JP2003140290A - Heat developable photosensitive material and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material with improved processability, raw preservability and storage property of an image after development. SOLUTION: The heat developable photosensitive material is characterized in containing at least (a) a photosensitive silver halide, (b) a reducible silver salt expressed by a specified structure, (c) a reducing agent for silver ion and (d) a binder on one face of a supporting body.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel photothermographic material having improved processability and image storability.

[0002]

2. Description of the Related Art In recent years, in the fields of medical diagnostic films and photoengraving films, there has been a strong demand for reducing the amount of processing waste liquid from the viewpoint of environmental protection and space saving. Therefore, heat development as a film for medical diagnosis and a film for photoengraving, which can be efficiently exposed by a laser imagesetter or a laser imager and can form a clear black image having high resolution and sharpness. There is a need for technology related to photosensitive materials. According to these photothermographic materials, it is possible to provide the customer with a photothermographic processing system that does not require solution-type processing chemicals and is simpler and does not damage the environment.

Although there are similar demands in the field of general image forming materials, particularly medical diagnostic images require fine depiction, so high image quality excellent in sharpness and graininess is required, and diagnostic images are required. There is a feature that a cold black image is preferred from the viewpoint of easiness. At present, various hard copy systems using pigments and dyes such as inkjet printers and electrophotography are in circulation as general image forming systems, but none are satisfactory as output systems for medical images.

On the other hand, thermal image forming systems utilizing reducible silver salts are disclosed in, for example, the specifications of US Pat. Nos. 3,152,904 and 3,457,075 and D.I. By Klosterboer "The Silver System Heat Treated"
(Thermally Processed Silver Systems) "(Imaging Processes & Materials (ImagingPr
ocesses and Materials) Neblette 8th Edition, J. Sturgi
(Sturge), V. Walworth, A. Shep (S
hepp), edited, Chapter 9, p. 279, 1989). In particular, a photothermographic material generally has a catalytically active amount of a photocatalyst (for example, silver halide), a reducing agent, a reducible silver salt (for example, a reducible silver salt), and if necessary, a color for controlling the color tone of silver. The formulation has a photosensitive layer dispersed in a binder matrix. The photothermographic material is heated to a high temperature (for example, 80 ° C. or higher) after image exposure,
The redox reaction between the reducible silver salt (which functions as an oxidant) and the reducing agent forms a black silver image. The redox reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, the black silver image is
It is formed in the exposed area. U.S. Patent 2910377, Japanese Patent Publication No. 43-
It is disclosed in many documents including 4924.

Reducible silver salts used in these photothermographic materials are relatively stable to light, but have an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. Silver salts are conventionally used which form a silver image when heated below 80 ° C. or above. Regarding such a non-photosensitive reducible silver salt, JP-A-06-1
30543, 08-314078, 09-127643, 10-62899
No. 0048 to 0049, Japanese Patent Laid-Open No. 10-94074,
No. 10-94075, European Patent Publication No. 0803764A1, page 18, line 24 to page 19, line 37, European Patent Publication No.
0962812A1, No. 1004930A2, JP-A-11-349591,
JP 2000-7683, 2000-72711, 2000-112057,
2000-155383, etc. Silver salt of organic acid,
In particular, a silver salt of a long-chain aliphatic carboxylic acid (having 10 to 30, preferably 15 to 28 carbon atoms) is used, and examples thereof include silver behenate, silver arachidate, silver stearate, and silver oleate.
Examples thereof include silver laurate, silver caproate, silver myristate, silver palmitate, and mixtures thereof.

US Pat. No. 4,504,575 discloses a silver salt of sulfonic acid, and JP-A-52-137321 discloses a silver complex of a tetrazole derivative, and JP-A-53-11614.
No. 4, JP-A-58-118638 discloses a silver complex of a triazole derivative, and JP-A No. 2000-292881 discloses a silver salt of a methacrylic acid / styrene copolymer. Examples of combined use of silver dicarboxylic acid straight chain alkyl monocarboxylic acid and straight chain alkyl dicarboxylic acid are disclosed in JP-A-4-358144 and JP-A-53-51729. However, in these conventional techniques, polycarboxylic acid such as dicarboxylic acid is used as an additive for improving image quality and storage stability, and polycarboxylic acid such as dicarboxylic acid is used as a silver ion source. The heat-developable photosensitive material has not been known so far.

The photothermographic material contains all the chemical substances necessary for development as described above, and an image can be formed by simply applying heat without using a processing solution. It has the feature that Therefore, with respect to the storability of unused photographic materials and the storability of images after processing, they have many handicaps with respect to the photographic materials that require conventional processing solutions. Efforts have been made. Further, the conventional photothermographic material contains a large amount of reducible silver salt as a solid content, so that the coating film is likely to be peeled off, and the workability is deteriorated.

[0008]

The problem to be solved by the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a photothermographic material having improved processability, raw storability, and image storability after development.

[0009]

The present invention has been achieved by the following means.

(1) at least (a) a photosensitive silver halide, (b) a reducible silver salt represented by the following formula (I), and (c) a silver ion on the same surface of the support. Reducing agent,
And (d) a photothermographic material having a binder. M ¹ O ₂ C-L ¹ -CO ₂ M ² Formula (I) In formula (I), L ¹ is an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, C (= O)-, -O-, -S
-, -S (= O)-, -S (= O) _2- , and -N
It represents a divalent group selected from (R ¹ )-, or a divalent composite group formed by a combination thereof. R ¹ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. M
¹ and M ² represent a hydrogen atom or a counter ion, and at least one of M ¹ and M ² represents a silver (I) ion. The compound represented by the formula (I) may further have a carboxyl group or a salt thereof.

(2) In the compound of formula (I), L ¹
Represents a group having at least one divalent composite group formed by a combination of -C (= O)-and -O-, and the photothermographic material according to (1) above.

(3) In the compound of formula (I), L ¹
Represents a group having at least one divalent composite group formed by a combination of —N (R ² ) — and an alkylene group, and R ²
Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an acyl group or a sulfonyl group, and the photothermographic material according to (1) above.

(4) In the compound of formula (I), L ¹
Represents an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a group having at least one group selected from a divalent heterocyclic group,
And at least one of these groups is --NHCO--R ³
Group, -CONHR ⁴ group, -OCOR ⁵ groups, -CO ₂ R ⁶ group,
-NHSO ₂ -R ⁷ groups, -SO ₂ NHR ⁸ group, -SO ₃ R
⁹ groups, -OSO ₂ R ¹⁰ groups (R ^{3 to} R ¹⁰ have the same meaning as R ² )
The photothermographic material as described in (1) above, which has as a substituent.

(5) In the compound of formula (I), L ¹
Is an alkylene group having at least one substituent, The photothermographic material according to (1) above.

(6) In the compound of formula (I), L ¹
Represents a group having at least one alkylene group, and L ¹ is a —NHCO—R ³ group (R ³ has the same meaning as R ² ).
(1), which has as a substituent,
The photothermographic material according to (4) or (5).

(7) In the compound of formula (I), L ¹
Represents a group having at least one aromatic group, and the photothermographic material according to (1) above. (8) The compound of formula (I) is a reducible silver salt having a molecular weight / the number of silver (I) ions per molecule of 160 or more and 400 or less, and the above (1) to (). The photothermographic material according to any one of 7).

(9) The photothermographic material according to any one of (1) to (8) above, wherein the melting point of the free carboxylic acid of the compound of formula (I) is from 30 ° C to 200 ° C. material.

(10) The photothermographic material as described in any of (1) to (9) above, wherein the compound of formula (I) has a phase transition temperature of 50 ° C. or higher and 180 ° C. or lower. (11) The photothermographic material according to any one of (1) to (10), which contains two or more kinds of the compound of formula (I).

(12) The compound of the formula (I) is contained in an amount of 70 mol% or more based on the total organic silver, and the above (1) to (1)
The photothermographic material according to any one of (11).

(13) An image forming method, which comprises thermally developing the photothermographic material according to any one of (1) to (12).

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The photothermographic material of the present invention comprises at least (a) photosensitive silver halide and (b) on the same surface of a support.
It is characterized by having a reducible silver salt represented by the above formula (I), (c) a reducing agent for silver ions, and (d) a binder.

First, the reducible silver salt represented by the above formula (I) (b) of the present invention will be described. In the formula (I), L ¹ is an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, —C (═O) —, —O—, —S—, —S. (= O)
It represents a divalent group selected from —, —S (═O) ₂ —, and —N (R ¹ ) —, or a divalent composite group formed by a combination thereof. R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. M ¹ and M ² represent a hydrogen atom or a counter ion. However, at least one of M ¹ and M ² represents a silver (I) ion. The compound represented by the formula (I) may further have a carboxyl group as a substituent.

In the formula (I), L ¹ preferably has 1 to 40 carbon atoms, more preferably 2 to 3 carbon atoms.
0, particularly preferably an alkylene group having 2 to 24 carbon atoms (eg, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group). Group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group,
1-methylethylene group, 1-ethylethylene group, cyclohexylmethylene group, etc.), C2-C40, more preferably C2-C30, and most preferably C2-C24 alkenylene group (for example, vinylene group). , Propenylene group, butylene group, pentynylene group, 4
-Methylpentynylene group, etc.), having 2 to 40 carbon atoms,
More preferably, it has 2 to 30 carbon atoms, and particularly preferably,
An alkynylene group having 2 to 24 carbon atoms (eg, ethynylene group, propynylene group, pentynylene group, etc.), 3 to 40 carbon atoms, more preferably 5 to 30 carbon atoms,
Particularly preferably, a cycloalkylene group having 5 to 24 carbon atoms (eg, 1,2-cyclopropylene group, 1,3-
A cyclopentylene group, a 1,4-cyclohexylene group, etc.), a carbon number of 6 to 40, more preferably a carbon number of 6 to 30, and particularly preferably a carbon number of 6 to 24 (eg, 1,2- Phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,8-naphthylene group, 1,5-naphthylene group, etc.), divalent heterocyclic group (2,3-thiophenediyl group, 3, 4-thiophenediyl group, 3,4-furandiyl group, 2,3-pyrrolediyl group, 1,3-pyrrolediyl group, 1,4-imidazolediyl group, 2,4-imidazolediyl group, 3,4
-Pyrazolediyl group, 2,3-pyridinediyl group,
2,4-pyridinediyl group, 2,5-pyridinediyl group, 2,6-pyridinediyl group, 3,4-pyridinediyl group, 3,5-pyridinediyl group, 2,3-pyrazinediyl group, 3,6 -Pyridazinediyl group, 1,2-indolediyl group, 2,8-purinediyl group, 2,4-quinolinediyl group, 1,4-phthalazinediyl group, 2,7-
Naphthyridindiyl group, 2,3-quinoxalinediyl group, 2,4-quinazolinediyl group, 6,7-pteridinediyl group, 2,9-carbazolediyl group, 2,7-carbazolediyl group, 1,2-pyrrolidinediyl group Base,
1,3-imidazolinediyl group, 1,2-pyrazolidinediyl group, 3,5-pyrazolidinediyl group, 1,4-piperidinediyl group, 2,4-piperidinediyl group, 1,
3-isoindolinediyl group, 3,4-morpholinediyl group, etc.), -C (= O)-, -O-, -S-, -S.
(= O) -, - S (= O) 2 -, and -N (R ¹⁾ - a divalent group selected from, or a divalent composite group by combinations thereof.

These divalent groups may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (cycloalkenyl group). Group, including bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and aryl Sulfonylurea Amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group,
Carboxyl group, carbamoyl group, aryl and heterocyclic azo group, imido group, phosphino group, phosphinyl group,
Examples include a phosphinyloxy group, a phosphinylamino group, and a silyl group. When it has a carboxyl group as a substituent, the compound represented by formula (I) may further have a counter ion such as silver ion.

More specifically, a halogen atom (eg, chlorine atom, bromine atom, iodine atom), an alkyl group [linear chain,
It represents a branched or cyclic substituted or unsubstituted alkyl group.
They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, icosyl, 2
-Chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably having 3 to 3 carbon atoms)
0 substituted or unsubstituted cycloalkyl group, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, carbon A monovalent group obtained by removing one hydrogen atom from the bicycloalkane of the numbers 5 to 30. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl. ), And further includes a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) also represents an alkyl group having such a concept. ], An alkenyl group [representing a linear, branched or cyclic, substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted C 3 to 30 carbon atom, or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of 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
To 30 substituted or unsubstituted bicycloalkenyl groups, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl and 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), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) Groups such as phenyl, p-
Tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group (preferably 5)
Alternatively, it is a monovalent group obtained by removing one hydrogen atom from a 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably 5 or 6 having 3 to 30 carbon atoms. Membered aromatic heterocyclic group. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl,
2-benzothiazolyl), cyano group, hydroxyl group,
Nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy,
t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t- Butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group ( Preferably, it has 2 to 3 carbon atoms.
0-substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) Carbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy. Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms) Substituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonyl having 1 to 30 carbon atoms) Amino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino,
3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N)
-Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino) , T-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, , Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino), sulfamoylamino group (preferably carbon) 0 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably A substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5- Trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms).
A substituted or unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenyl). Thio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-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-dimethylsulfamoyl, N
-Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl having 1 to 30 carbon atoms) A group, 6 to 30 substituted or unsubstituted arylsulfinyl groups, for example methylsulfinyl, ethylsulfinyl, phenylsulfinyl,
p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethyl Sulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, Carbon number 4 to 3
A heterocyclic carbonyl group linked to a carbonyl group at 0 substituted or unsubstituted carbon atoms, for example acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p- (n-octyloxy) phenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl, aryloxycarbonyl group (preferably substituted or unsubstituted with 7 to 30 carbon atoms). Substituted aryloxycarbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted with 2 to 30 carbon atoms) Alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carboxyl groups, carbamoyl groups (preferably having 1 carbon atom).
To 30 substituted or unsubstituted carbamoyl, such as 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, 3 carbon atoms)
To 30 substituted or unsubstituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo, imide groups (preferably N-succinimide, N
-Phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 30 carbon atoms). 30 substituted or unsubstituted phosphinyl groups, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy groups (preferably substituted or unsubstituted phosphinyl having 2 to 30 carbon atoms) Oxy group, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphinylamino groups, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl groups (preferably,
A substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl,
Phenyldimethylsilyl). Among the above-mentioned functional groups, those having a hydrogen atom may be substituted with the above-mentioned group after removing the hydrogen atom. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl groups.

