JP2002131864A - Silver salt light and heat photographic dry imaging material, method of recording image, and method of forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver salt light and heat photographic dry imaging material having high sensitivity and low fog and excellent in stability of a silver image after heat development, provide a method of recording the image using the same, and also provide a method of forming the image. SOLUTION: The silver salt light and heat photographic dry imaging material has at least one of layers containing a silver saving agent and has a photosensitive silver halide grain sensitized by an organic sensitizer, and when the material is exposed in an exposure amount of 280 μj/cm2 and is heat developed at 123 deg.C for 16.5 seconds, photosensitive silver halide grains of <=25 number % having a grain diameter in the range of >=10 nm but <=50 nm are free from contacting with developed silver.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver salt photothermographic dry imaging material, an image recording method using the same, and an image forming method.

[0002]

2. Description of the Related Art Conventionally, in the fields of medical treatment and printing plate making, waste liquid caused by wet treatment of an image forming material has been a problem in terms of workability. It is strongly desired to reduce the amount of waste liquid.

Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imager or a laser imagesetter and can form a high-resolution, clear black image.

As such techniques, for example, US Pat. Nos. 3,152,904 and 3,487,075,
(Dry Morgan (Dry Silver Photograph)
phy Material)) ”or D.P. H. "Thermal Pro Silver System (Thermally Pro)" by Klosterboer
cessed Silver Systems) "(Imaging Processes and Materials)
terials) Neblette Eighth Edition, Sturge, V.M. Walworth
rth), A. Editing Shepp, # 279
(1989), a silver salt photothermographic dry imaging material (photothermographic material) containing an organic silver salt, photosensitive silver halide particles, and a reducing agent on a support is known. ing. Since this silver salt photothermographic dry imaging material does not use any solution-based processing chemicals,
It is possible to provide a user with a system that is simpler and does not damage the environment.

[0005] These silver salt photothermographic dry imaging materials generally use a photosensitive silver halide particle provided in a photosensitive layer as a light sensor, an organic silver salt as a supply source of silver ions, and a built-in reducing agent. It is characterized in that an image is formed by heat development at a temperature of 140 ° C. and no fixing is performed. Therefore, in order to achieve both a smooth supply of silver ions to the silver halide and a prevention of a reduction in transparency due to light scattering, it is often necessary to improve the shape of organic silver particles which are easy to be appropriately arranged in the photosensitive layer and have little adverse effect on light scattering. Effort has been made.

[0006] However, in order to achieve the above-mentioned object, simply dispersing and / or pulverizing with a high energy using a disperser or the like to make the particles fine, the silver halide particles and the organic silver salt particles are not used. Damage increases fog, lowers sensitivity, and degrades image quality.Therefore, there is a need for a technology that can provide high light sensitivity and image density without increasing the amount of silver and reduce fog. Had been.

On the other hand, since a silver salt photothermographic dry imaging material contains an organic silver salt, photosensitive silver halide particles, and a reducing agent, fogging tends to occur during the storage period before thermal development and during thermal development. In addition, there is a problem that fogging or photolytic silver (printout silver) easily occurs during the storage period after the heat development. In particular, in the photosensitive material,
After exposure, usually, heat development is performed only at 80 to 250 ° C., and fixing is not performed. Therefore, during long-term storage under conditions where silver halide, organic silver salt, and reducing agent remaining in unexposed areas coexist, heat There was a problem that the silver image was discolored by light or light.

That is, the reaction with the organic silver salt tends to generate thermal fog due to the presence of the reducing agent in the photosensitive material, and the wavelength range different from the light for image recording after development. Printout silver in a system containing silver halide grains and organic silver salt, since the reducing agent functions as a hole trap in addition to the original function of reducing silver ions even when irradiated with light. Is considered to be part of the cause.

In addition to the above-mentioned causes, it is conceivable that fog nuclei which cause fogging in the manufacturing process of the photosensitive material are formed.

Techniques for solving these problems are disclosed in JP-A-6-208192, JP-A-8-267934, US Pat. No. 5,714,311 and references cited in these patent documents. Although these disclosed technologies have some effects, they are not yet enough technologies to satisfy the level required in the market.

On the other hand, further improvement in image quality is demanded as a so-called eternal theme of silver salt photothermographic dry imaging materials. In particular, in the field of medical imaging, there is a demand for higher image quality that enables more accurate diagnosis.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver salt photothermographic dry imaging material having high sensitivity, low fog, and excellent silver image stability after thermal development.
An object of the present invention is to provide an image recording method and an image forming method using the same.

[0013]

The above objects of the present invention have been attained by the following items.

1. A silver salt photothermographic dry imaging material having a photosensitive layer containing organic silver salt particles, photosensitive silver halide particles and a solvent, a photosensitive layer containing a reducing agent and a binder, and a non-photosensitive layer, At least one of the layer and the non-photosensitive layer contains a silver saving agent, and the photosensitive silver halide grains are subjected to chalcogen sensitization using an organic sensitizer containing a chalcogen atom; When the photothermographic dry imaging material is exposed at an exposure amount of 280 μJ / cm ² and thermally developed at 123 ° C. for 16.5 seconds, 25 photosensitive silver halide grains having a particle size in the range of 10 nm to 50 nm are obtained. % Or less is not in contact with developed silver.

2. 2. The silver salt photothermographic dry imaging material as described in 1 above, wherein the material has two or more photosensitive layers.

3. A compound that generates a reactive species capable of oxidizing silver by exposure to ultraviolet light or visible light, and a compound that generates a reactive species that inactivates a reducing agent and cannot reduce silver ions of an organic silver salt to silver 2. The silver salt photothermographic dry imaging material according to the above item 1, comprising at least two kinds of compounds selected from the group consisting of:

4. 4. The silver salt photothermographic dry imaging material according to any one of the above items 1 to 3, wherein the organic sensitizer is a compound having a group capable of adsorbing to silver halide grains and an unstable chalcogen atom site. .

5. 5. The silver salt photothermographic dry according to any one of items 1 to 4, wherein the organic sensitizer is a compound having a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond. Imaging materials.

6. Wherein the organic silver salt particles are a mixture of at least two types of organic acid silver salts.
The silver salt photothermographic dry imaging material according to any one of the above items.

[7] FIG. 7. When recording an image on the silver halide photothermographic dry imaging material according to any one of the above items 1 to 6, the exposure is performed using a laser beam scanning exposure device in which the scanning laser beam is a double beam. Image recording method.

8. 7. When recording an image on the silver halide photothermographic dry imaging material according to any one of the above items 1 to 6, the exposure is performed using a laser light scanning exposure device in which the scanning laser light is a vertical multi. Image recording method.

9. The image recording is performed on the silver salt photothermographic dry imaging material according to any one of the above items 1 to 6 by using the image recording method described in the above item 7 or 8, and subjected to heat development, and then specified by JIS Z 8729. Hue angle h
ab satisfies the formula (1).

Hereinafter, the present invention will be described in detail. The silver salt photothermographic dry imaging material of the present invention uses an organic sensitizer in which at least one of a photosensitive layer and a non-photosensitive layer contains a silver saving agent, and the photosensitive silver halide grains contain a chalcogen atom. Is chalcogen sensitized, and
The silver salt photothermographic dry imaging material was exposed at an exposure dose of 28.
When exposed at 0 μJ / cm ² and subjected to thermal development at 123 ° C. for 16.5 seconds, 25% by number or less of the photosensitive silver halide particles having a particle size in the range of 10 nm to 50 nm contact the developed silver. The silver halide photothermographic dry imaging material of the present invention, which has the above-mentioned characteristics, has high sensitivity, low fog, and high storage stability of an image after exposure and before development. It has been found that it shows excellent characteristics.

The photosensitive silver halide grains according to the present invention will be described. The photosensitive silver halide grains according to the present invention can inherently absorb visible light or infrared light by a physicochemical method inherently as an intrinsic property of silver halide crystals, or artificially, and Silver halide crystal grains that have been processed and manufactured such that physicochemical changes can occur in the silver halide crystal and / or at the crystal surface when absorbing visible light or infrared light, and contain chalcogen atoms A feature is that chalcogen sensitization is performed using an organic sensitizer.

The chalcogen sensitization applied to the silver halide grains according to the present invention is described in, for example, Japanese Patent Application No. 12-057004.
The method can be carried out with a compound that releases a chalcogen such as sulfur with reference to the description of compounds, addition methods and the like disclosed in JP-A Nos. 12-061942 and 12-061942. Along with the above-described chalcogen sensitization, it is also possible to form and impart a chemical sensitization center (chemical sensitization nucleus) by using a noble metal compound which releases a noble metal ion such as a gold ion. Further, in the present invention, it is preferable that chalcogen sensitization is performed with an organic sensitizer represented by the following general formula (S).

[0026]

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In the formula, A ¹ represents an atom group containing a group capable of adsorbing to silver halide, L ¹ represents a divalent linking group, Z ¹ represents an atom group containing an unstable chalcogen atom site, W ¹ ,
W ² and W ³ represents a carboxylic acid group, a sulfonic acid group, sulfinic acid group, a phosphoric acid group, phosphorous acid group and boric acid. m1
Represents 0 or 1; n1 represents an integer of 1 to 3;
1, 12 and 13 each represent an integer of 0 to 2. Also, l
1, l2, and l3 may be simultaneously 0, that is,
It may not have any water-soluble groups.

In the general formula (S), the atom group having a group adsorbable to silver halide represented by A ¹ includes an atom group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole, mercaptotriazole, Mercaptodiazole, mercaptothiazole,
Mercaptothiadiazole, mercaptooxazole,
Atomic groups having a thione group (mercaptoimidazole, mercaptobenzthiazole, mercaptobenzoxazole, mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2-mercaptopyridyl, mercaptophenyl, mercaptonaphthyl, etc.), and a thione group ( For example, thiazoline-
2-thione, oxazoline-2-thione, imidazoline-2-thione, benzthiazoline-2-thione, benzimidazoline-2-thione, thiazolidine-2-thione, etc.), an atom group forming imino silver (for example, triazole, Tetrazole, benztriazole, hydroxyazaindene, benzimidazole, indazole, etc.),
A group of atoms having an ethenyl group (for example, 2- [N- (2-
Propynyl) amino] benzthiazole, N- (2-propynyl) carbazole and the like.

The group of atoms having an unstable chalcogen atom site represented by Z ¹ in the general formula (S) is a group of compounds which form silver chalcogen in the presence of silver nitrate. In the group of atoms having these unstable chalcogen atom sites, the chalcogen atom preferably has a structural unit connected to a carbon atom or a phosphorus atom by a double bond, and the chalcogen atom is a sulfur atom, a selenium atom, a tellurium atom, Means an atom.

Specific examples of the atom group containing an unstable sulfur site include an atom group having a thiourea group (for example, N, N'-
Diethylthiourea, N-ethyl-N '-(2-thiazolyl) thiourea, N, N-dimethylthiourea, N-phenylthiourea, etc., an atom group having a thioamide group (eg, thiobenzamide, thioacetamide, etc.), polysulfide , A group of atoms having a phosphine sulfide group (for example, bis (pentafluorophenyl) phenyl phosphine sulfide, diethyl phosphine sulfide, dimethylphenyl phosphine sulfide, etc.), a group of atoms having a thioxoazolidinone group (for example, ethyl Rhodanine, 5-benzylidene-3-ethylrhodanine, 1,3-diphenyl-2-thiohydantoin, 3-
Each atom group such as ethyl-4-oxooxazolidine-2-thione.

