JP2002268182A - Heat developable photographic sensitive material and image forming method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photographic sensitive material having high sensitivity, low fog density, good shelf stability and good image stability and excellent in silver tone and to provide an image forming method for the material. SOLUTION: The heat developable photographic sensitive material contains at least one of compounds of formulae (1-1), (1-2), (1-3), (1-4), (1-5) and (1-6).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material which forms an image by heating and a method for forming the image.

[0002]

2. Description of the Related Art A heat-developable photographic light-sensitive material (hereinafter, also referred to as a heat-developable light-sensitive material or simply a light-sensitive material) for forming a photographic image by a heat-development method or a silver salt photothermographic dry imaging material is disclosed in, for example, US Pat. No. 3,152
No. 904, 3,457,075, or D.C. "Dry Silver Photographic" by Morgan
Material) ", or D.I. H. "Thermally Processed Silver System (Thermally Process)" by Klosterboer
ed Silver Systems) "(Imaging Processes and Materials (Imag)
ing Processes and Materialia
ls) Neblette Eighth Edition, Sturge (Stu
rge), V.I. Walworth,
A. Edited by Shepp, pp. 279, 198
9 years).

Such a photothermographic material comprises a reducible silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide particles) and a reducing agent, usually in an (organic) binder matrix. Contained in a dispersed state. The photothermographic material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, oxidation between a reducible silver source (functioning as an oxidizing agent) and a reducing agent is performed. Generates silver through a reduction reaction. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which is symmetrical with the unexposed areas, resulting in the formation of an image.

At the time of image formation, various antifoggants are used in the photosensitive material as needed for the purpose of controlling the generation of fog.

Conventionally, as an antifoggant, for example, 2- (4-chlorobenzoyl) benzoic acid, benzotriazole, tetrachlorophthalic acid and the like have been used. Many of the agents have a low fog prevention function, and further technical development has been required. As a method for solving these problems, various polyhalogen compounds have been disclosed, for example, US Pat. Nos. 3,874,946 and 4,452,88.
No. 5, No. 4,546,075, No. 4,756, 9
No. 99, 5,340, 712 and European Patent No. 60
No. 5,981A1, No. 622,666A1, No. 6
31,176A1, JP-B-54-165, JP-A-5
Nos. 9-90842, 61-129642, 62-
129845, JP-A-6-202268 and 6-2
08193, 6-340611, 7-2781
No., No. 7-5621, No. 9-160164, No. 9-
244178, 9-258367, 9-265
No. 150, No. 9-281640, No. 9-319022
And No. 10-171063. Also, in US Patent No. 5,686,228, a propene nitrile compound is described as an antifoggant,
U.S. Pat. No. 6,083,681 discloses a method for improving the raw storability and image storability of a photothermographic material by using a compound which forms a complex with silver.

However, in particular, the photothermographic material for medical laser imagers, or the photothermographic material for output of a printing imagesetter containing a contrasting agent and having an oscillation wavelength of 600 to 800 nm, is used as the above-mentioned photothermographic material. When each of the described antifoggants is applied, image storability and silver tone are not at a satisfactory level, and further improvements are eagerly sought.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above problems, and has as its object to provide a high sensitivity, low fog density, good storage stability, good image stability, and a silver tone. It is an object of the present invention to provide a heat-developable photographic light-sensitive material and an image forming method thereof.

[0008]

The above object of the present invention has been attained by the following constitutions.

1. The general formulas (1-1), (1-2),
A photothermographic material comprising at least one compound selected from (1-3), (1-4), (1-5) and (1-6).

[0010] 2. The above-mentioned item 1, wherein the support contains an organic silver salt, a binder and a photosensitive silver halide.
4. The photothermographic material according to item 1.

3. In a heat-developable photographic material having a photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support, at least one of the photosensitive layers has the general formula (1-1) or ( 1-2), (1-3),
A photothermographic material comprising at least one compound selected from (1-4), (1-5) and (1-6).

4. 4. The photothermographic material according to item 2 or 3, further comprising a hydrazine derivative or a compound represented by formula (2).

5. 5. The photothermographic material according to any one of the items 2 to 4, further comprising a compound represented by the general formula (3).

6. 6. The photothermographic material according to any one of the above items 1 to 5, wherein the photothermographic material is exposed to light using a laser light source and then subjected to heat development at 80 to 250 ° C. Image forming method of material.

Hereinafter, the present invention will be described in detail. In the invention according to claims 1 and 3, in the photothermographic material,
The general formulas (1-1), (1-2), (1-3), and (1)
-4), characterized by containing at least one compound selected from (1-5) and (1-6).

The compounds represented by formulas (1-1) to (1-6) will be described below. The general formula (1-
In 1), R ₁₁ represents a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, alkylthio group, arylthio group, sulfonyl group, alkylsulfonyl group, ureido group, hydroxy group, mercapto group, halogen atom, hydrazino group or heterocyclic group, preferably aryl Group, aryloxy group, acyl group, acyloxy group, acylamino group, sulfonylamino group, sulfamoyl group, alkylthio group, arylthio group, hydroxy group or heterocyclic group, more preferably aryl , An aryloxy group, an acyloxy group, an acylamino group, a sulfonylamino group,
It represents an alkylthio group or a heterocyclic group, or a group of nonmetal atoms necessary to form a cyclic structure condensed with a benzene ring to which R ₁₁ is bonded. Particularly preferred is an aryl group, an aryloxy group or an alkylthio group, and a preferred condensed ring when a cyclic structure is formed is a naphthalene ring, an anthracene ring or a 1,2-methylenedioxybenzene ring. These substituents and condensed ring further include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group) , 2-ethyl-hexyl group, octyl group, decyl group, etc.), cycloalkyl group (for example, cyclohexyl group,
A cycloheptyl group or the like), an aryl group (for example, a phenyl group or a carboxyphenyl group), a heterocyclic group (for example,
Imidazolyl group, thiazolyl group, benzoxazolyl group, pyridyl group, pyrrolyl group, indolyl group, pyrimidinyl group, etc., alkenyl group (for example, ethenyl-2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl) Group, 3-pentenyl group, 1-methyl-3-butenyl group, etc.), cycloalkenyl group (eg, 1-cycloalkenyl group, 2-cycloalkenyl group, etc.), alkynyl group (eg, ethynyl group, 1-propynyl group) Etc.), alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, etc.), acyloxy groups (eg, acetyloxy group,
Benzoyloxy group, etc.), aryloxy group (for example,
Phenoxy group, p-tolyloxy group, etc.), heteroaryloxy group (eg, 2-pyridyloxy group, pyrrolyloxy group, etc.), alkylthio group (eg, methylthio group, trifluoromethylthio group, etc.), arylthio group (eg, phenylthio group) , 2-naphthylthio group, etc.),
A heteroarylthio group (for example, a 3-thienylthio group, 3
-Pyrrolylthio group, etc.), aralkyl group (eg, benzyl group, 3-chlorobenzyl group, etc.), carboxyl group, acylamino group (eg, acetylamino group, benzoylamino group, etc.), acyloxycarbonylamino group (eg, acetyloxycarbonyl group) Amino group, benzoyloxycarbonylamino group, etc.), ureido group (eg, methylaminocarbonylamino group, phenylaminocarbonylamino group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), acyl group (Eg, acetyl group, benzoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, N-morpholino) A sulfonyl group), a sulfamoyl group (a sulfamoyl group, an N, N-dimethylsulfamoyl group, a morpholinosulfamoyl group, etc.), a trifluoromethyl group, a hydroxyl group, a styryl group, a nitro group, a cyano group, and a sulfonamide group. For example, a methanesulfonamide group, a butanesulfonamide group and the like, an amino group (for example, an amino group, an N, N-dimethylamino group, an N, N
-Diethylamino group, etc.), sulfo group, phosphono group, sulfite group, sulfino group, sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group) , Methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), and sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.) May be substituted. Also,
When there are two or more substituents, they may be the same or different.

