JP2002365760A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material for a scanner and an image setter suitable for a photomechanical process and having high sensitivity, high Dmax(maximum density) and low fog with improved stability of a coating liquid and an improved state of a coated surface in the production of the photosensitive material. SOLUTION: In the heat developable photosensitive material containing at least photosensitive silver halide, a reducible non-photosensitive organic silver salt, a reducer of formula (1) (where V<1> -V<8> are each H or a substituent; L is -CH(V<9> )- or -S-; and V<9> is H or a substituent), a binder, a compound of formula (2) (where X<1> is a substituent; X<2> -X<4> are each H or a substituent; and R<1> is H, alkyl, aryl, a heterocyclic group, amino or alkoxy) and a toning agent on the same face of the support, at least part of the toning agent is contained after a complex is formed beforehand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a scanner suitable for photolithography.
More specifically, the photothermographic material for an image setter is a photothermographic material having a high sensitivity, a high Dmax (maximum density) and a low fog, and has improved stability of a coating solution and a coated surface during the production of the photosensitive material. It relates to a photothermographic material.

[0002]

2. Description of the Related Art There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, there is a technique of forming an image by thermal development as a system that contributes to environmental conservation and can simplify an image forming unit. In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there is a need to develop a technology relating to a photothermographic material for photolithography, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a sharp black image having high resolution and sharpness. is needed. According to such a photothermographic material, it is possible to supply a customer with a simpler and more environmentally friendly photothermographic processing system that does not require solution-based processing chemicals.

A method of forming an image by thermal development is described in, for example, US Pat. Nos. 3,152,904 and 3,4,904.
57,075, and D.C. Morgan
And B. "Thermally Processed Silver Systems" by Shely
A "(Imaging Processes and Materials) Neblette
Eighth Edition, Sturge, V.E. Wallwards (Wa
lworth), A. Edited by Shepp, page 2, 19
1969). Such photothermographic materials typically comprise a non-photosensitive reducible silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent dispersed in an organic binder matrix. It is contained in a state. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or more) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image formed by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas becomes black and forms an image because it contrasts with the unexposed areas.

EP 762,196A and JP-A-9-90550 disclose that a photosensitive silver halide grain used in a photothermographic material contains a Group VII or VIII metal ion or a metal complex ion. It discloses that a hydrazine derivative can be contained in a light-sensitive material to obtain high-contrast photographic characteristics. No. 5,545,5.
No. 15 describes that hindered phenol is used as a reducing agent and an acrylonitrile compound is used as a nucleating agent (in the present specification, the nucleating agent is used synonymously with a super-high contrast agent).

[0005] Examples of using a phenol compound having an amino group substituted with an electron-withdrawing group as a reducing agent (eg, a sulfonamide phenol compound) as a reducing agent have already been reported. For example, JP
As described in JP-A-80386, JP-A-5-257227 and JP-A-10-221806, 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol are reduced. It is known to use a single agent as an agent. However, even with the use of these compounds, it has not been possible to improve the sensitivity or solve the problem (particularly, fogging) that the photographic performance changes during storage of the photosensitive material. on the other hand,
As reported in Japanese Patent Application Laid-Open No. 2000-267222, a method of using an aminophenol derivative in combination with a reducing agent is also known, but one that satisfies the requirements of high Dmax (maximum density), low fog, and high contrast. Was not. For this reason, it has been desired to provide a photothermographic material for photoengraving that has high sensitivity, high Dmax (highest density), low fog, and can obtain an image suitable for photoengraving with high contrast. .

[0006] In the photothermographic material, a wide range of color toning agents are used because they are preferable in increasing the image density and forming a black silver image. In particular, phthalazine compounds can be effectively used because high image density can be obtained, for example, JP-A-7-224070,
It is described in JP-A-11-218877 and the like. However, in the photothermographic material, a color tone agent and all other materials involved in the development reaction coexist in the photothermographic material. In particular, when a reducing agent and a development accelerator are contained in the light-sensitive material, it is useful in terms of photographic properties to include them in the same layer as the color tone agent. However, there is a problem in that the filterability becomes unstable and the filterability is deteriorated, and the surface quality of the coating film is deteriorated.

[0007]

In view of these problems of the prior art, the present invention relates to (1) a method for producing a photographic plate, particularly for a scanner or an image setter, which has a sensitivity and a Dma.
(2) To provide a photothermographic material capable of obtaining an image optimal for photolithography applications having a high x (highest density) and a low fog; An object of the present invention is to provide a heat-developable recording material having good coated surface quality and stable image recording performance.

[0008]

As a result of intensive studies, the present inventors have found that an organic silver salt, which is a reducible silver salt, a binder and a toning agent, and a photosensitive silver halide are provided on the same surface of a support. In a photothermographic material having a photosensitive silver halide emulsion layer (photosensitive layer), a specific bisphenol compound and a phenol compound are contained on the image forming layer side to increase sensitivity and Dmax (maximum density). It is possible to obtain a photothermographic material that is optimal for photoengraving applications with low fog, and further contains at least a part of the above-described color tone agent after forming a complex in advance,
The presence of the complex makes it possible to suppress the deterioration of filterability due to aggregates or the like generated during preparation of the coating solution, and to provide a photothermographic material having uniform and good coating surface quality and stable image recording performance. They have found that they can do so and have reached the present invention.

That is, the present invention provides at least (a) a photosensitive silver halide, (b) a reducible non-photosensitive organic silver salt, and (c) a compound represented by the following general formula (1) on the same surface of a support. In a photothermographic material containing a reducing agent, (d) a binder, (e) a compound represented by the following general formula (2), and (f) a toning agent, at least a part of the toning agent forms a complex in advance. The present invention provides a photothermographic material characterized in that the photothermographic material is contained after the heat treatment. Further, the present invention provides a method wherein at least (a) a photosensitive silver halide is provided on the same surface of a support;
(B) a reducible non-photosensitive organic silver salt, (c) a reducing agent represented by the following general formula (1), (d) a binder, (e) a compound represented by the following general formula (2), and ( f) In a photothermographic material containing a toning agent, 70 m
The present invention provides a photothermographic material characterized in that at least ol% forms a complex.

[0010]

Embedded image [In the formula (1), V ^{1 to} V ⁸ each independently represent a hydrogen atom or a substituent, and L represents -CH (V ⁹ )-or-
Represent S- consisting linking group, V ⁹ represents a hydrogen atom or a substituent. ]

[0011]

Embedded image [In the formula (2), X ¹ represents a substituent, and X ^{2 to} X ⁴ represent a hydrogen atom or a substituent. However, X ^{1 to} X ⁴ are not hydroxyl groups, and X ³ is not a sulfonamide group. The substituents represented by X ^{1 to} X ⁴ may combine with each other to form a ring. R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, or an alkoxy group. ]

In the photothermographic material of the present invention, it is preferable that at least a part of the color toning agent forms a complex with the reducing agent represented by the formula (1); It is preferable that a part forms a complex with the metal. When the color tone agent forms a complex with the metal, the metal is preferably Zn, Ni, Mg or Ca. Further, the color tone agent is preferably a phthalazine compound represented by the following formula (3).

Embedded image [In the formula (3), Y represents a hydrogen atom or a monovalent substituent, and m represents an integer of 1 to 6. (Y) m indicates that 1 to 6 Ys are independently present on the phthalazine ring, and when m is 2 or more, even if two adjacent Ys form an aliphatic or aromatic ring, Good. ]

The photothermographic material of the present invention preferably contains a nucleating agent. The photothermographic material of the present invention has an exposure time of 10 ^-6 seconds or less; a good image can be formed even when exposure is performed by a multi-beam equipped with two or more laser heads;
Further, the line speed of the thermal development processing is 140 cm / m.
Good photographic performance can be provided even if the ratio is in or more.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photothermographic material of the present invention will be described below in detail. In this specification, “to” is a range including numerical values described before and after it as a minimum value and a maximum value. The photothermographic material of the present invention comprises, on the same surface of a support, a photosensitive silver halide emulsion layer containing an organic silver salt, which is a reducible silver salt, a binder and a toning agent, and a photosensitive silver halide. Layer). Preferably, the image forming layer contains a photosensitive silver halide and also serves as a photosensitive layer. In addition, on the image forming layer side,
By containing a specific bisphenol compound and a phenol compound, it is possible to obtain a photothermographic material which is high in sensitivity, Dmax (maximum density) and low in fog, and is most suitable for photolithography. Further, by containing at least a part of the above-mentioned color tone agent after forming a complex in advance or as a complex, it is possible to suppress deterioration in filterability due to agglomerates or the like generated at the time of preparing a coating solution, and it is uniform and favorable. It is possible to provide a photothermographic material having excellent coating surface quality and stable image recording performance.

Component (c) of the photothermographic material of the present invention.
The reducing agent represented by the above formula (1) (hereinafter, sometimes referred to as “bisphenol compound”) will be described in detail. In the formula (1), V ^{1 to} V ⁸ each independently represent a hydrogen atom or a substituent. The substituents represented by V ^{1 to} V ⁸ may be the same or different from each other, and are preferably a halogen atom (for example, a fluorine atom, a chlorine atom,
A bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 13 carbon atoms, for example, methyl, ethyl , N-propyl, isopropyl, sec-butyl, tert-butyl, tert-
Octyl, n-amyl, tert-amyl, n-dodecyl, n-tridecyl, cyclohexyl, etc., alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably 2 to 12 carbon atoms) And, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like, and an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, still more preferably having 6 to 6 carbon atoms).
12, for example, phenyl, p-methylphenyl,
Naphthyl, etc.), an alkoxy group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, methoxy, ethoxy,
Propoxy, butoxy, etc.), an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms,
More preferably, it has 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy, and an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 carbon atoms).
To 16, more preferably 2 to 12 carbon atoms, for example, acetoxy, benzoyloxy and the like, and an amino group which may be alkyl-substituted or aryl-substituted (preferably 0 to 20 carbon atoms, more preferably 1 carbon atom) To 16, more preferably 1 to 12 carbon atoms, for example, dimethylamino group, diethylamino group, dibutylamino group, anilino group, etc., acylamino group (preferably 2 to 12 carbon atoms)
20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 13 carbon atoms, for example, acetylamino, tridecanoylamino, benzoylamino and the like, a sulfonylamino group (preferably 1 to 20 carbon atoms, It preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino and the like, a ureido group (preferably 1 to 20 carbon atoms, more preferably Number 1
To 16, more preferably 1 to 12 carbon atoms, for example, ureido, methylureide, phenylureide and the like, a carbamate group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, further preferably carbon Formulas 2 to 12, for example, methoxycarbonylamino,
Phenyloxycarbonylamino, etc.), carboxyl group, carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 carbon atom)
To 12, for example, carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl and the like, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms).
6, more preferably 2 to 12 carbon atoms, for example,
Methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms), and acyl group (preferably having 6 to 12 carbon atoms). 2 to 20, more preferably 2 to 16 carbon atoms, further preferably 2 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like), sulfo group, sulfonyl group (preferably 1 to 20 carbon atoms, More preferably, it has 1 to 16 carbon atoms, and still more preferably, it has 1 to 1 carbon atoms.
12; for example, mesyl, tosyl, etc.), a sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16 carbon atoms, and still more preferably having 0 to 12 carbon atoms, for example, sulfamoyl, methyl sulfa Moyl,
Dimethylsulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, mercapto group, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms) Yes,
For example, methylthio, butylthio, etc.), a heterocyclic group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms)
6, more preferably 2 to 12 carbon atoms, for example,
Pyridyl, imidazoyl, pyrrolidyl and the like). These substituents may be further substituted with another substituent. As the other substituents, those exemplified as the examples of the above substituents can be exemplified.

Particularly preferred substituents represented by V ^{1 to} V ⁸ are alkyl groups (for example, methyl, ethyl, n
-Propyl, isopropyl, sec-butyl, tert
-Butyl, tert-octyl, n-amyl, tert
-Amyl, n-dodecyl, n-tridecyl, cyclohexyl, etc.).

In the formula (1), L is -CH (V ⁹ )-
Or an -S- consisting linking group, V ⁹ represents a hydrogen atom or a substituent. Preferred examples of the substituent represented by V ⁹ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms). Preferably 1 to 16 carbon atoms, more preferably 1 to 13 carbon atoms,
For example, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, tert-octyl, n-amyl, tert-amyl, n-dodecyl, n-tridecyl, cyclohexyl, 2,4,4-trimethylpentyl Alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, still more preferably having 2 to 12 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like), Aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 carbon atoms)
-20, more preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl, etc.), alkoxy group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, further preferably It has 1 to 12 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy and the like, an aryloxy group (preferably 6 to 3 carbon atoms)
0, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, for example, phenyloxy, 2-
An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, still more preferably having 2 to 12 carbon atoms), for example, acetoxy,
Benzoyloxy, etc.), an amino group which may be alkyl-substituted or aryl-substituted (preferably having 0 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, dimethylamino group, diethylamino group, dibutylamino group, anilino group, etc.),
Acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 13 carbon atoms)
For example, acetylamino, tridecanoylamino, benzoylamino, etc.), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, more preferably 1 to 12 carbon atoms, for example,
Methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, ureido, methyl Ureido, phenylureide, etc.), carbamate group (preferably having 2 to 20, more preferably 2 to 16, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, phenyloxycarbonylamino, etc.) , A carboxyl group, a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms,
For example, carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl and the like, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 carbon atoms) -12, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.),
An acyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 to 12 carbon atoms, such as acetyl, benzoyl, formyl, and pivaloyl), a sulfo group, and a sulfonyl group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, mesyl, tosyl and the like, a sulfamoyl group (preferably 0 to 20 carbon atoms,
More preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, hydroxyl group, A mercapto group, an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, for example, methylthio, butylthio, etc.), a heterocyclic group (preferably having 2-2
0, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, pyridyl, imidazoyl, pyrrolidyl and the like. These substituents may be further substituted with another substituent.

[0018] Particularly preferred examples of the substituent represented by V ⁹ represents an alkyl group (e.g., methyl, ethyl, n- propyl, isopropyl, sec- butyl, tert- butyl, tert- octyl, n- amyl, n -Octyl, tert-amyl, n-dodecyl, n-tridecyl, cyclohexyl, 2,4,4-trimethylpentyl and the like, an alkenyl group (for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like), an aryl group ( Examples include phenyl, p-methylphenyl, naphthyl, etc.), hydroxyl group, mercapto group, alkylthio group (eg, methylthio, butylthio, etc.). Specific examples of the bisphenol compound represented by the formula (1) are shown below, but the bisphenol compound used in the present invention is not limited to these.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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The amount of the bisphenol compound represented by the formula (1) to be used in the present invention is from 0.1 to 1 m ² per photographic material.
01-4.0 g, preferably 0.2-2.0 g
g, more preferably 0.5 to 2.0 g. Further, it is preferably contained in an amount of 2 to 40 mol, more preferably 5 to 30 mol, per 1 mol of silver on the surface having the image forming layer. The bisphenol compound used in the present invention may be added by any method such as a solution, a powder, and a solid fine particle dispersion. Dispersion of solid fine particles can be performed by a known micronizing means (for example, ball mill, vibrating ball mill, sand mill, colloid mill,
Jet mill, roller mill, etc.). Also,
When dispersing the solid fine particles, a dispersing aid may be used. The bisphenol compound used in the present invention may be added to any layer as long as it is on the same surface as the photosensitive silver halide and the reducible silver salt on the support. It is preferable to add it to the layer adjacent thereto.

Next, the compound represented by the above formula (2), which is the component (e) of the photothermographic material of the present invention (hereinafter referred to as the compound (e))
The “phenol compound” may be described in detail.