R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. The alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group or sulfonyl group for R ¹ may further have a substituent, and a preferable substituent is the above-mentioned substituent for L ¹ . Preferred examples can be given.

R ¹ is preferably an alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, t-octyl. , Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl, henicosyl, docosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, cyclohexyl, cyclopentyl, 4-n-
Dodecylcyclohexyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), an acyl group or A sulfonyl group, more preferably an alkyl group, an aryl group or an acyl group,
Particularly preferred is an acyl group.

When L ¹ represents a composite substituent formed of a combination of divalent groups, examples of the composite substituent include ester (alkyloxycarbonyl, aryloxycarbonyl, carbonic acid ester), thiocarboxylic acid ester, dithiocarboxylic acid ester. , Amide (carbamoyl), urea substituted (ureylene), thiourea substituted, sulfonamide (sulfamoyl), imide, hydrazine, hydrazide (hydrazinocarbonyl), amidine, ether, thioether, acyl and the like. These groups may be further combined and may have a substituent.

As a preferred example of the compound of the formula (I), L
¹ represents a group having at least one divalent composite group formed by a combination of —N (R ² ) — and an alkylene group, and R ²
Is an alkyl group (preferably having 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 carbon atoms).
To 25), an alkenyl group (preferably having 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms), an alkynyl group (preferably having 2 to 40 carbon atoms, further preferably having carbon atoms). 4 to 30, particularly preferably 6 to 25 carbon atoms, aryl group (preferably 6 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, particularly preferably 6 to 3 carbon atoms)
0), an acyl group (preferably having 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms) or a sulfonyl group (preferably having 1 to 40 carbon atoms, more preferably 4 carbon atoms). To 30 and particularly preferably those having 6 to 25 carbon atoms.

The divalent composite group represented by the combination of -N (R ² )-and the alkylene group represented by L ¹ is-(C
H) _n N (R ² )-(CH) _m- (n, m is preferably 1
To 30),-(CH) ₁ N (R ² )-(CH) _n N
(R ² )-(CH) _m- (l, n, m are preferably 1 to 30) and the like. These alkylene groups may further have a substituent.

As a preferred example of the compound of formula (I), L
¹Is an alkylene group (preferably having 1 to 40 carbon atoms,
Preferably having 4 to 30 carbon atoms, particularly preferably carbon
Number 6 to 25), alkenylene group (preferably carbon number)
2 to 40, more preferably 4 to 30 carbon atoms,
Preferably having 6 to 25 carbon atoms, an alkynylene group
(Preferably having 2 to 40 carbon atoms, more preferably carbon
Number 4 to 30, particularly preferably number 6 to 2 carbon atoms
5), a cycloalkylene group (preferably having a carbon number of 3 to 3)
20, more preferably 5 to 20 carbon atoms, particularly preferred
Or 6 to 15 carbon atoms, an arylene group (preferably
6 to 40 carbon atoms, more preferably 6 to 3 carbon atoms
0, particularly preferably 6 to 20 carbon atoms, and divalent
A heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably
It preferably has 1 to 20 carbon atoms, particularly preferably 2 carbon atoms.
Group having at least one group selected from the following: 15)
And at least one of these groups is --NHC
OR³Group, -CONHR^FourGroup, -OCOR^FiveGroup, -CO₂
R⁶Group, -NHSO₂R⁷Group, -SO₂NHR⁸Group, -SO₃
R ⁹Group, -OSO₂R^TenGroup (R³~ R^TenIs R²Synonymous with
Also having as a substituent. L¹Is a chain
It may be in a shape or may be branched.

As a preferred example of the compound of formula (I), L
Those in which ¹ is an alkylene group having at least one substituent are also included. Examples of preferable substituents of the alkylene group 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, an aryl group, a heterocycle. Group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( (Including anilino group), -NHCOR
³ groups (R ³ has the same meaning as R ² ), aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino groups, mercapto group, alkylthio group, arylthio Group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group,
Examples thereof include an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. More preferably, an alkyl group (preferably having a carbon number of 1 to 40, further preferably a carbon number of 4 to 30, particularly preferably a carbon number of 6 to 25), an alkenyl group (preferably having a carbon number of 2 to 40, further preferably a carbon number). Four
To 30, particularly preferably 6 to 25 carbon atoms, an alkynyl group (preferably 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms), an aryl group (preferably carbon number) 6 to 4
0, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms, heterocyclic group, alkoxy group (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably carbon number) 6 to 2
5), an aryloxy group (preferably having 6 to 4 carbon atoms)
0, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms, heterocyclic oxy group, acyloxy group (preferably 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably carbon) C6 to C25), carbamoyloxy group (preferably C2 to C40, more preferably C4 to C30, particularly preferably C6 to C25), amino group (preferably C1 to C40, more preferably C4 to C30) Has 4 to 3 carbon atoms
0, particularly preferably 6 to 25 carbon atoms, -NHCO
R ³ group (R ³ has the same meaning as R ² ) (preferably having 1 carbon atom)
To 40, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms, sulfamoylamino group (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably carbon number) 6 to 2
5), an alkyl and arylsulfonylamino group (preferably having 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms), a sulfamoyl group (preferably having 1 to 40 carbon atoms, further preferably Has 4 to 30 carbon atoms, particularly preferably 6 carbon atoms
To 25), alkyl and arylsulfonyl groups (preferably having 1 to 40 carbon atoms, more preferably having 4 carbon atoms).
To 30, particularly preferably 6 to 25 carbon atoms, an acyl group (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms), an aryloxycarbonyl group (preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms,
Particularly preferably 6 to 25 carbon atoms, an alkoxycarbonyl group (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms), a carbamoyl group (preferably 1 to 40 carbon atoms). 40, more preferably 4 to 30 carbon atoms, and particularly preferably 6 to 25 carbon atoms.

Particularly preferred is an alkyl group (preferably having 1 to 40 carbon atoms, more preferably 4 to 3 carbon atoms).
0, particularly preferably 6 to 25 carbon atoms, an alkenyl group (preferably 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 2 carbon atoms).
5), an alkynyl group (preferably having 2 to 40 carbon atoms,
More preferably, it has 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms, and an aryl group (preferably 6 carbon atoms).
To 40, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms, an alkoxy group (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms). ), An aryloxy group (preferably having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 carbon atoms).
To 25), -NHCOR ³ group (R ³ has the same meaning as R ² ) (preferably 1 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, particularly preferably 6 to 2 carbon atoms).
5).

Examples of the divalent complex group in which L ¹ is a combination of —C (═O) — and —O—, which are mentioned as a preferred example of the compound of the formula (I), include an acyloxy group and a carbamoyloxy group. , An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and the like.

As a preferred example of the compound of formula (I), L
Those in which ¹ is a group having at least one aromatic group are also included. The aromatic group referred to herein is an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, etc.). , An aromatic heterocyclic group (preferably having 3 to 30 carbon atoms)
A 5- or 6-membered aromatic heterocyclic group of
Furyl, thienyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, quinoxalinyl, quinazolinyl, indazolyl, phthalazinyl, purinyl, pteridinyl, carbazolyl, etc., and these groups are
Further, it may have a substituent. Examples of substituents are:
The aforementioned substituents which L ¹ may have may be mentioned.

The compound of formula (I) has a quotient of the molecular weight of the compound of formula (I) divided by the number of silver (I) ions in one molecule of the compound of formula (I), preferably 160 or more and 400 or less. It is more preferably 250 or more and 400 or less, and particularly preferably 300 or more and 400 or less.

The melting point of the free carboxylic acid of the compound of formula (I) of the present invention is preferably 30 ° C. or higher and 200 ° C. or lower, more preferably 50 ° C. or higher and 180 ° C. or lower, and particularly preferably 6
It is 5 ° C. or higher and 150 ° C. or lower. As used herein, the free carboxylic acid of the compound of formula (I) is represented by a form in which all the carboxyl groups in the compound of formula (I) do not form a salt with a counter ion, ie, -COOH. A compound derived to a structure

The phase transition temperature of the compound of formula (I) of the present invention is preferably 50 ° C. or higher and 180 ° C. or lower, more preferably 70 ° C. or higher and 170 ° C. or lower, and particularly preferably 85 ° C. or higher and 150 ° C. or lower.

In the present invention, the compound of formula (I) is 70 mol% or more, preferably 85 mol% or more, based on the total organic silver.
It is preferably 95 mol% or more.

The compound of formula (I) of the present invention may be used alone or in combination of two or more kinds. Formula (I)
The compound used in combination of two or more kinds of the compounds may be two or more kinds of compounds having different plane structural formulas,
It may be a mixture of isomers such as geometric isomers, stereoisomers, diastereomers and enantiomers.

The compound represented by the formula (I) of the present invention may be produced by any known synthetic method, and may be prepared by the Chemical Society of Japan, 4th edition, Vol. 22, pp. 1-43, 193, ed.
It can be easily produced by those skilled in the art by referring to page 227 and the references described therein.

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

[0044]

[Chemical 1]

[0045]

[Chemical 2]

[0046]

[Chemical 3]

[0047]

[Chemical 4]

[0048]

[Chemical 5]

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical 12]

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

Known methods and the like can be applied to the method for producing the reducible silver salt used in the present invention and the dispersing method thereof. For example, JP-A-10-62899 and European Patent Publication 08 mentioned above.
03763A1, European Patent Publication No. 0962812A1, JP-A-11-34959
No. 1, JP 2000-7683, No. 2000-72711, Japanese Patent Application No. 11-348
No. 228-30, No. 11-203413, Japanese Patent Application No. 2000-90093, No. 2000
-195621, 2000-191226, 2000-213813, 200
0-214155 and 2000-191226 can be referred to.

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

In the present invention, it is possible to produce a light-sensitive material by mixing a reducible silver salt aqueous dispersion and a photosensitive silver salt aqueous dispersion, but the mixing ratio of the reducible silver salt and the photosensitive silver salt ( The molar ratio can be selected according to the purpose, but the ratio of the photosensitive silver salt to the reducible silver salt is preferably in the range of 1 to 30 mol%, more preferably 3 to 20 mol%, and particularly 5 to 15 mol%. preferable. Mixing two or more types of reducible silver salt aqueous dispersions and two or more types of photosensitive silver salt aqueous dispersions at the time of mixing is a method preferably used for controlling photographic characteristics.

[0068] (b) a reducible silver salt of the invention can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably from 1 to 3 g / m ^2.

(Explanation of Reducing Agent) The photothermographic material of the invention preferably contains a reducing agent for a reducible silver salt. The reducing agent for the reducible silver salt may be any substance (preferably organic substance) that reduces silver ions to metallic silver. Such reducing agents are described in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 0803764A1, page 7, line 34 to page 18, line 12. In the present invention, the reducing agent is preferably a hindered phenol reducing agent or a bisphenol reducing agent, more preferably a compound represented by the following general formula (R).

[0070]

[Chemical formula 22]

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

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

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

L represents a --S-- group or a --CHR ¹³ -group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may have a substituent. R ¹³
Specific examples of the unsubstituted alkyl group of are methyl group, ethyl group,
Examples thereof include a propyl group, a butyl group, a heptyl group, an undecyl group, an isopropyl group, a 1-ethylpentyl group and a 2,4,4-trimethylpentyl group. Examples of the substituent of the alkyl group are the same as the substituents of R ¹¹ , and include a halogen atom, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acylamino group, a sulfonamide group, a sulfonyl group, a phosphoryl group, an oxycarbonyl group, Examples thereof include a carbamoyl group and a sulfamoyl group.

R ¹¹ and R ¹¹ ′ are preferably a secondary or tertiary alkyl group having 3 to 15 carbon atoms, specifically, isopropyl group, isobutyl group, t-butyl group,
Examples thereof include t-amyl group, t-octyl group, cyclohexyl group, cyclopentyl group, 1-methylcyclohexyl group and 1-methylcyclopropyl group. R ¹¹ and R
¹¹ 'is more preferably a tertiary alkyl group having 4 to 12 carbon atoms, and among them, t-butyl group, t-amyl group, 1-
A methylcyclohexyl group is more preferred, and a t-butyl group is most preferred.