K represents an integer of 1 to 5, and when k is an integer of 2 to 5, R ₁₁ may be the same or different.

X ₁₁ represents O or S; Y ₁₁ represents OH, N
H _2, represents a S-M ⁺ or O-M ^+, M ⁺ represents a metal ion. Examples of metal ions include Na ⁺ , K ⁺ , L
i ⁺ , Ca ₂ ⁺ or Mg ₂ ^+, etc., preferably Na ⁺ , K ⁺ or Li ⁺ , and particularly preferably N
a ⁺ or K ⁺ .

In the general formula (1-2), R ₂₁ , R
₂₂ and R ₂₃ each independently represent a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Alkynyl group, aryl group, amino group, alkoxy group,
Aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl Group, alkylsulfonyl group,
Arylsulfonyl group, sulfinyl group, ureido group,
Examples include a phosphoric amide group, a hydroxy group, a mercapto group, a halogen atom, a hydrazino group, a silyl group, and a heterocyclic group. These substituents may further have a substituent described in the R _11.

M represents an integer of 1 to 5, and when m is an integer of 2 to 5, R ₂₃ may be the same and different, and are bonded to each other to form a 5- or 6-membered saturated carbocyclic ring, benzene, It may form a condensed ring such as a ring, a naphtho ring and a heterocyclic ring. These fused rings may have a substituent represented further by the R _11.

X ₂₁ represents O or S, and Y ₂₁ has the same meaning as Y _{11 in the} formula (1-1).

In the above formula (1-3), R ₃₁ and R ₃₂ each independently represent a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include those described above for R _11. .

X ₃₁ and A ₃₁ represent O or S, and Y ₄₁ represents
It has the same meaning as Y ₁₁ described in the general formula (1-1). n represents 0 or 1.

Z represents a heterocyclic ring.
For example, quinoline ring, isoquinoline ring, pyridine ring, pyran ring, pyrazine ring, pyrimidine ring, coumarin ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, benzofuran ring, indole ring, pyrazole ring or imidazole ring and the like. And preferably a quinoline ring, isoquinoline ring, pyridine ring, pyran ring, pyrazine, coumarin ring, pyrazole ring or imidazole ring, and more preferably a quinoline ring, isoquinoline ring, pyridine ring and pyran ring. These hetero rings may further have a substituent described in the R _11.

In the above formula (1-4), R ₄₁ , R
₄₂ , R ₄₃ and R ₄₄ each independently represent a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include those described above for R ₁₁ .

P is an integer of 0 to 5, and when p is an integer of 2 to 5, R ₄₄ may be the same or different, and are bonded to each other to form a 5- or 6-membered saturated carbocyclic ring, benzene, ring,
A condensed ring such as a naphtho ring and a hetero ring may be formed. These fused rings may have a substituent described in the R _11.

Y ₄₁ is a group represented by Y in the aforementioned general formula (1-1).
Synonymous with ₁₁ . In the general formula (1-5), R ₅₁
And R ₅₂ each independently represent a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include the substituents described above for R ₁₁ .

Q represents an integer of 0 to 5, and when q is an integer of 2 to 5, R ₅₂ may be the same or different and is bonded to each other to form a 5- or 6-membered saturated carbocyclic or benzene ring. ring,
A condensed ring such as a naphtho ring and a hetero ring may be formed. These fused rings may have a substituent described in the R _11.

A ₅₁ represents O or S, and Y ₅₁ has the same meaning as Y _{11 in the} formula (1-1).

In the above general formula (1-6), R ₆₁ , R
₆₂ and R ₆₃ each independently represent a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include the substituents described above for R ₁₁ .

R represents an integer of 0 to 5, and when r is an integer of 2 to 5, R ₆₃ may be the same or different, and are bonded to each other to form a 5- or 6-membered saturated carbocyclic ring, benzene, ring,
A condensed ring such as a naphtho ring and a hetero ring may be formed. These fused rings may have a substituent described in the R _11.

X ₆₁ represents O, S or NR ₆₄ , R ₆₄ represents a hydrogen atom or a substituent, and examples of the substituent include those described above for R ₁₁ .

Y ₆₁ is a group represented by the formula (1-1)
Synonymous with ₁₁ . Hereinafter, the general formulas (1-1) to (1-6)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

According to a fourth aspect of the present invention, the photothermographic material contains the compound represented by the general formulas (1-1) to (1-6) and the general formula (2) or a hydrazine derivative. The feature is that there is.

Hereinafter, the compound represented by formula (2) according to the present invention will be described. In the general formula (2), R ₇₁ , R ₇₂ and R ₇₃ each independently represent a hydrogen atom or a substituent, and the substituent is the same as R ₁₁ in the general formula (1-1). Can be mentioned.

Q represents a substituent, and examples of the substituent include the same substituents as those described for R ₁₁ in formula (1-1), and are preferably electron-withdrawing groups. The electron-withdrawing group is a substituent having a Hammett's substituent constant σp value of 0.15 or more, more preferably 0.2 or more.
Regarding the Hammett's substituent constant, Journal o
f Medicinal Chemistry, 197
3, Vol. 16, No. 11, 1207-1216 etc. can be referred to. Examples of the electron-withdrawing group include a halogen atom [a chlorine atom (σp value: 0.23),
Bromine atom (σp value: 0.23), iodine atom (σp value:
0.18)], trihalomethyl group [for example, tribromomethyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4) etc.], a cyano group (σp value: 0.66), a nitro group (σp value: 0.78), an aliphatic aryl or heterocyclic sulfonyl group [for example, a methanesulfonyl group (σp value: 0.
72) etc.], aliphatic aryl or heterocyclic acyl group [eg, acetyl group (σp value: 0.50), benzoyl group (σp value: 0.43), etc.), aliphatic aryl or heterocyclic oxycarbonyl group [ For example, a methoxycarbonyl group (σp value: 0.45), a phenoxycarbonyl group (σp value
p value: 0.45)] and a carbamoyl group (σp value: 0.
36), a sulfamoyl group (σp value: 0.57) and the like, and a cyano group is preferable.

R ₇₁ and Q, R ₇₁ and R ₇₂ , R ₇₂ and R ₇₃ and R
₇₃ and Q may be bonded to each other to form a cyclic structure.

In the formula (2), a compound in which R ₇₂ is an electron donating group and R ₇₃ is a hydrogen atom is preferred. The electron donating group referred to in the present invention is a substituent having a Hammett's substituent constant σp having a negative value. Examples of the electron donating group include a hydroxyl group (or a salt thereof),
A mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group; Or a phenyl group substituted with these electron donating groups.

Hereinafter, specific examples of the compound represented by the general formula (2) will be given, but the present invention is not limited thereto. In addition, in these compounds, when a tautomer or a geometric isomer exists, both of them are represented.

[0046]

Embedded image

[0047]

Embedded image

The hydrazine derivative that can be used in the present invention will be described below. Examples of the hydrazine derivative according to the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 23516 (Jan.
January issue, p. 346) and references cited therein,
U.S. Pat. Nos. 4,080,207 and 4,269,9
No. 29, No. 4,276,364, No. 4,278,
No. 748, No. 4,385,108, No. 4,45
No. 9,347, No. 4,478,928, No. 4,5
No. 60,638, No. 4,686,167, No. 4,
Nos. 912,016, 4,988,604, 4,994,365, 5,041,355, 5,104,769 and British Patent 2,011,39.
No. 1B, European Patent Nos. 217,310 and 301,7
No. 99, 356, 898, JP-A-60-1797
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, 2-220042, 2-221953,
2-221954, 2-285342, 2-
No. 285343, No. 2-289843, No. 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3-54549, No. 3-125134, No. 3
Nos. -184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, 3-282536, 4-51143, 4-56842, 4-84134, 2-230
No. 233, No. 4-96053, No. 4-216544
Nos. 5-45761, 5-45762, 5-
No. 45763, No. 5-45764, No. 5-45765
And Nos. 6-289524 and 9-160164.