In the formula (2), X ¹ represents a substituent that can be substituted on the benzene ring (it is not a hydrogen atom). However, X ¹ is not a hydroxyl group. Specific examples of the substituent represented by X ¹ include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, acylamino group, amino Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, E group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group,
Examples include a phosphinyloxy group, a phosphinylamino group, a silyl group and the like. More specifically, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom) and an alkyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably having 1 carbon atom).
To 30 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably having 3 carbon atoms) Up to 30 substituted or unsubstituted cycloalkyl groups such as cyclohexyl, cyclopentyl,
-N-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms) For example, bicyclo [1.2.2] heptane-2-yl, bicyclo [2.2.2] octan-3-yl), and a tricyclo structure having many ring structures are also included. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 carbon atoms)
~ 30 substituted or unsubstituted bicycloalkenyl groups,
That is, it is a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.2] oct-2-en-4-yl) are included. An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example,
Ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), hetero A ring group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 3 to 30 carbon atoms; A 5- or 6-membered aromatic heterocyclic group, for example, 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, nitro group, carboxyl group,
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably Is a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t
tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5
-Oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, having 2 to 3 carbon atoms)
0 substituted or unsubstituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy ), Carbamoyloxy group (preferably having 1 to carbon atoms)
30 substituted or unsubstituted carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy, N, N-
Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms) An oxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms) For example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an acylamino group (preferably,
Formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoyl Amino, 3,4,5
-Tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N , N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Ruboniruamino group, for example, phenoxycarbonylamino, p- chlorophenoxy carbonyl amino, m-n-octyloxy phenoxy carbonyl amino), sulfamoylamino group (preferably,
A substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups ( Preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,3 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), Ali Lucio group (preferably 6 carbon atoms
30 substituted or unsubstituted arylthio such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 2 carbon atoms)
30 substituted or unsubstituted heterocyclic thio groups, for example 2
-Benzothiazolylthio, 1-phenyltetrazole-
5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfo) Famoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) A substituted alkylsulfinyl group, a 6-30 substituted or unsubstituted arylsulfinyl group, for example,
Methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 carbon atom)
~ 30 substituted or unsubstituted alkylsulfonyl groups, 6
To 30 substituted or unsubstituted arylsulfonyl groups, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms) A carbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, 4 carbon atoms
A heterocyclic carbonyl group bonded to the carbonyl group by up to 30 substituted or unsubstituted carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl,
Benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl , O-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example,
Methoxycarbonyl, ethoxycarbonyl, tert-
Butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di -N-octylcarbamoyl, N
-(Methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, for example, phenylazo , P-chlorophenylazo, 5-ethylthio-1,
3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphospho Fino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably having 2 to 2 carbon atoms)
30 substituted or unsubstituted phosphinyl groups, for example,
Phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, Dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), A silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl) is exemplified. Preferred as the substituent represented by X ¹ are a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom and a bromine atom), an acylamino group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, formylamino, acetylamino, benzoylamino and the like, alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms). Particularly preferably, it has 1 to 8 carbon atoms, for example, methyl, ethyl, isopropyl, cyclohexyl and the like, and an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 8 carbon atoms). , For example, phenyl, naphthyl,
p-methylphenyl, etc.), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy and ethoxy), an aryloxy group (preferably carbon Numbers 6 to 20,
More preferably, it has 6 to 14 carbon atoms, particularly preferably 6 to 8 carbon atoms, such as phenoxy and 2-naphthyloxy, and an acyloxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, and particularly preferably). Is 1 carbon
-8, for example, acetoxy, benzoyloxy, etc.),
Sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 1 carbon atoms)
8, for example, methanesulfonylamino, benzenesulfonylamino and the like, a carbamoyl group (preferably having 1 to 1 carbon atoms)
20, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc., an acyl group (preferably 1 to 20 carbon atoms, more preferably Is a group having 1 to 14 carbon atoms, particularly preferably a group having 1 to 8 carbon atoms, for example, formyl, acetyl, benzoyl and the like, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably being carbon atom). A number of 2 to 12, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like, an aryloxycarbonyl group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms). , For example, phenoxycarbonyl, 2-naphthyloxycarbonyl, etc.), cyano group, A b group, more preferably a halogen atom, an acylamino group, an alkyl group, particularly preferably a chlorine atom, a bromine atom.

In the formula (2), X ³ represents a hydrogen atom or a substituent. However, X ³ is not a hydroxyl group or a sulfonamide group. Specific examples of the substituent represented by X ³ include the substituents mentioned as examples of X ^{1 in} the formula (2) (however, they are not sulfonamide groups). Preferred as X ³ are a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom and a bromine atom), and an acylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 20 carbon atoms). 1
-14, particularly preferably 1-8 carbon atoms, such as formylamino, acetylamino, benzoylamino, etc.),
An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, isopropyl, cyclohexyl and the like), and an aryl group (preferably having 6 to carbon atoms) 20, more preferably 6-14 carbon atoms, particularly preferably 6-carbon atoms.
8, for example, phenyl, naphthyl, p-methylphenyl, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 14 carbon atoms, and particularly preferably having 1 to 1 carbon atoms).
8, for example, methoxy, ethoxy, etc.), an aryloxy group (preferably having 6 to 20, more preferably 6 to 14, particularly preferably 6 to 8, such as phenoxy, 2-naphthyloxy), acyloxy Groups (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atoms)
To 14, particularly preferably 1 to 8 carbon atoms, such as acetoxy, benzoyloxy, etc., and a carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms).
4, particularly preferably 1 to 8 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl and the like; acyl group (preferably 1 to 2 carbon atoms)
0, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, formyl, acetyl, benzoyl and the like, and an alkoxycarbonyl group (preferably 2 to 14 carbon atoms)
20, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like, aryloxycarbonyl group (preferably 6 to 2 carbon atoms)
0, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, for example, phenoxycarbonyl, 2-
Naphthyloxycarbonyl), a cyano group and a nitro group, more preferably a halogen atom, an acylamino group and an alkyl group, particularly preferably a chlorine atom or a bromine atom.

It is preferable that at least one of the substituents represented by X ¹ and X ³ is an electron-withdrawing group. An electron-withdrawing group is a substituent having a positive Hammett's substituent constant σ _p value, and specific examples thereof include a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an imino group. An N-substituted imino group, thiocarbonyl group, perfluoroalkyl group, sulfonamide group, formyl group, phosphoryl group, carboxyl group,
A carbamoyl group, an acyl group, a sulfo group (or a salt thereof), an alkylsulfonyl group, an arylsulfonyl group,
Examples include a sulfamoyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, a heterocyclic group, and an aryl group substituted with an electron-withdrawing group.
X ¹ and X ³ are more preferably both electron-withdrawing groups,
More preferably, both are halogen atoms, and particularly preferably, both are chlorine atoms or bromine atoms.

In the formula (2), X ² and X ⁴ represent a hydrogen atom or a substituent. However, X ² and X ⁴ are not hydroxyl groups. Specific examples of the substituent include those represented by formula (2)
And the substituents mentioned as examples of X ¹ of the above. X ² , X ⁴
Are preferably a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom and a bromine atom), and an acylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom). -14, particularly preferably 1-8 carbon atoms, such as formylamino, acetylamino, benzoylamino, etc., alkyl group (preferably 1-20 carbon atoms, more preferably 1 carbon atom).
To 14, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, isopropyl, cyclohexyl, etc.), an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably carbon Numbers 6 to 8, for example, phenyl, naphthyl, p-methylphenyl, etc., alkoxy groups (preferably having 1 to 20, more preferably 1 to 14, particularly preferably 1 to 8, such as methoxy, ethoxy) Etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 14 carbon atoms, particularly preferably having 6 to 8 carbon atoms, such as phenoxy and 2-naphthyloxy), and an acyloxy group (preferably having 6 carbon atoms). 1 to
20, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, acetoxy, benzoyloxy and the like, a sulfonylamino group (preferably 1 to 2 carbon atoms)
0, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc., a carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms) Particularly preferably having 1 to 8 carbon atoms, for example, carbamoyl, N, N-
Dimethylcarbamoyl, N-phenylcarbamoyl and the like), an acyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 14 carbon atoms, particularly preferably having 1 to 8 carbon atoms,
For example, formyl, acetyl, benzoyl and the like, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and still more preferably having 2 to 2 carbon atoms)
12, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, still more preferably having 6 to 12 carbon atoms,
For example, phenoxycarbonyl, 2-naphthyloxycarbonyl, etc.), a cyano group, and a nitro group. More preferably, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, particularly preferably a hydrogen atom,
These are a methyl group and an ethyl group.

X¹~ X^FourMay be further substituted,
Specific examples of the substituent include X in the formula (2) ¹Mentioned as an example
Substituents. Also, X¹~ X^FourAre connected to each other
It may form a ring.

In the formula (2), R ¹ is a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 7 carbon atoms, for example,
Methyl, ethyl, isopropyl, cyclohexyl, etc.),
An aryl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 14 carbon atoms, particularly preferably having 6 to 8 carbon atoms, for example, phenyl, naphthyl, p-methylphenyl and the like), a heterocyclic group (for example, pyridyl group, Imidazolyl group, pyrrolidyl group), amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 14 carbon atoms, particularly preferably 0 to 0 carbon atoms)
8, for example, amino, methylamino, N, N-dimethylamino, N-phenylamino, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 14 carbon atoms,
Particularly preferably, it has 1 to 8 carbon atoms, such as methoxy and ethoxy. It is preferably a hydrogen atom, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an alkyl group having 1 to 7 carbon atoms, more preferably an aryl group or an alkyl group having 1 to 7 carbon atoms, and particularly preferably. An aryl group. R ¹ may be further substituted, and specific examples of the substituent include the substituents exemplified as X ^{1 in} the formula (2).

X¹~ X^Four, R¹Preferred as a combination of
Ha, X¹, X^ThreeAt least one is a halogen atom
, X^Two, X^FourIs a hydrogen atom or an alkyl group;¹Is
It is an aryl group or an alkyl group having 1 to 7 carbon atoms. Sa
A more preferred combination is X ¹, X^ThreeAre both chlorine atoms
Or a bromine atom, X^TwoIs a hydrogen atom or alkyl
X^FourIs a hydrogen atom, and R¹Is an aryl group
You.

The preferred range of the total molecular weight of the compound represented by the formula (2) is from 170 to 800, more preferably 2 to 800.
20-650, particularly preferably 220-500.

Specific examples of the compound represented by the formula (2) are shown below, but the present invention is not limited thereto.

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The amount of the compound represented by the formula (2) used in the present invention is 0.001 to 4.0 per m ² of the light-sensitive material.
g, more preferably 0.01 to 2.0 g, even more preferably 0.1 to 2.0 g. The amount of the compound represented by the general formula (2) used in the present invention is preferably 0.1 to 1000 mol, more preferably 1 to 100 mol, per 1 mol of the compound represented by the general formula (1). More preferably, it is particularly preferably from 5 to 50. The compound represented by the formula (2) may be used alone or in combination of two or more.

The compound represented by the formula (2) used in the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), Dimethylformamide, dimethylsulfoxide,
It can be used by dissolving it in methyl cellosolve or the like.
Alternatively, according to the well-known emulsification dispersion method,
An oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, diethyl phthalate or the like, or an auxiliary solvent such as ethyl acetate or cyclohexanone can be used to dissolve and mechanically prepare and use an emulsified dispersion. Alternatively, according to a well-known solid dispersion method, a powder of a compound represented by the formula (2) is dispersed in water by a ball mill, a colloid mill, a sand grinder mill, Mentongorin, a microfluidizer, or ultrasonic waves, Can be used.

The compound represented by formula (2) used in the present invention can be added to any layer on the same surface of the support as the photosensitive silver halide and the reducible silver salt. However, it is preferably added to a layer containing silver halide or a layer adjacent thereto.

Next, a compound called a toning agent which is a component (f) of the photothermographic material of the present invention will be described. This compound is added to a light-sensitive material for the purpose of improving the image density (image density) of a silver image, the color tone of silver, and the heat developability.

In a photothermographic material utilizing an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, JP-A-49-5020, JP-A-49-91215, JP-A-49-91215, JP-A-50-2524, JP-A-50-32927, JP-A-50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-27923, No. 52-14788, No. 52-99813, No. 53-1020, No. JP-A-53-76020, JP-A-54-156524 and JP-A-54-1565.
No. 25, 61-183642, and
JP-A-56848, JP-B-49-10727, JP-A-54-20333, U.S. Pat.
Nos. 2,941, 4,123,282, 4,51
0,236, British Patent No. 1,380,795, Belgian Patent No. 841,910, Japanese Patent Publication No.
It is disclosed in, for example, Japanese Patent Publication No. 25050. Examples of toning agents are phthalimide and N-hydroxyphthalimide;
Succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one,
Cyclic imides such as 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); -Mercapto-1,2,4-
Triazole, 2,4-dimercaptopyrimidine, 3-
Mercaptans exemplified by mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides; N,
N-dimethylaminomethyl) phthalimide and N, N
-(Dimethylaminomethyl) naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N-hexamethylenebis (1-carbamoyl-
3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl)
-Benzothiazole); and 3-ethyl-5 [(3
-Ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophenyl Derivatives such as tarazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and Combinations with tetrachlorophthalic anhydride, homophthalic acid and the like; phthalazine, phthalazine derivatives (for example, 4-
(1-naphthyl) phthalazine, 6-chlorophthalazine,
Derivatives such as 5,7-dimethoxyphthalazine, 6-isopropylphthalazine, 6-isobutylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-dihydrophthalazine) or metals Salts; Combinations of phthalazine and its derivatives with phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, homophthalic acid, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives A rhodium complex which functions not only as a color tone regulator but also in situ as a source of halide ions for silver halide formation, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate and hexachlororhodium (II
I) potassium acid and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide;
Benzoxazines such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione Pyrimidine and asymmetric triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto-); 1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene and 1,4-di (o-chlorophenyl)-
3,6-dimercapto-1H, 4H-2,3a, 5,6
a-tetraazapentalene).

These color toning agents are combined with other additives such as the performance required for the color toning agent (improvement of image density, silver color tone, heat development), characteristics such as volatilization and sublimation outside the light-sensitive material, and antifoggants. The search is advanced from the viewpoint of the characteristics of the photosensitive material at the time, and among them, it is known that a combination of a phthalazine represented by the following formula (3) and a phthalic acid derivative preferably used in the present invention is excellent. .

The photothermographic material of the present invention preferably contains a phthalazine compound represented by the above formula (3) as a toning agent. In the formula (3), Y represents a hydrogen atom or a monovalent substituent, and m represents an integer of 1 to 6.
(Y) m indicates that 1 to 6 Ys are independently present on the phthalazine ring, and when m is 2 or more, even if two adjacent Ys form an aliphatic or aromatic ring, Good.

As the substituent represented by Y, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 carbon atoms.
-8, for example, vinyl, allyl, 2-butenyl, 3
-Pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl,
Pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenyl,
p-Methylphenyl, naphthyl and the like. ),
An aralkyl group (preferably an aralkyl group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms, such as benzyl and α-methylbenzyl; , 2-phenylethyl, naphthylmethyl, (4-methylphenyl) methyl, etc.), an amino group (preferably having 0 to 0 carbon atoms).
20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably having 1 carbon atom)
-20, more preferably 1-12, particularly preferably 1-8, for example, methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 1 carbon atoms)
6, particularly preferably having 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms).
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 carbon atoms)
-16, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl, etc.), and an acyloxy group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms.
6, particularly preferably having 2 to 10 carbon atoms, such as acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like), and an alkoxycarbonylamino group (Preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 carbon atoms)
To 12, for example, phenyloxycarbonylamino and the like. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, etc.), and sulfamoyl. Group (preferably having 0 to 2 carbon atoms)
It has 0, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Equations 6 to 20,
More preferably, it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 carbon atoms.
To 12, for example, mesyl, tosyl, and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoramide and phenylphosphoramide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) )). These substituents may be further substituted.

Y is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, or an aryl group. Oxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, more preferably hydrogen atom, alkyl group, aryl group, aralkyl group, acyl group , Hydroxy group, halogen atom,
A cyano group, more preferably a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom,
Particularly preferably, a hydrogen atom, an alkyl group, an aryl group,
It is an aralkyl group.

M represents an integer of 1 to 6. m is more preferably 3 or less, and still more preferably 2 or less.
When m is 2 or more, two adjacent Ys are an aliphatic (preferably 3 to 8 members, more preferably 5 to 6 members) or aromatic (preferably benzene or naphthalene) ring,
Alternatively, a hetero ring (preferably a 5- to 6-membered ring) may be formed.

As a method for producing the phthalazine compound represented by the formula (3), for example, RGElderField, “Hetrocycling
ic Compounds ", John Wiley and Sons, Vol.
1950-1967 and ARKatritzky, "Comprehensive
Heterocyclic Chemistry ”, Pergamon Press, 198
4, a method of condensing a corresponding phthalic acid derivative (phthalaldehyde, phthalic anhydride, phthalic ester, etc.) with hydrazine to form a phthalazine skeleton, α, α, α ′, α ′ -Method of synthesizing phthalazine by condensing -tetrachloro-o-xylene with hydrazine, and Tetrahedron Letters, 22, 345 (1981)
A method of reacting an aryl aldazine derivative with a mixture of aluminum chloride and aluminum bromide under melting conditions to form a cyclized product as described in
A method of cyclizing an aldazine compound described in JP180961 with an aluminum chloride catalyst in an organic solvent and synthesizing the compound can be mentioned.

Preferred examples of the phthalazine compound represented by the formula (3) used in the present invention will be shown below, but the present invention is of course not limited thereto.

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As described in the section of the prior art, when a color tone agent is added, the image density can be increased. On the other hand, an agglomerate is formed by interacting with a reducing agent in a coating solution. For this reason, there are problems such as agglomeration or the like being clogged at the time of filtration performed for dust removal or the like and deterioration in filterability, and agglomeration or the like passing through the filter affecting the surface quality of coating. The present inventor has conducted intensive studies and found that adding a color-toning agent in the form of a complex with a reducing agent or a metal beforehand can suppress the effect on filterability and coating surface quality as compared with the case where the color-toning agent is added alone. Was found. This is presumably because the colorant forms a complex with the reducing agent or the metal to suppress the formation of aggregates due to the interaction with other materials.

Further, in the photothermographic material of the present invention, preferably 70% by mol or more, more preferably 85% by mol or more, still more preferably 95% or more, and most preferably 100% of the toning agent used forms a complex. Is desirable.

In the photothermographic material of the present invention, it is preferable that at least a part of the toning agent forms a complex with the reducing agent represented by the formula (1). When the color-toning agent and the reducing agent are previously complexed, the molar ratio of the color-toning agent and the reducing agent may be any ratio as long as the complex is stable,
1: 1, 1: 2, 2: 1 complexes are obtained relatively easily.
In addition, intermolecular hydrogen bonding is dominant as an intermolecular force for forming a complex. The amount of addition is preferably the same as or less than the molar amount of the toning agent molecule of the complex when added alone. That is, it is preferably contained in an amount of 0.1 to 50 mol per 1 mol of silver on the side having the image forming layer, and more preferably 0.5 to 20 mol. The complex is usually contained in one kind,
More than one kind may be contained. Also, to promote development,
A reducing agent may be independently contained in addition to the complex. At this time, the reducing agent is not necessarily the same as the reducing agent used for forming the complex.

A complex of a color tone agent and a reducing agent can be easily prepared by using the method shown in Production Example 1 below and a method analogous thereto.