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

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

R¹³When is a hydrogen atom, R¹²And R
¹²Is preferably an alkyl group having 2 to 5 carbon atoms,
Group and propyl group are more preferred, and ethyl group is most preferred.
Good R¹³Is a primary or secondary alkyl having 1 to 8 carbon atoms
When it is a group, R¹²And R ¹²'Is preferably a methyl group
Yes. R¹³A C1-C8 primary or secondary alkyl group
Are methyl group, ethyl group, propyl group, isopropyl group
Group, more preferably a methyl group, an ethyl group, a propyl group
Is more preferable. R¹¹, R¹¹', R¹²And R¹²'
When these are also methyl groups, R¹³Is a secondary alkyl group
Is preferred. In this case R¹³Secondary alkyl group
Examples include isopropyl group, isobutyl group, 1-ethyl group
Preferred is an ethyl group, and more preferred is an isopropyl group.

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

[0080]

[Chemical formula 23]

[0081]

[Chemical formula 24]

[0082]

[Chemical 25]

In the present invention, the addition amount of the reducing agent is 0.01
Is preferably 5.0 to 5.0 g / m ² , and 0.1 to 3.
The amount is more preferably 0 g / m ² , and is preferably 5 to 50% by mol, and more preferably 10 to 40% by mol based on 1 mol of silver on the surface having the image forming layer. The reducing agent is preferably contained in the image forming layer.

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

As the solid fine particle dispersion method, a powder of a reducing agent is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves to obtain a solid dispersion. There is a method of creating. At that time, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three different isopropyl group substitution positions) or the like) may be used. Good. The water dispersion may contain a preservative (for example, benzoisothiazolinone sodium salt).

(Explanation of Development Accelerator) In the photothermographic material of the present invention, a phenol derivative represented by the formula (A) described in Japanese Patent Application No. 11-73951 is preferably used as a development accelerator.

(Explanation of Hydrogen Bonding Compound) When the reducing agent in the present invention has an aromatic hydroxyl group (—OH),
Particularly in the case of the above-mentioned bisphenols, it is preferable to use a non-reducing compound having a group capable of forming a hydrogen bond with these groups in combination.

Examples of the group forming a hydrogen bond with a hydroxyl group or an amino group include a phosphoryl group, a sulfoxide group, a sulfonyl group, a carbonyl group, an amide group, an ester group, a urethane group, a ureido group, a tertiary amino group, and a nitrogen-containing aromatic group. Groups and the like. Among them, the phosphoryl group is preferable,
Sulfoxide group, amide group (provided that it has no> N-H group and is blocked as> N-Ra (Ra is a substituent other than H)), urethane group (provided that> N-H group). , And is blocked like> N-Ra (Ra is a substituent other than H) and a ureido group (provided that it has no> N-H group and> N-Ra (Ra is other than H). And the compound is blocked). In the present invention, a particularly preferable hydrogen-bonding compound is a compound represented by the following general formula (D).

[0089]

[Chemical formula 26]

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

Specific examples of the alkyl group represented by R ²¹ to R ²³ include methyl group, ethyl group, butyl group, octyl group, dodecyl group, isopropyl group, t-butyl group, t-amyl group, t-octyl group, Examples thereof include cyclohexyl group, 1-methylcyclohexyl group, benzyl group, phenethyl group and 2-phenoxypropyl group. As the aryl group, a phenyl group, a cresyl group, a xylyl group, a naphthyl group,
4-t-butylphenyl group, 4-t-octylphenyl group, 4-anisidyl group, 3,5-dichlorophenyl group and the like can be mentioned. As the alkoxy group, methoxy group, ethoxy group, butoxy group, octyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, dodecyloxy group, cyclohexyloxy group,
4-methylcyclohexyloxy group, benzyloxy group and the like can be mentioned. Aryloxy groups include phenoxy group, cresyloxy group, isopropylphenoxy group, 4
Examples thereof include -t-butylphenoxy group, naphthoxy group, biphenyloxy group and the like. Examples of the amino group include dimethylamino group, diethylamino group, dibutylamino group, dioctylamino group, N-methyl-N-hexylamino group, dicyclohexylamino group, diphenylamino group, N-methyl-N-phenylamino group and the like. .

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

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

[0094]

[Chemical 27]

[0095]

[Chemical 28]

Specific examples of the hydrogen-bonding compound include those described in Japanese Patent Application Nos. 2000-192191 and 2000-194811 in addition to the above. The compound of the general formula (D) of the present invention can be used in a light-sensitive material by containing it in a coating solution in the form of a solution, an emulsified dispersion, or a solid fine particle dispersion, like a reducing agent. The compound of the present invention forms a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state, and as a complex depending on the combination of the reducing agent and the compound of the general formula (D) of the present invention. It can be isolated in crystalline form. It is particularly preferable to use the crystal powder thus isolated as a solid fine particle dispersion in order to obtain stable performance. Further, a method in which a reducing agent and the compound of the general formula (D) of the present invention are mixed in a powder form and a complex is formed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can also be preferably used.

The compound of the general formula (D) of the present invention is preferably used in the range of 1 to 200 mol%, more preferably 10 to 150 mol%, further preferably 30% with respect to the reducing agent. To 100 mol%.

(Explanation of Silver Halide) The photosensitive silver halide used in the present invention is not particularly limited in halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and iodochloroodor. Silver halide can be used. Among them, silver bromide and silver iodobromide are preferable. The distribution of the halogen composition in the grain may be uniform, the halogen composition may be changed stepwise, or the halogen composition may be continuously changed. Further, silver halide grains having a core / shell structure can be preferably used. The preferred structure is a 2- to 5-fold structure, more preferably 2- to 5-fold structure.
Quadruple-structure core / shell particles can be used. Further, a technique of localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods of forming photosensitive silver halide are well known in the art, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,45.
Although the method described in No. 8 can be used, specifically, a photosensitive silver halide is prepared by adding a silver-providing compound and a halogen-providing compound to gelatin or another polymer solution, and then adding A method of mixing with a reducible silver salt is used. Further, the method described in paragraph Nos. 0217 to 0224 of JP-A No. 11-119374,
The methods described in Japanese Patent Application Nos. 11-98708 and 2000-42336 are also preferable.

The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less, More preferably, it is 0.02 μm or more and 0.12 μm or less. The grain size as used herein refers to the diameter when converted into a circular image having the same area as the projected area of silver halide grains (projected area of the principal plane in the case of tabular grains).

The shape of the silver halide grains is cubic,
Examples thereof include octahedra, tabular grains, spherical grains, rod-shaped grains, and potato-shaped grains, but cubic grains are particularly preferable in the present invention. Grains with rounded corners of silver halide grains can also be preferably used. There is no particular limitation on the surface index (Miller index) of the outer surface of the photosensitive silver halide grain, but the ratio of [100] surface, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, is high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, still more preferably 80% or more. The ratio of Miller index [100] planes is based on the adsorption dependence of [111] and [100] planes in the adsorption of sensitizing dyes.
i; J.Imaging Sci., 29, 165 (1985).

In the present invention, a silver halide grain having a hexacyano metal complex on the outermost surface of the grain is preferred. As the hexacyano metal complex, [Fe (CN) ₆ ] ^4- , [Fe (CN) ₆ ] ^3- ,
[Ru (CN) ₆ ] ^4- , [Os (CN) ₆ ] ^4- , [Co (CN) ₆ ] ^3- , [Rh (C
^{_{N) 6] 3-, [Ir}} (CN) 6] 3-, [Cr (CN) 6] 3 -, and the like ^{_{3- [Re (CN) 6]}} . In the present invention, a hexacyano Fe complex is preferable.

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

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

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

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

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

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

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

Further, a metal atom (eg, [Fe (CN) ₆ ]] that can be contained in the silver halide grain used in the present invention.
^4- ), desalting method and chemical sensitizing method of silver halide emulsion are disclosed in JP-A No. 11-84574, paragraphs 0046 to 0050 and JP-A No. 11-650.
No. 21, paragraphs 0025 to 0031, JP-A No. 11-119374, paragraph number 0
242-250.

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

The sensitizing dye applicable to the present invention is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for the spectral characteristics of the exposure light source. The sensitizing dye having can be advantageously selected. For the sensitizing dye and the addition method, see JP-A-11
-65021, paragraph numbers 0103 to 0109, JP-A-10-186572, compounds represented by general formula (II), JP-A-11-119374, dyes represented by general formula (I) and paragraph number 0106, US Japanese Patent Nos. 5,510,236 and 3,871,887, dyes described in Example 5, dyes disclosed in JP-A-2-96131 and JP-A-59-48753, European Patent Publication No. 0803764A1, page 19, page 3
Line 8 to page 20, line 35, Japanese Patent Application No. 2000-86865, Japanese Patent Application 2000-
No. 102560, Japanese Patent Application No. 2000-205399, etc. These sensitizing dyes may be used alone or in combination of two or more kinds. In the present invention, the sensitizing dye is added to the silver halide emulsion preferably after the desalting step and before coating, more preferably after the desalting step and before the start of chemical ripening.

The addition amount of the sensitizing dye in the present invention can be a desired amount depending on the sensitivity and fog performance, but it is 1 × 10 ^-6 to 1 mol per mol of silver halide in the photosensitive layer.
1 mol is preferable, and 1 × 10 ⁻⁴ to 10 is more preferable.
^-1 mol.

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

The photosensitive silver halide grains in the present invention are preferably chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method or a tellurium sensitizing method. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds, for example, the compounds described in JP-A-7-128768 can be used. Particularly in the present invention, tellurium sensitization is preferred, and compounds described in the literature of paragraph No. 0030 of JP-A No. 11-65021, JP-A No. 5-31
Compounds represented by formulas (II), (III) and (IV) in 3284 are more preferable.

In the present invention, chemical sensitization can be performed at any time after grain formation and before coating. After desalting, (1) before spectral sensitization, (2) simultaneously with spectral sensitization, ( 3)
After spectral sensitization, there may be (4) immediately before coating, or the like. In particular, it is preferably performed after spectral sensitization.

The amounts of the sulfur, selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but are 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably about 10 ⁻⁷ to 10 ⁻³ mol. The conditions for chemical sensitization in the present invention are not particularly limited, but pH is 5 to 8, pAg is 6 to 11, and temperature is about 40 to 95 ° C.
The silver halide emulsion used in the present invention includes European Patent Publication No.
A thiosulfonic acid compound may be added according to the method disclosed in Japanese Patent No. 293,917.

The photosensitive silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, and those having different crystal habits). , Different chemical sensitization conditions) may be used together. Gradation can be adjusted by using a plurality of photosensitive silver halides having different sensitivities.
Techniques related to these are disclosed in JP-A-57-119341 and 53-
106125, 47-3929, 48-55730, 46-5187,
50-73627, 57-150841 and the like. As a difference in sensitivity, it is preferable that each emulsion has a difference of 0.2 logE or more.

The amount of photosensitive silver halide added was 1 m for the light-sensitive material.
Indicated by the amount of coated silver per ^{2, 0.03~0.6g} / m ²
Is preferably, more preferably from 0.07~0.4g / m ^2, and most preferably from 0.05 to 0.3 g / m ^2, relative to the reducible silver salt 1 mole Is preferably 0.01 mol or more and 0.5 mol or less, and more preferably 0.02 mol or more and 0.3 mol or less.

Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and reducible silver salt, the prepared silver halide grains and reducible silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, A method of mixing with a colloid mill, a vibration mill, a homogenizer, etc., or a method of mixing a photosensitive silver halide prepared at any timing during preparation of a reducible silver salt to prepare a reducible silver salt. However, there is no particular limitation as long as the effects of the present invention are sufficiently exhibited. In addition, mixing two or more types of reducible silver salt aqueous dispersions and two or more types of photosensitive silver salt aqueous dispersions at the time of mixing is a preferable method for controlling photographic characteristics.

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

(Description of Binder) The binder of the reducible silver salt-containing layer of the present invention may be used in combination with any polymer in addition to the latex of the present invention, and a suitable binder is transparent or translucent and generally colorless. Yes, natural resins and polymers and copolymers, synthetic resins and polymers and copolymers, and other film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethyl celluloses, cellulose acetates, and cellulose acetate butyrate. , Poly (vinylpyrrolidone) s, casein, starch, poly (acrylic acid) s,
Poly (methylmethacrylic acid) s, Poly (vinyl chloride)
, Poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (vinyl acetal) s (for example, poly (vinyl formal) and Poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resin, poly (vinylidene chloride) s, poly (epoxides), poly (carbonates), poly (vinyl acetate) s, poly ( Olefin)
, Cellulose esters, and poly (amide) s.
The binder may be formed by coating with water, an organic solvent or an emulsion.

In the present invention, the glass transition temperature of the binder that can be used in combination with the layer containing the reducible silver salt is preferably 10 ° C. or higher and 80 ° C. or lower (hereinafter, referred to as high Tg binder), preferably 20 ° C. or higher. The temperature is more preferably 70 ° C., further preferably 23 ° C. or higher and 65 ° C. or lower.

In this specification, Tg is calculated by the following formula. 1 / Tg = Σ (Xi / Tgi) Here, it is assumed that the polymer is a copolymer of n monomer components from i = 1 to n. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer.
However, Σ is the sum of i = 1 to n. The homopolymer glass transition temperature (Tgi) of each monomer is Polymer H
andbook (3rd Edition) (J. Brandrup, EHImmergut (Wi
ley-Interscience, 1989)).

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

In the present invention, when the reducible silver salt-containing layer is formed by coating with a coating solution in which 30% by mass or more of the solvent is water and drying, a reducible silver salt-containing layer is further contained. Performance is improved when the binder of the layer is soluble or dispersible in an aqueous solvent (water solvent), particularly when it is composed of a polymer latex having an equilibrium water content of 2% by mass or less at 25 ° C. and 60% RH. The most preferable form is one prepared to have an ionic conductivity of 2.5 mS / cm or less. As such a preparation method, there is a method of purifying using a separation functional membrane after polymer synthesis.