In addition, other compounds represented by Chemical Formula 1 described in JP-B-6-77138, specifically, the compounds described on pages 3 and 4 of the same publication, or the compounds described in JP-B-6-93138
No. 082, specifically, the compounds of 1 to 38 described on pages 8 to 18 of the same publication, or the compound of the general formula (4) described in JP-A-6-230497. ) To (6), specifically, Compounds 4-1 to 4-1 described on pages 25 and 26 of the same publication.
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7 or compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compound 1-1 described on pages 5 to 7 of the same publication) ~ 1
17) and 2-1), or JP-A-6-313393
Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in No. 6, specifically, the compounds described on pages 6 to 19 of the same publication, or (Chemical Formula 1) described in JP-A-6-313951. Specifically, compounds described on pages 3 to 5 of the same publication, or compounds represented by the general formula (I) described in JP-A-7-5610. 5-5
Compounds I-1 to I-38 described on page 0 or compounds represented by general formula (II) described in JP-A-7-77783, and specifically, compounds described on pages 10 to 27 of the same publication. Compound
II-1 to II-102 or JP-A-7-104426
And the compounds represented by the general formula (H) and the general formula (Ha) described in (1), specifically, compounds H-1 to H-44 described on pages 8 to 15 of the publication. .

Hereinafter, specific examples of the hydrazine derivative that can be preferably used in the present invention are shown, but the present invention is not limited to these.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

The compound represented by the general formula (2) and the hydrazine derivative according to the present invention can be easily synthesized by a known method. There are also compounds that can be purchased directly from drug manufacturers.

As a layer to which the compound represented by the general formula (2) and the hydrazine derivative are added, the layer may be added to either a photosensitive layer containing an organic silver salt, a silver halide emulsion or the like, or a non-photosensitive layer. Although it is possible, it is preferably a photosensitive layer or a layer adjacent to the photosensitive layer. In addition, the general formula (2)
The amount of the compound and the hydrazine derivative represented by
Although there is no particular limitation, generally 10 mol per mol of silver halide is used.
The range is preferably about ^-6 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

The invention according to claim 5 is characterized in that the photothermographic material contains the compound represented by the general formula (3).

Hereinafter, the compound represented by formula (3) according to the present invention will be described. In the general formula (3), the halogen atoms represented by D ₁ and D ₂ are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom which may be the same or different, and preferably a chlorine atom, a bromine atom , Iodine atom, more preferably chlorine atom and bromine atom, particularly preferably bromine atom.

G represents a hydrogen atom, a halogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an amino group, an acyl group and an acyloxy group. Group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, sulfonyl group, alkylsulfonyl group, sulfinyl group, cyano group, heterocyclic group and the like.

J represents a divalent linking group. Examples of the linking group include —SO ₂ —, —CO—, —NHCO—, and
OOC—, —N (R ₉ ) SO ₂ —, and R ₉ represents a substituent.

T represents an alkyl group, an aryl group or a hetero ring, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an iso-pentyl group, a 2-ethyl-hexyl group, Octyl group, decyl group, adamantyl group or cyclohexyl group and the like, examples of the aryl group include, for example, phenyl group, naphthyl group and anthranyl group, and examples of the hetero ring include, for example, a pyridyl group, a benzoxazole group,
Examples include a benzothiazole group, a benzimidazole group, a pyrimidyl group, a pyrrolidyl group, a piperidyl group, and a morpholyl group.

W represents 0 or 1. Hereinafter, the general formula (3)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0062]

Embedded image

[0063]

Embedded image

As a layer to which the compound represented by the general formula (3) is added, any of a photosensitive layer containing an organic silver salt, a silver halide emulsion or the like, and a non-photosensitive layer can be added. It is preferably a photosensitive layer or a layer adjacent to the photosensitive layer. The amount of the compound represented by the general formula (3) is not particularly limited.
10 ^{-4 to} 1.0 mole per mole, particularly 10 ^{-3 to} 0.3
A molar range is preferred.

The general formulas (1-1) to (1-)
6), the compounds represented by the general formulas (2) and (3) and the hydrazine derivatives can be obtained by using a suitable organic solvent, alcohols (eg, methanol, ethanol, propanol, fluorinated alcohol), ketones (eg, Acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve and the like can be added. Further, it can be incorporated by an already well-known emulsification dispersion method, for example, a high-boiling organic solvent such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate and an auxiliary solvent such as ethyl acetate or cyclohexanone. After dissolving and mechanically emulsifying to prepare an emulsified dispersion, it can be added to a desired constituent layer.

Further, a method known as a solid dispersion method, for example, the general formulas (1-1) to (1-
6), powders of the compound represented by the general formula (2) and the general formula (3) and the hydrazine derivative are prepared by, for example, using a ball mill,
A water-based fine particle dispersion can be added to any constituent layer using a dispersing means such as a colloid mill or an ultrasonic disperser.

The photothermographic material of the present invention may further comprise, in addition to the above compounds, hydroxylamine compounds, alkanolamine compounds and ammonium phthalate compounds described in US Pat. No. 5,545,505, and US Pat. No. 5,545. , 5
07 hydroxamic acid compound, U.S. Pat.
N-acyl-hydrazine compounds described in US Pat. No. 558,983 and hydrogen atom donor compounds such as benzhydrol, diphenylphosphine, dialkylpiperidine and alkyl-β-ketoester described in US Pat. No. 5,937,449 are appropriately used. Can be added. By including these compounds, the maximum density Dmax can be further improved in an image formed using each of the compounds according to the present invention.

Next, the details of the photothermographic material of the present invention will be described. The organic silver salt used in the photothermographic material of the present invention is a reducible silver source, and a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source. 10 to 30 atoms, preferably 1
5-25) Aliphatic carboxylic acids and nitrogen-containing heterocycles are preferred. Organic or inorganic silver complexes in which the ligand has a value of 4.0 to 10.0 as a total stability constant for silver ions are also useful in the present invention. Examples of suitable silver salts are
RD No. 17029 and No. 29963, and include the following: silver salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, Silver salts such as lauric acid); carboxyalkylthiourea salts of silver (eg, 1
-(3-carboxypropyl) thiourea, silver salts such as 1- (3-carboxypropyl) -3,3-dimethylthiourea); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, , Aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (eg, salicylic acid,
Silver complex of the polymer reaction product with benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid);
Silver such as silver salts or complexes of thiones (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thione, and 3-carboxymethyl-4-thiazoline-2-thione) A salt or a complex); a nitric acid selected from imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole and silver; And silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate, silver stearate and mixtures thereof.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver. The mixing method includes forward mixing, reverse mixing, simultaneous mixing, and special mixing. A controlled double jet method or the like described in Japanese Unexamined Patent Publication No. 9-127463 is preferably used. For example, an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) is added to an organic acid, and an organic acid alkali metal salt soap (eg, sodium behenate,
After preparing sodium arachidate, the above-mentioned soap and silver nitrate are added by a controlled double jet method to prepare crystals of an organic silver salt. At this time, photosensitive silver halide grains described below (hereinafter, also simply referred to as silver halide grains) may be mixed.

The silver halide grains according to the present invention function as an optical sensor. In the present invention, the average particle size is preferably small, preferably 0.1 μm or less, more preferably 0.01 to 0. 0, in order to suppress white turbidity of the photosensitive material after image formation and obtain good image quality.
It is 1 μm, particularly preferably 0.02 to 0.08 μm. The grain size (grain size) as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral, so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere assuming a sphere equivalent to the volume of silver halide grains. The silver halide grains are preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less.
It is more preferably at most 30%, particularly preferably 0.1%.
The particles are 1% or more and 20% or less.

