JP2005106927A - Silver salt photothermographic dry imaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver salt photothermographic dry imaging material excellent in storage stability while having high sensitivity and low fog, wherein a silver image after heat development has a good color tone and is excellent particularly in storage stability, with a relatively small amount of silver used. <P>SOLUTION: The silver salt photothermographic dry imaging material contains nonphotosensitive silver salt of aliphatic carboxylic acid particles, photosensitive silver halide grains, a silver ion reducing agent and a binder, wherein a photographic speed (2) of the material is not more than 1/10 of a photographic speed (1) of the material determined under specified conditions, and the coefficient of determination value R<SP>2</SP>of the linear regression line is 0.998-1.000, which is obtained from the predetermined density points having a* and b* arranged in two-dimensional coordinates in which a* is used as the abscissa and b* is used as the ordinate of the CIE 1976(L*a*b*) color space, b* of the intersection point of the linear regression line with the ordinate is -5 to 5, and gradient (b*/a*) is 0.7-2.5. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver salt photothermographic dry imaging material.

  In recent years, in the fields of medical treatment and printing plate making, reduction of waste liquid accompanying wet processing of image forming materials has been strongly desired from the viewpoint of environmental protection and space saving.

  Therefore, technology related to photothermographic dry imaging materials for photographic technology that enables efficient exposure and can form clear black images with high resolution, such as laser imagers and laser imagesetters, is required. It has been said that.

  Examples of the technique relating to the photothermographic material include D.I. Morgan and B.M. U.S. Pat. Nos. 3,152,904, 3,487,075 by Shely or D.C. H. As described in "Dry Silver Photographic Materials" by Klosterboer (Handbook of Imaging Materials, Organics of Markel, Inc., page 48, 1991) and the like. Silver salt photothermographic dry imaging materials containing a silver salt, a photosensitive silver halide and a reducing agent are known. Since this silver salt photothermographic dry imaging material does not use any solution processing chemicals, it has an advantage that it can provide a user with a simpler system that does not impair the environment.

  These silver salt photothermographic dry imaging materials use photosensitive silver halide particles placed in the photosensitive layer as a photosensor, use organic silver salt as a source of silver ions, and are usually 80 to 80% depending on a built-in reducing agent. It is characterized in that an image is formed by heat development at 140 ° C. and fixing is not performed.

  However, since the silver salt photothermographic dry imaging material contains an organic silver salt, photosensitive silver halide grains and a reducing agent, fog is likely to occur during the storage period before thermal development. In addition, after the exposure, usually, heat development is usually performed at 80 to 250 ° C., and fixing is not performed. Therefore, even after heat development, all or part of silver halide, organic silver salt, reducing agent, etc. remain, In the storage process of the period, metallic silver is generated by heat and light, and there is a problem that the image quality such as the color tone of the silver image is easily changed.

  Techniques for solving these problems are cited in, for example, Cited Document 1, Cited Document 2, US Pat. No. 5,714,311, European Patent 1,096,310, and these patent documents. It is disclosed in the literature. However, although many of these disclosed technologies exhibit a certain degree of effect, they are not yet sufficient as technologies for satisfying the level required in the market.

  Further, in the research process of the inventors of the present application, the photosensitive silver halide grains contained in the silver salt photothermographic dry imaging material are reduced in size for the purpose of increasing the silver coverage (covering power, CP). When the number is increased, the color tone may deteriorate due to a shape change such as a reduction in the particle size of developed silver (cluster of silver atoms) formed by the development process, and the silver image after development It has been found that there is a problem that fluctuation and deterioration of the color tone of the silver image is further increased due to the influence of light received by the photosensitive silver halide grains during storage and observation.

  Further, techniques for using a chromogenic leuco dye or the like to correct and adjust the color tone of a silver image due to the shape of developed silver to a preferable color tone are disclosed in JP-A-50-36110, JP-A-59-206831, and JP-A-5-20631. Although disclosed in Japanese Patent Nos. 204087, 11-231460, JP-A Nos. 2002-169249, 2002-236334, etc., depending on these correction techniques, it is possible to prevent temporal changes in color tone during storage. I have also found that I can't do it enough.

  In addition, as a technique for preventing the fluctuation and deterioration of the silver image due to the influence of the light described above, conventionally, a halogen compound that oxidizes silver by light induction, which will be described later, is used. 4 and Japanese Patent Application Laid-Open No. 50-120328. However, these compounds generally have a propensity to develop an oxidation function even by thermal decomposition, and thus have the effect of preventing the formation and growth of fog. It has also become clear that there are drawbacks that cause adverse effects such as reducing the coverage.

  On the other hand, as a so-called eternal theme for silver salt photothermographic dry imaging materials, there is a demand for higher image quality. In particular, in the field of medical images, there is a demand for the development of high image quality technologies including the color tone of silver images to enable more accurate diagnosis.

Accordingly, there is a demand for the development of a new and dramatic improvement in image quality that can overcome the above-mentioned essential problems of the imaging material and the drawbacks of the conventional techniques.
JP-A-6-208192 JP-A-8-267934 Japanese Patent Laid-Open No. 7-2781 JP-A-6-208193

  The present invention has been made in view of the above-described background circumstances, and the object thereof is high sensitivity and low fog, excellent storage stability, and good color tone of a silver image after heat development and storage. An object of the present invention is to provide a silver salt photothermographic dry imaging material which is particularly excellent in stability and uses a relatively small amount of silver.

The above object of the present invention has been achieved by adopting any of the following means.
[Claim 1]
In a silver salt photothermographic dry imaging material containing a non-photosensitive aliphatic carboxylic acid silver salt particle, a photosensitive silver halide particle, a silver ion reducing agent and a binder, the material has a sensitivity (2 ) Is 1/10 or less of the sensitivity (1), and each of the optical density 0.5, 1.0, 1.5 and the lowest optical density of the silver image obtained by thermally developing the dry imaging material to determine the concentration, the horizontal axis of the ^{CIE 1976 (L * a * b} *) color space a ^*, vertical axis in the two-dimensional coordinates to b ^*, a ^* in the above each optical density, placing the b ^* of determination R ² of the linear regression line that was created is 1.000 or less than 0.998, b ^* values of the intersection of the longitudinal axis is at -5 to 5, and gradient (b ^* / a ^*) is Silver salt photothermographic dry imageon characterized by being from 0.7 to 2.5 Material.
Sensitivity (1): Sensitivity of the material obtained based on a characteristic curve obtained by heat development under normal heat development conditions after exposure through an optical wedge. Note that exposure at this time is performed with light having spectral characteristics appropriate for exposing the material (specifically, white light or light in a specific spectral sensitization region). The normal heat development conditions refer to conditions in a range that is appropriate for heat development of the material and often used for heat development.
Sensitivity (2): After exposure under the same conditions as thermal development in sensitivity (1) before exposure, after exposure through an optical wedge under the same conditions as sensitivity (1), the same thermal development conditions as in sensitivity (1) Sensitivity obtained based on the characteristic curve obtained by heat development with.
[Claim 2]
A silver salt photothermographic dry imaging material containing a non-photosensitive aliphatic carboxylic acid silver salt particle, a photosensitive silver halide particle, a silver ion reducing agent and a binder, wherein the photosensitive silver halide particle is subjected to a thermal development process. By converting from surface latent image type to internal latent image type, it is a silver halide grain whose surface sensitivity is lower than before thermal development, and contains at least one of yellow color developing leuco dye or cyan color developing leuco dye The silver salt photothermographic dry imaging material according to claim 1.
[Claim 3]
The silver salt photothermographic dry imaging material according to claim 1 or 2, wherein at least one of the silver ion reducing agents is represented by the following general formula (RED).

[Wherein, X ₁ represents a chalcogen atom or CHR ₁ , and R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₂ represents an alkyl group. R ₃ represents a hydrogen atom or a group that can be substituted on a benzene ring. R ₄ represents a substitutable group on the benzene ring, and m and n each represents an integer of 0 to 2. ]
[Claim 4]
The silver salt according to any one of claims 1 to 3, comprising at least two kinds of silver ion reducing agents having different chemical structures, or at least one kind of silver ion reducing agent and a development accelerator. Photothermographic dry imaging material.
[Claim 5]
The silver salt according to any one of claims 1 to 4, wherein 50% or more of the total aliphatic carboxylate silver constituting the non-photosensitive aliphatic carboxylate silver salt particles is silver behenate. Photothermographic dry imaging material.
[Claim 6]
A silver salt photothermographic dry imaging material containing non-photosensitive aliphatic carboxylic acid silver salt particles, photosensitive silver halide particles, a silver ion reducing agent and a binder, wherein the non-photosensitive aliphatic carboxylic acid silver salt particles are potassium Prepared in the presence of an alkali metal salt having a salt content of 50 mol% or more and that the photosensitive silver halide grains are converted from a surface latent image type to an internal latent image type in the heat development process, The silver salt photothermographic dry imaging material according to any one of claims 1 to 5, wherein the silver salt is a silver halide grain having a surface sensitivity lower than that before heat development.
[Claim 7]
A silver salt photothermographic dry imaging material containing non-photosensitive aliphatic carboxylic acid silver salt particles, photosensitive silver halide particles, a silver ion reducing agent and a binder, wherein the non-photosensitive aliphatic carboxylic acid silver salt particles are potassium Prepared in the presence of an alkali metal salt having a salt content of 50 mol% or more and an average grain size of 0.07 to 0.02 μm silver halide grains, and the photosensitive silver halide grains were thermally developed. The silver halide grains according to any one of claims 1 to 6, wherein the surface sensitivity is a silver halide grain whose surface sensitivity is lower than that before heat development by converting from a surface latent image type to an internal latent image type in the process. Silver salt photothermographic dry imaging material.
[Claim 8]
The silver salt photothermographic dry imaging material according to claim 1, comprising a compound represented by the following general formula (ST).

General formula (ST) Z-SO ₂ · SM
[Wherein, Z represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, and M represents a metal atom or an organic cation. ]
[Claim 9]
The silver salt photothermographic dry imaging material according to claim 1, comprising a compound represented by the following general formula (CV).

[Wherein, X represents an electron-withdrawing group, and W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, an acyl group, a thioacyl group, an oxalyl group, an oxy group. Oxalyl group, -S-oxalyl group, oxamoyl group, oxycarbonyl group, -S-carbonyl group, carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, -S-sulfonyl group, sulfamoyl group, oxysulfinyl Represents a group, -S-sulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, ammonium group, sulfonium group, phosphonium group, pyrylium group, or immonium group , R ₁ represents a hydroxyl group or a hydroxyl Represents salts, R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X and W each exclude a formyl group. X and W may combine with each other to form a cyclic structure. X and R ₁ are shown in cis form, but X and R ₁ include transformer form. ]
[Claim 10]
The silver salt photothermographic dry imaging material according to any one of claims 1 to 9, comprising a polymer having at least one repeating unit of a monomer having a halogen radical releasing group.
[Claim 11]
The silver salt photothermographic dry imaging according to any one of claims 1 to 10, wherein the photosensitive silver halide grains contain therein a dopant that functions as an electron trap after at least thermal development. material.
[Claim 12]
Spectral sensitizing dye is adsorbed on the surface of the photosensitive silver halide grains to effect spectral sensitization, and the effect of spectral sensitization substantially disappears after the thermal development process. Item 12. The silver salt photothermographic dry imaging material according to any one of Items 1 to 11.
[Claim 13]
The surface of the photosensitive silver halide grain is chemically sensitized, and the effect of the chemical sensitization substantially disappears after the thermal development process. The silver salt photothermographic dry imaging material according to claim 1.
[Claim 14]
The surface of the photosensitive silver halide grain is chemically sensitized, spectrally sensitized by adsorbing a spectral sensitizing dye, and subjected to chemical sensitization and spectral sensitization after the thermal development process. The silver salt photothermographic dry imaging material according to any one of claims 1 to 13, wherein the effect is substantially lost.

  According to the present invention, the silver salt can be used in a relatively small amount of silver, having high sensitivity and low fog, excellent storage stability, good color tone of the silver image after heat development, and particularly excellent storage stability. Photothermographic dry imaging materials can be provided.

  Details of the present invention will be described below.

[Silver halide grains]
First, photosensitive silver halide grains (hereinafter also simply referred to as silver halide grains) used in the silver salt photothermographic dry imaging material (hereinafter also simply referred to as photosensitive material) of the present invention will be described.

  The photosensitive silver halide grains in the present invention can inherently absorb light as an intrinsic property of silver halide crystals, or artificially physicochemically emit visible light or infrared light. Physicochemical changes can occur in the silver halide crystal or on the crystal surface when absorbing light in any region within the light wavelength range from the ultraviolet light region to the infrared light region. The silver halide crystal grains processed and manufactured as described above.

  The silver halide grains themselves used in the present invention are P.I. Chifie et Physique Photographic (published by Paul Montel, 1967) by Glafkides. F. Duffin's Photographic Emission Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared as a silver halide grain emulsion using the method described in Making and Coating Photographic Emulsion (published by The Focal Press, 1964) by Zelikman et al. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and the formation of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Of these methods, the so-called controlled double jet method, in which silver halide grains are prepared while controlling the formation conditions, is preferred.

  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. Silver chloride or silver iodide is particularly preferred.

  In the case of silver iodobromide, the iodine content is preferably in the range of 0.02 to 16 mol% / Agmol. Even if iodine is contained so as to be distributed throughout the silver halide grains, the iodine concentration in a specific portion of the silver halide grains, for example, the central portion of the grains is increased, and the concentration in the vicinity of the surface is decreased or substantially reduced. It may be a core / shell structure that is zero.

  Grain formation is usually divided into two stages: silver halide seed grain (nuclear grain) generation and grain growth, and these may be performed continuously at one time, or nucleus (seed grain) formation and grain growth are separated. It is also possible to do this. As the particle forming conditions, a controlled double jet method in which particles are formed by controlling pAg, pH and the like is preferable in that the particle shape and size can be controlled. For example, in the case of a method in which nucleation and grain growth are performed separately, first, a soluble silver salt and a soluble halogen salt are uniformly and rapidly mixed in an aqueous gelatin solution to perform nucleation (nucleation step). Silver halide grains are prepared by a grain growth process in which grains are grown while supplying a soluble silver salt and a soluble halogen salt under controlled pAg, pH, and the like.

  The silver halide grains used in the present invention preferably have a smaller grain size of the silver halide grains in order to keep white turbidity and color tone (yellowishness) after image formation low and to obtain good image quality. As a value when particles having a diameter of less than 0.02 μm are excluded from measurement, 0.030 μm or more and 0.055 μm or less are preferable.

  Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a so-called normal crystal of a cube or octahedron. Further, when the silver halide grain is a tabular grain, it means the 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 “monodispersed” as used herein means that the coefficient of variation of the particle diameter obtained by the following formula is 30% or less. Preferably it is 20% or less, More preferably, it is 15% or less.

Coefficient of variation of particle size = standard deviation of particle size / average value of particle size × 100 (%)
Examples of the shape of the silver halide grains include cubes, octahedrons, tetradecahedral grains, tabular grains, spherical grains, rod-shaped grains, and potato grains. Among these, in particular, cubic, octahedral, Tetrahedral and tabular silver halide grains are preferred.

  When tabular silver halide grains are used, the average aspect ratio is preferably 1.5 or more and 100 or less, more preferably 2 or more and 50 or less. These are described in US Pat. Nos. 5,264,337, 5,314,798, 5,320,958, etc., and the desired tabular grains can be easily obtained. Further, grains having rounded corners of silver halide grains can be preferably used.

  The crystal habit on the outer surface of the silver halide grain is not particularly limited, but when a spectral sensitizing dye having crystal habit (plane) selectivity is used in the adsorption reaction of the sensitizing dye on the surface of the silver halide grain. It is preferable to use silver halide grains having a relatively high proportion of crystal habits adapted to the selectivity. For example, when using a sensitizing dye that is selectively adsorbed on the crystal face of the Miller index [100], the proportion of the [100] face on the outer surface of the silver halide grain is preferably high, and this ratio is 50 % Or more, more preferably 70% or more, and particularly preferably 80% or more. Conversely, when using a sensitizing dye that selectively adsorbs on the crystal face of the Miller index [111], it is preferable to increase the proportion of the [111] face on the outer surface of the silver halide grains. The ratio of the Miller index [100] plane is a T.K. based on the adsorption dependency of the [111] plane and the [100] plane in the adsorption of the sensitizing dye. Tani, J .; Imaging Sci. 29, 165 (1985).

  The silver halide grains used in the present invention are preferably prepared using low molecular weight gelatin having an average molecular weight of 50,000 or less at the time of grain formation, and particularly preferably used at the time of nucleation of silver halide grains. The low molecular weight gelatin has an average molecular weight of 50,000 or less, preferably 2000 to 40000, more preferably 5000 to 25000. The average molecular weight of gelatin can be measured by gel filtration chromatography.

  The concentration of the dispersion medium at the time of nucleation is preferably 5% by mass or less, and more effective at a low concentration of 0.05 to 3.0% by mass.

  As the silver halide grains used in the present invention, a polyethylene oxide compound represented by the following general formula can be used at the time of grain formation.

Formula _{YO (CH 2 CH 2 O)} m (CH (CH 3) CH 2 O) p (CH 2 CH 2 O) n Y
In the formula, Y represents a hydrogen atom, —SO ₃ M, or —CO—B—COOM, and M represents an ammonium group substituted with a hydrogen atom, an alkali metal atom, an ammonium group, or an alkyl group having 5 or less carbon atoms. And B represents a chain or cyclic group forming an organic dibasic acid. m and n each represents 0 to 50, and p represents 1 to 100.

  The polyethylene oxide compound represented by the above general formula is used in the production of a light-sensitive material in which a gelatin aqueous solution is produced, a water-soluble halide and a water-soluble silver salt are added to the gelatin solution, and a silver halide emulsion is supported. It has been preferably used as an antifoaming agent for significant foaming when the emulsion raw material is stirred or moved, such as a coating step, and the technology used as the antifoaming agent is, for example, JP-A-44. No. 9497, the polyethylene oxide compound represented by the above general formula also functions as an antifoaming agent during nucleation.

  The polyethylene oxide compound represented by the above general formula is preferably used in an amount of 1% by mass or less, more preferably 0.01 to 0.1% by mass with respect to silver.

  The polyethylene oxide compound represented by the above general formula may be present at the time of nucleation and is preferably added in advance to the dispersion medium before nucleation, but may be added during nucleation, You may add and use for the silver salt aqueous solution and halide aqueous solution which are used at the time of nucleation. Preferably, it is used by adding 0.01 to 2.0% by mass to the aqueous halide solution or both aqueous solutions. Further, it is preferable to exist for at least 50% of the nucleation step, and more preferably for 70% or more. The polyethylene oxide compound represented by the above general formula may be added as a powder or dissolved in a solvent such as methanol.

