JPH09160164A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photosensitive material high in Dmax and sharp in the toe of the characteristic curve and high in contrast by incorporating at least one of specified compounds, and at least an organic acid silver salt and a hydrazine derivative. SOLUTION: This heat-developable photosensitive material contains at least the organic acid silver salt and silver halide and a hydrazine derivative, and at least one kind of compound represented by the formula in which Q is an aliphatic or aryl or heterocyclic group; each of X1 and X2 is a halogen atom; Y is a carbonyl or sulfonyl group; A is an H or halogen atom or an electron withdrawing group; and (n) is 0 to 1. The organic acid silver salt to be used for this heat-developable photosensitive material is an organic acid silver salt and a hetero organic acid. silver salt, and especially, the silver salt of a long- chain aliphatic carboxylic acid is preferably. The silver halide functions as a photosensor, and it is preferred that this average grain size is small in order to restrain white clouding after image formation to a low degree and to obtain good image quality.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photothermographic material, and more particularly to a photothermographic material suitable for printing plate making.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B. “Thermally Processed Silver Systems” by Shely (Imaging Processes and Materials (I
maging Processes and Materials) Neblette 8th Edition,
Sturge, V.I. Walworth,
A. Shepp, page 2, 1969. In such a photothermographic material, a reducible silver source (eg organic silver salt), a catalytically active amount of a photocatalyst (eg silver halide), a toning agent for controlling the tone of silver and a reducing agent are usually contained in a binder matrix. It is contained in a dispersed state. Although the photothermographic material is stable at room temperature, it can be reduced by a redox reaction between a silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature (for example, 80 ° C. or higher) after exposure. Produces silver. 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 contrasts with the unexposed areas, resulting in the formation of an image. Such a photothermographic material has been used for micro sensitive materials and X-rays, but it is only partially used as printing sensitive materials. The reason for this is that the image obtained has a low Dmax, is poorly distorted, and has a soft gradation, so that the image quality is extremely poor as a printing photosensitive material. On the other hand, with the recent development of lasers and light-emitting diodes, scanners and imagesetters having an oscillation wavelength of 600 to 800 nm have become widespread, and development of sensitive materials with high sensitivity, high Dmax, and suitable for these output machines. Was strongly desired. Also, demands for simple processing and dry processing are increasing.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is Dmax.
The object is to provide a photothermographic material having high contrast and good leg sharpness. An object of the present invention is to provide a photothermographic material for printing which has good image quality. Another object of the present invention is to provide a photothermographic material for printing which is completely dry processed without the need for wet processing.

[0004]

The above object of the present invention is characterized by containing at least one organic acid silver salt, a silver halide, a hydrazine derivative, and at least one compound represented by the following general formula (I). Achieved by a photothermographic material.

[0005]

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In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents a carbonyl group or a sulfonyl group. A represents a hydrogen atom, a halogen atom or an electron-withdrawing group. n represents 0 or 1.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photothermographic material of the present invention contains silver organic acid. Silver salts of organic acids and heteroorganic acids, especially long-chain (10-30, preferably 15-25 carbon atoms) aliphatic carboxylic acids are preferred. The ligand is 4.0-1
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 0.0 are also useful. An example of a suitable silver salt is Rese
Described in arch Disclosure Nos. 17029 and 29963 and include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkyl thioureas. Salt (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); Silver complex of polymer reaction product of aldehyde and hydroxy-substituted aromatic carboxylic acid (For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid,
5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene, and 3-carboxymethyl-4-). (Thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,
Complexes or salts of silver with a nitric acid selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime Silver salts such as; and silver salts of mercaptides. The preferred silver source is silver behenate. The amount of organic acid silver used is preferably 3 g / m ² or less in terms of silver amount. More preferably 2 g / m ²
It is as follows.