Monodispersity = [(standard deviation of particle size) / (average value of particle size)] × 100 (%) In the present invention, the silver halide particles have an average particle size of 0.1.
It is preferable that the particle size is not more than μm and that the particles are monodisperse particles. When the particle size falls within this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by T.M. using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani J. et al. Imaging Sci. 29
165 (1985).

Another preferred shape of the silver halide grains in the present invention is tabular grains. The term "tabular grain" as used herein means an aspect ratio where the square root of the projected area is r (μm) and the thickness in the vertical direction is h (μm).
r / h is 3 or more. Among them, preferably,
The aspect ratio is 3 to 50. The particle size of the tabular grains is preferably 0.1 μm or less, more preferably 0.01 to 0.08 μm. These tabular grains are described in U.S. Patent Nos. 5,264,337 and 5,31.
Nos. 4,798, 5,320,958 and the like can be easily obtained. In the present invention, the use of the tabular grains is preferable because the sharpness of an image can be further improved.

The halogen composition of the silver halide grains is not particularly limited, and may be silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide,
Any of silver iodobromide and silver iodide may be used. The silver halide emulsion used in the present invention is a P.I. Glafkids
Written by Chimie et Physique Photo
graphique (published by Paul Montel, 1
967); F. Photogr by Duffin
aphic Emulsion Chemistry
(Published by The Focal Press, 1966),
V. L. Making by Zelikman et al
and Coating Photographic
Emulsion (The FocalPress
Ed., 1964) and the like.

The silver halide grains according to the present invention contain ions or complex ions of metals belonging to Groups 6 to 10 of the Periodic Table of the Elements for the purpose of improving reciprocity failure characteristics and adjusting gradation. Is preferred. As the above metals,
W, Fe, Co, Ni, Cu, Ru, Rh, Pd, R
e, Os, Ir, Pt, and Au are preferred.

In the silver halide grains according to the present invention, unnecessary salts can be removed (desalted) by a method known in the art such as a noodle method or a flocculation method. The desalting may or may not be performed.

The silver halide grains according to the present invention are preferably subjected to chemical sensitization. Preferred chemical sensitization methods include those well known in the art, for example,
Sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization of gold compounds, platinum, palladium, iridium compounds and the like, reduction sensitization, and the like can be used.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is 0.5 g or more and 2.2 g or less per m ² in terms of silver. preferable. By setting the silver amount in this range,
A high-contrast image can be obtained. The ratio of the amount of silver halide to the total amount of silver is 50% or less by mass, preferably 25% or less, and more preferably 0.1 to 15%.

Examples of the reducing agent used in the photothermographic material of the present invention include generally known reducing agents, such as phenols, polyphenols having two or more phenol groups, naphthols and bisnaphthols. , 2
Polyhydroxybenzenes having at least two hydroxyl groups, 2
Polyhydroxynaphthalenes having at least two hydroxyl groups,
Ascorbic acids, 3-pyrazolidones, pyrazoline-
5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone monoethers,
Hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas and the like.
For example, US Pat. Nos. 3,615,533 and 3,6
No. 79,426, No. 3,672,904, No. 3,
Nos. 751,252, 3,782,949, 3,801,321, 3,794,488, 3,893,863, 3,887,376,
No. 3,770,448 and No. 3,819,382
No. 3,773,512, No. 3,839,04
No. 8, No. 3,887,378, No. 4,009,0
No. 39, No. 4,021,240, British Patent No. 1,4
86,148, Belgian Patent No. 786,086, JP-A-50-36143, JP-A-50-36110, and JP-A-50-36110.
No. 0-116023, No. 50-99719, No. 50-
140113, 51-51933, 51-23
No. 721, No. 52-84727, Japanese Patent Publication No. 51-358
The reducing agent specifically exemplified in No. 51 can be mentioned, and in the present invention, it can be appropriately selected and used from the known reducing agents described above. The most efficient selection method is to actually prepare a photothermographic material containing a reducing agent and directly evaluate the photographic performance of the material to confirm the suitability of the reducing agent.

Among the above reducing agents, when a silver aliphatic carboxylate is used as the organic silver salt, a preferable reducing agent is a polyphenol in which two or more phenol groups are linked by an alkylene group or sulfur, especially An alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) ) Is a polyphenol in which two or more of the phenol groups substituted by an alkylene group or sulfur, for example, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,
5,5-trimethylhexane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,1-bis (2-hydroxy-3,5-di-tert-)
Butylphenyl) methane, (2-hydroxy-3-t-
Butyl-5-methylphenyl)-(2-hydroxy-5
-Methylphenyl) methane, 6,6'-benzylidene-
Bis (2,4-di-t-butylphenol), 6,6 ′
-Benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene-bis (2,4-
Dimethylphenol), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane,
1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5
U.S. Pat. Nos. 3,589,903 and 4,021,249; British Patent 1,486,148;
No. 3, No. 50-36110, No. 50-116023
Nos. 52-84727 and JP-B-51-35727; U.S. Pat.
Bisnaphthols described in No. 72,904, for example, 2,2'-dihydroxy-1,1'-binaphthyl,
6,6'-dibromo-2,2'-dihydroxy-1,
1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-
1,1'-dihydroxy-2,2'-binaphthyl and the like, as well as sulfonamidophenols or sulfonamidonaphthols as described in U.S. Pat. No. 3,801,321, for example, 4-benzenesulfonamidophenol; 2-benzenesulfonamidophenol, 2,6
-Dichloro-4-benzenesulfonamidophenol,
4-benzenesulfonamide naphthol and the like can be mentioned.

The appropriate amount of the reducing agent used in the photothermographic material of the present invention is not uniform depending on the kind of the organic silver salt used, the type of the reducing agent, and other additives.
0.05 to 10 mol, preferably 0.1 to 3 per mol
A molar range is appropriate. Further, within this range, two or more of the above-mentioned reducing agents may be used in combination. In the present invention, it is preferable to add the reducing agent to the coating solution for the photosensitive layer immediately before coating and apply the solution in order to reduce fluctuations in photographic performance due to the stagnation time of the coating solution for the photosensitive layer.

Examples of the binder suitable for the photothermographic material of the present invention include transparent or translucent, generally colorless, natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and the like. Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) ), Li (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
Cellulose esters, poly (amide) s and the like can be mentioned. The binder may be hydrophilic or hydrophobic, but in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after the heat development process. Examples include butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, and polyurethane.
Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate and polyester are particularly preferably used.

In order to protect the surface of the light-sensitive material and prevent abrasion, it is preferable to provide a non-light-sensitive layer outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the heat development rate. More preferably, 1.7-8 g
/ M ² . If it is less than 1.5 g / m ² , the density (Dmin) of the unexposed portion will increase significantly, which may cause a practical problem.

In the present invention, it is preferable to add a matting agent to the photosensitive layer side, and to prevent the image after thermal development from being damaged, the amount of the matting agent disposed on the surface of the photosensitive material depends on the amount of the matting agent. From 0.5 to the total weight of all binders
It is preferable to contain 30%. In the case where a non-photosensitive layer is provided on the surface opposite to the photosensitive layer with the support interposed therebetween, at least one layer on the non-photosensitive layer side may contain a matting agent to prevent slippage or fingerprints. It is also preferable for preventing adhesion, and the amount of the matting agent is preferably 0.5 to 40% by mass relative to the entire binder of the non-photosensitive layer.
The shape of the matting agent may be either a fixed shape or an irregular shape, but is preferably a fixed shape, particularly preferably a spherical shape.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. Also,
In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer, or an antihalation dye layer on the opposite side, a so-called backing layer, or A dye or pigment may be directly contained in the active layer.

These non-photosensitive layers may contain a slipping agent such as a polysiloxane compound, waxes or liquid paraffin in addition to the binder and the matting agent.

