubstituted phenylene group, 2-methylphenylene group, naphthylene group).

In the general formulas (A-1) and (A-2), Y
Examples of the group represented by ¹⁴ and Y ¹⁴ 'include an alkyl group (eg, methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, 2-pentyl group, n-hexyl group, n-octyl group). , 2-ethylhexyl group, 2-hydroxyethyl group, n-butoxymethyl group), COOH
Group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), OH, N (CH ₃ ) ₂ , NPh ₂ , OCH ₃ , OP
h, SCH ₃ , SPh, CHO, COCH ₃ , COPh,
COOC ₄ H ₉ , COOCH ₃ , CONHC ₂ H ₅ , CON
(CH ₃ ) ₂ , SO ₃ CH ₃ , SO ₃ C ₃ H ₇ , SO ₂ NHCH
₃ , SO ₂ N (CH ₃ ) ₂ , SO ₂ C ₂ H ₅ , SOCH ₃ , CS
Ph and CSCH ₃ can be mentioned. As Ar ¹ and Ar ¹ ′ represented by the general formulas (A-1) and (A-2),
Substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, 2-methylphenyl group, naphthyl group), substituted or unsubstituted heterocyclic group (eg, pyridyl group, 3-phenylpyridyl group, piperidyl) Group, morpholyl group).

L ² represented by the general formulas (A-1) and (A-2) includes NH, NCH ₃ , NC ₄ H ₉ and NC ₃ H _7.
(I), NPh, NPh- CH 3, O, S, Se, Te
Is mentioned. As the cyclic structure of the general formula (A-3),
An unsaturated 5- to 7-membered ring and a hetero ring (for example, a furyl group, a piperidyl group, a morpholyl group) can be mentioned. General formula (A
-1) and (Y ¹² of A-2) in, Y ^13, Y ^14, A
r ¹ , L ² , Y ¹² ′, Y ¹³ ′, Y ¹⁴ ′, Ar ¹ ′ and the cyclic structure in the general formula (A-3) may further have the above-mentioned substituent Y and the like.

General formulas (A-1), (A-2) and (A
-3) A preferable example is shown. In formulas (A-1) and (A-2), Y ¹² , Y ¹² ′, Y ¹³ and Y are preferable.
¹³ ′ each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkylene group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Y ¹⁴ and Y ¹⁴ ′ have 1 carbon atoms. To 6 substituted or unsubstituted alkyl groups, amino groups mono- or di-substituted with alkyl groups having 1 to 4 carbon atoms, carboxylic acids, halogens or 1 carbon atoms
~ 4 carboxylic acid esters, Ar ¹ and Ar ¹ '
Is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Q ² and Q ² ′ are O, S or Se, and m ³
And m ⁴ is 0 or 1, n ⁴ is 1 to 3,
L ² is an alkyl-substituted amino group having 0 to 3 carbon atoms. The cyclic structure represented by the general formula (A-3) has 5 to 7
It is preferably a membered heterocycle.

In the general formulas (A-1) and (A-2),
And preferably Y¹², Y¹²’, Y ¹³And Y¹³'Is each
Independently substituted or unsubstituted alkyl having 1 to 4 carbon atoms
A group or an alkylene group, and Y¹⁴And Y¹⁴'Is carbon
An unsubstituted alkyl group having 1 to 4 carbon atoms, a monoalkyl having 1 to 4 carbon atoms
A mino- or diamino-substituted alkyl group
R, Ar¹And Ar¹'Is a C6-10 substitution
Is an unsubstituted aryl group, Q²And Q²'Is O again
Is S and m³And m^FourIs 0 and n^FourIs 1
L²Is an alkyl-substituted amino group having 0 to 3 carbon atoms
Is. The cyclic structure represented by the general formula (A-3) has 5 to
A 6-membered heterocycle is more preferred. General formula
In the moiety of (I) where A is bonded to X or L, X is a general formula
Y when represented by (A-1) and (A-2)¹², Y
¹³, Ar¹, Y¹²’, Y¹³’Or Ar¹Select from '
To be done. Specific examples of A in the general formula (I) will be given below.
A that can be adopted in the present invention is limited to these specific examples.
It is not fixed.

[0069]

[Chemical 16]

[0070]

[Chemical 17]

[0071]

[Chemical 18]

[0072]

[Chemical 19]

[0073]

[Chemical 20]

[0074]

[Chemical 21]

Next, B of the general formula (I) will be described in detail. When B is a hydrogen atom, it is oxidized and then deprotonated by an intramolecular base to generate a radical A. Preferred B is one having a hydrogen atom and the following general formula. General formula (B-1), (B-2), (B-3)

[0076]

[Chemical formula 22]

General formulas (B-1), (B-2) and (B
-3), W represents Si, Sn or Ge, Y ¹⁶ independently represents an alkyl group, and Ar ² independently represents an aryl group. The general formulas (B-2) and (B-3) can be bonded to the adsorption group X. General formula (B-
1), (B-2) and (B-3) will be described in detail. In the formula, the alkyl group represented by Y ¹⁶ is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, tert-butyl group, 2-pentyl group, n-hexyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, 2
-Hydroxyethyl group, 1-hydroxyethyl group, n-
Butoxyethyl group, methoxymethyl group), carbon number 6 to 1
And a substituted or unsubstituted aryl group of 2 (for example, a phenyl group, a 2-methylphenyl group). Y ¹⁶ and Ar ² in the general formulas (B-1), (B-2) and (B-3) may further have the above-mentioned substituent Y and the like.

General formulas (B-1), (B-2) and (B
The preferable example of -3) is shown below. In general formulas (B-2) and (B-3), Y ¹⁶ is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Ar ² is a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. Is an aryl group of
W is Si or Sn. In the general formulas (B-2) and (B-3), more preferably Y ¹⁶ has 1 to 3 carbon atoms.
Is a substituted or unsubstituted alkyl group, and Ar ² is a substituted or unsubstituted aryl group having 6 to 8 carbon atoms,
W is Si. Among the general formulas (B-1), (B-2) and (B-3), the most preferable is COO of (B-1).
^- and a Si- (Y ¹⁶⁾ ₃ in (B-2). In general formula (I), preferable n is 1. Specific examples of AB in the general formula (I) are shown below, but the AB that can be employed in the present invention is not limited to these.

[0079]

[Chemical formula 23]

[0080]

[Chemical formula 24]

[0081]

[Chemical 25]

[0082]

[Chemical formula 26]

[0083]

[Chemical 27]

[0084]

[Chemical 28]

Examples of the counter ion necessary for the charge balance of AB are sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion, and tetramethylguanidinium ion.

The preferable oxidation potential of AB is 0 to 1.5 V.
And more preferably 0 to 1.0 V, and further preferably 0.3 to 1.0 V. The preferable oxidation potential of the radical A · (E ₂ ) generated from the bond cleavage reaction is −
0.6 to -2.5 V, more preferably -0.9 to
-2V, more preferably -0.9 to -1.6V
Is the range.

The method for measuring the oxidation potential is as follows. E
¹ can be performed by the cyclic voltammetry method. The electron donor A is dissolved in a solution of acetonitrile / water containing 80% / 20% (volume%) containing 0.1 M lithium perchlorate. A glassy carbon disk is used as the working electrode, a platinum wire is used as the counter electrode and a saturated calomel electrode (SCE) is used as the reference electrode. 0.1V / at 25 ° C
It is measured at a potential scanning speed of 2 seconds. The oxidation potential vs. SCE is taken at the peak potential of the cyclic voltammetry wave.
The E ¹ values of these AB compounds are European Patent No. 93,731.
It is described in A1 publication. Radical oxidation potential measurements are made by transient electrochemistry and pulse radiolysis. These are described in J. Am. Chem. Soc. 19
88, 110, 132, 1974, 96, 1287,
1974, 96, 1295. Specific examples of the compound represented by formula (I) are shown below, but the compound used in the present invention is not limited thereto.

[0088]

[Chemical 29]

[0089]

[Chemical 30]

[0090]

[Chemical 31]

[0091]

[Chemical 32]

[0092]

[Chemical 33]

[0093]

[Chemical 34]

[0094]

[Chemical 35]

[0095]

[Chemical 36]

[0096]

[Chemical 37]

[0097]

[Chemical 38]

[0098]

[Chemical Formula 39]

[0099]

[Chemical 40]

The synthetic method of the compound represented by the general formula (I) is described in US Pat. No. 5,747,235 and US Pat.
747,235, European Patent Publication 786,692.
A1 publication, 893,731 A1 publication, 893
It can be easily synthesized by a method described in 732A1 publication, WO99 / 05570 publication, or the like, or a method similar thereto.

In the production of the heat-developable image recording material of the present invention, the compound represented by the general formula (I) is used at any stage during the emulsion preparation step for coating and the production step of the heat-developable image recording material. You may. For example, during particle formation, desalting step,
It can be used during chemical sensitization or before coating. In addition, during these steps, it may be added in plural times. The compound represented by the general formula (I) is preferably added by dissolving it in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound whose solubility increases with increasing pH may be dissolved with increasing pH. On the other hand, when the compound is dissolved in water, the compound whose solubility is improved by lowering the pH may be dissolved by lowering the pH.

The compound represented by the general formula (I) is preferably used in the image forming layer (emulsion layer), but it is added to the protective layer or the intermediate layer together with the image forming layer and diffused at the time of coating. May be. The compound represented by the general formula (I) may be added before or after the addition of the sensitizing dye, preferably 1 × 10 ^{−9 to} 5 × 10 ⁻¹ mo per mol of silver halide.
1, more preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻¹ mol in the image forming layer containing silver halide.

(Photosensitive Silver Halide) The photosensitive silver halide used in the present invention will be described in detail below.
The photosensitive silver halide of the present invention has an average silver iodide content of 5
It is preferably ˜100 mol%. The average silver iodide content is more preferably 10 to 100 mol%, and 40 to 1
00 mol% is more preferable, 70-100 mol% is especially preferable, and 90-100 mol% is the most preferable.

The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or the halogen composition may be continuously changed.
Further, silver halide grains having a core / shell structure can be preferably used. 2 is preferable as a structure
It is possible to use core / shell structured particles having a quintuple-fold structure, and more preferably a quadruple-fold structure. Although there is a limit to the solid solution of iodine with other halogen compositions, the iodine content can be arbitrarily set by adopting the core / shell structure or the junction structure as described above.

The photosensitive silver halide of the present invention is 350 n
It is preferable to exhibit direct transition absorption derived from the silver iodide crystal structure at a wavelength between m and 450 nm. Whether these silver halides have direct transition light absorption is 40
It can be easily distinguished by the fact that exciton absorption due to direct transition is observed in the vicinity of 0 nm to 430 nm.

Such a direct transition light absorption type high silver iodide phase may exist alone, but it may be a silver bromide emulsion, a silver chloride emulsion, or a silver iodobromide emulsion, silver iodochloride, or a silver halide emulsion. A compound such as a mixed crystal which is present by being bonded to silver halide exhibiting indirect transition absorption in the wavelength range of 350 mm to 450 nm is also preferably used.

It is also preferable that the core / shell structure is taken as described above, or that the core / shell structure is present as an indefinite structure due to iodide conversion. Also in these cases, the total silver iodide content is preferably 5 to 100 mol% as the halogen composition of the silver halide grains. The silver iodide content is more preferably 10 to 100 mol%, further preferably 40 to 100 mol%, and 70 to 1
00 mol% is particularly preferable, and 90 to 100 mol% is the most preferable.

A silver halide phase which absorbs light by such a direct transition generally exhibits strong light absorption, but has a lower sensitivity than an indirect transition silver halide phase which exhibits only weak absorption, and is conventionally industrially less It wasn't used much. The present invention has found that preferable high sensitivity can be obtained by using such a silver halide light-sensitive material with at least one compound represented by the general formula (I) of the present invention.

The photosensitive silver halide of the present invention exhibits more preferable characteristics when its average grain size is 5 nm to 80 nm. In particular, in a silver halide grain having a phase having direct transition absorption, the grain size is 80 nm.
It has been found that a preferable high sensitivity can be obtained by making it small as follows.

The average grain size of the photosensitive silver halide is more preferably 5 nm to 70 nm, further preferably 10 nm to 50 nm. The average grain size as used herein means a diameter when converted into a circular image having the same area as the projected area of silver halide grains (projected area of the main plane in the case of tabular grains). Hereinafter, this average particle size may be simply referred to as a particle size.

The method of forming the photosensitive silver halide is well known in the art, and for example, the method described in Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458 is used. Specifically, a method is used in which a photosensitive silver halide is prepared by adding a silver-providing compound and a halogen-providing compound into gelatin or another polymer solution, and thereafter, a method of mixing with a silver salt is used. In addition, JP-A-11
The methods described in paragraph Nos. 0217 to 0224 of JP-A-119374, and the methods described in JP-A Nos. 11-352627 and 2000-347335 are also preferable.

The shape of the silver halide grains is cubic,
Examples thereof include octahedral particles, tabular particles, spherical particles, rod-shaped particles, and potato-shaped particles. In the present invention, cubic particles are particularly preferable. Grains with rounded corners of silver halide grains can also be preferably used. The surface index (Miller index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the {100} plane, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, may be high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, particularly preferably 80% or more. The ratio of the Miller index {100} plane is measured by T.M., which utilizes the adsorption dependence of the {111} plane and the {100} plane in the adsorption of the sensitizing dye. Tani; J. Imaging
Sci. , <29>, 165 (1985).

In the present invention, the hexacyano metal complex is granulated.
A silver halide grain present on the outermost surface of the child is preferable. Six
Examples of cyano metal complexes include [Fe (CN)₆]^Four-, [F
e (CN)₆]^3-, [Ru (CN)₆]^Four-, [Os (C
N)₆]^Four-, [Co (CN)₆] ^3-, [Rh (CN)₆]
^3-, [Ir (CN)₆]^3-, [Cr (CN)₆]^3-,
[Re (CN)₆]^3-Etc. In the present invention
Is preferably a hexacyano Fe complex.

Since the hexacyano metal complex exists in the form of an ion in an aqueous solution, the counter cation is not important, but it is easily miscible with water and is suitable for the precipitation operation of a silver halide emulsion. Use of alkali metal ions such as ions, rubidium ions, cesium ions and lithium ions, ammonium ions, alkylammonium ions (for example, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetra (n-butyl) ammonium ion) Is preferred.

The hexacyano metal complex is a mixed solvent with water or a suitable organic solvent miscible with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) and gelatin. It can be mixed with and added.

The addition amount of the hexacyano metal complex is preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less, and more preferably 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻³ mol or less per 1 mol of silver. Is.

In order to allow the hexacyano metal complex to exist on the outermost surface of the silver halide grain, sulfur hexasensitization, selenium sensitization and tellurium sensitization are carried out after the hexacyano metal complex has been added to the silver nitrate aqueous solution used for grain formation. Of the chalcogen sensitization or gold sensitization before the chemical sensitization step before the chemical sensitization step, the washing step, the dispersion step, or the chemical sensitization step. In order to prevent silver halide fine grains from growing, it is preferable to add the hexacyano metal complex immediately after the grain formation, and preferably before the end of the charging step.

The addition of the hexacyano metal complex may be started after the addition of 96% by mass of the total amount of silver nitrate added for grain formation, or after the addition of 98% by mass. More preferably, and particularly preferably after addition of 99% by mass.