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

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

The term "equilibrium water content at 25 ° C. 60% RH" means the weight W1 of the polymer in humidity controlled equilibrium under the atmosphere of 25 ° C. 60% RH and the weight WO of the polymer in the absolutely dry state at 25 ° C. It can be expressed as follows.
Equilibrium water content at 25 ° C. and 60% RH = [(W1-W
0) / W0] × 100 (mass%)

For the definition and measurement method of the water content, see, for example, Polymer Engineering Course 14, Polymer Materials Testing Method (edited by the Polymer Society of Japan,
You can refer to Jijijinkan.

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

In the present invention, a polymer dispersible in an aqueous solvent is particularly preferable. Examples of the dispersed state include a latex in which fine particles of a water-insoluble hydrophobic polymer are dispersed, and a state in which polymer molecules are dispersed in a molecular state or in the form of micelles, and both are preferable. The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably 5 to
The range of about 1000 nm is preferable. The particle size distribution of the dispersed particles is not particularly limited, and may be a wide particle size distribution or a monodisperse particle size distribution.

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

The polymer latexes described above are commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635,471
8,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx81
FINETEX ES65 is an example of poly (ester) s such as 1, 814, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.).
0, 611, 675, 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD
HYDRAN AP10, 20, 30, 40 as an example of poly (urethane) such as -size, WMS (above Eastman Chemical)
Examples of rubbers such as (manufactured by Dainippon Ink & Chemicals, Inc.) are LACSTAR 7310K, 3307B, 4700H, 7132C (manufactured by Dainippon Ink & Chemicals, Inc.), Nipol Lx416, 410, 438C, 250.
Examples of poly (vinyl chloride) s such as 7 (all manufactured by Nippon Zeon Co., Ltd.) include G351 and G576 (all manufactured by Nippon Zeon Co., Ltd.), and examples of poly (vinylidene chloride) such as L502, Examples of poly (olefin) s such as L513 (all manufactured by Asahi Kasei Corporation) are Chemipearl S120 and SA10.
0 (above, manufactured by Mitsui Petrochemical Co., Ltd.) and the like.

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

(Preferable Latex) As the polymer latex used in the present invention, a latex of styrene-butadiene copolymer is particularly preferable. The weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is 40:60 to 95:
It is preferably 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by mass. The preferred molecular weight range is the same as above.

Styrene preferably used in the present invention-
As the latex of the butadiene copolymer, the above-mentioned P-3
~ P-8,15, LACSTAR-3307B, 7132C, Nipol which is a commercial product
Lx416 etc. are mentioned.

If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose may be added to the reducible silver salt-containing layer of the light-sensitive material of the present invention. The addition amount of these hydrophilic polymers is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total binder of the reducible silver salt-containing layer.

The reducible silver salt-containing layer (that is, the image forming layer) of the present invention is preferably formed using a polymer latex. The amount of binder in the reducible silver salt-containing layer is such that the weight ratio of total binder / reducible silver salt is 1/1.
The range of 0 to 10/1, more preferably 1/5 to 4/1 is preferable.

Further, such a reducible silver salt-containing layer is usually also a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt. In such a case,
The total binder / silver halide weight ratio is preferably in the range of 400 to 5, more preferably 200 to 10.

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

(Preferred Solvent for Coating Solution) In the present invention, the solvent for the reducible silver salt-containing layer coating solution for the light-sensitive material (for simplicity, the solvent and the dispersion medium are collectively referred to as the solvent).
Is preferably an aqueous solvent containing 30% by mass or more of water. As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide or ethyl acetate may be used. The water content of the solvent of the coating liquid is 50% by mass or more, more preferably 70% by mass.
The above is preferable.

As examples of preferred solvent compositions, in addition to water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide =
80/15/5, water / methyl alcohol / ethyl cellosolve = 85/1
0/5, water / methyl alcohol / isopropyl alcohol = 8
There are 5/10/5 etc. (numerical value is% by mass).

(Explanation of Antifoggant) Antifoggants and antifoggant precursors that can be used in the present invention are described in JP-A No. 10-62899, paragraph No. 0070, and European Patent Publication No. 0803764A1, No. 20. Examples include the compounds described on page 57, line 57 to page 21, line 7, and the compounds described in JP-A Nos. 9-281637 and 9-329864. The antifoggants preferably used in the present invention are organic halides, and examples thereof include those disclosed in the patents described in paragraph Nos. 0111 to 0112 of JP-A No. 11-65021. In particular, organic halogen compounds represented by the formula (P) of Japanese Patent Application No. 11-87297, organic polyhalogen compounds represented by the general formula (II) of Japanese Patent Application Laid-Open No. 10-339934, Japanese Patent Application No. 11-205330 are disclosed. The described organic polyhalogen compounds are preferred.

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

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

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

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

Examples of such an electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.2).
3), iodine atom (σp value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp value: 0) .54)), a cyano group (σp value: 0.6)
6), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, Acetyl (σp value: 0.5
0), benzoyl (σp value: 0.43)), alkynyl group (for example, C≡CH (σp value: 0.23)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value)). : 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value:
0.57), a sulfoxide group, a heterocyclic group, a phosphoryl group and the like.

The σp value is preferably 0.2 to 2.0.
Is more preferable, and the range of 0.4 to 1.0 is more preferable. Particularly preferable as the electron-withdrawing group are a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group and an alkylphosphoryl group, and among them, a carbamoyl group is the most preferable.

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

Y is preferably -C (= O)-, -SO-.
Or represents —SO ₂ —, more preferably —C (═O)
-, - SO ₂ -, and particularly preferably -SO ₂ - it is. n represents 0 or 1, and is preferably 1.

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

[0154]

[Chemical 29]

[0155]

[Chemical 30]

The compound represented by the general formula (H) of the present invention is 1 × 10 ⁻⁴ to 1 mol per mol of the non-photosensitive silver salt in the image forming layer.
It is preferably used in the range of 1 mol, more preferably in the range of 1 × 10 ^{−3 to} 0.8 mol, and further preferably in the range of 5 × 10 ^{−3 to} 0.5 mol. In the present invention, examples of the method of incorporating the antifoggant into the light-sensitive material include the methods described in the method of incorporating the reducing agent, and the organic polyhalogen compound is also preferably added in the form of solid fine particle dispersion.

(Other Antifoggants) Other antifoggants include mercury (I) disclosed in paragraph No. 0113 of JP-A No. 11-65021.
I) Salt, benzoic acids of paragraph No. 0114 of the same item, JP 2000-20664 A
No. 2, a salicylic acid derivative, a formalin scavenger compound represented by the formula (S) of JP-A-2000-221634, JP-A-11-3
Triazine compound according to claim 9 of 52624, JP-A-6-16-1
A compound represented by the general formula (III) of 1791, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene and the like can be mentioned.

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

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

In the present invention, a mercapto compound, a disulfide compound or a thione compound is contained for the purpose of suppressing or accelerating the development to control the development, improving the spectral sensitization efficiency, and improving the storage stability before and after the development. Nos. 0067 to 0069 in JP-A-10-62899, compounds represented by the general formula (I) in JP-A-10-186572 and paragraphs 0033 to 0052 as specific examples thereof, European Patent Publication No.
0803764A1, page 20, lines 36-56, Japanese Patent Application No. 11-
No. 273670, etc. Of these, mercapto-substituted heteroaromatic compounds are preferable.

(Explanation of Color Tone Agent) In the photothermographic material of the present invention, it is preferable to add a color tone agent, and the color tone agent is described in JP-A No. 10-62899, paragraphs 0054 to 0055, and European Patent Publication No. 08.
No. 03764A1, page 21, lines 23 to 48, JP-A-2000-356317
No. 2000-187298 and particularly phthalazinones (phthalazinone, phthalazinone derivatives or metal salts; for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazide Non and 2,
3-dihydro-1,4-phthalazinedione); phthalazinones and phthalic acids (eg phthalic acid, 4-methylphthalic acid, 4
-Nitrophthalic acid, diammonium phthalate, sodium phthalate, potassium phthalate and tetrachlorophthalic anhydride); phthalazines (phthalazine, phthalazine derivatives or metal salts; eg 4- (1-naphthyl))
Phthalazine, 6-isopropylphthalazine, 6-t-butylflatazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine); a combination of phthalazines and phthalic acids is preferable, A combination of phthalazines and phthalic acids is particularly preferable.

(Other Additives) The plasticizers and lubricants that can be used in the photosensitive layer of the present invention are described in JP-A-Hei.
No. 11-65021, paragraph 0117, regarding the ultra-high contrast agent for forming ultra-high contrast image and the addition method and amount thereof, the same paragraph No. 01
18, JP-A-11-223898, paragraph numbers 0136 to 0193, Japanese Patent Application No. 11-
Compounds of formula (H), formulas (1) to (3), formulas (A) and (B) of 87297, compounds of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652 (specifically Compounds: Chemical formulas 21 to 24), and contrast enhancing agents are described in JP-A No. 11-65021, paragraph No. 0102 and JP-A No. 11-223898, paragraph Nos. 0194 to 0195.

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

When a super-high contrast agent is used in the photothermographic material of the present invention, it is preferable to use an acid formed by hydration of diphosphorus pentaoxide or a salt thereof in combination. Examples of the acid formed by hydration of diphosphorus pentoxide or a salt thereof include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline. Acid (salt)
And so on. Particularly preferably used as an acid formed by hydration of phosphorus pentoxide or a salt thereof,
Examples thereof include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and the like.

The amount of the acid or salt thereof formed by hydration of diphosphorus pentaoxide (coating amount per 1 m ^{2 of the} light-sensitive material) may be a desired amount depending on the sensitivity and performance such as fog, but
1 to 500 mg / m ² is preferable, 0.5 to 100 mg /
m ² is more preferable.

(Explanation of Layer Structure) The photothermographic material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer. The surface protective layer may be a single layer,
It may have multiple layers. For the surface protective layer, see
No. 11-65021, paragraph numbers 0119 to 0120, and Japanese Patent Application No. 2000-171936. Gelatin is preferred as the binder for the surface protective layer of the present invention, but polyvinyl alcohol (PV
It is also preferable to use or use A) together. As gelatin, inert gelatin (for example, Nitta gelatin 75
0), phthalated gelatin (eg, Nitta gelatin 801) and the like can be used. As PVA, Japanese Patent Laid-Open No. 2000-171
Those described in paragraph numbers 0009 to 0020 of No. 936,
Completely saponified PVA-105, partially saponified PVA
Preferred examples thereof include -205, PVA-335, and modified polyvinyl alcohol MP-203 (these are trade names of Kuraray Co., Ltd.). The polyvinyl alcohol coating amount (per 1 m ^{2 of the} support) of the protective layer (per layer) is preferably 0.3 to 4.0 g / m ² , and 0.3 to 2.0 g / m ^2.
m ² is more preferable.

Especially when the photothermographic material of the present invention is used for printing applications where dimensional change is a problem, it is preferable to use polymer latex for the surface protective layer and the back layer.
Regarding such polymer latex, "Synthetic resin emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Kobunshi Kogyokai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Takashi) Molecular Publishing (1993)), "Chemistry of Synthetic Latex (Souichi Muroi, Polymer Publishing (1970))", and more specifically, methyl methacrylate (33.5% by mass).
/ Ethyl acrylate (50% by mass) / Methacrylic acid (16.5% by mass) copolymer latex, methyl methacrylate (4
7.5% by mass / butadiene (47.5% by mass) / itaconic acid (5% by mass)
%) Copolymer latex, ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate (58.9% by mass) / 2-ethylhexyl acrylate (2
5.4% by mass) / styrene (8.6% by mass) / 2-hydroxyethyl methacrylate (5.1% by mass) / acrylic acid (2.0% by mass) copolymer latex, methyl methacrylate (64.0% by mass) / styrene (9.0% by mass) / butyl Acrylate (20.0
Mass%) / 2-hydroxyethyl methacrylate (5.0 mass
%) / Acrylic acid (2.0 mass%) copolymer latex.

Further, as a binder for the surface protective layer, a combination of polymer latexes of Japanese Patent Application No. 11-6872, paragraphs 0021 to 0 of Japanese Patent Application No. 11-143058.
Paragraph number 00 of the technology described in 025, Japanese Patent Application No. 11-6872
The techniques described in paragraphs 0023 to 0041 of the specification of Japanese Patent Application No. 10-199626 may be applied. The ratio of polymer latex in the surface protection layer is 10 of the total binder.
Mass% or more and 90 mass% or less are preferable, and especially 20 mass% or more
It is preferably 80% by mass or less.

The total coating amount (including water-soluble polymer and latex polymer) of the surface protective layer (per layer) is 0.3 to 5.0 g / m ² (per 1 m ^{2 of the} support).
² is preferable, and 0.3 to 2.0 g / m ² is more preferable.

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

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

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

In the photothermographic material of the present invention, the antihalation layer can be provided on the side farther from the light source than the photosensitive layer.