  The temperature at the time of nucleation is 5 to 60 ° C., preferably 15 to 50 ° C. Even if the temperature is constant, the temperature rising pattern (for example, the temperature at the start of nucleation is 25 ° C. It is preferable to control the temperature within the above temperature range even when the temperature is gradually raised and the temperature at the end of nucleation is 40 ° C.) and vice versa.

The concentration of the silver salt aqueous solution and halide aqueous solution used for nucleation is preferably 3.5 mol / L or less, and more preferably used in a low concentration range of 0.01 to 2.5 mol / L. The addition rate of silver ions during nucleation is preferably 1.5 × 10 ^{−3 to} 3.0 × 10 ⁻¹ mol / min, more preferably 3.0 × 10 ^{−3 to} 8.0, per liter of the reaction solution. × 10 ^-2 mol / min.

  The pH at the time of nucleation can be set in the range of 1.7 to 10, but the pH on the alkali side is preferably 2 to 6 in order to broaden the particle size distribution of nuclei to be formed. Moreover, pBr at the time of nucleation is about 0.05 to 3.0, preferably 1.0 to 2.5, and more preferably 1.5 to 2.0.

[Inner latent type silver halide grains after heat development]
The photosensitive silver halide grain according to the present invention is a silver halide grain whose surface sensitivity is lowered by converting from a surface latent image type to an internal latent image type by heat development. That is, in the exposure before thermal development, a latent image that can function as a catalyst for a development reaction (reduction reaction of silver ions by a silver ion reducing agent) is formed on the surface of the silver halide grains, and the exposure after the thermal development process has passed. Then, since many latent images are formed inside the surface of the silver halide grains, the silver halide grains are characterized in that the formation of latent images on the surface is suppressed. It has not been known in the past to use silver halide grains whose latent image forming function greatly changes before and after the heat development processing as a dry imaging material.

  In general, when photosensitive silver halide grains are exposed, the silver halide grains themselves or spectral sensitizing dyes adsorbed on the surface of the photosensitive silver halide grains are photoexcited to freely move electrons. Although generated, these electrons are competitively trapped (captured) by an electron trap (photosensitive center) existing on the surface of the silver halide grain or an electron trap inside the grain. Therefore, if there are more chemical sensitization centers (chemical sensitization nuclei) and dopants effective as electron traps on the surface than the inside of the silver halide grains, a latent image is preferentially formed on the surface and development is possible. It becomes. On the contrary, when there are more chemical sensitization centers (chemical sensitization nuclei) and dopants effective as electron traps in the inside than the silver halide grain surface, a latent image is preferentially formed inside, and the surface Development becomes difficult. In other words, in the former case, the surface sensitivity is higher than in the interior, and in the latter case, it can be said that the surface sensitivity is lower than in the interior (reference: (1) edited by TH James, “The Theory of the Photographic Process”. “Fourth Edition, Macmillan Publishing Co., Ltd. 1977, (2) The Japan Photographic Society,“ Revised Photographic Engineering Basics (Silver Salt Photography) ”, Corona, 1998).

  In the photosensitive silver halide grain according to the present invention, it is preferable in terms of sensitivity and image storage stability to contain a dopant functioning as an electron trapping dopant at least during exposure after heat development. .

  In addition, a dopant that functions as a hole trap during the exposure for image formation before heat development, changes in the heat development process, and functions as an electron trap after heat development, Particularly preferred.

  The electron trapping dopant used here is an element or compound other than silver and halogen constituting silver halide grains, and the dopant itself has a property of trapping (capturing) free electrons, or the dopant is halogen. It is the one in which a site such as an electron trapping lattice defect is generated by being contained in a silver halide grain. For example, a metal ion other than silver or a salt or complex thereof, a chalcogen (oxygen group element) such as sulfur, selenium or tellurium, or an inorganic compound or organic compound containing a nitrogen atom or a metal complex thereof, a rare earth ion or a complex thereof, etc. Can be mentioned.

  Examples of metal ions or salts or complexes thereof include lead ions, bismuth ions, gold ions, etc., or lead bromide, lead nitrate, lead carbonate, lead sulfate, bismuth nitrate, bismuth chloride, bismuth trichloride, bismuth carbonate, sodium bismutate, Examples thereof include chloroauric acid, lead acetate, lead stearate, bismuth acetate and the like.

  As the compound containing chalcogen such as sulfur, selenium, and tellurium, various chalcogen-releasing compounds generally known as chalcogen sensitizers in the photographic industry can be used. Moreover, as an organic substance containing chalcogen or nitrogen, a heterocyclic compound is preferable. For example, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, Tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine, tetrazaindene, preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, oxadiazole, quinoline, phthalazine, Naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, o Sasol, benzimidazole, benzoxazole, benzthiazole, a tetrazaindene.

  The above heterocyclic compound may have a substituent, and the alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group are preferable as the substituent. 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 and heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonyl group Amino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, acyl group An acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group, or a heterocyclic group.

  The silver halide grains used in the present invention include groups 6 to 11 in the periodic table so that they function as electron trapping dopants as described above or as hole trapping dopants. Transition metal ions belonging to the above may be contained by chemically adjusting the oxidation state of the metal with a ligand or the like. As the transition metal, W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, and Pt are preferable.

  In the present invention, the above various dopants may be used alone or in combination of two or more of the same or different compounds or complexes. However, at least one kind needs to function as an electron trapping dopant at the time of exposure after thermal development. These dopants may be introduced into the silver halide grains in any chemical form.

  In the present invention, an embodiment in which any one of Ir or Cu complex or salt is used alone is not preferable.

The preferable content of the dopant is preferably in the range of 1 × 10 ⁻⁹ to 1 × 10 mol and more preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol with ^respect to 1 mol of silver. Furthermore, 1 * 10 ^{< -6} > ^-1 * 10 ^<-2> mol is preferable.

  However, since the optimum amount depends on the kind of dopant, the grain size and shape of the silver halide grains, and other environmental conditions, it is preferable to examine optimization of the dopant addition conditions according to these conditions.

  In the present invention, the transition metal complex or complex ion is preferably represented by the following general formula.

General formula [ML ₆ ] ^m
In the formula, M represents a transition metal selected from Group 6 to 11 elements in the periodic table, L represents a ligand, and m represents 0,-, 2-, 3-, or 4-. Specific examples of the ligand represented by L include halogen ions (for example, fluorine ion, chlorine ion, bromine ion, iodine ion), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Each ligand includes nitrosyl, thionitrosyl, and the like, preferably aco, nitrosyl, thionitrosyl, and the like. When an acoligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

  The compounds providing these metal ions or complex ions are preferably added at the time of silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening In addition, it may be added at any stage before or after chemical sensitization, but it is particularly preferably added at the stage of nucleation, growth and physical ripening, and more preferably at the stage of nucleation and growth, Most preferably, it is added at the stage of nucleation. In addition, it may be divided and added several times, and can be uniformly contained in the silver halide grains. For example, JP-A-63-29603, JP-A-2-306236, 3 As described in JP-A Nos. 167545, 4-76534, 6-110146, 5-273683, etc., the particles can be contained with a distribution.

  These metal compounds can be added by dissolving in water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation, or the silver salt solution and the halide solution are mixed simultaneously. When adding a third aqueous solution, a method of preparing silver halide grains by a method of simultaneous mixing of three liquids, a method of introducing an aqueous solution of a required amount of a metal compound into a reaction vessel during grain formation, or a silver halide preparation There is a method of adding and dissolving another silver halide grain that has been previously doped with metal ions or complex ions. In particular, a method of adding an aqueous solution of a metal compound powder or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together is added to the water-soluble halide solution. When added to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particle, during or after physical ripening, or at the time of chemical ripening.

  In addition, a nonmetallic dopant can also be introduce | transduced inside a silver halide by the method similar to said metallic dopant.

  In the imaging material according to the present invention, whether or not the above dopant has an electron trapping property can be evaluated by a method generally used in the photographic industry as follows. That is, a silver halide emulsion comprising silver halide grains doped with the above-mentioned dopant or a decomposition product thereof in silver halide grains is subjected to a photoconductivity measurement by a microwave photoconductivity measurement method or the like, and the halogenation does not contain a dopant. It can be evaluated by measuring the degree of decrease in photoconduction with a silver grain emulsion as a reference. Alternatively, it can be performed by a comparative experiment of the internal sensitivity and surface sensitivity of the silver halide grains.

  Alternatively, a method for evaluating the effect of the electron trapping dopant according to the present invention after preparing a photothermographic dry imaging material is, for example, by heating the imaging material under the same conditions as normal practical thermal development conditions before exposure. Then, for a certain period of time (for example, 30 seconds), white light or light in a specific spectral sensitization region (when spectral sensitization is performed on laser light in a specific wavelength region, When spectral sensitization is applied to infrared light, infrared light) is exposed through an optical wedge, and further subjected to thermal development under the same thermal development conditions, resulting in a characteristic curve (sensitometry curve). The sensitivity obtained based on this can be evaluated by comparing with the sensitivity of the imaging material using the silver halide grain emulsion not containing the electron trapping dopant. That is, it is necessary to confirm that the sensitivity of the former sample containing the silver halide grain emulsion containing the dopant according to the present invention is lower than the sensitivity of the latter sample not containing the dopant.

  The material is exposed to white light or light in a specific spectral sensitization region (for example, infrared light) through an optical wedge for a certain period of time (for example, 30 seconds), and then subjected to heat development under normal heat development conditions. For the sensitivity of the sample obtained on the basis of the characteristic curve obtained, the sample is heated under the same conditions as normal heat development conditions before exposure, and then subjected to the same constant time and constant exposure as described above. Further, the sensitivity obtained based on the characteristic curve obtained by heat development under normal heat development conditions is 1/10 or less, preferably 1/20 or less, and further when the silver halide emulsion is chemically sensitized, A low sensitivity of 1/50 or less is preferable.

  The silver halide grains of the present invention may be added to the photosensitive layer by any method. At this time, the silver halide grains are arranged so as to be close to a reducible silver source (aliphatic carboxylic acid silver salt). However, it is preferable to obtain an imaging material with high sensitivity and high covering power (CP).

  The silver halide grains of the present invention are prepared in advance and added to a solution for preparing aliphatic carboxylic acid silver salt grains to prepare a silver halide grain preparation step and aliphatic carboxylic acid silver salt grain preparations. Although the process can be handled separately and is most preferable in terms of production control, as described in British Patent No. 1,447,454, when preparing aliphatic carboxylic acid silver salt particles, such as halide ions By making a halogen component coexist with an aliphatic carboxylate silver salt-forming component and injecting silver ions into this, silver halide grains produced almost simultaneously with the production of aliphatic carboxylate silver salt particles can also be used in combination. . It is also possible to prepare a silver halide grain by allowing a halogen-containing compound to act on an aliphatic carboxylic acid silver salt and converting the aliphatic carboxylic acid silver salt, and use the grain together. That is, a silver halide-forming component is allowed to act on a solution or dispersion of an aliphatic carboxylic acid silver salt prepared in advance, or a sheet material containing the aliphatic carboxylic acid silver salt, so that a part of the aliphatic carboxylic acid silver salt is removed. It can also be converted to photosensitive silver halide.

  Examples of the silver halide grain forming component include inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Specific examples thereof are US Pat. No. 4,009,039. No. 3,457,075, No. 4,003,749, British Patent No. 1,498,956 and JP-A-53-27027, No. 53-25420.

  You may use together the silver halide grain manufactured by converting a part of aliphatic carboxylic acid silver salt into the silver halide grain separately prepared as mentioned above.

  These silver halide grains are separately prepared silver halide grains, 0.001 to 0.7 mol per 1 mol of aliphatic carboxylic acid silver salt, and silver halide grains obtained by conversion of aliphatic carboxylic acid silver salt. Preferably it is used at 0.03-0.5 mol.

  Separately prepared photosensitive silver halide grains are desalted by a known desalting method such as noodle method, flocculation method, ultrafiltration method, electrodialysis method, etc. However, it can be used without desalting.

[Non-photosensitive aliphatic carboxylic acid silver salt]
The non-photosensitive aliphatic carboxylic acid silver salt according to the present invention is a reducible silver source, and a silver salt of a long-chain aliphatic carboxylic acid having 10 to 30, preferably 15 to 25 carbon atoms is preferable. Examples of suitable silver salts include the following.

  Examples thereof include silver salts such as gallic acid, succinic acid, behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid, and preferable silver salts include silver behenate, silver arachidate and silver stearate.

  In the present invention, it is preferable that two or more kinds of aliphatic carboxylic acid silver salts are mixed in order to improve developability and form a silver image having a high density and a high contrast. It is preferable to prepare by mixing a silver ion solution with an aromatic carboxylic acid mixture.

  On the other hand, from the viewpoint of the storage stability of the image after development, the melting point of the aliphatic carboxylic acid which is a raw material for the aliphatic carboxylate silver is 50 ° C or higher, preferably 60 ° C or higher. The content ratio is preferably 50% or more, preferably 70% or more, and more preferably 80% or more. From this viewpoint, specifically, it is preferable that the content of silver behenate is high.

  The aliphatic carboxylic acid silver salt is obtained by mixing a water-soluble silver compound and a compound that forms a complex with silver, and is described in Japanese Patent Application Laid-Open No. 9-127643. The controlled double jet method as described above is preferably used. For example, an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) is added to an organic acid to produce an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate), and then a controlled double jet. According to the method, the soap and silver nitrate are mixed to produce an aliphatic carboxylic acid silver salt crystal. At that time, seed crystal grains of silver aliphatic carboxylate, silver halide grains, and the like may be mixed.

  Examples of the alkali metal salt used in the present invention include sodium hydroxide, potassium hydroxide, and lithium hydroxide, but it is preferable to use sodium hydroxide and potassium hydroxide in combination. The combined ratio is preferably such that the molar ratio of both of the above-mentioned hydroxide salts is in the range of 10:90 to 75:25. When used in the above range when reacted with an aliphatic carboxylic acid to form an alkali metal salt of an aliphatic carboxylic acid, the viscosity of the reaction solution can be controlled in a good state.

  In addition, when preparing an aliphatic carboxylate silver salt in the presence of silver halide grains having an average particle diameter of 0.050 μm or less, the alkali metal of the alkali metal salt is preferably a halide having a higher potassium ratio. It is preferable because dissolution of silver particles and Ostwald ripening are prevented. Moreover, the size of fatty acid silver salt particle | grains can be made small, so that the ratio of potassium salt is high. A preferable ratio of the potassium salt is 50 to 100% based on the total alkali metal salt used in the step of producing the aliphatic carboxylate. The concentration of the alkali metal salt is preferably 0.1 to 0.3 mol / 1000 ml.

[High silver conversion rate silver salt particles]
The emulsion containing the aliphatic carboxylic acid silver salt grains according to the present invention is a mixture of a free aliphatic carboxylic acid and an aliphatic carboxylic acid silver salt that do not form a silver salt, but the former ratio is relative to the latter. Low is preferable from the viewpoint of image storage stability and the like. That is, the emulsion according to the present invention preferably contains 3 to 10 mol% of an aliphatic carboxylic acid with respect to the aliphatic carboxylic acid silver salt grains. Particularly preferably, the content is 4 to 8 mol%.

  Specifically, by determining the total aliphatic carboxylic acid amount and the free aliphatic carboxylic acid amount by the following method, respectively, the aliphatic carboxylic acid silver salt and the free aliphatic carboxylic acid amount and the respective ratios or The ratio of free fatty acid to total aliphatic carboxylic acid is calculated.

(Quantification of total aliphatic carboxylic acid content (total of those derived from both the above aliphatic carboxylic acid silver salts and free acids))
(1) About 10 mg of sample (the mass removed when peeling from the photosensitive material) is accurately weighed and placed in a 200 ml eggplant type flask.
(2) Add 15 ml of methanol and 3 ml of 4 mol / L hydrochloric acid and ultrasonically disperse for 1 minute.
(3) Add Teflon (R) zeolite and reflux for 60 minutes.
(4) After cooling, add 5 ml of methanol from the top of the cooling tube, and wash the material adhering to the cooling tube into the eggplant-shaped flask (twice).
(5) The obtained reaction solution is extracted with ethyl acetate (100 ml of ethyl acetate and 70 ml of water are added and liquid separation extraction is performed twice).
(6) Vacuum dry at room temperature for 30 minutes.
(7) Add 1 ml of benzanthrone solution as an internal standard to a 10 ml volumetric flask (dissolve about 100 mg of benzanthrone in toluene and make up to 100 ml with toluene).
(8) Dissolve the sample in toluene and put it in the volumetric flask of (7), and make a constant volume with toluene.
(9) Perform gas chromatography (GC) measurement under the following measurement conditions.

Apparatus: HP-5890 + HP-Chemical station Column: HP-1 30 m × 0.32 mm × 0.25 μm (manufactured by HP)
Inlet: 250 ° C
Detector: 280 ° C
Oven: constant 250 ° C. Carrier gas: He
Head pressure: 80 kPa
(Quantification of free aliphatic carboxylic acid content)
(1) About 20 mg of a sample is accurately weighed, placed in a 200 ml eggplant-shaped flask, 10 ml of methanol is added, and ultrasonic dispersion is performed at 25 ° C. for 1 minute (free organic carboxylic acid is extracted).
(2) It is filtered, and the filtrate is put into a 200 ml eggplant type flask and dried (free organic carboxylic acid is separated).
(3) Add 15 ml of methanol and 3 ml of 4 mol / L hydrochloric acid and perform ultrasonic dispersion for 1 minute.
(4) Put a Teflon (R) boiling stone and reflux for 60 minutes.
(5) 60 ml of water and 60 ml of ethyl acetate are added to the resulting reaction solution, and the methyl esterified product of organic carboxylic acid is extracted into the ethyl acetate phase. Ethyl acetate extraction is performed twice.
(6) The ethyl acetate phase is dried and vacuum dried for 30 minutes.
(7) Add 1 ml of benzanthrone solution (internal standard: about 100 mg of benzanthrone dissolved in toluene to a constant volume of 100 ml) in a 10 ml volumetric flask.
(8) Dissolve (6) with toluene, put into the volumetric flask of (7), and make a constant volume with toluene.
(9) Perform GC measurement under the following measurement conditions.

Apparatus: HP-5890 + HP-Chemical station Column: HP-1 30 m × 0.32 mm × 0.25 μm (manufactured by HP)
Inlet: 250 ° C
Detector: 280 ° C
Oven: constant 250 ° C. Carrier gas: He
Head pressure: 80 kPa
[Structure and shape of aliphatic carboxylic acid silver salt]
The aliphatic carboxylic acid silver salt according to the present invention may be a crystal particle having a core / shell structure as disclosed in European Patent 1168069A1 and Japanese Patent Application Laid-Open No. 2002-23303. In the case of a core / shell structure, all or part of either the core part or the shell part is an organic silver salt other than the aliphatic carboxylate silver, for example, silver of an organic compound such as phthalic acid or benzimidazole. A salt may be used as a constituent of the crystal particles.