The silver halide in the present invention functions as an optical sensor. The silver halide preferably has a small average grain size in order to suppress white turbidity after image formation and obtains good image quality, and the average grain size is 0.20 μm or less, more preferably 0.03 μm.
m to 0.15 μm, particularly 0.03 μm to 0.11 μm is preferable. The term "grain size" as used herein refers to the length of the edges of silver halide grains when the silver halide grains are cubic or octahedral so-called normal crystals. Also, in the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it means the diameter when considering the sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grain is not particularly limited, but it is preferable that the ratio of Miller index [100] faces is high, and the ratio is 50% or more, and further 7%.
It is preferably 0% or more, and particularly preferably 80% or more. The ratio of Miller index [100] planes is based on the adsorption dependence of [111] planes and [100] planes in the adsorption of sensitizing dyes.
T. Tani, J. Imaging Sci., 29, 165 (1985)
Can be obtained by

The halogen composition is not particularly limited and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. Preferred is silver bromide or silver iodobromide. The photographic emulsion used in the present invention is P. G.
Chimie et Physique Photographique (Paul by lafkides
Montel, 1967), GF Duffin Photogr
aphic Emulsion Chemistry (The Focal Press, 196
6 years), VL Zelikman et al, Making and Coating P
hotographic Emulsion (The Focal Press, 1964
Year)). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. The silver halide may be prepared by converting a part or all of silver in the organic acid silver into a silver halide by the reaction of the organic acid silver and a halogen ion, or the silver halide may be prepared in advance. It may be added to the solution for preparing the organic silver salt, or a combination of these methods is possible. The latter is preferred. Generally, silver halide is 0.75 with respect to a reducible silver source (organic acid silver).
It is preferred to contain an amount of -30% by weight.

The silver halide grains used in the present invention are
Those containing an ion or a complex ion of a metal belonging to Group VII or Group VIII of the periodic table are preferable. The above metals include Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re,
There are Os, Ir, Pt, Au, but among them, Rh, Re, Ru, Os, Ir,
It is preferably selected from Co and Fe, and particularly preferably Fe and Ir. One kind of these metal ions or complex ions may be used, or two or more kinds of the same kind of metal and different kinds of metal may be used in combination. The content of these metal ions or complex ions is generally 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, and preferably 1 × 10 ⁻⁸ to 1 per mol of silver halide. It is × 10 ^-4 mol. A compound providing an ion or complex ion of these metals is preferably added at the time of silver halide grain formation and incorporated into the silver halide grain. Preparation of the silver halide grain, that is, nucleation, growth, physical ripening , It may be added at any stage before and after the chemical sensitization, but it is particularly preferable to add it at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth. It is preferably added at the stage of nucleation. Upon addition, the silver halide grains may be added dividedly over several times, or may be uniformly contained in the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683.
It is also possible to have a distribution within the particles, as described in the above publication. Preferably, it can have a distribution inside the particles. These metal compounds are water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides).
Can be added after being dissolved in, for example, an aqueous solution of a powder of a metal compound or a metal compound and NaCl, KCl.
An aqueous solution in which and are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation,
Alternatively, when a silver salt solution and a halide solution are simultaneously mixed, they are added as a third aqueous solution, and a method for preparing silver halide grains by a three-liquid simultaneous mixing method, and a necessary amount of an aqueous solution of a metal compound is reacted during grain formation. There are a method of charging in a container and a method of adding and dissolving another silver halide grain which has been previously doped with metal ions or complex ions at the time of preparing silver halide. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl or KCl are dissolved together to a water-soluble halide solution is preferable. When added to the particle surface, a necessary amount of an aqueous solution of a metal compound can be added to the reaction vessel immediately after particle formation, during or during physical ripening, or at the time of chemical ripening.

As the rhodium compound, a water-soluble rhodium compound can be used. For example, a halogenated rhodium (III) compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaammine rhodium ( III) complex salts, trioxalatrodium (III) complex salts and the like.