In the photothermographic material of the present invention, it is also preferable that at least a part of the toning agent forms a complex with a metal. When the color-toning agent and the metal are complexed in advance, the type of the color-toning agent is not particularly limited as long as at least a part of the used color-toning agent can form a complex with the metal.
Further, the type and structure of the formed complex are not particularly limited. In the photothermographic material of the present invention, a complex-forming toning agent and a complex-free toning agent may be mixed. At this time, the color-forming agent forming a complex and the color-forming agent not forming a complex may be the same or different.

The metal used to form a complex between the color-toning agent and the metal is not particularly limited as long as it forms a complex with the color-toning agent. The complex referred to in the present invention means a complex in which a negative, neutral or positive monodentate ligand or polydentate ligand is coordinated around an atom or ion of a metal and a metal-like element. It is not limited to transition metals. Preferred metals include Zn, N
i, Mg, Ca, Hg, Cd, Pd, Pt and the like. Particularly, Zn and Ni are preferable.

The molar ratio between the colorant and the metal constituting the complex may be any ratio as long as the complex is stable, but 1: 1 or 2: 1 can be relatively easily obtained. The complex is usually contained in one type, but may be contained in two or more types. When two or more kinds of complexes are contained, the toning agent and the metal constituting the two or more kinds of complexes may be different from each other, or the toning agents may be of the same kind but differing only in the metal, or May be of the same type and differ only in the toning agent. The amount of the complex to be added is preferably 0.1 to 50 mol, more preferably 0.5 to 20 mol, per 1 mol of silver on the side having the image forming layer. The method for preparing the complex is not particularly limited.

The complex of a toning agent and a metal was prepared according to Production Example 2 described below.
Can be easily prepared by using the method shown in (1) or a method analogous thereto.

The complex of the color toning agent and the metal can be applied by mixing with a coating solution, applying the mixture on a support, and drying. The form when the complex is added to the coating liquid and the form of the complex in the coating liquid may be any form such as a solution, a powder, and a solid fine particle dispersion. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used. As a preferred embodiment of the present invention, it is preferable to add a solid fine particle dispersion.

Next, the reducible non-photosensitive organic silver salt which is the component (b) of the photothermographic material of the present invention will be described. The reducible non-photosensitive organic silver salt that can be used in the photothermographic material of the present invention is relatively stable to light, but is exposed to an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and A silver salt that forms a silver image when heated to 80 ° C. or higher in the presence of a reducing agent. The organic silver salt can be any organic material including a source of reducible silver ions. Silver salts of organic acids, especially (C 10 to C 3
Silver salts of 0, preferably 15 to 28) long chain fatty carboxylic acids are preferred. Also preferred are organic or inorganic silver salt complexes in which the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver donor is preferably present in about 5 to 70
% By weight. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Specific examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids,
It is not limited to these. Preferred examples of the silver salt of the aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphorate, mixtures thereof and the like can be mentioned.

In the present invention, in the above-mentioned organic acid silver or a mixture of the organic acid silver, a silver behenate content of 75 m
ol% or more of organic acid silver, more preferably 85% by mole or more of silver behenate. Here, the content of silver behenate indicates the mole fraction of silver behenate with respect to the organic acid silver used. As the organic acid silver other than silver behenate contained in the organic acid silver used in the present invention, the above-mentioned exemplified organic acid silver can be preferably used.

The silver salt of an organic acid preferably used in the present invention is
It is prepared by reacting silver nitrate with a solution or suspension of the above-mentioned alkali metal salt of an organic acid (including Na salt, K salt, Li salt and the like). These preparation methods are described in paragraph No. 00 of JP-A-2000-292882.
The methods described in 19 to 0021 can be used.

In the present invention, a method of preparing an organic silver salt by adding an aqueous solution of silver nitrate and a solution of an alkali metal salt of an organic acid into a sealing means for mixing the liquid can be preferably used. Specifically, JP-A-200
The method described in JP-A-292882 can be used. In the present invention, when preparing the organic acid silver,
A water-soluble dispersant can be added to the aqueous silver nitrate solution, the organic acid alkali metal salt solution, or the reaction solution. The type and amount of the dispersant used here are described in paragraph No. 00 of JP-A-2000-305214.
52 shows a specific example.

The organic acid silver used in the present invention is preferably prepared in the presence of a tertiary alcohol. As the tertiary alcohol, a compound having a total carbon number of 15 or less is preferable, and a compound having a total carbon number of 10 or less is particularly preferable. Preferred examples of the tertiary alcohol include tert-butanol, but the tertiary alcohol that can be used in the present invention is not limited to this. The tertiary alcohol used in the present invention may be added at any time during the preparation of the organic acid silver salt.
It is preferable to dissolve and use the organic acid alkali metal salt. Further, the tertiary alcohol used in the present invention is 0.01 to 1 in weight ratio to water as a solvent at the time of preparing the silver salt of an organic acid.
Although it can be used in the range of 0, it is preferable to use in the range of 0.03-1.

The shape and size of the organic silver salt which can be used in the present invention are not particularly limited.
It is preferable to use those described in paragraph No. 0024 of No. 2882. The shape of the organic silver salt can be determined from a transmission electron microscope image of the organic silver salt dispersion. Another method for measuring monodispersity is to determine the standard deviation of the volume-weighted average diameter of the organic silver salt. The percentage (coefficient of variation) divided by the volume-weighted average diameter is preferably 80% or less, Preferably not more than 50%, more preferably 30%
% Or less. As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with a laser beam, and an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained from a particle size (volume weighted average diameter) obtained. be able to. The average particle size in this measurement method is 0.1.
A solid fine particle dispersion of from 0.05 μm to 10.0 μm is preferred. A more preferred average particle size is 0.1 μm to 5.0.
μm, more preferably the average particle size is 0.1 μm to
2.0 μm.

The organic silver salt used in the present invention is preferably desalted. The desalting method is not particularly limited, and known methods can be used, but centrifugal filtration, suction filtration,
Known filtration methods such as ultrafiltration and floc-forming water washing by a coagulation method can be preferably used. As a method for ultrafiltration, a method described in JP-A-2000-305214 can be used.

In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, an organic silver salt which is an image forming medium and a photosensitive silver salt are substantially contained. It is preferable to use a dispersion method in which a water dispersion liquid which is not included in the liquid is converted into a high-speed flow and then the pressure is reduced. As for these dispersion methods, the methods described in Paragraph Nos. 0027 to 0038 of JP-A-2000-292882 can be used.

The particle size distribution of the organic silver salt solid fine particle dispersion used in the present invention is preferably monodispersed. Specifically, the percentage (coefficient of variation) of the value obtained by dividing the standard deviation of the volume load average diameter by the volume load average diameter is 80% or less, more preferably 50% or less, and still more preferably 30% or less.

The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio of the organic silver salt to water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by weight, and particularly preferably 10 to 30% by weight.
Although it is preferable to use the above-mentioned dispersing aid, it is preferable to use the dispersing aid in the minimum amount within a range suitable for minimizing the particle size.
A range of 15% by weight is preferred.

The organic silver salt used in the present invention can be used in a desired amount, but the silver amount is preferably 0.1 to 5 g / m ² ,
More preferably, it is 1 to 3 g / m ² .

In the present invention, it is preferable to add a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt. Regarding addition of metal ions selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt,
It is preferably added in the form of a water-soluble metal salt which is not a halide, and specifically, it is preferably added in the form of a nitrate or a sulfate. The addition of a halide is not preferable because it deteriorates the image storability of the processed photosensitive material due to light (such as room light or sunlight), that is, the so-called printout property. For this reason, in the present invention, it is preferable to add in the form of a water-soluble metal salt which is not a halide.

Ca, Mg, Zn preferably used in the present invention
The addition time of the metal ion selected from Ag and Ag may be any time after the formation of the particles of the non-photosensitive organic silver salt and immediately before the coating, such as immediately after the formation of the particles, before the dispersion, after the dispersion and before and after the preparation of the coating solution. It may be during the period, preferably after dispersion and before and after preparation of the coating solution.

In the present invention, Ca, Mg, Zn and A
The addition amount of the metal ion selected from g is preferably 10 ^-3 to 10 ^-1 mol, and particularly preferably 5 × 10 ^{-3 to} 5 × 10 ^-2 mol, per 1 mol of non-photosensitive organic silver.

Next, the photosensitive silver halide which is a component (a) of the photothermographic material of the present invention will be described. The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. The grain formation of the photosensitive silver halide emulsion is described in JP-A-11-11.
The particles can be formed by the method described in paragraphs 0217 to 0224 of No. 9374, but it is not particularly limited to this method. The shapes of silver halide grains are cubic, octahedral, tetrahedral, tabular, spherical,
Rod-like, potato-like and the like can be mentioned, and in the present invention, cubic particles or tabular particles are particularly preferable. The characteristics of the particle shape, such as the particle aspect ratio and the surface index, are the same as those described in paragraph No. 0225 of JP-A-11-119374. Also,
The distribution of the halogen composition may be uniform inside and on the surface of the silver halide grains, and the halogen composition may be changed stepwise or may be changed continuously. Further, silver halide grains having a core / shell structure can be preferably used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

In the particle size distribution of the silver halide grains used in the present invention, the value of the monodispersity is 30% or less, preferably 1%.
-20%, and even 5-15%. Here, the monodispersity is defined as a percentage (%) (coefficient of variation) of a value obtained by dividing the standard deviation of the particle size by the average particle size. For the sake of convenience, the grain size of silver halide grains is represented by a ridge length in the case of cubic grains, and other grains (octahedral, tetradecahedral, tabular, etc.) are calculated by projected area circle equivalent diameters.

The photosensitive silver halide grains used in the present invention
Is a metal of Group VII or VIII of the Periodic Table
Or it contains a metal complex. Group VII of the periodic table
Or a group VIII metal or a central metal of a metal complex.
And preferably rhodium, rhenium, ruthenium, osuni
And iridium. Particularly preferred metal complexes are
(NH_Four)_ThreeRh (H_TwoO) Cl_Five, K_TwoRu (NO) C
l_Five, K_ThreeIrCl₆, K_FourFe (CN)₆It is. these
One kind of metal complex may be used,
May be used in combination of two or more. Preferred content is silver
1 × 10 for 1 mol^-9mol ~ 1 × 10^-3mol
Preferably in the range 1 × 10^-8mol ~ 1 × 10 ^-Fourmol
Is more preferable. Specific structure of metal complex
Has a structure described in JP-A-7-225449 and the like.
Metal complexes can be used. The types of these heavy metals,
Regarding the addition method, see JP-A-11-119374.
Paragraph Nos. 0227 to 0240 are described.

The photosensitive silver halide grains can be desalted by a water washing method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. . The photosensitive silver halide emulsion used in the present invention is preferably chemically sensitized. The chemical sensitization is described in paragraph No. 02 of JP-A-11-119374.
It is preferable to use the methods described in JP-A Nos. 42 to 0250. A thiosulfonic acid compound may be added to the silver halide emulsion used in the present invention by a method described in European Patent Publication EP 293,917A.

As the gelatin contained in the photosensitive silver halide used in the present invention, a low molecular weight gelatin is used in order to maintain a good dispersion state of the photosensitive silver halide emulsion in an organic silver salt-containing coating solution. Is preferred. The low molecular weight gelatin has a molecular weight of 500 to 60,000, preferably 1,000 to 40,000. These low molecular weight gelatins may be used at the time of grain formation or at the time of dispersion after desalting, but are preferably used at the time of dispersion after desalting. When forming particles, use normal gelatin (molecular weight of about 100,000),
Low-molecular-weight gelatin may be used at the time of dispersion after desalting.

The concentration of the dispersion medium can be 0.05 to 20% by weight, but a concentration range of 5 to 15% by weight is preferable for handling. As the type of gelatin, alkali-treated gelatin is usually used, and in addition, acid-treated gelatin,
Modified gelatin such as phthalated gelatin can also be used.

The silver halide emulsions used in the present invention may be used alone or in combination of two or more (for example, those having a different average grain size, those having a different halogen composition, those having a different crystal habit, and those having a different chemical habit). With different feeling conditions) may be used in combination.

The amount of the photosensitive silver halide used in the present invention is preferably from 0.01 mol to 0.5 mol, and more preferably from 0.02 mol to 1 mol of the organic silver salt.
mol to 0.3 mol, more preferably 0.03 mol
~ 0.25 mol is particularly preferred. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the silver halide particles and the organic silver salt which have been respectively prepared are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, There is a method of mixing with a homogenizer or the like, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt. There is no particular limitation as long as it is sufficiently obtained. Mixing two or more aqueous dispersions of organic silver salts with two or more aqueous dispersions of photosensitive silver salts is a preferable method for adjusting photographic characteristics.

Sensitizing dyes can be used in the photothermographic material of the present invention. Sensitizing dyes that can be used in the present invention are those capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and have a spectral sensitivity suitable for the spectral characteristics of an exposure light source. The sensitizing dye to be used can be advantageously selected. For example, 550 nm to 7
Examples of the dye that spectrally sensitizes a wavelength region of 50 nm include a dye represented by the general formula (II) in JP-A-10-186572, and specifically, II-6, II-7, and I-6.
I-14, II-15, II-18, II-23, II
The dye of -25 can be exemplified as a preferable dye. Examples of the dye that spectrally sensitizes the wavelength region of 750 to 1400 nm include a dye represented by the general formula (I) in JP-A-11-119374, and specifically, (25) and (26) , (30), (32), (36),
The dyes of (37), (41), (49) and (54) can be exemplified as preferred dyes. Furthermore, Jb
US Pat. No. 5,510,510, and US Pat.
Preferred dyes include the dyes described in Example 5 of JP-A Nos. 236 and 3,871,887 and the dyes disclosed in JP-A-2-96131 and JP-A-59-48753. Examples can be given. These sensitizing dyes may be used alone or in combination of two or more.

The addition of these sensitizing dyes can be carried out by the method described in paragraph No. 0106 of JP-A-11-119374, but is not particularly limited to this method. The addition amount of the sensitizing dye in the present invention can be a desired amount in accordance with the sensitivity and the performance of fog.
The amount is preferably 10 ^-6 to ¹ mol, more preferably 10 ^-4 to 10 ^-1 mol.

The photothermographic material of the present invention has a spectral sensitizing efficiency
In order to improve the sensitization, a supersensitizer can be used.
As the supersensitizer used in the present invention, European Patent Publication EP
587,338A, U.S. Pat. No. 3,877,94.
No. 3 and No. 4,873,184.
Compounds, heteroaromatic or aliphatic mercapto
Compound, heteroaromatic disulfide compound, stilbene,
Examples include compounds selected from hydrazine and triazine.
I can do it. Particularly preferred supersensitizers are described in JP-A-5-34.
No. 1432 heteroaromatic mercapto
Compound, heteroaromatic disulfide compound, JP-A-4-1
The compound represented by the general formula (I) or (II) in
Compounds disclosed in JP-A-10-111543
Stilbene compound represented by formula (I)
A compound represented by the general formula (I) described in
You. Specifically, M-1 disclosed in JP-A-5-341432
To M-24, described in JP-A-4-18239.
Compounds of d-1) to d-14), JP-A-10-1115
No. 43, compounds of SS-01 to SS-07,
31, 32, 37, 38 of JP-A-11-109547,
41 to 45 and 51 to 53. These strong colors
The sensitizer was added in an amount of 1 mol silver halide per emulsion layer.
10 ^-FourTo 1 mol, preferably silver halide.
The range of 0.001-0.3mol per 1mol is more
preferable.

It is preferable to use a nucleating agent in the photothermographic material of the present invention. The type of nucleating agent that can be used in the present invention is not particularly limited, but as a preferable nucleating agent,
A hydrazine derivative represented by the formula (H) described in Japanese Patent Application No. 2000-284399 (specifically, Tables 1 to
Hydrazine derivatives described in Table 4), JP-A-10-106
No. 72, JP-A-10-161270, JP-A-10-62898, JP-A-9-304870, JP-A-9-304872, and JP-A-9-304
No. 871, JP-A-10-31282, US Pat. No. 5,496,695, European Patent Publication EP7
All hydrazine derivatives described in JP-A-41,320A can be exemplified. Also, Japanese Patent Application 2000-284
No. 399, substituted alkene derivatives represented by formulas (1) to (3), substituted isoxazole derivatives and specific acetal compounds, more preferably formula (A) or formula (B) described in the same specification And specifically, compounds 1 to 7 described in Chemical Formulas 8 to 12 of the same specification.
2 can also be used.

Also, JP-A-11-119372,
JP-A-10-339932, JP-A-11-845
No. 75, JP-A-11-84576, JP-A-1
JP-A-1-95365, JP-A-11-95366, JP-A-11-11047, JP-A-11-1
09546, JP-A-11-119373,
JP-A-11-133545, JP-A-11-133
546, JP-A-11-149136, JP-A-11-231459, JP-A-2000-1627
No. 33, U.S. Pat. No. 5,545,515,
U.S. Pat. No. 5,635,339, U.S. Pat. No. 5,654,130, U.S. Pat.
No. 228, and the compounds described in US Pat. No. 5,705,324 can also be used. Also, Patent Application 2
001-46809, paragraph Nos. 0025-002
The imidazoline derivatives represented by Formulas (A-1) to (A-36) described in 8 can also be used. Further, a plurality of these nucleating agents may be used in combination.

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

In addition to the above compounds, US Pat.
Nos. 545,515, 5,635,339 and 5,654,130, International Publication WO
97/34196, US Pat. No. 5,686,22.
No. 8 or the compound described in JP-A-11-1
19372, JP-A-11-133546,
JP-A-11-119373, JP-A-11-109
Compounds described in JP-A-546-546, JP-A-11-95365, JP-A-11-95366, and JP-A-11-149136 may be used.