  In the aliphatic carboxylic acid silver salt according to the present invention, the average equivalent circle diameter is preferably 0.05 μm or more and 0.8 μm or less, and the average thickness is preferably 0.005 μm or more and 0.07 μm or less. Particularly preferably, the average equivalent circle diameter is not less than 0.2 μm and not more than 0.5 μm, and the average thickness is not less than 0.01 μm and not more than 0.05 μm.

  When the average equivalent circle diameter is 0.05 μm or less, the transparency is excellent, but the image storage stability is poor, and when the average particle diameter is 0.8 μm or more, devitrification is severe. When the average thickness is 0.005 μm or less, the surface area is large, and silver ions are rapidly supplied during development. In particular, the low density area is not used for silver images, and there is a large amount of silver ions remaining in the film. The image storage stability is significantly deteriorated. On the other hand, when the average thickness is 0.07 μm or more, the surface area is reduced and the image stability is improved. However, the silver supply during development is slow, and the developed silver shape is uneven in the high density portion, resulting in the highest result. Concentration tends to be low.

  In order to obtain the average equivalent circle diameter, the dispersed aliphatic carboxylic acid silver salt is diluted and dispersed on a grid with a carbon support film, a transmission electron microscope (for example, JEOL Ltd., 2000FX type), direct magnification 5000 An image is taken at a magnification, a negative is captured as a digital image by a scanner, and 300 or more particle diameters (equivalent circle diameters) are measured using appropriate image processing software, and an average particle diameter can be calculated.

  The average thickness can be calculated by a method using a TEM (transmission electron microscope) as shown below.

  First, the photosensitive layer coated on the support is attached to an appropriate holder with an adhesive, and an ultrathin slice having a thickness of 0.1 to 0.2 μm is produced using a diamond knife in a direction perpendicular to the support surface. To do. The prepared ultra-thin slice is supported on a copper mesh, transferred onto a carbon film that has been hydrophilized by glow discharge, and cooled with liquid nitrogen to −130 ° C. or lower using a transmission electron microscope (hereinafter referred to as TEM). The bright field image is observed at a magnification of 5,000 to 40,000, and the image is quickly recorded on a film, an imaging plate, a CCD camera or the like. At this time, it is preferable to appropriately select a portion where the section is not torn or slack as the field of view to be observed.

  As the carbon film, it is preferable to use a film supported by an organic film such as a very thin collodion or form bar. More preferably, the carbon film is formed on a rock salt substrate and dissolved and removed. It is a carbon-only film obtained by removal by organic solvent and ion etching. The acceleration voltage of TEM is preferably 80 to 400 kV, particularly preferably 80 to 200 kV.

  In addition, for details of electron microscope observation techniques and sample preparation techniques, see “The Japan Electron Microscopy Society Kanto Branch / Medical and Biological Electron Microscopy” (Maruzen), “The Japan Electron Microscopy Society Kanto Branch / Electron Microscope Biological Samples” "Manufacturing method" (Maruzen) can be referred to respectively.

  A TEM image recorded on a suitable medium is preferably decomposed into at least 1024 pixels × 1024 pixels, preferably 2048 pixels × 2048 pixels or more, and image processing by a computer is performed. In order to perform image processing, it is preferable that an analog image recorded on a film is converted into a digital image by a scanner or the like, and shading correction, contrast / edge enhancement, and the like are performed as necessary. Thereafter, a histogram is prepared, and a portion corresponding to the aliphatic carboxylate silver is extracted by binarization processing.

  The thickness of the extracted aliphatic carboxylic acid silver salt particles is manually measured with an appropriate software of 300 or more, and an average value is obtained.

  The method for obtaining the aliphatic carboxylic acid silver salt particles having the above-mentioned shape is not particularly limited. For example, the mixed state at the time of forming the organic acid alkali metal salt soap or the mixed state at the time of adding silver nitrate to the soap. It is effective to keep it good, and to set the ratio of the organic acid to the soap and the ratio of the silver nitrate that reacts with the soap optimally.

  In the present invention, tabular aliphatic carboxylic acid silver salt particles (aliphatic carboxylic acid having an average equivalent circle diameter of 0.05 μm to 0.8 μm and an average thickness of 0.005 μm to 0.07 μm) The acid silver salt particles) are preferably pre-dispersed with a binder, a surfactant or the like, if necessary, and then dispersed and ground with a media disperser or a high-pressure homogenizer. As the preliminary dispersion method, for example, a general stirrer such as an anchor type or a propeller type, a high speed rotary centrifugal radiation type stirrer (dissolver), or a high speed rotary shear type stirrer (homomixer) can be used.

  Further, as the media disperser, for example, a rolling mill such as a ball mill, a planetary ball mill, a vibrating ball mill, a bead mill that is a medium agitation mill, an attritor, and other basket mills can be used, and as a high-pressure homogenizer Various types can be used, such as a type that collides with a wall, a plug, etc., a type in which liquids are collided with each other at high speed, and a type through which a thin orifice is passed.

  Ceramics used for the ceramic beads used when dispersing media include yttrium-stabilized zirconia and zirconia-reinforced alumina (ceramics containing these zirconia) because of the low generation of impurities due to friction with the beads and the dispersing machine during dispersion. Is abbreviated as zirconia in the following).

  In the apparatus used for dispersing the tabular aliphatic carboxylic acid silver salt particles according to the present invention, examples of the material of the member in contact with the aliphatic carboxylic acid silver salt particles include zirconia, alumina, silicon nitride, and boron nitride. It is preferable to use ceramics such as the above or diamond, and it is preferable to use zirconia. When the above dispersion is performed, the binder concentration is preferably added in an amount of 0.1 to 10% of the mass of the aliphatic silver carboxylate, and it is preferable that the liquid temperature does not exceed 45 ° C. from the preliminary dispersion through the main dispersion. As preferable operating conditions for this dispersion, for example, when a high-pressure homogenizer is used as the dispersing means, 29 to 100 MPa, and the number of operations is preferably 2 or more. Moreover, when using a media disperser as a dispersion | distribution means, 6-13 m / sec of peripheral speed is mentioned as preferable conditions.

  In the present invention, it is preferable that the non-photosensitive aliphatic carboxylic acid silver salt particles are formed in the presence of a compound that functions as a crystal growth inhibitor or a dispersant. Moreover, it is preferable that the compound which functions as a crystal growth inhibitor or a dispersing agent is an organic compound having a hydroxyl group or a carboxyl group.

  In the present invention, the compound that functions as a crystal growth inhibitor or dispersant for the aliphatic carboxylate silver particles refers to a silver aliphatic carboxylate under the conditions in which the compound coexists in the production process of the aliphatic carboxylate particles. A compound having a function and an effect of reducing the particle size or monodispersing than when it is produced under conditions that do not coexist. Specific examples include monohydric alcohols having 10 or less carbon atoms, preferably secondary alcohols, tertiary alcohols, glycols such as ethylene glycol and propylene glycol, polyethers such as polyethylene glycol, and glycerin. A preferable addition amount is 10 to 200% by mass with respect to the aliphatic carboxylate silver.

  On the other hand, branched aliphatic carboxylic acids containing isomers such as isoheptanoic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, isobehenic acid and isohexaconic acid are also preferred. In this case, a preferable side chain includes an alkyl group or alkenyl group having 4 or less carbon atoms. In addition, aliphatic unsaturated carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, moloctic acid, eicosenoic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, and ceracolonic acid It is done. A preferable addition amount is 0.5 to 10 mol% of the silver aliphatic carboxylate.

  Glycosides such as glucoside, galactoside and fructoside, trehalose type disaccharides such as trehalose and sucrose, polysaccharides such as glycogen, dextrin, dextran and alginic acid, cellosolves such as methyl cellosolve and ethyl cellosolve, sorbitan, sorbit, ethyl acetate and acetic acid Water-soluble organic solvents such as methyl and dimethylformamide, water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyvinylpyrrolidone and gelatin Are also preferred compounds. A preferable addition amount is 0.1 to 20% by mass with respect to the aliphatic carboxylate silver.

  Alcohols having 10 or less carbon atoms, preferably secondary alcohols such as isopropyl alcohol and tertiary alcohols such as t-butyl alcohol are used to increase the solubility of the alkali metal salt of aliphatic carboxylic acid in the particle production process. By reducing the viscosity and increasing the stirring efficiency, it is monodispersed and the particle size is reduced. Branched aliphatic carboxylic acids and aliphatic unsaturated carboxylic acids have higher steric hindrance than the main component linear aliphatic carboxylic acid silver when crystallization of the aliphatic carboxylic acid silver, and the disorder of the crystal lattice is large. Therefore, large crystals are not generated, and as a result, the particle size is reduced.

[Anti-foggant and image stabilizer]
As described above, compared with the conventional silver halide photographic light-sensitive material, the biggest difference in the structure of the silver salt photothermographic dry imaging material is that the latter material, before and after the development processing, That is, it contains a large amount of photosensitive silver halide, organic silver salt and reducing agent that may cause fogging and printout silver (baked-out silver). For this reason, silver salt photothermographic dry imaging materials require advanced antifogging and image stabilization techniques in order to maintain storage stability not only before development but also after development. In addition to aromatic heterocyclic compounds that inhibit growth and development, mercury compounds such as mercury acetate, which have the function of oxidizing and extinguishing fog nuclei, have been used as very effective storage stabilizers. The use of mercury compounds has been a problem in terms of safety and environmental conservation.

  Regarding the technology for preventing fogging and stabilizing the image, basically, the silver ions or metal silver is prevented from being reduced by the silver ions being reduced during storage before and after development. It is also important to consider the fact that the generated silver (metallic silver) is oxidized and disappeared, or that the metallic silver is prevented from functioning as a catalyst for the reaction of reducing silver ions. It is done.

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

  In the silver salt photothermographic dry imaging material of the present invention, as described later, the silver ion reducing agent is mainly characterized by using bisphenols, but the imaging material is stored before development. It is preferable that a compound capable of inactivating the reducing agent is contained under the conditions and under storage conditions after heat development. Preferably, a compound capable of preventing generation of a phenoxyl radical from the reducing agent or a compound capable of trapping the generated phenoxyl radical and stabilizing it so as not to function as a silver ion reducing agent Is preferred. Suitable compounds having such functions and functions include non-reducing compounds having a group capable of forming a hydrogen bond with the hydroxyl group of bisphenols, such as phosphoryl group, sulfoxide group, sulfonyl group, carbonyl group, amide And compounds having a group, an ester group, a urethane group, a ureido group, a tertiary amino group, a nitrogen-containing aromatic group, and the like. Particularly preferred are compounds having a sulfonyl group, a sulfoxide group, or a phosphoryl group. Specific examples are disclosed in JP-A-6-208192, JP-A-2001-215648, JP-A-350235, JP-A-2002-6444, JP-A-2002-18264, and the like. Further, specific compounds having a vinyl group are disclosed in JP 2000-515995 A, JP 2002-207273 A, JP 2003-140298 A, and the like.

  Also used in combination with compounds that can oxidize silver (metal silver), for example, compounds that can oxidize silver by releasing an oxidizing halogen radical or interacting with silver to form a charge transfer complex can do. Specific examples of compounds having such functions include JP-A-50-120328, JP-A-59-57234, JP-A-4-232939, JP-A-6-208193, JP-A-10-197989, and the United States. It is disclosed in Japanese Patent No. 5,460,938, Japanese Patent Application Laid-Open No. 7-2781, and the like. In particular, in the imaging material according to the present invention, specific examples of preferable compounds include halogen radical releasing compounds that can be represented by the following general formula (OFI).

Formula _{(OFI) Q 2 -Y-C} (X 1) (X 3) (X 2)
In general formula (OFI), Q ₂ represents an aryl group or a heterocyclic group. X ₁ , X ₂ and X ₃ each 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 represents —C (═O) —, —SO— or —SO ₂ —.

The aryl group represented by Q ₂ may be monocyclic or condensed, and is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, etc.), more preferably Is a phenyl group or a naphthyl group, more preferably a phenyl group.

The heterocyclic group represented by Q ₂ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one atom of N, O or S, which may be monocyclic, Furthermore, you may form a condensed ring with another ring.

  The heterocyclic group is preferably a 5- to 6-membered unsaturated heterocyclic group which may have a condensed ring, and more preferably a 5- to 6-membered aromatic heterocyclic ring which may have a condensed ring. It is a group. More preferably, it is a 5- to 6-membered aromatic heterocyclic group optionally having a condensed ring containing a nitrogen atom, and particularly preferably 5 a condensed ring containing 1 to 4 nitrogen atoms. A 6-membered aromatic heterocyclic group. The heterocyclic ring in such a heterocyclic group is 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, benzthiazole, indolenine, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, Triazine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinoaline Zolin, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, Quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole, and benzthiazole are preferable, and pyridine, thiadiazole, quinoline, and benzthiazole are particularly preferable.

The aryl group and heterocyclic group represented by Q ₂ may have a substituent in addition to —Y—C (X ₁ ) (X ₂ ) (X ₃ ), and the substituent is preferably an alkyl 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, aryl Oxy group, acyl group, acylamino group, alkoxycarbonylamino , Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group Group, aryloxy group, acyl group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, halogen atom, cyano group, nitro group, heterocyclic group, particularly preferably alkyl group, aryl group, halogen atom .

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

Y represents —C (═O) —, —SO— or —SO ₂ —, preferably —SO ₂ —.

The amount of these compounds added can be 1 × 10 ⁻⁴ to 1 mol, preferably 1 × 10 ^{−3 to} 5 × 10 ⁻² mol, per mol of silver.

  In addition, in the imaging material which concerns on this invention, it can use similarly to the compound which is disclosed by Unexamined-Japanese-Patent No. 2003-5041 and can be represented by said general formula (OFI).

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

[Polymer PO inhibitor]
Furthermore, in the photothermographic imaging material according to the present invention, a polymer having at least one repeating unit of a monomer having a halogen radical releasing group as disclosed in JP-A No. 2003-91054 is used as an image stabilizer. However, the silver image can be further stabilized, and it is also preferable from the viewpoint of high sensitivity and high CP. In particular, the photothermographic imaging material according to the present invention provides unexpectedly good results.

  Specific examples of the polymer having a halogen radical releasing group are shown below, but the present invention is not limited thereto.

  In addition to the above compound, the silver salt photothermographic dry imaging material of the present invention may contain a compound conventionally known as an antifoggant. For example, U.S. Pat. Nos. 3,589,903, 4,546,075, 4,452,885, JP-A-59-57234, U.S. Pat. No. 3,874,946, No. 4,756,999, JP-A-9-288328 and JP-A-9-90550. Further, other antifoggants include compounds disclosed in US Pat. No. 5,028,523 and European Patents 600,587, 605,981, and 631,176. .

[Polycarboxyl compound]
In the imaging material according to the present invention, it is also preferable to use a compound represented by the following general formula (PC) as an antifoggant and a storage stabilizer for the material.

Formula (PC) R- (CO-OM) _n
[Wherein, R represents an atom, an aliphatic group, an aromatic group, a heterocyclic group, or an atomic group that can be bonded to each other to form a ring. M represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group. n represents an integer of 2 to 20. ]
In the general formula (PC), examples of the connectable atom represented by R include atoms such as nitrogen, oxygen, sulfur, and phosphorus.

  Examples of the aliphatic group represented by R include a linear or branched alkyl, alkenyl, alkynyl or cycloalkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl , Cyclohexyl, cyclododecyl and the like.

  Examples of the aromatic group represented by R include those having 6 to 20 carbon atoms, and specific examples thereof include phenyl, naphthyl, and anthranyl groups.

  The heterocyclic group represented by R may be a monocyclic ring or a condensed ring, and includes a 5- to 6-membered heterocyclic group having at least one of O, S, and N atoms and an amine oxide group in the ring. . Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, And groups derived from tetrazole, thiadiazole, oxadiazole, and these benzerogues.

If R is formed by R ₁ and R _2, R ₁ and R ₂ have the same meanings as R, and, R ₁ is may be the same as or different from R _2. Examples of the ring forming with R ₁ and R ₂ include a 4- to 7-membered ring. Preferably it is a 5-7 membered ring. Preferred groups for R ₁ and R ₂ are aromatic groups and heterocyclic groups. The aliphatic group, aromatic group or heterocyclic group represented by R ₁ and R ₂ may be further substituted with a substituent, such as a halogen atom (for example, chlorine atom, bromine atom, etc.), alkyl Groups (eg, methyl, ethyl, isopropyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl groups (eg, cyclopentyl, cyclohexyl, etc.), aralkyl groups (eg, benzyl) Group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), Aryloxy groups (eg phenoxy group, 4-methoxyphenoxy group etc.), cyano groups, acylamino groups (eg Tilamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, p-methylphenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, Benzenesulfonylamino group), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, diethylsulfate) Famoylamino group, etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycal Nyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, Acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxy group, nitro group, nitroso group, amine oxide group (eg pyridine-oxide group etc.), imide Groups (for example, phthalimido group, etc.), disulfide groups (for example, benzene disulfide group, benzthiazolyl-2-disulfide group, etc.), heterocyclic groups (for example, pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.) It is done. R ₁ and R ₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above-described substituent. R ₁ and R ₂ may be the same or different. The general formula (PC-1) is also effective as an oligomer or polymer (R- (COOM) _n0 ) _m . n is 2 to 20, and m is preferably 1 to 100 or a molecular weight of 50000 or less.

  The acid anhydride of the general formula (PC-1) of the present invention refers to a compound formed by dehydration reaction from two carboxyl groups of the compound represented by the general formula (PC-1). Preferably, a compound having 3 to 10 carboxyl groups and an acid anhydride as a derivative thereof are preferable.

  JP-A-58-95338, JP-A-10-288824, JP-A-11-174621, JP-A-11-218877, JP-A-2000-10237, JP-A-2000-10236, JP-A-2000-10235, 2000-2000. The dicarboxylic acids described in Nos. -10233, 2000-10232, and 2000-10231 can be preferably used in combination.

[Thiosulfonic acid inhibitors]
The imaging material according to the present invention preferably contains a compound represented by the general formula (ST).

  Hereinafter, the compound will be described in detail.

  In the compound represented by the general formula (ST), the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocyclic ring represented by Z in the formula may be substituted. Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carboxyl group. be able to. Examples of the heterocycle represented by Z include thiazole, benzthiazole, imidazole, benzimidazole, and oxazole ring. The metal atom represented by M is preferably an alkali metal atom such as sodium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group.

  Specific examples of the compound represented by the general formula (ST) include the following, but the present invention is not limited thereto.

  The compound represented by the general formula (ST) can be synthesized by a generally well-known method. For example, it can be synthesized by reacting the corresponding sulfonyl fluoride and sodium sulfide, or reacting the corresponding sodium sulfinate and sulfur. On the other hand, these compounds can also be easily obtained as commercial products.