As a specific example of an atom group containing an unstable selenium site, an atom group having a selenourea group (eg, N, N
-Dimethylselenourea, selenourea, N-acetyl-
N, N'-diethylselenourea, N-trifluoroacetyl-N ', N'-dimethylselenourea, N-ethyl-
N '-(2-thiazolyl) selenourea, N, N'-diphenylselenourea, etc., an atom group having a selenoamide group (for example, N-methyl-selenobenzamide, N-phenyl-selenobenzamide, N-ethyl-seleno) Benzamide), an atom group having a phosphine selenide group (for example, triphenylphosphine selenide, diphenyl- (pentafluorophenyl) phosphine selenide, tris (m-chlorophenyl) phosphine selenide, etc.), selenophos An atom group having a phosphate group (for example, tris (p-tolyl) selenophosphate, etc.),
A group of atoms having a selenoester group (for example, p-methoxyselenobenzoic acid = O-isopropyl ester, selenobenzoic acid = Se- (3′-oxobutyl) ester, p-methoxyselenobenzoic acid = Se- (3 '-Oxocyclohexyl) ester, etc.), an atom group having a selenide group (for example, bis (2,6-dimethoxybenzoyl) selenide, bis (n
-Butoxycarbonyl) selenide, bis (benzyloxycarbonyl) selenide, bis (N, N-dimethylcarbamoyl) selenide, etc.), and an atomic group having a triselenane group (for example, 2,4,6-tris (p-methoxy) Phenyl) triselenane, etc.), an atom group having a selenoketone group (for example, 4-methoxyselenoacetophenone,
Atom group such as 4,4-methoxyselenobenzophenone).

As a specific example of the atom group containing an unstable tellurium site, an atom group having a phosphine telluride group (for example, butyl-di-isopropylphosphine telluride,
An atom group having a tellurourea group (eg, N, N′-diethyl-N, N′-diethylenetellurourea, N, N′-dimethylene-N, N′-dimethyltellurourea) Atom group having a telluroamide group (eg, N, N-dimethyl-tellurobenzamide, N, N-tetramethylene- (p-tolyl) tellurobenzamide, etc.), and an atom group having a tellurophosphate group (eg, tris Atomic groups such as (p-tolyl) tellurophosphate, trisbutyltellurophosphate and the like, and an atomic group having a tellurophosphoric amide group (for example, hexamethyltellurophosphoric amide and the like).

As the group of atoms having unstable selenium and tellurium sites, see JP-A-4-25832 and JP-A-4-25832.
-109240, 4-147250, 4-33
No. 043, No. 5-40324, No. 5-24332,
Nos. 5-24333, 5-303157, 5-3
No. 06268, No. 5-306269, No. 6-2775
No. 3, 6-43576, 6-75328, 6
No. 17528, No. 6-180478, No. 6-175
No. 29, No. 6-208184, No. 6-208186
No. 6-317678, No. 7-92599, No. 7
-98483, 7-104415, 7-140
579, 7-301880 and the like.

The compound represented by formula (S) may have a water-soluble group. Examples of the water-soluble group include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group,
Examples include a phosphite group and a boric acid group.

Further, the above-mentioned compound has at least one group capable of adsorbing to silver halide and at least one unstable chalcogen atom site, and has at least one group capable of adsorbing to silver halide and an unstable chalcogen atom. The sites may be bonded directly or via a linking group. When the compound has a water-soluble group, the water-soluble group, the group capable of adsorbing to silver halide and the unstable chalcogen atom site may be directly bonded or bonded via a linking group.

The divalent linking group represented by L ¹ is a group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc., and specifically has 1 to 20 carbon atoms. Alkylene group (for example, methylene, ethylene, propylene, hexylene, etc.), arylene group (for example, phenylene, naphthylene, etc.), -CONR ₁ -,-
SO ₂ NR _2- , -O-, -S-, -NR _3- , -NR ₄ C
_{O -, - NR 5 SO 2} -, - NR 6 CONR 7 -, - CO-
O-, -O-CO-, -CO- and the like and a plurality of these linked groups can be mentioned.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group. As the aliphatic group represented by R _{1 to} R ₇ , a linear or branched alkyl group having 1 to 20 carbon atoms (for example, each group such as methyl, ethyl, isopropyl, 2-ethyl-hexyl), an alkenyl group ( For example, propenyl, 3-pentenyl, 2-butenyl, cyclohexenyl, etc.), alkynyl group (eg, propargyl, 3-pentynyl, etc.), aralkyl group (eg, benzyl,
Each group such as phenethyl). The alicyclic group is an alicyclic group having 5 to 8 carbon atoms (for example, each group such as cyclopentyl and cyclohexyl), and the aromatic group is a monocyclic or condensed ring group having 6 to 10 carbon atoms. Specific examples include a phenyl group or a naphthyl group, and the heterocyclic group includes a 5- to 7-membered monocyclic ring containing an oxygen atom, a sulfur atom or a nitrogen atom or a condensed ring group condensed with another ring. Specific examples include groups such as furyl, thienyl, benzfuryl, pyrrolyl, indolyl, thiazolyl, imidazolyl, morpholyl, piperazyl, and pyrazyl. Each of the groups represented by R _{1 to} R ₇ can be substituted with an arbitrary atom or group at an arbitrary position. Examples of the substituted atom and the substituent include:
For example, a hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, an amino group (eg, each group such as methylamino, anilino, diethylamino, 2-hydroxyethylamino), acyl Groups (e.g., acetyl, benzoyl, propanoyl, etc.), carbamoyl groups (e.g., carbamoyl, N-
Groups such as methylcarbamoyl, N, N-tetramethylenecarbamoyl, N-methanesulfonylcarbamoyl, and N-acetylcarbamoyl), and alkoxy groups (for example, groups such as methoxy, ethoxy, 2-hydroxyethoxy, and 2-methoxyethoxy). , Alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), sulfonyl group (eg, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.), sulfamoyl group (Eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, N-ethylsulfamoyl, etc.), acylamino group (eg, acetamido, trifluoroacetamido, benzamide) Thieno carbonylamino, each group such as benzenesulfonamide), an alkoxycarbonylamino group (e.g., methoxycarbonylamino, N-
Groups such as methyl-ethoxycarbonylamino).

Carboxylic acid groups represented by W ¹ , W ² and W ³ ;
The sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group and boric acid group may be in a free form or form a counter salt with an alkali metal, an alkaline earth metal, ammonium or an organic amine.

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

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The organic sensitizer containing a chalcogen atom is preferably a compound having a group capable of adsorbing to silver halide and a site of an unstable chalcogen atom.

These organic sensitizers are disclosed in
-150046, JP-A-4-109240, 11
Organic sensitizers having various structures disclosed in, for example, JP-A-218874 can be used. Among them, compounds having a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond can be used. Preferably, at least one kind is used.

In the present invention, the amount of the chalcogen compound used as the organic sensitizer depends on the chalcogen compound used, silver halide grains, the reaction environment for chemical sensitization, and the like. 10 ^-8 to 10
^-2 mol is preferable, and more preferably 10 ^-7 to 10 ^-3 mol is used. Although there is no particular limitation on the chemical sensitizing environment in the present invention, in the presence of a compound capable of extinguishing or reducing the size of chalcogenide silver or silver nuclei on photosensitive silver halide grains, and particularly, in the presence of silver nuclei, It is preferable to perform chalcogen sensitization using an organic sensitizer containing a chalcogen atom in the presence of an oxidizing agent capable of oxidizing the chalcogen atom. As the sensitizing condition, the pAg is preferably 6 to 11,
More preferably, it is 7 to 10, and the pH is preferably 4 to 10, more preferably 5 to 8, and the temperature is 30.
It is preferable to perform sensitization at a temperature of not more than ° C. Therefore, in the silver salt photothermographic dry imaging material of the present invention, the photosensitive silver halide uses an organic sensitizer containing a chalcogen atom in the presence of an oxidizing agent capable of oxidizing silver nuclei on the grains. It is preferable to use a photosensitive emulsion which has been subjected to chemical sensitization at a temperature of 30 ° C. or lower, mixed with an organic silver salt, dispersed, dehydrated and dried.

The chemical sensitization using these organic sensitizers is preferably carried out in the presence of a spectral sensitizing dye or a heteroatom-containing compound having adsorptivity to silver halide grains. By performing chemical sensitization in the presence of a compound having adsorptivity to silver halide, dispersion of the chemical sensitization center nucleus can be prevented, and high sensitivity and low fog can be achieved. The spectral sensitizing dye used in the present invention will be described later, and the heteroatom-containing compound having adsorptivity to silver halide is preferably a nitrogen-containing heterocyclic compound described in JP-A-3-24537. can give. In the nitrogen-containing heterocyclic compound used in the present invention, the heterocyclic ring is a pyrazole ring, a pyrimidine ring, a 1,2,4-triazole ring, a 1,2,3-triazole ring, a 1,3,4-
Thiadiazole ring, 1,2,3-thiadiazole ring,
1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, and these rings are 2-3
Individually bonded rings such as a triazolotriazole ring, a diazaindene ring, a triazaindene ring, and a pentaazaindene ring can be exemplified. A condensed heterocyclic ring of a monocyclic heterocyclic ring and an aromatic ring, for example, a phthalazine ring, a benzimidazole ring, an indazole ring, a benzthiazole ring and the like can also be applied.

Preferred among these are azaindene rings and azaindene compounds having a hydroxyl group as a substituent, for example, hydroxytriazaindene,
Tetrahydroxyazaindene, hydroxypentaazaindene compounds and the like are more preferred.

The heterocyclic ring may have a substituent other than a hydroxyl group. Examples of the substituent include an alkyl group, a substituted alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, and a cyano group. You may.

The amount of the heterocyclic compound to be added varies over a wide range depending on the size, composition, and other conditions of the silver halide grains, but the approximate amount is 10 to 10 mol per mol of silver halide. The range is from ^-6 mol to 1 mol, preferably from 10 ^-4 mol to 10 ^-1 mol.

As described above, the silver halide grains according to the present invention can be sensitized with a noble metal using a compound that releases a noble metal ion such as a gold ion. For example,
Chloroaurate or an organic gold compound can be used as the gold sensitizer.

In addition to the above-described sensitization methods, reduction sensitization methods and the like can also be used. Examples of shell-like compounds for reduction sensitization include ascorbic acid, thiourea dioxide, stannous chloride, and hydrazine derivatives. , Borane compounds, silane compounds, polyamine compounds and the like can be used. Further, reduction sensitization can be performed by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less.

The silver halide to be subjected to chemical sensitization according to the present invention may be formed in the presence of an organic silver salt, or may be formed in the absence of an organic silver salt. May be mixed.

The silver salt photothermographic dry imaging material of the present invention was exposed at an exposure amount of 280 μJ / cm ² ,
When heat development is performed at 3 ° C. for 16.5 seconds, the particle size is 10 nm to
2 of the photosensitive silver halide grains in the range of 50 nm.
It is characterized in that 5% by number or less does not contact developed silver, but it is more preferable that 20% or less of the above-described photosensitive silver halide particles do not contact developed silver. . Here, heat development at 123 ° C. for 16.5 seconds means that a silver salt photothermographic dry imaging material is brought into contact with a heat development drum having a surface temperature of 123 ° C. for 16.5 seconds,
This means that heat development is performed.

The number% of photosensitive silver halide grains not in contact with developed silver can be determined as follows.

First, the photosensitive layer applied on the support is attached to an appropriate holder with an adhesive, and the thickness is 0.1 to 0.2 using a diamond knife in a direction perpendicular to the surface of the support.
Make ultra-thin sections of μm. Next, the prepared ultrathin section is transferred onto a carbon film supported by a copper mesh and hydrophilized by glow discharge, and cooled to −120 ° C. or lower with liquid nitrogen while being transmitted through a transmission electron microscope (specifically, JEM
-2000FX type; Acceleration voltage 200 from JEOL Ltd.
Used at kV. A bright-field image is observed at a magnification of 5,000 to 40,000 times using a TEM). Images are quickly recorded on film, imaging plates, CCD cameras, etc. At this time, as the visual field to be observed, it is preferable to appropriately select a portion where there is no break or looseness in the section.

It is preferable to use a carbon film supported by an organic film such as ultra-thin collodion, formbar or the like. More preferably, the carbon film is formed on a rock salt substrate and obtained by dissolving and removing the substrate. This is a carbon-only film obtained by removing the film by an organic solvent and ion etching.