In the present invention, in order to form a super-high contrast image, a high contrast accelerator can be used in combination with the nucleating agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5,
Hydroxamic acids described in U.S. Pat. No. 5,545,507, specifically HA-1 to HA-11, acrylonitriles described in U.S. Pat. No. 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in U.S. Pat. No. 5,558,983, specifically, CA-1 to CA-6, JP-A-9-297.
No. 368, onium salts, specifically A-
1 to A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

In a photothermographic material having a non-photosensitive organic silver salt, a photosensitive silver halide and a binder, formic acid or formate is a strong fogging substance. In the present invention, the content of formic acid or formate on the side having the image forming layer containing the photosensitive silver halide of the photothermographic material is preferably 5 mmol or less, more preferably 1 mmol or less per 1 mol of silver.

In the photothermographic material of the present invention, an acid or a salt thereof formed by hydration of diphosphorus pentoxide is preferably used in combination with a nucleating agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline Acids (salts) and the like can be mentioned. Particularly preferred acids and salts thereof formed by hydration of diphosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and the like. The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto in that a desired effect is exhibited in a small amount. Use amount of the oxidizing acid or salt thereof formed by hydration of diphosphorus (coating amount per photographic material 1 m ²⁾ may be a desired amount depending on the performance such as sensitivity and fog, but, 0.1 to 500 mg / m ² is preferred, and 0.5
-100 mg / m ² is more preferred.

The surface pH of the photothermographic material of the present invention before the heat development is preferably 6.0 or less, more preferably 5.5 or less. The lower limit is not particularly limited, but is about 3. The adjustment of the film surface pH is preferably performed using an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is preferable in achieving a low film surface pH since ammonia is easily volatilized and can be removed before the application step and the heat development. Note that the film surface p
The method for measuring H is described in paragraph No. 0123 of Japanese Patent Application No. 2000-284399.

In the photothermographic material of the present invention, the silver halide emulsion and / or the organic silver salt may contain an antifoggant,
Stabilizers and stabilizer precursors can further protect against the formation of additional fog and stabilize against reduced sensitivity during inventory storage. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are described in US Pat. No. 2,131,03.
No. 8, No. 2,694,716, azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605, U.S. Pat. No. 2,728,663, mercury salts described in U.S. Pat. No. 3,287,135, urazole described in U.S. Pat. No. 3,287,135, U.S. Pat. No. 3,235,652.
Patent No. 62, UK Patent No. 62
Oxime, nitrone, nitroindazole described in US Pat. No. 3,448, polyvalent metal salt described in US Pat. No. 2,839,405, US Pat. No. 3,220,839.
No. 2,566,263 and U.S. Pat. No. 2,597,9.
15, palladium, platinum and gold salts; U.S. Pat. Nos. 4,108,665 and 4,4;
No. 4,128,557 and U.S. Pat. Nos. 4,137,079 and 4,138,365.
And the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The photothermographic material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acid used in the present invention may be any benzoic acid derivative, but a preferred example is described in US Pat.
No. 939, No. 4,152,160, JP-A-9-329863, JP-A-9-329864, and JP-A-9-281637. The benzoic acid may be added to any layer of the photothermographic material, but is preferably added to the layer on the image forming layer side with respect to the support, more preferably to the organic silver salt-containing layer. The addition of benzoic acids may be performed at any step in the preparation of the coating solution, and when the benzoic acid is added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed, but the coating is performed after the preparation of the organic silver salt. Immediately before is preferred.
The benzoic acid may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a color tone agent. The benzoic acid may be added in any amount, but may be 1 × 10 ⁻⁶ mol to 2 mol per mol of silver.
1 is preferable, and 1 × 10 ⁻³ mol to 0.5 mol is more preferable.

Although not essential for practicing the present invention,
Mercury (II) salt was added to the image forming layer as an antifoggant
May be advantageous. Preferred for this purpose
Mercury (II) salts are mercury acetate and mercury bromide. Book
The added amount of mercury used in the present invention is as follows.
preferably 1 × 10 per mol^-9mol ~ 1 × 10 ^-3
mol, more preferably 1 × 10^-8mol ~ 1 × 10
^-Fourmol range.

The antifoggant particularly preferably used in the present invention is an organic halide.
Nos. 89020, 50-119624, 5
Nos. 0-120328, 50-137126, 51-121332, 54-58022
JP-A-56-70543, JP-A-56-9933
No. 5, JP-A-59-57234, JP-A-59-908.
No. 42, No. 61-129,642, No. 62-1
29845, JP-A-6-208191, 7-5621, 7-2781, 8-1
Nos. 5809, 9-160164, 9-1
60167, 9-244177, 9-
244178, 9-258367, 9
-265150, 9-319022, 10-197988, 11-242304, JP-A-2000-002963, and 2000-
Japanese Patent Publication Nos. 112070 and 11-90095, 1
Nos. 1-89773 and 11-205330,
U.S. Pat. Nos. 3,874,946 and 4,75.
No. 6,999, No. 5,340,712, No. 5,369,000, No. 5,46
Compounds such as those disclosed in US Pat.

A hydrophilic organic halide represented by the formula (P) described in Japanese Patent Application No. 2000-284399 is preferably used as an antifoggant. Specifically, (P-1) to (P-118) described in the same specification are preferably used. The addition amount of the organic halide is represented by a mol amount (mol / molAg) based on 1 mol of Ag, preferably 1 × 10 ^{−5 to 2} mol / molAg, more preferably 5 × 10 ^{−5 to 1} mol / molAg, and still more preferably 1 × 10 ^{−5 to} 1 mol / molAg. × 10 ^{-4 to} 5 × 10 ^-1 mol / mol Ag. These may be used alone or in combination of two or more.

The salicylic acid derivative represented by the formula (Z) described in Japanese Patent Application No. 2000-284399 is preferably used as an antifoggant. Specifically, (A-1) to (A-60) described in the same specification are preferably used. The addition amount of the salicylic acid derivative represented by the formula (Z) is a mol amount (mol / molA) relative to 1 mol of Ag.
g), preferably 1 × 10 ^{-5 to} 5 × 10 ^-1 mo
1 / mol Ag, more preferably 5 × 10 ⁻⁵ to 1 × 10
⁻¹ mol / mol Ag, more preferably 1 × 10 ⁻⁴ to
It is 5 × 10 ^-2 mol / mol Ag. These may be used alone or in combination of two or more.

As a fog inhibitor preferably used in the present invention, formalin scavenger is effective.
1) to (S-24).

The antifoggant used in the present invention may be water or a suitable organic solvent such as alcohols (methanol, methanol, etc.).
It can be used by dissolving in ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. In addition, dibutyl phthalate,
Oils such as tricresyl phosphate, glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone,
An emulsified dispersion can be prepared and used mechanically. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer or an ultrasonic wave by a method known as a solid dispersion method.

The antifoggant used in the present invention may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on this layer side. It is preferable to add it to an adjacent layer. The image forming layer is a layer containing a reducible silver salt (organic silver salt), and is preferably an image forming layer further containing a photosensitive silver halide.

The photothermographic material of the present invention may contain a mercapto compound, a disulfide compound, or a thione compound for the purpose of controlling or suppressing the development by suppressing or accelerating the development, or improving the storability before and after the development. Can be. When a mercapto compound is used in the present invention, any structure may be used, but Ar-SM, Ar
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy ( For example, it may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and aryl (which may have a substituent). Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole,
6-ethoxy-2-mercaptobenzothiazole, 2,
2'-dithiobis- (benzothiazole), 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2- Mercaptoquinoline, 8-mercaptopurine,
2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5
6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto- 1,2,
4-triazole, 4-hydrokilocy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-
Methyl pyrimidine hydrochloride, 3-mercapto-5
-Phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, sodium 3- (5-mercaptotetrazole) -benzenesulfonate, N-
Methyl-N '-{3- (5-mercaptotetrazolyl)
Examples include phenyl diurea and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto. The amount of the mercapto compound added is 0.0001 to 1.0 m per mol of silver in the image forming layer.
ol is preferable, and more preferably, 1 mol of silver
The amount is 0.001 to 0.3 mol per 1.

The photothermographic material of the present invention is provided on a support.
It is preferable that the image forming layer has an image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide, and at least one protective layer is provided on the image forming layer. Further, the photothermographic material of the present invention preferably has at least one back layer on the side (back surface) opposite to the image forming layer with respect to the support. The image forming layer, the protective layer, and the binder of the back layer are preferably used. As the polymer latex. By using a polymer latex for these layers, aqueous coating using a solvent (dispersion medium) containing water as a main component becomes possible, which is advantageous in terms of environment and cost, and causes wrinkles during thermal development. A heat-developable photosensitive material can be obtained. Further, by using a support which has been subjected to a predetermined heat treatment, a photothermographic material having a small dimensional change before and after thermal development can be obtained.

Next, the binder which is a component (d) of the photothermographic material of the present invention will be described. As the binder used in the present invention, the polymer latex described below is preferable. At least one of the image forming layers containing the photosensitive silver halide of the photothermographic material of the present invention is preferably an image forming layer using the polymer latex described below in an amount of 50% by weight or more of the total binder. Further, the polymer latex may be used not only for the image forming layer but also for the protective layer and the back layer. In particular, when the photothermographic material of the present invention is used for printing in which dimensional change is problematic, the protective layer or the back layer It is preferable to use a polymer latex also for the layer. However, the "polymer latex" referred to here is a polymer in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and the molecular chains themselves are molecularly dispersed. Any of them may be used. The polymer latex used in the present invention is described in "Synthetic Resin Emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (19
78)) ”,“ Applications of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Published by Polymer Publishing Association (1)
993))), “Synthesis of Synthetic Latex (Souichi Muroi,
Published by Kobunshi Kankokai (1970)). The average particle size of the dispersed particles is preferably in the range of about 1 to 50,000 nm, more preferably about 5 to 1,000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

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

The glass transition temperature (T.sub.T) of the polymer latex preferably used as the binder used in the present invention
In g), preferred ranges are different between the protective layer, the back layer and the image forming layer. In the image forming layer, the temperature is preferably from -30 to 40 ° C. in order to promote diffusion of the photographically useful material during thermal development. When used for the protective layer or the back layer, a glass transition temperature of 25 to 70 ° C. is preferable for contacting various devices.

The minimum film forming temperature (MFT) of the polymer latex used in the present invention is preferably from -30 ° C to 90 ° C, more preferably from about 0 ° C to 70 ° C. A film-forming aid may be added to control the minimum film-forming temperature. The film forming aid is an organic compound (usually an organic solvent) which is also called a plasticizer and lowers the minimum film forming temperature of the polymer latex. For example, the above-mentioned "Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Kankokai (1970)") )"It is described in.

The polymer used in the polymer latex used in the present invention includes acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or a copolymer thereof. And the like.
The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The number average molecular weight of the polymer is preferably 5,000 to 1,000,000, and more preferably 10,000 to 100,000. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the image forming layer of the photothermographic material of the present invention include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / butadiene / itaconic acid copolymer latex. Latex of ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl Latex of methacrylate / vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / Such as latex of methacrylic acid copolymers. More specifically, methyl methacrylate / ethyl acrylate / methacrylic acid = 33.5.
/50/16.5 (wt%) copolymer latex,
Methyl methacrylate / butadiene / itaconic acid = 4
A copolymer latex of 7.5 / 47.5 / 5 (% by weight), a copolymer latex of ethyl acrylate / methacrylic acid = 95/5 (% by weight), and the like can be given. Such polymers are also commercially available, for example, Sebian A-4635,465 as an example of an acrylic resin.
83, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), N
ipol LX811, 814, 821, 820, 85
7 (all made by Nippon Zeon Co., Ltd.), VONCORT-R3
As polyester resins such as 340, R3360, R3370, 4280 (all manufactured by Dainippon Ink and Chemicals, Inc.), FINETEX ES650, 611, 675, 8
50 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-siz
e, WMS (all manufactured by Eastman Chemical Co., Ltd.) such as HYDRAN AP10, 20,
Rubber-based resins such as 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR 7310K, 330
7B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol LX410, 430, 43
5, 438C (manufactured by Nippon Zeon Co., Ltd.), vinyl chloride resins such as G351 and G576 (manufactured by Nippon Zeon Co., Ltd.), and vinylidene chloride resin, L50
2, L513 (all manufactured by Asahi Kasei Corporation), Aron D7
020, D504, D5071 (Mitsui Toatsu Co., Ltd.
Chemical Pearl S12 as an olefin resin
0, SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone or as a mixture of two or more as necessary.

The image forming layer contains 50% by weight of the total binder.
As the above, the above-mentioned polymer latex is preferably used, and it is more preferable to use the above-mentioned polymer latex as 70% by weight or more.

If necessary, hydrophilic polymers such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and hydroxypropylmethylcellulose may be added to the image forming layer in a range of 50% by weight or less of the whole binder. . The amount of the hydrophilic polymer to be added is preferably 30% by weight or less, more preferably 15% by weight or less of the total binder in the image forming layer.

The image forming layer is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 60% by weight or more of the solvent (dispersion medium) of the coating liquid is water. Components other than water in the coating solution are methyl alcohol, ethyl alcohol, isopropyl alcohol,
Water-miscible organic solvents such as methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10,
Water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent weight%.)

The total amount of binder in the image forming layer is 0.2 to 3
0 g / m ^2, more preferably in the range of 1 to 15 g / m ^2. A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer.

Further, as a binder for the protective layer, JP-A-2000-267226, paragraphs [0025] to [0025]
A combination of polymer latexes having different I / O values obtained by dividing an inorganic value by an organic value based on the organic conceptual diagram described in 0029 can be preferably used.

In the present invention, if necessary,
Nos. 00-267226, Paragraph Nos. 0021-002
5 plasticizer (eg, benzyl alcohol, 2,2,
4-trimethylpentanediol-1,3-monoisobutyrate) can be added to control the film formation temperature. Further, as described in Paragraph Nos. 0027 to 0028 of JP-A-2000-267226, a hydrophilic polymer may be added to a polymer binder, and a water-miscible organic solvent may be added to a coating solution.

Each of the layers is described in JP-A-2000-019.
No. 678, using a first polymer latex having a functional group introduced therein and a crosslinking agent having a functional group capable of reacting with the first polymer latex and / or a second polymer latex. You can also. The functional group is a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, an oxazolinyl group, and the like.As a crosslinking agent, an epoxy compound, an isocyanate compound, a blocked isocyanate compound, a methylol compound, a hydroxy compound, It is selected from a carboxyl compound, an amino compound, an ethyleneimine compound, an aldehyde compound, a halogen compound and the like. Specific examples of the cross-linking agent include hexamethylene isocyanate and duranate WB4 as isocyanate compounds.
0-80D, WX-1741 (manufactured by Asahi Kasei Corporation),
Bayhijur 3100 (Sumitomo Bayer Urethane Co., Ltd.)
Manufactured), Takenate WD725 (Takeda Pharmaceutical Co., Ltd.)
Aquanate 100, 200 (manufactured by Nippon Polyurethane Co., Ltd.), water-dispersible polyisocyanate described in JP-A-9-160172; Sumitex Resin M-3 as an amino compound (manufactured by Sumitomo Chemical Co., Ltd.) An epoxy compound such as Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.); and a halogen compound such as sodium 2,4-dichloro-6-hydroxy-1,3,5-triazine.

The total amount of the binder for the image forming layer is from 0.2 to
30 g / m ^2, more preferably in the range of 1.0~15g / m ^2. The total binder amount for the protective layer is 0.2 to 1
0.0 g / m ² , more preferably 0.5 to 6.0 g / m ²
Is preferable. The total amount of binder for the back layer is 0.
01 to 10.0 g / m ² , more preferably 0.05 to
Range of 5.0 g / m ² is preferred.

Each of these layers may be provided in two or more layers. When the image forming layer has two or more layers, it is preferable to use a polymer latex as a binder for all the layers. Further, the protective layer is a layer provided on the image forming layer, and may have two or more layers.
Preferably, a polymer latex is used for the layer, especially the outermost protective layer. The back layer is a layer provided on the undercoat layer on the back surface of the support, and there may be two or more layers. However, it is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.

A slipping agent can be used in the photothermographic material of the present invention. As used herein, the term "slip agent" means a compound that reduces the coefficient of friction on the surface of an object when present on the surface of the object as compared with the case where it is not present. The type is not particularly limited.

The slip agent used in the present invention is disclosed in
Paragraph Nos. 0061 to 0064 of 1-84573,
Paragraph No. 0049 of JP-A-2000-47083
Compounds described in 0062 can be mentioned. Specific examples of preferred slip agents include Cellolsol 524 (main component carnauba wax), Polylon A, 393, H-481.
(Main component polyethylene wax), high micron G-1
10 (main component ethylene bisstearic amide), Himicron G-270 (main component stearic amide)
(Above, Chukyo Yushi Co.), etc. _{W-1 C 16 H 33 -O} -SO 3 Na W-2 C 18 H 37 -O-SO 3 Na and the like. The amount of the slip agent used is 0.1 to 50% by weight of the binder amount of the added layer, preferably 0.5 to 50% by weight.
30% by weight.