  The compound represented by the general formula (ST) may be added at any point in the process before the coating process in the manufacturing process of the imaging material according to the present invention, but is preferably added to the coating liquid immediately before coating.

The amount of the compound represented by the general formula (ST) is not particularly limited, but is preferably in the range of 1 × 10 ^{−6 to} 1 g per mole of total silver including the organic silver salt and the silver halide.

  Similar compounds are disclosed in JP-A-8-314059.

[Vinyl type inhibitor having electron withdrawing group]
In this invention, it is preferable to use together the fog inhibitor represented by the said general formula (CV) described in Japanese Patent Application No. 2003-199555.

  Next, the compound represented by the general formula (CV) will be described in detail.

  The electron withdrawing group represented by X is a substituent whose Hammett's substituent constant σp can take a positive value. Specifically, a substituted alkyl group (such as halogen-substituted alkyl), a substituted alkenyl group (such as cyanovinyl), a substituted or unsubstituted alkynyl group (such as trifluoromethylacetylenyl, cyanoacetylenyl, formylacetylenyl), Substituted aryl groups (such as cyanophenyl), substituted and unsubstituted heterocyclic groups (such as pyridyl, triazinyl, benzoxazolyl), halogen atoms, cyano groups, acyl groups (such as acetyl and trifluoroacetyl), thioacyl groups (such as thioformyl) , Thioacetyl etc.), oxalyl group (methyl oxalyl etc.), oxyoxalyl group (ethoxalyl etc.), -S-oxalyl group (ethyl thiooxalyl etc.), oxamoyl group (methyl oxamoyl etc.), oxycarbonyl group (ethoxycarbonyl, carboxyl) Etc.), -S-carbonyl group (ethyl) Ocarbonyl), carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group (ethoxysulfonyl etc.), -S-sulfonyl group (ethylthiosulfonyl etc.), sulfamoyl group, oxysulfinyl group (methoxysulfinyl etc.) , -S-sulfinyl group (such as methylthiosulfinyl group), sulfinamoyl group, phosphoryl group, nitro group, imino group (imino, N-methylimino, N-phenylimino, N-pyridylimino, N-cyanoimino, N-nitroimino, etc.), N -Carbonylimino group (N-acetylimino, N-ethoxycarbonylimino, N-ethoxalylimino, N-formylimino, N-trifluoroacetylimino, N-carbamoylimino, etc.), N-sulfonylimino group (N-methanes) Phonylimino, N-trifluoromethanesulfonylimino, N-methoxysulfonylimino, N-sulfamoylimino, etc.), ammonium group, sulfonium group, phosphonium group, pyrylium group, immonium group, etc., ammonium group, sulfonium group In addition, a heterocyclic group in which a phosphonium group, an immonium group or the like forms a ring is also included. However, X excludes a formyl group. The σp value is preferably 0.2 or more, and more preferably 0.3 or more.

  W includes a hydrogen atom, an alkyl group (methyl, ethyl, trifluoromethyl, etc.), an alkenyl group (vinyl, halogen-substituted vinyl, cyanovinyl, etc.), an alkynyl group (acetylenyl, cyanoacetylenyl, etc.), an aryl group (phenyl, chlorophenyl). , Nitrophenyl, cyanophenyl, pentafluorophenyl, etc.), heterocyclic groups (pyridyl, pyrimidyl, pyrazinyl, quinoxalinyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, benzoxazolyl, etc.) Halogen atom, cyano group, acyl group, thioacyl group, oxalyl group, oxyoxalyl group, -S-oxalyl group, oxamoyl group, oxycarbonyl group, -S-carbonyl group, carbamoyl group, thiocarbamoyl group, sulfonyl , Sulfinyl group, oxysulfonyl group, -S-sulfonyl group, sulfamoyl group, oxysulfinyl group, -S-sulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group , Ammonium group, sulfonium group, phosphonium group, pyrylium group, immonium group and the like. However, the formyl group is excluded as W.

  W is preferably an electron withdrawing group other than a formyl group in which Hammett's substituent constant σp can take a positive value, as well as an aryl group and a heterocyclic group as described above.

  X and W may be bonded to each other to form a cyclic structure. Examples of the ring formed by X and W include a saturated or unsaturated carbocycle or heterocycle which may have a condensed ring, and may be a cyclic ketone. As the heterocyclic ring, those containing at least one atom, more preferably 1-2, of N, O and S are preferable.

R ₁ includes a hydroxyl group or an organic or inorganic salt of a hydroxyl group. Specific examples of the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₂ include the examples of the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group exemplified as W. It is done.

In the present invention, X, W and R ₂ may all contain a diffusion-resistant group. The anti-diffusion group is called a ballast group in a photographic coupler or the like, and has a bulky molecular weight so that the added compound does not move in the film of the photosensitive material.

In the present invention, X, W and R ₂ may contain an adsorption promoting group for silver salt. Adsorption promoting groups for silver salts include thioamide groups, aliphatic mercapto groups, aromatic mercapto groups, heterocyclic mercapto groups and benzotriazoles, triazoles, tetrazoles, indazoles, benzimidazoles, imidazoles, benzothiazoles, thiazoles, benzoxazoles, Examples include groups represented by 5- to 6-membered nitrogen-containing heterocycles such as oxazole, thiadiazole, oxadiazole, and triazine.

  In the present invention, it is preferable that at least one of X and W represents a cyano group, or X and W are bonded to each other to form a cyclic structure.

In the present invention, a compound containing a thioether group (—S—) in the substituents represented by X, W and R ₂ is preferred.

  Further, among X and W, those having at least one alkene group represented by the following general formula (CV1) are particularly preferred.

Formula (CV1) -C (R) = C (Y) (Z)
In the above formula, R represents a hydrogen atom or a substituent, and Y and Z each represent a hydrogen atom or a substituent, and at least one of Y and Z represents an electron-withdrawing group.

  Examples of the electron-withdrawing group among the substituents represented by Y and Z include those mentioned as the electron-withdrawing groups for X and W described above and the formyl group.

  Examples of X and W represented by the general formula (CV1) include the following groups.

  Further, it is also preferable that at least one of X and W has the following alkyne group.

R ₅ represents a hydrogen atom or a substituent, and the substituent is preferably an electron-withdrawing group as exemplified in X and W described above. Examples of X and W represented by the general formula (CV1) include the following groups.

  In addition, among X and W, those having at least one acyl group selected from a substituted alkylcarbonyl group, an alkenylcarbonyl group, and an alkynylcarbonyl group are also preferred. Examples of X and W include the following groups.

  Moreover, what has at least one oxalyl group among X and W is also preferable, and the following groups are mentioned as X and W which have an oxalyl group, for example.

_{And, -COCOCH 3, -COCOOC 2 H 5} , -COCONHCH 3, -COCOSC 2 H 5, -COCOOC 2 H 4 SCH 3, -COCONHC 2 H 4 SCH 3.

  In addition, it is preferable that at least one of X and W has an aryl group substituted with an electron-withdrawing group or a nitrogen-containing heterocyclic group. Examples of such X and W include the following groups.

In the present invention, the alkene compound represented by the general formula (CV) includes all isomers when it can take an isomer structure with respect to the double bond substituted by X, W, R ₁ and R ₂ . In addition, all isomers are included when a tautomeric structure such as ketoeenol can be taken.

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

  The compound represented by the general formula (CV) of the present invention can be synthesized by various methods. For example, the compound can be synthesized with reference to the synthesis method described in JP-T-2000-515995.

  Illustrative compound CV-5 can be synthesized, for example, by the following route.

  Other compounds represented by the general formula (CV) of the present invention can be synthesized in the same manner.

The compound represented by the general formula (CV) may be contained in at least one of the photosensitive layer of the photothermographic material or the non-photosensitive layer on the photosensitive layer side, and preferably contained in at least the photosensitive layer. is there. The amount of the compound represented by the general formula (1) is preferably 1 × 10 ⁻⁸ to 1 mol, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, relative to 1 mol of silver, 1 ×. 10 ⁻⁴ to 1 × 10 ⁻² mol is most preferred.

  The compound represented by formula (CV) can be added to the photosensitive layer or the non-photosensitive layer according to a known method. That is, it can be dissolved in an alcohol such as methanol or ethanol, a ketone such as methyl ethyl ketone or acetone, or a polar solvent such as dimethyl sulfoxide or dimethylformamide, and added to the coating solution for the photosensitive layer or the non-photosensitive layer. Further, fine particles of 1 μm or less can be dispersed and added in water or an organic solvent. Many techniques for fine particle dispersion are disclosed, but they can be dispersed according to these techniques.

[Silver ion reducing agent]
In the present invention, US Pat. Nos. 3,589,903, 4,021,249 or British Patent 1,486,148 are used as silver ion reducing agents (sometimes referred to simply as reducing agents). And polyphenol compounds described in JP-A-51-51933, JP-A-50-36110, JP-A-50-116023, JP-A-52-84727 or JP-B-51-35727, such as 2,2′-dihydroxy- Bisnaphthols described in US Pat. No. 3,672,904 such as 1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl, For example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol , It can be used sulfonamidophenols or sulfonamidonaphthols, such as described in U.S. Patent No. 3,801,321, such as 4-benzenesulfonamide naphthol.

  However, in the present invention, the silver ion reducing agent is preferably a compound represented by the above general formula (RED).

  The general formula (RED) will be described in detail below.

In the general formula (RED), X ₁ represents a chalcogen atom or CHR ₁ . The chalcogen atom is sulfur, selenium or tellurium, preferably a sulfur atom. CHR R ₁ in ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, the alkyl group substituted or An unsubstituted alkyl group having 1 to 20 carbon atoms is preferred. Specific examples include methyl, ethyl, propyl, butyl, hexyl, heptyl, cycloalkyl, etc. Examples of the alkenyl group include vinyl, allyl, butenyl, hexenyl, hexadienyl, ethenyl-2-propenyl, 3-butenyl, 1-methyl- 3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, cyclohexenyl, etc., aryl groups such as benzene ring, naphthalene ring, etc., heterocyclic groups such as thiophene, furan, imidazole, pyrazole, pyrrole, etc. is there. In particular, a cyclic group such as a cycloalkyl group and a cycloalkenyl group is preferable.

  These groups may further have a substituent. Specific examples of the substituent include a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group (methyl, ethyl, propyl, butyl, pentyl, i-pentyl). , 2-ethylhexyl, octyl, decyl, etc.), cycloalkyl groups (cyclohexyl, cycloheptyl, etc.), alkenyl groups (ethenyl-2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl) -3-butenyl, etc.), cycloalkenyl groups (1-cycloalkenyl, 2-cycloalkenyl groups, etc.), alkynyl groups (ethynyl, 1-propynyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, etc.), alkylcarbonyloxy groups (Acetyloxy, etc.), alkylthio groups (methylthio, trifluoromethylthio, etc.), potassium Boxyl group, alkylcarbonylamino group (acetylamino etc.), ureido group (methylaminocarbonylamino etc.), alkylsulfonylamino group (methanesulfonylamino etc.), alkylsulfonyl group (methanesulfonyl, trifluoromethanesulfonyl etc.), carbamoyl group ( Carbamoyl, N, N-dimethylcarbamoyl, N-morpholinocarbonyl, etc.), sulfamoyl group (sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfamoyl etc.), trifluoromethyl group, hydroxyl group, nitro group, cyano group Alkylsulfonamide groups (methanesulfonamide, butanesulfonamide, etc.), alkylamino groups (amino, N, N-dimethylamino, N, N-diethylamino, etc.), sulfo groups, phosphono groups, sulfite Group, sulfino group, alkylsulfonylaminocarbonyl group (methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl, etc.), alkylcarbonylaminosulfonyl group (acetamidosulfonyl, methoxyacetamidosulfonyl, etc.), alkynylaminocarbonyl group (acetamidocarbonyl, methoxyacetamidocarbonyl, etc.) ), Alkylsulfinylaminocarbonyl groups (methanesulfinylaminocarbonyl, ethanesulfinylaminocarbonyl, etc.) and the like. Moreover, when there are two or more substituents, they may be the same or different.

  A particularly preferred substituent is an alkyl group.

R ₂ represents an alkyl group. The alkyl group is preferably a substituted or unsubstituted one having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, t-pentyl, t-octyl. , Cyclohexyl, cyclopentyl, 1-methylcyclohexyl, 1-methylcyclopropyl and the like.

Although the substituent of the alkyl group is not particularly limited, for example, aryl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonamido group, sulfonyl group, phosphoryl group, acyl group, carbamoyl group, An ester group, a halogen atom, etc. are mentioned. Or it may form a saturated ring with (R _{4) n} and (R _{4) m.} R ₂ is preferably a secondary or tertiary alkyl group, and preferably has 2 to 20 carbon atoms. A tertiary alkyl group is more preferred, t-butyl, t-pentyl and 1-methylcyclohexyl are more preferred, and t-butyl is most preferred.

R ₃ represents a hydrogen atom or a group that can be substituted on a benzene ring. Examples of the group that can be substituted on the benzene ring include halogen atoms such as fluorine, chlorine, bromine, alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, amino groups, acyl groups, acyloxy groups, Examples include acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, sulfonyl group, alkylsulfonyl group, sulfinyl group, cyano group, and heterocyclic group.

R ₃ is preferably methyl, ethyl, i-propyl, t-butyl, cyclohexyl, 1-methylcyclohexyl, 2-hydroxyethyl and the like. More preferred are methyl and 2-hydroxyethyl.

These groups may further have a substituent, and the substituents exemplified in the above R ₁ can be used as the substituent.

R ₃ is more preferably an alkyl group having 1 to 10 carbon atoms. In particular, a hydroxyl group as disclosed in the specification of Japanese Patent Application No. 2002-120842, or an alkyl group having a group capable of forming a hydroxyl group by being deprotected, such as a 2-hydroxyethyl group, etc. Is mentioned. Such a reducing agent having an alkyl group should be used alone in order to obtain a high maximum density (Dmax) with a constant applied silver amount, that is, a silver image density with a high silver coverage (covering power, CP). Or it is preferable to use together with another kind of reducing agent.

The most preferred combination of R ₂ and R ₃ is that R ₂ is a tertiary alkyl group (t-butyl, 1-methylcyclohexyl, etc.), R ₃ is an alkyl group, and is a hydroxyl group or deprotected. An alkyl group having a group capable of forming a hydroxyl group as a substituent, for example, a 2-hydroxyethyl group. The plurality of R ₂ and R ₃ may be the same or different.

R ₄ represents a substitutable group on the benzene ring, specifically, an alkyl group having 1 to 25 carbon atoms (methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, cyclohexyl, etc.), Halogenated alkyl group (trifluoromethyl, perfluorooctyl etc.), cycloalkyl group (cyclohexyl, cyclopentyl etc.), alkynyl group (propargyl etc.), glycidyl group, acrylate group, methacrylate group, aryl group (phenyl etc.), heterocyclic ring Groups (pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, selenazolyl, sriphoranyl, piperidinyl, pyrazolyl, tetrazolyl, etc.), halogen atoms (chlorine, bromine, iodine, fluorine), alkoxy groups (methoxy, ethoxy) , Pyroxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, etc.), aryloxy groups (phenoxy, etc.), alkoxycarbonyl groups (methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, etc.), aryloxycarbonyl groups (phenyloxycarbonyl) ), Sulfonamide groups (methanesulfonamide, ethanesulfonamide, butanesulfonamide, hexanesulfonamide group, cyclohexanesulfonamide, benzenesulfonamide, etc.), sulfamoyl groups (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylamino) Sulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, phenylaminosulfonyl, 2-pyridylaminos Sulfonyl, etc.), urethane groups (methylureido, ethylureido, pentylureido, cyclohexylureido, phenylureido, 2-pyridylureido, etc.), acyl groups (acetyl, propionyl, butanoyl, hexanoyl, cyclohexanoyl, benzoyl, pyridinoyl, etc.), Carbamoyl group (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl group, cyclohexylaminocarbonyl, phenylaminocarbonyl, 2-pyridylaminocarbonyl), amide group (acetamide, propionamide, butanamide, hexaneamide, Benzamide etc.), sulfonyl group (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, Phenylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, anilino, 2-pyridylamino, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, An oxamoyl group can be exemplified. These groups may be further substituted with these groups. n and m represent an integer of 0 to 2, and most preferably n and m are 0. A plurality of R ₄ may be the same or different.

R ₄ may form a saturated ring with R ₂ and R ₃ . R ₄ is preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom.

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

  These compounds (bisphenol compounds) represented by the general formula (RED) can be easily synthesized by a conventionally known method (for example, see Reference: Japanese Patent Application No. 2002-147562).

  Specific examples of the synthesis method are shown below.

Synthesis of Compound (RED-13) 1.97 g of sodium hydroxide was dissolved in 5.94 ml of water, 30.1 g of 2,4-xylenol and 15 ml of toluene were added, and water and toluene were distilled off at 120 ° C. The reaction solution was returned to room temperature, 13.65 g of 2,4-dimethyl-3-cyclohexenecarboxaldehyde was added, and the mixture was stirred at 120 ° C. for 8 hours. Furthermore, heating and stirring were performed for 12 hours while distilling off generated water. When the heating was stopped and the internal temperature of the reaction solution reached 80 ° C., 64 ml of heptane was gradually added to disperse the reaction solution. After allowing to cool to room temperature, a mixed solution of 5.28 g of concentrated hydrochloric acid and 14.4 ml of water was added and stirred for 4 hours. The mixture was further stirred for 4 hours under cooling with ice water, filtered, and washed with 54 ml of heptane to obtain crude crystals. The obtained crude crystals were dissolved by heating in 133 ml of acetonitrile, filtered, added with 88 ml of water, and stirred at room temperature for 4 hours. The mixture was further stirred for 4 hours under cooling with ice water, and the precipitated crystals were collected by filtration to obtain 28.8 g (yield 80%) of the target compound.

The crystal was a mixed crystal of cis isomer 25% and trans isomer 75% (molar percentage). Melting point: 198.5-199.5 ° C.
(Method for separating cis bodies)
In the same manner as described above, 100 g of a cis / trans mixture was obtained, dissolved in 800 ml of acetonitrile by heating, allowed to cool to room temperature, and stirred overnight. The precipitated crystals were collected by filtration and dried under reduced pressure at 60 ° C. for 15 hours to obtain crystals containing a trans isomer as a main component. On the other hand, the mother liquor was concentrated to about 1/3 amount to obtain 10.9 g of crystals mainly composed of cis. Further, the mother liquor was concentrated to 2/3 amount, seeded with cis isomers and stirred to obtain 3.2 g of crystals mainly composed of cis isomers. Next, the crystals mainly composed of the above two cis bodies are dissolved in 100 ml of tetrahydrofuran, 300 ml of hexane is added while partially concentrating with an evaporator, and the crystals precipitated after concentration to about 100 ml are collected by filtration and filtered at 60 ° C. for 4 hours. It was dried under reduced pressure to obtain 11.1 g of crystals (1) mainly composed of cis body.