The acceleration voltage of the TEM is 80 to 400 k
V is preferable, and particularly preferably 80 to 200 kV.

The number of photosensitive silver halide grains present in a fixed area A of the recorded image is counted, and the number of photosensitive silver halide grains per 1 μm ³ is measured by the following equation.

The number of grains per 1 μm ³ = the number of photosensitive silver halide grains present in a fixed area A of the recorded image / the fixed area A (μm ² ) of the recorded image × thickness of the section (μm). The number of fields of view was determined so that the number of non-reactive silver halide grains was 1000 or more.
After taking the M-photograph, the temperature is returned to normal temperature, the section is embedded in an epoxy resin, and the section is measured by observing a cross section.

Next, exposure was performed at an exposure amount of 280 μJ / cm ² ,
123 ° C., for films was 16.5 seconds thermal development, in the same manner as described above, after performing the prepared sections TEM observation, counting the silver halide does not contact the developed silver per 1 [mu] m ³ The remaining silver halide is calculated. At this time, the number of fields of view is determined so that the number of remaining silver halides is at least 100.

Number of silver halide not in contact with developed silver = (number of silver halide not in contact with developed silver per 1 μm ³ ) / (number of silver halide per 1 μm ^{3 in} raw film) × 100 For more information on electron microscopy techniques and sample preparation techniques, refer to
Biological Electron Microscope Observation Method ”(Maruzen),“ The Japanese Society of Electron Microscopy Kanto Chapter / Electron Microscope Biological Sample Preparation Method ”(Maruzen)
Can be referred to respectively.

The silver halide grains used in the present invention may be P.I. Chimie et P by Glafkids
hysique Photographique (Pa
ulMontel, 1967); F. Duf
fin Photographic Emulsio
n Chemistry (The Focal Pre
ss, 1966); L. Zelikman e
Making and Coating P by tal
photographic Emulsion (The
Focal Press, 1964) can be used as a silver halide grain emulsion. 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, a combination thereof and the like. Of these methods, the so-called controlled double jet method for preparing silver halide grains while controlling the formation conditions is preferable. 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.

The silver halide according to the present invention preferably has a small average grain size in order to suppress white turbidity after image formation and obtain good image quality, and more preferably has an average grain size of 0.2 μm or less. Is from 0.01 μm to 0.
17 μm, particularly preferably 0.01 μm to 0.05 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface.

In the present invention, the silver halide grains are preferably monodispersed. The term “monodisperse” as used herein means that the coefficient of variation of the particle size obtained by
It means 0% or less. It is preferably at most 20%, more preferably at most 15%.

Coefficient of variation of grain size = standard deviation of grain size / mean value of grain size × 100 When tabular silver halide grains are used, the average aspect ratio is preferably 1.5 or more and 10 or more.
It is preferably 0 or less, more preferably 2 or more and 50 or less. These are disclosed in U.S. Patent Nos. 5,264,337 and 5,314,534.
No. 798, 5,320,958, etc., and the desired tabular grains can be easily obtained.

The silver halide grains according to the present invention may be added to the image forming layer by any method. In this case, the silver halide grains are arranged so as to be close to a reducible silver source (organic silver salt). Is preferred.

The silver halide according to the present invention is prepared in advance, and is added to a solution for preparing organic silver salt grains by separating the silver halide preparing step and the organic silver salt preparing step. However, as described in British Patent No. 1,447,454, a halogen component such as halide ion coexists with an organic silver salt-forming component when preparing organic silver salt particles, as described in British Patent No. 1,447,454. By injecting silver ions into this, it is possible to generate organic silver salt particles almost simultaneously with the generation thereof.

It is also possible to prepare a silver halide grain by subjecting an organic silver salt to a halogen-containing compound and converting the organic silver salt. That is, a silver halide forming component is applied to a solution or dispersion of an organic silver salt prepared in advance or a sheet material containing the organic silver salt to convert a part of the organic silver salt into photosensitive silver halide. Can also.

These silver halide grains were prepared in an amount of 0.001 mol per mol of the organic silver salt, both from separately prepared silver halide grains and silver halide grains obtained by conversion of an organic silver salt.
It is preferable to use 1 to 0.7 mol, preferably 0.03 to 0.5 mol.

The silver halide according to the present invention preferably contains transition metal ions belonging to Groups 6 to 11 of the periodic table. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred. These may be used alone or in combination of two or more of the same or different metal complexes. These metal ions may be directly introduced into silver halide as a metal salt, but can be introduced into silver halide in the form of a metal complex or complex ion. The preferred content is 1 to 1 mole of silver.
The range of × 10 ^-9 to 1 × 10 ^-2 mol is preferable, and
The range of ^-8 to 1 x ^10-4 mol is more preferable. In the present invention, the transition metal complex or complex ion is preferably represented by the following general formula.

In the formula [ML ₆ ] ^m , M represents a transition metal selected from elements of Groups 6 to 11 of the periodic table, L represents a ligand, and m represents 0,-, 2-, 3-.
Or represents 4-. Specific examples of the ligand represented by L include halogen ion (fluoride ion, chloride ion, bromide ion, iodide ion), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Specific examples of the transition metal coordination complex ion are shown below. 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^4- 7: [IrCl _6] ^4- 8: [IrCl _6] ^3- 9: [Ru (NO) Cl _5] ^2- 10: [RuBr ₄ (H ₂ O)] ^2- 11: [Ru (NO) (H ₂ O ) Cl _4] ^- 12: [RhCl ₅ (H ₂ O)] ^2- 13: [Re (NO) Cl _5] ^2- 14: [Re (NO) (CN) _5] ^2- 15: [Re (NO ) Cl (CN) _4] ^2- 16: [Rh (NO) ₂ Cl _4] ^- 17: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 18: [Ru (NO) (CN) _5] ^{2 -} 19: [Fe (CN) _6] ^3- 20: [Rh (NS) Cl _5] ^2- 21: [Os (NO) Cl _5] ^2- 22: [Cr (NO) Cl _5] ^2- 23: [Re (NO) Cl _5] ^- 24: [ _{Os (NS) Cl 4 (TeCN} ) ] ^2- 25: [Ru (NS) Cl _5] ^2- 26: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 27: [Os (NS) Cl (SCN) ₄ ] ^2-28 : [Ir (NO) Cl ₅ ] ^2- A compound that provides an ion or a complex ion of these metals is preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, may be added at any stage before and after chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth, physical ripening, Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation. In the addition, it may be added in several divided portions, and may be uniformly contained in the silver halide grains.
No. 03, JP-A-2-306236 and JP-A-3-16754
No. 5, No. 4-76534, No. 6-110146, No. 5-273683, etc., the particles can be contained in the particles with distribution.

The silver saving agent according to the present invention will be described.
The silver saving agent according to the present invention refers to a compound capable of reducing the amount of silver required to obtain a constant silver image density. Although there are various possible mechanisms for the function of reducing the function, a compound having a function of improving the covering power of the developed silver is preferable. Here, the covering power of the developed silver means an optical density per unit amount of silver.

Examples of the silver saving agent include hydrazine derivative compounds represented by the following general formula [H], vinyl compounds represented by the following general formula (G), and quaternary onium compounds represented by the following general formula (P) Are preferred examples.

[0080]

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[0081]

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In the general formula [H], A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a —G ₀ -D ₀ group which may have a substituent, and B ₀ represents a blocking group. A ₁ and A ₂ each represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. Here, G ₀ is a -CO- group, a -COCO- group,-
CS-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -S
Represents an O ₂ — group or a —P (O) (G ₁ D ₁ ) — group, where G ₁ is a mere bond, an —O— group, a —S— group, or —N (D ₁ )
Represents a group, and D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Preferred D ₀ is a hydrogen atom,
Examples include an alkyl group, an alkoxy group, and an amino group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferable examples include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group). Group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group.
For example, a benzene ring or a naphthalene ring is mentioned, and A ₀
The heterocyclic group represented by is preferably a heterocyclic ring containing at least one hetero atom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring,
Examples include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring. Aromatic groups A _0, heterocyclic group and -G ₀ -D ₀
The group may have a substituent. Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable,
Examples of the ballast group include a photographically inactive alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group, and the like. Preferably, there is.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group and special groups. 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P
(O) represents a (G ₁ D ₁ ) — group. Preferred G0 is-
A CO— group, a —COCO— group, G1 represents a mere bond, a —O— group, a —S— group or a —N (D ₁ ) — group, and D ₁ represents an aliphatic group, an aromatic group, Represents a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ , A ₂
Are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (ethoxalyl group, etc.) Represents

Next, specific examples of the compound represented by the general formula [H] are shown below, but it should not be construed that the invention is limited thereto.

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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More preferred hydrazine derivatives are represented by the following formulas (H-1), (H-2), (H-3) and (H-4)
It is represented by

[0097]

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In the general formula (H-1), R₁₁, R₁₂Passing
And R₁₃Is independently substituted or unsubstituted aryl
Represents a group or a heteroaryl group.
Specifically, for example, phenyl, p-methylphenyl, na
Futil and the like. As a heteroaryl group,
Physically, triazole residues, imidazole residues,
Residues, furan residues, thiophene residues, etc.
You. Also, R₁₁, R₁₂And R₁₃Is any linking group
May be combined via R₁₁, R₁₂And R₁₃Is a substituent
When having, as the substituent, for example, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group,
Heterocyclic group containing quaternized nitrogen atom, hydroxyl
Group, alkoxy group (ethyleneoxy group or propylene
Oxy group unit)
Xy, acyloxy, acyl, alkoxycarbo
Nyl group, aryloxycarbonyl group, carbamoyl
Group, urethane group, carboxyl group, imide group, amino
Group, carbonamido group, sulfonamido group, ureido
Group, thioureido group, sulfamoylamino group, semica
Rubazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium groups, (alkyl, aryl, or
Terrorist ring) thio group, mercapto group, (alkyl or ant
)) Sulfonyl group, (alkyl or aryl) sulf
Finyl group, sulfo group, sulfamoyl group, acyl sulf
Famoyl group, (alkyl or aryl) sulfoni
Luureido group, (alkyl or aryl) sulfoni
Rucarbamoyl group, halogen atom, cyano group, nitro
Group, phosphoric acid amide group and the like. R ₁₁, R₁₂as well as
R₁₃Are preferably substituted or unsubstituted
And more preferably R₁₁, R₁₂And R
₁₃Is an unsubstituted phenyl group.

R ₁₄ represents a heteroaryloxy group or a heteroarylthio group. Specific examples of the heteroaryloxy group include a pyridyloxy group, a pyrimidyloxy group, an indolyloxy group, a benzothiazolyloxy group,
Examples include a benzimidazolyloxy group, a furyloxy group, a thienyloxy group, a pyrazolyloxy group, and an imidazolyloxy group. Specific examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

A ₁ and A ₂ are both a hydrogen atom, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.) or an oxalyl group (ethoxalyl, etc.). ). Preferably, A ₁ and A ₂ are both hydrogen atoms.

In the general formula (H-2), R ₂₁ represents a substituted or unsubstituted alkyl group, an aryl group or a heteroaryl group. Specific examples of the alkyl group include a methyl group, an ethyl group and a t-butyl group. Group, 2-octyl group, cyclohexyl group, benzyl group, diphenylmethyl group and the like. Specific examples of the aryl group and the heteroaryl group include those similar to R ₁₁ , R ₁₂ and R ₁₃ . When R ₂₁ has a substituent, specific examples of the substituent include those similar to the substituents of R ₁₁ , R ₁₂ and R ₁₃ . R ₂₁ is preferably an aryl group or a heteroaryl group, and particularly preferably a substituted or unsubstituted phenyl group.

R ₂₂ represents hydrogen, an alkylamino group, an arylamino group, or a heteroarylamino group. Specific examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and a dimethylamino group. Examples include an amino group, a diethylamino group, and an ethylmethylamino group. As the arylamino group, an anilino group,
Examples of the heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. R ₂₂ is preferably a dimethylamino group or a diethylamino group. A ₁ and A ₂ are represented by the general formula (H
The same as A ₁ and A ₂ described in -1).