In the present invention, JP-A-2000-1719
No. 35, as described in JP-A-2000-47083, the preheating unit is conveyed by an opposing roller, and the heat development processing unit drives the roller having the image forming layer on the side having the image forming layer so that the back surface on the opposite side is rotated. In the case of using a heat development processing apparatus which conveys the heat-developable image recording material by sliding it on a smooth surface, the ratio of the friction coefficient between the outermost surface layer of the heat-developable image recording material having the image forming layer and the outermost surface layer of the back surface at the development processing temperature is as follows. , 1.5 or more,
The upper limit is not particularly limited, but is about 30. Also, μ
b is 1.0 or less, preferably 0.05 to 0.8.
This value is obtained by the following equation. Ratio of friction coefficient = dynamic friction coefficient (μe) between the roller member of the heat developing machine and the surface having the image forming layer / dynamic friction coefficient (μb) between the smooth surface member and the back surface of the heat developing machine (heat development processing temperature) The sliding property of the outermost layer on the surface having the heat-development processing machine member and the image forming layer and / or the opposite surface thereof can be adjusted by including a slipping agent in the outermost layer and changing the amount of addition. it can.

On both sides of the support, JP-A-64-2054
4, JP-A-1-180537, JP-A-1-18037
No. 209443, JP-A-1-285939,
JP-A-1-296243, JP-A-2-24649
JP, JP-A-2-24648, JP-A-2-18-18
4844, JP-A-3-109545, JP-A-3-137637, JP-A-3-141346, JP-A-3-141347, JP-A-4-96
No. 055, U.S. Pat. No. 4,645,731, JP-A-4-68344, and Japanese Patent No. 2,557,
No. 641, page 2, right column, line 20 to page 3, right column, line 30;
Paragraph No. 0020 of JP-A-2000-039684
It is preferable to provide an undercoat layer containing a vinylidene chloride copolymer containing at least 70% by weight of a repeating unit of a vinylidene chloride monomer described in paragraphs 0063 to 0080 of JP-A-2000-47083.

When the amount of the vinylidene chloride monomer is less than 70% by weight, sufficient moisture-proof properties cannot be obtained, and the dimensional change over time after thermal development becomes large. Further, the vinylidene chloride copolymer preferably contains a repeating unit of a carboxyl group-containing vinyl monomer as another constituent repeating unit of the vinylidene chloride monomer. It is only vinyl chloride monomer that contains such a repeating unit,
The polymer (polymer) crystallizes, making it difficult to form a uniform film when applying a moisture-proof layer, and a carboxyl group-containing vinyl monomer is indispensable for stabilizing the polymer (polymer). Because there is. The molecular weight of the vinylidene chloride copolymer used in the present invention is 450,000 in weight average molecular weight.
00 or less, more preferably 10,000 to 45,000. When the molecular weight is increased, the adhesiveness between the vinylidene chloride copolymer layer and a support layer such as polyester tends to deteriorate.

The content of the vinylidene chloride copolymer used in the present invention is 0.3 μm or more as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer.
Preferably, it is in the range of 0.3 μm to 4 μm.

The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support, and is usually provided one layer on each side. May be provided in two or more layers.
When a multilayer structure having two or more layers is used, the total amount of the vinylidene chloride copolymer may be within the range of the present invention.
Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer.

The support may be coated with an undercoat layer using SBR, polyester, gelatin or the like as a binder, if necessary, in addition to the vinylidene chloride copolymer layer. These undercoat layers may have a multilayer structure or may be provided on one side or both sides of the support. The thickness of the undercoat layer (per layer) is generally 0.01 to 5 μm, more preferably 0.1 to 5 μm.
05 to 1 μm.

Next, the support used for the photothermographic material of the present invention will be described. In the photothermographic material of the present invention,
Various supports can be used. Typical supports include polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetal, syndiotactic polystyrene, polycarbonate, and paper supports coated on both sides with polyethylene. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferred in terms of strength, dimensional stability, chemical resistance and the like. The thickness of the support is preferably 90 to 180 μm as a base thickness excluding the undercoat layer.

As the support used in the photothermographic material of the present invention, JP-A-10-48772 and JP-A-10-48772.
10676, JP-A-10-10677, JP-A-11-65025, JP-A-11-13864
No. 8, polyester which has been subjected to a heat treatment in a temperature range of 130 to 185 ° C. in order to alleviate internal strain remaining in the film at the time of biaxial stretching and eliminate heat shrinkage strain generated during thermal development processing. Particularly, polyethylene terephthalate is preferably used.

The support 12 after such heat treatment was used.
The dimensional change rate by heating at 0 ° C. for 30 seconds is −0.03% to + 0.01% in the vertical direction (MD), and 0 in the horizontal direction (TD).
Preferably, it is 0.04%.

The photothermographic material of the present invention has been disclosed in JP-A-11-84573, paragraph numbers 0040 to 0051, for the purpose of reducing dust adhesion, preventing the occurrence of static marks, and preventing transport failure in the automatic transport step. Can be prevented by using the conductive metal oxide and / or the fluorine-based surfactant described in (1). As the conductive metal oxide, US Pat. No. 5,575,957, JP-A-11-22
Needle-like conductive tin oxide doped with antimony described in paragraphs 0012 to 0020 of JP-A-3901 and fibrous tin oxide doped with antimony described in JP-A-4-29134 are preferably used.

The surface resistivity (surface resistivity) of the metal oxide-containing layer is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less in an atmosphere at 25 ° C. and a relative humidity of 20%. Thereby, good antistatic properties can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually about 10 ⁷ Ω.

The Beck smoothness of at least one of the surface having the image forming layer of the photothermographic material of the invention and the outermost layer surface opposite to the image forming layer is preferably 2000 seconds or less, more preferably 10 seconds to 2000 seconds. The Beck smoothness in the present invention is based on Japanese Industrial Standard (JIS).
It can be easily obtained according to P8119 “Smoothness test method of paper and paperboard with Beck tester” and TAPPI standard method T479. The Beck smoothness of the outermost layer on the surface having the image forming layer of the photothermographic material and the outermost layer on the opposite side are described in paragraph No. 00 of JP-A-11-84573.
As described in 52 to 0059, it can be controlled by appropriately changing the particle size and the amount of the matting agent contained in the layers on both surfaces.

In the present invention, a water-soluble polymer is preferably used as a thickener for imparting coatability, and may be a natural product or a synthetic polymer, and the type thereof is not particularly limited. Specifically, as natural products, starches (corn starch,
Starch, etc.), seaweed (agar, sodium alginate, etc.), vegetable glue (gum arabic, etc.), animal protein (glue, casein, gelatin, egg white, etc.), fermented glue (pullulane, dextrin, etc.), etc. Semi-synthetic polymers such as starchy materials (soluble starch, carboxyl starch, dextran, etc.) and celluloses (viscose, methylcellulose, ethylcellulose,
Carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc.), and synthetic polymers (polyvinyl alcohol, polyacrylamide,
Polyvinyl pyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl ether, polyethylene imine, polystyrene sulfonic acid or its copolymer, polyvinyl sulfanic acid or its copolymer, polyacrylic acid or its copolymer, acrylic acid or its copolymer Maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropanesulfonic acid or a copolymer thereof).

Among these, the water-soluble polymers preferably used are sodium alginate, gelatin, dextran, dextrin, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, Polystyrene sulfonic acid or its copolymer, polyacrylic acid or its copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid or its copolymer, and the like are particularly preferably used as a thickener.

Of these, particularly preferred thickeners include gelatin, dextran, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polystyrenesulfonic acid or a copolymer thereof, polyacrylic acid or a copolymer thereof. And a maleic acid monoester copolymer. These compounds are described in detail in "Applications and Markets of New Water-Soluble Polymers" (published by CMC Corporation, edited by Shinji Nagatomo, issued on November 4, 1988).

The amount of the water-soluble polymer used as a thickener is not particularly limited as long as the viscosity increases when added to a coating solution. Generally, the concentration in the liquid is 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight. The viscosity obtained by these methods is 1 to 200 mPa as an increase from the initial viscosity.
S is preferable, and more preferably 5 to 100 mPa · s.
It is. The viscosity is a value measured at 25 ° C. with a B-type rotational viscometer. When adding to a coating solution or the like, it is generally desirable to add the thickener in a solution as dilute as possible. In addition, it is preferable to perform sufficient stirring during addition.

The surfactant used in the present invention will be described below. Surfactants used in the present invention are classified into dispersants, coating agents, wetting agents, antistatic agents, photographic control agents, and the like depending on the purpose of use, and the surfactants described below are appropriately selected and used. These objectives can be achieved by doing so. The surfactant used in the present invention may be either nonionic or ionic (anion, cation, betaine). Further, a fluorine-based surfactant is also preferably used.

Preferred nonionic surfactants include:
Polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl and a surfactant having a nonionic hydrophilic group of sorbitan can be mentioned. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether , Polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, and triethanolamine fatty acid partial ester. be able to.

Examples of the anionic surfactant include a carboxylate, a sulfate, a sulfonate and a phosphate ester. Representative examples thereof include a fatty acid salt, an alkylbenzene sulfonate and an alkylnaphthalenesulfonic acid. Salt, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyltaurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxy Examples include ethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, and naphthalene sulfonate formaldehyde condensate. Can be.

Examples of the cationic surfactant include amine salts,
Examples thereof include quaternary ammonium salts and pyridium salts, and include primary to tertiary fatty amine salts and quaternary ammonium salts (tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridium salts, alkylimidazolium salts and the like). ).

Examples of the betaine-based surfactant include carboxybetaine and sulfobetaine.
-Trialkyl-N-carboxymethylammonium betaine, N-trialkyl-N-sulfoalkyleneammonium betaine and the like.

These surfactants are described in “Applications of Surfactants” (written by Koshobo and Takao Karimei, published on September 1, 1980).
It is described in. In the present invention, a preferred surfactant is not particularly limited in its use amount, and any surfactant may be used as long as desired surfactant properties can be obtained. The amount of the fluorine-containing surfactant applied is 0.01 mg / m ^{2 or} more.
250 mg is preferred.

Specific examples of the surfactant are described below, but are not limited thereto (here, -C ₆ H _4- represents a phenylene group). _{WA-1: C 16 H 33} (OCH 2 CH 2) 10 OH WA-2: C 9 H 19 -C 6 H 4 - (OCH 2 CH 2) 12 O
H WA-3: Sodium dodecylbenzenesulfonate WA-4: Sodium tri (isopropyl) naphthalenesulfonate WA-5: Sodium tri (isobutyl) naphthalenesulfonate WA-6: Sodium dodecyl sulfate WA-7: Di-α-sulfosuccinate (2-ethylhexyl) ester sodium salt _{WA-8: C 8 H 17} -C 6 H 4 - (CH 2 CH 2 O) 3 (C
_{H 2) 2 SO 3 K WA} -10: cetyltrimethylammonium chloride _{WA-11: C 11 H 23} CONHCH 2 CH 2 N (+) (C
^{_{H 3) 2 -CH 2 COO (}} -) WA-12: C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
O) ₁₆ H WA-13: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COO
_{K WA-14: C 8 F} 17 SO 3 K WA-15: C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
_{O) 4 (CH 2) 4} SO 3 Na WA-16: C 8 F 17 SO 2 N (C 3 H 7) (CH 2) 3 O
^{_{CH 2 CH 2 N (+)}} (CH 3) 3 -CH 3 · C 6 H 4 -SO 3 (-) WA-17: C 8 F 17 SO 2 N (C 3 H 7) CH 2 CH 2 C
H ₂ N ⁽⁺⁾ (CH ₃ ) ₂ —CH ₂ COO ⁽⁻⁾

In a preferred embodiment of the present invention, an intermediate layer may be provided, if necessary, in addition to the image forming layer and the protective layer. For the purpose of improving productivity and the like, it is preferable that these plural layers are simultaneously coated in an aqueous system. Coating methods include extrusion coating, slide bead coating, curtain coating, and the like.
The slide bead coating method shown in FIG. 1 of JP-A-02964 is particularly preferable.

In the case of a silver halide photographic light-sensitive material using gelatin as a main binder, the material is rapidly cooled in a first drying zone provided downstream of a coating die, and as a result, gelatinization of gelatin occurs and the coating film is cooled. Is solidified. The coating film that has been cooled and solidified and has stopped flowing is guided to the subsequent second drying zone, where the solvent in the coating liquid is volatilized and formed into a film in the subsequent drying zone. As a drying method after the second drying zone, an air loop method in which a jet is blown from a U-shaped duct to a roller-supported support, or a support in which the support is wound around a cylindrical duct in a helical shape, and conveyed and dried. A fire method (air floating method) and the like can be mentioned.

When a layer is formed using a coating liquid in which the main component of the binder is a polymer latex, the flow of the coating liquid cannot be stopped by rapid cooling, so that the preliminary drying is insufficient only in the first drying zone. In some cases.
In this case, in a drying method such as used in a silver halide photographic light-sensitive material, flow unevenness and drying unevenness occur, and a serious defect is easily generated on the coated surface.

The preferred drying method in the present invention is a horizontal drying method regardless of the first drying zone or the second drying zone described in JP-A-2000-002964, at least until the constant-rate drying is completed. This is a method of drying in a drying zone. The transfer of the support from the time immediately after the coating until the support is guided to the horizontal drying zone may or may not be horizontal, and the rising angle of the coating machine with respect to the horizontal direction may be between 0 and 70 °. In addition, the horizontal drying zone in the present invention only needs to be conveyed within ± 15 ° up and down with respect to the horizontal direction of the coating machine, and does not mean horizontal conveyance.

The constant-rate drying in the present invention means a drying process in which the liquid film temperature is constant and all the heat flowing in is used for evaporating the solvent. At the end of drying, the rate of drying decreases at the end of drying due to various factors (such as the rate of diffusion of the material inside the material that controls the movement of water and the retreat of the evaporation surface), and the applied heat is also used to raise the liquid film temperature. Drying process. The critical moisture content at which the transition from the constant rate process to the rate reduction process is 200-3
00%. When constant-rate drying is completed, drying proceeds sufficiently until the flow stops, and a drying method such as a silver halide photographic light-sensitive material can also be employed. It is preferred to dry in the horizontal drying zone to the drying point.

The drying conditions when forming the image forming layer and / or the protective layer are such that the liquid film surface temperature during constant rate drying is 3 to less than the minimum film forming temperature (MTF; usually, the glass transition temperature Tg of the polymer) of the polymer latex. (5 ° C. higher) or more. Normally 25 ° C to 40 ° C due to limitations of manufacturing equipment
Often. Further, the dry-bulb temperature during the rate-decreasing drying is preferably a temperature lower than the Tg of the support (usually 80 ° C. or lower in the case of PET). The liquid film surface temperature in this specification refers to the solvent liquid film surface temperature of the coating liquid film applied to the support, and the dry bulb temperature refers to the temperature of the drying air in the drying zone.

When drying is performed under the condition that the liquid film surface temperature during constant-rate drying is low, the drying tends to be insufficient. For this reason, particularly, the film forming property of the protective layer is significantly reduced, and cracks are easily generated on the film surface. In addition, the film strength is weakened, and serious problems such as susceptibility to scratches during transportation in an exposure machine or a heat developing machine are likely to occur.

On the other hand, when dried under the condition that the liquid film surface temperature becomes high, the protective layer mainly composed of the polymer latex quickly forms a film, while the lower layer such as the image forming layer has fluidity. Since the surface is not stopped, irregularities are likely to be generated on the surface. Further, when excessive heat higher than Tg is applied to the support (base), the dimensional stability and the curl resistance of the photosensitive material tend to deteriorate.

[0164] The same applies to the sequential coating in which the lower layer is coated and dried and then the upper layer is coated. In particular, the coating for performing the simultaneous multi-layer coating in which the upper layer is coated before the lower layer is dried and both layers are dried simultaneously. As the liquid properties, the pH difference between the coating solution for the image forming layer and the coating solution for the protective layer is preferably 2.5 or less, and the smaller the difference in pH, the more preferable. Coating solution pH
When the difference is large, micro-aggregation is likely to occur at the interface of the coating solution, and a serious surface failure such as a coating streak tends to occur during long continuous coating.

The coating solution viscosity of the image forming layer is 15 to 25 ° C.
100 mPa · s is preferred, and more preferably 30 to
70 mPa · s. On the other hand, the coating liquid viscosity of the protective layer is 2
The temperature is preferably 5 to 75 mPa · s at 5 ° C., more preferably 20 to 50 mPa · s. These viscosities are measured by a B-type viscometer.

Winding after drying is preferably carried out under the conditions of a temperature of 20 to 30 ° C. and a relative humidity of 45 ± 20%. Good or inside. Further, when the processing form is a roll product, it is also preferable to adopt a roll form wound on the side opposite to the winding form at the time of processing in order to remove the curl generated in the winding form. The relative humidity of the photosensitive material is 20 to
It is preferable that the temperature be controlled in the range of 55% (measured at 25 ° C.).

In a conventional photographic emulsion coating solution which is a viscous solution containing a silver halide and containing a silver halide, bubbles are dissolved and disappear in the solution simply by sending the solution under pressure. Even when it is returned, there is almost no occurrence of bubbles. However, in the case of an image forming layer coating solution containing an organic silver salt dispersion and a polymer latex which are preferably used in the present invention, defoaming tends to be insufficient only by pressurized liquid feeding, so that a gas-liquid interface does not occur. It is preferable to remove the bubbles by applying ultrasonic vibration while feeding the liquid.

In the present invention, the defoaming of the coating liquid is performed by deaeration under reduced pressure before the coating liquid is applied, and further, 1.5 kg / cm ^2.
It is preferable to apply the ultrasonic vibration while continuously feeding the liquid while maintaining the above-mentioned pressurized state and avoiding the gas-liquid interface. Specifically, Japanese Patent Publication No. 55-6405 (4)
The method described on page 20, line 7 to page 7, line 11) is preferred. As an apparatus for performing such defoaming, JP-A-2000-2000
The apparatus shown in the embodiment of FIG. 3 and FIG. 3 can be preferably used.