  24.4 g of the residue obtained by collecting and concentrating the mother liquor was separated by column chromatography (silica gel 500 g, isopropyl ether / hexane = 1/4) into a fraction containing many trans isomers and a fraction containing cis isomers. The residue obtained by concentrating the fraction containing a large amount of was dissolved in tetrahydrofuran, hexane was added while partially concentrating, and the precipitated crystals were collected by filtration to obtain 12.5 g of crystals mainly containing cis form. This was again dissolved in 100 ml of tetrahydrofuran, 300 ml of hexane was added, and the mixture was concentrated to about 100 ml, and the precipitated crystals were collected by filtration, dried under reduced pressure at 60 ° C. for 4 hours, and crystals containing cis body as the main component (2) 8 g was obtained.

  Next, 11.1 g of crystal (1) and 7.8 g of crystal (2) containing cis body as a main component are combined and dissolved in 300 ml of tetrahydrofuran, treated with activated carbon, and then 1000 ml of hexane is added while partially concentrating to about 300 ml. The crystals precipitated after concentration were collected by filtration, dried under reduced pressure at 60 ° C. for 4 hours, further suspended in 200 ml of hexane, stirred for 30 minutes, filtered and dried under reduced pressure at 60 ° C. for 15 hours to obtain cis-form crystals ( Purity 99.9%) 15.3g was obtained. Melting point: 190 ° C.

First step of synthesis of compound (RED-10) A 100 ml 4-head Kolben was combined with a refluxing device and a stirring device, and 10.0 g (7.24 × 10 ⁻² mol) of 4-hydroxyphenethyl alcohol, 85% phosphoric acid 13 in the Kolben 0.7 g (1.19 × 10 ⁻¹ mol) and 50.0 ml of toluene were added, and the mixture was heated and stirred, heated to 95-100 ° C., and then 5.90 g (7.96 × 10 ⁻² mol) of t-butyl alcohol. Then, a solution of 6.00 ml of toluene is dropped in 30 minutes while maintaining a temperature of 90 to 100 ° C.

After completion of the dropwise addition, the mixture is stirred at the same temperature for 1 hour and then cooled to an internal temperature of 50 ° C. After washing three times with 50.0 ml of water, the pH is adjusted to 6 to 7 with Na ₂ CO ₃ water. Further, after washing with a saturated saline solution, water in the organic layer is removed with MgSO ₄ .

After removing water, MgSO ₄ is filtered off and the solvent is distilled off under reduced pressure. After the completion of distillation, it becomes a water tank. The yield is 14.0 g, which is dissolved in 28 ml of toluene and used as it is in the next step.
Second Step 100 ml Kolben is combined with a reflux device and a stirring device, and the total amount of the first step product (toluene solution), 1.4 g of p-toluenesulfonic acid monohydrate (7.24 × 10 ⁻³ mol) in Kolben. , 1.2 g (3.98 × 10 ⁻² mol) of paraformaldehyde is added and reacted at 70 to 75 ° C. for 3 hours.

  After completion of the reaction, 30.0 ml of ethyl acetate and 20.0 ml of water are added to the contents, and the contents are transferred to a separatory funnel.

Wash with 20.0 ml of water until pH = 6-7. Further, after washing with a saturated saline solution, water in the organic layer is removed with MgSO ₄ . After removing water, MgSO ₄ is filtered off and the solvent is distilled off under reduced pressure. After the completion of distillation, it becomes a water tank. This was column purified ^{* 1} was separated the desired product, dissolved in dichloromethane 11.5 ml, crystallized by cooling ice water to obtain crude crystals. Crude yield 9.5 g (65%).

The crude crystals are dissolved in 9.5 ml of ethyl acetate and crystallized by cooling with ice water to obtain the desired product. Yield 8.8 g (60%).
* 1; Column purification is unavoidable due to the trace amount of impurities produced in the first step, which makes it difficult to crystallize.

  Since the reaction rate in the second step is high, column purification becomes unnecessary if the impurities in the first step can be sufficiently removed.

  The amount of the silver ion reducing agent used in the photothermographic dry imaging material of the present invention varies depending on the type of organic silver salt, the reducing agent, and other additives. A suitable amount is from 05 mol to 10 mol, preferably from 0.1 mol to 3 mol. Within this range, two or more silver ion reducing agents of the present invention may be used in combination. That is, it is preferable from the viewpoints of obtaining a high-quality and high-CP image that the use of reducing agents having different reactivity due to having different chemical structures is excellent in storage stability.

  In the present invention, it may be preferable that the reducing agent is added to and mixed with a photosensitive emulsion solution composed of photosensitive silver halide and organic silver salt grains and a solvent immediately before coating, because photographic performance fluctuation due to stagnation time is small. is there.

  In the silver salt photothermographic material of the present invention, the general formulas (1) to (4) described in JP-A No. 2003-43614 and JP-A No. 2003-66559 are used as development accelerators used in combination with the above reducing agent. Hydrazine derivatives and phenol derivatives represented by the general formulas (1) to (3) described in Japanese Patent Publication No. 1 are preferably used.

  The oxidation potential of the development accelerator used in the silver salt photothermographic material of the present invention is preferably 0.01 V to 0.4 V lower than the compound represented by the general formula (RED). More preferably, it is 0.01 V to 0.3 V lower than the compound represented by (RED). The development accelerator has an oxidation potential of 0.2 V or more by polarography measurement at the SCE counter electrode in a tetrahydrofuran: Britton / Robinson buffer solution adjusted to pH = 6 = 3: 2 mixed solvent. It is preferably 6 V or less, more preferably 0.3 V or more and 0.55 V or less. The pKa value in a 3: 2 mixed solvent of tetrahydrofuran: water is preferably 3 or more and 12 or less, more preferably 5 or more and 10 or less. Tetrahydrofuran adjusted to pH = 6: Britton-Robinson buffer solution = 3: 2 In a mixed solvent, the oxidation potential measured by polarography at the SCE counter electrode is 0.3 V or more and 0.55 V or less, tetrahydrofuran: water The pKa value in the 3: 2 mixed solvent is particularly preferably 5 or more and 10 or less.

  As the silver ion reducing agent according to the present invention, various reducing agents disclosed in European Patent No. 1,278,101 and Japanese Patent Application Laid-Open No. 2003-15252 can also be used.

  The amount of the silver ion reducing agent used in the photothermographic dry imaging material of the present invention varies depending on the type of organic silver salt, the reducing agent, and other additives. A suitable amount is from 05 mol to 10 mol, preferably from 0.1 mol to 3 mol. Within this range, two or more silver ion reducing agents of the present invention may be used in combination. That is, it is preferable from the viewpoints of obtaining a high-quality and high-CP image that the use of reducing agents having different reactivity due to having different chemical structures is excellent in storage stability.

  In the present invention, it may be preferable that the reducing agent is added to and mixed with a photosensitive emulsion solution composed of photosensitive silver halide and organic silver salt grains and a solvent immediately before coating, because photographic performance fluctuation due to stagnation time is small. is there.

[Chemical sensitization]
The photosensitive silver halide grains according to the present invention can be chemically sensitized. For example, use of a compound that releases a chalcogen such as sulfur, selenium, tellurium, or a noble metal ion that releases a noble metal ion such as gold ion by the methods described in JP-A Nos. 2001-249428 and 2001-249426 Thus, it is possible to form and impart a chemical sensitization center (chemical sensitization nucleus) capable of capturing electrons or holes generated by photoexcitation of photosensitive silver halide grains or spectral sensitizing dyes on the grains. In particular, it is preferably chemically sensitized with an organic sensitizer containing a chalcogen atom.

  These organic sensitizers containing chalcogen atoms are preferably compounds having groups capable of adsorbing to silver halide and unstable chalcogen atom sites.

  These organic sensitizers are disclosed in JP-A-60-150046, JP-A-4-109240, JP-A-11-218874, JP-A-11-218875, JP-A-11-218876, JP-A-11-194447, etc. Organic sensitizers having various structures can be used, and among them, at least one compound having a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond It is preferable. In particular, a thiourea derivative having a heterocyclic group and a triphenylphosphine sulfide derivative are preferred.

  As a method for chemical sensitization, techniques according to various chemical sensitization techniques conventionally used in the production of conventional silver halide light-sensitive materials for wet processing can be used (reference: (1) T Edited by H. James “The Theory of the Photographic Process” 4th edition, Macmillan Publishing Co., Ltd., 1977, (2) The Japan Photographic Society, “Basics of Photographic Engineering (Silver Salt Photography), Corona, 1979) In particular, when the silver halide grain emulsion is previously chemically sensitized and then mixed with non-photosensitive organic silver salt grains, it can be chemically sensitized by a conventional method.

The amount of the chalcogen compound used as the organic sensitizer varies depending on the chalcogen compound used, silver halide grains, reaction environment for chemical sensitization, etc., but is 10 ⁻⁸ to 10 ⁻ per mol of silver halide. ² mol is preferred, more preferably 10 ⁻⁷ to 10 ⁻³ mol. The environmental conditions for chemical sensitization are not particularly limited, but in the presence of a compound capable of annihilating or reducing the size of silver chalcogenide or silver nuclei on photosensitive silver halide grains. In particular, it may be preferable to perform chalcogen sensitization using an organic sensitizer containing a chalcogen atom in the presence of an oxidizing agent capable of oxidizing silver nuclei. The sensitizing conditions in this case are preferably 6 to 11 as pAg, more preferably 7 to 10, pH 4 to 10, more preferably 5 to 8, and the temperature increases at 30 ° C. or lower. It is preferable to give a feeling.

  In addition, chemical sensitization using these organic sensitizers is preferably performed in the presence of a heteroatom-containing compound having adsorptivity to spectral sensitizing dyes or silver halide grains. By performing chemical sensitization in the presence of a compound having an adsorptivity to silver halide, dispersion of the chemical sensitization central core can be prevented, and high sensitivity and low fog can be achieved. Although the spectral sensitizing dye will be described later, preferred examples of the heteroatom-containing compound having adsorptivity to silver halide include nitrogen-containing heterocyclic compounds described in JP-A-3-24537. In the nitrogen-containing heterocyclic compound, examples of the heterocyclic ring include pyrazole ring, pyrimidine ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 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, these rings Can be mentioned, for example, a triazolotriazole ring, a diazaindene ring, a triazaindene ring, a pentaazaindene ring, and the like. A heterocyclic ring in which a monocyclic heterocyclic ring and an aromatic ring are condensed, for example, a phthalazine ring, a benzimidazole ring, an indazole ring, a benzthiazole ring, or the like can also be applied.

  Of these, an azaindene ring is preferable, and an azaindene compound having a hydroxyl group as a substituent, for example, a hydroxytriazaindene, tetrahydroxyazaindene, hydroxypentaazaindene compound, or the like is more preferable.

  The heterocyclic ring may have a substituent other than the 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 have.

The amount of the heterocyclic compound 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 ^-6 per mole of silver halide. It is in the range of ˜1 mol, preferably in the range of 10 ⁻⁴ to 10 ⁻¹ mol.

  The photosensitive silver halide according to the present invention can be subjected to noble metal sensitization using a compound that releases noble metal ions such as gold ions. For example, a chloroaurate or an organic gold compound can be used as a gold sensitizer. The gold sensitization technique disclosed in JP-A-11-194447 is useful as a reference.

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

  In the present invention, the silver halide grains subjected to chemical sensitization may be formed in the presence of an aliphatic carboxylic acid silver salt, or in the absence of the organic silver salt, A mixture of the two may be used.

  In the present invention, when chemical sensitization is performed on the surface of the photosensitive silver halide grains, it is necessary that the chemical sensitization effect substantially disappears after the thermal development process. Here, the chemical sensitization effect substantially disappears when the sensitivity of the imaging material obtained by the chemical sensitization technique is 1.1 when the chemical sensitization is not performed after the thermal development process. Say to decrease below. In order to eliminate the chemical sensitization effect in the heat development process, an oxidant capable of destroying the chemical sensitization center (chemical sensitization nucleus) by an oxidation reaction at the time of heat development, for example, the above-mentioned halogen radical releasing compound, etc. It is necessary to contain an appropriate amount of the above in the emulsion layer and / or the non-photosensitive layer of the imaging material. The content of the oxidizing agent is preferably adjusted in consideration of the oxidizing power of the oxidizing agent, the reduction range of the chemical sensitization effect, and the like.

[Spectral sensitization]
The photosensitive silver halide in the present invention is preferably subjected to spectral sensitization by adsorbing a spectral sensitizing dye. As spectral sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. For example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, JP-A-63-304242, JP-A-63-15245, US Pat. No. 4,639,414, No. 4,740,455, No. 4,741,966, No. 4,751,175, No. 4,835,096 can be used.

  Useful sensitizing dyes used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) 17643IV-A (December 1978 p.23), RD18431X (August 1978 p.437). It is described in the literature described or cited. In particular, it is preferable to use a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light sources of various laser imagers and scanners. For example, compounds described in JP-A Nos. 9-34078, 9-54409, and 9-80679 are preferably used.

  Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus and imidazole nucleus. Useful merocyanine dyes are preferably acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus in addition to the basic nuclei described above. Including.

  In the present invention, a sensitizing dye having spectral sensitivity particularly in the infrared can also be used. Examples of infrared spectral sensitizing dyes preferably used include infrared spectral sensitization disclosed in US Pat. Nos. 4,536,473, 4,515,888, 4,959,294, and the like. Examples include dyes.

  In the silver salt photothermographic dry imaging material according to the present invention, the sensitizing dye represented by the following general formula (SD-1) as described in Japanese Patent Application No. 2003-102726 and the following general formula (SD) It is preferable that at least one selected from the sensitizing dyes represented by -2) is contained.

[Wherein, Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom, a selenium atom, or a —CH═CH— group, and L _{1 to} L ₉ each represent a methine group. R ₁ and R ₂ each represents an aliphatic group. R ₃ , R ₄ , R ₂₃ and R ₂₄ each represent a lower alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. W ₁ , W ₂ , W ₃ , and W ₄ are each a hydrogen atom, a substituent, or a nonmetallic atom necessary for bonding between W ₁ and W ₂ , W ₃ and W ₄ to form a condensed ring. Represents a group. Or R ₃ and W ₁ , R ₃ and W ₂ , R ₂₃ and W ₁ , R ₂₃ and W ₂ , R ₄ and W ₃ , R ₄ and W ₄ , R ₂₄ and W ₃ , R ₂₄ and W ₄ Represents a group of non-metallic atoms necessary to form a 5-membered or 6-membered condensed ring by bonding. X ₁ represents an ion necessary for canceling the charge in the molecule, and k 1 represents the number of ions necessary for canceling the charge in the molecule. m1 represents 0 or 1. n1 and n2 each represents 0, 1 or 2. However, n1 and n2 are not 0 at the same time. ]
The above-mentioned infrared sensitizing dyes are described in, for example, HM Hammer, The Chemistry of Heterocyclic Compounds, Vol. 18, The Cyanine Dies and Related Compounds, published by A. Weissberger ed. It can be easily synthesized by this method.

  These infrared sensitizing dyes may be added at any time after the silver halide is prepared. For example, silver halide grains or halogens may be added in a so-called solid dispersion state added to a solvent or dispersed in a fine particle form. It can be added to a light-sensitive emulsion containing silver halide grains / aliphatic carboxylic acid silver salt grains. Similarly to the heteroatom-containing compound having adsorptivity to the silver halide grains, chemical sensitization can be performed after adding and adsorbing to the silver halide grains prior to chemical sensitization. Thus, dispersion of the chemical sensitization central core can be prevented, and high sensitivity and low fog can be achieved.

  In the present invention, one kind of spectral sensitizing dye may be used alone, but as described above, it is preferable to use a combination of plural kinds of spectral sensitizing dyes. The combination is often used for the purpose of supersensitization and enlargement or adjustment of the photosensitive wavelength region.

  The emulsion containing the photosensitive silver halide and the aliphatic carboxylic acid silver salt used in the silver salt photothermographic dry imaging material of the present invention is not only a sensitizing dye but also a dye having no spectral sensitizing action itself or visible light. In the emulsion, a substance that does not substantially absorb the color and expresses a supersensitization effect may be contained in the emulsion, whereby the silver halide grains may be supersensitized.

  Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in RD17643 (issued in December, 1978), page 23, Section J, or Japanese Patent Publication No. 9-25500, 43-4933, JP-A-59-19032, JP-A-59-192242, JP-A-5-341432, and the like. Examples of supersensitizers include heteroaromatic mercapto represented by the following. A compound or a mercapto derivative compound is preferred.

Ar-SM
In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium, or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzthiazole, naphthothiazole, benzoxazole, naphthoxazole, benzselenazole, benztelrazole, imidazole, oxazole, pyrazole, triazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine , Purine, quinoline, or quinazoline. However, other heteroaromatic rings are also included.

  In addition, mercapto derivative compounds that substantially produce the above mercapto compounds when contained in a dispersion of an aliphatic carboxylic acid silver salt or silver halide grain emulsion are also included. In particular, mercapto derivative compounds represented below are preferred examples.

Ar-SS-Ar
Ar in the formula has the same meaning as in the case of the mercapto compound represented above.

  The heteroaromatic ring includes, for example, a halogen atom (for example, chlorine, bromine, iodine), a hydroxyl group, an amino group, a carboxyl group, and an alkyl group (for example, one or more carbon atoms, preferably 1 to 4 carbon atoms). It may have a substituent selected from the group consisting of those having a carbon atom) and alkoxy groups (for example, those having 1 or more carbon atoms, preferably 1 to 4 carbon atoms).

  In addition to the above supersensitizers, macrocycles having heteroatoms disclosed in JP-A-2001-330918 can also be used as supersensitizers.

  The supersensitizer according to the present invention is preferably used in an amount of 0.001 to 1.0 mol per mol of silver in a photosensitive layer containing an organic silver salt and silver halide grains. Particularly preferred is an amount of 0.01 to 0.5 mole per mole of silver.

  In the present invention, it is necessary that the spectral sensitizing dye is adsorbed on the surface of the photosensitive silver halide grain to effect spectral sensitization, and that the spectral sensitizing effect should substantially disappear after the thermal development process. It is. Here, the spectral sensitization effect substantially disappears when the sensitivity of the imaging material obtained by a sensitizing dye, supersensitizer, etc. is the sensitivity when spectral sensitization is not performed after the thermal development process. It means to decrease to 1.1 times or less.

  In order to eliminate the chemical sensitization effect in the thermal development process, a spectral sensitizing dye that is easily detached from the silver halide grains by heat is used during thermal development or / and the spectral sensitizing dye is destroyed by an oxidation reaction. It is necessary to contain an appropriate amount of an oxidizing agent that can be formed, for example, the above-mentioned halogen radical releasing compound in the emulsion layer and / or the non-photosensitive layer of the imaging material. The content of the oxidizing agent is preferably adjusted in consideration of the oxidizing power of the oxidizing agent, the reduction range of the spectral sensitization effect, and the like.