In the general formula (H-3), R ₃₁ and R ₃₂ represent a monovalent substituent, and examples of the monovalent substituent include R ₁₁ and R ₁₁ .
The groups exemplified as the substituents of R ₁₂ and R ₁₃ are exemplified, and preferably, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, and an amino group are exemplified. More preferably, it is an aryl group or an alkoxy group. Particularly preferred is that at least one of R ₃₁ and R ₃₂ is tert.
-Butoxy group, another preferred structure is
When R ₃₁ is a phenyl group, R ₃₂ is a tert-butoxy group.

G ₃₁ and G _{32 each} represent a —CO— group or a —COCO—
Group, -C (= S)-, sulfonyl group, sulfoxy group,-
P (＝ O) R ₃₃ — or an iminomethylene group;
₃₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or an amino group. However,
When G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. G ₃₁ and G ₃₂ are preferably -CO- group, -CO
A CO— group, a sulfonyl group or —CS—, more preferably a —CO— group or a sulfonyl group; A _1, A ₂ is A _1, A ₂ as described in the general formula (H-1)
Is the same as

In the general formula (H-4), R₄₁, R₄₂You
And R₄₃Is R in general formula (H-1)₁₁, R₁₂And
And R₁₃Is synonymous with R₄₁, R₄₂And R₄₃As preferred
Or both are substituted or unsubstituted phenyl groups.
And more preferably R₄₁, R ₄₂And R₄₃None of
It is a substituted phenyl group. R₄₄, R₄₅Is unsubstituted or replaced
Represents a substituted alkyl group, but specific examples include a methyl group,
Ethyl group, t-butyl group, 2-octyl group, cyclohexyl
A sil group, a benzyl group, a diphenylmethyl group and the like.
You. R₄₄, R₄₅Are preferably ethyl groups
You. A₁, A_TwoIs A described in the general formula (H-1)₁, A_TwoWhen
The same is true.

Hereinafter, the general formulas (H-1) to (H) of the present invention will be described.
Specific examples of the compound represented by -4) are shown below, but the present invention is not limited thereto.

[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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The general formulas (H-1) to (H-
The compound represented by 4) can be easily synthesized by a known method. For example, US Pat. No. 5,464,7
No. 38 and 5,496,695 can be synthesized.

Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in columns 11 to 20 of US Pat. No. 5,545,505 and column 9 of US Pat. No. 5,464,738. Compounds 1 to 12 described in Nos. 1 to 11. These hydrazine derivatives can be synthesized by a known method.

In the general formula (G), X and R are represented in the form of cis. However, the general formula (G) includes the form of X and R in the form of trans. This is the same in the structural representation of a specific compound.

In the general formula (G), X represents an electron-withdrawing group, and W is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom,
Acyl, thioacyl, oxalyl, oxyoxalyl, thiooxalyl, oxamoyl, oxycarbonyl, thiocarbonyl, carbamoyl, thiocarbamoyl, sulfonyl, sulfinyl, oxysulfinyl, thiosulfinyl, sulfamoyl Group, oxysulfinyl group, thiosulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, dicyanethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group, Represents an immonium group.

R represents a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group, an alkylthio group, an arylthio group, Organic or inorganic salts of a ring thio group, an alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, a hydroxyl group or a mercapto group (for example,
Sodium salt, potassium salt, silver salt, etc.), amino group, alkylamino group, cyclic amino group (for example, pyrrolidino group), acylamino group, oxycarbonylamino group, heterocyclic group (5- to 6-membered nitrogen-containing heterocycle, For example, it represents a benztriazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, etc.), a ureido group or a sulfonamide group. X and W, and X and R may be bonded to each other to form a cyclic structure. Examples of the ring formed by X and W include pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β-ketolactam and the like.

The general formula (G) will be further described.
The electron-withdrawing group represented by is a substituent whose substituent constant σp can take a positive value. Specifically, a substituted alkyl group (eg, halogen-substituted alkyl), a substituted alkenyl group (eg, cyanovinyl), a substituted / unsubstituted alkynyl group (eg, trifluoromethylacetylenyl, cyanoacetylenyl),
Substituted aryl group (cyanophenyl, etc.), substituted / unsubstituted heterocyclic group (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atom, cyano group, acyl group (acetyl, trifluoroacetyl, formyl, etc.), thioacetyl group (Thioacetyl, thioformyl, etc.), oxalyl group (methyloxalyl, etc.), oxyoxalyl group (ethoxalyl, etc.), thiooxalyl group (ethylthiooxalyl, etc.), oxamoyl group (methyloxamoyl, etc.), oxycarbonyl group (ethoxycarbonyl, etc.) , Carboxyl group, thiocarbonyl group (such as ethylthiocarbonyl),
Carbamoyl group, thiocarbamoyl group, sulfonyl group,
Sulfinyl group, oxysulfonyl group (ethoxysulfonyl, etc.), thiosulfonyl group (ethylthiosulfonyl, etc.), sulfamoyl group, oxysulfinyl group (methoxysulfinyl, etc.), thiosulfinyl group (methylthiosulfinyl, etc.), sulfinamoyl group, phosphoryl group, nitro Group, imino group, N-carbonylimino group (N
-Acetylimino, etc.), N-sulfonylimino group (N-
Methanesulfonylimino, etc.), dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group, immonium group, and the like. Heterocyclic ring in which ammonium group, sulfonium group, phosphonium group, immonium group, etc. form a ring Also included. σp
Substituents having a value of at least 0.30 are particularly preferred.

Examples of the alkyl group represented by W include methyl, ethyl, trifluoromethyl and the like, examples of the alkenyl group include vinyl, halogen-substituted vinyl and cyanovinyl, and examples of the alkynyl group include acetylenyl and cyanoacetylenyl. Examples of the aryl group include nitrophenyl, cyanophenyl, and pentafluorophenyl, and examples of the heterocyclic group include pyridyl, pyrimidyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, and benzoxazolyl. W is σ
A p-value is preferably a positive electron-withdrawing group, and more preferably, the value is 0.30 or more.

Among the above substituents for R, preferred are a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, a halogen atom, an organic or inorganic salt of a hydroxyl group or a mercapto group, and a heterocyclic group. Examples thereof include an organic or inorganic salt of a hydroxyl group, an alkoxy group, a hydroxyl group or a mercapto group, and a heterocyclic group, and particularly preferably an organic or inorganic salt of a hydroxyl group, a hydroxyl group or a mercapto group.

Among the substituents of X and W, those having a thioether bond in the substituent are preferable.

Next, specific examples of the compound represented by formula (G) are shown below, but it should not be construed that the invention is limited thereto.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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In the general formula (P), Q represents a nitrogen atom or a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Note that R ₁
To R ₄ may combine with each other to form a ring.

As the substituent represented by R _{1 to} R ₄ , an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like.

The ring which may be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group. As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formula (Pa):
A compound represented by (Pb) or (Pc); and a compound represented by the following general formula [T].

[0154]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A ¹ , A ² , A ³ , A ⁴
And preferred examples of A ⁵ are, 5-6 membered ring can be mentioned (pyridine, imidazole, Chiozoru, oxazole, pyrazine, each ring of the pyrimidine, and the like), More preferred examples include a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1. Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene _{group, -SO 2 -, - SO -} , -
O -, - S -, - CO -, - N (R 6) - (R 6 is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. Further, R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² , A ³ , A ⁴
And the substituents mentioned as the substituents for A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0159] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0160]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σp) indicating electron-withdrawing degree.

The Hammett's sigma value at the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
chemistry, 20, 304, 1977. The groups having a particularly preferable negative sigma value include, for example, a methyl group (σp = −0.17, hereinafter referred to as a σp value) and an ethyl group (C. Hansch et al.). -0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), i
So-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound are shown below, but it should not be construed that the invention is limited thereto.

[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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The quaternary onium compound can be synthesized by referring to a known method.
chemical Reviews vol. 55 p.
335-483 can be referred to. The addition amount of the above-mentioned high contrast agent is 10 ^-5 to 1 mol per 1 mol of the organic silver salt,
Preferably it is in the range of 10 ^{-4 to} 5 × 10 ^-1 mol.

The organic silver salt according to the present invention will be described.
In the present invention, the organic silver salt is a reducible silver source, and is a silver salt of an organic acid and a hetero organic acid.
0-30, preferably 15-25) Silver salts of aliphatic carboxylic acids and nitrogen-containing heterocyclic compounds are preferred. Also preferred are the organic or inorganic complexes described in RD 17029 and 29963, wherein the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions. Examples of these suitable silver salts include the following.

Silver salts of organic acids, for example, gallic acid, oxalic acid,
Silver salts such as behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, and aldehydes with hydroxy-substituted aromatic carboxylic acids Silver salts or complexes of polymer reaction products, for example, silver salts of reaction products of aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) Or complexes, silver salts or complexes of thiones, for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2
Silver salts or complexes such as -thione, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,2;
A complex or salt of silver and a nitrogen acid selected from 4-triazole and benzotriazole, a silver salt such as saccharin and 5-chlorosalicylaldoxime, and a silver salt of mercaptides. Among them, preferred silver salts include silver behenate, silver arachidate and silver stearate.
In the present invention, it is preferable that two or more kinds of organic silver salts are mixed in order to enhance developability and to form a high-concentration, high-contrast silver image. For example, a silver ion solution is added to a mixture of two or more kinds of organic acids. Are preferably prepared by mixing.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate, sodium arachidate, etc., the above-mentioned soap and silver nitrate are mixed by a controlled double jet method to produce an organic silver salt crystal. At that time, silver halide grains may be mixed.

The tabular organic silver salt particles according to the present invention are preliminarily dispersed together with a binder, a surfactant and the like, if necessary.
It is preferable to carry out dispersion pulverization with a media disperser or a high-pressure homogenizer. For the above preliminary dispersion, a general stirrer such as an anchor type or a propeller type, a high-speed rotation centrifugal radiation type stirrer (dissolver), and a high-speed rotation shear type stirrer (homo mixer)
Can be used.

Examples of the media dispersing machine include a rolling mill such as a ball mill, a planetary ball mill and a vibrating ball mill, a bead mill as a medium stirring mill, an attritor, and the like.
Other basket mills and the like can be used,
Various types can be used as the high-pressure homogenizer, such as a type that collides with a wall, a plug, or the like, a type in which liquids are divided into a plurality of pieces and then the liquids collide at high speed, and a type that passes through a thin orifice.

In carrying out the above dispersion, the binder concentration is preferably 0.1 to 10% of the mass of the organic silver, and the liquid temperature is preferably not higher than 45 ° C. from the preliminary dispersion to the main dispersion. Preferred operating conditions for the dispersion include, for example, when a high-pressure homogenizer is used as the dispersing means, 29.42 MPa to 98.06 MPa, and the number of times of operation is preferably 2 or more. When using a media dispersing machine as a dispersing means,
Preferred conditions include a peripheral speed of 6 m / sec to 13 m / sec.

In order to prevent devitrification of the light-sensitive material of the present invention,
The total amount of silver halide and organic silver salt is 1 in terms of silver.
It is preferable that the amount is 0.5 g or more and 1.7 g or less per m ² . With this range, a high-contrast image can be obtained.

In the present invention, the biggest difference in the structure of the silver halide silver salt photothermographic dry imaging material compared to the conventional silver halide photographic light-sensitive material is that the latter light-sensitive material has Regardless of before and after processing, a large amount of photosensitive silver halide, silver carboxylate and a developer which may cause fogging and generation of printout silver (printed silver) are contained.
For this reason, silver salt photothermographic dry imaging materials include:
Advanced fog prevention technology and image stabilization technology to maintain storage stability not only before development but also after development are essential, but conventionally, aromatic heterocyclic compounds that suppress the growth and development of fog nuclei In addition, mercury compounds such as mercury acetate, which has the function of oxidizing and eliminating fogging nuclei, have been used as effective storage stabilizers. However, the use of these mercury compounds is a problem in terms of safety / environmental conservation. there were.