The pressure condition is preferably 1.5 kg / cm ² or more, more preferably 1.8 kg / cm ² or more. There is no particular upper limit, but usually 5 kg / cm ²
It is about. The applied ultrasonic sound pressure is 0.2V or more,
The sound pressure is preferably 0.5 V to 3.0 V, and in general, it is preferable that the sound pressure be high. However, if the sound pressure is too high, the temperature becomes partially high due to caption, which causes fogging. The frequency is not particularly limited, but is usually 10 kHz or more,
Preferably, it is 20 kHz to 200 kHz. In addition, decompression degassing refers to deaeration by increasing the air bubble diameter in the coating solution, increasing the buoyancy, and degassing the inside of the tank (usually a liquid preparation tank or a storage tank). Depressurization conditions are -200 mmHg or lower pressure conditions,
Preferably, the pressure condition is -250 mmHg or lower, and the lowest pressure condition is not particularly limited, but is usually about -800 mmHg. Decompression time is more than 30 minutes,
It is preferably 45 minutes or more, and the upper limit is not particularly limited.

In the present invention, the image forming layer, the protective layer of the image forming layer, the undercoat layer and the back layer are described in JP-A-11-84.
No. 573, paragraphs 0204 to 0208, JP-A-20
Paragraph Nos. 0240 to 0241 of JP-A-00-47083
A dye can be contained for the purpose of preventing halation as described in (1).

Various dyes and pigments can be used in the image forming layer from the viewpoint of improving color tone and preventing irradiation. Although any dyes and pigments can be used for the image forming layer, for example, compounds described in paragraph No. 0297 of JP-A-11-119374 can be used. As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds to be used is determined depending on the desired absorption amount, but it is generally preferable to use them in the range of 1 × 10 ⁻⁶ g to 1 g per 1 m ² .

When an antihalation dye is used in the present invention, the dye has a desired absorption in a desired range, has a sufficiently low absorption in the visible region after the treatment, and has a desirable absorbance spectrum shape of the back layer. Any compound can be used, if possible. For example, a compound described in paragraph No. 0300 of JP-A-11-119374 can be used. Further, as described in Belgian Patent No. 733,706, a method in which the concentration of a dye is reduced by erasing by heating, or as described in JP-A-54-17833, by erasing by light irradiation. A method of lowering the concentration or the like can also be used.

When the photothermographic material of the present invention is used as a mask when preparing a printing plate using a PS plate after the heat development, the photothermographic material after the heat development is exposed to the PS plate in a plate making machine under the exposure conditions for the PS plate. Information to set,
Information for setting plate-making conditions such as a transfer condition of a mask original and a PS plate is carried as image information. Therefore, said irradiation dye, halation dye,
The concentration (use amount) of the filter dye is limited to read them. Since this information is read by LED or laser, Dm of the wavelength range of the sensor
In (minimum concentration) needs to be low, and the absorbance needs to be 0.3 or less. For example, a plate making machine S-FNRIII manufactured by Fuji Photo Film Co., Ltd. uses a light source having a wavelength of 670 nm as a detector for detecting register marks and a barcode reader. In addition, plate making machine AP manufactured by Shimizu Seisakusho
A light source of 670 nm is used as a bar code reader of the ML series. That is, Dmi around 670 nm
When n (minimum density) is high, information on the film cannot be accurately detected, and a work error occurs in a plate making machine such as a conveyance failure and an exposure failure. Therefore, in order to read information with a 670 nm light source, Dmin around 670 nm needs to be low, and the absorbance at 660 to 680 nm after thermal development needs to be 0.3 or less. More preferably, it is 0.25 or less. The lower limit is not particularly limited, but is usually about 0.10.

In the present invention, the exposure apparatus used for imagewise exposure may be any apparatus capable of exposing for an exposure time of 10 ⁻⁶ seconds or less, but is generally a laser diode (LD) or a light emitting diode. An exposure apparatus using (LED) as a light source is preferably used. In particular, LD has high output,
More preferable in terms of high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

The exposure in the present invention is performed by overlapping the light beams of the light source. The overlap means that the sub-scanning pitch width is smaller than the beam diameter. For example, the overlap is determined by changing the beam diameter to a half value width (FW) of the beam intensity.
HM), it can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient). In the present invention, the overlap coefficient is preferably 0.2 or more.

The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. Also,
The light source channel may be a single channel or a multi-channel, but in the case of a cylindrical outer surface type, a multi-channel is preferably used.

The photothermographic material of the present invention has a low haze at the time of exposure and tends to generate interference fringes. As a technique for preventing the generation of the interference fringes, a technique disclosed in Japanese Patent Application Laid-Open No. Hei 5-113548, for example, in which a laser beam is obliquely incident on a photosensitive material, or WO95 / 3175.
A method using a multi-mode laser disclosed in, for example, Japanese Patent Application Laid-Open No. 4 (Kokai) No. 4 is known, and it is preferable to use these techniques.

The heat development step of the image forming method used in the present invention may be any method, but usually the image development is carried out by elevating the temperature of the photothermographic material exposed to light. As a preferred embodiment of the thermal developing machine to be used, a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum is disclosed in Japanese Patent Publication No. 5-56499, Japanese Patent Laid-Open No. 9-292695, and Japanese Patent Laid-Open No. Developing machine described in Japanese Patent Application Laid-Open No. HEI 7-132 as a non-contact type.
No. 94, International Publication Nos. WO 97/28489, JP 97/28488 and JP 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is from 80 to 250C, more preferably from 100 to 14C.
0 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds. The line speed is preferably 140 cm / min or more, more preferably 150 cm / min or more.

As a method for preventing processing unevenness due to a dimensional change of the photothermographic material at the time of thermal development, a temperature of 80.degree.
It is effective to adopt a method in which an image is not formed at a temperature of less than 15 ° C., heated for 5 seconds or more, and then thermally developed at 110 ° C. to 140 ° C. to form an image (a so-called multi-step heating method). .

When the photothermographic material of the present invention is subjected to thermal development processing, it is exposed to a high temperature of 110 ° C. or more, so that some of the components contained in the material or some of the components decomposed by thermal development are exposed. Volatilizes. These volatile components may cause uneven development, corrode the components of the heat developing machine, precipitate at low temperatures, cause deformation of the screen as foreign matter, and adhere to the screen and become dirty. Is known to have a bad effect. As a method for eliminating these effects, it is known to install a filter in the heat developing machine and optimally adjust the flow of air in the heat developing machine. These methods can be used effectively in combination.

International Publication Nos. WO95 / 30933, WO97 / 21150, and JP-T10-500496 disclose first and second openings for binding and absorbing particles and introducing volatile components. It is described that a filter cartridge having an opening is used in a heating device for heating the film in contact with a film. In addition, International Publication WO96
Japanese Patent Application Laid-Open No. 12213/1990 and Japanese Patent Application Laid-Open No. 10-507403 describe the use of a filter combining a heat-conductive condensation collector and a gas-absorbing fine particle filter. In the present invention, these can be preferably used. U.S. Pat. No. 4,518,845 and Japanese Patent Publication No. 3-54331 disclose a device for removing vapor from a film, a pressurizing device for pressing the film against a heat transfer member, and heating of the heat transfer member. A configuration having an apparatus for performing the above is described. Further, International Publication WO98 / 27458 describes removing a component which increases fog volatilized from a film from the film surface. These can also be preferably used in the present invention.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine of FIG. 1 includes a carry-in roller pair 11 (an upper roller is a silicon rubber roller and a lower roller is an aluminum heat roller) for carrying the heat-developable photosensitive material 10 into a heating section while correcting and preheating the heat-developable photosensitive material 10 into a planar shape. It has a carry-out roller pair 12 that carries out the heat-developable photothermographic material 10 after the heat development to a flat shape and carries it out of the heating unit. The photothermographic material 10 has a carry-in roller pair 1
While being transported from 1 to the discharge roller pair 12, it is thermally developed. In the conveying means for conveying the photothermographic material 10 during the heat development, a plurality of rollers 13 are provided on the side where the surface having the image forming layer contacts, and the non-woven fabric (for example, Smooth surface 14 on which aromatic polyamide or Teflon (registered trademark) is bonded.
Is installed. The photothermographic material 10 is conveyed while the back surface is slid over the smooth surface 14 by driving a plurality of rollers 13 that come into contact with the surface having the image forming layer. A heater 1 is provided on the upper portion of the roller 13 and the lower portion of the smooth surface 14 so as to be heated from both sides of the photothermographic material 10.
5 is installed. As a heating means in this case, a plate heater or the like can be used. Although the clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, it is appropriately adjusted to a clearance that can transport the photothermographic material 10.
Preferably it is 0 to 1 mm.

Surface Material of Roller 13 and Smooth Surface 1
The member 4 is durable at high temperatures and may be anything as long as it does not hinder the conveyance of the photothermographic material 10, but the material of the roller surface is made of silicon rubber, and the member of the smooth surface is made of aromatic polyamide or Teflon (PTFE). Non-woven fabrics are preferred. It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section is composed of a preheating section A having a carry-in roller pair 11 and a heat development heating section B having a heating heater 15. A is lower than the heat development temperature (for example, 10 to 3
(Lower by about 0 ° C.), it is desirable to set the temperature and time to be sufficient to evaporate the amount of water in the photothermographic material 10 and to be higher than the glass transition temperature (Tg) of the support of the photothermographic material 10. It is preferable to set the temperature so that uneven development does not occur. The temperature distribution of the preheating section and the heat development section is preferably ± 1 ° C. or less, more preferably ± 0.1 ° C.
5 ° C. or lower is preferred. Further, a guide plate 16 is provided downstream of the thermal development processing section B, and a slow cooling section C having the carry-out roller pair 12 and the guide plate 16 is provided. Guide plate 16
Is preferably a material having a low thermal conductivity.
The cooling is preferably performed gradually so as not to cause deformation, and the cooling rate is preferably 0.5 to 10 ° C./sec.

Although the above has been described with reference to the illustrated examples, the invention is not limited to this. For example, various types of thermal developing machines used for thermal development of the photothermographic material of the present invention, such as those described in JP-A-7-13294, can be used. It may be of a configuration. In the case of the multi-stage heating method preferably used in the present invention, two or more heat sources having different heating temperatures may be provided in the above-described apparatus, and heating may be performed continuously at different temperatures.

The photothermographic material of the present invention is described in
000-2066653, paragraphs 0014-00
26 or according to JP-A-20
Paragraph Nos. 0020 to 0045 of JP-A-01-13632
Is preferably packaged by the packaging method described in (1).

[0187]

EXAMPLES The present invention will be described more specifically below with reference to production examples and examples. Materials, used amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore,
The scope of the present invention should not be construed as being limited by the specific examples described below.

<Production Example 1> Preparation Example of Complex of Toning Agent and Reducing Agent Compound Example III-7 (57 g), Compound Example I-
After 1 (112 g) was dissolved in 500 ml of acetone, acetone was distilled off under reduced pressure. 300 ml of toluene was added to the obtained oily substance, which was again distilled under reduced pressure. 500 ml of hexane was added to the obtained oil and stirred at room temperature to precipitate white crystals. As a result of filtering and drying the crystals, 128 g of a complex of Compound Example III-7 and Compound Example I-1 at a molar ratio of 1: 1 was obtained as white crystals.

<Preparation Example 2> Preparation Example of Color Tone-Metal Complex The above compound example III-7 having a stoichiometric ratio (1: 1 by molar ratio)
And Zn (NO ₃ ) ₂ .6 hydrate were mixed in ethanol at room temperature and, after filtration, the solvent was slowly evaporated to give colorless, air and light stable crystals. The crystals were filtered, washed and air-dried in the dark. The presence of Compound Example III-7 was confirmed by elemental microanalysis of the obtained crystals, and the presence of Zn was confirmed by fluorescent X-ray analysis.

<Example 1><< Preparation of silver halide emulsion A >> Alkali-treated gelatin (calcium content: 2700 ppm) was added to 700 ml of water.
Below) 11 g, potassium bromide 30 mg, and sodium 4-methylbenzenesulfonate 1.3 g were dissolved,
The pH was adjusted to 6.5 at 45 ° C. Then, silver nitrate 1
159 ml of an aqueous solution containing 8.6 g and 1 m of potassium bromide
ol / L, 5 × 10 ⁻⁶ (NH ₄ ) ₂ RhCl ₅ (H ₂ O)
mol / L and K ₃ IrCl ₆ at 2 × 10 ⁻⁵ mol / L
Was added over 6 minutes and 30 seconds by the control double jet method while maintaining the pAg at 7.7. Next, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / L of potassium bromide and 2 × 10 ₅ of K ₃ IrCl ₆ were added.
^-5 mol / L of a halogen salt aqueous solution containing pAg of 7.7
28 minutes 3 by the control double jet method while keeping
Added over 0 seconds. Thereafter, the pH is lowered to cause coagulation and sedimentation, and desalting treatment is carried out.
The pH was adjusted to 5.9 and the pAg to 8.0 by adding 1.1 g.
The obtained particles were cubic particles having an average particle size of 0.11 μm, a projection area variation coefficient of 9%, and a (100) plane ratio of 90%.

The obtained silver halide grains were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and after 3 minutes, 71 μmol of triethylthiourea was added, followed by aging for 100 minutes. hydroxy-6-methyl-1,3,3a, 7- tetrazaindene a 5 × 10 ^-4 mol, the following compounds a 0.17 g
After the addition, the temperature was lowered to 40 ° C. Thereafter, the temperature was maintained at 40 ° C., and 4.7 × 10 ⁻² per mol of silver halide.
mol potassium bromide (added as aqueous solution), 12.8
× 10 ⁻⁴ mol of the following sensitizing dye A (added as an ethanol solution) and 6.4 × 10 ⁻³ mol of the following compound B (added as a methanol solution) are added with stirring, and after 20 minutes, rapidly cooled to 30 ° C. Thus, the preparation of silver halide emulsion A was completed.

[0192]

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<< Preparation of Silver Behenate Dispersion A >> Behenic acid (Edenor C22-85R, manufactured by Henkel)
6 kg, 423 L of distilled water, 49.2 L of a 5 mol / L aqueous solution of NaOH, and 120 L of tert-butyl alcohol were mixed and reacted at 75 ° C. for 1 hour with stirring to obtain a sodium behenate solution. Separately, silver nitrate 40.4k
g of an aqueous solution (206.2 L) was prepared and kept at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of tert-butyl alcohol was kept at 30 ° C., and while stirring, the entire amount of the sodium behenate solution and the entire amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes 10 seconds and 60 minutes, respectively. Added over minutes. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the start of the silver nitrate aqueous solution addition, and then the sodium behenate solution was started to be added. After 9 minutes and 30 seconds after the completion of the silver nitrate aqueous solution addition, only the sodium behenate solution was added. It was made to be added. At this time, the temperature in the reaction vessel was set to 30 ° C., and the liquid temperature was controlled so as not to rise. In addition, the piping for the addition system of the sodium behenate solution
The temperature was maintained by steam tracing, and the amount of steam was controlled so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. When the morphology of the obtained silver behenate particles was evaluated by electron microscopy,
Average projected area diameter 0.52 μm, average grain thickness 0.14 μm
m, a scale-like crystal having a coefficient of variation of the average equivalent spherical diameter of 15%.

Next, a dispersion of silver behenate was prepared by the following method. For a wet cake having a dry solid content of 100 g, polyvinyl alcohol (Kuraray Co., Ltd., PVA
-217, average degree of polymerization: about 1700) and water were added to bring the total amount to 385 g, and the mixture was predispersed with a homomixer. Next, the pre-dispersed undiluted solution is dispersed in a dispersing machine (Microfluidizer M-110SE-E manufactured by Microfluidics International Corporation).
H, using a G10Z interaction chamber) was adjusted to 1750 kg / cm ² and treated three times to obtain a silver behenate dispersion A. At this time, a desired dispersion temperature was set by adjusting the temperature of the refrigerant by mounting the coiled heat exchangers before and after the interaction chamber, respectively. The silver behenate particles contained in the obtained silver behenate dispersion A had a volume-weighted average diameter of 0.52 μm and a variation coefficient of 15
% Particles. Particle size measurement is available from MalvernInstr
uments Ltd. Performed with MasterSizerX made by KK. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.
5, the grain thickness was 0.14 μm, and the average aspect ratio (the ratio of the circle equivalent diameter of the projected area of the grain to the grain thickness) was 5.1. The obtained silver behenate dispersion A was used for preparing the following coating liquid.

<< Preparation of Solid Fine Particle Dispersion of Reducing Agent >> Reducing agent [1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane] (Exemplified Compound I- 1) 400 g of Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.), 640 g of methanol, and 16 kg of water were added to 10 kg and 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203). Mix well to form a slurry. The slurry was sent by a diaphragm pump, and was fed for 3 hours by a horizontal bead mill (UVM-2, manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm.
After dispersing for 0 minute, 4 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the dispersion thus obtained had a median diameter of 0.44 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of the average particle diameter of 19%. The resulting dispersion is
After filtration with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, the mixture was used for preparing the following coating solution. Regarding the reducing agent Exemplified Compound I-2, a solid fine particle dispersion was obtained in the same manner as described above.