Rhenium, ruthenium and osmium compounds are disclosed in European Patents (EP) 0336689A, 0336427A1, 0336425A1 and 0.
The water-soluble complex salts described in JP-A-336426A1, JP-A-63-2042, JP-A-1-285941 and JP-A-2-20855 are preferred. A hexadentate complex represented by the following formula is particularly preferable.
[ML ₆ ] ^-n M is rhenium, ruthenium or osmium, and n represents 0, 1, 2, 3 or 4. L is a ligand, preferably a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand,
A thionitrosyl ligand etc. are mentioned. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Specific examples include the following. (ReCl ₆ ) ^-3 (ReBr ₆ ) ^-3 (ReCl ₅ (NO)) ^-2 (Re (NS) Br ₅ ) ^-2 (Re (NO) (CN) ₅ ) ^-2 (Re (O) ₂ ( CN) ₄ ) ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) ₆ ] ^{- 4} (Ru (CO) ₃ Cl ₃ ) ^-2 (Ru (CO) Cl ₅ ) ^-2 (Ru (CO) Br ₅ ) ^-2 (OsCl ₆ ) ^-3 (OsCl ₅ (NO)) ^-2 (Os ( NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

As the iridium compound, various compounds can be used. For example, hexachloroiridium (III) complex salt, hexachloroiridium (IV) complex salt, hexabromoiridium (III) complex salt, hexabromoiridium (IV) complex salt, hexaiodoiridium ( III) Complex salt, hexaiodoiridium (IV) complex salt, hexaammineiridium (III)
Examples thereof include complex salts, hexaammineiridium (IV) complex salts, hexacyanoiridium (III) complex salts, triogizaratiridium complex salts, and the like.

Although various compounds can be used as the cobalt compound, a hexacyano complex is particularly preferable, and an example thereof is [Co (CN) ₆ ] ^-3 (a counter ion is not important, for example, ammonium, Alkali metal ions are included).

The iron compound is a divalent or trivalent water-soluble iron ion-containing compound, and specifically, ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, citric acid. Ferrous iron, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate , Ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate, ferrous ammonium nitrate, basic ferric acetate, ferric albumin, ferric ammonium acetate, bromide Ferric, ferric chloride, ferric chlorate, ferric citrate, ferric fluoride, ferric formate, ferric glycerophosphate, ferric hydroxide, acidic phosphoric acid Ferric, ferric nitrate, ferric phosphate, ferric pyrophosphate, ferric sodium pyrophosphate, ferric thiocyanate, ferric sulfate, ferric sulfate ammonium Arm, ferric guanidine sulfate, ferric ammonium citrate, hexane potassium cyano iron (II) acid, ferrous potassium preventor cyano ammine, sodium ferric ethylene dinitrilo tetraacetic acid, hexacyanoferrate (II
I) Potassium acid, tris (dipyridyl) ferric chloride, potassium pentacyanonitrosyl ferric, and ferric hexarea chloride. Among these, especially hexacyanoiron (I
I) and hexacyanoferrate (III) show remarkable effects.

The hydrazine derivative used in the present invention is
A compound represented by the following general formula (II) is preferable. General formula (II)

[0018]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
A —SO ₂ — group, a —SO— group,

[0020]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (II), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (II),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring,
Pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, hydrazide Group having a quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl Group, halogen atom, cyano group, phosphoric acid amide group, diacylamino group, imide group, group having an acylurea structure, group containing a selenium atom or tellurium atom, tertiary sulfonium structure, etc. Is a group having a quaternary sulfonium structure. Preferred examples of the substituent include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety having a carbon number of 1 to 20). Monocyclic or bicyclic one to three), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
0), a ureido group (preferably having 1 to 3 carbon atoms)
0), a phosphoric amide group (preferably having 1 carbon atom)
To 30).