When these hexacyano metal complexes are added after the addition of the aqueous silver nitrate solution just before the completion of grain formation, they can be adsorbed on the outermost surface of the silver halide grain, and most of them are hardly soluble with silver ions on the grain surface. Form a salt. Since this silver salt of hexacyanoiron (II) is less soluble than AgI, redissolution by fine particles can be prevented, and fine silver halide fine particles having a small grain size can be produced. .

The photosensitive silver halide grain of the present invention can contain a metal or a metal complex of Group 8 to Group 10 of the Periodic Table (showing Groups 1 to 18). The metal of Group 8 to 10 of the periodic table or the central metal of the metal complex is preferably rhodium, ruthenium or iridium. One of these metal complexes may be used, or two or more of the same metal complex and different metal complexes may be used in combination. The preferred content is 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per mol of silver.
A molar range is preferred. Regarding these heavy metals and metal complexes and the method of adding them, paragraph Nos. 0018 of JP-A-7-225449 and JP-A-11-65021.
To 0024, paragraph Nos. 0227 to 0240 of JP-A No. 11-119374.

Further, a metal atom which can be contained in the silver halide grain used in the present invention (for example, [Fe (C
N) ₆ ] ^4- ), the desalting method and the chemical sensitizing method of a silver halide emulsion are disclosed in paragraph No. 0 of JP-A No. 11-84574.
046 to 0050, paragraph numbers 0025 to 0031 of JP-A No. 11-65021, and JP-A No. 11-119374.
Paragraph Nos. 0242 to 0250 of the publication.

Various gelatins can be used as the gelatin contained in the photosensitive silver halide emulsion used in the present invention. In order to maintain a good dispersion state in the coating solution containing the organic silver salt of the photosensitive silver halide emulsion, it is preferable to use low molecular weight gelatin having a molecular weight of 500 to 60,000. These low molecular weight gelatins may be used during grain formation or dispersion after desalting treatment, but are preferably used during dispersion after desalting treatment.

In the present invention, a sensitizing dye can be used. The sensitizing dye of the present invention is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for the spectral characteristics of the exposure light source. Can be advantageously selected. Regarding the sensitizing dye and the addition method, paragraph Nos. 0103 to 0109 of JP-A No. 11-65021, a compound represented by JP-A No. 10-186572, a general formula (II), and a general formula (I of JP-A No. 11-119374) ) And a paragraph number 0106, U.S. Pat.No. 5,510,236,
3,871,887, the dye described in Example 5, JP-A-2-96131,
Dyes disclosed in JP-A-59-48753, page 19 line 38 to page 20 line 35 of European Patent Publication No. 0803764A1.
Line, Japanese Patent Application No. 2000-86865, Japanese Patent Application 2000-102560, Japanese Patent Application 2000-
No. 205399 etc. These sensitizing dyes may be used alone or in combination of two or more kinds. In the present invention, the sensitizing dye is added to the silver halide emulsion preferably after the desalting step and before coating, and more preferably after the desalting step and before the completion of chemical ripening. The addition amount of the sensitizing dye in the present invention can be a desired amount according to the sensitivity and fog performance, but is preferably 10 ^-6 to 1 mol per 1 mol of silver halide in the image forming layer, and more preferably Is 10 ^-4 to 10 ^-1 mol.

In order to improve the spectral sensitization efficiency of the present invention,
A supersensitizer can be used. Examples of the supersensitizer applied to the present invention include European Patent Publication No. 587,338, U.S. Patent Nos. 3,877,943, 4,873,184, and JP-A-5-341432.
No. 11-109547, No. 10-111543 and the like.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method or a tellurium sensitizing method. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds, for example, the compounds described in JP-A-7-128768 can be used. Particularly in the present invention, tellurium sensitization is preferable, and compounds described in the literature described in paragraph No. 0030 of JP-A No. 11-65021, JP-A No.
The compounds represented by formulas (II), (III) and (IV) in 313284 are more preferable.

The photosensitive silver halide grain in the invention is preferably chemically sensitized by a gold sensitizing method in combination with the chalcogen sensitization or alone. The gold sensitizer preferably has a gold valence of +1 or +3, and the gold sensitizer is preferably a gold compound usually used. Typical examples are chloroauric acid, bromioric acid, potassium chloroaurate, potassium brouroate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate and pyridyl trichlorogold. Are preferred. Further, the gold sensitizers described in US Pat. No. 5,858,637 and Japanese Patent Application No. 2001-79450 are also preferably used.

In the present invention, chemical sensitization can be performed at any time after grain formation and before coating. After desalting, (1) before spectral sensitization, (2) simultaneously with spectral sensitization, ( There may be 3) after spectral sensitization and (4) immediately before coating. The amount of the sulfur, selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is 10 ⁻⁸ to 10 ⁻² mol, preferably 1 ⁻⁸ mol, per mol of silver halide. About 10 ⁻⁷ to 10 ⁻³ mol is used. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is 10 ^-7 to 10 ^-3 mol, and more preferably 10 ^-10 mol per mol of silver halide.
^-6 mol to 5 × 10 ^-4 mol. The chemical sensitization conditions in the present invention are not particularly limited, but the pH is 5 to
8, 6 to 11 as pAg, 40 to 95 as temperature
It is about ℃. The silver halide emulsion used in the present invention includes
By the method shown in European Patent Publication No. 293,917,
A thiosulfonic acid compound may be added.

A reducing agent is preferably used for the photosensitive silver halide grains in the present invention. As a specific compound for the reduction sensitization method, ascorbic acid and thiourea dioxide are preferable, and stannous chloride, aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound, a silane compound, and a polyamine compound are preferably used. . The reduction sensitizer may be added at any stage of the photosensitive emulsion production process from crystal growth to the preparation process immediately before coating. Further, it is preferable to carry out reduction sensitization by ripening while maintaining the pH of the emulsion at 7 or more or pAg at 8.3 or less,
It is also preferable to carry out reduction sensitization by introducing a single addition part of silver ions during grain formation.

The photosensitive silver halide emulsion in the photosensitive recording material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, and different crystal habits). Those having different chemical sensitization conditions) may be used in combination. Gradation can be adjusted by using a plurality of photosensitive silver halides having different sensitivities. As a technique relating to these, JP-A-57-119341,
53-106125, 47-3929, 48-55730, 46-518
No. 7, No. 50-73627, No. 57-150841, etc.
As a difference in sensitivity, it is preferable that each emulsion has a difference of 0.2 logE or more.

The amount of photosensitive silver halide added was 1 m for the light-sensitive material.
Indicated by the amount of coated silver per ^{2, 0.03~0.6g} / m ²
It is preferably, more preferably from 0.07~0.4g / m ^2, and most preferably from 0.05 to 0.3 g / m ^2, relative to the organic silver salt 1 mole, The photosensitive silver halide is preferably 0.01 mol or more and 0.3 mol or less, more preferably 0.02 mol or more and 0.2 mol or less, still more preferably 0.03 mol or more and 0.15 mol or less.

Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide grains and organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, and a vibration. There are a method of mixing with a mill, a homogenizer, etc., or a method of mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt to prepare the organic silver salt.

Thus, the silver halide of the present invention is preferably formed in the absence of organic acid silver. In addition, mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions at the time of mixing is a preferable method for controlling photographic characteristics.

The silver halide of the present invention is preferably added to the coating solution for the image forming layer 180 minutes before and immediately before coating, preferably 60 minutes before 10 seconds before coating. Is not particularly limited as long as the effects of the present invention are sufficiently exhibited. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount sent to the coater is set to a desired time, and N. Harnby, MF Edwards, AW Nienow, translated by Koji Takahashi. There is a method of using a static mixer described in Chapter 8 of "Liquid mixing technology" (published by Nikkan Kogyo Shimbun, 1989).

The gradation of the photosensitive recording material is arbitrary, but in order to effectively bring out the effect of the present invention, the average contrast from density 1.5 to density 3.0 is 1.5 or more and 10 or less. Is preferred. Here, the average contrast is a characteristic curve in which the horizontal axis represents the logarithm of the laser exposure amount and the horizontal axis represents the optical density of the photosensitive recording material exposed with the exposure amount. And the slope of the line connecting the density 3.0. It is preferable that the average contrast is 1.5 or more and 10 or less in order to improve the performance of character breaks. It is particularly preferably 2.0 or more and 7 or less. It is more preferably 2.5 or more and 6 or less.

(Non-Photosensitive Organic Silver Salt) The organic silver salt which can be used in the present invention is relatively stable to light,
A silver salt that forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. The organic silver salt may be any organic substance containing a source capable of reducing silver ions.

Regarding such non-photosensitive organic silver salt, paragraph Nos. 0048 to 0049 of JP-A-10-62899,
European Patent Publication No. 0803764A1, page 18, line 24-
Page 19, Line 37, European Patent Publication No. 0962812A1,
It is described in JP-A Nos. 11-349591, 2000-7683, 2000-72711 and the like. Silver salts of organic acids, especially (10 carbon atoms
Silver salts of long chain aliphatic carboxylic acids (~ 30, preferably 15-28) are preferred. Preferred examples of the fatty acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, and a mixture thereof. In the present invention, among these fatty acid silver salts, the silver behenate content is preferably 50 mol% or more, more preferably 80 mol% or more.
It is preferable to use at least mol%, more preferably at least 90 mol% of fatty acid silver.

The shape of the organic silver salt that can be used in the present invention is not particularly limited and may be needle-like, rod-like, tabular or flaky. In the present invention, a flaky organic silver salt is preferred. In addition, short needle-shaped, rectangular parallelepiped, cubic or potato-shaped amorphous particles having a major axis-uniaxial length ratio of 5 or less are also preferably used. These organic silver particles are characterized by less fog during thermal development than long needle-shaped particles having a major axis to uniaxial length ratio of 5 or more.

In the present specification, the flaky organic silver salt is defined as follows. By observing the organic acid silver salt with an electron microscope, the shape of the organic acid silver salt particles was approximated to a rectangular parallelepiped, and the sides of this rectangular parallelepiped were set to a, b, and c from the shortest side (c is the same as b. Also, the shorter numerical value a, b
And calculate x as follows. x = b / a

In this way, when x is obtained for about 200 particles and the average value x (average) is taken, the one satisfying the relationship of x (average) ≧ 1.5 is made into a flaky shape. Preferably 30 ≧ x (average) ≧ 1.5, more preferably 2
0 ≧ x (average) ≧ 2.0. By the way, needle-shaped is 1 ≦ x
(Average) <1.5.

In the scale-like grains, a can be regarded as the thickness of a tabular grain having a plane having sides b and c as a main plane. The average of a is preferably 0.01 μm or more and 0.23 μm, more preferably 0.1 μm or more and 0.20 μm or less.
The average of c / b is preferably 1 or more and 6 or less, more preferably 1.05 or more and 4 or less, still more preferably 1.1 or more 3
The ratio is particularly preferably 1.1 or more and 2 or less.

The particle size distribution of the organic silver salt is preferably monodisperse. Monodisperse is preferably 100% or less, more preferably 80% or less, still more preferably 50%, of 100% of the value obtained by dividing the standard deviation of the length of each of the minor axis and the major axis by each of the minor axis and the major axis. It is the following. The shape of the organic silver salt can be measured by a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of obtaining the standard deviation of the volume weighted average diameter of the organic silver salt, and the percentage (variation coefficient) of the value divided by the volume weighted average diameter is preferably 100% or less, It is preferably 80% or less, more preferably 50% or less. As a measuring method, for example, the particle size (volume-weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with laser light and obtaining an autocorrelation function with respect to the time change of the fluctuation of scattered light You can

Known methods and the like can be applied to the method for producing the organic silver salt used in the invention and the dispersing method thereof. For example, Japanese Unexamined Patent Publication No. 10-62899 and European Patent Publication No. 0803763A described above.
1, European Patent Publication No. 0962812A1, JP-A-11-349591,
JP 2000-7683, 2000-72711, Japanese Patent Application No. 11-348228 ~
No. 30, No. 11-203413, Japanese Patent Application No. 2000-90093, No. 2000-1956
21, 2000-191226, 2000-213813, 2000-214
Reference can be made to Nos. 155 and 2000-191226.

When a photosensitive silver salt is allowed to coexist during the dispersion of the organic silver salt, fog increases and the sensitivity remarkably decreases. Therefore, it is more preferable that the photosensitive silver salt is not substantially contained during the dispersion. In the present invention, the amount of the photosensitive silver salt in the dispersed aqueous dispersion is preferably 1 mol% or less, more preferably 0.1 mol% or less, based on 1 mol of the organic acid silver salt in the liquid. It is more preferable that the photosensitive silver salt is not added positively.

In the present invention, it is possible to produce a photosensitive recording material by mixing an organic silver salt aqueous dispersion and a photosensitive silver salt aqueous dispersion. The mixing ratio of the organic silver salt and the photosensitive silver salt depends on the purpose. The ratio of the photosensitive silver salt to the organic silver salt is preferably in the range of 1 to 30 mol%, more preferably 2 to 20 mol%, and particularly preferably 3 to 15 mol%. Mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions at the time of mixing is a method preferably used for controlling photographic characteristics.

[0145] The organic silver salt of the present invention can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably 0.3 to 3 g / m ^2, more preferably 0.5
~ ² g / m ² .

(Reducing Agent) The heat-developable image recording material of the present invention preferably contains a heat developing agent which is a reducing agent for the organic silver salt. The reducing agent for the organic silver salt may be any substance (preferably organic substance) that reduces silver ions to metallic silver. Examples of such reducing agents include those disclosed in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 080376.
It is described on page 7, line 34 to page 18, line 12 of 4A1.

In the present invention, the reducing agent is preferably a so-called hindered phenol type reducing agent or a bisphenol type reducing agent having a substituent at the ortho position of the phenolic hydroxyl group, and a compound represented by the following general formula (R) is more preferable. preferable.

[0148]

[Chemical 41]

In the general formula (R), R ¹¹ and R ¹¹ '
Each independently represents an alkyl group having 1 to 20 carbon atoms. R ¹²
And R ¹² ′ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring. L is -S- group or -CHR
Represents a ¹³ -group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ and X ¹ 'each independently represent a hydrogen atom or a group capable of substituting for a benzene ring.

The general formula (R) will be described in detail. R
¹¹ and R ¹¹ 'each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the substituent of the alkyl group is not particularly limited, but preferably an aryl group,
Hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonamide group, sulfonyl group, phosphoryl group, acyl group,
Examples thereof include carbamoyl group, ester group, ureido group, urethane group and halogen atom.

R ¹² and R ¹² ′ each independently represent a hydrogen atom or a substituent capable of substituting on a benzene ring, and X ¹ and X ¹ ′ each independently represent a hydrogen atom or a group capable of substituting on a benzene ring. Preferable examples of the group capable of substituting on the benzene ring include an alkyl group, an aryl group, a halogen atom, an alkoxy group and an acylamino group.

L represents a --S-- group or a --CHR ¹³ --group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may have a substituent. R ¹³
Specific examples of the unsubstituted alkyl group of are methyl group, ethyl group,
Examples thereof include a propyl group, a butyl group, a heptyl group, an undecyl group, an isopropyl group, a 1-ethylpentyl group and a 2,4,4-trimethylpentyl group. Examples of the substituent of the alkyl group include the same groups as the substituent of R ¹¹ .