<< Preparation of Solid Fine Particle Dispersion of Compound Represented by Formula (2) and Comparative Compounds Y-1 to Y-3 >> Phenol Compound Represented by Formula (2) (Exemplified Compound II-1)
1 kg, modified polyvinyl alcohol (Kuraray Co., Ltd.,
2 kg of a 10% by mass aqueous solution of Poval MP203), 40 g of Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.), 42 g of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate, and 0.95 kg of water were added.
Mix well to form a slurry. This slurry was fed by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm in a horizontal bead mill (IMEX Co., Ltd.)
And UVM-2) for 5 hours, and water was added to adjust the concentration of Exemplified Compound II-1 to 20% by mass to obtain a solid fine particle dispersion. The particles of Exemplified Compound II-1 contained in the obtained dispersion have a median diameter of 0.33.
μm, the maximum particle diameter was 2.0 μm or less, and the coefficient of variation of the average particle diameter was 18%. The resulting dispersion had a pore size of 3.0.
After filtration with a μm polypropylene filter to remove foreign substances such as dust, the mixture was used for preparing the following coating solution. Solid fine particle dispersions of phenol compounds represented by formula (2) and comparative compounds Y-1 to Y-3 (types described in Table 1 described later) other than those described above were obtained in the same manner as described above. In addition, comparative compounds Y-1 to Y-3 of the compound represented by the formula (2) used in the present invention are shown below. These comparative compounds are compounds described in JP-A-2000-267222.

[0197]

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<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound A >> 10 kg of the following organic polyhalogen compound A [tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone] and modified polyvinyl Alcohol (Poval MP20, manufactured by Kuraray Co., Ltd.)
10 kg of a 20% by mass aqueous solution of 3) and a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate 6
39 g, Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.)
400 g, 640 g of methanol and 16 kg of water were added and mixed well to form a slurry. The slurry was fed by a diaphragm pump, dispersed in a horizontal bead mill (UVM-2, manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then water was added thereto to add an organic polyhalogen compound A. Was adjusted to be 25% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound A. The organic polyhalogen compound particles contained in the dispersion thus obtained have a median diameter of 0.36.
μm, the maximum particle diameter was 2.0 μm or less, and the coefficient of variation of the average particle diameter was 18%. The resulting dispersion had a pore size of 3.0.
After filtration with a μm polypropylene filter to remove foreign substances such as dust, the mixture was used for preparing the following coating solution.

<< Preparation of Dispersion of Solid Fine Particles of Organic Polyhalogen Compound B >> 5 kg of the following organic polyhalogen compound B [tribromomethylnaphthyl sulfone] and a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.) 2.5 kg, 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate 213
g and 10 kg of water were added and mixed well to form a slurry. This slurry is fed by a diaphragm pump, and a horizontal bead mill filled with zirconia beads having an average diameter of 0.5 mm (UVM-2 manufactured by Imex Co., Ltd.)
After dispersing for 5 hours in a solution, 2.5 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the organic polyhalogen compound B to 23.5% by mass. A fine particle dispersion was obtained. Organic polyhalogen compound particles contained in the obtained dispersion,
The median diameter was 0.38 μm, the maximum particle diameter was 2.0 μm or less, and the coefficient of variation of the average particle diameter was 20%. The resulting dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and then used for preparing the following coating solution.

<< Preparation of Aqueous Solution of Organic Polyhalogen Compound C >> While stirring at room temperature, 75.0 ml of water and sodium tripropylnaphthalenesulfonate (20% aqueous solution)
8.6 ml, 6.8 ml of sodium dihydrogen orthophosphate dihydrate (5% aqueous solution) and 1 part of potassium hydroxide
9.5 ml of a mol / L aqueous solution was added in sequence, and the mixture was stirred and mixed for 5 minutes after completion of the addition. Further, while stirring, 4.0 g of powder of the following organic polyhalogen compound C [3-tribromomethanesulfonylbenzoylaminoacetic acid] was added, and the mixture was uniformly dissolved until the solution became transparent to obtain 100 ml of an aqueous solution. The obtained aqueous solution was filtered through a 200-mesh polyester screen to remove foreign substances such as dust, and then used for preparing the following coating solution.

<< Preparation of emulsified dispersion of compound Z >> R-054 manufactured by Sanko Co., Ltd. containing 85% by mass of the following compound Z was prepared.
After mixing 0 kg and 11.66 kg of MIBK, the mixture was replaced with nitrogen and dissolved at 80 ° C. for 1 hour. 25.52k of water
g and MP polymer manufactured by Kuraray Co., Ltd. (M
12.76 kg of a 20% by mass aqueous solution of P-203) and 0.44 kg of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate were added, and the mixture was added at 20 to 40 ° C.
The mixture was emulsified and dispersed at 600 rpm for 60 minutes. In addition, Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.) 0.0
8 kg and 47.94 kg of water were added and distilled under reduced pressure.
After removing K, the concentration of compound Z was adjusted to be 10% by mass. The particles of compound Z contained in the dispersion thus obtained had a median diameter of 0.19 μm and a maximum particle diameter of 1.5.
μm or less, and the variation coefficient of the particle diameter was 17%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 6-isopropylphthalazine compound dispersion >> Modified polyvinyl alcohol (Poval MP, manufactured by Kuraray Co., Ltd.) while stirring 62.35 g of water at room temperature
203) 2.0 g was added so as not to form a lump, and stirred and mixed for 10 minutes. Thereafter, the mixture was heated and heated until the internal temperature reached 50 ° C., and the mixture was stirred for 90 minutes to be uniformly dissolved. The internal temperature was lowered to 40 ° C. or lower, and a 10% aqueous solution of polyvinyl alcohol (PVA-217, manufactured by Kuraray Co., Ltd.) 25.5 was used.
g of sodium tripropylnaphthalenesulfonate
3.0 g of a 0% aqueous solution and 7.15 g of 6-isopropylphthalazine (70% aqueous solution: Exemplified Compound III-7) were added, and the mixture was stirred for 30 minutes to obtain 100 g of a transparent dispersion. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Complex of Toning Agent and Reducing Agent >> 10 kg of a 1: 1 complex of Exemplified Compound III-7 and Exemplified Compound I-1 and modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) Poval MP203) 2
16 kg of water was added to 10 kg of a 0% by mass aqueous solution and mixed well to form a slurry. This slurry was fed by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm in a horizontal sand mill (IMEX Co., Ltd.)
And 3 hours 30 minutes by UVM-2), 4 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the reducing agent to 25% by mass, and a solid fine particle dispersion of the reducing agent was added. I got The reducing agent particles contained in the dispersion thus obtained have a median diameter of 0.44 μm and a maximum particle diameter of 2.
The average particle diameter was 0% or less, and the coefficient of variation was 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored. Solid fine particle dispersions were obtained in the same manner as described above for other complexes of a color tone agent and a reducing agent (types described in Table 1 below).

<< Preparation of Solid Fine Particle Dispersion of Color Tone-Metal Complex >>
n) 1 kg of modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203) for 4 kg of a 1: 1 complex of
And 15 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 7 hours. The concentration of the complex was adjusted to be 10% by mass to obtain a solid fine particle dispersion of the color-toning agent-metal complex. The particles of the colorant-metal complex contained in the dispersion thus obtained had a median diameter of 0.44 μm, a maximum particle diameter of 3.0 μm or less, and a coefficient of variation of the particle diameter of 17%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored. Solid fine particle dispersions were obtained in the same manner as described above for other color tone agents and metal complexes (types described in Table 1 below).

<< Preparation of Solid Fine Particle Dispersion of Nucleating Agent >> With respect to 1 kg of the following nucleating agents (nucleating agents AA-1 to AA-3),
Polyvinyl alcohol (made by Kuraray Co., Ltd., Poval PV)
A-217) 0.25 kg and 9 kg of water were added and mixed well to form a slurry. This slurry was fed by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm in a horizontal bead mill (IMEX Co., Ltd., U.S.A.).
After dispersing in VM-2) for 12 hours, 1 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the nucleating agent to 10% by mass to obtain a solid fine particle dispersion of the nucleating agent. Was. The particles of the nucleating agent contained in the obtained dispersion have a median diameter of 0.34 μm and a maximum particle diameter of 3.0 μm.
m or less, and the coefficient of variation of the particle diameter was 19%. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and then used for preparing the following coating liquid.

<< Preparation of Coating Solution for Image Forming Layer >> The following binder, material, and silver halide emulsion were added to 1 mol of silver of the organic acid silver salt prepared above, and water was added to form an image. A layer coating solution was prepared. After preparation, pressure 0.54
Vacuum deaeration was performed for 45 minutes at atm. The coating solution had a pH of 7.7 and a viscosity of 50 mPa · s at 25 ° C. Binder; SBR latex (St / Bu / AA = 68/29/3 (% by weight), using Na ₂ S ₂ O ₈ as a polymerization initiator) 397 g as a solid content Reducing agent of formula (1) described in Table 1 Kind and addition amount Phenol compound of formula (2) or comparative compound Y-1 to Y-3 Kind and addition amount shown in Table 1 Organic polyhalogen compound B 36.3 g Organic polyhalogen compound C Solid content 2 0.34 g Sodium ethylthiosulfonate 0.47 g Benzotriazole 1.02 g Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235) 10.8 g Color tone compound alone or complex thereof Type and amount described in Table 1 Compound Z 9.0 g as solid content Nucleating agent AA-1 0.02 mol Dye A shown below (mixture with low molecular weight gelatin having an average molecular weight of 15,000) Coating amount at which the optical density at 783 nm becomes 0.3 (solid content: 0.40 g) Silver halide emulsion A: Ag amount: 0.06 mol Preservative: 40 ppm in compound A coating solution (coating amount: 2 0.5 mg / m ² ) 1% by mass as the total amount of methanol in the coating solution of methanol 2% by mass as the total amount of solvent in the coating solution of ethanol (The glass transition temperature of the coating film was 17 ° C.)

[0207]

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[0208]

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<< Preparation of Coating Solution for Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2
-Hydroxyethyl methacrylate / acrylic acid = 5
8.9 / 8.6 / 25.4 / 5.1 / 2 (% by mass) of a polymer latex solution (glass transition temperature of copolymer: 46
° C (calculated value), a solid content concentration of 21.5 mass%, 100 ppm of compound A, and 15 mass% of the following compound D based on the solid content of the latex as a film-forming aid, and a glass transition temperature of a coating solution. Was added to 943 g of water, 114.8 g of an aqueous solution of organic polyhalogen compound C, 17.0 g of organic polyhalogen compound A as a solid content, and sodium dihydrogen orthophosphate. 0.69 g of hydrate as a solid content,
1.58 g of a matting agent (polystyrene particles, average particle diameter 7 μm, variation coefficient of average particle diameter 8%) and 29.3 g of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.)
1.62 g of the following compound E was added, and water was further added to prepare a coating solution (containing 0.8% by mass of a methanol solvent).
After the preparation, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The resulting protective layer coating solution had a pH of 5.5 and a viscosity of 25.
It was 45 mPa · s at ° C.

<< Preparation of Coating Solution for Lower Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) of polymer latex solution (glass transition temperature of copolymer 46 ° C. (calculated value), solid content concentration 21.5 mass%, compound A 100 ppm), and compound D as latex Water was added to 625 g of a coating solution having a glass transition temperature of 24 ° C .;
0.23 g of the following compound C, 0.13 g of the compound E, 11.7 g of the following compound F, 2.7 g of the following compound H and polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-2
35) 11.5 g was added, and water was further added to prepare a coating solution (containing 0.1% by mass of a methanol solvent). After the preparation, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes.
The coating solution has a pH of 2.6 and a viscosity of 30 mPa · s at 25 ° C.
Met.

<< Preparation of Coating Solution for Upper Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) of polymer latex solution (glass transition temperature of copolymer 46 ° C. (calculated value), solid content concentration 21.5 mass%, compound A 100 ppm), and compound D as latex Water was added to 649 g of the coating solution containing 15% by mass based on the solid content, and the glass transition temperature of the coating solution was set at 24 ° C .; average particle size of 116 nm; 18.4 g of a 30% by mass solution of a silicone content of less than 5 ppm, 0.23 g of compound C, 1.85 g of compound E, 1.0 g of the following compound G, matting agent (polystyrene particles, average particle diameter 7 μm, average particle Coefficient of variation of diameter 8
%) And 26.5 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235) were added, and water was further added to prepare a coating liquid (containing 1.1% by mass of a methanol solvent). After the preparation, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The pH of the coating solution is 5.3 and the viscosity is 2
It was 25 mPa · s at 5 ° C.

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<< Preparation of Polyethylene Terephthalate (PET) Support with Back / Undercoat Layer >> (1) Preparation of PET Support Using terephthalic acid and ethylene glycol, the intrinsic viscosity IV = 0.66 (phenol PET / measured at 25 ° C in tetrachloroethane = 6/4 (mass ratio)
I got This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., and extruded from a T-die. Thereafter, the film was rapidly cooled to prepare an unstretched film having a thickness of 120 μm after heat setting. This was longitudinally stretched 3.3 times at 110 ° C. using rolls having different peripheral speeds, and then horizontally stretched 4.5 times at 130 ° C. using a tenter. Then, after heat-setting at 240 ° C. for 20 seconds, it was relaxed by 4% in the lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling is performed on both ends, and 4.8 kg
/ Cm ² . In this way, the width 2.4 m,
A roll-shaped PET support having a length of 3500 m and a thickness of 120 μm was obtained.

(2) Preparation of Undercoat Layer and Back Layer Undercoat First Layer After subjecting the PET support to a corona discharge treatment at 0.375 kV · A · min / m ² , a coating solution having the following composition .2 ml / m ² on a support,
30 seconds at 150 ° C., then 30 seconds at 150 ° C., then 185 ° C.
For 30 seconds. Latex-A 280 g KOH 0.5 g Polystyrene fine particles (average particle diameter 2 μm, coefficient of variation of average particle diameter 7%) 0.03 g 2,4-dichloro-6-hydroxy-s-triazine 1.8 g The following compound-Bc- C 0.097g Distilled water Amount that total amount becomes 1000g

Latex-A: core-shell type latex having 90% by weight of core and 10% by weight of shell. Core: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93.
/3/3/0.9/0.1 (% by mass) Shell part Vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 8
8/3/3/3/3 (% by mass) Weight average molecular weight 38,000

Second layer of undercoat A coating solution having the composition shown below was applied on the first layer of undercoat so as to have a concentration of 5.5 ml / m ^2. Dry at 30 ° C. for 30 seconds.

Deionized gelatin (Ca ²⁺ content: 0.6 ppm, jelly strength: 230 g) 10 g Acetic acid (20% by mass aqueous solution) 10 g The following compound-Bc-A 0.04 g Methyl cellulose (2% by mass aqueous solution) 25 g Polyethyleneoxy compound 0 0.3g Distilled water Amount that total amount is 1000g

The first back layer has a surface of 0.375 kV ·
A · min / m ² of corona discharge treatment, and a coating solution having the following composition was applied to the surface so as to have a composition of 13.8 ml / m ² at 125 ° C. for 30 seconds, and then at 150 ° C. for 30 seconds. Further, it was dried at 185 ° C. for 30 seconds.

23 g of 30% by weight aqueous dispersion (Julima ET410, manufactured by Nippon Pure Chemical Co., Ltd.) 23 g of alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 4.44 g deionized gelatin (Ca ²⁺ content: 0.4) 0.84 g Compound-Bc-A 0.02 g Dye-Bc-A below (adjusted to an optical density of 1.3 to 1.4 at 783 nm) 0.88 g as a guide Polyoxyethylene phenyl ether 7g soluble melamine compound (Sumitomo chemical Co., Ltd., SUMITEX resin M-3, 8 wt% aqueous solution) 15 g Sb-doped SnO ₂ of aqueous dispersion of acicular particles (Ishihara Sangyo Kaisha, Ltd., FS-10D ) 24 g polystyrene fine particles (average particle diameter 2 μm, coefficient of variation of average particle diameter 7%) 0.03 g distilled water The amount that the total amount becomes 1000 g

Back second layer A coating solution having the composition shown below was applied on the first back layer so as to have a concentration of 5.5 ml / m ^2.
It was dried at 50 ° C. for 30 seconds and further at 170 ° C. for 30 seconds.

30% by mass aqueous dispersion (Nippon Pure Chemical Industries, Ltd., Julimer ET410) 57.5 g Polyoxyethylene phenyl ether 1.7 g Water-soluble melamine compound (Sumitec Resin M-, manufactured by Sumitomo Chemical Co., Ltd.) 15g 30% by mass aqueous solution (Cerosol 524, manufactured by Chukyo Yushi Co., Ltd.) 6.6g Distilled water Amount that the total amount becomes 1000g

Back third layer The same coating solution as that for the first undercoat layer was applied on the second back layer so as to have a concentration of 6.2 ml / m ^2. Dry at 30 ° C. for 30 seconds.

Fourth Back Layer A coating solution having the composition shown below was applied to the third back layer so as to have a concentration of 13.8 ml / m ^2, and was applied at 125 ° C. for 30 seconds, then at 150 ° C. for 30 seconds, and further at 170 ° C. For 30 seconds.