In the photothermographic material of the present invention, various surfactants can be used as a coating aid. Among them, a fluorine-based surfactant is particularly preferably used for improving charging characteristics and preventing spot-like coating failure.

The photosensitive layer may be composed of a plurality of layers, or a plurality of layers such as a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting gradation.

Examples of suitable toning agents which can be used in the present invention are disclosed in RD No. 17029, which can be referred to.

The photothermographic material of the present invention may contain a mercapto compound to control or enhance development and to control development intensity, to improve spectral sensitization efficiency, or to improve storage stability before and after development. , A disulfide compound, a thione compound and the like.

The photothermographic material of the present invention may contain, for example, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. These additives and other additives described above include RD No. 17029 (1978).
June, p. Compounds described in 9 to 15) can be preferably used.

The above-mentioned various additives may be added to any of the photosensitive layer, the non-photosensitive layer and other forming layers.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. , Polyethylene naphthalate).

Among them, preferred supports include plastic supports containing polyethylene terephthalate and a styrenic polymer having a syndiotactic structure. The thickness of the support is 50 to 300 μm
Degree, preferably 70 to 180 μm.

Further, a heat-treated plastic support may be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support is
After forming the support, before the photosensitive layer is coated, at a temperature higher than the glass transition point of the support by 30 ° C. or higher, preferably at a temperature higher by 35 ° C. or higher, more preferably at a temperature higher by 40 ° C. or higher. Refers to heating.

In the present invention, a conductive compound such as a metal oxide and a conductive polymer can be included in the constituent layer in order to improve the charging characteristics. These compounds may be contained in any of the layers, but preferably include an undercoat layer, a backing layer, and a layer between the photosensitive layer and the undercoat.

The photothermographic material of the present invention includes, for example, JP-A-63-159814 and JP-A-60-140335.
Nos. 63-231437, 63-259,651, 63-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455
No. 4,741,966, No. 4,751,17
The sensitizing dyes described in No. 5, No. 4,835,096 can be appropriately selected and used.

Specific examples of useful sensitizing dyes that can be used in the present invention include, for example, RD No. 17643, IV-A (p.23, December 1978, p.23) and 18431X (1).
August 979 p. 437) or in the literature cited.

In the present invention, in particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) Japanese Patent Application Laid-Open No. 60-162247 discloses an argon laser light source.
JP-A-2-48653, U.S. Pat. No. 2,161,33
No. 1, West German Patent No. 936,071, JP-A-5-113
No. 89, etc .; B) For a helium-neon laser light source, see JP-A-50-62.
No. 425, No. 54-18726, No. 59-10222
And trinuclear cyanine dyes described in JP-A No. 9-287.
338, C) LED light source and red semiconductor laser are disclosed in JP-B-48-42172.
Thiacarbocyanines described in JP-A-51-9609, JP-A-55-39818, JP-A-62-284343 and JP-A-2-105135. No. 59-191032, 6
0-80841 tricarbocyanines;
JP-A-59-192242 and JP-A-3-67242 disclose a compound represented by the general formula (IIIa) or (IIIb).
Dicarbocyanines containing a quinoline nucleus are advantageously selected.

These sensitizing dyes may be used alone or in combination thereof. In the case of a combination of sensitizing dyes, the sensitizing dyes may be used together with sensitizing dyes often used for supersensitization. A dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the silver halide emulsion.

Exposure of the photothermographic material of the present invention is performed by using an Ar laser (488 nm) and a He-Ne laser (633n).
m), a red semiconductor laser (670 nm), or an infrared semiconductor laser (780 nm, 830 nm) or the like, and preferably an infrared semiconductor laser in which the wavelength of the laser light source is 700 to 1000 nm. .

The photothermographic material of the present invention can be provided with a dye-containing layer as an antihalation layer as described above. In this case, an Ar laser, a He—Ne laser, and a red semiconductor laser are used. , 400 nm to 75
It is preferable to add a dye so that absorption is at least 0.3 or more, preferably 0.8 or more at an exposure wavelength in the range of 0 nm. Further, for an infrared semiconductor laser, it is preferable to add a dye so as to absorb at least 0.3 or more, preferably 0.8 or more at an exposure wavelength of 750 nm to 1500 nm. One or more dyes may be used in combination. The dye can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the side opposite to the photosensitive layer.

The photothermographic material of the present invention may be developed by any method. In the invention according to the sixth aspect, the temperature of the photothermographic material exposed imagewise is raised to 80 to 250 ° C. And a heat development treatment, preferably at 100 to 140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

[0105]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 << Preparation of Subbed Substrate 1 >> Colored in blue with a commercially available biaxially stretched heat-fixed thickness of 175 μm and an optical density of 0.170 (measured with a Konica Densitometer PDA-65). 8 W / m on both sides of a polyethylene terephthalate film
The corona discharge treatment for ² minutes is performed, and the following undercoating coating solution a-1 is applied on one surface so as to have a dry film thickness of 0.8 μm.
It was dried to form an undercoat layer A-1, and on the opposite side, an undercoat coating solution b-1 shown below was applied so as to have a dry film thickness of 0.8 μm, and was dried to form an undercoat layer B-1. did.

<Undercoating Coating Solution a-1> Copolymer of butyl acrylate (30% by mass), t-butyl acrylate (20% by mass) styrene (25% by mass), 2-hydroxyethyl acrylate (25% by mass) Latex liquid (solid content 30%) 270 g C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 L with water <Undercoat coating solution b-1> Butyl acrylate (40% by mass) ), Styrene (20% by mass), glycidyl acrylate (40% by mass) copolymer latex liquid (solid content 30%) 270 g C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1L with water Then, on each surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Is applied, and a coating liquid a-2 for the undercoating layer described below is applied on the undercoating layer A-1 so as to have a dry film thickness of 0.1 μm. A-2, and an undercoating layer B- having an antistatic function so that the following undercoating layer coating solution b-2 has a dry film thickness of 0.8 μm on the undercoating layer B-1.
The support 1 was prepared by coating as No. 2.

<Undercoating upper layer coating solution a-2> Mass of gelatin 0.4 g / m ² C-1 0.2 g C-2 0.2 g C-3 0.1 g Silica particles (average particle size 3 μm) 0 <1 g of water <1 g of water><Coating solution b-2 for lower layer> C-4 60 g Latex liquid containing C-5 as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g C-6 12 g Polyethylene glycol (weight average) (Molecular weight 600) 6g Finish to 1L with water

[0109]

Embedded image

[0110]

Embedded image

<< Coating on Back Side >> (Preparation of Backing Layer Coating Solution) Cellulose acetate butyrate (Eastman Chemical) was stirred while 830 g of methyl ethyl ketone (hereinafter abbreviated as MEK) was stirred.
al., CAB381-20) (84.2 g) and a polyester resin (Bostic, Vitel PE2200)
B) 4.5 g was added and dissolved. Next, 0.30 g of infrared dye 1 was added to the dissolved solution, and 4.5 g of a fluorinated surfactant (Asahi Glass Co., Ltd., Surflon KH40) dissolved in 43.2 g of methanol and a fluorinated surfactant ( Dai Nippon Ink, Megafag F120K) 2.3
g, and the mixture was sufficiently stirred until it was dissolved. Finally, silica (WR Gra) dispersed in methyl ethyl ketone at a concentration of 1% by mass with a dissolver-type homogenizer.
(CE company, Syloid 64X6000) was added and stirred to prepare a backing layer coating solution.

(Coating of Backing Layer) The above prepared coating solution for the backing layer was extruded onto the undercoating upper layer B-2 of the prepared undercoating support 1 so that the dry film thickness became 3.5 μm. , And dried over 5 minutes using a drying air having a drying temperature of 100 ° C. and an outdoor temperature of 10 ° C. to form a backing layer.