[Silver saving agent]
In the present invention, the photosensitive layer or the non-photosensitive layer can contain a silver saving agent.

  The silver saving agent used in the present invention refers to a compound that can reduce the amount of silver necessary to obtain a certain silver image density. Various action mechanisms of the function of decreasing can be considered, but a compound having a function of improving the covering power of developed silver is preferable. Here, the covering power of developed silver refers to the optical density per unit amount of silver. This silver saving agent can be present in the photosensitive layer, the non-photosensitive layer, or both.

  Preferred examples of the silver saving agent include hydrazine derivatives represented by the following general formula (H), vinyl compounds represented by the following general formula (G), quaternary onium compounds represented by the following general formula (P), and the like. Can be mentioned.

In the general formula [H], A ₀ represents an aliphatic group, aromatic group, heterocyclic group or -G ₀ -D ₀ group which may have a substituent, and B ₀ represents a blocking group. , A ₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. Here, G ₀ is —CO— group, —COCO— group, —CS— group, —C (═NG ₁ D ₁ ) — group, —SO— group, —SO ₂ — group or —P (O) ( G ₁ D ₁ ) — group, G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group, D ₁ represents an aliphatic group, aromatic group, complex When a ring group or a hydrogen atom is represented and a plurality of D ₁ are present in the 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 includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group and the like.

In the general formula [H], the aliphatic group represented by A ₀ is preferably one having 1 to 30 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples thereof 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, a sulfoxy group). Group, sulfonamido 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 aryl group, such as a benzene ring or a naphthalene ring, and the heterocyclic group represented by A ₀ is A heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen atoms in a single ring or a condensed ring is preferred, such as a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, Examples include a thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ 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 anti-diffusion group or silver halide adsorption group. As the anti-diffusion group, a ballast group commonly used in an immobile photographic additive such as a coupler is preferable. As the ballast group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, phenyl, which are photographically inactive, are preferable. Group, phenoxy group, alkylphenoxy group and the like, and the total number of carbon atoms in the substituent portion is preferably 8 or more.

  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 JP-A-64. And the adsorbing group described in -90439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents a -CO- group, a -COCO- group, a -CS- group, -C (= NG ₁ D ₁ ) — group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D ₁ ) — group. Preferred examples of G ₀ include —CO— group and —COCO— group, G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group, and D ₁ represents fatty acid. Represents a group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the 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, An amino group etc. are mentioned. A ₁ and 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.), sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or oxalyl group (Etoxalyl group, etc.).

  These compounds represented by the general formula [H] can be easily synthesized by known methods. For example, it can be synthesized with reference to US Pat. Nos. 5,464,738 and 5,496,695.

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

  In the general formula (G), X and R are shown in a cis form, but a form in which X and R are trans is also included in the general formula (G). The same applies to the structure display of a specific compound.

  In General Formula (G), X represents an electron-withdrawing group, and W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxy group. Oxalyl, thiooxalyl, oxamoyl, oxycarbonyl, thiocarbonyl, carbamoyl, thiocarbamoyl, sulfonyl, sulfinyl, oxysulfinyl, thiosulfinyl, sulfamoyl, oxysulfinyl, thiosulfinyl, Sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group, immonium group are represented.

  R is a halogen atom, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkenyloxy group, acyloxy group, alkoxycarbonyloxy group, aminocarbonyloxy group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group , An alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, an organic or inorganic salt of 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 (5-6 membered nitrogen-containing heterocycle such as benztriazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, etc.), Ureido group, sulfonamido It represents a group. X and W, 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 X is a substituent whose substituent constant σp can take a positive value. Specifically, a substituted alkyl group (such as halogen-substituted alkyl), a substituted alkenyl group (such as cyanovinyl), a substituted / unsubstituted alkynyl group (such as trifluoromethylacetylenyl, cyanoacetylenyl), a substituted aryl group (such as cyano) Phenyl, etc.), substituted / unsubstituted heterocyclic groups (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atoms, cyano groups, acyl groups (acetyl, trifluoroacetyl, formyl, etc.), thioacetyl groups (thioacetyl, thioformyl, etc.) ), Oxalyl group (such as methyloxalyl), oxyoxalyl group (such as etoxalyl), thiooxalyl group (such as ethylthiooxalyl), oxamoyl group (such as methyloxamoyl), oxycarbonyl group (such as ethoxycarbonyl), carboxyl group, thiol Carbonyl group (ethylthiocarboni ), Carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group (ethoxysulfonyl etc.), thiosulfonyl group (ethylthiosulfonyl etc.), sulfamoyl group, oxysulfinyl group (methoxysulfinyl etc.), thiosulfinyl group (Such as methylthiosulfinyl), 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 include a heterocyclic group in which an ammonium group, sulfonium group, phosphonium group, immonium group and the like form a ring. A substituent having a σp value of 0.30 or more is particularly preferable.

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

  Among the substituents of R, 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 are preferable, and a hydroxyl group, An organic or inorganic salt of an alkoxy group, a hydroxyl group or a mercapto group, or a heterocyclic group is exemplified, and an organic or inorganic salt of a hydroxyl group, a hydroxyl group or a mercapto group is particularly preferred.

  Of the substituents X and W, those having a thioether bond in the substituent are preferred.

In the general formula (P), Q ₃ 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. R _{1 to} R ₄ may be connected to each other to form a ring.

Examples of the substituent represented by R _{1 to} R ₄ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group), an alkenyl group (for example, an allyl group, a butenyl group). Group), alkynyl group (eg, propargyl group, butynyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group) , Thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

Examples of the ring that R _{1 to} R ₄ can be formed by connecting to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

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

Examples of the anion represented by X ⁻ include inorganic and organic anions such as halogen ions, sulfate ions, nitrate ions, acetate ions, and p-toluenesulfonate ions.

The quaternary onium compound can be easily synthesized in accordance with a known method. For example, the tetrazolium compound can be synthesized by referring to Chemical Reviews vol. 55 p. The method described in 335-483 can be referred to. The amount of the silver saving agent added is in the range of 10 ⁻⁵ to 1 mol, preferably 10 ^{−4 to} 5 × 10 ⁻¹ mol, per mol of the aliphatic carboxylic acid silver salt.

  In the present invention, it is also preferred that at least one silver saving agent is a silane compound. In the present invention, the silane compound used as a silver saving agent is an alkoxysilane compound having two or more primary or secondary amino groups or a salt thereof as disclosed in Japanese Patent Application Laid-Open No. 2003-5324. Is preferred.

  As a silver saving agent, when an alkoxysilane compound or a salt thereof, or a Schiff base is added to the image forming layer, it is preferably added in a range of usually 0.00001 to 0.05 mol with respect to 1 mol of silver. . The same category applies when both an alkoxysilane compound or a salt thereof and a Schiff base are added to the image forming layer.

〔binder〕
Binders suitable for the silver salt photothermographic dry imaging materials of the present invention are transparent or translucent and generally colorless and are natural polymer synthetic resins, polymers and copolymers, and other media forming films such as: gelatin, gum arabic, Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters) ) , Poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and polyamides. It may be hydrophilic or non-hydrophilic.

  Preferred binders for the photosensitive layer of the silver salt photothermographic dry imaging material of the present invention are polyvinyl acetals, and a particularly preferred binder is polyvinyl butyral. Details will be described later. In addition, for non-photosensitive layers such as overcoat layers and undercoat layers, particularly protective layers and backcoat layers, cellulose esters which are polymers having a higher softening temperature, particularly triacetyl cellulose, cellulose acetate butyrate, etc. Polymers are preferred. In addition, as needed, said binder can be used in combination of 2 or more type.

Such a binder is used in an effective range to function as a binder. The effective range can be easily determined by one skilled in the art. For example, as an index for holding at least an aliphatic carboxylic acid silver salt in the photosensitive layer, the ratio of the binder to the aliphatic carboxylic acid silver salt is 15: 1 to 1: 2, particularly 8: 1 to 1: 1. The range of is preferable. That is, it is preferable amount of the binder in the photosensitive layer is 1.5~6g / m ^2. More preferably, it is 1.7-5 g / m < ² >. If it is less than 1.5 g / m ² , the density of the unexposed area is significantly increased and may not be used.

  In the present invention, the heat transition temperature after development at a temperature of 100 ° C. or higher is preferably 46 ° C. or higher and 200 ° C. or lower, more preferably 70 ° C. or higher and 105 ° C. or lower. The heat transition temperature referred to in the present invention is a value indicated by the VICAT softening point or ring-and-ball method, and is a differential scanning calorimeter (DSC), for example, EXSTAR 6000 (manufactured by Seiko Denshi), DSC220C (manufactured by Seiko Denshi Kogyo). DSC-7 (manufactured by Perkin Elmer) or the like is used to indicate the endothermic peak when the thermally developed photosensitive layer is isolated and measured. Generally, a polymer compound has a glass transition point Tg, but in a silver salt photothermographic dry imaging material, a large endothermic peak is present at a position lower than the Tg value of the binder resin used in the photosensitive layer. Appear. As a result of diligent investigation focusing on this thermal transition point temperature, by setting the thermal transition point temperature to 46 ° C. or higher and 200 ° C. or lower, not only the fastness of the formed coating film is increased, but also the sensitivity, maximum The inventors have newly found that photographic performance such as density and image storage stability is greatly improved, and have reached the present invention.

  The glass transition temperature (Tg) was obtained by the method described in “Polymer Handbook” pages III-139 to III-179 (1966, Wiley and Sun, Inc.) by Brandrup et al. Tg in the case of a polymer resin is obtained by the following formula.

Tg (copolymer) (° C.) = V ₁ Tg ₁ + v ₂ Tg ₂ +... + V _n Tg _{n
Wherein, v 1, v 2 ··· v} n represents the mass fraction of the monomer in the _{copolymer, Tg 1, Tg 2 ··· Tg} n are each monomer in the copolymer Tg (° C.) of a single polymer obtained from the body. ]
The accuracy of Tg calculated according to the above equation is ± 5 ° C.

  In the silver salt photothermographic dry imaging material of the present invention, as the binder contained in the photosensitive layer containing aliphatic carboxylic acid silver salt, photosensitive silver halide grains, reducing agent, etc. on the support, a conventionally known high Molecular compounds can be used. The Tg is 70 to 105 ° C., the number average molecular weight is 1,000 to 1,000,000, preferably 10,000 to 500,000, and the degree of polymerization is about 50 to 1,000. Examples of such include vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, There are compounds made of a polymer or copolymer containing an ethylenically unsaturated monomer such as vinyl ether as a constituent unit, polyurethane resins, and various rubber resins.

  Moreover, phenol resin, epoxy resin, polyurethane curable resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicone resin, epoxy-polyamide resin, polyester resin, and the like can be given. These resins are described in detail in “Plastic Handbook” issued by Asakura Shoten. There is no restriction | limiting in particular in these high molecular compounds, A homopolymer or a copolymer may be sufficient if the glass transition temperature (Tg) of the induced | guided | derived polymer exists in the range of 70-105 degreeC.

  Polymers or copolymers containing such ethylenically unsaturated monomers as structural units include acrylic acid alkyl esters, acrylic acid aryl esters, methacrylic acid alkyl esters, methacrylic acid aryl esters, alkyl cyanoacrylates. Ester, cyanoacrylic acid aryl ester and the like, and the alkyl group and aryl group thereof may or may not be substituted. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, cyclohexyl, benzyl, chlorobenzyl, octyl, stearyl, sulfopropyl, N-ethyl-phenylaminoethyl, 2- (3-phenylpropyloxy) ethyl , Dimethyl Minophenoxyethyl, furfuryl, tetrahydrofurfuryl, phenyl, cresyl, naphthyl, 2-hydroxyethyl, 4-hydroxybutyl, triethylene glycol, dipropylene glycol, 2-methoxyethyl, 3-methoxybutyl, 2-acetoxyethyl, 2 -Acetoacetoxyethyl, 2-ethoxyethyl, 2-iso-propoxyethyl, 2-butoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- (2-butoxyethoxy) Examples thereof include ethyl, 2-diphenylphosphorylethyl, ω-methoxypolyethylene glycol (addition mole number n = 6), allyl, dimethylaminoethylmethyl chloride salt and the like.

  In addition, the following monomers can be used. Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate. N-substituted acrylamides, N-substituted methacrylamides and acrylamides, methacrylamides: N-substituents include methyl, ethyl, propyl, butyl, tert-butyl, cyclohexyl, benzyl, hydroxymethyl, methoxyethyl, dimethyl Aminoethyl, phenyl, dimethyl, diethyl, β-cyanoethyl, N- (2-acetoacetoxyethyl), diacetone and the like; olefins: for example, dicyclopentadiene, ethylene, propylene, 1- Ten, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc .; styrenes: for example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene , Chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester, etc .; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether N-substituted maleimides: As N-substituent, methyl, ethyl, propyl, butyl, tert-butyl, cyclohexyl , Benzyl, n-dodecyl, phenyl, 2-methylphenyl, 2,6-diethylphenyl, 2-chlorophenyl, etc .; others include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate , Diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N -Vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalonnitrile, vinylidene chloride and the like can be mentioned.

  Among these, particularly preferred examples include methacrylic acid alkyl esters, methacrylic acid aryl esters, styrenes, and the like. Among such polymer compounds, it is preferable to use a polymer compound having an acetal group. The polymer compound having an acetal group is preferable because it is excellent in compatibility with the aliphatic carboxylic acid to be produced and has a great effect of preventing the film from being softened.

  As the polymer compound having an acetal group, a compound represented by the following general formula (V) is particularly preferable.

[Wherein, R ₁ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, but is preferably a group other than an aryl group. R ₂ represents an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, —COR ₃ or —CONHR ₃ . R ₃ has the same meaning as R ₁ . ]
The unsubstituted alkyl group represented by R ₁ , R ₂ , or R ₃ is preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 6 carbon atoms. These may be linear or branched, and preferably a linear alkyl group. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, t-amyl, n -Hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, t-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, etc. Is particularly preferably a methyl group or a propyl group.

  As an unsubstituted aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the group that can be substituted with the above alkyl group or aryl group include an alkyl group (for example, a methyl group, an n-propyl group, a t-amyl group, a t-octyl group, an n-nonyl group, a dodecyl group), an aryl group. (For example, phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (for example, methoxy group), aryloxy group (for example, phenoxy group), acyloxy group (for example, acetoxy group), Acylamino group (for example, acetylamino group), sulfonamide group (for example, methanesulfonamide group), sulfamoyl group (for example, methylsulfamoyl group), halogen atom (for example, fluorine atom, chlorine atom, bromine atom) ), Carboxy group, carbamoyl group (for example, methylcarbamoyl group, etc.), alkoxycarbonyl group (for example, metho Shiruboniru group), a sulfonyl group (e.g., methyl sulfonyl group). When there are two or more substituents, they may be the same or different. The total carbon number of the substituted alkyl group is preferably 1-20, and the total carbon number of the substituted aryl group is preferably 6-20.

The R _2, -COR ₃ (R ₃ is an alkyl group or an aryl group), - CONHR ₃ (R ₃ is an aryl group). a, b, and c are values representing the mass of each repeating unit in mol (mol)%, a is 40 to 86 mol%, b is 0 to 30 mol%, and c is in the range of 0 to 60 mol%. A + b + c = 100 mol%, particularly preferably a is in the range of 50 to 86 mol%, b is 5 to 25 mol%, and c is 0 to 40 mol%. Each repeating unit having each composition ratio of a, b, and c may be composed of only the same one or may be composed of different ones.

As the polyurethane resin that can be used in the present invention, known resins such as polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, and polycaprolactone polyurethane can be used. For all of the polyurethane shown here, if _{necessary, -COOM, -SO 3 M, -OSO} 3 M, -P = O (OM) 2, -O-P = O (OM) 2, (M is hydrogen Represents an atom or an alkali metal base), —N (R ₄ ) ₂ , —N ⁺ (R ₄ ) ₃ (R ₄ represents a hydrocarbon group, and a plurality of R ₄ may be the same or different); It is preferable to use one in which at least one polar group selected from an epoxy group, —SH, —CN and the like is introduced by copolymerization or addition reaction. The amount of such a polar group is 10 ⁻¹ to 10 ⁻⁸ mol / g, preferably 10 ⁻² to 10 ⁻⁶ mol / g. In addition to these polar groups, it is preferable to have at least one OH group in total, at least one at the end of the polyurethane molecule. Since OH groups are cross-linked with polyisocyanate which is a curing agent to form a three-dimensional network structure, it is more preferable that the OH groups are contained in the molecule. In particular, it is preferable that the OH group is at the molecular end because the reactivity with the curing agent is high. The polyurethane preferably has 3 or more OH groups at the molecular terminals, and particularly preferably 4 or more. When polyurethane is used, the glass transition temperature is preferably 70 to 105 ° C., the elongation at break is 100 to 2000%, and the stress at break is preferably 0.5 to 100 N / mm ² .

  In the present invention, the polymer compound represented by the general formula (V) is synthesized by a general synthesis method described in “vinyl acetate resin” edited by Ichiro Sakurada (Polymer Chemistry Publishing Society, 1962) and the like. Can do.

  Examples of typical synthesis methods are given below, but the present invention is not limited to these typical synthesis examples.

Synthesis Example 1: Synthesis of P-1 20 g of polyvinyl alcohol (GOHSENOL GH18) manufactured by Nippon Gosei Co., Ltd. and 180 g of pure water were charged and dispersed in pure water so that the polyvinyl alcohol became a 10% by mass solution. The temperature was raised to 95 ° C. to dissolve the polyvinyl alcohol, and then cooled to 75 ° C. to prepare an aqueous polyvinyl alcohol solution. Further, 1.6 g of 10% by mass hydrochloric acid as an acid catalyst was added to the aqueous polyvinyl alcohol solution, This was designated as Droplet A. Subsequently, 11.5 g of a mixture of butyraldehyde and acetaldehyde in a molar ratio of 4: 6 was weighed, and this was designated as Droplet B. 100 ml of pure water was put into a 1000 ml four-necked flask equipped with a condenser and a stirrer, heated to 85 ° C. and vigorously stirred. To this, a dropping funnel in which the dropping liquid A and the dropping liquid B were kept at 75 ° C. was added dropwise simultaneously with stirring for 2 hours. At this time, the reaction was carried out while paying attention to the stirring speed and preventing fusion of the precipitated particles. After completion of the dropping, 7 g of 10% by mass hydrochloric acid was added as an acid catalyst, and the mixture was stirred at a temperature of 85 ° C. for 2 hours to sufficiently react. Then, it cooled to 40 degreeC, neutralized using baking soda, and after repeating water washing 5 times, it separated by filtration, the polymer was taken out and dried, and P-1 was obtained. When Tg was measured for the obtained P-1 using DSC, Tg was 83 degreeC.