R ¹¹ and R ¹¹ ′ are preferably a secondary or tertiary alkyl group having 3 to 15 carbon atoms, specifically, isopropyl group, isobutyl group, t-butyl group, t
Examples include -amyl group, t-octyl group, cyclohexyl group, cyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclopropyl group. R ¹¹ and R ¹¹ ′ are more preferably a tertiary alkyl group having 4 to 12 carbon atoms, among which a t-butyl group, a t-amyl group, 1
A -methylcyclohexyl group is more preferable, and a t-butyl group is most preferable.

R ¹² and R ¹² ′ are preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, isopropyl group, t-
Butyl group, t-amyl group, cyclohexyl group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group,
Examples include methoxyethyl group. More preferably, methyl group, ethyl group, propyl group, isopropyl group, t-
It is a butyl group. X ¹ and X ¹ ′ are preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom.

L is preferably a --CHR ¹³ --group. R
¹³ is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and the alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a 2,4,4-trimethylpentyl group. Particularly preferred as R ¹³ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or an isopropyl group.

R¹³When is a hydrogen atom, R¹²And R
¹²'Is preferably an alkyl group having 2 to 5 carbon atoms, and
A tyl group and a propyl group are more preferable, and an ethyl group is the most preferable.
Good R¹³Is a primary or secondary alky having 1 to 8 carbon atoms
R is a radical¹²And R ¹²'Is preferably a methyl group
Yes. R¹³A C1-C8 primary or secondary alkyl group
Are methyl group, ethyl group, propyl group, isopropyl group
Group, more preferably a methyl group, an ethyl group, a propyl group
Is more preferable.

When R ¹¹ , R ¹¹ ′, R ¹² and R ¹² ′ are all methyl groups, R ¹³ is preferably a secondary alkyl group. In this case, the secondary alkyl group for R ¹³ is preferably an isopropyl group, an isobutyl group or a 1-ethylpentyl group, more preferably an isopropyl group. The reducing agent has different heat developability, developed silver color tone and the like depending on the combination of R ¹¹ , R ¹¹ ′, R ¹² , R ¹² ′ and R ¹³ .
Since these can be adjusted by combining two or more reducing agents, it is preferable to use two or more reducing agents depending on the purpose.

Specific examples of the reducing agent of the present invention including the compounds represented by the general formula (R) of the present invention are shown below.
The present invention is not limited to these.

[0159]

[Chemical 42]

[0160]

[Chemical 43]

[0161]

[Chemical 44]

[0162]

[Chemical formula 45]

In the present invention, the reducing agent is added in an amount of 0.1 to 10.
It is preferably 3.0 g / m ² , more preferably 0.2 to 1.5 g / m ² , and further preferably 0.3 to
It is 1.0 g / m ² . It is preferably contained in an amount of 5 to 50% by mole, more preferably 8 to 30% by mole, and 10 to 20% by mole based on 1 mole of silver on the surface having the image forming layer.
Is more preferably included. The reducing agent is preferably contained in the image forming layer.

The reducing agent may be contained in the coating liquid and contained in the photosensitive recording material by any method such as a solution form, an emulsion dispersion form and a solid fine particle dispersion form. Well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion A method of producing the same can be given.

As the solid fine particle dispersion method, a reducing agent powder is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves to obtain a solid dispersion. There is a method of creating. At that time, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three different isopropyl group substitution positions) or the like) may be used. Good. In the above mills, beads such as zirconia are usually used as a dispersion medium, and Z that elutes from these beads is used.
r and the like may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1 ppm to 1000 ppm. If the content of Zr in the light-sensitive material is 0.5 mg or less per 1 g of silver, there is no problem in practical use. The water dispersion preferably contains a preservative (for example, benzoisothiazolinone sodium salt).

(Development Accelerator) In the heat-developable image recording material of the present invention, a compound represented by the general formula (A) described in JP-A-2000-267222 or 2000-330234 is used as a development accelerator. Sulfonamide Phenol Compounds
A hindered phenolic compound represented by the general formula (II) described in 01-92075, JP-A-10-62895 and JP-A-11-62895.
-15116 General formula (I) described in the specification etc., Japanese Patent Application 2001-0742
A hydrazine-based compound represented by the general formula (1) described in Japanese Patent No. 78, and a phenol- or naphthol-based compound represented by the general formula (2) described in Japanese Patent Application No. 2000-76240 Is preferably used. These development accelerators are used in the range of 0.1 to 20 mol% with respect to the reducing agent, preferably in the range of 0.5 to 10 mol%, and more preferably in the range of 1 to 5 mol%. The method of introducing into the light-sensitive material may be the same as that of the reducing agent, but it is particularly preferable to add it as a solid dispersion or an emulsion dispersion. When added as an emulsified dispersion, it is added as an emulsified dispersion dispersed using a high-boiling solvent and a low-boiling auxiliary solvent that are solid at room temperature, or as a so-called oilless emulsified dispersion that does not use a high-boiling solvent. It is preferable to add. Among the above development accelerators in the present invention, Japanese Patent Application No. 2001-07427
No. 8 hydrazine-based compound represented by the general formula (1) and Japanese Patent Application No. 2000-76240 described phenol-based or naphthol-based compound represented by the general formula (2) Is particularly preferable. Preferred specific examples of the development accelerator of the invention are to be described below. The present invention is not limited to these.

[0167]

[Chemical formula 46]

[0168]

[Chemical 47]

(Hydrogen-bonding Compound) Next, the hydrogen-bonding compound used in the present invention will be described. When the reducing agent in the present invention has an aromatic hydroxyl group (—OH), particularly in the case of the above-mentioned bisphenols, a non-reducing compound having a group capable of forming a hydrogen bond with these groups. Is preferably used in combination. Examples of the group forming a hydrogen bond with a hydroxyl group or an amino group include a phosphoryl group, a sulfoxide group, a sulfonyl group, a carbonyl group, an amide group, an ester group, a urethane group, a ureido group, a tertiary amino group, and a nitrogen-containing aromatic group. Can be mentioned.

Of these, preferred are a phosphoryl group, a sulfoxide group and an amide group (provided that they do not have a> N—H group,
> N-Ra (wherein Ra is a substituent other than H). ), A urethane group (provided that it has no> N-H group and is blocked as> N-Ra (Ra is a substituent other than H)), and a ureido group (provided that the> N-H group is It is a compound which does not have and has a block like> N-Ra (Ra is a substituent other than H).

In the present invention, a particularly preferable hydrogen bonding compound is a compound represented by the following general formula (D).

[0172]

[Chemical 48]

In formula (D), R ²¹ to R ²³ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these groups may be unsubstituted. It may have a substituent.
When R ²¹ to R ²³ have a substituent, the substituent is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an alkylthio group, an arylthio group, a sulfonamide group, an acyloxy group, Examples thereof include an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, and a phosphoryl group. Preferred substituents are an alkyl group or an aryl group such as a methyl group, an ethyl group, an isopropyl group,
Examples thereof include t-butyl group, t-octyl group, phenyl group, 4-alkoxyphenyl group and 4-acyloxyphenyl group.

Specific examples of the alkyl group represented by R ²¹ to R ²³ include methyl group, ethyl group, butyl group, octyl group, dodecyl group, isopropyl group, t-butyl group, t-amyl group, t-octyl group, Examples thereof include cyclohexyl group, 1-methylcyclohexyl group, benzyl group, phenethyl group and 2-phenoxypropyl group. As the aryl group, a phenyl group, a cresyl group, a xylyl group, a naphthyl group,
4-t-butylphenyl group, 4-t-octylphenyl group, 4-anisidyl group, 3,5-dichlorophenyl group and the like can be mentioned.

As the alkoxy group, a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a 2-ethylhexyloxy group, a 3,5,5-trimethylhexyloxy group, a dodecyloxy group, a cyclohexyloxy group, 4-
Examples thereof include a methylcyclohexyloxy group and a benzyloxy group. A phenoxy group as the aryloxy group,
Cresyloxy group, isopropylphenoxy group, 4-t
-Butylphenoxy group, naphthoxy group, biphenyloxy group and the like can be mentioned. Examples of the amino group include dimethylamino group, diethylamino group, dibutylamino group, dioctylamino group, N-methyl-N-hexylamino group, dicyclohexylamino group, diphenylamino group, N-methyl-N-phenylamino group and the like. .

As R ²¹ to R ²³ , an alkyl group, an aryl group, an alkoxy group and an aryloxy group are preferable.
From the viewpoint of the effect of the present invention, at least one or more of R ²¹ to R ²³ is preferably an alkyl group or an aryl group, and more preferably two or more are an alkyl group or an aryl group. Further, it is preferable that R ²¹ to R ²³ are the same group in that they can be obtained at low cost.

Specific examples of the hydrogen-bonding compound including the compound of the general formula (D) in the present invention are shown below.
The present invention is not limited to these.

[0178]

[Chemical 49]

[0179]

[Chemical 50]

[0180]

[Chemical 51]

Specific examples of the hydrogen-bonding compound are, in addition to the above, the specifications of European Patent 1096310, Japanese Patent Application Nos. 2000-270498 and 2001-1.
No. 24796 is mentioned. The compound of the general formula (D) of the present invention can be used in a photosensitive recording material by containing it in a coating solution in the form of a solution, an emulsified dispersion, or a solid dispersion of fine particles, like a reducing agent. The compound of the present invention forms a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state, and as a complex depending on the combination of the reducing agent and the compound of the general formula (D) of the present invention. It can be isolated in crystalline form. It is particularly preferable to use the crystal powder thus isolated as a solid fine particle dispersion in order to obtain stable performance. Further, a method in which a reducing agent and the compound of the general formula (D) of the present invention are mixed in a powder form and a complex is formed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can also be preferably used.

The compound of the general formula (D) of the present invention is preferably used in the range of 1 to 200 mol%, more preferably 10 to 150 mol%, further preferably 20% with respect to the reducing agent. To 100 mol%.

(Binder) Next, the binder used in the present invention will be described. The binder of the organic silver salt-containing layer of the present invention may be any polymer, suitable binders are transparent or translucent, generally colorless, natural resins and polymers and copolymers, synthetic resins and polymers and copolymers, etc. Film forming media such as gelatins, gums, poly (vinyl alcohol) s, hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrate, poly (vinylpyrrolidone) s, casein, starch, poly (acrylic acid) ), Poly (methylmethacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers ,
Poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resin, poly (vinylidene chloride) s, poly (epoxides), Poly (carbonates), poly (vinyl acetate) s, poly (olefins), cellulose esters, poly (amides)
There are kinds. The binder may be formed by coating with water, an organic solvent or an emulsion.

In the present invention, the glass transition temperature of the binder that can be used in combination with the layer containing the organic silver salt is 10 ° C. or higher and 80 ° C. or higher.
It is preferably the following (hereinafter sometimes referred to as high Tg binder), more preferably 15 ° C. to 70 ° C., and further preferably 20 ° C. or more and 65 ° C. or less.

In this specification, Tg was calculated by the following formula. 1 / Tg = Σ (Xi / Tgi) Here, it is assumed that the polymer is a copolymer of n monomer components from i = 1 to n. Xi is the mass fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Where Σ is
Take the sum of i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer is shown in Polymer Handbook (3rd
Edition) (J. Brandrup, EHImmergut (Wiley-Intersci
ence, 1989)).

Two or more binders may be used in combination, if desired. Further, those having a glass transition temperature of 20 ° C. or higher and those having a glass transition temperature of less than 20 ° C. may be used in combination. When two or more polymers having different Tg's are blended and used, the mass average Tg is preferably within the above range.

In the present invention, it is preferable that the organic silver salt-containing layer is coated with a coating solution in which 30% by mass or more of the solvent is water and dried to form a film. In the present invention, when the organic silver salt-containing layer is formed by coating using a coating liquid in which 30% by mass or more of the solvent is water and drying, the binder of the organic silver salt-containing layer further contains an aqueous solvent ( Water solvent)
When it is soluble or dispersible in water, especially at 25 ℃ 60%
Performance is improved when the equilibrium water content at RH is made of a polymer latex having a content of 2% by mass or less. The most preferable form is prepared so that the ionic conductivity is 2.5 mS / cm or less, and such a preparation method includes a method of purifying using a separation functional membrane after polymer synthesis.

The aqueous solvent in which the polymer is soluble or dispersible as used herein is water or a mixture of water and 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include, for example, alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol,
Examples thereof include cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, ethyl acetate, dimethylformamide, and the like.

The term "aqueous solvent" is used here also in the case of a system in which the polymer is not thermodynamically dissolved and exists in a so-called dispersed state.

"Equilibrium water content at 25 ° C. 60% RH" means the mass W _{1 of the} polymer in humidity controlled equilibrium in the atmosphere of 25 ° C. 60% RH and the mass W of the polymer in the absolutely dry state at 25 ° C. It can be expressed as follows using ₀ .
Equilibrium water content at 25 ° C. and 60% RH = {(W ₁ −W ₀ ) / W ₀ ]
× 100 (mass%)

The definition and measurement method of the water content can be referred to, for example, Polymer Engineering Course 14, Polymer Material Testing Method (edited by The Polymer Society of Japan, Jijijinkan).

25 ° C. of the binder polymer of the present invention 60 ° C.
The equilibrium water content in% RH is preferably 2% by mass or less, more preferably 0.01% by mass or more and 1.5% by mass or more.
The amount is preferably not more than mass%, more preferably not less than 0.02 mass% and not more than 1 mass%.

In the present invention, a polymer dispersible in an aqueous solvent is particularly preferable. Examples of the dispersed state may be latex in which fine particles of a water-insoluble hydrophobic polymer are dispersed, or those in which polymer molecules are dispersed in a molecular state or forming micelles, but latex dispersed particles are more preferable. preferable.

The average particle size of the dispersed particles is 1 to 50000n.
m, preferably in the range of 5-1000 nm, more preferably in the range of 10-500 nm, still more preferably 50-
It is in the range of 200 nm. The particle size distribution of the dispersed particles is not particularly limited, and may be a wide particle size distribution or a monodisperse particle size distribution. Mixing and using two or more kinds having a monodisperse particle size distribution is also a preferable use method for controlling the physical properties of the coating solution.

In the present invention, preferred examples of the polymer dispersible in an aqueous solvent include acrylic polymers, poly (esters), rubbers (for example, SBR resin), poly (urethane) s, poly (vinyl chloride) s, Hydrophobic polymers such as poly (vinyl acetate) s, poly (vinylidene chloride) s, and poly (olefins) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more kinds of monomers. The copolymer may be a random copolymer or a block copolymer. The number average molecular weight of these polymers is 5,000 to 1,000,000, preferably 10,000 to 200,000. If the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and if it is too large, the film formability is poor and it is not preferred. A crosslinkable polymer latex is particularly preferably used.

Specific examples of the preferred polymer latex are shown below, but the present invention is not limited thereto. In the following, the raw material monomers are used, and the numerical values in parentheses are mass% and the molecular weights are number average molecular weights. When a polyfunctional monomer is used, the concept of molecular weight cannot be applied because a crosslinked structure is formed, so the term "crosslinkable" is used and the description of molecular weight is omitted. Tg represents a glass transition temperature.