<< Preparation of Photosensitive Silver Halide Emulsion A >> (Solution A1) Phenylcarbamoylated gelatin 88.3 g Compound A (* 1: 10% aqueous methanol solution) 10 ml Potassium bromide 0.32 g Finish up to 5429 ml with water (B1) Solution) 0.67 mol / L silver nitrate aqueous solution 2635 ml (C1 solution) Potassium bromide 51.55 g Potassium iodide 1.47 g Finish up to 660 ml with water (D1 solution) Potassium bromide 154.9 g Potassium iodide 4.41 g Iridium chloride (Liquid) (1% solution) 0.93 ml Finish to 1982 ml with water (E1 solution) 0.4 mol / L aqueous potassium bromide solution Silver potential control amount below (F1 solution) Potassium hydroxide 0.71 g Finish to 20 ml with water (G1 solution) 56 18.0% aqueous acetic acid solution (H1 solution) 1.72 g of anhydrous sodium carbonate with water Finish 151 ml * 1 Compound _{A: HO (CH 2 CH 2} O) n - [CH (CH ₃₎ CH ₂ O] _{17 - (CH 2 CH 2 O} ) m H m + n = 5~7 JP-B-58-58288 Using the mixing stirrer described in 1), while controlling the 1/4 amount of the solution B1 and the total amount of the solution C1 in the solution A1 at a temperature of 45 ° C. and a pAg of 8.09, it took 4 minutes and 45 seconds by the simultaneous mixing method. And nucleation was performed. One minute later, the entire amount of solution F1 was added. During this time, pA
The adjustment of g was performed appropriately using the solution E1. After a lapse of 6 minutes, 3/4 of the amount of the solution B1 and the entire amount of the solution D1 were heated at a temperature of 4
While controlling at 5 ° C. and pAg 8.09, the mixture was added over 14 minutes and 15 seconds by a double jet method. After stirring for 5 minutes, 4
The temperature was lowered to 0 ° C., and the whole amount of the solution G1 was added to precipitate a silver halide emulsion. The supernatant liquid was removed, leaving 2000 ml of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. Settling portion 1500ml
, The supernatant was removed, and 10 liters of water was further added. After stirring, the silver halide emulsion was settled. After removing the supernatant liquid leaving 1500 ml of the sedimented portion, the solution H
1 was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and water was added so that the amount became 1161 g per mol of silver, whereby photosensitive silver halide emulsion A was obtained.

This photosensitive silver halide emulsion A had an average grain size of 0.058 μm and a variation coefficient of grain size of 12 μm.
%, And [100] face ratio of 92% were monodispersed cubic silver iodobromide grains.

<< Preparation of Powdered Organic Silver Salt >> In 4720 ml of pure water, 130.8 g of behenic acid and 67.7 g of arachidic acid were used.
g, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 mol / l aqueous sodium hydroxide solution was added, and 6.9 concentrated nitric acid was added.
After adding ml, the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. The temperature of the above fatty acid sodium solution is 55 ° C.
, 45.3 g of the above-mentioned photosensitive silver halide emulsion A and 450 ml of pure water were added thereto, followed by stirring for 5 minutes.

Next, a 1 mol / L silver nitrate solution 702.6
ml was added over 2 minutes and stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and drainage are repeated until the conductivity of the wastewater becomes 2 μS / cm, and centrifugal dehydration is performed. The obtained organic silver salt in a cake form is washed with a flash-type drier flash jet drier (Seisin). The organic silver salt was dried until the water content reached 0.1% by appropriately setting the nitrogen gas atmosphere and the temperature of hot air at the entrance of the dryer, to obtain a dried organic silver salt powder.

The water content of the organic silver salt composition was measured by
This was performed using an infrared moisture meter. << Preparation of Preliminary Dispersion >> Polyvinyl butyral powder (Mo
Butvar B-79, manufactured by nsanto) 14.5
7g was dissolved in 1457g of MEK, and VMA-GETZ was dissolved.
Mannmann dissolver DISPERMAT CA-4
The powdered organic silver salt 50 prepared above was stirred with a 0M mold.
A preliminary dispersion was prepared by gradually adding 0 g and mixing well.

<< Preparation of Photosensitive Emulsion Dispersion 1 >> 0.5 mm diameter zirconia beads (Toray Co., Ltd., Treceram) were prepared by using a pump and using a pump so that the residence time in the mill was 1.5 minutes. Disperser DISPERMAT SL-C12EX (VMA
-GETZMANN), mill peripheral speed 8m / s
To prepare a photosensitive emulsion dispersion liquid 1.

<< Preparation of Photosensitive Layer Coating Solution 1 >> In an inert gas atmosphere (97% by volume of nitrogen), 50 g of the photosensitive emulsion dispersion liquid 1 and 15.11 g of MEK were kept at 21 ° C. while stirring. Then, 1000 μl of a chemical sensitizer S-5 (0.5% methanol solution) was added, and 2 minutes later, 390 μl of an antifoggant 1 (10% methanol solution) was added.
Stirred for hours. Furthermore, after adding 494 μl of calcium bromide (10% methanol solution) and stirring for 10 minutes, a gold sensitizer Au equivalent to 1/20 mol of the chemical sensitizer S-5 was added.
-5 was added, and the mixture was further stirred for 20 minutes. Subsequently, 167 ml of the following stabilizer liquid was added, and the mixture was stirred for 10 minutes.
2 g of the following infrared sensitizing dye solution was added and stirred for 1 hour.
Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C, polyvinyl butyral (M
onsanto Butvar B-79) 13.3
After adding 1 g and stirring for 30 minutes, 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added and the mixture was stirred for 15 minutes. While further stirring, 12.4
3 g of the following additive solution a, 1.6 ml of DesmodurN
3300 / Mobay's aliphatic isocyanate (1
(0% MEK solution), 4.27 g of the following additive solution b was sequentially added and stirred to prepare a photosensitive layer coating solution 1.

(Preparation of stabilizer liquid) 1.0 g of stabilizer 1,
0.31 g of potassium acetate was dissolved in 4.97 g of methanol to prepare a stabilizer solution.

(Preparation of infrared sensitizing dye solution) 19.2 mg of sensitizing dye 1, 1.488 g of 2-chloro-benzoic acid,
2.779 g of Stabilizer 2 and 365 mg of 5-methyl-2-mercaptobenzimidazole were dissolved in 31.3 ml of MEK in the dark to prepare an infrared sensitizing dye solution.

(Preparation of Additive Solution a) 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl)-
27. 3,5,5-trimethylhexane (developer 1).
98 g and 1.54 g of 4-methylphthalic acid, 0.48 g
Dye 1 was dissolved in 110 g of MEK to prepare an additive liquid a.

(Preparation of Additive Solution b) 3.43 g of phthalazine was dissolved in 40.9 g of MEK to prepare an additive solution b.

<< Preparation of Coating Solution for Surface Protective Layer >>
While stirring 5 g, cellulose acetate butyrate (Eastman Chemical Co., CAB171)
-15), 96 g of polymethyl methacrylic acid (ROHM &
Haas, 4.5 g of paraloid A-21), 1.5 g of vinylsulfone compound and 1.0 g of benzotriazole
g, fluorine-based surfactant (Asahi Glass Co., Ltd., Surflon KH4
0) was added and dissolved. Next, 30 g of the following matting agent dispersion was added and stirred to prepare a coating solution for the surface protective layer.

(Preparation of Matting Agent Dispersion) Cellulose acetate butyrate (Eastman Chemical)
Co., Ltd., 7.5 g of CAB171-15)
g of calcium carbonate (Specia)
liter Minerals, Super-Pfle
x200), and dispersed with a dissolver-type homogenizer at 8000 rpm for 30 minutes to prepare a matting agent dispersion.