  Other polymer compounds (polymers) listed in Table 1 were synthesized in the same manner.

  These polymer compounds may be used alone as a binder, or two or more kinds may be blended and used. In the photosensitive silver salt-containing layer (preferably photosensitive layer) of the present invention, the above polymer is used as a main binder. The main binder as used herein refers to “a state in which the polymer occupies 50% by mass or more of the total binder of the photosensitive silver salt-containing layer”. Therefore, other polymers may be blended and used within a range of less than 50% by weight of the total binder. These polymers are not particularly limited as long as the polymers of the present invention are soluble. More preferably, polyvinyl acetate, a polyacrylic resin, a urethane resin, etc. are mentioned.

  Below, the structure of the high molecular compound preferably used for this invention is shown. In the table, Tg is a value measured by a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc.

  In Table 1, P-9 is a polyvinyl butyral resin B-79 manufactured by Solusia.

  In the present invention, it is known that the use of a crosslinking agent with respect to the binder improves the film formation and reduces development unevenness. However, it prevents fogging during storage and produces printed silver after development. There is also an inhibitory effect.

  Examples of the crosslinking agent used in the present invention include various crosslinking agents conventionally used for silver halide photographic light-sensitive materials, such as aldehyde-based, epoxy-based, and ethyleneimine described in JP-A-50-96216. , Vinyl sulfone, sulfonic acid ester, acryloyl, carbodiimide, and silane compound crosslinking agents may be used, but the following isocyanate compounds, silane compounds, epoxy compounds, or acid anhydrides are preferred.

  An isocyanate-based and thioisocyanate-based crosslinking agent represented by the following general formula [IC], which is one of the preferred ones, will be described.

General Formula [IC] X = C = N-L- (N = C = X)
In the formula, v is 1 or 2, L is an alkyl group, an alkenyl group, an aryl group or an alkylaryl group, a v + 1 valent linking group, and X is an oxygen or sulfur atom.

  In the compound represented by the above general formula [IC], the aryl ring of the aryl group may have a substituent. Examples of preferred substituents are selected from halogen atoms (for example, bromine atoms or chlorine atoms), hydroxyl groups, amino groups, carboxyl groups, alkyl groups and alkoxy groups.

  The isocyanate-based crosslinking agent includes isocyanates having at least two isocyanate groups and adducts thereof (adducts), and more specifically, aliphatic diisocyanates and aliphatic diisocyanates having a cyclic group. Benzene diisocyanates, naphthalene diisocyanates, biphenyl isocyanates, diphenylmethane diisocyanates, triphenylmethane diisocyanates, triisocyanates, tetraisocyanates, adducts of these isocyanates and divalent or trivalent with these isocyanates Examples include adducts with polyalcohols.

  As specific examples, isocyanate compounds described on pages 10 to 12 of JP-A-56-5535 can be used.

  Note that the adduct body of isocyanate and polyalcohol has particularly high ability to improve interlayer adhesion, and prevent layer peeling, image shift, and bubble generation. Such isocyanates may be placed in any part of the silver salt photothermographic dry imaging material. For example, the photosensitivity of the support in the support (especially when the support is paper, it can be included in the size composition), photosensitive layer, surface protective layer, intermediate layer, antihalation layer, subbing layer, etc. It can be added to any layer on the layer side, and can be added to one or more of these layers.

  As the thioisocyanate-based crosslinking agent that can be used in the present invention, compounds having a thioisocyanate structure corresponding to the above-mentioned isocyanates are also useful.

  The amount of the crosslinking agent used in the present invention is in the range of 0.001 to 2 mol, preferably 0.005 to 0.5 mol, with respect to 1 mol of silver.

  The isocyanate compound and thioisocyanate compound that can be contained in the present invention are preferably compounds that function as the above-mentioned crosslinking agent. However, in the above general formula, v is zero (0), that is, the functional group is one. Even if it is a compound which has only, a good result is obtained.

  Examples of the silane compound that can be used as a crosslinking agent in the present invention include compounds represented by general formula (1) or general formula (2) described in JP-A-2002-22203.

In these general formulas, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a linear, branched or cyclic carbon group having 1 to 30 carbon atoms which may be substituted. Alkyl group (methyl group, ethyl group, butyl group, octyl group, dodecyl group, cycloalkyl group, etc.), alkenyl group (propenyl group, butenyl group, nonenyl group, etc.), alkynyl group (acetylene group, bisacetylene group, phenylacetylene) Group), aryl group or heterocyclic group (phenyl group, naphthyl group, tetrahydropyran group, pyridyl group, furyl group, thiophenyl group, imidazole group, thiazole group, thiadiazole group, oxadiazole group, etc.), substituent As an electron-withdrawing substituent or an electron-donating substituent.

^{R 1, R 2, R 3} , R 4, preferably R ^5, R ^6, at least 1 Tsuga耐diffusion group or adsorptive group substituents selected from R ⁷ and R ^8, especially R ² It is preferably a diffusion-resistant group or an adsorptive group.

  The non-diffusible group is also called a ballast group, and is preferably an aliphatic group having 6 or more carbon atoms or an aryl group into which an alkyl group having 3 or more carbon atoms is introduced. Diffusion resistance varies depending on the amount of binder and cross-linking agent used, but by introducing a diffusion-resistant group, the intramolecular movement distance at room temperature is suppressed, and the reaction over time can be suppressed.

  The epoxy compound that can be used as the crosslinking agent is not particularly limited as long as it has one or more epoxy groups and the number of epoxy groups, molecular weight, and the like. The epoxy group is preferably contained in the molecule as a glycidyl group via an ether bond or an imino bond. Moreover, any of a monomer, an oligomer, a polymer, etc. may be sufficient as an epoxy compound, and the number of the epoxy groups which exist in a molecule | numerator is about 1-10 normally, Preferably it is 2-4. When the epoxy compound is a polymer, it may be a homopolymer or a copolymer, and the particularly preferred range of the number average molecular weight Mn is about 2000 to 20000.

  As an epoxy compound, the compound represented by the following general formula (EP) is preferable.

In the general formula (EP), the substituent of the alkylene group represented by R is preferably a group selected from a halogen atom, a hydroxyl group, a hydroxyalkyl group, or an amino group. The linking group represented by R preferably has an amide linking moiety, an ether linking moiety, or a thioether linking moiety. -SO ₂ The divalent linking group represented by _{X -, - SO 2 NH -} , - S -, - O-, or -NR ₁ - is preferred. Here, R ₁ is a monovalent group and is preferably an electron withdrawing group.

These epoxy compounds may be used alone or in combination of two or more. The addition amount is not particularly limited, but is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / m ² , more preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² . It is.

  The epoxy compound can be added to any layer on the photosensitive layer side of the support, such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer, an undercoat layer, and one or two of these layers. It can be added to the above. Moreover, it can add to the arbitrary layer on the opposite side to the photosensitive layer of a support body collectively. In addition, any layer may be sufficient in the type of photosensitive material in which a photosensitive layer exists on both surfaces.

  An acid anhydride is a compound having at least one acid anhydride group represented by the following structural formula.

-CO-O-CO-
The acid anhydride is not particularly limited as long as it has one or more acid anhydride groups, and the number, molecular weight, and the like of the acid anhydride groups are not limited, but a compound represented by the following general formula (SA) is preferable.

  In the general formula (SA), Z represents an atomic group necessary for forming a monocyclic or polycyclic system. These ring systems may be unsubstituted or substituted. Examples of substituents include alkyl groups (eg, methyl, ethyl, hexyl), alkoxy groups (eg, methoxy, ethoxy, octyloxy), aryl groups (eg, phenyl, naphthyl, tolyl), hydroxyl groups, aryloxy groups (Eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group Sulfonylamino group, acyloxy group (for example, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, and amino group. As the substituent, those not containing a halogen atom are preferable.

These acid anhydrides may be used alone or in combination of two or more. The addition amount is not particularly limited, but is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / m ² , more preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² . It is.

  In the present invention, the acid anhydride can be added to any layer on the photosensitive layer side of the support, such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer, and an undercoat layer. It can be added to a layer or two or more layers. Moreover, you may add to the same layer as the said epoxy compound.

(Color adjustment)
Next, the color tone of an image obtained by heat developing the imaging material will be described.

  Regarding the color tone of an output image for medical diagnosis such as a conventional X-ray photographic film, it is said that a cold tone image tone is easier for a reader to obtain a more accurate diagnostic observation result of a recorded image. Here, a cool image tone is a pure black tone or a bluish black tone with a black image, and a warm image tone is a black tone with a brown tone. However, in order to allow a more precise quantitative discussion, the following explanation is based on the expression recommended by the International Commission on Illumination (CIE).

Terminology of color "more Hiyacho" and "more temperature control" can be represented by the hue angle h _ab at the lowest density Dmin and optical density D = 1.0. That is, the hue angle h _ab represents the color coordinates a ^* and b ^* of the color space L ^* a ^* b ^* color space, which is a color space having a perceptually uniform rate recommended by the International Commission on Illumination (CIE) in 1976. Using the following formula.

h _ab = tan ⁻¹ (b ^* / a ^* )
As a result of the examination based on the expression method based on the hue angle, the color tone after development of the silver salt photothermographic imaging material according to the present invention preferably has a hue angle _hab range of 180 degrees < _hab <270 degrees. More preferably, it was found that 200 degrees < _hab <270 degrees, and most preferably 220 degrees < _hab <260 degrees. This is disclosed in Japanese Patent Application Laid-Open No. 2002-6463.

Conventionally, the CIE 1976 (L ^* u ^* v ^* ) color space or the (L ^* a ^* b ^* ) color space in the vicinity of an optical density of 1.0 is specified as u ^* , v ^* or a ^* , b ^* . It is known that a diagnostic image having a preferable visual color tone can be obtained by adjusting the numerical value, and is described in, for example, Japanese Patent Application Laid-Open No. 2000-29164.

As a result of further intensive studies on the silver salt photothermographic imaging material according to the present invention, the horizontal axis is u ^{* in} the CIE 1976 (L ^* u ^* v ^* ) color space or (L ^* a ^* b ^* ) color space. When a linear regression line is created by plotting u ^* , v ^* or a ^* , b ^* at various photographic densities on a graph with a ^* and the vertical axis representing v ^* or b ^* , the linear regression line is plotted. It was found that by adjusting the value to a specific range, it has a diagnostic ability equal to or higher than that of the conventional wet silver salt light-sensitive material. In the following, the condition range of the present invention will be described.

The optical density of the imaging material is measured at 0.5, 1.0, 1.5 and the lowest optical density. The horizontal axis of the CIE 1976 (L ^* a ^* b ^* ) color space is a ^* , and the vertical axis is the two-dimensional coordinate in terms of the b ^*, a ^* in the above each optical density, coefficient of determination of the linear regression line that created arranged b ^* (multiple determination) R ² is 1.000 or less than 0.998.

Furthermore, the b ^* value of the intersection with the vertical axis of the linear regression line is −5 or more and 5 or less, and the slope (b ^* / a ^* ) is 0.7 or more and 2.5 or less.

Note that the linear regression line determination coefficient (multiple determination) R ² created by arranging u ^* and v ^* at each optical density is 0.998 or more and 1.000 or less, and the vertical line of the linear regression line is vertical. The v ^* value at the intersection with the axis is preferably −5 or more and 5 or less, and the slope (v ^* / u ^* ) is preferably 0.7 or more and 2.5 or less.

Next, an example of a method for creating the above-described linear regression line, that is, a method for measuring u ^* , v ^* and a ^* , b ^{* in} the CIE 1976 color space will be described.

A four-stage wedge sample including an unexposed portion and optical densities of 0.5, 1.0, and 1.5 is prepared using a heat development apparatus. Each wedge density part thus produced is measured with a spectrocolorimeter (example: CM-3600d; manufactured by Minolta Co., Ltd.) to calculate u ^* , v ^* or a ^* , b ^* . The measurement conditions at that time are F7 light source as the light source, the viewing angle is 10 °, and the measurement is performed in the transmission measurement mode. Plot u ^* , v ^*, a ^* , b ^* measured on a graph with u ^* or a ^{* on} the horizontal axis and v ^* or b ^{* on the} vertical axis to obtain a linear regression line and determine coefficient (multiple determination) R ² Find the intercept and slope.

  Next, a specific method for obtaining a linear regression line having the above characteristics will be described.

  In the present invention, the developed silver shape is adjusted by adjusting the addition amount of the above-described toning agent, developer, silver halide grains, and compounds such as aliphatic carboxylic acid silver which are directly and indirectly involved in the development reaction process. Optimized and preferred color tone. For example, when the developed silver shape is dendritic, it becomes a bluish direction, and when it is a filament shape, it becomes a yellowish direction. That is, it can be adjusted in consideration of the tendency of the developed silver shape.

  Conventionally, phthalazinone or phthalazine and phthalic acids and phthalic anhydrides are generally used as toning agents. Examples of suitable toning agents are RD17029, U.S. Pat. Nos. 4,123,282, 3,994,732, 3,846,136, and 4,021,249. Is disclosed.

  In addition to such a toning agent, it is preferable to adjust the color tone using a coupler disclosed in JP-A-11-288057, EP11334611A2, etc. and a leuco dye described in detail below.

  Further, by using silver halide grains that are converted into the internal latent image type after heat development according to the present invention, it is possible to unexpectedly prevent color tone fluctuations during storage of silver images.

[Leuco dye]
A leuco dye is used in the silver salt photothermographic dry imaging material of the present invention.

  The leuco dye is preferably any colorless or slightly colored compound that is oxidized to a colored form when heated at a temperature of about 80-200 ° C. for about 0.5-30 seconds, and is oxidized by silver ions. Any leuco dye that forms a pigment can be used. Compounds that are pH sensitive and can be oxidized to a colored state are useful.

  Representative leuco dyes suitable for use in the present invention are not particularly limited. For example, biphenol leuco dyes, phenol leuco dyes, indoalilin leuco dyes, acrylated azine leuco dyes, phenoxazine leuco dyes, phenodiazine leuco dyes. And phenothiazine leuco dye. Also useful are U.S. Pat. Nos. 3,445,234, 3,846,136, 3,994,732, 4,021,249, 4,021,250, 4 No. 4,022,617, No. 4,123,282, No. 4,368,247, No. 4,461,681, and JP-A-50-36110, No. 59-206931, JP-A-5-204087. No. 11-231460, JP-A Nos. 2002-169249, 2002-236334, and the like.

  In order to adjust to a predetermined color tone, it is preferable to use leuco dyes of various colors singly or in combination of a plurality of types. In the present invention, the color tone is excessively yellowish with the use of a highly active reducing agent, or the image is excessively high at a high density portion of 2.0 or more by using fine silver halide. It is preferable to use a leuco dye that develops in cyan to prevent redness, but a yellow leuco dye and other leuco dyes that develop in cyan are also used for fine-tuning the color tone. It is preferable to do this.

  The color density is preferably adjusted appropriately in relation to the color tone of the developed silver itself. In the present invention, the sum of the maximum densities at the absorption maximum wavelength of the dye image formed by the leuco dye is usually 0.01 or more and 0.30 or less, preferably 0.02 or more and 0.20 or less, particularly preferably 0.02 or more. It is preferable to adjust the color tone so that the color is developed so as to have a value of 0.10 or less and an image having a preferable color tone range described later is obtained.

(Yellow coloring leuco dye)
In the present invention, a color image forming agent represented by the following general formula (YL), which increases the absorbance at 360 to 450 nm when oxidized, is particularly preferably used as a yellow coloring leuco dye.

  Hereinafter, the compound represented by formula (YL) will be described in detail.

In the general formula (YL), the alkyl group represented by R ₁ is preferably an alkyl group having 1 to 30 carbon atoms, and may have a substituent. Specifically, methyl, ethyl, butyl, octyl, i-propyl, t-butyl, t-octyl, t-pentyl, sec-butyl, cyclohexyl, 1-methyl-cyclohexyl and the like are preferable, and steric rather than i-propyl. Are preferably large groups (i-propyl, i-nonyl, t-butyl, t-amyl, t-octyl, cyclohexyl, 1-methyl-cyclohexyl, adamantyl, etc.), among which secondary or tertiary alkyl Group is preferable, and tertiary alkyl groups such as t-butyl, t-octyl, and t-pentyl are particularly preferable. Examples of the substituent that R ₁ may have include a halogen atom, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an alkylthio group, an arylthio group, a sulfonamide group, an acyloxy group, an oxycarbonyl group, and a carbamoyl group. , Sulfamoyl group, sulfonyl group, phosphoryl group and the like.

R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group or an acylamino group, respectively. The alkyl group represented by R ₂ is preferably an alkyl group having 1 to 30 carbon atoms, and the acylamino group is preferably an acylamino group having 1 to 30 carbon atoms. Among these, the description of the alkyl group is the same as that for R ₁ .

The acylamino group represented by R ₂ may be unsubstituted or substituted, and specific examples include an acetylamino group, an alkoxyacetylamino group, and an aryloxyacetylamino group. R ₂ is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 24 carbon atoms, and specific examples include methyl, i-propyl, and t-butyl. R ₁ and R ₂ are not 2-hydroxyphenylmethyl groups.

R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and the description of the alkyl group is the same as that for R ₁ . R ₃ is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 24 carbon atoms, and specific examples include methyl, i-propyl, and t-butyl. Further, it is preferable either R _12, R ₁₃ is a hydrogen atom.

R ₄ represents a group capable of substituting on the benzene ring and is, for example, the same group as described for the substituent R ₄ in the general formula (RED). R ₄ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or an oxycarbonyl group having 2 to 30 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Examples of the substituent of the alkyl group include an aryl group, an amino group, an alkoxy group, an oxycarbonyl group, an acylamino group, an acyloxy group, an imide group, and a ureido group, and more preferable examples include an aryl group, an amino group, an oxycarbonyl group, and an alkoxy group. preferable. These alkyl group substituents may be further substituted with these substituents.

  Next, among the compounds represented by the general formula (YL), a compound (bisphenol compound) preferably used in the present invention is represented by the following formula.

[Wherein, Z represents —S— or —C (R ₁ ) (R ₁ ′) —, and R ₁ and R ₁ ′ each represents a hydrogen atom or a substituent. Examples of the substituent represented by R ₁ and R ₁ ′ include the same groups as the substituents exemplified in the description of R _{1 in} the general formula (RED). R ₁ and R ₁ ′ are preferably a hydrogen atom or an alkyl group.

R ₂ , R ₃ , R ₂ ′ and R ₃ ′ each represent a substituent, and examples of the substituent include the same groups as those described for R ₂ and R ₃ in the general formula (RED). ]
R ₂ , R ₃ , R ₂ ′ and R ₃ ′ are preferably an alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, with an alkyl group being more preferred. Examples of the substituent on the alkyl group include the same groups as those described in the description of the substituent in the general formula (RED).