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

Regarding the anti-halation layer, Japanese Patent Laid-Open No. 11-1999
-65021, paragraph numbers 0123 to 0124, JP-A Nos. 11-223898 and 9
-230531, 10-36695, 10-104779, 11-23145
No. 7, No. 11-352625, No. 11-352626, etc. The antihalation layer contains an antihalation dye having absorption at the exposure wavelength. When the exposure wavelength is in the infrared region, an infrared absorbing dye may be used, and in that case, a dye having no absorption in the visible region is preferable. When using a dye having absorption in the visible region to prevent halation, it is preferable that the color of the dye does not substantially remain after image formation, and a means for erasing by heat of heat development is used. It is particularly preferable to add a heat-decolorizable dye and a base precursor to the non-photosensitive layer so that the non-photosensitive layer functions as an antihalation layer. These techniques are described in JP-A-11-231457 and the like.

The addition amount of the decolorizing dye is determined depending on the use of the dye. Generally, it is used in such an amount that the optical density (absorbance) measured at a target wavelength exceeds 0.1. The optical density is preferably 0.2 to 2. The amount of dye used to obtain such an optical density is generally 0.00
It is about 1 to 1 g / m ² .

By decoloring the dye in this way, the optical density after thermal development can be lowered to 0.1 or less. Two or more kinds of decolorizable dyes may be used together in the thermally decolorizable recording material or the photothermographic material. Similarly, two or more kinds of base precursors may be used in combination. In thermal erasing using such an erasing dye and a base precursor,
It is preferable to use a substance (for example, diphenyl sulfone or 4-chlorophenyl (phenyl) sulfone) that lowers the melting point by 3 ° C. (deg) or more when mixed with a base precursor as described in JP-A No. 11-352626, in order to improve the thermal decoloring property. Etc. are preferable.

In the present invention, a colorant having an absorption maximum at 300 to 450 nm can be added for the purpose of improving the color tone of the silver and the change with time of the image. Such colorants are disclosed in JP-A-62-210458, JP-A-63-104046, and JP-A-63-103235.
No. 63, No. 63-208846, No. 63-306436, No. 63-314535,
It is described in JP-A No. 01-61745 and Japanese Patent Application No. 11-276751. Such a coloring agent is usually 0.1 mg / m ² to
The back layer provided on the opposite side of the photosensitive layer is preferably added in the range of 1 g / m ² .

The photothermographic material in the present invention is a so-called single-sided photosensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of a support and a back layer on the other side. Preferably there is.

In the present invention, it is preferable to add a matting agent in order to improve transportability.
It is described in paragraph Nos. 0126 to 0127 of JP-A No. 11-65021. The matting agent is preferably 1 to 400 mg / m ² , and more preferably 5 to 300 mg / m ² when expressed as the coating amount per 1 m ² of the light-sensitive material. The matteness of the emulsion surface may be anything as long as stardust failure does not occur, but the Bekk smoothness is preferably 30 seconds or more and 2000 seconds or less, and particularly 40.
It is preferably from 1 second to 1500 seconds. Beck's smoothness can be easily determined by Japanese Industrial Standards (JIS) P8119 "Smoothness test method for Beck tester of paper and board" and TAPPI standard method T479.

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

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer close to the outer surface, and a layer which functions as a so-called protective layer. It is preferably contained.

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

In the photothermographic material of the present invention, the pH of the film surface before the heat development treatment is preferably 7.0 or less, more preferably 6.6 or less. The lower limit is not particularly limited, but is about 3. Most preferred pH range is 4 to
The range is 6.2. From the viewpoint of reducing the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia for adjusting the film surface pH. Ammonia is particularly volatile so that it can be removed before the coating step or heat development, which is preferable for achieving a low film surface pH. It is also preferable to use a non-volatile base such as sodium hydroxide, potassium hydroxide or lithium hydroxide in combination with ammonia. The film surface pH is measured by Japanese Patent Application No. 11-87297.
No. 0123 of the specification.

A hardener may be used in each layer such as the photosensitive layer, the protective layer and the back layer of the present invention. An example of a hardener is T.
H. James "THE THEORY OF THE PHOTOGRAPHIC PROCESS F
OURTH EDITION "(published by Macmillan Publishing Co., Inc., 1
977) Each of the methods described on pages 77 to 87 includes chromium alum, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N, N -In addition to propylene bis (vinyl sulfone acetamide), polyvalent metal ions described on page 78 of the same book, polyisocyanates such as U.S. Pat.No. 4,281,060 and JP-A-6-208193, epoxy compounds such as U.S. Pat. Vinyl sulfone compounds such as Kai 62-89048 are preferably used.

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

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

The transparent support is a polyester heat-treated in the temperature range of 130 to 185 ° C. in order to alleviate the internal strain remaining in the film during biaxial stretching and eliminate the heat shrinkage strain generated during the heat development treatment. Especially, polyethylene terephthalate is preferably used. In the case of a heat-developable photosensitive material for medical use, the transparent support has a blue dye (for example, JP-A-8-
It may be colored with the dye-1) described in Example No. 240877 or may be uncolored. The support includes a water-soluble polyester of JP-A No. 11-84574, a styrene-butadiene copolymer of JP-A No. 10-186565, a vinylidene chloride of JP-A No. 2000-39684 and Japanese Patent Application No. 11-106881, paragraphs 0063 to 0080. It is preferable to apply an undercoating technique such as a copolymer. Further, regarding the antistatic layer or the undercoat, JP-A-56-143430 and JP-A-56-1434
31, 58-62646, 56-120519, JP-A-11-84573
Nos. 0040 to 0051 of U.S. Pat. No. 5,575,957, and paragraphs 0078 to 0084 of JP-A No. 11-223898 can be applied.

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

The photothermographic material may further contain an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber or a coating aid. Various additives are added to either the photosensitive layer or the non-photosensitive layer. About them WO98
/ 36322, EP803764A1, JP-A-10-186567, 10-18
You can refer to No. 568 etc.

The photothermographic material of the invention may be coated by any method. Specifically, extrusion coating, slide coating, curtain coating, dip coating, knife coating,
Various coating operations are used, including flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294, Stephen F. Kis.
"LIQUID FILM COATING" by Tler, Petert M. Schweizer (C
HAPMAN & HALL, 1997) Extrusion coating described in pages 399 to 536, or slide coating is preferably used, and slide coating is particularly preferably used. For an example of the shape of the slide coater used for slide coating, see Figure 11 on page 427 of the same book.
It is in b.1. If desired, the method described on pages 399 to 536 of the same document, U.S. Patent No. 2,761,791 and British Patent No. 837,
Two or more layers can be coated simultaneously by the method described in 095.

The coating solution for the reducible silver salt-containing layer in the present invention is preferably a so-called thixotropic fluid. Regarding this technique, reference can be made to JP-A-11-52509. The reducible silver salt-containing layer coating solution of the present invention has a viscosity of 400 mPa · s or more at a shear rate of 0.1 S ⁻¹ .
It is preferably 0,000 mPas or less, more preferably 500 mPas.
・ S or more and 20,000 mPa ・ s or less. Also, the shear rate is 1000
In S ^-1 , 1 mPa · s or more and 200 mPa · s or less are preferable,
More preferably, it is 5 mPa · s or more and 80 mPa · s or less.

Examples of the technique which can be used for the photothermographic material of the present invention include EP803764A1, EP883022A1 and WO98.
/ 36322, JP-A-56-62648, JP-A-58-62644, JP-A-9-
43766, 9-281637, 9-297367, 9-304869, 9
-311405, 9-329865, 10-10669, 10-62899
No. 10, No. 10-69023, No. 10-186568, No. 10-90823, No. 1
0-171063, 10-186565, 10-186567, 10-186
569 ~ 10-186572, 10-197974, 10-197982
No. 10, No. 10-197983, No. 10-197985 ~ No. 10-197987,
10-207001, 10-207004, 10-221807, 10-
282601, 10-288823, 10-288824, 10-30736
No. 5, No. 10-312038, No. 10-339934, No. 11-7100, No.
11-15105, 11-24200, 11-24201, 11-30832
No. 11, No. 11-84574, No. 11-65021, No. 11-109547, No. 1
1-125880, 11-129629, 11-133536 ~ 11-133
No. 539, No. 11-133542, No. 11-133543, No. 11-223898
No. 11, No. 11-352627, No. 11-305377, No. 11-305378,
11-305384, 11-305380, 11-316435, 11-
327076, 11-338096, 11-338098, 11-33809
No. 9, No. 11-343420, Japanese Patent Application No. 2000-187298, No. 2000-1022
No. 9, 2000-47345, 2000-206642, 2000-98530
No. 2000, No. 2000-98531, No. 2000-112059, No. 2000-112060
No. 2000-112104, 2000-112064, 2000-17193
No. 6 is also mentioned.

(Explanation of Packaging Material) The light-sensitive material of the present invention has a low oxygen permeability and / or a low moisture permeability in order to suppress fluctuations in photographic performance during raw storage or to improve curl, curl and the like. It is preferable to wrap with a packaging material. Specific examples of the packaging material having a low oxygen transmission rate and / or a water transmission rate include, for example, JP-A-8-25479.
No. 3, and the packaging material described in JP-A-2000-206653.

(Explanation of Heat Development) The photothermographic material of the present invention may be developed by any method, but it is usually developed by raising the temperature of the imagewise exposed photothermographic material.
The developing temperature is preferably 80 to 250 ° C, more preferably 100 to 140 ° C. The developing time is preferably 1 to 60 seconds, more preferably 5 to 30 seconds, and particularly preferably 10 to 20 seconds.

A plate heater method is preferable as the heat development method. The heat development method using the plate heater method is preferably the method described in JP-A-11-133572, and a heat treatment for obtaining a visible image by bringing the heat-developable photosensitive material on which a latent image is formed into contact with a heating means in the heat development section. A developing device,
The heating means is composed of a plate heater, and a plurality of pressing rollers are arranged to face each other along one surface of the plate heater, and the photothermographic material is passed between the pressing roller and the plate heater. And a thermal development device for performing thermal development. 2 to plate heater
It is preferable to lower the temperature of the tip portion by about 1 to 10 ° C. in 6 stages. Such a method is disclosed in JP-A-54-30032.
The water content and the organic solvent contained in the photothermographic material can be excluded from the system.
It is also possible to suppress changes in the shape of the support of the photothermographic material due to rapid heating of the photothermographic material.

The light-sensitive material of the present invention may be exposed by any method, but a laser beam is preferable as an exposure light source.
The laser light according to the present invention includes a gas laser (Ar ⁺ ,
He-Ne), YAG laser, dye laser, semiconductor laser and the like are preferable. Alternatively, a semiconductor laser and a second harmonic wave generating element may be used. Preferred is a gas of red to infrared emission or a semiconductor laser.

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

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

[0200]

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

(Preparation of PET support) Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 according to a conventional method.
(Phenol / tetrachloroethane = 6/4 (weight ratio) 25
PET (measured at ° C) was obtained. After pelletizing this 1
After being dried at 30 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die and rapidly cooled to prepare an unstretched film having a thickness of 175 μm after heat setting.

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

(Surface corona treatment) Both sides of the support were treated at 20 m / min at room temperature using a solid state corona treatment machine 6KVA model manufactured by Pillar Co. Current at this time,
From the voltage reading, 0.375 kV · A was applied to the support.
-It was found that a treatment of min / m ² was performed. The processing frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[0204] (Preparation of undercoat support) (1) Preparation of coating liquid for undercoat layer Prescription (for undercoat layer on photosensitive layer)   Takamatsu Yushi Co., Ltd. pestle resin A-520 (30 mass% solution) 59g   Polyethylene glycol monononyl phenyl ether (Average number of ethylene oxide = 8.5) 10 mass% solution 5.4g   Soken Chemical Co., Ltd. MP-1000 (polymer particles, average particle size 0.4 μm) 0.91 g   Distilled water 935ml

[0205] Prescription (for back surface first layer)   Styrene-butadiene copolymer latex 158g   (Solid content 40 mass%, styrene / butadiene weight ratio = 68/32)   2,4-dichloro-6-hydroxy-S-     Triazine sodium salt 8 mass% aqueous solution 20 g   10 ml of 1% by mass aqueous solution of sodium laurylbenzene sulfonate   Distilled water 854ml

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

(Preparation of Undercoat Support) Thickness 175 μm Above
After performing the corona discharge treatment on both sides of the biaxially stretched polyethylene terephthalate support, the wet coating amount of the undercoat coating liquid formulation on one side (the photosensitive layer side) with a wire bar of 6.6 ml / m ² (one side And then dried at 180 ° C. for 5 minutes, and then apply the above-mentioned undercoating liquid formulation to the back surface (back surface) with a wire bar so that the wet coating amount becomes 5.7 ml / m ^2. And dry at 180 ° C for 5 minutes, and then apply the undercoat coating solution formulation on the back surface (back surface) with a wire bar so that the wet coating amount is 7.7 ml / m ² and dry at 180 ° C for 6 minutes. A subbing support was prepared.

(Preparation of coating liquid for back surface) (Preparation of solid fine particle dispersion liquid (a) of base precursor) 64 g of base precursor compound 11, 28 g of diphenyl sulfone, and surfactant Demol N 1 manufactured by Kao Corporation
0 g was mixed with 220 ml of distilled water, the mixture was dispersed in beads using a sand mill (1/4 Gallon Sand Grinder Mill, manufactured by AIMEX Co., Ltd.), and the average particle diameter was 0.2 μm.
A solid fine particle dispersion (a) of the base precursor compound of m was obtained.