P-1; -MMA (70) -EA (27) -MAA (3) -latex (molecular weight 37,000, Tg 61 ° C.) P-2; -MMA (70) -2EHA (20) -St (5 ) -AA (5) -latex (Mw 40,000, Tg59 ℃) P-3; -St (50) -Bu (47) -MAA (3) -latex (crosslinkable, Tg-
17 ℃) P-4; -St (68) -Bu (29) -AA (3) -latex (crosslinkable, Tg17
℃) P-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg24
℃) P-6; -St (70) -Bu (27) -IA (3) -latex (crosslinkable) P-7; -St (75) -Bu (24) -AA (1) -latex (Crosslinkability, Tg29
℃) P-8; -St (60) -Bu (35) -DVB (3) -MAA (2) -latex (crosslinkable) P-9; -St (70) -Bu (25) -DVB ( 2) -AA (3) -latex (crosslinkable) P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5) -latex (molecular weight 80,000) P-11; -VDC (85) -MMA (5) -EA (5) -MAA (5) -latex (molecular weight 67000) P-12; -Et (90) -MAA (10) -latex (molecular weight 12000) P-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130
000, Tg43 ℃) P-14; -MMA (63) -EA (35) -AA (2) latex (molecular weight 330
00, Tg47 ℃) P-15; -St (70.5) -Bu (26.5) -AA (3) -latex (crosslinking,
Tg23 ℃) P-16; -St (69.5) -Bu (27.5) -AA (3) -latex (crosslinkable,
(Tg20.5 ° C)

The abbreviations for the above structures represent the following monomers:
MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2-ethylhexyl acrylate, St; styrene, Bu; butadiene, AA; acrylic acid, DVB; divinylbenzene, VC; vinyl chloride, AN;
Acrylonitrile, VDC; vinylidene chloride, Et; ethylene, IA; itaconic acid.

The polymer latexes described above are commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635,471
8,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx81
FINETEX ES65 is an example of poly (ester) s such as 1, 814, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.).
0, 611, 675, 850 (all manufactured by Dainippon Ink and Chemicals, Inc.),
Examples of poly (urethane) s such as WD-size and WMS (above Eastman Chemical) are HYDRAN AP10, 20, 30,
As examples of rubbers such as 40 (all manufactured by Dainippon Ink and Chemicals, Inc.), LACSTAR 7310K, 3307B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx416, 410, 438C,
Examples of poly (vinyl chloride) s such as 2507 (above Nippon Zeon Co., Ltd.) include G351, G576 (above all Nippon Zeon Co., Ltd.), examples of poly (vinylidene chloride) L502, Examples of poly (olefin) s such as L513 (all manufactured by Asahi Kasei Corporation) are Chemipearl S120 and SA10.
0 (above, manufactured by Mitsui Petrochemical Co., Ltd.) and the like.

These polymer latices may be used alone, or may be used by blending two or more kinds as required.

As the polymer latex used in the present invention, a latex of styrene-butadiene copolymer is particularly preferable. The mass ratio of the styrene monomer unit and the butadiene monomer unit in the styrene-butadiene copolymer is preferably 40:60 to 95: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is 60 to 99% by mass.
Is preferred. The polymer latex of the present invention preferably contains acrylic acid or methacrylic acid in an amount of 1 to 6% by mass, more preferably 2 to 5% by mass, based on the sum of styrene and butadiene. The polymer latex of the present invention preferably contains acrylic acid.

Styrene preferably used in the present invention-
As the latex of the butadiene acid copolymer, the above-mentioned P-
3 to P-8,15, LACSTAR-3307B, 7132C, Nipol which are commercial products
Lx416 etc. are mentioned. The preferred Tg of the latex of such a styrene-butadiene acid copolymer is 10 ° C. or higher and 3
It is 0 ° C or lower, and more preferably 17 ° C or higher and 25 ° C or lower.

If desired, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose or the like may be added to the organic silver salt-containing layer of the photosensitive recording material of the present invention. The addition amount of these hydrophilic polymers is preferably 30% by mass or less, more preferably 20% by mass or less based on the total amount of binders in the organic silver salt-containing layer.

The organic silver salt-containing layer (that is, the image forming layer) of the present invention is preferably formed using a polymer latex. The amount of the binder in the organic silver salt-containing layer is such that the total binder / organic silver salt mass ratio is 1/10 to 10/1, more preferably 1/3 to 5/1, and further preferably 1
The range is / 1 to 3/1.

Further, such an organic silver salt-containing layer is usually also a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt, and in such a case, all binders are contained. The mass ratio of / silver halide is in the range of 400 to 5, more preferably 200 to 10.

The total amount of binder in the image forming layer of the present invention is preferably 0.2 to 30 g / m ² , more preferably 1 to 15
g / m ^2, more preferably in the range of 2 to 10 g / m ^2. A cross-linking agent for cross-linking, a surfactant for improving coatability, and the like may be added to the image forming layer of the present invention.

(Preferable Solvent for Coating Liquid) In the present invention, the solvent for the coating liquid for the organic silver salt-containing layer of the photosensitive recording material (for simplicity, the solvent and the dispersion medium are collectively referred to as the solvent).
Is preferably an aqueous solvent containing 30% by mass or more of water. As components other than water, methyl alcohol, ethyl alcohol,
Any water-miscible organic solvent such as isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate may be used. The water content of the solvent of the coating liquid is preferably 50% by mass or more, more preferably 70% by mass or more. Examples of preferred solvent compositions include water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / Ethyl cellosolve = 85/10/5, water / methyl alcohol / isopropyl alcohol = 85/10/5, etc. (numerical values are% by mass).

(Antifoggant) Next, the antifoggant used in the present invention will be described. Antifoggants, stabilizers and stabilizer precursors that can be used in the present invention are disclosed in paragraph No. 0070 of JP-A-10-62899, European Patent Publication No. 08.
No. 03764A1, page 20, line 57 to page 21, line 7, patents, JP-A-9-281637, JP-A-9-329864, compounds described in US Patents 6,083,681, 6,083,681, European Patents Ten
The compound described in 48975 is mentioned. Further, the antifoggants preferably used in the present invention are organic halides, for these, the paragraph number of JP-A No. 11-65021.
Examples include those disclosed in the patents described in 0111 to 0112. Particularly, an organic halogen compound represented by the formula (P) in JP-A-2000-284399 and a general formula (II) in JP-A-10-339934.
The organic polyhalogen compounds represented by the following are preferred, and the organic polyhalogen compounds described in JP 2001-31644 A and JP 2001-33911 A are preferable.

The organic polyhalogen compound preferred in the present invention will be specifically described below. The preferred polyhalogen compound of the present invention is a compound represented by the following general formula (H).

General formula (H) Q- (Y) n-C (Z ₁ ) (Z ₂ ) X

In the general formula (H), Q is an alkyl group,
It represents an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, Z ₁ and Z ₂ represent a halogen atom, and X represents a hydrogen atom or an electron-withdrawing group.

In the general formula (H), Q preferably represents a phenyl group substituted with an electron-withdrawing group whose Hammett's substituent constant σp has a positive value. For the Hammett's substituent constant, see Journal of Medicinal Chemistry, 1973, Vol.
16, No. 11, 1207-1216, etc. can be referred to.

Examples of such an electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.2).
3), iodine atom (σp value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp value: 0) .54)), a cyano group (σp value: 0.6)
6), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, Acetyl (σp value: 0.5
0), benzoyl (σp value: 0.43)), alkynyl group (for example, C≡CH (σp value: 0.23)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value)). : 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value:
0.57), a sulfoxide group, a heterocyclic group, a phosphoryl group and the like. The σp value is preferably 0.2 to
It is in the range of 2.0, and more preferably in the range of 0.4 to 1.0. Particularly preferable as the electron-withdrawing group are a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group and an alkylphosphoryl group, and among them, a carbamoyl group is the most preferable.

X is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group. A group, a carbamoyl group, a sulfamoyl group,
Particularly preferred is a halogen atom. Among the halogen atoms, chlorine atom, bromine atom and iodine atom are preferable, chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable. Y is preferably -C (= O)
-, - SO- or -SO ₂ -; more preferably, -C (= O) -, - SO 2 - , and particularly preferably -
SO ₂ −. n represents 0 or 1, and is preferably 1.

Specific examples of the compound represented by formula (H) of the present invention are shown below.

[0216]

[Chemical 52]

[0217]

[Chemical 53]

The compound represented by the general formula (H) of the present invention is 1 × 10 ⁻⁴ to 1 mol per mol of the non-photosensitive silver salt in the image forming layer.
It is preferably used in the range of 0.5 mol, more preferably in the range of 10 ^{−3 to} 0.1 mol, and further preferably in the range of 5 × 10 ^{−3 to} 0.05 mol. In the present invention, examples of the method of incorporating the antifoggant into the photosensitive recording material include the methods described in the method of incorporating the reducing agent, and the organic polyhalogen compound is also preferably added as a solid fine particle dispersion.

Other antifoggants are disclosed in JP-A-11-6.
5021, paragraph 0113, mercury (II) salt, same, paragraph 0114
Benzoic acid, a salicylic acid derivative of JP-A-2000-206642, a formalin scavenger compound represented by the formula (S) of JP-A-2000-221634, a triazine compound according to claim 9 of JP-A-11-352624, 6-11791 general formula
Compound represented by (III), 4-hydroxy-6-methyl-1,3,3
Examples include a, 7-tetrazaindene and the like.

The heat-developable image recording material in the invention may contain an azolium salt for the purpose of preventing fog. Examples of the azolium salt include compounds represented by the general formula (XI) described in JP-A-59-193447, compounds described in JP-B-55-12581, and general formula (II) described in JP-A-60-153039. The compounds represented may be mentioned. The azolium salt may be added to any part of the light-sensitive recording material, but as an addition layer, it is preferably added to the layer having the photosensitive layer, and more preferably to the organic silver salt-containing layer. The azolium salt may be added at any step in the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be at any step from the preparation of the organic silver salt to the preparation of the coating solution, but after the preparation of the organic silver salt. Therefore, immediately before coating is preferable. The azolium salt may be added by any method such as powder, solution and fine particle dispersion. Also, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a toning agent.

In the present invention, the addition amount of the azolium salt may be any amount, but it is 1 × 10 ^-6 per mol of silver.
The molar ratio is preferably 2 mol or more and 2 mol or less, more preferably 1 × 10 ⁻³ mol or more and 0.5 mol or less.

(Others) In the present invention, a mercapto compound, a disulfide compound, a thione compound is used for the purpose of suppressing or accelerating the development to control the development, improving the spectral sensitization efficiency, and improving the preservability before and after the development. Paragraph No. 0067 of JP-A-10-62899
~ 0069, compounds represented by the general formula (I) of JP-A-10-186572 and specific examples thereof are described in paragraph Nos. 0033 to 0052, European Patent Publication No. 0803764A1, page 20, lines 36 to 56. There is. Among them, JP-A-9-297367, JP-A-9-304875, JP-A-2001-100358, and Japanese Patent Application No. 2001-104213
Nos. 4,096,096 and No. 2001-104214, and the like, are preferably mercapto-substituted heteroaromatic compounds.

In the heat-developable image recording material of the present invention, it is preferable to add a toning agent. As for the toning agent, paragraph Nos. 0054 to 0055 of JP-A-10-62899 and page 23 to 23 of EP-A-0803764A1 are mentioned. 48 lines, JP 2000-356317 and Japanese Patent Application 200
0-187298, particularly phthalazinones (phthalazinone, phthalazinone derivatives or metal salts;
For example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinones and phthalic acids (eg, phthalic acid) , 4-methylphthalic acid, 4-nitrophthalic acid, diammonium phthalate, sodium phthalate, potassium phthalate and tetrachlorophthalic anhydride); phthalazines (phthalazine, phthalazine derivatives or metal salts; eg 4- (1 -Naphthyl) phthalazine, 6-isopropylphthalazine, 6-t-butylflatadine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3.
-Dihydrophthalazine); a combination of phthalazines and phthalic acids is preferable, and a combination of phthalazines and phthalic acids is particularly preferable. Among them, a particularly preferable combination is 6-isopropylphthalazine and phthalic acid or 4-
It is a combination with methylphthalic acid.

Regarding the plasticizers and lubricants that can be used in the photosensitive layer of the present invention, paragraph No. of JP-A No. 11-65021
Regarding the super-high contrast agent for super-high contrast image formation and the addition method and amount thereof, paragraph No. 0118 of the same item, JP-A No. 11-22389.
No. 8 paragraphs 0136 to 0193, compounds of formula (H), formulas (1) to (3), formulas (A) and (B) of JP-A 2000-284399, and general description in Japanese Patent Application No. 11-91652. Regarding the compounds of formulas (III) to (V) (specific compounds: Chemical formulas 21 to 24) and the contrast enhancing accelerator, JP-A No. 11-65021, paragraph No. 0102 and JP-A No. 11-223.
No. 898, paragraph numbers 0194 to 0195.

To use formic acid or formate as a strong fogging substance, 5 mmol or less, more preferably 1 mol or less, per mol of silver on the side having an image forming layer containing a photosensitive silver halide.
It is preferable that the content is not more than mmol.

When a super-high contrast agent is used in the heat-developable image recording material of the present invention, it is preferable to use an acid formed by hydration of diphosphorus pentaoxide or a salt thereof in combination. Examples of the acid formed by hydration of diphosphorus pentoxide or a salt thereof include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline. Examples thereof include acids (salts).

Particularly preferably used acids formed by hydration of diphosphorus pentoxide or salts thereof are orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and the like. The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide (coating amount per 1 m ^{2 of the} photosensitive recording material) may be a desired amount according to the performance such as sensitivity and fog, but is 0.1 to 500 mg.
/ M ² is preferable, and 0.5 to 100 mg / m ² is more preferable.

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. The surface protective layer may be a single layer or a plurality of layers. The surface protective layer is described in paragraph Nos. 0119 to 0120 of JP-A No. 11-65021 and Japanese Patent Application No. 2000-171936.

Gelatin is preferred as the binder for the surface protective layer of the present invention, but polyvinyl alcohol (PVA)
It is also preferable to use or to use. As gelatin, inert gelatin (for example, Nitta gelatin 75
0), phthalated gelatin (eg Nitta gelatin 801) and the like can be used. As PVA, JP 2000-1
71936, paragraph numbers 0009 to 0020, which include fully saponified PVA-105 and partially saponified P.
VA-205, PVA-335, modified polyvinyl alcohol MP-203 (these are trade names of Kuraray Co., Ltd.)
And the like are preferable. The polyvinyl alcohol coating amount (per 1 m ^{2 of} support) of the protective layer (per 1 layer) is preferably 0.3 to 4.0 g / m ² , and 0.3 to 2.0 g
/ M ² is more preferable.

Especially when the heat-developable image recording material of the present invention is used for printing applications where dimensional change is a problem, polymer latex is preferably used for the surface protective layer and the back layer. Regarding such polymer latex, "Synthetic resin emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Kobunshi Kogyokai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Takashi) Molecular Publishing (1993)), "Chemistry of Synthetic Latex (Souichi Muroi, Polymer Publishing (1970))", etc., and specifically methyl methacrylate (33.5% by mass). / Ethyl acrylate (50% by mass) / methacrylic acid (16.5% by mass) copolymer latex, methyl methacrylate (47.5% by mass) / butadiene (4
7.5% by mass) / itaconic acid (5% by mass) copolymer latex, ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate (58.9% by mass) / 2-ethylhexyl acrylate (25.4% by mass) / Styrene (8.6% by mass) / 2-hydroxyethyl methacrylate (5.1% by mass) / Acrylic acid (2.
0% by mass) latex of copolymer, methyl methacrylate (64.0% by mass) / styrene (9.0% by mass) / butyl acrylate (20.0% by mass) / 2-hydroxyethyl methacrylate (5.0% by mass) / Examples thereof include a latex of acrylic acid (2.0% by mass) copolymer.