The antifoggant and image stabilizer used in the silver salt photothermographic dry imaging material of the present invention will be described below.

In the light-sensitive material, as described below, since a reducing agent having a proton, such as bisphenols or sulfonamidophenols, is mainly used as described below, these hydrogens are extracted. It is preferable that a compound capable of inactivating the reducing agent by generating an active species that can be used is contained. Preferably, as the colorless photo-oxidizable substance, a compound capable of generating a free radical as a reactive species upon exposure is preferable.

Accordingly, any compound having these functions may be used, but an organic free radical comprising a plurality of atoms is preferred. A compound having any structure may be used as long as it has such a function and does not cause any particular adverse effect on the photothermographic material.

The compound capable of generating a free radical may be a carbocyclic or heterocyclic compound so that the generated free radical has such a stability that the free radical can be contacted with a reducing agent for a sufficient time to be inactivated. Those having a cyclic aromatic group are preferred.

Representative of these compounds are the following biimidazolyl compounds and iodonium compounds.

Examples of the biimidazolyl compound include compounds represented by the following general formula [1].

[0190]

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In the formula, each of R ₁ , R ₂ and R ₃ (which may be the same or different) is an alkyl group (for example, a methyl group, an ethyl group, a hexyl group) or an alkenyl group (for example, Vinyl group, allyl group), alkoxy group (for example, methoxy group, ethoxy group, octyloxy group), aryl group (for example, phenyl group, naphthyl group, tolyl group), hydroxyl group, halogen atom, aryloxy group (for example, Phenoxy group), alkylthio group (eg, methylthio group, butylthio group), arylthio group (eg, phenylthio group), acyl group (eg, acetyl group, propionyl group, butyryl group, valeryl group),
A sulfonyl group (eg, a methylsulfonyl group, a phenylsulfonyl group), an acylamino group, a sulfonylamino group, an acyloxy group (eg, an acetoxy group, a benzoxy group), a carboxyl group, a cyano group, a sulfo group, and an amino group. Among these, more preferred substituents are an aryl group, an alkenyl group and a cyano group.

The above biimidazolyl compounds are disclosed in US Pat. No. 3,734,733 and British Patent 1,271,17.
It can be produced by the production method described in No. 7 and a method analogous thereto. Preferred specific examples are shown below.

[0193]

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[0194]

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Further, similarly suitable compounds include iodonium compounds represented by the following general formula [2].

[0196]

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In the formula, Q includes atoms necessary for completing a 5-, 6- or 7-membered ring, and the necessary atoms are selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. R
¹ , R ² and R ³ (same or different) each represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a hexyl group), an alkenyl group (eg, a vinyl group, an allyl group), an alkoxy group (eg, , Methoxy, ethoxy, octyloxy), aryl (for example, phenyl, naphthyl, tolyl), hydroxyl, halogen, aryloxy (for example, phenoxy), alkylthio (for example, methylthio) Group, butylthio group), arylthio group (for example, phenylthio group), acyl group (for example, acetyl group, propionyl group, butyryl group, valeryl group), sulfonyl group (for example, methylsulfonyl group, phenylsulfonyl group), acylamino group, Sulfonylamino group, acyloxy group (for example, acetoxy group, Nzoxy group), carboxyl group, cyano group, sulfo group and amino group. Among these, more preferred substituents are an aryl group, an alkenyl group and a cyano group.

[0198] R ⁴ is acetate, benzoate, carboxylate group such as trifluoroacetate and O ^-
Is shown. W represents 0 or 1.

[0199] X ^- is an anionic counterion, as suitable ^{_{examples, CH 3 CO 2 -, CH}} 3 SO 3 - and PF ₆ ^- is.

The [0200] When R ³ is a sulfo group or a carboxyl group, W is 0, and R ⁴ is O ^-.

Incidentally, any of R ¹ , R ² and R ³ may be bonded to each other to form a ring. Among them, particularly preferred compounds are represented by the following general formula [3].

[0202]

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In the formula, R ¹ , R ² , R ³ , R ⁴ , X ^- and W have the same meaning as in the above formula [2], and Y is a carbon atom (-C
H =; a benzene ring) or a nitrogen atom (-N
=; Pyridine ring).

The above iodonium compounds are described in Org. Sy
n. , 1961 and "Advanced by Fieser
Organic Chemistry "(Reinh
old, N .; Y. , 1961) and a method analogous thereto.

Preferred specific examples are shown below.

[0206]

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[0207]

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The amount of the compound represented by the general formulas [1] and [2] is 0.001 to 0.1 mol / m ² , preferably 0.005 to 0.05 mol / m ² . Range.
The compound can be contained in any of the constituent layers in the light-sensitive material of the present invention, but is preferably contained near the reducing agent.

In the present invention, as the compound that inactivates the reducing agent and prevents the reducing agent from reducing the organic silver salt to silver, it is preferable that the reactive species is not a halogen atom. The compound which releases as an active species can also be used in combination with the compound of the present invention which releases an active species which is not a halogen atom. Many compounds capable of releasing a halogen atom as an active species are known, and a good effect can be obtained by using them in combination.

Specific examples of the compounds which generate these active halogen atoms include the compounds of the following general formula [4].

[0211]

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In the general formula [4], Q represents an aryl group or a heterocyclic group. X ₁ , X ₂ and X ₃ represent a hydrogen atom, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or an aryl group, at least one of which is a halogen atom. Y is -C
(= O) -, - SO- or -SO ₂ - represents a.

The aryl group represented by Q may be monocyclic or condensed, and is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.)
And more preferably a phenyl group and a naphthyl group, and further preferably a phenyl group.

The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one atom of N, O or S, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring.

The heterocyclic group is preferably a 5- or 6-membered unsaturated heterocyclic group optionally having a condensed ring, and more preferably a 5- or 6-membered aromatic group optionally having a condensed ring. Group heterocyclic group. More preferably, it is a 5- or 6-membered aromatic heterocyclic group which may have a condensed ring containing a nitrogen atom, particularly preferably a condensed ring which may have 1 to 4 nitrogen atoms. And a 6-membered aromatic heterocyclic group. As the heterocycle in such a heterocyclic group, preferably, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, tetrazaindene Yes, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benz Thiazole and tetrazaindene, and more preferably imidazole and pyridene. Down, pyrimidine, pyrazine,
Pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole and benzthiazole, particularly preferably pyridine, thiadiazole, quinoline and benzthiazole.

The aryl group and the heterocyclic group represented by Q may have a substituent in addition to -YC (X ₁ ) (X ₂ ) (X ₃ ). Group, alkenyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group,
Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group,
Sulfamoyl group, carbamoyl group, sulfonyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group,
Sulfo group, carboxyl group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric amide group, halogen atom, cyano group, nitro group, heterocyclic group,
More preferred are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group, and a heterocyclic group, and particularly preferred. An alkyl group, an aryl group, and a halogen atom.

X ₁ , X ₂ and X ₃ are preferably a halogen atom, a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group and a heterocyclic group, more preferably A halogen atom, a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a sulfonyl group, more preferably a halogen atom and a trihalomethyl group, and particularly preferably a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

Y is -C (= O)-, -SO-, -SO ₂
- represents preferably -SO ₂ - is.

Specific examples of the compound represented by the general formula [4] are shown below, but the invention is not limited thereto.

[0220]

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[0221]

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[0222]

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[0223]

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[0224]

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[0225]

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[0226]

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[0227]

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The addition amount of these compounds is preferably within a range in which the increase in printout silver due to the formation of silver halide does not cause any problem.
More preferably, it is preferably 100% or less.

In addition to the compounds described above, the silver salt photothermographic dry imaging material of the present invention may contain a compound conventionally known as an antifoggant. The compound may be a compound capable of generating a reactive species or a compound having a different antifogging mechanism. For example, US Pat. No. 3,589,903,
Nos. 4,546,075 and 4,452,885
JP-A-59-57234, U.S. Pat.
4,946, 4,756,999, JP-A-9-
Compounds described in JP-A-288328 and JP-A-9-90550. Further, other antifoggants include compounds disclosed in US Pat. No. 5,028,523 and European Patent Nos. 600,587, 605,981 and 631,176. .

[0230] The reducing agent according to the present invention will be described. Examples of suitable reducing agents incorporated in the silver salt photothermographic dry imaging material of the present invention are described in US Pat. No. 3,770,44.
No. 8, 3,773, 512, 3,593, 8
No. 63 and Research Disclosure
(Hereinafter sometimes abbreviated as RD) 17029 and 2996
3, and can be appropriately selected from known reducing agents. When an aliphatic silver carboxylate is used as the organic silver salt, two or more phenol groups are alkylene groups. Group or a sulfur-linked polyphenol, particularly an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyclohexyl group, etc.) or an acyl group at at least one position adjacent to the hydroxy-substituted position of the phenol group. Bisphenols in which two or more phenol groups substituted with a group (eg, acetyl group, propionyl group, etc.) are linked by an alkylene group or sulfur, for example, a compound represented by the following general formula (A) are preferred.

[0231]

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In the formula, R is a hydrogen atom or a group having 1 carbon atom.
Represents an alkyl group (e.g., an isopropyl group, a butyl group, a 2,4,4-trimethylpentyl group),
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, a t-butyl group, etc.).

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

[0234]

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[0235]

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In addition, US Pat. No. 3,589,903
No. 4,021,249 or British Patent No. 1,
Nos. 486,148 and JP-A-51-51933.
No., No. 50-36110, No. 50-116023,
No. 52-84727 or JP-B-51-35727
Polyphenol compounds, for example, 2,
2'-dihydroxy-1,1'-binaphthyl, 6,6 '
Bisnaphthols described in U.S. Pat. No. 3,672,904, such as -dibromo-2,2'-dihydroxy-1,1'-binaphthyl; furthermore, for example, 4-benzenesulfonamidophenol, 2-benzenesulfone Also mentioned are sulfonamidophenols or sulfonamidonaphthols as described in U.S. Pat. No. 3,801,321 such as amidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 4-benzenesulfonamidonaphthol. I can do it.

The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

The amount of the reducing agent used in the silver salt photothermographic dry imaging material of the present invention varies depending on the kind of the organic silver salt, the reducing agent, and other additives. 0.05 to 10 mol, preferably 0.1 to 10 mol / mol
1-3 moles are suitable. Further, within the range of this amount, two or more of the above-mentioned reducing agents may be used in combination. In the present invention, it is preferable that the reducing agent is added and mixed with a photosensitive emulsion solution composed of photosensitive silver halide and organic silver salt particles and a solvent immediately before coating and coating is performed, because photographic performance fluctuation due to stagnation time is small, which is preferable. is there.

The binder according to the present invention will be described.
Suitable binders for the silver salt photothermographic dry imaging materials 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 , 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 (vinyl chloride) Acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. It may be hydrophilic or non-hydrophilic.

The preferred binder for the photosensitive layer of the photothermographic dry imaging material according to the present invention is polyvinyl acetal, and the particularly preferred binder is polyvinyl butyral. Further, for non-photosensitive layers such as an overcoat layer and an undercoat layer, particularly a protective layer and a backcoat layer, polymers having a higher softening temperature, such as cellulose esters, particularly triacetyl cellulose, and a polymer such as cellulose acetate butyrate. preferable. If necessary, the above-mentioned binders may be used in combination of two or more.

[0241] Such a binder is used in a range effective to function as a binder. Effective ranges can be readily determined by one skilled in the art. For example, as an index when at least the organic silver salt is retained in the photosensitive layer, the ratio of the binder to the organic silver salt is 15: 1 to 1: 2, particularly 8:
A range of 1 to 1: 1 is preferred. That is, the binder amount of the photosensitive layer is preferably 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

The toning agent according to the present invention will be described. Examples of suitable toning agents used in the present invention include:
h Disclosure No. 17029, U.S. Patent Nos. 4,123,282, 3,994,732, 3,846,136 and 4,021,249.
For example, there are the following.