(Preparation of Dye Solid Fine Particle Dispersion) 9.6 g of cyanine dye compound 13 and 5.8 g of sodium p-dodecylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixture was sand milled (1/4 Gallon sand grinder). The beads were dispersed using a mill and a product of IMEX Co., Ltd. to obtain a dye solid fine particle dispersion having an average particle diameter of 0.2 μm.

(Preparation of coating liquid for antihalation layer) 17 g of gelatin, 9.6 g of polyacrylamide, 70 g of solid fine particle dispersion of the above base precursor (a), 56 g of solid dispersion of dye solid fine particles, and monodisperse polymethylmethacrylate fine particles (average) Particle size 8 μm, particle size standard deviation 0.
4) 1.5 g, benzoisothiazolinone 0.03 g, sodium polyethylene sulfonate 2.2 g, blue dye compound 14 0.2 g, yellow dye compound 15 3.9 g,
844 ml of water was mixed to prepare a coating liquid for antihalation layer.

(Preparation of Back Surface Protective Layer Coating Solution)
Keep warm at 0 ° C, gelatin 50 g, sodium polystyrene sulfonate 0.2 g, N, N-ethylenebis (vinyl sulfone acetamide) 2.4 g, sodium t-octylphenoxyethoxyethane sulfonate 1 g, benzoisothiazolinone 30 mg, fluorine System surfactant (F-1:
N-perfluorooctylsulfonyl-N-propylalanine potassium salt) 37 mg, fluorinated surfactant (F-
2: Polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [ethylene oxide average degree of polymerization 15]) 0.15
g, fluorosurfactant (F-3) 64 mg, fluorosurfactant (F-4) 32 mg, acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) 8.8
g, Aerosol OT (American Cyanamid)
0.6 g, 1.8 g of liquid paraffin emulsion as liquid paraffin, and 950 ml of water were mixed to obtain a back surface protective layer coating liquid.

(Preparation of silver halide emulsion) << Preparation of silver halide emulsion 1 >> 1 to 1421 ml of distilled water
3.1 ml of a mass% potassium bromide solution was added, and a further 0.1.
While stirring a liquid containing 3.5 ml of 5 mol / L sulfuric acid and 31.7 g of phthalated gelatin in a reaction vessel made of stainless steel while maintaining the liquid temperature at 30 ° C., 22.22 g of silver nitrate
Distilled water was added to the solution to dilute it to 95.4 ml, and solution B was prepared by diluting potassium bromide (15.3 g) and potassium iodide (0.8 g) with distilled water to a volume of 97.4 ml at a constant flow rate of 45
The total amount was added over a second. Thereafter, 10 ml of a 3.5 mass% hydrogen peroxide aqueous solution was added, and further, 10.8 ml of a 10 mass% aqueous solution of benzimidazole was added. Further, distilled water was added to 51.86 g of silver nitrate to obtain 317.5 m.
The total amount of Solution C diluted to 1 with 44.2 g of potassium bromide and 2.2 g of potassium iodide to a volume of 400 ml with distilled water was added over 20 minutes at a constant flow rate to obtain Solution D. Was added by the controlled double jet method while maintaining pAg at 8.1. 1 per mole of silver
1 from the start of adding solution C and solution D of hexachloroiridium (III) acid potassium salt to a concentration of × 10 ^-4 mol
The total amount was added after 0 minutes. Further, 5 seconds after the addition of the solution C was completed, an aqueous solution of potassium hexacyanoferrate (II) cyanide was added in an amount of 3 × 10 ⁻⁴ mol per mol of silver. The pH was adjusted to 3.8 with sulfuric acid having a concentration of 0.5 mol / L, stirring was stopped, and precipitation / desalting / water washing steps were performed. The pH was adjusted to 5.9 with 1 mol / L sodium hydroxide, and pAg
A silver halide dispersion of 8.0 was prepared.

While stirring the above silver halide dispersion, 3
Maintaining at 8 ° C, add 5 ml of 0.34% by mass of 1,2-benzisothiazolin-3-one in methanol,
After minutes, the temperature was raised to 47 ° C. After 20 minutes of heating, sodium benzenethiosulfonate was added to the solution of methanol in an amount of 7.6 × 10 ^-5 mol per mol of silver, and after 5 minutes, tellurium sensitizer C was added.
2.9 × 10 ^-4 mol per mol silver with methanol solution
Aged for 91 minutes. Then, spectral sensitizing dye A and sensitizing dye B
1.2 × 10 ⁻³ mol of a total of sensitizing dyes A and B was added per mol of silver in a methanol solution of 3: 1 at a molar ratio of 1: 1 and after 1 minute, 0.8 mass of N, N′-dihydroxy-N ″ -diethylmelamine was added. %
Add 1.3 ml of methanol solution, and after 4 minutes, add 5-methyl
-2-Mercaptobenzimidazole in methanol solution 4.8 × 10 ^-3 mol per 1 mol of silver, 1-phenyl-2-heptyl-
Methanol solution of 5-mercapto-1,3,4-triazole to 5.4 × 10 ^-3 mol per mol of silver and 1- (3-methylureido) -5-mercaptotetrazole sodium salt to 1 mol of silver with an aqueous solution. 8.5 × 10 ⁻³ mol was added to prepare a silver halide emulsion 1.

The grains in the prepared silver halide emulsion are
Average equivalent sphere diameter 0.042 μm, coefficient of variation of equivalent sphere diameter 20
% Silver iodobromide grains uniformly containing 3.5 mol% of iodine. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The [100] plane ratio of this grain is
It was determined to be 80% using the Kubelka-Munk method.

<< Preparation of Silver Halide Emulsion 2 >> In the preparation of silver halide emulsion 1, the liquid temperature at the time of grain formation was 30 ° C.
The temperature was changed to 7 ° C., the solution B was changed to dilute 15.9 g of potassium bromide with distilled water to a volume of 97.4 ml, and the solution D was 45.8 g of potassium bromide with a volume of 400 m of distilled water.
A silver halide emulsion 2 was prepared in the same manner except that the solution C was diluted to 1, the solution C was added for 30 minutes, and potassium hexacyanoferrate (II) was removed. Precipitation / desalting / washing / dispersion were carried out in the same manner as in the silver halide emulsion 1.

Further, the tellurium sensitizer C is added in an amount of 1.1 × 10 ⁻⁴ mol per mol of silver, the spectral sensitizing dye A and the spectral sensitizing dye B are added.
The amount of the methanol solution added at a molar ratio of 3: 1 was 7.0 × 10 ⁻⁴ as the total amount of the sensitizing dye A and the sensitizing dye B per mol of silver.
Mol, 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in an amount of 3.3 × 10 ⁻³ mol and 1 mol per mol of silver.
-(3-Methylureido) -5-mercaptotetrazole sodium salt was spectrally sensitized, chemically sensitized and treated with 5-methyl in the same manner as in Emulsion 1 except that 4.7 × 10 ^-3 mol of sodium salt was changed to 1 mol of silver. 2-Mercaptobenzimidazole and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole were added to obtain a silver halide emulsion 2. The emulsion grains of the silver halide emulsion 2 have an average equivalent spherical diameter of 0.080 μm,
The particles were pure silver bromide cubic grains having a variation coefficient of 20% of the equivalent spherical diameter.

<< Preparation of Silver Halide Emulsion 3 >> In the preparation of silver halide emulsion 1, the liquid temperature at the time of grain formation was set to 2 ° C.
Silver halide emulsion 3 was similarly prepared except that the temperature was changed to 7 ° C.
Was prepared. Further, precipitation / desalting / washing / dispersion were carried out in the same manner as in the silver halide emulsion 1. The molar ratio of the spectral sensitizing dye A and the spectral sensitizing dye B was 1: 1 as a solid dispersion (gelatin aqueous solution), and the addition amount was 6 × 10 ⁻ as the total amount of the sensitizing dye A and the sensitizing dye B per 1 mol of silver. ^A silver halide emulsion 3 was obtained in the same manner as the emulsion 1, except that the amount of the ³ mol tellurium sensitizer B added was changed to 5.2 × 10 ⁻⁴ mol per mol of silver.
The emulsion grains of the silver halide emulsion 3 have an average equivalent spherical diameter of 0.0
The silver iodobromide grains were 34 μm in size and uniformly contained 3.5 mol% of iodine having a coefficient of variation of equivalent spherical diameter of 20%.

<< Preparation of Mixed Emulsion A for Coating Liquid >> 70% by mass of silver halide emulsion 1, 15% by mass of silver halide emulsion 2 and 15% by mass of silver halide emulsion 3 were dissolved to prepare benzothiazolium iodide. In a 1% by mass aqueous solution, 7 × 10 ⁻³ mol of silver was added per mol of silver. Furthermore, mixed emulsion for coating liquid 1
The content of silver halide per kg is 38.2 g as silver.
Water so that it becomes 0 per 1 kg of mixed emulsion for coating liquid.
1- (3-Methylureido) -5-mercaptotetrazole sodium salt was added so that the amount became 34 g.

<< Preparation of reducible silver salt dispersion >>: Preparation of reducible silver salt dispersion A Behenic acid (product name EDENOR C2 manufactured by COGNIS DEUTSCHLAND GmbH
2-85JP GW) 87.6 kg, distilled water 423 L, 5 mol /
49.2 L of NaOH aqueous solution of L concentration and 120 L of tert-butanol are mixed and stirred at 75 ° C. for 1 hour to react,
A sodium behenate solution was obtained. Separately, silver nitrate 40.4
Prepare 206.2 L of an aqueous solution of 20 kg (pH 4.0), and
It was kept warm at 0 ° C. 635 L of distilled water and 30 L of tert-
Keep the temperature of the reaction vessel containing butanol at 30 ° C., and while sufficiently stirring, keep the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution at a constant flow rate of 93 minutes 15 seconds and 9 minutes, respectively.
Added over 0 minutes. At this time, only the silver nitrate aqueous solution is added for 11 minutes after the addition of the silver nitrate aqueous solution is started,
Then, the sodium behenate solution was started to be added, and only the sodium behenate solution was added for 14 minutes and 15 seconds after the addition of the silver nitrate aqueous solution was completed. At this time, the temperature inside the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The piping of the sodium behenate solution addition system was kept warm by circulating hot water outside the double tube, and the liquid temperature at the outlet of the addition nozzle tip was adjusted to 75 ° C. Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The position of addition of the sodium behenate solution and the position of addition of the aqueous solution of silver nitrate were symmetrically arranged around the stirring axis, and the height was adjusted so as not to come into contact with the reaction solution.

After the addition of the sodium behenate solution was completed, the mixture was allowed to stir at the same temperature for 20 minutes, and the mixture was cooled to 35 minutes over 30 minutes.
The temperature was raised to 0 ° C., and then aged for 210 minutes. Immediately after completion of the aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. that time,
In order to promote the decrease in conductivity, pure water was added to the wet cake to form a slurry, which was repeated three times. The obtained fatty acid silver wet cake was shaken off for 1 hour in a state where the centrifugal force G was 700. G is expressed as 1.119 × 10 ^-5 × container radius (cm) × rotational speed (rpm) ² . The solid content of the fatty acid silver wet cake thus obtained (measured by drying 1 g of wet cake at 110 ° C. for 2 hours) was 44%.

The morphology of the obtained silver behenate particles was evaluated by electron microscopic photography, and the average value was a = 0.14 μ.
It was a flaky crystal having m, b = 0.4 μm, c = 0.6 μm, an average aspect ratio of 5.2, an average equivalent sphere diameter of 0.52 μm, and a variation coefficient of the equivalent sphere diameter of 15%. (A, b, c are the rules of the text)

For a wet cake having a dry solid content of 260 kg, polyvinyl alcohol (trade name: PVA-2) was used.
17) Add 19.3 kg and water to bring the total volume to 100
After being set to 0 kg, it is slurried with a dissolver blade, and is further added to a pipeline mixer (Mizuho Kogyo: PM-10).
Type).

Next, the pre-dispersed stock solution is adjusted to a pressure of 1 by a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidex International Corporation, using Z type interaction chamber).
It was adjusted to 260 kg / cm ² and treated three times to obtain a silver behenate dispersion. For the cooling operation, a spiral heat exchanger was attached before and after the interaction chamber, and the dispersion temperature was set to 18 ° C. by adjusting the temperature of the refrigerant.

Preparation of Reducible Silver Salt Dispersions C-X Similar to the preparation of reducible silver salt dispersion A, COGNIS DEUTS
Behenic acid manufactured by CHLAND GmbH (Product name EDENOR C22-85JP GW)
With respect to the compound, an equimolar amount of the compound as a carboxyl group, the amount of which is listed in Table 1, 423 L of distilled water, 5 mol / L of N
An aOH aqueous solution (49.2 L) and tert-butanol (120 L) were mixed and stirred at 75 ° C. for 1 hour for reaction to obtain a sodium salt solution. Separately, an aqueous solution of 40.4 kg of silver nitrate 20
6.2 L (pH 4.0) was prepared and kept warm at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of tert-butanol was kept at 30 ° C., and while stirring sufficiently, the total amount of the sodium salt solution and the total amount of the silver nitrate aqueous solution were kept constant at 93 minutes 15 seconds and 90 minutes, respectively. Added over minutes.
At this time, only the silver nitrate aqueous solution was added for 11 minutes after the addition of the silver nitrate aqueous solution was started, and then the addition of the sodium salt solution was started and 14 minutes after the addition of the silver nitrate aqueous solution was completed.
Only the sodium salt solution was added for 5 seconds. At this time, the temperature inside the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The piping of the sodium salt solution addition system was kept warm by circulating hot water outside the double tube, and the liquid temperature at the outlet of the addition nozzle tip was adjusted to 75 ° C. Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The position of addition of the sodium salt solution and the position of addition of the aqueous solution of silver nitrate were symmetrically arranged with respect to the stirring axis, and the height was adjusted so as not to come into contact with the reaction solution.