In the general formula (II), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
A hydrogen atom, an alkyl group (eg, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (eg, an o-hydroxybenzyl group, etc.), Aryl group (for example, phenyl group, 3,5
- dichlorophenyl group, o- methanesulfonamidophenyl group, 4-methanesulfonyl phenyl, and 2-hydroxymethyl phenyl _{group), - C 2 F 4 COOM} (M: a hydrogen atom, an alkali metal atom) and the like. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferred.
As G in the general formula (II), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (II) may be further substituted, and preferable examples include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (II) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (II) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, Or a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (as a substituent, an electron-withdrawing group or a hydroxymethyl group at the 2-position is used. Preferred) hydrazine derivative. Note that any combination of the above R ₁ and R ₂ options is possible and preferred.

Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to the following compounds.

[0030]

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[0031]

[Chemical 6]

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
Nos. 4,912,016 and 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 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, No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 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
No. 6-289524 can be used.

In addition to these, compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the publication. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by the general formula (6), specifically, Compounds 4-1 to 4- described on pages 25 and 26 of the publication.
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same publication
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
A compound represented by (Chemical Formula 1) described in No. 13951, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I described in JP-A-7-77783)
The compound represented by I), specifically, pages 10 to 2 of the same publication.
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
compounds represented by a), specifically, pages 8 to 15 of the same publication.
Compounds H-1 to H-44 described on page. It is possible to use those described in.

The addition amount of the hydrazine derivative in the present invention is 1 × 10 ^{−6 to} 1 × 10 ⁶ mol per mol of silver.
^-1 mol is preferable, and a range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.

The hydrazine derivative of the present invention is a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method. In the present invention, it is preferable to use indazoles (for example, nitroindazole) as an antifoggant in combination with a hydrazine derivative.

It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative to the light-sensitive material in combination with the hydrazine derivative. Examples of compounds for the nucleation accelerator are given below.

[0047]

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[0048]

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The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol per 1 mol of silver, and 1 × 10 ^−5.
２2 × 10 ⁻² mol is more preferred, and 2 × 10 ^-5 −1 × 1
0 ^-2 mol is most preferred.

The photothermographic material of the present invention forms a photographic image using a photothermographic process. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan
(Morgan) and B. “Thermally Processed Silver Syst” by Shely
ems) "(Imaging Processes and Materials) Neblette
Eighth Edition, Sturge, V.I. Walworth
worth), A. Edited by Shepp, page 2, 1969
Year). As described in the above documents, it is preferable to incorporate a developer in the photothermographic material of the present invention.

Examples of suitable developers are described in US Pat. No. 3,770.
Nos. 448, 3773512, 3959633, and Research Disclosure Nos. 17029 and 29.
963 and include the following: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, as precursors for developers) (eg, Piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (eg Np-
Methylphenyl-N-hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamide anilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; azines and sulfones Combination of amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
Combination of dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agent; 2-phenylindane-1,3-dione, etc .; chromane; 1,4-dihydropyridines (eg 2,6-dimethoxy-3 , 5-dicarboethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol (m
esitol), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,5-ethylidene-bis (2-
t-butyl-6-methyl) phenol), UV-sensitive ascorbic acid derivatives and 3-pyrazolidones. Ultra-high contrast and high Dmax due to combination of hydrazine derivative and silver halide containing heavy metal ion or complex ion
The hindered phenols are particularly suitable developers for achieving the effect of increasing the sensitivity and increasing the sensitivity without increasing the fog. This selection was based on the fact that dihydroxybenzenes and ascorbic acids were the developers that had been considered appropriate in the field of silver halide light-sensitive materials to be processed by using a developing solution, to cause high contrast and high sensitivity of hydrazine derivatives. In light of this, it can be said to be extremely peculiar. Examples of the hindered phenols include compounds represented by the following general formula (A).

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In the formula, R represents a hydrogen atom or a carbon atom number of 1 to
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group (e.g., methyl 1 to 5 carbon atoms, ethyl, t- butyl ).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

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The amount of the developer such as the compound represented by the general formula (A) used is preferably 1 × 10 6 per mol of silver.
^{It is -2} to 10 mol, especially 1 x 10 ^{-2 to} 1.5 mol.