Imides (for example, succinimide, phthalimide, naphthalimide, N-hydroxy-1,8
-Naphthalimide); mercaptans (for example, 3-
Mercapto-1,2,4-triazole); phthalazinone derivatives or metal salts of these derivatives (for example, phthalazinone, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, And 2,3-dihydro-1,4-phthalazinedione); phthalazine and phthalic acids (for example, phthalic acid,
-Methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic acid); phthalazine and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example, phthalic acid) , 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride).
Particularly preferred toning agents are phthalazinone or a combination of phthalazine with phthalic acids and phthalic anhydrides.

As for the color tone of an output image for medical diagnosis, it is said that a cold image tone makes it easier for a reader of an X-ray photograph to obtain a more accurate diagnostic observation result of a recorded image. Here, the cool image tone is a pure black tone or a blue-black tone in which a black image is bluish, and the warm image tone is a warm black tone in which a black image is brownish. Say

The terms “cooler image tone” and “hoter image tone” regarding the color tone are defined as the minimum density Dmin.
And JIS Z 872 at optical density D = 1.0
It is determined by the hue angle “hab” defined by “9”. The hue angle hab is an XYZ color system defined by JIS Z8701 or a tristimulus value X, Y, Z or X10, Y10, Z.
From 10, L * a * specified in JIS Z 8729
hab = tan using color coordinates a * and b * of the b * color system
^-1 (b * / a *).

In the present invention, the preferable range of hab is 180 ° <hab <270 °, more preferably 200 ° <hab <270 °, and most preferably 220 °.
<Hab <260 °.

The dye used in the present invention will be described. In the silver salt photothermographic dry imaging material of the present invention, in order to control the amount or wavelength distribution of light transmitted through the photosensitive layer, a filter layer is formed on the same side as or opposite to the photosensitive layer, or a dye is formed on the photosensitive layer. Alternatively, a pigment is preferably contained.

As the dye used in the present invention, known compounds that absorb light in various wavelength ranges according to the color sensitivity of the light-sensitive material can be used.

For example, when the silver salt photothermographic dry imaging material of the present invention is used as an image recording material by infrared light, a squarylium dye having a thiopyrylium nucleus as disclosed in Japanese Patent Application No. 11-255557. A squarylium dye having a pyrylium nucleus (herein referred to as a pyrylium squarylium dye), a thiopyrylium croconium dye similar to the squarylium dye, or a pyrylium croconium dye Preference is given to using dyes.

The compound having a squarylium nucleus refers to 1-cyclobutene-2-hydroxy- in the molecular structure.
The compound having a 4-one and the compound having a croconium nucleus are compounds having 1-cyclopentene-2-hydroxy-4,5-dione in the molecular structure. Here, the hydroxyl group may be dissociated. Hereinafter, in the present specification, these dyes are collectively referred to as a squarylium dye for convenience.

Among them, the compound represented by formula (B), which is preferably used in the present invention, will be described.

[0252]

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In the formula, R ₁ and R ₂ each represent a substituent. The substituent is not particularly limited, but may be an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, a methoxyethyl group, a methoxyethoxyethyl group,
It is preferably a 2-ethylhexyl group, a 2-hexyldecyl group, a benzyl group, etc.) or an aryl group (eg, a phenyl group, a 4-chlorophenyl group, a 2,6-dimethylphenyl group), and more preferably an alkyl group. Preferably
Particularly preferred is a tertiary butyl group.
R ₁ and R ₂ may form a ring together. m and n each represent an integer of 0 to 4, and preferably 2 or less.
Incidentally, compounds described in JP-A-8-201959 can also be preferably used as the dye.

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

[0255]

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[0256]

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[0257]

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The coating technique used in the present invention will be described. The silver salt photothermographic dry imaging material of the present invention is formed by preparing a coating solution obtained by dissolving or dispersing the above-described constituent layer materials in a solvent, applying a plurality of these coating solutions simultaneously and then performing a heat treatment. Preferably.
Here, “multi-layer coating at the same time” means that a coating solution for each constituent layer (for example, a photosensitive layer and a protective layer) is prepared, and when the coating solution is applied to a support, coating and drying are repeated for each layer individually. In other words, it means that each constituent layer can be formed in a state where the steps of simultaneously performing the multilayer coating and drying can be performed at the same time. That is, the upper layer is provided before the remaining amount of the entire solvent in the lower layer becomes 70% by mass or less.

There are no particular restrictions on the method of simultaneously applying a plurality of constituent layers in a multi-layered manner. For example, known methods such as a bar coater method, a curtain coat method, an immersion method, an air knife method, a hopper application method, and an extrusion application method. Can be used. Of these, a pre-metering type coating method called an extrusion coating method is more preferable. The extrusion coating method is suitable for precision coating and organic solvent coating since there is no volatilization on the slide surface unlike the slide coating method. This coating method has been described on the side having the photosensitive layer, but the same applies to the case where the backcoat layer is provided and the coating is performed together with the undercoating.

The development conditions applied to the silver salt photothermographic dry imaging material of the present invention will be described.

In the present invention, the development conditions vary depending on the equipment, apparatus, or means used, but typically the photothermographic dry imaging material exposed imagewise at a suitable high temperature is heated. Accompanies you. The latent image obtained after the exposure has a moderately high temperature (for example, about 80 to 200 ° C.,
The photothermographic material can be developed by heating the photothermographic material at a temperature of preferably about 100 to 200 ° C. for a sufficient time (generally about 1 second to about 2 minutes).

If the heating temperature is lower than 80 ° C., a sufficient image density cannot be obtained in a short time, and if the heating temperature is higher than 200 ° C., the binder is melted and transferred to a roller. Also has an adverse effect. By heating, a silver image is generated by an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This reaction process proceeds without any supply of a processing liquid such as water from the outside.

The apparatus, apparatus or means for heating may be performed by a typical heating means such as a hot plate, an iron, a hot roller, or a heat generator using carbon or white titanium. More preferably, in the photothermographic material provided with the protective layer according to the present invention, the surface on the side having the protective layer is brought into contact with a heating means to perform heat treatment. It is preferable from the viewpoint of properties and the like, and it is preferable that the surface is conveyed while being in contact with a heat roller, subjected to heat treatment, and developed.

The exposure conditions for recording on the silver salt photothermographic dry imaging material of the present invention will be described.

For the exposure of the silver salt photothermographic dry imaging material of the present invention, it is desirable to use a light source appropriate for the color sensitivity imparted to the photosensitive material. For example, when the light-sensitive material can be sensed by infrared light, the light-sensitive material can be applied to any light source in the infrared light range, but the laser power is high and the light-sensitive material can be made transparent. From these points, an infrared semiconductor laser (780 nm, 820 nm) is more preferably used.

In the present invention, the exposure is preferably performed by laser scanning exposure, but various exposure methods can be employed. For example, as a first preferred method,
There is a method using a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular.

Here, "not substantially vertical" means that the angle is most vertical during laser scanning, preferably 55 to 88 degrees, more preferably 60 to 86 degrees, and still more preferably. Is 65 degrees or more and 84 degrees or less,
Most preferably, it is not less than 70 degrees and not more than 82 degrees.

When a laser beam is scanned on the photosensitive material, the beam spot diameter on the exposed surface of the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. This is preferable because the smaller the spot diameter is, the less the angle of deviation of the laser incident angle from the vertical can be reduced. In addition,
The lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of interference fringe-like unevenness.

As a second method, it is preferable that the exposure in the present invention is performed by using a laser scanning exposure machine that emits a scanning laser beam that is a multi-scan. Image quality deterioration such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode.

[0270] In order to form the vertical multiple, a method such as multiplexing, using return light, or superimposing a high frequency is preferable.
In addition, the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more.
nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

Further, as a third mode, it is preferable to form an image by scanning exposure using two or more lasers.

As an image recording method using such a plurality of lasers, an image writing means of a laser printer or a digital copying machine for writing an image by a plurality of lines in one scan due to a demand for higher resolution and higher speed. This is a technique used and is known, for example, from JP-A-60-166916. This is a method in which a laser beam emitted from a light source unit is deflected and scanned by a polygon mirror to form an image on a photoreceptor via an fθ lens or the like. This is a laser scanning optical system which is basically the same as a laser imager and the like. Device.

The image formation of the laser beam on the photosensitive member in the image writing means of the laser printer or the digital copier is performed from the image formation position of one laser beam for the purpose of writing an image by a plurality of lines in one scan. The next laser light is imaged shifted by one line. Specifically, the two light beams are close to each other at an interval of several tens of μm on the image plane in the sub-scanning direction, and have a print density of 400 dpi (in the present invention, 1 inch or 2.54 cm per inch). The dot printing density is defined as dpi (dot per inch), and the pitch of the two beams in the sub-scanning direction is 6
3.5 μm, 42.3 μm at 600 dpi. Unlike such a method in which the resolution is shifted by the resolution in the sub-scanning direction, the present invention is characterized in that two or more lasers are condensed on the exposure surface at the same location by changing the incident angle to form an image. In this case, one ordinary laser (wavelength λ [n
m]), the exposure energy on the exposure surface is E
When N lasers used for exposure have the same wavelength (wavelength λ [nm]) and the same exposure energy (En), 0.9 × E ≦ En × N ≦ 1.1 × E It is preferred to be within the range. By doing so, energy is secured on the exposed surface, but the reflection of each laser beam to the image forming layer is reduced due to the low exposure energy of the laser, and thus the generation of interference fringes is suppressed.

[0274]

Hereinafter, the present invention will be described with reference to examples.
The present invention is not limited to these.

Example 1 [Preparation of Subbed Photographic Support] <Preparation of PET Subbed Photographic Support> Commercially available biaxially stretched heat-fixed 175 μm thick, 0.170 optical density
(Measured with a densitometer PDA-65 manufactured by Konica Corp.) 8 W / m ^{2 on} both sides of a blue colored PET film
・ A corona discharge treatment is performed for one minute, and the undercoating coating liquid a-1 shown below is applied to one surface so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The surface was coated with the following undercoating coating solution b-1 so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl Acrylate (30% by Mass) T-Butyl Acrylate (20% by Mass) Styrene (25% by Mass) 2-Hydroxyethyl Acrylate (25% by Mass) Copolymer Latex Solution (Solid content: 30%) 270 g C-1 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << Subtraction coating solution b-1 >> Butyl acrylate (40% by mass) Styrene (20% by mass) Copolymer latex liquid of glycidyl acrylate (40% by mass) (solid content: 30%) 270 g C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g To 1 liter with water Finishing The upper surface of the undercoat layer A-1 and the undercoat layer B-1 is subjected to a corona discharge of 8 W / m ² · min.
1 was coated with the following undercoating upper layer coating solution a-2 having a dry film thickness of 0.
The undercoating layer B-2 is formed as the undercoating upper layer A-2 so as to have a thickness of 1 μm.
1 was coated with the following undercoating upper layer coating solution b-2 with a dry film thickness of 0.8.
The coating was applied as a subbing upper layer B-2 having an antistatic function so as to have a thickness of μm.

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

[0278]

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[0279]

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<< Coating on Back Side >> While stirring 830 g of methyl ethyl ketone (MEK), cellulose acetate butyrate (Eastman Chemical) was used.
Co., CAB381-20) 84.2 g and polyester resin (Bostic, VitelPE2200B)
4.5 g were added and dissolved. Next, in the dissolved solution,
0.30 g of infrared dye 1 was added, and methanol 4 was added.
4.5 g of F-based activator (Asahi Glass Co., Surflon KH40) dissolved in 3.2 g and 2.3 g of F-based activator (Dainippon Ink Co., Ltd., Megafag F120K) were added and sufficiently stirred until dissolved. Was. Lastly, silica (WR Grace, Syloid 64 × 6) dispersed in methyl ethyl ketone at a concentration of 1% by mass with a dissolver-type homogenizer.
000) was added and stirred to prepare a coating solution for the back surface side.