[0126]

Embedded image

[0127]

Embedded image

<< Preparation of Photothermographic Photosensitive Material Sample 1-1 >> On the prepared undercoating upper layer A-2 of the undercoated support 1, the prepared photosensitive layer coating liquid 1 and surface protective layer coating liquid were applied. Simultaneous multi-layer coating was performed using an extrusion-type extrusion coater. In the coating, the photosensitive layer was coated with 1.9 g of silver.
m ² , and the surface protective layer was formed so as to have a dry film thickness of 2.5 μm. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C., thereby preparing Sample 1-1 which is a photothermographic material.

<< Preparation of Samples 1-2 to 1-22 >> In the preparation of Sample 1-1, as shown in Table 1, the additive solution a used for preparing the coating solution for the photosensitive layer was added with the general formula ( 1-1) ~
Compound (1-6) or Comparative Compounds A and B
× 10 ^-3 mol added, and / or except that the general formula (3) compounds represented by the addition 9 × 10 ^-3 mol in additive solution b were similarly prepared sample 1-2～1-22 .

[0130]

[Table 1]

[0131]

Embedded image

<< Evaluation of Photothermographic Material >> Samples 1-1 to 1-22 produced as described above were subjected to exposure and heat development according to the following methods, and then evaluated for each characteristic.

(Exposure and heat development treatment) From the side of the photosensitive layer coated surface of each of the samples prepared above, a wavelength of 800
Exposure was performed by laser scanning using an exposure machine that used a semiconductor laser that had been converted into a vertical multi-mode of nm to 820 nm. At this time, an image was formed by setting the angle between the exposure surface of the sample and the exposure laser beam to 75 degrees. The angle condition was less uneven than when the angle was set to 90 degrees, and an image having unexpectedly good sharpness and the like was obtained.

Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum so that the surface protective layer of the sample was in contact with the drum surface. At that time, exposure and development were performed in an atmosphere conditioned at 23 ° C. and 50% RH.

(Evaluation of each characteristic) <Measurement of sensitivity and fog density> The density of each image obtained as described above was measured using a densitometer (PDA-65 manufactured by Konica Corporation). A characteristic curve consisting of the horizontal axis and the exposure amount is created, and the sensitivity and fog density (minimum density, Dmi
n) was measured. The sensitivity was defined as the reciprocal of the exposure amount required to obtain a density of +1.0 from the minimum density as the sensitivity, and was expressed as a relative sensitivity with the sensitivity value of Sample 1-1 being 100.

<Evaluation of Storage Stability> Three parts of each sample were stacked in a closed container kept at 25 ° C. and an atmosphere of 55% relative humidity under light shielding, sealed, and sealed at 50 ° C. For 7 days. This sample is called a forced storage sample. After the preservation treatment, the above-mentioned exposure and heat development treatments are applied to the second sample of the laminated forced preservation samples and the comparative sample (the sample stored in a light-shielding container at room temperature), and then, in the same manner, The fog density of each sample was measured, and fog density fluctuation 1 was determined by the following equation, and this was used as a measure of storage stability.

Fog density fluctuation 1 = Fog density of forcedly preserved sample−Fog density of comparative sample <Evaluation of image storability> A sample that had been subjected to heat development by the same method as described in the above-described measurement of sensitivity and fog density was used. Two parts were prepared, one part was protected from light for 7 days in an atmosphere at 25 ° C. and a relative humidity of 55%, and the other part was exposed to natural light at 25 ° C. and a relative humidity of 55% for 7 days. Was measured, and the fog density fluctuation 2 was obtained by the following formula, and this was used as a measure of image preservability.

Fog density fluctuation 2 = Fog density of sample exposed to natural light−Fog density of sample stored under light shielding <Evaluation of silver tone> The density after heat development was 1.1 ± 0.0.
The heat development treatment was performed by appropriately adjusting the exposure amount so as to be 5, and each sample for silver tone evaluation was prepared. The sample was irradiated for 10 hours under a light source having a color temperature of 7,700 Kelvin and an illuminance of 1,1600 lux, and the silver tone was visually evaluated according to the evaluation criteria described below. Note that the number of ranks having no quality problem is 4 or more.

5: Pure black tone and no yellowness felt 4: Not pure black but almost no yellowness 3: Partially slightly yellowish 2: Slightly yellowish over the entire surface 1: At first glance, a yellow color is felt. Table 1 also shows the evaluation results obtained as described above.

As is clear from Table 1, each sample of the present invention has a sufficient sensitivity and a low fog density.
It can be seen that storage stability, image storage stability and silver tone are excellent.

Example 2 << Preparation of Subbed Support 2 >> In the subbed support 1 prepared in Example 1, a commercially available biaxially stretched and heat-fixed support having a thickness of 175 μm and an optical density of 0.1 was used. 170 (measured with a Konica Densitometer PDA-65) was replaced with a commercially available biaxially stretched and heat-fixed polyethylene terephthalate film having a thickness of 100 μm in place of the polyethylene terephthalate film colored blue. Subtractive support 2 was prepared.

<< Preparation of Photosensitive Silver Halide Emulsion B >> Water 9
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 00 ml, adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (9)
370 ml of an aqueous solution containing potassium bromide, potassium iodide and rhodium chloride in a molar ratio of 1 × 10 ⁻⁴ mol per mol of silver (8/2) in a controlled double jet method while maintaining the pAg at 7.7. For 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,3,3
0.3 g of a, 7-tetrazaindene was added, and NaOH was added.
Adjust the pH to 5.0 with 0.06μ average particle size
m, coefficient of variation of projected diameter area 8%, [100] face ratio 8
7% of cubic silver iodobromide grains were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant to perform desalting treatment, and then 0.1 g of phenoxyethanol was added to the emulsion, pH 5.9, pAg
The mixture was adjusted to 7.5 to prepare a silver halide emulsion B.

<< Preparation of Silver Behenate Dispersion >>
According to the method described in Example 1 of No. 27643, a silver behenate dispersion was prepared.

(Preparation of sodium behenate solution) 340
34 ml of behenic acid were dissolved at 65 ° C. in ml of isopropanol. Next, a 0.25 mol / L aqueous solution of sodium hydroxide was added thereto with stirring so that the pH became 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required. Next, this sodium behenate aqueous solution was concentrated under reduced pressure to reduce the concentration of sodium behenate to 8.9% by mass.
To prepare a sodium behenate solution.

(Preparation of Silver Behenate Dispersion) To a solution of 30 g of ossein gelatin dissolved in 750 ml of distilled water was added a 2.94 mol / L silver nitrate solution to adjust the silver potential to 400 mV. Into this, 374 ml of the above sodium behenate solution was added at a speed of 44.6 ml / min at a temperature of 78 ° C. using a controlled double jet method, and at the same time, a 2.94 mol / L aqueous silver nitrate solution was added
It was added so that the silver potential became 400 mV. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.0
92 mol and 0.101 mol. After the addition was completed, the mixture was further stirred for 30 minutes, and water-soluble salts were removed by ultrafiltration to prepare a silver behenate dispersion.

<< Preparation of Photosensitive Emulsion >> The above-mentioned photosensitive silver halide emulsion B was added to the above-prepared dispersion of silver behenate in 0.0
1 mol, and further stirring while stirring the polyvinyl acetate
100 g of a butyl solution (1.2% by mass) was gradually added to form a floc of the dispersion, water was removed, washed twice with water and water was removed, and then polyvinyl butyral average molecular weight was used as a binder. Of a 1: 2 mixed solution of 2.5 mass% butyl acetate and isopropyl alcohol having a molecular weight of 3,000, and then added to the mixture of gel-like silver behenate and silver halide as a binder with polyvinyl butyral (average). (Molecular weight: 4,000) and isopropyl alcohol were added and dispersed to prepare a photosensitive emulsion.

<< Preparation of Photothermographic Material >> The following layers were sequentially coated on the above-prepared undercoated support 2 to prepare a photothermographic material.