The photothermographic material of the invention contains at least one compound represented by the following general formula (I). General formula (I)

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(In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents a carbonyl group or a sulfonyl group. A represents A It represents a hydrogen atom, a halogen atom or an electron-withdrawing group, and n represents 0 or 1.) Next, the compound represented by formula (I) will be described in detail. The aliphatic hydrocarbon group represented by Q is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, further preferably 1 to 12 carbon atoms,
For example, methyl, ethyl, iso-propyl, tert-
Butyl, n-octyl, n-decyl, cyclopropyl,
Examples include cyclopentyl and cyclohexyl. ),
Alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 12 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably). Has 2 to 3 carbon atoms
0, more preferably 2 to 20, still more preferably 2 to 12
And examples thereof include propargyl and 3-pentenyl. ), Which may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group and a ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group. The aryl group represented by Q preferably has 6 to 30 carbon atoms.
Is a monocyclic or bicyclic aryl group (eg, phenyl, naphthyl, etc.), more preferably a phenyl group having 6 to 20 carbon atoms, and further preferably a phenyl group having 6 to 12 carbon atoms.
The aryl group may have a substituent, and as the substituent,
For example, carboxy group, acyl group, acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group,
Examples include an oxycarbonylamino group and an ureido group.
The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O or S atoms, which may be a single ring, A condensed ring may be formed with the ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and further preferably a nitrogen atom having 1 to 2 atoms. And a 5- or 6-membered aromatic heterocyclic group. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine,
Piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine. , Acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole,
Examples thereof include benzoxazole and benzthiazole. The heterocycle is preferably thiophene, furan,
Pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole,
Benzoxazole, benzthiazole, indolenine, more preferably triazine, quinoline, thiadiazole, benzthiazole, particularly preferably,
Quinoline and thiadiazole. Q is preferably an aromatic nitrogen-containing heterocyclic group. The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably Chlorine atom and bromine atom are preferred, and bromine atom is particularly preferred. Y represents a carbonyl group or a sulfonyl group,
Preferred is a sulfonyl group. The halogen atom represented by A is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably bromine. Is an atom. The electron-withdrawing group represented by A is preferably a substituent having a σ _p value of 0.01 or more, more preferably 0.1 or more. Examples of the electron-withdrawing group include a trihalomethyl group, a cyano group,
Examples thereof include a nitro group, a sulfonyl group, a carbonyl group, an alkenyl group, an alkynyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group and a sulfamoyl group, and preferably a sulfonyl group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Is. A is preferably a halogen atom, more preferably a chlorine atom, a bromine atom or an iodine atom, still more preferably a chlorine atom or a bromine atom, and particularly preferably a bromine atom. n represents 0 or 1, and is preferably 1 when Y is a sulfonyl group. Among the compounds represented by the general formula (I), the compounds represented by the following general formula (Ia) are preferable. General formula (Ia)

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(In the formula, X ₁ , X ₂ , A and n have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. Q ′ represents an aromatic nitrogen-containing heterocyclic group. The aromatic nitrogen-containing heterocyclic group represented by Q ′ is preferably a 5- to 6-membered aromatic heterocycle containing 1 to 3 nitrogen atoms, such as pyrrole, imidazole, pyrazole, pyridine and pyrazine. , Pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,
Examples include cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole and indolenine, and more preferably pyridine, triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole. ,
Thiazole, oxazole, benzimidazole, benzoxazole, benzthiazyl and indolenine are more preferable, triazine, thiadiazole, quinoline and benzothiazole are more preferable, and quinoline and thiadiazole are particularly preferable. Among the compounds represented by the general formula (I), the compounds represented by the following general formula (Ib) are preferable. General formula (Ib)