[0281]

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The back surface coating solution thus prepared was
Coating and drying were performed with an extrusion coater so that the dry film thickness became 3.5 μm. Drying temperature 100 ° C, dew point 1
It dried for 5 minutes using the drying air of 0 degreeC.

<< Preparation of Photosensitive Silver Halide Emulsion A >> (A1) Phenylcarbamoylated gelatin 88.3 g Compound (A) (10% aqueous methanol solution) 10 ml Potassium bromide 0.32 g Finish up to 5429 ml with water (B1) 0 2.67 mol / L silver nitrate aqueous solution 2635 ml (C1) Potassium bromide 51.55 g Potassium iodide 1.47 g Make up to 660 ml with water (D1) Potassium bromide 154.9 g Potassium iodide 4.41 g Iridium chloride (1% solution) 0 .93 ml with water to make 1982 ml (E1) 0.4 mol / L aqueous potassium bromide solution Silver potential control amount below (F1) Potassium hydroxide 0.71 g Finish with water to 20 ml (G1) 56% acetic acid aqueous solution 18.0 ml (H1 ) Anhydrous sodium carbonate 1.72g Finished to 151ml with water That 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) Japanese Patent Publication No. 58-58288 The solution (B1) was added to the solution (A1) using a mixing stirrer shown in JP-A-58-58289.
を amount and the whole amount of the solution (C1) at a temperature of 45 ° C. and pAg
While controlling at 8.09, the mixture was added by the simultaneous mixing method in 4 minutes and 45 seconds to form nuclei. One minute later, the solution (F
The whole amount of 1) was added. Adjustment of pAg during this time (E1)
Was performed as appropriate. After a lapse of 6 minutes, the solution (B1) 3
/ 4 amount and the total amount of the solution (D1) at a temperature of 45 ° C. and pAg
While controlling to 8.09, 14 minutes 15
It was added over seconds. After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (G1) was added to precipitate a silver halide emulsion. The supernatant was removed except for 2000 ml of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. Leaving 1500 ml of sedimentation,
The supernatant was removed, and 10 liters of water was further added. After stirring, the silver halide emulsion was settled. Settling part 1500
After removing the supernatant liquid while leaving the ml, the solution (H1) 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 the pH was adjusted to 1 per mole of silver.
Water was added so as to be 161 g to obtain a photosensitive silver halide emulsion A. This emulsion had an average grain size of 0.058μ.
m, coefficient of variation of particle size 12%, [100] face ratio 9
It was 2% monodispersed cubic silver iodobromide grains.

<< Preparation of Photosensitive Silver Halide Emulsion B >> One part of the solution (B1) was added to the solution (B1) using a mixing stirrer described in JP-B-58-58288 and JP-B-58-58289.
/ 4 amount and the whole amount of the solution (C1) at a temperature of 40 ° C., pAg8.
While controlling to 09, the addition was carried out by the simultaneous mixing method in 4 minutes and 45 seconds to form nuclei. One minute later, the entire amount of the solution (F1) was added. During this time, pAg was appropriately adjusted using (E1). After a lapse of 6 minutes, 3/4 of the solution (B1) and the entire amount of the solution (D1) were heated at a temperature of 45 ° C. and a pAg of 8.0.
While controlling to 9, the mixture was added over 14 minutes and 15 seconds by the double jet method. After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (G1) was added to precipitate a silver halide emulsion. The supernatant was removed except for 2000 ml of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. The supernatant was removed, leaving 1500 ml of sedimentation, 10 liters of water was added, and after stirring,
The silver halide emulsion was allowed to settle. Settling portion 1500ml
After removing the supernatant, the solution (H1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally p
H was adjusted to 5.8, and 11 per mole of silver
Water was added so as to be 61 g to obtain a photosensitive silver halide emulsion B. This emulsion had an average grain size of 0.048μ.
m, coefficient of variation of particle size 15%, [100] face ratio 8
It was 8% monodispersed cubic silver iodobromide grains.

<< Preparation of Powdered Organic Silver Salt A >> Behenic acid 130.8 g and arachidic acid 67.7 in 4720 ml of pure water.
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 M aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the above fatty acid sodium solution at 55 ° C., 45.3 g of the above-mentioned photosensitive silver halide emulsion A and 450 ml of pure water were added and stirred for 5 minutes.

Next, 702.6 ml of a 1 M silver nitrate solution was added to 2
And the mixture was 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 draining are repeated until the conductivity of the waste water reaches 2 μS / cm, and centrifugal dehydration is performed. Seisin Company)
Was dried under a nitrogen gas atmosphere and operating conditions of hot air temperature at the entrance of the dryer until the water content became 0.1% to obtain a dried organic silver salt A of an organic silver salt. In addition, an infrared moisture meter was used for measuring the water content of the organic silver salt composition.

<< Preparation of Powdered Organic Silver Salt B >> Powdered organic silver salt B was prepared using photosensitive silver halide emulsion B instead of photosensitive silver halide emulsion A.

<< Preparation of Preliminary Dispersion A >> Polyvinyl butyral powder (Butvar B- manufactured by Monsanto)
79) 14.57 g was dissolved in 1457 g of methyl ethyl ketone, and a dissolver DI manufactured by VMA-GETZMANN was used.
Preliminary dispersion liquid A was prepared by gradually adding 500 g of powdered organic silver salt A while stirring with a SPERMAT CA-40M type, and mixing well.

<< Preparation of Preliminary Dispersion B >> Preparative dispersion B was prepared using B instead of powdered organic silver salt A. << Preparation of Photosensitive Emulsion Dispersion 1 >> The preparatory dispersion A was prepared by using a pump so that the residence time in a mill was 1.5 minutes.
Media type disperser DISPERM filled with zirconia beads (Toray Treceram) having a diameter of 5 mm and an inner volume of 80%.
AT SL-C12EX type (VMA-GETZMANN
The emulsion was dispersed at a mill peripheral speed of 8 m / s to prepare a photosensitive emulsion dispersion liquid 1.

<< Preparation of Photosensitive Emulsion Dispersion 2 >> A photosensitive emulsion dispersion 2 was prepared using B in place of the preliminary dispersion A.

<< 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 Liquid >> 19.2 mg of infrared sensitizing dye 1, 1.488 g of 2-chloro-benzoic acid, 2.779 g of stabilizer 2, and 365 mg of 5-methyl-2 31.3 ml of mercaptobenzimidazole
Was dissolved in MEK (methyl ethyl ketone) in a dark place to prepare an infrared sensitizing dye solution.

<< Preparation of Additive Solution a >> 1,1 as a developer
-Bis (2-hydroxy-3,5-dimethylphenyl)
27.98 g of -2-methylpropane (A-3) and 1.
54 g of 4-methylphthalic acid and 0.48 g of the infrared dye 1 were dissolved in 110 g of MEK (methyl ethyl ketone) to prepare an additive liquid a.

<< Preparation of Additive Solution b >> 3.56 g of the antifoggant 2, 3.43 g of phthalazine were dissolved in 40.9 g of MEK (methyl ethyl ketone) to obtain an additive solution b.

<< Preparation of Photosensitive Layer Coating Solutions 101 to 106 >> In an inert gas atmosphere (nitrogen 97%), the photosensitive emulsion dispersion liquid 1 (50 g) and 15.11 g of MEK (methyl ethyl ketone) were stirred at 21 ° C. Keep warm, Table 1
Organic sensitizer (0.5% methanol solution) 100
0 μl was added, and 2 minutes later, 390 μl of antifoggant 1 (10% methanol solution) was added, followed by stirring for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes. Then, 167 ml of stabilizer liquid
After stirring for 10 minutes, 1.32 g of the infrared sensitizing dye solution was added, followed by stirring 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 (Monsanto)
After adding 13.31 g of Butvar B-79) and stirring for 30 minutes, 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added and stirred for 15 minutes. While further stirring, 12.43 g of additive solution a, 1.6 ml of Desmodur N3300 (10% MEK solution of aliphatic isocyanate manufactured by Mobay),
4.27 g of the additive solution b and the silver saving agent shown in Table 1 were sequentially added and stirred to obtain photosensitive layer coating solutions 101 to 106.

<< Preparation of Photosensitive Layer Coating Solution 107 >> The photosensitive emulsion coating solution 10 was prepared using
7 was prepared.

<< Preparation of Matting Agent Dispersion >> Cellulose acetate butyrate (Eastman Chemical)
Co., Ltd., 7.5 g of CAB171-15) was dissolved in 42.5 g of MEK (methyl ethyl ketone), and calcium carbonate (Specialty Minerals) was added thereto.
Co., Ltd., Super-Pflex 200) was added, and the mixture was treated with a dissolver-type homogenizer at 8000 rpm for 30 minutes.
The mixture was dispersed for a minimum to prepare a matting agent dispersion.

<< Preparation of Coating Solution for Surface Protection Layer >> While 865 g of MEK (methyl ethyl ketone) was stirred, cellulose acetate butyrate (Eastman Chemical) was used.
al, CAB171-15), 96 g, polymethylmethacrylic acid (Rohm & Haas, Paraloid A-21)
4.5 g, and 1.5 g of a vinyl sulfone compound (VSC).
g, benzotriazole (1.0 g) and an F-based activator (Asahi Glass Co., Ltd., Surflon KH40) were added and dissolved. Next, 30 g of the above matting agent dispersion was added and stirred,
A coating solution for the surface protective layer was prepared.

[0299]

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<< Preparation of photosensitive material >> The photosensitive layer coating solution 10
The photosensitive material 101 was prepared by simultaneously applying the coating solution 1 and the coating solution for the surface protective layer on the reverse side of the back surface coating using an extrusion coater. The photosensitive layer is coated with 1.5 g of silver.
/ M ² , and the surface protective layer was applied so as to have a dry film thickness of 2.5 μm. After that, drying temperature 75 ° C, dew point temperature 10
Drying was performed for 10 minutes using a drying air at ℃.

Next, except that each of the photosensitive layer coating solutions 102 to 107 was used instead of the photosensitive layer coating solution 101,
In the same manner as in the production of the photosensitive material 101, the photosensitive materials 102 to
107 was produced.

<< Evaluation of Photographic Performance >> Photosensitive Materials 101 to 10
7 and processed by the following method to perform sensitometry. The light-sensitive materials 101 to 107 were kept at 25 ° C. and 55% RH at a temperature and humidity of 10% after application, and were allowed to stand at room temperature for DryPro.
Exposure was performed stepwise using 722 (manufactured by Konica Corporation) while reducing the amount of exposure energy by 0.05 logE for each step from the maximum output, developing temperature 123 ° C., processing time 1
The self-developing process was performed in 3.5 seconds. The obtained sensitometry sample was subjected to a PDM65 transmission densitometer (manufactured by Konica Corporation).
Was used to measure the concentration, and the measurement result was processed by a computer to obtain a characteristic curve. For the sensitivity, an exposure amount that gives an optical density higher than Dmin by 1.0 is obtained, and the exposure amount of each sample and the sample N
o. Table 1 shows the reciprocal of the ratio of the exposure amount 101.

<< Evaluation of Photosensitive Silver Halide Particle Ratio Not in Contact with Developed Silver After Thermal Development >> As described above, JEM-2000FX manufactured by JEOL Ltd. was used as a TEM (transmission electron microscope). The acceleration voltage is 200kV
The raw film has a particle count of 1 or more, and the developed film has a particle count of 1 or more.
Photographing was performed at 5,000 times so that the number was 00 or more. The observation and photographing were performed by cooling to -120 ° C.
Measure the thickness of the section taken as described above,
The number of silver halide per 1 μm ^{2 and the} like were calculated. The results are summarized in Table 1.

<< Measurement of Covering Power >> The value obtained by dividing the maximum density of the photosensitive material prepared above by the amount of silver applied is referred to as covering power. Assuming that the value of the photosensitive material 101 is 100,
Table 1 shows the relative values of each.