The following latex-B 286 g The following compound-Bc-B 2.7 g The compound-Bc-C 0.6 g The following compound-Bc-D 0.5 g 2,4-dichloro-6-hydroxy-s-triazine 2.5 g Poly Methyl methacrylate (10% by mass aqueous dispersion, average particle diameter 5 μm, coefficient of variation of average particle 7%)

Latex-B: methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 59/9/26/5/1 (% by mass) copolymer

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

<< Preparation of Photothermographic Material >> A slide beat coating method shown in FIG. 1 of JP-A-2000-2964 was applied onto the undercoating second layer of a PET support.
The coating solution for the image forming layer was applied so that the amount of silver applied was 1.5 g / m ² . Further, the protective layer coating solution was further coated with the solid content of the polymer latex at 1.29 g /
was simultaneously coated with the coating solution for the image forming layer so that the m ^2. Thereafter, the coating solution of the lower overcoat layer was coated on the protective layer with a solid content of the polymer latex of 1.97.
g / m ² and the upper layer overcoat layer coating solution were simultaneously and multi-layer coated together with the lower layer overcoat coating solution such that the solid content of the polymer latex was 1.07 g / m ² to prepare a photothermographic material. Drying at the time of coating is carried out at a constant temperature step and a decreasing rate step at a dry-bulb temperature of 70 to 75 ° C and a dew point of 8 to 2.
In a range of 5 ° C. and a liquid film surface temperature of 35 ° C. to 60 ° C., a horizontal drying zone (where the support is at an angle of 1.5 ° to 3 ° with respect to the horizontal direction of the coating machine) up to the vicinity of a drying point at which the flow of the coating liquid is almost eliminated. )
I went in. Winding after drying was performed under the conditions of a temperature of 25 ± 5 ° C. and a relative humidity of 45 ± 5%. . Note that the envelope relative humidity of the photothermographic material is 20 to
At 40% (measured at 25 ° C.), the film surface pH on the image forming side of the obtained photothermographic material was 5.0, the Beck smoothness was 750 seconds, and the film surface pH on the opposite side was 5.9. Smoothness is 6
00 seconds.

<< Evaluation of photographic performance >> (Exposure processing) The obtained photothermographic material was exposed to light using a multi-channel cylindrical outer surface (30 semiconductor laser heads equipped with 50 mW semiconductor laser, and the laser energy density on the photothermographic material surface was 75 μJ). / Cm ² ) and heat development.

(Heat Developing Process) The exposed photothermographic material was subjected to a heat developing process using the heat developing machine shown in FIG. The roller surface material of the heat development processing section was made of silicone rubber, the smooth surface was made of Teflon nonwoven fabric, and the conveying line speed was set at 150 cm / min. The thermal development processing is performed for 12.2 seconds in the pre-heating unit (the driving systems of the pre-heating unit and the thermal development unit are independent, and the speed difference between the thermal development unit and the thermal development unit is -0.5%
Set to ~ -1%, set the temperature of the metal roller in each preheating section,
The time was 67 ° C. for the first roller, 2.0 seconds, 82 ° C. for the second roller, 2.0 seconds, 98 ° C. for the third roller,
2.0 seconds, fourth roller temperature 107 ° C., 2.0 seconds,
The temperature of the fifth roller was 115 ° C., 2.0 seconds, the temperature of the sixth roller was 120 ° C., 2.0 seconds), 17.2 seconds in the heat development processing section (temperature of the photothermographic material surface temperature, 120 ° C.), slow cooling section At 1
Performed for 3.6 seconds. The temperature accuracy in the width direction is ± 0.5 ° C
Met. The temperature of each roller was set to be 5 cm longer on both sides than the width of the photothermographic material (for example, 61 cm in width), and the temperature was applied to that portion so that the temperature accuracy was improved. Since the temperature of both ends of each roller is drastically lowered, the portion which is 5 cm longer than the width of the photothermographic material is set so that the temperature is 1-3 ° C. higher than the center of the roller, and the photothermographic material ( Care was taken to ensure that the image density (within a width of, for example, 61 cm) was uniform.

<< Evaluation Method of Photographic Performance >> The obtained images were evaluated using a Macbeth TD904 densitometer (visible density). The measurement results were evaluated by fog, sensitivity, contrast (γ), and Dmax (maximum density). The sensitivity is a relative value of the ratio of the reciprocal of the exposure amount giving a density 1.5 higher than the fog, and the larger the value, the higher the sensitivity. (The sensitivity of Sample No. 1 was set to 100). γ is the density 0.3 obtained by subtracting the Dmin part from the logarithm of the exposure amount on the horizontal axis.
It was represented by the slope of a straight line connecting the points 3.0 and 3.0. In practice,
Preferably, fog is 0.15 or less, Dmax is 3.5 or more, and contrast is 12 or more. Further, fog is 0.13 or less, Dmax is 4.0 or more, and contrast is most preferably 16 or more. . It is more preferable that the sensitivity be high without fog increase or γ decrease.

<< Evaluation of Filterability of Emulsion Layer Coating Solution >> A part of the emulsion layer coating solution prepared above was sampled and filtered through a polypropylene filter having a pore size of 10 μm (filtration area: 0.79).
cm ² , liquid sending speed: 20 ml / min, total filtration amount: 50
0 ml), and the filterability was evaluated by measuring the liquid pressure immediately before the filter. Five levels were evaluated according to the following criteria based on the degree of increase in the filtration pressure (the internal pressure for 6 minutes from the start of liquid supply was set to 0, and the amount of increase in filtration pressure when liquid was supplied for 20 minutes thereafter). ◎ The internal pressure rise is within 0 to 0.10 kgf / cm ² and liquid can be sent well. ○ The internal pressure can be sent within 0.10 to 0.15 kgf / cm ² △ The internal pressure rise is 0.15 to 0.20 kgf. / Cm ² , the allowable limit level × The internal pressure rise is 0.20 to 0.50 kgf / cm ² , and a predetermined amount cannot be supplied stably. ×× The internal pressure rise cannot be more than 0.50 kgf / cm ² , the liquid cannot be supplied.

<< Evaluation of Coated Surface State >> The surface of the coated photosensitive material on the image forming layer side was visually evaluated, and the presence or absence of unevenness on the surface such as unevenness and streaks was evaluated. ◎ Good surface quality without dripping ○ Good with slight unevenness △ Good unevenness is seen, but practically acceptable limit level × unpractical level

The results of the above evaluation are shown in Table 1.

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Sample No. 2 containing no phenolic compound of formula (2) Sample Nos. 1, 6, 20 and the comparative compound added
In 2, 4, γ and Dmax are insufficient. Sample No.
In 3, 5, and 21, the desired sensitivity, γ, and Dmax are obtained, but the filterability of the coating solution and the surface state of the coating are deteriorated. Sample No. In 3, the fog rise is large. On the other hand, in the sample having the configuration of the present invention, it can be seen that the desired sensitivity, γ and Dmax were obtained without fog deterioration, and that the filterability and the surface condition were good. In Example 1,
The nucleating agent AA-1 added to the image forming layer was changed to AA-2 and AA-3, and the same performance evaluation was carried out as described above. As a result, the sample having the structure of the present invention exhibited good results as described above. Performance was obtained.

Example 2 << Preparation of Coating Solution for Image Forming Layer >> The following binder, material, and 1 mol of silver of the organic acid silver salt prepared in Example 1 were used.
Then, a silver halide emulsion was added, and water was added to obtain an image forming layer coating solution. After completion, deaeration under reduced pressure is 0.54.
Performed at atm for 45 minutes. The pH of the coating solution is 7.3 to 7.
7. The viscosity was 40 to 50 mPa · s at 25 ° C.

Binder; SBR latex (St / Bu / AA = 68/29/3 (% by weight), using Na ₂ S ₂ O ₈ as a polymerization initiator) 397.0 g as solid content Formula (1) used in the present invention The same amount as in Example 1 Organic polyhalogen compound A 40.0 g as solid content Organic polyhalogen compound B 12.0 g as solid content Organic polyhalogen compound C 2.0 g as solid content Formula (2) used in the present invention 2.5 mol% with respect to the reducing agent sodium ethyl thiosulfonate 0.3 g benzotriazole 1.2 g polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 10.8 g 6-isopropylphthalazine or a color tone agent Complex of reducing agent or metal Same amount as in Example 1. Compound Z 9.6 g as solid content Compound C 0.2 g Nucleating agent AA 0.02 mol Dye A (added as a mixture with low molecular weight gelatin having an average molecular weight of 15,000) Coating amount at which optical density at 783 nm becomes 0.3 (as a guide, solid content: 0.40 g) Silver halide emulsion A Ag amount 0.06 mol as a preservative 40 ppm in compound A coating solution (2.5 mg / m ² as coating amount) 1% by mass as total solvent amount in coating solution of methanol 2% by mass as total solvent amount in coating solution of ethanol pH NaOH was used as a regulator. (The glass transition temperature of the coating film was 17 ° C.)

<< Preparation of Coating Solution for Lower Layer Protection Layer >> Methyl acrylate / methyl methacrylate = 70/30 (mass ratio, average particle size 110 nm, mass average molecular weight 800,00)
0) polymer latex solution (copolymer glass transition temperature 30 ° C., solid content concentration 28.0%, compound A 100
Water was added to 900 g of
g, polyvinyl alcohol (Kuraray Co., Ltd., PVA-
235) was added, and water was further added to prepare a coating liquid (containing 0.5% by mass of a methanol solvent). After the preparation, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The coating solution has a pH of 5.2 and a viscosity of 35 mPa at 25 ° C.
-It was s.

<< Preparation of Coating Solution for Upper Protective Layer >> Methyl acrylate / methyl methacrylate = 70/30 (mass ratio, average particle size 110 nm, mass average molecular weight 800,00)
0) in 900 g of a polymer latex solution (copolymer, glass transition temperature: 30 ° C., solid content: 28.0%, compound A: 100 ppm), carnava wax (manufactured by Chukyo Yushi Co., Ltd., Cellosol 524, silicone) The content is less than 5 ppm).
g, 0.3 g of compound C, 1.2 g of compound E, 25.0 g of compound F, 6.0 g of compound H, matting agent (polystyrene particles, average particle diameter 7 μm, coefficient of variation of average particle diameter 8)
%) And 40.0 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235), and further added water to prepare a coating solution (containing 1.5% by mass of a methanol solvent). After the preparation, the reaction was performed at a pressure of 0.47 atm for 60 minutes. The coating solution has a pH of 2.4 and a viscosity of 35 at 25 ° C.
mPa · s.

<< Preparation of Photothermographic Material >> A slide plate shown in FIG. 1 of JP-A-2000-2964 is placed on an undercoat layer of a PET support coated with an undercoat layer as described in Example 1. The above-mentioned protective layer lower layer coating solution is coated with the above-mentioned protective layer lower layer coating solution in such a manner that the solid content of the polymer latex is adjusted so that the coating amount of the above-mentioned image forming layer becomes 1.5 g / m ² by using a coating method. as becomes 1.0 g / m ^2, further such that the solid content coating amount of the upper to the upper protective layer coating liquid polymer latex is 1.3 g / m ^2, the image forming layer and the protective layer underlying and The upper three layers were simultaneously coated.

The drying conditions at the time of coating are such that the first drying zone (low-speed air drying area) has a dry bulb temperature of 70 to 75 ° C. and a dew point of 9 to 23.
C., the air velocity on the support surface is 8-10 m / s, and the liquid film surface temperature is 35-40 C. ~ 23
And dried at a wind speed of 20 to 25 m / s on the surface of the support. The residence time in the first drying zone was 2/3 of the constant-rate drying period in this zone, and the zone was moved to the second drying zone and dried. The first drying zone is a horizontal drying zone (the support is at an angle of 1.5 ° to 3 ° with respect to the horizontal direction of the coating machine).
It is. The coating speed was 60 m / min. Winding after drying was performed under the conditions of a temperature of 25 ± 5 ° C. and a relative humidity of 45 ± 10%. The winding shape was adjusted to the subsequent processing form (image forming layer surface side outer winding), and the image forming layer surface side was turned out. The humidity of the wrapping of the photosensitive material is 20 to 40% relative humidity (25%).
Of the resulting photothermographic material, the film surface pH on the image forming side is 5.1, the Beck smoothness is 5000 seconds, the film surface pH on the opposite side is 5.9, and the Beck smoothness is 500. Seconds.

Example 1 except that the coating method was changed
A sample was prepared and evaluated in the same manner as in Example 1.
Similarly, the sample having the configuration of the present invention showed good performance.

Example 3 In the same manner as in Example 2, a coating solution for the lower protective layer was prepared. The coating solution for the upper protective layer was prepared in exactly the same manner as in Example 2 except that 5.0 g of polystyrene particles having an average particle diameter of 11 μm (coefficient of variation of average particle diameter of 8%) was used as a matting agent. Then, on the undercoat layer of the PET support coated with the undercoat layer as described in Example 1, the slide bead coating method shown in FIG. The coating solution for the image forming layer was coated so that the coating amount of silver was 1.5 g / m ^2, and the coating solution for the lower layer of the protective layer was further coated thereon so that the solid content of the polymer latex was 1.2 g / m ² . Further, the above-mentioned coating liquid for the upper layer of the protective layer was simultaneously coated with three layers of the image forming layer and the lower and upper layers of the protective layer so that the coating amount of the solid content of the polymer latex was 1.4 g / m ² .

The drying conditions and winding appearance at the time of coating were the same as in Example 2, and the image forming layer surface side was set to the outside in accordance with the subsequent processing mode (image forming layer surface side outer winding). The humidity of the envelope of the photosensitive material was 20 to 40% relative humidity (measured at 25 ° C.), and the film surface pH on the image forming side of the obtained photothermographic material was 5.1.
The Beck smoothness was 1300 seconds, the pH of the film surface on the opposite side was 5.9, and the Beck smoothness was 500 seconds. The sample thus obtained was evaluated by the same method as in Example 1. As a result, the sample having the structure of the present invention showed good performance as in Example 1.

<Example 4> The photosensitive materials prepared in Examples 1, 2, and 3 were used in a DRY SYSTEM PROCESSOR FDS-6100X.
(Fuji Photo Film) line speed 150c
When heat development was performed at m / min, Example 1,
The samples having the configuration of the present invention as in Nos. 2 and 3 showed good performance.

Example 5 A photothermographic material containing no nucleating agent was prepared from the photothermographic material described in Example 1, and evaluated in the same manner as in Example 1. As a result, the sample having the configuration of the present invention had high Dmax, high sensitivity, low fog, and good filterability of the coating solution and good surface condition.

[0248]

The photothermographic material of the present invention gives high Dmax (maximum density) and high contrast in the presence of a nucleating agent, has low fog, and has optimal photographic characteristics for photolithography. In addition, even when no nucleating agent is contained, high D
Provides good photographic characteristics with a maximum, high sensitivity and low fog.
Further, it is possible to provide a photothermographic material having good filterability of a coating solution and good surface condition of the coated photosensitive material at the time of manufacturing the photosensitive material and having stable image recording performance.

[Brief description of the drawings]

FIG. 1 is a side view showing an example of a configuration of a heat developing machine used for a heat development process of a photothermographic material according to the present invention.

[Explanation of symbols]

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

Continued on the front page (72) Inventor Hirokazu Kyoda 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H123 AB00 AB03 AB23 AB28 BB00 BB25 BB31 BB39 CA00 CA05 CB00 CB03

Claims (10)

[Claims] 1. A support comprising at least (a) a photosensitive silver halide, (b) a reducible non-photosensitive organic silver salt, and (c) a reducing agent represented by the following general formula (1) on the same surface of a support. , (D)
A photothermographic material containing a binder, (e) a compound represented by the following general formula (2), and (f) a toning agent, wherein at least a part of the toning agent is contained after forming a complex in advance. A photothermographic material comprising: Embedded image [In the formula (1), V ^{1 to} V ⁸ each independently represent a hydrogen atom or a substituent, and L represents -CH (V ⁹ )-or-
Represent S- consisting linking group, V ⁹ represents a hydrogen atom or a substituent. ] [In the formula (2), X ¹ represents a substituent, and X ^{2 to} X ⁴ represent a hydrogen atom or a substituent. However, X ^{1 to} X ⁴ are not hydroxyl groups, and X ³ is not a sulfonamide group. The substituents represented by X ^{1 to} X ⁴ may combine with each other to form a ring. R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, or an alkoxy group. ] 2. A support comprising at least (a) a photosensitive silver halide, (b) a reducible non-photosensitive organic silver salt, and (c) a reducing agent represented by the following general formula (1) on the same surface of a support. , (D)
In a photothermographic material containing a binder, (e) a compound represented by the following general formula (2), and (f) a toning agent, 70 mol% or more of the toning agent forms a complex. Photothermographic material. Embedded image [In the formula (1), V ^{1 to} V ⁸ each independently represent a hydrogen atom or a substituent, and L represents -CH (V ⁹ )-or-
Represent S- consisting linking group, V ⁹ represents a hydrogen atom or a substituent. ] [In the formula (2), X ¹ represents a substituent, and X ^{2 to} X ⁴ represent a hydrogen atom or a substituent. However, X ^{1 to} X ⁴ are not hydroxyl groups, and X ³ is not a sulfonamide group. The substituents represented by X ^{1 to} X ⁴ may combine with each other to form a ring. R ¹ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, or an alkoxy group. ] 3. The photothermographic material according to claim 1, wherein at least a part of the color tone agent forms a complex with the reducing agent represented by the formula (1). 4. The photothermographic material according to claim 1, wherein at least a part of the color tone agent forms a complex with a metal. 5. The method according to claim 1, wherein the metal is Zn, Ni, Mg or Ca.
The photothermographic material according to claim 4, wherein 6. The photothermographic material according to claim 1, wherein the color tone agent is a phthalazine compound represented by the following formula (3). Embedded image [In the formula (3), Y represents a hydrogen atom or a monovalent substituent, and m represents an integer of 1 to 6. (Y) m indicates that 1 to 6 Ys are independently present on the phthalazine ring, and when m is 2 or more, even if two adjacent Ys form an aliphatic or aromatic ring, Good. ] 7. The photothermographic material according to claim 1, further comprising a nucleating agent. 8. The photothermographic material according to claim 1, which is used for exposing in less than 10 ^-6 seconds when forming an image. 9. The photothermographic material according to claim 1, wherein the photothermographic material is exposed by a multi-beam having two or more laser heads. 10. The photothermographic material according to claim 1, which is used for heat development at a line speed of 140 cm / min or more.