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(In the formula, X ₁ and X ₂ have the same meanings as those in formula (I), and the preferred ranges are also the same. Q ′ has the same meaning as that in formula (Ia). And the preferred range is also the same. X ₃ represents a halogen atom.) The halogen atom represented by X ₃ is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom. , And particularly preferably a bromine atom. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

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If possible, the above compounds may be used in the form of salts. The compound represented by the general formula (I) of the present invention is, for example, US Pat.
46, European Patent Nos. 622666A1 and 60598.
1A1, JP-A-7-2781, JP-B-54-165
Can be synthesized according to the method described in No. The addition amount of the compound represented by the general formula (I) is not particularly limited, but 10 ^-4
Mol to 1 mol / Ag mol is preferable, and particularly 10 ⁻³ mol to
0.3 mol / Ag mol is preferred.

In the present invention, the addition of a toning agent is highly desirable. Examples of suitable toning agents are disclosed in Research Report 17029, and include: Imides (eg,
Phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-
Phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (eg N-hydroxy-
1,8-naphthalimide); cobalt complex (for example,
Cobalt hexamine trifluoroacetate), mercaptans (eg, 3-mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl))
Phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N 'hexamethylene (1
-Carbamoyl-3,5-dimethylpyrazole), 1,
8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole in combination);
Merocyanine dye (for example, 3-ethyl-5-((3-
Ethyl-2-benzothiazolinylidene
lidene)) -1-Methylethylidene) -2-thio-2,
4-oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4- (1-naphthyl) phthalazinone, 6
-Chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (eg, 6-chlorophthalazinone + benzenesulfinic acid) Sodium or 8-methylphthalazinone + sodium p-trisulfonate); combination of phthalazine + phthalic acid; phthalazine (including phthalazine adduct) and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or Combination with at least one compound selected from o-phenylene acid derivatives and their anhydrides (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine , Naltoxazine derivatives; Benzoxa Down-2,4-diones (for example,
1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6-dimerocapto-1, 4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene Preferred toners include phthalazone and phthalazine.

In the photothermographic material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used. Suitable binders are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, acacia, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, Cellulose acetate butyrate,
Poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile) , Copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resin, poly (vinylidene chloride) , Poly (epoxides), poly (carbonates), poly (vinyl acetate) s, cellulose esters, poly (amides). The binder may be coated from water or an organic solvent or emulsion.

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, including a reducible silver source (organic acid silver), a catalytically active amount of the above silver halide, It is preferable that the photothermographic material contains a hydrazine derivative, a developer, and, if necessary, a color tone suppressing agent for controlling the color tone of silver in a state of being normally dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but at a high temperature (for example, 80 ° C or higher) after exposure.
It is developed by heating to. By heating, silver is produced through a redox reaction between the organic acid silver (which functions as an oxidizing agent) and the developer. This redox reaction is promoted by the catalytic action of the latent image generated on the silver halide upon exposure. The silver produced by the reaction of the organic acid silver in the exposed areas provides a black image, which contrasts with the unexposed areas and is imaged. This reaction process proceeds without supplying a treatment liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side or on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitive layer / low sensitive layer or a low sensitive layer / high sensitive layer for adjusting the gradation. Various additives may be added to any of the light-sensitive layer, non-light-sensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. Suitable binders are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film forming media such as: gelatin, gum arabic,
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) ), Poly (urethane) s, phenoxy resin, poly (vinylidene chloride), poly (epoxide) s,
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione); naphthalimides (eg, , N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles, isothiuronium (isot
hiuronium) derivatives and certain photobleaching combinations (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzpthiazolinylidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione; a combination of phthalazinone and a sulfinic acid derivative (eg, ,
6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); combination of phthalazine + phthalic acid; phthalazine (including adduct of phthalazine), maleic anhydride, and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) in combination with at least one compound; quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-dione (Eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg
3,6-dimerocapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene. The preferred toning agent is phthalazone.