(Back side coating) A backing layer having the following composition was coated so that the wet film thickness was 80 μm.
The undercoated support 2 was coated on the undercoating upper layer B-2.
The drying was performed at 75 ° C. for 5 minutes.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye 170 mg (photosensitive layer surface side coating)
As the photosensitive layer, the coated silver amount becomes 2.0 g / m ² , and the binder polyvinyl butyral becomes 3.2 g / m ² ,
Also, so that the wet thickness of the surface protective layer is 100 μm,
Coating on the undercoating upper layer A-2 of the undercoated support 2,
Samples 2-1 to 2-22 were produced. Drying is 75 ° C
For 5 minutes.

<Preparation of Coating Solution for Photosensitive Layer> Photosensitive Emulsion An amount of 2.0 g / m ² in terms of silver sensitizing dye 1 (0.1% DMF solution) 2 mg Exemplary compound 2 of general formula (3) % Methyl ethyl ketone solution (details of exemplary compounds are described in Table 2) 3 ml 10% methyl ethyl ketone solution of exemplary compounds of general formulas (1-1) to (1-6) (details of exemplary compounds are described in Table 2) 5 ml Phtharazone (4.5% DMF solution) 8 ml Developer 1 (10% methyl ethyl ketone solution) 13 ml 1% methanol / DMF = 4: 1 solution of hydrazine derivative, exemplary compound of general formula (2) (for details of the exemplary compounds, see Table 1). 2) <Preparation of surface protective layer> MEK 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g 4-methylphthalic acid 0 0.72 g tetrachlorophthalic acid 0.22 g phthalazine 1.0 g tetrachlorophthalic anhydride 0.5 g monodisperse silica having an average particle size of 4 μm 0.08 g

[0151]

[Table 2]

<< Evaluation of Photothermographic Material >> (Exposure and Thermal Development Processing)
Light emission time 1 through an interference filter with a peak at nm
It was exposed in a xenon flash light of 0 ^-3 seconds. Thereafter, a heat development treatment was performed at 115 ° C. for 15 seconds using a heat drum.

(Measurement of Sensitivity, Fog Density and γ Value) After measuring the density in the same manner as described in Example 1, a characteristic curve was prepared, and the sensitivity and the fog density were calculated in the same manner. . The sensitivity was defined as the reciprocal of the amount of exposure required to obtain a density of 3.0, and expressed as a relative sensitivity with the sensitivity of Sample 2-1 being 100. Further, the γ value is determined by the slope (tan) of a straight line connecting the density points 0.1 and 1.5 in the characteristic curve.
θ) was defined as the γ value.

(Evaluation of Storage Stability, Image Storage, and Silver Tone) In the same manner as described in Example 1, storage stability,
The image storability and silver tone were evaluated.

Table 2 also shows the evaluation results obtained as described above. As is clear from Table 2, each sample of the present invention has sufficient sensitivity, high gamma, good contrast, low fog density, storage stability, image storage and silver tone. It turns out that it is excellent.

[0156]

According to the present invention, high sensitivity, low fog,
A heat-developable photographic light-sensitive material excellent in storage stability and image storability and excellent in silver tone and an image forming method thereof can be provided. In particular, the provision of a heat-developable photographic material for laser imagers that does not increase the fog density during storage over time, and has excellent high contrast, high sensitivity, low fog density, and storage stability A heat-developable photographic material for an imagesetter output film having excellent image stability and silver tone can be provided.

Claims (6)

[Claims] 1. The following general formulas (1-1), (1-2),
A photothermographic material comprising at least one compound selected from (1-3), (1-4), (1-5) and (1-6). Embedded image [In the general formula (1-1), Y ₁₁ is OH, SH, NH
₂ , S-M ⁺ or OM ⁺ , where M ⁺ represents a metal ion. X ₁₁ represents O or S, k is an integer of 1 to 5.
R ₁₁ is a cycloalkyl group, alkenyl group, alkynyl group, aryl group, amino group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino Group, sulfonylamino group, sulfamoyl group, alkylthio group, arylthio group, sulfonyl group, alkylsulfonyl group, ureido group, hydroxy group, mercapto group,
It represents a non-metal atom group necessary for forming a cyclic structure condensed with a halogen atom, a hydrazino group, a heterocyclic group, or a benzene ring to which R ₁₁ is bonded. When k is an integer of 2 to 5,
R ₁₁ may be the same or different. [In the general formula (1-2), Y ₂₁ is OH, SH, NH
₂ , S-M ⁺ or OM ⁺ , where M ⁺ represents a metal ion. X ₂₁ represents O or S, and m represents an integer of 1 to 5.
R _21, R ₂₂ and R ₂₃ each independently represents a hydrogen atom, a halogen atom or a substituent. When m is an integer of 2 to 5, R ₂₃ may be the same or different. However, R ₂₁ and R ₂₂ are not hydrogen atoms at the same time. In] [Formula (1-3), R ₃₁ and R ₃₂ each independently represent a hydrogen atom, a halogen atom or a substituent, X ₃₁ and A ₃₁ represents O or S, n represents 0 or 1 , Z represents a heterocyclic ring. Y ₃₁ is OH, SH, NH ₂ , SM ⁺ or O
Represents -M ^+, M ⁺ represents a metal ion. [In the general formula (1-4), R ₄₁ , R ₄₂ , R ₄₃ and R
₄₄ independently represents a hydrogen atom, a halogen atom or a substituent, and p represents an integer of 0 to 5. Y ₄₁ is OH, SH, NH
₂ , S-M ⁺ or OM ⁺ , where M ⁺ represents a metal ion. when p is integer of 2 to 5, R ₄₄ may be the same or different, it may be bonded to form a cyclic structure. [In the general formula (1-5), R ₅₁ and R ₅₂ each independently represent a hydrogen atom, a halogen atom or a substituent, and q represents 0 to
Represents an integer of 5. A ₅₁ represents O or S, Y ₅₁ is OH,
SH, NH _2, represents a S-M ⁺ or O-M ^+, M ⁺ represents a metal ion. When q is an integer of 2 to 5, R ₅₂ may be the same or different, and may be bonded to each other to form a cyclic structure. [In the general formula (1-6), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, a halogen atom or a substituent;
Represents an integer of 0 to 5. X ₆₁ represents O, S or NR ₆₄ , and R ₆₄ represents a hydrogen atom or a substituent. Y ₆₁ is OH, S
H, NH _2, represents a S-M ⁺ or O-M ^+, M ⁺ represents a metal ion. When r is an integer of 2 to 5, R ₆₃ may be the same or different, and may be bonded to each other to form a cyclic structure. ] 2. A support comprising an organic silver salt, a binder and a photosensitive silver halide on a support.
2. The photothermographic material according to item 1. 3. A photothermographic material having a photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support, wherein at least one of the photosensitive layers comprises:
The general formulas (1-1), (1-2), (1-3), and (1)
(4) A photothermographic material comprising at least one compound selected from (1-5) and (1-6). 4. A hydrazine derivative or the following general formula (2)
3. The composition according to claim 2, which comprises a compound represented by the formula:
Or a photothermographic material according to item 3. Embedded image Wherein, R _71, R ₇₂ and R ₇₃ each independently represent a hydrogen atom or a substituent, Q is a substituent. R ₇₁ and Q, R ₇₁ and R
₇₂ , R ₇₂ and R ₇₃ and R ₇₃ and Q may be bonded to each other to form a cyclic structure. ] 5. The photothermographic material according to claim 2, further comprising a compound represented by the following general formula (3). Embedded image [Wherein, D ₁ and D ₂ represent a halogen atom, and G represents a hydrogen atom, a halogen atom, or a substituent. J represents a divalent linking group, and w represents 0 or 1. T represents an alkyl group, an aryl group or a hetero ring. ] 6. The photothermographic material according to claim 1, which is exposed to light using a laser light source and then subjected to a heat development process at 80 to 250 ° C. For forming an image on a photothermographic material.