Further, as a binder for the surface protective layer, a combination of polymer latexes of Japanese Patent Application No. 11-6872, paragraphs 0021 to 0 of Japanese Patent Application No. 11-143058.
Paragraph number 00 of the technology described in 025, Japanese Patent Application No. 11-6872
The techniques described in paragraphs 0023 to 0041 of the specification of Japanese Patent Application No. 10-199626 may be applied.

The ratio of the polymer latex in the surface protective layer is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less of the total binder. Coating amount of all binders (including water-soluble polymer and latex polymer) in the surface protective layer (per layer) (support 1 m ²
As (per hit), 0.3 to 5.0 g / m ² is preferable,
0.3 to 2.0 g / m ² is more preferable.

The preparation temperature of the coating solution for the image forming layer of the present invention is 3
0 ° C or higher and 65 ° C or lower is preferable, and more preferable temperature is 35 ° C.
℃ or more and less than 60 ℃, more preferable temperature is 35 ℃ or more 55
It is below ℃. Further, the temperature of the coating liquid for the image forming layer immediately after the addition of the polymer latex is preferably maintained at 30 ° C. or higher and 65 ° C. or lower.

The image forming layer of the present invention comprises one or more layers on the support. When it is composed of a single layer, it consists of an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, and optionally contains additional materials such as a toning agent, a coating aid and other auxiliary agents. When composed of two or more layers, the first image-forming layer (usually the layer adjacent to the support) contains an organic silver salt and a photosensitive silver halide, and some of the second image-forming layer or both layers are contained. Must contain other ingredients of. The composition of the multicolor photosensitive photothermographic material may include a combination of these two layers for each color,
It may also include all components in a single layer as described in US Pat. No. 4,708,928. In the case of multi-dye multicolor light-sensitive photothermographic materials, each emulsion layer generally comprises a functional or non-functional barrier layer between each light-sensitive layer as described in U.S. Pat.No. 4,460,681. By being used, they are retained separately from each other.

The photosensitive layer of the present invention contains various dyes and pigments (for example, CI Pigment Blue 60, C.I., etc.) from the viewpoint of improving color tone, preventing interference fringes during laser exposure, and preventing irradiation.
I.Pigment Blue 64, CI Pigment Blue 15: 6) can be used. About these, WO98 / 36322, JP
It is described in detail in Nos. 10-268465 and 11-338098.

In the heat-developable image recording material of the present invention,
It is preferable to provide the antihalation layer on the side far from the light source with respect to the photosensitive layer.

The heat developable image recording material generally has a non-photosensitive layer in addition to the photosensitive layer. The non-photosensitive layer is (1) a protective layer provided on the photosensitive layer (the side farther than the support) from the arrangement, (2) between a plurality of photosensitive layers or between the photosensitive layer and the protective layer. Can be classified into an intermediate layer provided in (3), (3) an undercoat layer provided between the photosensitive layer and the support, and (4) a back layer provided on the opposite side of the photosensitive layer. The filter layer is
It is provided on the photosensitive recording material as the layer (1) or (2). The antihalation layer is provided on the photosensitive recording material as the layer (3) or (4).

Regarding the antihalation layer, Japanese Patent Application Laid-Open No. 11-1999
-65021, paragraph numbers 0123 to 0124, JP-A Nos. 11-223898 and 9
-230531, 10-36695, 10-104779, 11-23145
No. 7, No. 11-352625, No. 11-352626, etc. The antihalation layer contains an antihalation dye having absorption at the exposure wavelength. In the case of the present invention, since the wavelength of the exposure laser has a peak wavelength from 350 nm to 440 nm, it is preferable to use a dye that also absorbs this wavelength for antihalation.

When antihalation is carried out by using a dye having absorption in the visible region, it is preferable that the color of the dye does not substantially remain after image formation. Is preferably used, and it is particularly preferable to add a heat-decolorizing dye and a base precursor to the non-photosensitive layer to function as an antihalation layer. These techniques are described in JP-A-11-231457 and the like.

The addition amount of the decolorizing dye is determined depending on the use of the dye. In general, it is preferable to use an optical density (absorbance) of more than 0.1 when measured at a target wavelength. The optical density is preferably 0.15 to 2, more preferably 0.2 to 1. The amount of dye used to obtain such an optical density is generally 0.00
It is about 1 to 1 g / m ² .

By decoloring the dye in this way, the optical density after thermal development can be lowered to 0.1 or less. Two or more kinds of decolorizable dyes may be used together in the thermal decolorizable recording material or the heat-developed image recording material. Similarly, two or more kinds of base precursors may be used in combination.

In the thermal bleaching using such a decolorizing dye and a base precursor, when it is mixed with a base precursor as described in JP-A-11-352626, the melting point is 3 ° C. (de
g) It is preferable from the viewpoint of thermal decoloring property to use together a substance capable of lowering the amount (eg, diphenyl sulfone, 4-chlorophenyl (phenyl) sulfone), 2-naphthyl benzoate and the like.

In the present invention, a colorant having an absorption maximum at 300 to 450 nm can be added for the purpose of improving the silver tone and the change with time of the image. Such colorants are disclosed in JP-A-62-210458, JP-A-63-104046, and JP-A-63-103235.
No. 63, No. 63-208846, No. 63-306436, No. 63-314535,
It is described in JP-A Nos. 01-61745 and 2001-100363. Such a coloring agent is usually 0.1 mg / m ² to
The back layer is preferably added in the range of 1 g / m ² , and the layer to be added is preferably a back layer provided on the opposite side of the photosensitive layer.

The heat-developable image recording material in the present invention has a photosensitive layer containing at least one silver halide emulsion on one side of the support and a back layer on the other side, so-called single-sided photosensitive recording. It is preferably a material.

In the present invention, it is preferable to add a matting agent for improving the transportability.
It is described in paragraph Nos. 0126 to 0127 of JP-A No. 11-65021. The matting agent is preferably 1 to 400 mg / m ² , and more preferably 5 to 300 mg / m ² in terms of coating amount per 1 m ² of the light-sensitive recording material. In the present invention, the shape of the matting agent may be either regular or amorphous, but is preferably regular and spherical is preferably used. Average particle size is 0.5-
It is preferably 10 μm, more preferably 1.0
˜8.0 μm, more preferably 2.0 to 6.0 μm. The coefficient of variation of the size distribution is 50
% Or less, more preferably 40% or less, and further preferably 30% or less. Here, the coefficient of variation is (standard deviation of particle size) / (average value of particle size) × 10
It is a value represented by 0. It is also preferable to use two kinds of matting agents having a small coefficient of variation and having a ratio of average particle diameters of more than 3.

The matteness of the emulsion surface may be anything as long as stardust failure does not occur, but the Beck's smoothness is preferably 30 seconds or more and 2000 seconds or less, and particularly 40 seconds or more 1500.
Seconds or less are preferable. Beck's smoothness is based on Japanese Industrial Standards (J
IS) P8119 "Smoothness test method for paper and board by Beck tester" and TAPPI standard method T479.

In the present invention, the Bekk smoothness of the back layer is preferably 1200 seconds or less and 10 seconds or more, more preferably 800 seconds or less and 20 seconds or more, and further preferably 500 seconds or less and 40 seconds or more.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the photosensitive recording material, a layer functioning as the outermost surface layer, or a layer close to the outer surface, and a layer acting as a so-called protective layer. Is preferably contained in

The back layer applicable to the present invention is described in paragraph Nos. 0128 to 0130 of JP-A No. 11-65021.

In the heat-developable image recording material of the present invention, the pH of the film surface before the heat-development treatment is preferably 7.0 or less, more preferably 6.6 or less. The lower limit is not particularly limited, but is about 3. Most preferred pH range is 4
The range is from to 6.2. From the viewpoint of reducing the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia for adjusting the film surface pH. Ammonia is particularly volatile so that it can be removed before the coating step or heat development, which is preferable for achieving a low film surface pH.

It is also preferable to use a non-volatile base such as sodium hydroxide, potassium hydroxide or lithium hydroxide in combination with ammonia. The method for measuring the film surface pH is described in Japanese Patent Application No. 11-87297, paragraph 012.
3 are described.

A hardener may be used in each of the layers such as the photosensitive layer, the protective layer and the back layer of the present invention. An example of a hardener is T.
"THE THEORY OF THE PHOTOGRAPHIC PROCESS" by H. James
FOURTH EDITION ”(Macmillan Publishing Co., Inc.
1977) pp. 77-87. Chromium alum, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N , N-propylene bis (vinyl sulfone acetamide), ibid. 78
Polyvalent metal ions described in pages, U.S. Pat.No. 4,281,060,
Polyisocyanates such as JP-A-6-208193, epoxy compounds such as US Pat. No. 4,791,042, JP-A-62-8904
Vinyl sulfone compounds such as No. 8 are preferably used.

The hardening agent is added as a solution, and the timing of adding this solution to the protective layer coating solution is from 180 minutes before to immediately before coating, preferably from 60 minutes before to 10 seconds before coating. The mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount sent to the coater is a desired time and N. Harnby, MF Edwards, by AW Nienow,
"Liquid mixing technology" translated by Koji Takahashi (Published by Nikkan Kogyo Shimbun, 1989
There is a method of using a static mixer described in Chapter 8 etc.

The surfactant applicable to the present invention is described in JP-A No. 11-65021, Paragraph No. 0132, the solvent is Paragraph No. 0133, the support is Paragraph No. 0134, and the antistatic or conductive layer is the same. No. 0135, No. 0136 of the same item for a method of obtaining a color image, and JP-A No. 11-84573, paragraphs 0061 to 0064 and Japanese Patent Application No.
No. 11-106881, paragraph numbers 0049 to 0062 are described.

In the present invention, it is preferable to have a conductive layer containing a metal oxide. As the conductive material of the conductive layer, a metal oxide in which oxygen defects and foreign metal atoms are introduced into the metal oxide to enhance the conductivity is preferably used. As an example of the metal oxide, ZnO, TiO ₂ , and SnO ₂ are preferable, and ZnO
For ₂ Al, the addition of an In, S for SnO ₂
It is preferable to add b, Nb, P, a halogen element, or the like, and to TiO ₂ , add Nb, Ta, or the like. SnO ₂ containing Sb is particularly preferable.

The addition amount of the heteroatom is 0.01 to 30 mol.
% Is preferable, and 0.1 to 10 mol% is more preferable. The shape of the metal oxide may be spherical, acicular, or plate-like, but in terms of the effect of imparting conductivity, the major axis / uniaxial ratio is 2.0 or more, preferably 3.0 to 50 acicular particles. Good.

The amount of the metal oxide used is preferably 1 mg /
In the range of m to 1000 mg / m ² , more preferably 10 m
g / m to 500 mg / m ² , more preferably 20
The range is from mg / m to ²⁰⁰ mg / m ² . The conductive layer of the present invention may be provided on either the emulsion surface side or the back surface side, but it is preferably provided between the support and the back layer. Specific examples of the conductive layer of the present invention are described in JP-A-7-295146 and JP-A-11-223901.

In the present invention, it is preferable to use a fluorinated surfactant. Specific examples of the fluorine-based surfactant are JP-A-10-197985, JP-A-2000-19680, and JP-A-2000-21.
Examples thereof include compounds described in No. 4554 and the like. Further, a polymeric fluorine-based surfactant described in JP-A-9-281636 is also preferably used. In the present invention, it is particularly preferable to use the fluorine-based surfactant described in Japanese Patent Application No. 2000-206560.

The transparent support is a polyester heat-treated in the temperature range of 130 to 185 ° C. in order to relax the internal strain remaining in the film during biaxial stretching and eliminate the heat shrinkage strain generated during the heat development treatment. Especially, polyethylene terephthalate is preferably used. In the case of a heat-developable image recording material for medical use, the transparent support may be colored with a blue dye (for example, Dye-1 described in Examples of JP-A-8-240877) or may be uncolored.

As the support, a water-soluble polyester described in JP-A No. 11-84574, a styrene-butadiene copolymer described in JP-A No. 10-186565, a paragraph No. 0 in JP-A-2000-39684 and Japanese Patent Application No. 11-106881.
It is preferable to apply an undercoating technique such as a vinylidene chloride copolymer of 063 to 0080. Further, regarding the antistatic layer or undercoat, JP-A-56-143430, JP-A-56-143431,
58-62646, 56-120519, JP-A-11-84573, paragraph numbers 0040 to 0051, U.S. Pat.No. 5,575,957, JP-A-11-22
The technique described in paragraph numbers 0078 to 0084 of No. 3898 can be applied.

The heat-developable image recording material is preferably a monosheet type (a type capable of forming an image on the heat-developable image recording material without using another sheet such as an image receiving material).

An antioxidant, stabilizer, plasticizer, ultraviolet absorber or coating aid may be further added to the heat-developable image recording material. Various additives are added to either the photosensitive layer or the non-photosensitive layer. About them WO
98/36322, EP803764A1, JP-A-10-186567, 10-
You can refer to No. 18568 etc.

The heat-developable image recording material in the invention may be applied by any method. Specifically, extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or US Patent No. 2,681,294.
Various coating operations were used, including extrusion coating with hoppers of the type described in No.
"LIQUID FILM COATIN" by Kistler, Petert M. Schweizer
G ″ (published by CHAPMAN & HALL, 1997) pages 399 to 536, extrusion coating or slide coating is preferably used, and slide coating is particularly preferably used. The shape of the slide coater used for slide coating is preferably used. For an example, see page 427 of the same book.
ure 11b.1. Also, if desired, pages 399 to 536 of the same book.
Two or more layers can be coated simultaneously by the method described on page, U.S. Pat. No. 2,761,791 and British Patent No. 837,095.

The coating solution for the organic silver salt-containing layer in the present invention comprises
It is preferably a so-called thixotropic fluid. Regarding this technique, reference can be made to JP-A-11-52509. The coating solution for the organic silver salt-containing layer in the present invention has a viscosity at a shear rate of 0.1 S ⁻¹ of 400 mPa · s or more, 100,
It is preferably 000 mPa · s or less, more preferably 5
It is not less than 00 mPa · s and not more than 20,000 mPa · s. Also, at a shear rate of 1000 S ⁻¹ , 1 mPa ·
It is preferably s or more and 200 mPa · s or less, and more preferably 5 mPa · s or more and 80 mPa · s or less.

Techniques that can be used for the heat-developable image recording material of the present invention include EP803764A1 and EP883022A1.
WO98 / 36322, JP-A-56-62648, JP-A-58-62644, JP-A-9-43766, JP-A-9-281637, JP-A-9-297367, JP-A-9-304869
No. 9, No. 9-311405, No. 9-329865, No. 10-10669, No. 10
-62899, 10-69023, 10-186568, 10-90823
No., No. 10-171063, No. 10-186565, No. 10-186567,
10-186569 ~ 10-186572, 10-197974, 10-
197982, 10-197983, 10-197985 to 10-19798
No. 7, No. 10-207001, No. 10-207004, No. 10-221807,
10-282601, 10-288823, 10-288824, 10-
307365, 10-312038, 10-339934, 11-7100
No. 11, No. 15-15105, No. 11-24200, No. 11-24201, No. 11
-30832, 11-84574, 11-65021, 11-109547
No. 11, No. 11-125880, No. 11-129629, No. 11-133536 ~
11-133539, 11-133542, 11-133543, 11-
No. 223898, No. 11-352627, No. 11-305377, No. 11-30537
No. 8, No. 11-305384, No. 11-305380, No. 11-316435,
11-327076, 11-338096, 11-338098, 11-
338099, 11-343420, Japanese Patent Application No. 2000-187298, 2000
-10229, 2000-47345, 2000-206642, 2000-
98530, 2000-98531, 2000-112059, 2000-1
12060, 2000-112104, 2000-112064, 2000-
171936 can also be mentioned.