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver halide, silver chlorobromide, silver iodobromide, chloroiodo odor). However, it is preferable that the iodide ion is contained. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

Reducible silver sources are silver salts of organic and heteroorganic acids containing a source of reducible silver ions, especially long chain (10
Aliphatic carboxylic acids of up to 30 (preferably 15 to 25 carbon atoms) are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Dis
closures described in 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1-
(3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids) (Eg, salicylic acid,
Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2). -Thioene, and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4- Complexes and salts of silver with a nitric acid selected from triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides, the preferred silver source being silver behenate. The amount of silver is preferably 3 g / m ² or less, and more preferably 2 g / m ² or less.

An antifoggant may be contained in such a light-sensitive material. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 03. However, mercury compounds are environmentally unfavorable. As the non-mercury antifoggant, for example, the antifoggants disclosed in U.S. Pat. Nos. 4,456,075 and 4,458,885 and JP-A-59-57234 are preferable.

The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-63-259651.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 1
7643 IV-A (p.23, December 1978), I
tem 1831X (August 1978, p. 437). 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. 2,161,3
No. 31, West German Patent 936,071, Japanese Patent Application No. 3-189
No. 532, simple merocyanines, and B) a helium-neon laser light source.
No. 25, No. 54-18726, No. 59-102229
No. 6-1032
JP-B-48-42172 discloses merocyanines, C) LED light sources and red semiconductor lasers described in
Thiacarbocyanines described in JP-A-62-284343 and JP-A-2-105135; Tricarbocyanines described in JP-A-59-19032 and JP-A-60-80841; JP-A-59-192242; JP-A-3-6724.
4- (4-) described in the general formulas (IIIa) and (IIIb) of No. 2
Dicarbocyanines containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The heat-developable photosensitive material of the present invention is exposed to Ar laser (488 nm) and He-Ne laser (633n).
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 830 nm) and the like are preferable.

The photothermographic material of the invention may be provided with a layer containing a dye as an antihalation layer.
For an Ar laser, a He-Ne laser, and a red semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at an exposure wavelength within a range of 400 nm to 750 nm. For an infrared semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range 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 support used in the present invention is paper, synthetic paper, paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate). A metal plate (eg, aluminum, aluminum alloy, zinc, iron, copper), a paper or plastic film on which the above metal is laminated or vapor-deposited, and the like are used. On the other hand, when the plastic film is passed through the thermal processor, the size of the film expands and contracts. When used as a printing photosensitive material, this expansion and contraction is a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having a small dimensional change. For example, there are a styrene-based polymer having a syndiotactic structure and a heat-treated polyethylene. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyarylate and the like can be used.

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (Preparation of Photosensitive Silver Halide Grain A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water to adjust the temperature to 35 ° C. and pH to 3.0, and then silver nitrate. 7
370 ml of an aqueous solution containing 4 g and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) were pAg 7.7.
While maintaining the above, the addition was performed by the controlled double jet method over 10 minutes. At this time, 5
Hexacyanoferrate (III) salt and hexachloroiridium (III) complex salt are added at 1 × 10 ^-5 mol / Ag mol over a period of time. Then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added to 0.3 g, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average grain size of 0.06 μm, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87%. Silver particles were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5.

(Preparation of Photosensitive Emulsion A Containing Silver Organic Fatty Acid) 10.6 g of behenic acid was put in 300 ml of water and dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was added with sufficient stirring. , It was left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.13 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, silver halide grains A prepared in advance were added while stirring at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid. Further, 25 ml of 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was left stirring for 1 hour. While stirring the aqueous mixture, 37 g of a 1.2 wt% solution of polyvinyl acetate in n-butyl acetate was gradually added to form flocs of the dispersion, water was removed, and water was washed twice and water was removed. Then, 20 g of a 1: 2 mixed solution of 2.5 wt% of butyl acetate and isopropyl alcohol of polyvinyl butyral (average molecular weight: 3000) was added with stirring, and the thus obtained gel-like behenic acid and silver halide were added. 12.5 g of polyvinyl butyral (average molecular weight: 4000) was added to the mixture.
7 g was added and dispersed.