Table 1 shows the results obtained above.

[0306]

[Table 1]

From Table 1, it is clear that the sample of the present invention is a good photographic material having sufficient sensitivity, high covering power and low fog compared to the comparative sample.

Example 2 << Preparation of Photosensitive Material 200 >> (Preparation of Photosensitive Layer Coating Solution A) In an inert gas atmosphere (nitrogen 9
7%), the above-mentioned photosensitive emulsion dispersion liquid 1 (50 g) and 15.11 g of methyl ethyl ketone (MEK) were kept at 21 ° C. while stirring, and the organic sensitizer S-5 containing a chalcogen atom (0.5% methanol) was stirred. Solution) (1000 μl), and 2 minutes later, 390 μl of antifoggant 1 (10% methanol solution) was added, followed by stirring for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 10 minutes. Then, a gold sensitizer Au-5 corresponding to 1/20 mol of the organic sensitizer was added, and the mixture was further stirred for 20 minutes. Subsequently, 167 ml of the stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the 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 maintaining the temperature at 13 ° C, polyvinyl butyral (Monsanto Butvar)
B-79) After adding 13.31 g and stirring for 30 minutes, tetrachlorophthalic acid (9.4 mass% MEK solution)
1.084 g was added and stirred for 15 minutes. While further stirring, 12.43 g of additive liquid a, 1.6 ml of Desmodur N3300 / Mobay's aliphatic isocyanate (10% MEK solution), additive liquid b, silver saving agent H-1-5 (440 mg) ), Image stabilizer BI-4
(2500 mg) and I-1 (300 mg) were sequentially added and stirred to obtain a photosensitive layer coating solution A.

[0309]

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(Preparation of Matting Agent Dispersion) Cellulose acetate butyrate (Eastman Chemical)
Co., Ltd., 7.5 g of CAB171-15) was dissolved in 42.5 g of MEK (methyl ethyl ketone), and calcium carbonate (Specialty Minerals) was added thereto.
5 g of Super-Pflex 200) and 30 mi at 8000 rpm using a dissolver-type homogenizer.
n was dispersed to prepare a matting agent dispersion.

(Preparation of Surface Protective Layer Coating Solution) While stirring 865 g of MEK (methyl ethyl ketone), cellulose acetate butyrate (Eastman Chemical) was used.
al, CAB171-15), 96 g, polymethylmethacrylic acid (Rohm & Haas, Paraloid A-21)
4.5 g, and 1.5 g of a vinyl sulfone compound (VSC).
g, benzotriazole (1.0 g) and an F-based activator (Asahi Glass Co., Ltd., Surflon KH40) (1.0 g) were added and dissolved. Next, 30 g of the above matting agent dispersion was added and stirred,
A coating solution for the surface protective layer was prepared.

The photosensitive layer coating solution A and the surface protective layer coating solution obtained above were extruded (extrusion) shown in FIG.
A photosensitive material 200 was prepared by simultaneously coating two layers, photosensitive layer A and one protective layer, using a coater. The coating was performed such that the photosensitive layer A had a coated silver amount of 2.0 g / m ² and the surface protective layer had a dry film thickness of 2.5 μm. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 50 ° C and a dew point temperature of 10 ° C.

<< Preparation of Photosensitive Material 201A >> (Preparation of Photosensitive Layer Coating Solution B) In an inert gas atmosphere (nitrogen 9
7%), the above-mentioned photosensitive emulsion dispersion liquid 1 (50 g) and 15.11 g of MEK (methyl ethyl ketone) were kept at 21 ° C. while stirring to obtain an organic sensitizer S-5 containing a chalcogen atom (0.5% methanol). Solution) 1000 μl
Was added, and 2 minutes later, 390 μl of antifoggant 1 (10% methanol solution) was added, and the mixture was stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 10 minutes. Then, a gold sensitizer Au-5 corresponding to 1/20 mol of the organic sensitizer was added, and the mixture was further stirred for 20 minutes. Subsequently, 167 ml of a stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the 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 (Monvarto Butvar B)
-79) After adding 13.31 g and stirring for 30 minutes, tetrachlorophthalic acid (9.4 mass% MEK solution) 1.0
84 g was added and stirred for 15 minutes. While further stirring, 12.43 g of additive solution a, 1.6 ml of Des
modurN3300 / Mobay's aliphatic isocyanate (10% MEK solution) and additive solution b were sequentially added,
The photosensitive layer coating liquid B was obtained by stirring.

(Preparation of Photosensitive Layer Coating Solution C) The above photosensitive emulsion dispersion 1 was prepared under an inert gas atmosphere (nitrogen: 97%).
(50 g) and MEK (methyl ethyl ketone) 15.
While stirring 11 g, the temperature was kept at 21 ° C. with stirring, and the chemical sensitizer S-
5 (0.5% methanol solution) 1000 μl,
After 1 minute, antifoggant 1 (10% methanol solution) 390
μl was added and stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 10 minutes. Then, a gold sensitizer Au-5 corresponding to 1/20 mol of the organic sensitizer was added, and the mixture was further stirred for 20 minutes. Subsequently, 167 ml of a stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the infrared sensitizing dye solution was added and stirred for 1 hour. Then, the temperature was lowered to 13 ° C.
Stirred for 0 minutes. While keeping the temperature at 13 ° C., polyvinyl butyral (Butvar B-7 from Monsanto)
9) After adding 13.31 g and stirring for 30 minutes, tetrachlorophthalic acid (9.4 mass% MEK solution) 1.084
g was added and stirred for 15 minutes. While further stirring, 12.43 g of additive solution a, 1.6 ml of Desmo
durN3300 / Mobay's aliphatic isocyanate (10% MEK solution), 4.27 g of additive solution b, no silver saving agent added, image stabilizer BI-4 (2500 m
g) and I-1 (300 mg) were sequentially added and stirred to obtain a photosensitive layer coating solution C.

The photosensitive layer coating solution B and photosensitive layer coating solution C obtained above and the surface protective layer coating solution described above were coated with the photosensitive layer B, photosensitive layer C and protective layer using an extrusion (extrusion) coater shown in FIG. A total of three layers, one layer, were coated simultaneously to form a photosensitive material 201A. The coating amount of the photosensitive layer B was 0.7 g / m ² , the thickness of the photosensitive layer C was 0.3 g / m ² , and the thickness of the surface protective layer was 2.5
μm. Then, drying temperature 50
Drying was performed for 10 minutes using a drying air at 10 ° C. and a dew point temperature of 10 ° C.

<< Preparation of Photosensitive Material 201B >> The photosensitive layer coating solution B, photosensitive layer coating solution C, and surface protective layer coating solution described above were coated with the photosensitive layer B and the protective layer using an extrusion (extrusion) coater shown in FIG. A photosensitive material 201B is prepared by simultaneously applying a total of two layers, one layer in total, and further simultaneously applying a total of two layers, a photosensitive layer C and a protective layer, to the opposite side of the coated surface across the support. did. The coating was performed such that the photosensitive layer B had a coated silver amount of 0.7 g / m ² , the photosensitive layer C had a coated silver amount of 0.3 g / m ² , and the surface protective layer had a dry film thickness of 2.5 μm. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 50 ° C and a dew point temperature of 10 ° C.

<< Photosensitive Materials 202A, 203A, 204
A, 205A> The above photosensitive materials were each produced in the same manner as in the production of the photosensitive material 201A, except that the chalcogen sensitizer, the silver saving agent, and the image stabilizer were changed as shown in Table 2.

<< Photosensitive Materials 202B, 203B, 204
Preparation of B and 205B >> Each of the above photographic materials was prepared in the same manner as the preparation of the photographic material 201B except that the chalcogen sensitizer, the silver saving agent and the image stabilizer were changed as shown in Table 2.

Note that each sample No. When the support has two or more emulsion layers on one side of the support, A is added at the end of the number, and when the support has photosensitive layers on both sides, B is added at the end of the number.

For each of the photosensitive materials obtained above,
The sensitivity and fog were measured in the same manner as in Example 1, and the image storability was evaluated using the following method.

<< Evaluation of Image Preservation Property >> In the same manner as in the evaluation of photographic performance described in Example 1, the coated photosensitive material was left to stand at 25 ° C. and 55% RH for 10 days after coating, and then developed. After being left under a fluorescent lamp at 25 ° C. and 55% RH for 7 days, the color tone was observed and evaluated based on the following criteria. This is also shown in Table 2.

Rank Evaluation criteria (visual evaluation) 5 No problem color tone 4 Color tone without practical problem 3 Slightly yellowish color, but no problem color tone 2 Unpleasant color tone, may be problematic Color tone 1 A remarkable change was recognized, and the color tone became a problem in practice. The obtained results are shown in Table 2.

[0323]

[Table 2]

From Table 2, it is clear that the sample of the present invention has higher sensitivity, lower fog, and better image storability than the comparative sample. The sample of the present invention is JIS
When the value of the hue angle specified by Z8729 exceeds 180 °,
In addition, it was found to be less than 270 °, to have a cool image tone, and to obtain an appropriate output image as a diagnostic image.

[0325]

According to the present invention, it is possible to provide a silver salt photothermographic dry imaging material having excellent stability of a silver image after thermal development, and an image recording method and an image forming method using the same.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a coating apparatus used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 coating backup roll 3 coating die 4 coating liquid P liquid sending pump

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03B 27/32 G03B 27/32 H G03C 5/08 351 G03C 5/08 351

Claims (9)

[Claims] 1. A silver salt photothermographic dry imaging method having a photosensitive layer containing organic silver salt particles, photosensitive silver halide particles and a solvent, a photosensitive layer containing a reducing agent and a binder, and a non-photosensitive layer on a support. In the material, at least one of the photosensitive layer and the non-photosensitive layer contains a silver saving agent, and the photosensitive silver halide grains are subjected to chalcogen sensitization using an organic sensitizer containing a chalcogen atom, When the silver salt photothermographic dry imaging material was exposed at an exposure amount of 280 μJ / cm ² and heat-developed at 123 ° C. for 16.5 seconds,
A silver salt photothermographic dry imaging material characterized in that 25% by number or less of the photosensitive silver halide particles having a particle size in the range of 10 nm to 50 nm do not contact developed silver. 2. The silver salt photothermographic dry imaging material according to claim 1, wherein the material has two or more photosensitive layers. 3. A compound generating a reactive species capable of oxidizing silver by exposure to ultraviolet light or visible light, and a reactive activity for inactivating a reducing agent so that silver ions of an organic silver salt cannot be reduced to silver. 2. The silver salt photothermographic dry imaging material according to claim 1, wherein the silver salt photothermographic material contains at least two compounds selected from the group consisting of seed-generating compounds. 4. The silver according to claim 1, wherein the organic sensitizer is a compound having a group capable of adsorbing to silver halide grains and an unstable chalcogen atom site. Salt photothermographic dry imaging material. 5. The compound according to claim 1, wherein the organic sensitizer has a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond. Silver salt photothermographic dry imaging materials. 6. A method according to claim 1, wherein the organic silver salt particles are a mixture of silver salts of at least two kinds of organic acids.
The silver salt photothermographic dry imaging material according to any one of the above items. 7. When recording an image on the silver halide photothermographic dry imaging material according to any one of claims 1 to 6, the exposure is performed using a laser beam scanning exposure machine in which the scanning laser beam is a double beam. Performing an image recording method. 8. When an image is recorded on the silver halide photothermographic dry imaging material according to claim 1, the exposure is performed using a laser light scanning exposure device in which the scanning laser light is a vertical multi. An image recording method characterized by performing. 9. The silver salt photothermographic dry imaging material according to claim 1, wherein the material is a silver salt photothermographic dry imaging material.
An image forming method comprising the steps of: performing image recording using the image recording method described in (1), performing a heat development process, and then satisfying the following expression (1) with a hue angle hab defined by JIS Z8729. Formula (1) 180 ° <hab <270 °