The photosensitive recording material of the present invention is packaged with a packaging material having a low oxygen transmission rate and / or a water transmission rate in order to suppress fluctuations in photographic performance during raw storage or to improve curl, curl and the like. It is preferable. Oxygen permeability is
It is preferably 50 ml / atm · m ² · day or less at 25 ° C, more preferably 10 ml / atm · m ² · day or less, and further preferably
It is less than 1.0 ml / atm · m ² · day. Water permeability is 10g / atm
It is preferably m ² · day or less, more preferably 5 g /
It is atm · m ² · day or less, more preferably 1 g / atm · m ² · day or less. Specific examples of the packaging material having a low oxygen transmission rate and / or a low water transmission rate include, for example, JP-A-8-254.
No. 793. The packaging material is described in JP-A-2000-206653.

(Heat Development Method) The heat development image recording material of the present invention may be developed by any method, but it is usually developed by heating the heat development image recording material exposed imagewise. The developing temperature is preferably 80 to 250 ° C, more preferably 100 to 140 ° C, further preferably 100 to 120 ° C, and most preferably 105 to 11 ° C.
It is 5 ° C. The development time is preferably 1 to 60 seconds,
More preferably 3 to 30 seconds, even more preferably 5 to 25 seconds.
Seconds, 7 to 15 seconds are particularly preferable.

As the thermal development system, either a drum type heater or a plate type heater may be used, but the plate heater type is more preferable. The heat development method using the plate heater method is preferably the method described in JP-A No. 11-133572, and a visible image is obtained by bringing the heat-developable image recording material on which a latent image is formed into contact with heating means in the heat-development section. In the heat developing device, the heating means is composed of a plate heater, and a plurality of pressing rollers are arranged to face each other along one surface of the plate heater, and the pressing roller is arranged between the pressing roller and the plate heater. A thermal development apparatus, which performs thermal development by passing a thermal development image recording material.
The plate heater is divided into 2 to 6 stages and the tip is 1
It is preferable to lower the temperature by about 10 ° C. For example, there is an example in which four sets of plate heaters that can be independently temperature controlled are used and are controlled to 112 ° C., 119 ° C., 121 ° C. and 120 ° C., respectively. Such a method is disclosed in
No. 54-30032, it is possible to exclude water and organic solvent contained in the heat-developable image recording material from the system, and by rapidly heating the heat-developable image recording material. It is also possible to suppress changes in the shape of the support of the heat-developable image recording material.

The photosensitive recording material of the present invention is preferably exposed for a short time with light having a high illuminance of 1 mW / mm ² or more. When exposure is performed at such a high illuminance, sufficient sensitivity can be obtained even in the heat developing material containing the high iodide silver halide emulsion of the present application and the non-photosensitive organic silver salt. That is, high sensitivity can be obtained in the high illuminance exposure of the present application, as compared with the low illuminance exposure.
More preferably, the illuminance is ² mW / mm ² or more and 50 W / mm ²
Or less, more preferably 10 mW / mm ² or more 5
It is 0 W / mm ² or less.

Any light source may be used as long as it is such a light source, but a laser beam can be preferably used. As a laser beam which is preferably used in the present invention, a gas laser (Ar ⁺ , Kr), a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a laser and a second harmonic generating element can be used. A gas or semiconductor laser emitting red to infrared light is preferable. A blue-violet emitting semiconductor laser is also preferable,
An example of a high output semiconductor laser emitting blue to purple is Nichia's "NLHV3000E" semiconductor laser.

Fuji Medical Dry Laser Imager FM-DP L can be mentioned as a medical laser imager equipped with an exposure section and a heat development section.
Regarding FM-DP L, Fuji Medical Review No.
It is needless to say that those techniques are applied as a laser imager of the heat-developable image recording material of the present invention. It can also be applied as a heat-developable image recording material for a laser imager in "AD network" proposed by Fuji Medical System as a network system adapted to the DICOM standard.

The heat-developable image recording material of the present invention forms a black and white image by a silver image, and is a heat-developable image recording material for medical diagnosis, heat-developable image recording material for industrial photography, heat-developable image recording material for printing, COM. It is preferably used as a heat-developable image recording material.

[0273]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. [Example 1]

(Preparation of PET support) Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 according to a conventional method.
(Phenol / tetrachloroethane = 6/4 (mass ratio) in 25 ℃
PET) was obtained. After pelletizing this, 13
It was dried at 0 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die and rapidly cooled to prepare an unstretched film having a thickness of 175 μm after heat setting.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then laterally stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C and 130 ° C, respectively.
Then, after heat setting at 240 ° C. for 20 seconds, 4% relaxation was carried out in the lateral direction at the same temperature. After slitting the chuck part of the tenter, both ends were knurled and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

(Surface corona treatment) Using a solid state corona treatment machine "6KVA model" manufactured by Pillar, both sides of the support were subjected to corona treatment at room temperature at 20 m / min. From the readings of current and voltage at this time,
It was found that 0.375 kV · A · min / m ² was processed.
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.

[0277]   (Preparation of undercoat support) (1) Preparation of coating liquid for undercoat layer   <Prescription: For undercoat layer on photosensitive layer side> -"Pethresin A-520" (30 mass% solution) made by Takamatsu Yushi Co., Ltd. 59 g ・ Polyethylene glycol monononyl phenyl ether   (Average ethylene oxide number = 8.5) 10 mass% solution 5.4 g ・ "MP-1000" manufactured by Soken Chemical Industry Co., Ltd.   (Polymer fine particles, average particle size 0.4 μm) 0.91 g ・ Distilled water 935 ml

[0278]   <Prescription: Back side first layer> ・ Styrene-butadiene copolymer latex 158 g   (Solid content 40 mass%, styrene / butadiene mass ratio = 68/32) * 2,4-dichloro-6-hydroxy-S-triazine sodium salt   (8 mass% aqueous solution) 20 g ・ Sodium laurylbenzene sulfonate (1% by mass aqueous solution) 10 ml ・ Distilled water 854ml

<Prescription: For Back Side Second Layer> SnO ₂ / SbO (9/1 mass ratio, average particle size 0.038 μm, 17 mass% dispersion) 84 g Gelatin (10 mass% aqueous solution) 89.2 g Shin-Etsu Chemical Co., Ltd. "Metroses TC-5" (2 mass% aqueous solution) 8.6 g-Soken Chemical Co., Ltd. "MP-1000" 0.01 g-Sodium dodecylbenzene sulfonate (1 mass% aqueous solution) 10 ml ・ NaOH (1 mass%) 6 ml ・ "Proxel" made by ICI 1 ml ・ Distilled water 805 ml

Both sides of the 175 μm-thick biaxially stretched polyethylene terephthalate support were subjected to the corona discharge treatment, and then one side (the photosensitive layer side) of the undercoat coating solution formulation was coated with a wire bar to give a wet coating amount of 6.6. ml /
m ² (per side) and dry at 180 ° C for 5 minutes, then apply the above-mentioned undercoat solution formulation to the back side (back side) with a wire bar so that the wet coating amount becomes 5.7 ml / m ² . Apply and dry at 180 ° C for 5 minutes, and then apply the above-mentioned undercoating liquid formulation on the back side with a wire bar to apply a wet amount of 7.7 m.
l / m ² was applied and dried at 180 ° C for 6 minutes to prepare an undercoat support.

(Preparation of backside coating liquid) (Preparation of solid fine particle dispersion liquid (a) of base precursor) 1.5 kg of base precursor compound 1 and 225 g of surfactant (trade name: DEMOL N, manufactured by Kao Corporation) , 937.5 g of diphenyl sulfone, 15 g of para-hydroxybenzoic acid butyl ester (trade name: Platin: manufactured by Ueno Pharmaceutical Co., Ltd.) and distilled water were added to a total amount of 5.0 kg and mixed, and the mixture was mixed in a horizontal sand mill (UVM-2: AIMEX ( Beads) were dispersed using Dispersion method: average diameter of mixed liquid 0.5m
The UVM-2 filled with m zirconia beads was fed by a diaphragm pump and dispersed under an internal pressure of 50 hPa or more until a desired average particle size was obtained. The dispersion was measured for spectroscopic absorption and the ratio of the absorbance at 450 nm and the absorbance at 650 nm (D450 / D650) in the spectral absorption of the dispersion was 2.
Dispersed to a point of 2 or more. The resulting dispersion is
Dilute with distilled water so that the concentration of the base precursor is 20% by mass, and filter for removing dust (average pore size: 3 μm).
m polypropylene filter) was used for practical use.

(Preparation of Dye Solid Fine Particle Dispersion) 6.0 kg of cyanine dye compound-1 and 3.0 kg of sodium p-dodecylbenzenesulfonate, 0.6 kg of surfactant Demol SNB manufactured by Kao Corporation, and defoaming agent ( Brand name: Surfynol 104E, manufactured by Nisshin Chemical Co., Ltd. 0.15 kg was mixed with distilled water to give a total liquid volume of 60 kg. The mixed solution was dispersed with 0.5 mm zirconia beads using a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.). The dispersion is measured by spectroscopic absorption measurement to determine the spectral absorption of the dispersion.
Ratio of absorbance at 650 nm and absorbance at 750 nm (D650
/ D750) was dispersed up to a value of 5.0 or more. The obtained dispersion was diluted with distilled water so that the concentration of the cyanine dye was 6% by mass, filtered with a filter (mean pore size: 1 μm) for dust removal, and put into practical use.

(Preparation of coating liquid for antihalation layer) Gelatin 30 g, polyacrylamide 24.5 g, 1 mol / l caustic 2.2 g, monodisperse polymethylmethacrylate fine particles (average particle size 8 μm, particle size standard deviation 0.4) 2.4 g, benzo Isothiazolinone 0.08 g, the above dye solid fine particle dispersion 35.9
g, 74.2% of the solid fine particle dispersion (a) of the above base precursor.
g, sodium polyethylene sulfonate 0.6 g, blue dye compound-1 0.21 g, yellow dye compound-1 0.15 g, acrylic acid / ethyl acrylate copolymer latex (copolymerization ratio 5/95) 8.3 g, and water At 8183
The anti-halation layer coating solution was prepared in the amount of ml.

(Preparation of Backside Protective Layer Coating Solution) The container was kept warm at 40 ° C., gelatin 40 g, liquid paraffin emulsion as liquid paraffin 1.5 g, benzisothiazolinone 35 mg,
1 mol / l caustic 6.8 g, sodium t-octylphenoxyethoxyethane sulfonate 0.5 g, sodium polystyrene sulfonate 0.27 g, fluorine-based surfactant (F
-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt) 37 mg, fluorine-based surfactant (F
-2: Polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [ethylene oxide average degree of polymerization 15]) 150 mg, fluorine-based surfactant (F-3) 64 mg, fluorine-based interface 32 mg of activator (F-4), 6.0 g of acrylic acid / ethyl acrylate copolymer (copolymerization mass ratio 5/95), and 2.0 g of N, N-ethylenebis (vinylsulfoneacetamide) were mixed, and 10 liters of water were mixed. Was used as the backside protective layer coating solution.

(Preparation of Silver Halide Emulsion) <Preparation of Silver Halide Emulsion 1> To 1421 ml of distilled water was added 3.1 ml of 1% by mass potassium bromide solution, and 3.5 ml of sulfuric acid having a concentration of 0.5 mol / L was further phthalated. While stirring the liquid containing 31.7 g of gelatin in a stainless steel reaction pot, keep the liquid temperature at 35 ° C,
Solution A prepared by adding distilled water to 22.22 g of silver nitrate and diluting it to 195.6 ml.
A solution B prepared by diluting 13.7 g of potassium bromide and 2.6 g of potassium iodide with distilled water to a volume of 218 ml was added over 45 seconds at a constant flow rate. Then, 10 ml of 3.5 mass% hydrogen peroxide aqueous solution was added, and 10.8 ml of 10 mass% benzimidazole aqueous solution was further added.

Further, distilled water was added to 51.86 g of silver nitrate to obtain 317.
A solution C prepared by diluting 5 ml of solution C, 31.9 g of potassium bromide and 6.1 g of potassium iodide with distilled water to a volume of 600 ml was prepared.
Solution C was added at a constant flow rate over 120 minutes, and solution D was added.
Was added by the controlled double jet method while maintaining pAg at 8.1. 10 minutes after starting the addition of Solution C and Solution D, the total amount of potassium hexachloroiridium (III) salt was added so that the concentration was 1 × 10 ⁻⁴ mol per mol of silver.
Further, 5 seconds after the addition of the solution C was completed, an aqueous solution of potassium iron (II) cyanide cyanide was added in an amount of 3 × 10 ⁻⁴ mol per mol of silver. Adjust the pH to 3.8 with 0.5 mol / L sulfuric acid,
The stirring was stopped and the sedimentation / desalting / water washing steps were performed. 1 mol / L
Adjust to pH 5.9 with concentrated sodium hydroxide and p
A silver halide dispersion of Ag8.0 was prepared.

While stirring the above silver halide dispersion,
0.34% by mass of 1,2-benzisothiazoline maintained at
After adding 5 ml of a methanol solution of -3-one and 40 minutes later, a methanol solution having a molar ratio of the spectral sensitizing dye A and the sensitizing dye B of 1: 1 was added to the total amount of the sensitizing dyes A and B per silver mole of 1.2 ×. 10 ^-3
A mole was added, and 1 minute later, the temperature was raised to 47 ° C. After 20 minutes of heating, sodium benzenethiosulfonate was added to a solution of silver in silver.
Add 7.6 × 10 ^-5 mol to 1 mol, and after 5 minutes, add tellurium sensitizer C with methanol solution to 2.9 × 10 ^-4 per mol of silver.
A mole was added and the mixture was aged for 91 minutes. 1.3 ml of 0.8 mass% methanol solution of N, N'-dihydroxy-N "-diethylmelamine was added, and 4 minutes later, 5-methyl-2-mercaptobenzimidazole was added in methanol solution to 4.8 × 10 ^-3 per 1 mol of silver. And 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in methanol solution at 5.4 × 1 for 1 mol of silver.
Silver halide emulsion 1 was prepared by adding 0 ^-3 mol and mercapto compound-2 in an aqueous solution at 1.5 × 10 ^-2 mol per mol of silver.

The grains in the prepared silver halide emulsion are as follows:
The silver iodobromide grains had an average equivalent sphere diameter of 0.042 μm and a variation coefficient of the equivalent sphere diameter of 18% and uniformly contained 12 mol% of iodine. Here, the particle size and the like were determined from the average of 1000 particles using an electron microscope.

<Preparation of Mixed Emulsion A for Coating Solution> Silver halide emulsion 1 was dissolved, and benzothiazolium iodide was added in an amount of 1% by mass aqueous solution to 7 × 10 ⁻³ mol per mol of silver. Then, the compound represented by the general formula (I) shown in Table 1 was added in an amount of 1 × 10 ⁻³ mol per mol of silver halide, and the content of silver halide per 1 kg of the mixed emulsion for coating solution was silver. Was added to give 38.2 g.