Samples were prepared by sequentially forming the following layers on the heat-treated polyethylene terephthalate support.
The drying was carried out at 75 ° C. for 5 minutes.

Back surface side coating: A liquid having the following composition was coated on the base surface opposite to the photosensitive layer so that the wet thickness was 100 μm. Polyvinyl butyral # 4000-2 (manufactured by Denki Kagaku Kogyo KK) 10% isopropyl alcohol solution 60 g isopropyl alcohol 10 g 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) Dye S-1 was added to the above solution of 8% acetic acid ethyl ester solution in 8 g. Dye S-10.
A product obtained by dissolving 2 g in 10 g of methanol + 20 g of acetone is added so that the absorption of the exposure wavelength becomes 0.8. (633 nm in Example 1)

[0090]

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Photosensitive layer surface side coating Photosensitive layer 1: A liquid having the following composition was coated so that the coated silver amount was 1.5 g / m ² . Photosensitive emulsion A 73 g Sensitizing dye 1 (0.05% methanol solution) 2 ml Additive-1 (0.01% methanol solution) 3 ml Phthalazine (5% methanol solution) 8 ml Developer-1 (10% acetone solution) 13 ml 2 ml of hydrazine derivative H-1 (1% methanol solution)

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Photosensitive layer 2: In place of the additive-1 used in the photosensitive layer 1, an additive-2 was added. Other than that, photosensitive layer 1
Photosensitive layer 2 was obtained in the same manner as in.

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Photosensitive layer 3: In the same manner as in Photosensitive layer 1 except that the compound of the general formula (I) was added instead of the comparative additives used in Photosensitive layers 1 and 2, photosensitive layers 3-1 to 3-3 were prepared. I got -4. Further, a photosensitive layer 3-5 was prepared in which a compound corresponding to the additive-1 was not added.

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Surface protective layer: Wet a liquid having the following composition with a thickness of 1
It was applied so as to be 00 microns. Acetone 175 ml Methanol 15 ml Cellulose acetate 8.0 g 4-methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g

Sensitometry The photothermographic material prepared above was exposed to xenon flash light with an emission time of 10 ⁻³ seconds through an interference filter having a peak at 633 nm. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. The reciprocal of the exposure dose giving a density of 3.0 was taken as the sensitivity and shown as relative sensitivity. In addition, the slope of the straight line connecting the points of density 0.1 and 1.5 on the characteristic curve is shown as the gradation (γ ₀₁₁₅ ) representing the leg _break . The dye in the back layer was erased by irradiating a halogen lamp for 15 seconds after the heat development treatment. Image quality evaluation The image quality was evaluated by generating halftone dots with the same exposure machine as in sensitometry. The quality of halftone dots when our scanner film LS5500 was exposed by our color scanner MAGNASCAN was set to 4 and, if it was better than that, 5, 6
point. If it is bad, the evaluation is made by a 6-point method of 3, 2, and 1. mainly,
The sharpness of the points was evaluated. It should be noted that three or more points are at a practical level as a photosensitive material for printing.

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[Table 1]

As can be seen from Table 1, the photothermographic material of the present invention has a high sensitivity and a high Dmax, and has a good leg image and very good image quality.

Claims (2)

[Claims] 1. An organic acid silver salt, a silver halide,
A photothermographic material comprising a hydrazine derivative and at least one compound represented by the following general formula (I). Embedded image In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents a carbonyl group or a sulfonyl group.
A represents a hydrogen atom, a halogen atom or an electron-withdrawing group. n represents 0 or 1. 2. The photothermographic material according to claim 1, wherein an image having γ> 5 is formed by a heat development process. However, γ represents the slope when the concentrations 0.1 and 0.15 are connected by a straight line.