After the addition of the sodium salt solution was completed, the mixture was left to stir at the same temperature for 20 minutes, heated to 35 ° C. over 30 minutes, and then aged for 210 minutes. Immediately after completion of the aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. At that time, in order to promote a decrease in conductivity, pure water was added to the wet cake to form a slurry three times. The obtained fatty acid silver wet cake was shaken off for 1 hour in a state where the centrifugal force G was 700. G is 1.119 × 10 ⁻⁵ × container radius (c
m) × revolution (rpm) ² The solid content of the fatty acid silver wet cake thus obtained (measured by drying 1 g of the wet cake at 110 ° C. for 2 hours) is shown in Table 1.

Polyvinyl alcohol (PVA-217) (19.3 kg) and water were added to the wet cake in an amount necessary to obtain the same silver content as the silver salt dispersion A, and the total amount was adjusted to 1000 kg. To a slurry with a dissolver blade and further preliminarily dispersed with a pipeline mixer (PM-10 type manufactured by Mizuho Industry Co., Ltd.).

Next, the pre-dispersed stock solution was adjusted to a pressure of 1 by a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidex International Corporation, using Z type interaction chamber).
It was adjusted to 260 kg / cm ² and treated three times to obtain a silver behenate dispersion. For the cooling operation, a spiral heat exchanger was attached before and after the interaction chamber, and the dispersion temperature was set to 18 ° C. by adjusting the temperature of the refrigerant.

[0228]

[Table 1]

(Preparation of Reducing Agent Dispersion) << Preparation of Reducing Agent-1 Dispersion >> Reducing Agent-1 (1,1-bis
20 mass% of (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane) 10 kg and denatured polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203)
16 kg of water was added to 10 kg of the aqueous solution and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. 0.2 g and water were added to prepare a reducing agent having a concentration of 25% by mass to obtain a reducing agent-1 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.42 μm and a maximum particle diameter of 2.0 μm.
It was m or less. The resulting reducing agent dispersion has a pore size of 10.0.
After filtering with a μm polypropylene filter to remove foreign substances such as dust, the product was stored.

<< Preparation of Reducing Agent-2 Dispersion >> Reducing Agent-2
16 kg of water was added to 10 kg of (2,2′-isobutylidene-bis- (4,6-dimethylphenol)) and a modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) of 10 mass% and 16 kg of water. Mix to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. Add 0.2g and water to reduce the concentration of reducing agent to 25
The reducing agent-2 dispersion was prepared by adjusting the amount to be% by mass.
The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.38 μm and a maximum particle diameter of 2.0 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign matters such as dust and stored.

<< Preparation of reducing agent complex-3 dispersion >> 10 kg of reducing agent complex-3 (1: 1 complex of 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol) and triphenylphosphine oxide) , 10% by mass aqueous solution of triphenylphosphine oxide (0.12 kg) and modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203) 1
To 6 kg, 7.2 kg of water was 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 4 hours and 30 minutes, and then benzoisothiazolinone sodium salt. Add 0.2g and water to reduce the concentration of reducing agent to 25
The reducing agent complex-3 dispersion was prepared by adjusting the amount to be% by mass. The reducing agent complex particles contained in the thus obtained reducing agent complex dispersion had a median diameter of 0.46 μm and a maximum particle diameter of 1.6 μm.
It was m or less. The resulting reducing agent complex dispersion has a pore size of 3.
Filter with a polypropylene filter of 0 μm,
Foreign substances such as dust were removed and stored.

<< Preparation of Reducing Agent-4 Dispersion >> Reducing Agent-4
6 kg of water was added to 20 kg of a 10 mass% aqueous solution of (2,2′-methylenebis- (4-ethyl-6-tert-butylphenol)) and a modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203), Mix well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. Add 0.2g and water to reduce the concentration of reducing agent to 25
The reducing agent-4 dispersion was prepared by adjusting the amount to be% by mass.
The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Reducing Agent-5 Dispersion >> Reducing Agent-5
6 kg of water was added to 20 kg of a 10 mass% aqueous solution of (2,2′-methylenebis- (4-methyl-6-tert-butylphenol)) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203), Mix well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. Add 0.2g and water to reduce the concentration of reducing agent to 25
The reducing agent-5 dispersion was obtained by adjusting the amount to be% by mass.
The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.38 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Hydrogen Bonding Compound-2 Dispersion >> Hydrogen Bonding Compound-2 (tri (4-t-butylphenyl))
10 kg of water was added to 20 kg of a 10% by mass aqueous solution of phosphine oxide) and modified polyvinyl alcohol (Kovara Co., Ltd., Poval MP203) to prepare a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. 0.2 g and water were added to prepare a reducing agent having a concentration of 22% by mass to obtain a hydrogen-bonding compound-2 dispersion. The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.35 μm and a maximum particle diameter of 1.5 μm or less. The obtained hydrogen-bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

(Preparation of Polyhalogen Compound) << Preparation of Organic Polyhalogen Compound-1 Dispersion >> 10 kg of organic polyhalogen compound-1 (2-tribromomethanesulfonylnaphthalene) and modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) 20% by weight aqueous solution of 10 kg, 0.4% of 20% by weight aqueous solution of sodium triisopropylnaphthalene sulfonate, and 16 kg of water.
Was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and the average diameter is 0.5 mm.
Horizontal sand mill filled with zirconia beads (UVM
-2: after dispersing for 5 hours with IMEX Co., Ltd.), 0.2 g of benzoisothiazolinone sodium salt and water were added to prepare an organic polyhalogen compound having a concentration of 23.5% by mass, An organic polyhalogen compound-1 dispersion was obtained. The organic polyhalogen compound particles contained in the thus obtained polyhalogen compound dispersion have a median diameter of 0.
The particle size was 36 μm and the maximum particle size was 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Organic Polyhalogen Compound-2 Dispersion >> 20% by mass of 10 kg of organic polyhalogen compound-2 (tribromomethanesulfonylbenzene) and modified polyvinyl alcohol (POVAL MP203 manufactured by Kuraray Co., Ltd.)
10 kg of an aqueous solution, 0.4 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate, and 1 part of water
4 kg was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump to have an average diameter of 0.
Horizontal sand mill filled with 5mm zirconia beads
(UVM-2: manufactured by IMEX Co., Ltd.), dispersed for 5 hours, and then benzoisothiazolinone sodium salt 0.2 g
And water were added to adjust the concentration of the organic polyhalogen compound to 26% by mass to obtain an organic polyhalogen compound-2 dispersion. The organic polyhalogen compound particles contained in the thus obtained polyhalogen compound dispersion have a median diameter of 0.
The particle size was 41 μm and the maximum particle size was 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Dispersion of Organic Polyhalogen Compound-3 >> 10 kg of organic polyhalogen compound-3 (N-butyl-3-tribromomethanesulfonylbenzamide) and modified polyvinyl alcohol (POVAL MP manufactured by Kuraray Co., Ltd.)
20 kg of a 10% by weight aqueous solution of 203), 0.4 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate, and 8 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm (UVM-2: IMEX Co., Ltd.).
Manufactured by K.K.) for 5 hours, and then 0.2 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the organic polyhalogen compound to 25% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-3 dispersion. The organic polyhalogen compound particles contained in the thus obtained polyhalogen compound dispersion had a median diameter of 0.36 μm and a maximum particle diameter of 1.5 μm or less.
The obtained organic polyhalogen compound dispersion has a pore size of 3.0 μm.
m polypropylene filter to remove foreign matters such as dust, and stored.

<< Preparation of Phthalazine Compound-1 Solution >> 8k
Denatured polyvinyl alcohol MP20 manufactured by Kuraray Co., Ltd.
3 was dissolved in 174.57 kg of water, and then 3.15 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28 kg of a 70 mass% aqueous solution of phthalazine compound-1 (6-isopropylphthalazine) were added, and phthalazine was added. A 5 mass% solution of compound-1 was prepared.

<< Preparation of Mercapto Compound-1 Aqueous Solution >> Mercapto Compound-1 (1- (3-sulfophenyl) -5
-Mercaptotetrazole sodium salt) 7 g of water 99
It was dissolved in 3 g to prepare a 0.7 mass% aqueous solution.

<< Preparation of Pigment-1 Dispersion >> CI Pigment Bl
64 g of ue 60, 6.4 g of Demol N manufactured by Kao Corporation, and 250 g of water were added and mixed well to form a slurry. Prepare 800 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and use a disperser (1/4 G sand grinder mill: manufactured by AIMEX Co., Ltd.) to
The pigment was dispersed for 5 hours to obtain a pigment-1 dispersion. The pigment particles contained in the thus obtained pigment dispersion had an average particle diameter of 0.21 μm.

<< Preparation of SBR Latex Liquid >> Tg = 23
The SBR latex at ℃ was adjusted as follows. Using ammonium persulfate as a polymerization initiator and an anionic surfactant as an emulsifier, emulsion polymerization of 70.5 mass of styrene, 26.5 mass of butadiene and 3 mass of acrylic acid was carried out, followed by aging at 80 ° C. for 8 hours. Then 40 ° C
The mixture was cooled to pH 7.0, adjusted to pH 7.0 with aqueous ammonia, and Sandet BL manufactured by Sanyo Kasei Co., Ltd. was added so as to be 0.22%. Next, a 5% aqueous sodium hydroxide solution was added to adjust the pH to 8.3, and the pH was further adjusted with aqueous ammonia.
It was adjusted to be 8.4. Na ⁺ used at this time
The molar ratio of ions to NH ₄ ⁺ ions was 1: 2.3.
Further, 0.15 ml of a 7% aqueous solution of benzoisothiazoline nonone sodium salt was added to 1 kg of this liquid to prepare an SBR latex liquid.

(SBR latex: -St (70.5) -Bu (26.5)
-AA (3) -latex) Tg 23 ℃, average particle size 0.1μm, concentration 43 mass%, 25 ℃ 60% R
Equilibrium water content in H at 0.6% by mass, ionic conductivity 4.
2 mS / cm (Ion conductivity was measured using Toa Denpa Kogyo Co., Ltd. conductivity meter CM-30S, latex undiluted solution (43% by mass) was measured at 25 ° C.), and SBR latexes having different pH 8.4 Tg were measured. The ratio of styrene and butadiene was appropriately changed and adjusted by the same method.

<< Emulsion Layer (Photosensitive Layer) Coating Solutions-1A, 1C
~ Preparation of 1X >> Reducible silver salt dispersions A and C obtained above
~ X each 1000 g, water 125 ml, reducing agent-1
Dispersion 113 g, reducing agent-2 dispersion 91 g, pigment-1 dispersion 27 g, organic polyhalogen compound-1 dispersion 82
g, organic polyhalogen compound-2 dispersion 40 g, phthalazine compound-1 solution 173 g, SBR latex (T
g: 20.5 ° C.) liquid 1082 g, mercapto compound-1
9 g of an aqueous solution was sequentially added, 158 g of silver halide mixed emulsion A was added immediately before coating, and the well mixed emulsion layer coating solution was sent to the coating die as it was for coating.

The viscosity of the emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki Co., Ltd. at 40 ° C. (No. 1 rotor, 60 rp).
It was 85 [mPa · s] in m).

Rheometrics Far East Co., Ltd. RFS Fluid Spectrometer at 25 ° C.
The viscosities of the coating solutions at the shear rates of 0.1, 1, 10, 10
1500 and 22 at 0 and 1000 [1 / sec], respectively
It was 0, 70, 40, 20 [mPa · s].

<< Emulsion Layer (Photosensitive Layer) Coating Solution-2A, 2
Preparation of J, 2K, 2S >> 1000 g of each of the reducible silver salt dispersions A, J, K, S obtained above, 104 m of water
1, pigment-1 dispersion 30 g, organic polyhalogen compound-
2 dispersion 21g, organic polyhalogen compound-3 dispersion 6
9 g, phthalazine compound-1 solution 173 g, SBR latex (Tg: 23 ° C.) solution 1082 g, reducing agent complex-3 dispersion 258 g, and mercapto compound-1 solution 9 g were sequentially added, and immediately before coating, silver halide mixed emulsion A110 g was added. The emulsion layer coating solution added and mixed well was sent to the coating die as it was and coated.

<< Emulsion Layer (Photosensitive Layer) Coating Solution-3A, 3
Preparation of J, 3K, 3S >> 1000 g of each of the reducible silver salt dispersions A, J, K, S obtained above, 95 ml of water,
73 g of reducing agent-4 dispersion, 68 g of reducing agent-5 dispersion, 30 g of pigment-1 dispersion, 21 g of organic polyhalogen compound-2 dispersion, 69 g of organic polyhalogen compound-3 dispersion,
Phthalazine compound-1 solution 173 g, SBR core-shell type latex (core Tg: 20 ° C./shell Tg: 30 ° C. =
70/30 weight ratio) Liquid 1082g, hydrogen bonding compound-
124 g of 2 dispersions and 9 g of mercapto compound-1 solution were sequentially added, and 110 g of silver halide mixed emulsion A immediately before coating.
Was mixed well and the emulsion layer coating solution was sent to the coating die as it was and coated.