<Preparation of silver fatty acid dispersion> 87.6 Kg of behenic acid (product name "Edenor C22-85R") manufactured by Henkel, distilled water 42
3 L, 49.2 L of a 5 mol / L concentration aqueous NaOH solution, and 120 L of t-butyl alcohol were mixed and stirred at 75 ° C. for 1 hour to react to obtain a sodium behenate solution. Separately, 206.2 L (pH 4.0) of an aqueous solution of 40.4 kg of silver nitrate was prepared and kept at 10 ° C. 635
Keep the reaction vessel containing 30 L of distilled water and 30 L of t-butyl alcohol at 30 ° C., and while thoroughly stirring, keep the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution at a constant flow rate for 93 minutes 15 seconds respectively. And added over 90 minutes.

At this time, only the silver nitrate aqueous solution was added for 11 minutes after the addition of the silver nitrate aqueous solution was started, and then the sodium behenate solution was added, and the sodium behenate solution was added for 14 minutes and 15 seconds after the addition of the silver nitrate aqueous solution was completed. Only the additive was added. At this time, the temperature in the reaction vessel is 30
The external temperature was controlled so that the solution temperature became constant. In addition, the piping of the addition system of the sodium behenate solution is
The temperature was maintained by circulating hot water outside the double pipe, and the liquid temperature at the outlet of the addition nozzle tip was adjusted to 75 ° C.
Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The position of addition of the sodium behenate solution and the position of addition of the aqueous solution of silver nitrate were symmetrically arranged around the stirring axis, and the height was adjusted so as not to 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, heated to 35 ° C. over 30 minutes, and then aged for 210 minutes. Immediately after aging,
The solid content is separated by centrifugal filtration, and the solid content has a conductivity of filtered water.
It was washed with water until it reached 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without being dried.

The morphology of the obtained silver behenate particles was observed by an electron microscope. As a result, the average value was a = 0.14 μm and b =
It was a scaly crystal having 0.4 μm, c = 0.6 μm, an average aspect ratio of 5.2, an average equivalent sphere diameter of 0.52 μm, and a variation coefficient of the equivalent sphere diameter of 15%. (A, b, c are as defined in this specification)

[0294] Polyvinyl alcohol (trade name "PVA-217") was added to a wet cake having a dry solid content of 260 kg.
3 kg and water were added to make the total amount 1000 kg, and the mixture was slurried with a dissolver blade and further preliminarily dispersed with a pipeline mixer ("PM-10 type" manufactured by Mizuho Industry Co., Ltd.).

Next, the pre-dispersed stock solution was adjusted to a pressure of 12 with a disperser (trade name "Microfluidizer M-610", manufactured by Microfluidex International Corporation, using Z type interaction chamber).
It was adjusted to 60 kg / cm ² and treated three times to obtain a silver behenate dispersion. The cooling operation was performed by installing a spiral heat exchanger in front of and behind the interaction chamber, and adjusting the temperature of the refrigerant to set the dispersion temperature to 18 ° C.

(Preparation of reducing agent dispersion)

<Preparation of Reducing Agent-1 Dispersion> Reducing Agent-1 (6,
6'-di-t-butyl-4,4'-dimethyl-2,2'-butylidene diphenol) and modified polyvinyl alcohol (Kuraray Co., Ltd.)
16 kg of a 10 mass% aqueous solution of "Poval MP203" manufactured by
0 kg was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and the average diameter is 0.5 mm.
After dispersing for 3 hours and 30 minutes in a horizontal sand mill ("UVM-2" manufactured by IMEX Co., Ltd.) filled with zirconia beads, 0.2 g of benzoisothiazolinone sodium salt and water were added to reduce the concentration of the reducing agent to 25. The reducing agent-2 dispersion was prepared by adjusting the amount to be% by mass. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 1.5.
It was less than μm. The resulting reducing agent dispersion has a pore size of 3.0μ.
m was filtered through a polypropylene filter to remove foreign matters such as dust and stored.

<Preparation of Hydrogen-bonding Compound-1 Dispersion> 10 kg of hydrogen-bonding compound-1 (tri (4-t-butylphenyl) phosphine oxide) and modified polyvinyl alcohol (POVAL MP203 manufactured by Kuraray Co., Ltd.) 10 mass% aqueous solution 16K
10 g of water was added to g 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 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt 0.2. Add g and water to adjust the concentration of the reducing agent to 25% by mass,
A dispersion of hydrogen bonding compound-1 was obtained. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.35 μm.
m, and the maximum particle diameter was 1.5 μm or less. The obtained hydrogen-bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<Preparation of Development Accelerator-1 Dispersion> 10 kg of development accelerator-1 and modified polyvinyl alcohol (Kuraray Co., Ltd.)
Manufactured by Poval MP203), 20 kg of 10 mass% aqueous solution, 10 kg of water
Was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed for 3 hours and 30 minutes by a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to adjust the concentration of the reducing agent to 20% by mass to obtain a dispersion of development accelerator-1. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.48 μm and a maximum particle diameter of 1.4.
It was less than μm. The resulting reducing agent dispersion has a pore size of 3.0μ.
m polypropylene filter to remove foreign matters such as dust, and stored.

The solid dispersions of Development Accelerator-2, Development Accelerator 3 and Color Tone Adjuster-1 were also dispersed in the same manner as in Development Accelerator-1 to obtain a 20% by mass dispersion.

(Preparation of Polyhalogen Compound) <Preparation of Organic Polyhalogen Compound-1 Dispersion> 10 kg of organic polyhalogen compound-1 (tribromomethanesulfonylbenzene) and modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) 20 mass% aqueous solution 10 kg and 20 mass% aqueous solution of sodium triisopropylnaphthalene sulfonate
0.4 kg and 14 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump, and after being dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, 0.2 g of benzoisothiazolinone sodium salt was added. Water was added to adjust the concentration of the organic polyhalogen compound to 26% by mass to obtain an organic polyhalogen compound-1 dispersion. The organic polyhalogen compound particles contained in the thus obtained polyhalogen compound dispersion have a median diameter of 0.41 μm,
The maximum particle size was 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign matters such as dust and stored.

<Preparation of Organic Polyhalogen Compound-2 Dispersion> 10 kg of organic polyhalogen compound-2 (N-butyl-3-tribromomethanesulfonylbenzamide) and a modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) 1
20 kg of a 0 mass% aqueous solution and 0.4 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump, and after being dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, 0.2 g of benzoisothiazolinone sodium salt was added. Water was added so that the concentration of the organic polyhalogen compound was adjusted to 30% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-2 dispersion. The organic polyhalogen compound particles contained in the thus obtained polyhalogen compound dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 1.3 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<Preparation of Phthalazine Compound-1 Solution> 8 kg of modified polyvinyl alcohol MP203 manufactured by Kuraray Co., Ltd. in water 17
Dissolve in 4.57Kg, then 3.15Kg of 20 mass% aqueous solution of sodium triisopropylnaphthalene sulfonate and 70 mass% of phthalazine compound-1 (6-isopropylphthalazine)
An aqueous solution of 14.28 Kg was added to prepare a 5 mass% solution of phthalazine compound-1.

(Preparation of mercapto compound) <Preparation of mercapto compound-1 aqueous solution> 7 g of mercapto compound-1 (1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt) was dissolved in 993 g of water to give 0.7
A mass% aqueous solution was used.

<Preparation of Mercapto Compound-2 Aqueous Solution> Mercapto Compound-2 (1- (3-methylureido) -5-
20 g of mercaptotetrazole sodium salt) 980 g of water
To give a 2.0 mass% aqueous solution.

<Preparation of Pigment-1 Dispersion> CI Pigment Blue
To 64 g of 60 and 6.4 g of Demol N manufactured by Kao Corporation, 250 g of water was added and mixed well to obtain a slurry. Prepare 800 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and disperse them with a disperser (1 / 4G sand grinder mill: manufactured by AIMEX Co., Ltd.) for 25 hours to obtain pigment-1 dispersion. It was The pigment particles contained in the thus-obtained pigment dispersion had an average particle diameter of 0.21 μm.

<Preparation of SBR Latex Liquid> SBR latex having Tg = 22 ° C. was prepared as follows. Ammonium persulfate was used as a polymerization initiator, an anionic surfactant was used as an emulsifier, and 70.0 mass of styrene and 2 parts of butadiene were used.
After emulsion polymerization of 7.0 mass and 3.0 mass of acrylic acid, aging was carried out at 80 ° C. for 8 hours. Thereafter, the mixture was cooled to 40 ° C., pH was adjusted to 7.0 with aqueous ammonia, and Sandet BL manufactured by Sanyo Kasei Co., Ltd. was further added so as to be 0.22%. Next, a 5% aqueous sodium hydroxide solution was added to adjust the pH to 8.
The pH was adjusted to 3, and the pH was adjusted to 8.4 with aqueous ammonia. The molar ratio of Na ⁺ ion and NH ₄ ⁺ ion used at this time was 1: 2.3. Further, 0.15 ml of a 7% aqueous solution of benzoisothiazolinenon sodium salt was added to 1 kg of this solution to prepare an SBR latex solution.

(SBR latex: -St (70.0) -Bu (27.0) -AA
(3.0) -Latex) Tg = 22 ℃, average particle size 0.1μm, concentration 43 mass%, equilibrium water content 0.6 mass% at 25 ℃ 60% RH, ionic conductivity 4.2mS / cm (Ion conductivity is measured by Toa Using Denki Kogyo Co., Ltd. CM-30S conductivity meter,
Latex stock solution (43% by mass) measured at 25 ℃), pH 8.4Tg
Different SBR latices can be adjusted by the same method by appropriately changing the ratio of styrene and butadiene.

<Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1> 1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, 32.8 g of pigment-1 dispersion, 21 g of organic polyhalogen compound-1 dispersion, Organic polyhalogen compound-2 dispersion 58g, phthalazine compound-1 solution 173g, SBR latex (Tg: 20 ° C) solution 1082
g, reducing agent-2 dispersion 155 g, hydrogen bonding compound-1 dispersion 55 g, development accelerator-1 dispersion 6 g, development accelerator-
2 g of Dispersion 2; Development Accelerator-3, 3 g; Color Toner-1 Dispersion, 2 g; Mercapto Compound-1 Aqueous Solution 9 ml;
27 ml of an aqueous solution of mercapto compound-2 was sequentially added, and 117 g of silver halide mixed emulsion A was added immediately before coating, and the well mixed emulsion layer coating solution was directly sent to a coating die for coating.

The viscosity of the emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki Co., Ltd., and it was 4 at 40 ° C. (No. 1 rotor, 60 rpm).
It was 0 [mPa · s]. The viscosity of the coating solution at 25 ° C using a Rheometrics Far East Co., Ltd. RFS fluid spectrometer has shear rates of 0.1, 1, 10, 10
530, 144, 96, 51, 28 at 0 and 1000 [1 / sec] respectively
It was [mPa · s]. The amount of zirconium in the coating solution is 1 g of silver
Per 0.25 mg.

<Preparation of coating solution for intermediate layer on emulsion side> Polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) 1000 g, 5% by mass of pigment
272 g of dispersion, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5/2) 19% by mass latex 4200 ml aerosol OT (American Cyana (Manufactured by Mido Co., Ltd.) 27 ml of 5% by mass aqueous solution, 135 ml of 20% by mass aqueous solution of diammonium phthalate salt, water is added to a total amount of 10,000 g, and the pH is adjusted to 7.5 with NaOH to apply the intermediate layer. The solution was sent to the coating die at 9.1 ml / m ² . The viscosity of the coating liquid was 58 [mPa · s] at 40 ° C. with a B type viscometer (No. 1 rotor, 60 rpm).

<Preparation of Coating Solution for Emulsion Surface Protective Layer 1st Layer> 64 g of inert gelatin was dissolved in water to prepare methyl methacrylate /
Styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5
/ 2) Latex 27.5 mass% liquid 80g, phthalic acid 10 mass%
23 ml of methanol solution, 23 ml of 10 mass% 4-methylphthalic acid aqueous solution, 28 ml of 0.5 mol / L sulfuric acid, aerosol OT
5 ml of a 5 mass% aqueous solution of (American Cyanamid),
Phenoxyethanol 0.5 g, benzisothiazolinone 0.
Add 1 g and add water to make a total amount of 750 g to make a coating solution, and mix 26 ml of 4% by weight chromium alum just before coating with a static mixer and send it to a coating die at 18.6 ml / m ^2. Liquor The viscosity of the coating liquid was 20 [mPa · s] at 40 ° C. with a B type viscometer (No. 1 rotor, 60 rpm).

<Preparation of Coating Solution for Second Layer of Emulsion Protective Layer> 80 g of inert gelatin was dissolved in water to prepare methyl methacrylate /
Styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5
/ 2) 102 g of latex 27.5% by mass liquid, 3.2 ml of 5% by mass solution of fluorosurfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt), fluorosurfactant (F -2: Polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-
Aminoethyl) ether [Ethylene oxide average degree of polymerization = 1
5]) 2% by mass aqueous solution 32 ml, Aerosol OT (manufactured by American Cyanamid) 23% by mass solution, polymethylmethacrylate fine particles (average particle size 0.7 μm) 4 g, polymethylmethacrylate fine particles (average particle size) Diameter 4.5 μm) 21 g, 4-methylphthalic acid 1.6 g, phthalic acid 4.8 g, 0.5 mol / L concentration of sulfuric acid
44 ml, benzisothiazolinone 10 mg with water added to bring the total amount to 650 g, and a mixture of 4% by mass chromium alum and 445 ml of an aqueous solution containing 0.67% by mass phthalic acid in a static mixer just before coating was applied to the surface. The coating solution for the protective layer was sent to the coating die at 8.3 ml / m ² . The viscosity of the coating liquid is B type viscometer 40 ℃ (No.1 rotor, 60rp
It was 19 [mPa · s] in m).

<Preparation of heat-developable image recording material-1> An antihalation layer coating solution was applied to the back side of the undercoat support so that the gelatin coating amount was 0.44 g / m ^2, and the back side protective layer coating solution was used. Was coated at the same time so that the gelatin coating amount was 1.7 g / m ² and dried to form a back surface layer.

Simultaneous multilayer coating was performed on the surface opposite to the back surface from the undercoating surface in the order of emulsion layer, intermediate layer, protective layer first layer, protective layer second layer by a slide bead coating method, and a sample of a heat-developable image recording material was obtained. Created. At this time, the emulsion layer and the intermediate layer are 31 ° C.
The temperature of the first protective layer was adjusted to 36 ° C, and the temperature of the first protective layer was adjusted to 37 ° C.

The coating amount (g / m ² ) of each compound in the emulsion layer is as follows.・ Silver behenate 5.55 ・ Pigment (CIPigment Blue 60) 0.036 ・ Polyhalogen compound-1 0.12 ・ Polyhalogen compound-2 0.37 ・ Phthalazine compound-1 0.19 ・ SBR latex 9.97 ・Reducing agent-1 0.81 ・ Hydrogen-bonding compound-1 0.30 ・ Development accelerator-1 0.024 ・ Development accelerator-2 0.010 ・ Development accelerator-3 0.015 ・ Color tone adjuster-1 0.010 ・ Mercapto compound-1 0.002 ・ Mercapto compound-2 0.012 ・ Silver halide (as Ag) 0.091

The coating and drying conditions are as follows. The coating was performed at a speed of 160 m / min, the gap between the tip of the coating die and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set to 196 to 882 Pa lower than the atmospheric pressure. Prior to coating, the support was neutralized with an ionic wind. In the subsequent chilling zone,
After cooling the coating liquid with a wind having a dry-bulb temperature of 10 to 20 ° C., the coating liquid is conveyed in a non-contact type, and a dry-bulb temperature of 23 to 45 ° C. and a wet-bulb temperature of 15 to 21 are measured by a spinning type non-contact type drying device. It was dried with a drying air of ° C. After drying, the humidity was adjusted to 40 to 60% RH at 25 ° C, and then the film surface was heated to 70 to 90 ° C.
After heating, the film surface was cooled to 25 ° C.

The matte degree of the produced heat-developable image recording material was Beck smoothness, 550 seconds on the side of the photosensitive layer and 130 seconds on the back side. Also, when the pH of the film surface on the photosensitive layer side was measured
It was 6.0.

The chemical structures of the compounds used in the examples of the present invention are shown below.

[0320]

[Chemical 54]

[0321]

[Chemical 55]

[0322]

[Chemical 56]

[0323]

[Chemical 57]

The obtained sample was cut into half-size pieces, packaged in the following packaging materials in an environment of a temperature of 25 ° C. and a humidity of 50%, and stored at room temperature for 2 weeks. (Packaging material) PET 10μm / PE 12μm / Aluminum foil 9μm / Ny 15μm / Polyethylene 50μm containing 3% carbon Oxygen permeability: 0.02ml / atm ・ m ²・ 25 ℃ ・ day, Moisture permeability: 0.10g / atm ・m ² · 25 ℃ · day

<Preparation of heat-developable image recording materials-2 to 8> In the same manner as in <Preparation of silver halide emulsion 1>, but by changing the halogen composition to be added, a uniform composition as shown in Table 1 can be obtained. A silver halide emulsion having a different halogen composition,
3 was prepared. The grain size of silver halide can be adjusted by changing the temperature at the time of grain formation to obtain an average equivalent spherical diameter of 0.
040 μm was prepared. The same procedure as in the heat-developable image recording material-1 except that the compounds represented by the general formula (I) were changed as shown in Table 1 by using the above silver halide emulsions 1, 2, and 3. Heat developable image recording materials-2 to 8 were prepared.

<Evaluation of Photosensitive Recording Material> The sample was exposed with a Fuji Medical Dry Laser Imager “FM-DPL” (equipped with a 660 nm semiconductor laser with a maximum output of 60 mW (IIIB)) and exposed (112 ° C.-119 ° C.-121). Thermal development was performed with four panel heaters set at a temperature of (C-121C) for a total of 14 seconds.

(Evaluation of Sample) The density of the obtained image was measured with a densitometer, and a characteristic curve of the density with respect to the logarithm of the exposure dose was prepared. The optical density of the unexposed portion was taken as the fog, and the reciprocal of the exposure amount at which the optical density of 3.0 was obtained was taken as the sensitivity, and the sensitivity of the photosensitive recording material 1 was taken as 100 and expressed as relative values. Also, the average contrast of the optical densities of 1.5 and 3.0 was measured. The results are shown in Table 1.

(Evaluation of Printout Performance) The photosensitive recording material after the development treatment was placed in a room at a temperature of 25 ° C. and a relative humidity of 60% and left under a fluorescent lamp at 100 lux for 30 days.
Under the above conditions, the fog density immediately after development was 3
The difference in fog density after leaving for 0 days was defined as the printout performance. It is preferable that the fog does not increase so much even if it is left under such conditions. The results are shown in Table 1.

[0329]

[Table 1]

As is clear from Table 1, the photosensitive recording material of the present invention has high sensitivity and low fog, and has preferable gradation.
It was found that the printout performance was excellent.

Example 2 <Preparation of Silver Halide Emulsion 4> To 1421 ml of distilled water was added 4.3 ml of 1% by mass potassium iodide solution, 3.5 ml of 0.5 mol / L sulfuric acid and 36.7 g of phthalated gelatin were added. While stirring the solution with added in a stainless steel reaction pot, keep the solution temperature at 42 ° C, add distilled water to 22.22 g of silver nitrate and dilute to 195.6 ml with solution A and 21.8 g of potassium iodide with a volume of distilled water. Solution B diluted to 218 ml was added at a constant flow rate over 9 minutes.

Thereafter, 1% of a 3.5% by mass hydrogen peroxide aqueous solution is added.
0 ml was added, and 10.8 ml of a 10 mass% aqueous solution of benzimidazole was further added. Further, distilled water was added to 30.64 g of silver nitrate to dilute it to 187.6 ml, and solution D of 40.0 g of potassium bromide to a volume of 400 ml was added to the solution C at a constant flow rate for 12 minutes. Then, the solution D had a pAg of 8.1.
It was added by the controlled double jet method while maintaining

After that, distilled water was added to 22.2 g of silver nitrate to prepare 13
Solution E containing 0.0 ml and solution Fto prepared by diluting 21.7 g of potassium iodide with distilled water to a volume of 217 ml were added by the controlled double jet method while maintaining pAg at 6.3. 10 minutes after starting the addition of Solution C and Solution D, the total amount of potassium hexachloroiridium (III) salt was added so that the concentration was 1 × 10 ⁻⁴ mol per mol of silver. Also, the 5 seconds after completing the addition of the solution C, hexacyanoferrate (II) and silver with an aqueous solution of potassium per mole 3 × 10 ^{- 4} mol the total amount was added. Adjust the pH to 3.8 with 0.5 mol / L sulfuric acid, stop stirring, and settle
A desalting / washing process was performed. The pH was adjusted to 5.9 with sodium hydroxide at a concentration of 1 mol / L to prepare a silver halide dispersion having a pAg of 8.0.

While stirring the above silver halide dispersion, 38
0.34% by mass of 1,2-benzisothiazoline maintained at
5 ml of 3-one methanol solution was added, and 1 minute later, the temperature was raised to 47 ° C. Sodium benzene thiosulfonate after 20 minutes of heating 7.6 × 10 ^-5 mol was added per mol of silver in methanol solution, per mol of silver 2.9 × 10 further tellurium sensitizer B in methanol solution after 5 minutes ^{- 4} mol was added and aged for 91 minutes.
1.3 ml of 0.8% by mass methanol solution of N, N'-dihydroxy-N "-diethylmelamine was added, and after further 4 minutes, 5-methyl-2
-Mercaptobenzimidazole silver in methanol 1
4.8 × 10 ^-3 mol and 1-phenyl-2-heptyl-5 per mol
-Mercapto-1,3,4-triazole in methanol solution with 5.4 × 10 ^-3 mol per mol of silver and mercapto compound-
Silver halide emulsion 1 was prepared by adding 1.5 × 10 ^-2 mol per mol of silver in an aqueous solution.

The grains in the prepared silver halide emulsion are as follows:
The particles were pure silver iodide grains having an average equivalent spherical diameter of 0.042 μm and a coefficient of variation of equivalent spherical diameter of 18%. The particle size and the like were obtained from the average of 1000 particles using an electron microscope.

<Preparation of silver halide emulsions 5 to 17> In the same manner as in <Preparation of silver halide emulsion 4>, except that the solution B,
By changing the halogen composition of D and F, a silver halide emulsion having a halogen structure as shown in Table 2
17 was prepared. Regarding the grain size of the silver halide, the average spherical equivalent diameter of 0.04 μm was prepared by changing the temperature at the time of grain formation.

<Preparation of silver halide emulsions 18 to 21> Potassium iodide was added to the emulsion in which grains were formed in the same manner as in <Preparation of silver halide emulsion 9> so that the average iodide composition shown in Table 2 was obtained. After adding the aqueous solution, silver halide emulsions 18 and 19 were prepared by performing a precipitation / desalting / washing step. Similarly to <Preparation of silver halide emulsion 6>, silver halide emulsions 20 and 21 shown in Table 2 were prepared. Among these silver halide emulsions 5 to 21, the emulsion having a crystal structure of silver iodide had light absorption due to strong direct transition.

[0338]

[Table 2]

<Preparation of heat-developable image recording material-9 to 31> In the same manner as in <Preparation of heat-developable image recording material-1> in Example 1, except that the compound represented by formula (I) is Thermal development image recording materials-9 to 31 as shown in Table 3 were prepared in the same manner as the development image recording material-1.

The obtained heat-developable image recording material was evaluated as follows. (Exposure of Photosensitive Recording Material) The photosensitive recording material obtained in Example 2 was exposed as follows. Fuji Medical Dry Laser Imager "FM-DPL" exposed area is equipped with Nichia Corporation's "NLHV3000E" semiconductor laser as a semiconductor laser light source, and the beam diameter is narrowed to reduce the beam diameter of the photosensitive recording material surface illuminance. Was varied between 0 and 1 to 1000 mW / mm ² , and the photosensitive material was exposed for 10 ⁻⁶ seconds. The emission wavelength of laser light is 405 nm
Met.

(Development of Photosensitive Recording Material) The exposed light-sensitive material was subjected to heat development treatment as follows. Fuji Medical Dry Laser Imager "FM-DP L" heat development part, 4 panel heaters 112 ℃ -110 ℃
Thermal development was carried out by setting the temperature to -110 ° C-110 ° C and increasing the film transport speed so that the total thermal development time was 14 seconds. The sample was evaluated in the same manner as in Example 1, and the obtained results are shown in Table 3.

[0342]

[Table 3]

As is clear from Table 3, the photosensitive recording material of the present invention was found to exhibit excellent performance even under blue laser exposure.

[Example 3] Pure silver iodide emulsion 22 having an average grain size of 100 nm was prepared in the same manner as in <Preparation of silver halide emulsion 4> in Example 2, except that the temperature during grain formation was changed. It was created. This pure silver iodide emulsion 2
The thermal development image recording materials 32, 33 and 34 shown in Table 4 were prepared in the same manner as the photosensitive recording material 9 of Example 2 except that the coating amount of 2 was changed. The photographic properties were evaluated in the same manner as in Example 2. Here, the maximum optical density of the sample after heat development was defined as Dmax. The results are shown in Table 34.
Shown in.

[0345]

[Table 4]

As is clear from Table 4, when the average grain size of the silver iodide emulsion was as large as 100 nm, sufficient sensitivity could not be obtained and Dmax was lowered. Normally, the absorption of silver halide is proportional to the cube of the average grain size, and therefore a larger size silver halide should provide higher sensitivity.
The high silver iodide type emulsion in the present invention does not always have to be such. By decreasing the average particle size, the sensitivity is high relative to the size, and at the same time, Dmax is also increased, which is preferable.

[Example 4] Pure iodine having an average grain size of 70 nm and a coefficient of variation of 8% was prepared in the same manner as in <Preparation of silver halide emulsion 4> in Example 2 except that the temperature during grain formation was raised. A silver halide emulsion 23 was prepared. Similarly, by changing the temperature at the time of particle formation, the average particle size is 28 nm,
A pure silver iodide emulsion 24 having a coefficient of variation of 12% was prepared.

Thermal development image recording material-9, except that a mixture of silver halide emulsions 4, 23 and 24 in a ratio of 60:15:25 was added in place of the silver halide emulsion 4 in the heat-developable image recording material-9. A heat-developable image recording material 35 was prepared in the same manner as in Example 2. As a result of performing the same evaluation as in Example 2, favorable results were obtained. The average contrast of the photosensitive recording material 35 was 2.7. Similarly, the silver halide emulsion 12 and the silver halide emulsion 23 were mixed at a ratio of 85:15 to prepare a heat developable image recording material 36. As a result of performing the same evaluation as in Example 2, favorable results were obtained. In this way, the silver halide emulsions of the present invention can be mixed with each other in an arbitrary ratio and used.

[Example 5] In the same manner as in <Preparation of silver halide emulsions 4 to 21> of Example 2, except that 3 minutes after the addition of the tellurium sensitizer, potassium iodoaurate was added to 5 mol per mol of silver. A silver halide emulsion 25 was prepared in the same manner as in the silver halide emulsions 4 to 21 of Example 2 except that x10 ^-4 mol and 2 × 10 ^-3 mol of potassium thiocyanate were added per mol of silver. ~ 42 was prepared. Using these emulsions, thermal development image recording materials 37 to 54 were prepared in the same manner as the thermal development image recording material 9 of Example 2. As a result of performing the same evaluation as in Example 2, the sensitivity was doubled, but no fog and printout performance were observed, and favorable results were obtained.

[Example 6] In the heat-developable image recording material 9 of Example 2, the fluorine-containing surfactants F-1, F-2, F-3 and F-4 in the back surface protective layer and the emulsion surface protective layer were used. , Except that they are changed to F-5, F-6, F-7, and F-8, respectively.
A thermal development image recording material 55 was prepared in the same manner as the thermal development image recording material 9. When evaluated in the same manner as in Example 2, the same favorable results as with the heat-developable image recording material 9 were obtained.

[0351]

[Chemical 58]

[0352]

[Chemical 59]

[0353]

According to the present invention, it is possible to provide a high-sensitivity and high-quality heat-developable image recording material comprising a high silver iodide type silver halide photosensitive recording material and a heat-development method using the same.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H123 AB00 AB03 AB06 AB23 AB28                       BB00 BB22 BB33 CB00 CB03                       CB20

Claims (12)

[Claims] 1. A heat-developable image recording material containing at least one layer of a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder on a support, and the average iodide of the photosensitive silver halide. A heat-developable image recording material comprising a silver halide having a silver content of 5 to 100 mol% and at least one compound represented by the following general formula (I). [Chemical 1] [In the Formula, X is at least 1 of N, S, P, Se, or Te.
Represents a silver halide adsorption group or a light absorption group having one atom. L represents a (k + n) -valent linking group having at least one atom of C, N, S and O. A represents an electron-donating group, B represents a leaving group or a hydrogen atom, and AB represents an oxidized group,
It is desorbed or deprotonated to generate a radical A. k
Represents an integer of 0 to 3, m represents 0 or 1, and n represents 1 or 2. However, when k = 0 and n = 1, m = 0
Is. ] 2. The average silver iodide content of the silver halide is 10 to 100 mol%.
The heat-developable image recording material described in 1. 3. The average silver iodide content of the silver halide is 40 to 100 mol%.
The heat-developable image recording material described in 1. 4. The heat-developable image recording material according to claim 1, wherein the silver halide grains have a direct transition absorption derived from a high silver iodide crystal structure. 5. The maximum temperature for heat development of the heat-developable image recording material according to claim 1 is 100 to 120 ° C.
And a heat development method. 6. The maximum temperature for heat development of the heat-developable image recording material according to claim 1 is 105 to 115 ° C.
And a heat development method. 7. The heat development is carried out by transporting the heat-developable image recording material according to any one of claims 1 to 4 while contacting the heat-development section comprising two to six plate-shaped heat development heaters. 7. The heat development method according to claim 5, wherein 8. The average grain size of the silver halide is
The heat-developable image recording material according to any one of claims 1 to 4, which has a thickness of 5 to 80 nm. 9. The average grain size of the silver halide is
The heat-developable image recording material according to any one of claims 1 to 4, which has a thickness of 5 to 70 nm. 10. The maximum temperature for heat development of the heat-developable image recording material according to claim 8 is 100 to 1.
A heat development method, wherein the temperature is 20 ° C. 11. The maximum temperature for heat development of the heat-developable image recording material according to claim 8 is 105 to 1
A heat development method, characterized in that the temperature is 15 ° C. 12. The heat development is carried out by transporting the heat-developable image recording material according to claim 8 while contacting the heat-development section comprising two to six plate-shaped heat development heaters. 12. The method according to claim 10 or 11, wherein
The heat development method described in.