<< Preparation of Coating Solution for Intermediate Layer of Emulsion Side >> 772 g of 10% by weight aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), 20% by weight dispersion of pigment 5.3
g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20/5/2) latex 27.5 mass% liquid 226 g with aerosol OT (American Cyana (Manufactured by Mido) 2 ml of 5% by weight aqueous solution, 10.5 ml of 20% by weight aqueous solution of diammonium phthalate salt, total 8
Water was added to 80 g, and the pH was adjusted to 7.5 with NaOH to prepare a coating solution for the intermediate layer, 10 ml / m 2.
^The solution was fed to the coating die so that it became ² . The viscosity of the coating solution is 21 with a B type viscometer at 40 ° C (No.1 rotor, 60 rpm).
It was [mPa · s].

<< Preparation of Coating Solution for Emulsion Surface Protective Layer First Layer >> 64 g of inert gelatin was dissolved in water to prepare a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9). /
20/5/2) 80 g of 27.5 mass% latex, 23 ml of 10 mass% methanol solution of phthalic acid, 23 ml of 10 mass% aqueous solution of 4-methylphthalic acid, 0.5 mol / L
28 ml of sulfuric acid having a concentration, 5 ml of a 5 mass% aqueous solution of Aerosol OT (manufactured by American Cyanamid Co., Ltd.), 0.5 g of phenoxyethanol, benzoisothiazolinone.
1 g was added, and water was added so that the total amount became 750 g to prepare a coating solution, and 26 ml of 4% by mass chromium alum was mixed with a static mixer immediately before coating to 18.6 ml.
The solution was fed to the coating die so that the amount became / m ² . The viscosity of the coating liquid is B type viscometer 40 ° C (No.1 rotor, 60 rpm)
It was 17 [mPa · s].

<< Preparation of Coating Solution for Second Layer of Emulsion Surface Protective Layer >> 80 g of inert gelatin was dissolved in water to prepare a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9). /
20/5/2) 102 g of latex 27.5% by mass solution, 3.2 ml of 5% by mass solution of fluorine-based surfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt), fluorine 32 ml of a 2 mass% aqueous solution of a surfactant (F-2: polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [ethylene oxide average degree of polymerization = 15]), aerosol OT 23 ml of a 5 mass% solution of (American Cyanamid), 4 g of polymethylmethacrylate fine particles (average particle size 0.7 μm), 21 g of polymethylmethacrylate fine particles (average particle size 4.5 μm),
4-methylphthalic acid 1.6 g, phthalic acid 4.8 g, 0.
Water was added to 44 ml of 5 mol / L sulfuric acid and 10 mg of benzisothiazolinone so that the total amount was 650 g.
7. A surface protective layer coating solution was prepared by mixing 445 ml of an aqueous solution containing 4% by mass of chromium alum and 0.67% by mass of phthalic acid with a static mixer immediately before coating, and 8.
The solution was fed to the coating die so that the amount became 3 ml / m ² . The viscosity of the coating liquid is B type viscometer 40 ℃ (No.1 rotor, 6
It was 9 [mPa · s] at 0 rpm).

<< Preparation of Photothermographic Materials-1A, 1C to 1X >> An antihalation layer coating solution was applied to the back surface side of the undercoat support at a solid content of solid fine particle dye of 0.04.
such that g / m ^2, also simultaneous multilayer coating for the back surface protective layer coating solution for the coating amount of gelatin of 1.7 g / m ^2, and dried to prepare a back layer.

Samples of photothermographic materials were coated on the surface opposite to the back surface from the undercoat surface in the order of emulsion layer, intermediate layer, protective layer first layer, protective layer second layer by slide bead coating method. It was created. At this time, the emulsion layer and the intermediate layer are 31
℃, the first protective layer is 36 ℃, the first protective layer is 37 ℃
The temperature was adjusted to. Coating amount of each compound in the emulsion layer (g /
m ² ) is as follows.

[0253] Reducible silver salts A, C to X (as Ag) 1.49 Reducing agent-1 0.67 Reducing agent-2 0.54 Pigment (C.I.Pigment Blue 60) 0.032 Polyhalogen compound-1 0.46 Polyhalogen compound-2 0.25 Phthalazine compound-1 0.21 SBR Latex 11.1 Mercapto compound-1 0.002 Silver halide (as Ag) 0.145

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

The matteness of the prepared photothermographic material is Bekk smoothness of 550 seconds on the side of the photosensitive layer and 13 on the back side.
It was 0 seconds. The pH of the film surface on the photosensitive layer surface side was measured and found to be 6.0.

<< Heat developable photosensitive materials-2A, 2J, 2K, 2
Preparation of S >> Emulsion layer coating liquids-1A, 1C-1X were added to emulsion layer coating liquids-2A, 2J, 2 for photothermographic material-1.
K and 2S, and the photothermographic material except that the yellow dye compound 15 was removed from the antihalation layer.
A photothermographic material-2 was prepared in the same manner as in 1. The coating amount (g / m ² ) of each compound in the emulsion layer at this time is as follows.

[0257] Reducible silver salts A, J, K, S (as Ag) 1.49 Pigment (C.I.Pigment Blue 60) 0.036 Polyhalogen compound-2 0.13 Polyhalogen compound-3 0.41 Phthalazine compound-1 0.21 SBR Latex 11.1 Reducing agent complex-3 1.54 Mercapto compound-1 0.002 Silver halide (as Ag) 0.10

<< Heat Development Photosensitive Material-3A, 3J, 3K, 3
Preparation of S >> Emulsion layer coating liquids-1A, 1C-1X were added to photothermographic material-1, emulsion layer coating liquids-3A, 3J, 3
K and 3S were changed, and the yellow dye compound 15 was removed from the antihalation layer. Further, the fluorine-containing surfactants F-1, F-2, F of the second protective layer and the back protective layer
-3 and F-4 have the same weight of F-5, F-6,
Changed to F-7 and F-8. Others are the same as in the photothermographic material-1, and the photothermographic materials-3A, 3J, 3
K and 3S were produced. The coating amount (g / m ² ) of each compound in the emulsion layer at this time is as follows.

[0259] Reducible silver salts A, J, K, S (as Ag) 1.34 Pigment (C.I.Pigment Blue 60) 0.032 Reducing agent-4 0.40 Reducing agent-5 0.36 Polyhalogen compound-2 0.12 Polyhalogen compound-3 0.37 Phthalazine compound-1 0.19 SBR latex 10.0 Hydrogen-bonding compound-2 0.59 Mercapto compound-1 0.002 Silver halide (as Ag) 0.09

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

[0261]

[Chemical 31]

[0262]

[Chemical 32]

[0263]

[Chemical 33]

[0264]

[Chemical 34]

[0265]

[Chemical 35]

[0266]

[Chemical 36]

Evaluation of workability The obtained sample was fixed to the lower blade by using an upper blade having a rake angle of 1 ° and a blade angle of 89 °, and a lower blade having a ridge angle of 0 ° and a blade angle of 90 °. The cutting speed of the upper blade is 1 m / sec with respect to the lower blade
I cut it. Both cut surfaces of the cut sample were observed with an optical microscope at a magnification of 100 to evaluate workability. Evaluation: ◎: No film peeling occurred and the cut surface was smooth. ○: No film peeling occurred, but the surface was rough. △: Film peeled, but peeled off even after rubbing by hand. There is no problem in practical use. X: Film peeling occurs and peels off by rubbing by hand. I went.

(Evaluation of Sensitivity) The obtained sample was cut into half-size pieces, packaged in the following packaging materials in an environment of 25 ° C. and 50%, stored in an environment of 40 ° C. for 4 weeks, and after packaging, The sensitivity was evaluated. The sensitivity of the sample of the heat-developable photosensitive material 1A stored in a frozen state was set to 100.

(Packaging material) PET 10 μm / PE 12 μm / Aluminum foil 9 μm / Ny 15 μm / Polyethylene containing 3% carbon
50μm Oxygen permeability: 0ml / atm ・ m ²・ 25 ℃ ・ day, Moisture permeability: 0g
/ atm ・ m ²・ 25 ℃ ・ day

The sample was exposed and heat-developed with a Fuji Medical Dry Laser Imager FM-DPL (equipped with a 660 nm semiconductor laser with a maximum output of 60 mW (IIIB)) (1
The obtained image was evaluated by a densitometer by using four panel heaters set at 12 ° C-119 ° C-121 ° C-121 ° C for a total of 24 seconds).

Evaluation of image storability A sample cut into half-size pieces was exposed and heat-developed with a Fuji Medical Dry Laser Imager FM-DPL in the same manner as the raw storability evaluation. The image obtained is at 25 ° C for 5
After conditioning the humidity in a 0% environment for 2 hours, it was sealed in a moistureproof bag protected from light and stored in an environment at 60 ° C. for 1 d. The obtained image was evaluated with a densitometer and the rate of change of Dmin was calculated.

-Measurement of melting point and phase transition point Put a sample in a glass capillary and make it into Buchi 53
The melting point was measured with a 0 type melting point measuring device. Further, the phase transition temperature of the sample was measured with a DSC6200 differential scanning calorimeter manufactured by Seiko Instruments.

[0273]

[Table 2]

The following can be seen from Table 2. The photothermographic materials 1A, 1C, 2A, and 3A using behenic acid or silver benzotriazole, which is out of the scope of the present invention as a silver salt, all have film peeling and have a large Dmin change rate. In terms of stability and storability, it is an issue to be improved. On the other hand, the photothermographic materials 1D, 1E, 1G to 1X of the present invention,
2J to 2S and 3J to 3S are all excellent in workability and have a small Dmin change rate. Among them, photothermographic materials (for example, 1J, 1K, 1V) using the compound of the present invention in which the melting point of free carboxylic acid is 30 ° C or more and 200 ° C or less are excellent in sensitivity and excellent. From the above, the effect of the present invention is clear.

Example 2 Compounds I-233, I-234 and I-23 were prepared in the same manner as in Example 1 except that two reducible silver salts were used in combination.
A photothermographic material using 6 was prepared and evaluated in the same manner. As a result, the photothermographic material of Example 2 was also evaluated to be excellent in processability and image storability.

[0276]

As described above, according to the present invention, a photothermographic material having improved processability, raw storability and image storability after development can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takayoshi Oyamada             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. (72) Inventor Kozaburo Yamada             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. (72) Inventor Itsuo Fujiwara             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H123 AB00 AB03 AB25 AB28 CB00                       CB03

Claims (13)

[Claims] 1. At least (a) on the same surface of the support.
A photothermographic material having a photosensitive silver halide, (b) a reducible silver salt represented by the following formula (I), (c) a reducing agent for silver ions, and (d) a binder. material. M ¹ O ₂ C-L ¹ -CO ₂ M ² Formula (I) [In Formula (I), L ¹ is an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -C (= O)-, -O-, -S
-, -S (= O)-, -S (= O) _2- , and -N
It represents a divalent group selected from (R ¹ )-, or a divalent composite group formed by a combination thereof. R ¹ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group. M
¹ and M ² represent a hydrogen atom or a counter ion, and at least one of M ¹ and M ² represents a silver (I) ion. The compound represented by the formula (I) may further have a carboxyl group or a salt thereof. ] 2. A compound of formula (I) wherein L ¹ is -C.
The photothermographic material according to claim 1, which represents a group having at least one divalent composite group formed by a combination of (= O)-and -O-. 3. A compound of formula (I) wherein L¹Is -N
(R²)-And a divalent combination of alkylene groups
Represents a group having at least one composite group of ²Is al
Kill group, alkenyl group, alkynyl group, aryl group,
Claims characterized by representing a sil group or a sulfonyl group
Item 1. A photothermographic material according to Item 1. 4. A compound of the formula (I), wherein L ¹ has at least one group selected from an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a divalent heterocyclic group. And at least one of these groups is a —NHCO—R ³ group,
CONHR ⁴ group, -OCOR ⁵ group, -CO ₂ R ⁶ group, -NH
SO ₂ -R ⁷ groups, -SO ₂ NHR ⁸ group, -SO ₃ R ⁹ groups, -O
The photothermographic material according to claim 1, which has an SO ₂ R ¹⁰ group (R ^{3 to} R ¹⁰ have the same meaning as R ² ) as a substituent. 5. The photothermographic material according to claim 1, wherein in the compound of formula (I), L ¹ is an alkylene group having at least one substituent. 6. In the compound of formula (I), L ¹ represents a group having at least one alkylene group, and L ¹
There photothermographic material according to claim 1, 4 or 5, characterized in that it has -NHCO-R ³ group a (R ³ has the same meaning as R ²⁾ as a substituent. 7. The photothermographic material according to claim 1, wherein in the compound of formula (I), L ¹ represents a group having at least one aromatic group. 8. The compound of formula (I) is a reducible silver salt having a molecular weight / the number of silver (I) ions per molecule of 160 or more and 400 or less.
7. The photothermographic material according to any of 7. 9. The free carboxylic acid of the compound of formula (I) has a melting point of 30 ° C. or higher and 200 ° C. or lower,
The photothermographic material according to claim 1. 10. The compound of formula (I) has a phase transition temperature of 50.
The temperature is not lower than 180 ° C and not higher than 180 ° C.
10. The photothermographic material according to any one of to 9. 11. The photothermographic material according to claim 1, which contains two or more compounds of formula (I). 12. The compound of formula (I) is 70% in total organic silver.
The photothermographic material according to claim 1, wherein the photothermographic material is at least mol%. 13. An image forming method, comprising thermally developing the photothermographic material according to claim 1.