R ₂ , R ₃ , R ₂ ′ and R ₃ ′ are more preferably tertiary alkyl groups such as t-butyl, t-pentyl, t-octyl and 1-methyl-cyclohexyl.

R ₄ and R ₄ ′ each represent a hydrogen atom or a substituent, and examples of the substituent include the same groups as those described in the description of R ₄ in the general formula (RED).

  Examples of the compound represented by the general formula (YL) (bisphenol compound) include compounds (II-1) to (II-40) described in paragraphs “0032” to “0038” of JP-A No. 2002-169249, EP1, Examples thereof include compounds (ITS-1) to (ITS-12) described in paragraph “0026” of No. 211,093.

  Although the specific example of a compound represented by general formula (YL) below is shown, this invention is not limited to these.

  The addition amount of the compound represented by the general formula (YL) is usually 0.00001 to 0.01 mol, preferably 0.0005 to 0.01 mol, more preferably 0.001 to 1 mol per 1 mol of silver. 0.008 mol.

(Cyan coloring leuco dye)
Next, the cyan color-forming leuco dye will be described. In the present invention, a color image forming agent that increases its absorbance at 600 to 700 nm when oxidized is particularly preferably used as a cyan color developing dye. JP-A-59-206831 (especially, λmax is 600 to 700 nm). And compounds of general formula (I) to general formula (IV) in JP-A-5-204087 (specifically, (1) to (18) described in paragraphs “0032” to “0037”) ) And compounds of general formula 4 to general formula 7 of JP-A No. 11-231460 (specifically, compounds of No. 1 to No. 79 described in paragraph “0105”).

  The cyan color-forming leuco dye particularly preferably used in the present invention is represented by the following general formula (CL).

[Wherein R ₁ and R ₂ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkoxy group, and an NHCO-R ₁₀ group wherein R ₁₀ is an alkyl group, an aryl group or a heterocyclic group. Or R ₁ and R ₂ are groups which are linked to each other to form an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring or a heterocyclic ring. A is a —NHCO— group, —CONH— group or —NHCONH— group, R ₃ is a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, or —A—R ₃ is a hydrogen atom. , W is a hydrogen atom or —CONH—R ₅ group, —CO—R ₅ group or —CO—O—R ₅ group, wherein R ₅ is a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, R ₄ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₆ is a —CONH—R ₇ group, a —CO—R ₇ group or a —CO—O—R ₇ group, wherein R ₇ is a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. X represents a substituted or unsubstituted aryl group or heterocyclic group. ]
In the general formula (CL), fluorine, bromine, chlorine, etc. as halogen atoms, alkyl groups having up to 20 carbon atoms (methyl, ethyl, butyl, dodecyl etc.) as alkyl groups, and alkenyl groups having carbon atoms Up to 20 alkenyl groups (vinyl, allyl, butenyl, hexenyl, hexadienyl, ethenyl-2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, etc.), alkoxy groups Is an alkoxy group having up to 20 carbon atoms (methoxy, ethoxy, etc.), an aryl group is a group having 6 to 20 carbon atoms such as phenyl, naphthyl, thienyl, and a heterocyclic group is thiophene, furan, imidazole. , Pyrazole, pyrrole and the like. A is a —NHCO— group, —CONH— group or —NHCONH— group, and R ₃ is a substituted or unsubstituted alkyl group (preferably up to 20 carbon atoms such as methyl, ethyl, butyl, dodecyl), an aryl group (preferably phenyl with 6 to 20 carbon atoms is, naphthyl, thienyl, etc.) or a Hajime Tamaki (thiophene, furan, imidazole, pyrazole, or pyrrole, etc.), or -A-R _3, is a hydrogen atom, W is a hydrogen atom Or R ₅ is a substituted or unsubstituted alkyl group (preferably up to 20 carbon atoms such as methyl, ethyl, butyl, dodecyl, etc.), aryl group (preferably having 6 to 20 carbon atoms such as phenyl, naphthyl, thienyl, etc.) or heterocyclic ring —CONH—R ₅ group, —CO—R ₅ group or —CO, which is a group (thiophene, furan, imidazole, pyrazole, pyrrole, etc.) —O—R ₅ group, wherein R ₄ is a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a chain or cyclic alkyl group (eg, methyl group, butyl group, dodecyl group, cyclohexyl group). Etc.), alkoxy groups (for example, methoxy group, butoxy group, tetradecyloxy group, etc.), carbamoyl groups (for example, diethylcarbamoyl group, phenylcarbamoyl group, etc.), or nitrile groups are preferable. Among these, hydrogen atom, alkyl Groups are more preferred. R ₁ and R ₂ , R ₃ and R ₄ may be linked to each other to form a ring structure. The above groups may further have a single substituent or a plurality of substituents. For example, typical substituents that can be introduced into an aryl group include halogen atoms (fluorine, chlorine, bromine, etc.), alkyl groups ( Methyl, ethyl, propyl, butyl, dodecyl, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (methoxy, ethoxy, etc.), alkylsulfonamide group (methylsulfonamide, octylsulfonamide, etc.), arylsulfonamide group (phenyl) Sulfonamides, naphthylsulfonamides, etc.), alkylsulfamoyl groups (butylsulfamoyl etc.), arylsulfamoyls (phenylsulfamoyl etc.), alkyloxycarbonyl groups (methoxycarbonyl etc.), aryloxycarbonyl groups (phenyl) Oxycarbonyl, etc.), aminosulfone Bromide group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group include an amino group. Two different groups of these groups can be introduced into the aryl group. R ₁₀ or R ₈₅ is preferably a phenyl group, more preferably a phenyl group having a plurality of substituents including a halogen atom and a cyano group.

R ₆ is (methyl up to several preferably 20 carbon atoms, ethyl, butyl, dodecyl, etc.) R ₇ is a substituted or unsubstituted alkyl group, (phenyl preferably 6 to 20 carbon atoms, naphthyl, thienyl, etc.) an aryl group or A —CONH—R ₇ group, a —CO—R ₇ group or a —CO—O—R ₇ group which is a heterocyclic group (thiophene, furan, imidazole, pyrazole, pyrrole, etc.). As the substituent for the alkyl group represented by R _7, the same substituents as those for R _{1 to} R ₄ can be used. X ₈ represents a substituted or unsubstituted aryl group or heterocyclic group. Examples of the aryl group include groups having 6 to 20 carbon atoms such as phenyl, naphthyl, and thienyl, and examples of the heterocyclic group include thiophene, furan, imidazole, pyrazole, and pyrrole. As the substituent that the group represented by X can have, the same substituents as those in R _{1 to} R ₄ can be used. The group represented by X is preferably an aryl group or a heterocyclic group substituted with an alkylamino group (such as a diethylamino group) at the para position. These may contain photographically useful groups.

  Specific examples of the cyan chromogenic leuco dye (CL) are shown below, but are not limited thereto.

  The addition amount of the cyan coloring leuco dye is usually 0.00001 to 0.05 mol / Ag1 mol, preferably 0.0005 to 0.02 mol / Ag1 mol, more preferably 0.001 to 0.01 mol. / Ag1 mol.

  As a method for adding the compound represented by the general formula (YL) and the cyan color-forming leuco dye, it can be added in the same manner as the method for adding the reducing agent represented by the general formula (RED), You may make it contain in a coating liquid by arbitrary methods, such as an emulsified dispersion form and a solid fine particle dispersion form, and may make it contain in a photosensitive material.

  The compound of the general formula (YL) and the cyan color-forming leuco dye are preferably contained in an image forming layer containing an organic silver salt, but one is in the image forming layer and the other is adjacent to the image forming layer. You may make it contain in a forming layer, and may make both contain in a non-image forming layer. When the image forming layer is composed of a plurality of layers, they may be contained in separate layers.

[Coating aids, etc.]
In the present invention, the surface layer of the silver salt photothermographic dry imaging material (when the photosensitive layer side or the non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support sandwiched) is handled before development. It is preferable to contain a matting agent in order to prevent scratches on the image after heat development, and 0.1 to 30% by mass with respect to the binder.

  The material of the matting agent may be either organic or inorganic. Examples of inorganic substances include silica described in Swiss Patent No. 330,158 and the like, glass powder described in French Patent No. 1,296,995 and the like, and alkali described in British Patent No. 1,173,181 and the like. Earth metals or carbonates such as cadmium and zinc can be used as the matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037 and the like, starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol described, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, polyacrylonitrile described in US Pat. No. 3,079,257, US Pat. No. 3,022,169 etc. An organic matting agent such as a polycarbonate can be used.

  The matting agent preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. The coefficient of variation of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

  Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100
The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed and applied in advance in the coating solution, or a method in which the matting agent is sprayed after the coating solution is applied and before drying is completed. May be. When a plurality of types of matting agents are added, both methods may be used in combination.

[Fluorosurfactant]
In the imaging material according to the present invention, it is preferable to use fluorine-based surfactants represented by the following general formulas (SA-1) to (SA-3).

Formula (SA-1) (Rf-L) _p -Y- (A) _q
Formula _{(SA-2) LiO 3 S-} (CF 2) n -SO 3 Li
Formula _{(SA-3) MO 3 S-} (CF 2) n -SO 3 M
(In the formula, M represents a hydrogen atom, a sodium atom, a potassium atom, or an ammonium group, and n represents a positive integer, n = 1 to 6 and 8 when M = H, and n when M = Na. = 4, when M = K, n = 1 to 6, and when M = ammonium group, n = 1 to 8.)
In the general formula (SA-1), Rf represents a substituent containing a fluorine atom. Examples of the substituent containing a fluorine atom include an alkyl group having 1 to 25 carbon atoms (for example, a methyl group, an ethyl group, and the like). Group, butyl group, octyl group, dodecyl group, octadecyl group and the like) or alkenyl group (for example, propenyl group, butenyl group, nonenyl group, dodecenyl group, etc.) and the like.

  L represents a divalent linking group having no fluorine atom. Examples of the divalent linking group having no fluorine atom include an alkylene group (for example, methylene group, ethylene group, butylene group, etc.), alkylene Oxy group (methyleneoxy group, ethyleneoxy group, butyleneoxy group, etc.), oxyalkylene group (for example, oxymethylene group, oxyethylene group, oxybutylene group, etc.), oxyalkyleneoxy group (for example, oxymethyleneoxy group, oxy Ethyleneoxy group, oxyethyleneoxyethyleneoxy group, etc.), phenylene group, oxyphenylene group, phenyloxy group, oxyphenyloxy group, or a combination of these groups.

  A represents an anionic group or a base thereof, for example, a carboxylic acid group or a base thereof (sodium salt, potassium salt and lithium salt), a sulfonic acid group or a base thereof (sodium salt, potassium salt and lithium salt) and a phosphoric acid group or Examples thereof include sodium base and potassium salt.

  Y represents a trivalent or tetravalent linking group having no fluorine atom. For example, an atom composed of a trivalent or tetravalent linking group having no fluorine atom and centering on a carbon atom or a nitrogen atom. Groups. p represents an integer of 1 to 3, and q represents an integer of 2 to 3.

  The fluorine-based surfactant represented by the general formula (SA-1) is an alkyl compound having 1 to 25 carbon atoms into which a fluorine atom has been introduced (for example, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorobutyl group, A compound having a fluorooctyl group and a perfluorooctadecyl group) and an alkenyl compound (for example, a perfluorohexenyl group and a perfluorononenyl group), and a trivalent to hexavalent alkanol compound in which no fluorine atom is introduced, An anionic group (A) is further added to a compound (partially Rf-modified alkanol compound) obtained by addition reaction or condensation reaction with an aromatic compound or hetero compound having 3 to 4 hydroxyl groups, for example by sulfate esterification. It can be obtained by introduction.

  Examples of the trivalent to hexavalent alkanol compound include glycerin, pentaerythritol, 2-methyl-2-hydroxymethyl 1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentene, and 1,2,6-hexane. Examples include triol, 1,1,1-tris (hydroxymethyl) propane, 2,2-bis (butanol) -3, aliphatic triol, tetramethylolmethane, D-sorbitol, xylitol, D-mannitol and the like.

  Examples of the aromatic compound and hetero compound having 3 to 4 hydroxyl groups include 1,3,5-trihydroxybenzene and 2,4,6-trihydroxypyridine.

  N in general formula (SA-2) represents the integer of 1-4.

  In General Formula (SA-3), M represents a hydrogen atom, a sodium atom, a potassium atom, or an ammonium group, n represents a positive integer, and when M = H, n = 1 to 6 and 8; When n = Na, n = 4, when M = K, n = 1-6, and when M = ammonium group, n = 1-8.

  As a method of adding the fluorine-based surfactant represented by the general formulas (SA1) to (SA-3) to the coating solution, it can be added according to a known addition method. That is, it can be dissolved and added in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion, and added. Many techniques for fine particle dispersion are disclosed, but they can be dispersed according to these techniques. The fluorosurfactant is preferably added to the outermost protective layer.

The amount of the fluorosurfactant added is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol per 1 m ^2, particularly preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. If it is less than the former range, charging characteristics cannot be obtained, and if it exceeds the former range, the humidity dependence is large and the storage stability under high humidity deteriorates.

  Note that surfactants represented by the general formula (SA-1), the general formula (SA-2), and the general formula (SA-3) are disclosed in JP-A-2003-57786, Japanese Patent Application No. 2002-178386, and JP-A-2002-237882, respectively. It is disclosed in the specification.

  Examples of the support material used in the silver salt photothermographic dry imaging material of the present invention include various polymer materials, glass, wool cloth, cotton cloth, paper, metal (for example, aluminum), etc. In terms of handling, a material that can be processed into a flexible sheet or roll is suitable. Therefore, as a support in the silver salt photothermographic dry imaging material of the present invention, a plastic film (for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyethylene naphthalate film, polyamide film, polyimide film, cellulose triacetate film, polycarbonate film, etc. In the present invention, a biaxially stretched polyethylene terephthalate film is particularly preferable. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

  In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be included in the constituent layers in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like. In the present invention, the conductive compounds described in US Pat. No. 5,244,773, columns 14 to 20 are preferably used.

  The silver salt photothermographic dry imaging material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. For example, a protective layer is provided on the photosensitive layer for the purpose of protecting the photosensitive layer, and on the opposite side of the support to prevent sticking between the photosensitive materials or in the photosensitive material roll. A layer is preferably provided. Binders used in these protective layers and backcoat layers have a glass transition point higher than that of the heat-developable layer, and polymers such as scratches and deformations, such as cellulose acetate and cellulose acetate butyrate, are the above-mentioned binders. It is chosen from among them. For gradation adjustment and the like, in the present invention, the photosensitive layer is preferably composed of two or more layers. For example, two or more photosensitive layers may be provided on one side of the support, or the support. One or more layers may be installed on both sides.

  In the silver salt photothermographic dry imaging material of the present invention, a filter layer is formed on the same side as or opposite to the photosensitive layer in order to control the amount of light transmitted through the photosensitive layer or the wavelength distribution. It is preferable to contain a dye or pigment in the layer.

  As the dye used, known compounds that absorb light in various wavelength regions can be used depending on the color sensitivity of the photosensitive material.

  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 (this specification) Used as a thiopyrylium squarylium dye) and a squarylium dye having a pyrylium nucleus (referred to herein as a pyrylium squarylium dye), or a thiopyrylium croconium dye similar to a squarylium dye, or a pyrylium croconium dye. It is preferable to do.

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

  As the dye, a compound described in JP-A-8-201959 is also preferable.

[Layer structure and coating conditions]
The silver salt photothermographic dry imaging material of the present invention is formed by preparing a coating liquid in which the above-described constituent layers are dissolved or dispersed in a solvent, and applying a plurality of these coating liquids simultaneously, followed by heat treatment. It is preferable. Here, "multiple simultaneous multi-layer coating" means that a coating solution for each constituent layer (for example, a photosensitive layer and a protective layer) is prepared, and each layer is repeatedly coated and dried when it is coated on a support. Rather, it means that each constituent layer can be formed in such a state that a multilayer coating and drying process can be performed simultaneously.

  There are no particular restrictions on the method of applying multiple layers of each constituent layer simultaneously, and for example, a known method such as a bar coater method, curtain coating method, dipping method, air knife method, hopper coating method, or extrusion coating method may be used. Can do. Of these, a pre-weighing type coating method called an extrusion coating method is more preferable. Since the extrusion coating method does not volatilize on the slide surface unlike the slide coating method, it is suitable for precision coating and organic solvent coating. This coating method has been described on the side having the photosensitive layer, but the same applies to the case of coating with undercoating when providing the backcoat layer.

In the present invention, the silver coating amount is preferably 0.5 g / m ² or more and 2.0 g / m ² or less, more preferably 1.0 g / m ² or more and 1.5 g / m ² or less.

In the present invention, the silver equivalent of silver halide grains having a grain size of 0.030 μm or more and 0.055 μm or less in the silver halide grain emulsion has a silver coating amount of 0.5 g / m ² or more and 1.5 g. It is preferably 3% or more and 15% or less in the range of / m ² or less.

  Among the applied silver amount, those derived from silver halide preferably occupy 2 to 18%, more preferably 3 to 15%, based on the total silver amount.

In the present invention, the coating density of silver halide grains of 0.01 μm or more (equivalent particle diameter equivalent to sphere) is preferably 1 × 10 ¹⁴ particles / m ² or more and 1 × 10 ¹⁸ particles / m ² or less. Furthermore, 1 × 10 ¹⁵ pieces / m ² or more and 1 × 10 ¹⁷ pieces / m ² or less are preferable.

Furthermore, the coating density of the aliphatic carboxylic acid silver salt of the present invention is 10 ⁻¹⁷ g or more, 10 ⁻¹⁵ g or less, more preferably 10 μg per silver halide grain of 0.01 μm or more (equivalent particle diameter equivalent to sphere). ^-16 g or more and 10 ^-14 g or less is preferable.

  When coated under the conditions within the above range, it is preferable from the viewpoint of the optical maximum density of the silver image per fixed coated silver amount, that is, the silver coating amount (covering power) and the color tone of the silver image. Results are obtained.

[Exposure conditions]
In the exposure of the silver salt photothermographic dry imaging material of the present invention, it is desirable to use an appropriate light source for the color sensitivity imparted to the photosensitive material. For example, when the photosensitive material is sensitive to infrared light, it can be applied to any light source as long as it is in the infrared light range. However, the laser power is high and the photosensitive material can be transparent. In view of the above, 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 methods can be adopted as the exposure method. For example, as a first preferred method, there is a method using a laser scanning exposure machine in which the angle formed by the exposure surface of the photosensitive material and the scanning laser beam is not substantially perpendicular.

  Here, “substantially not perpendicular” means that the angle closest to the vertical during laser scanning is preferably 55 degrees or more and 88 degrees or less, more preferably 60 degrees or more and 86 degrees or less, and further Preferably it is 65 degrees or more and 84 degrees or less, Most preferably, it is 70 degrees or more and 82 degrees or less.

  The beam spot diameter on the photosensitive material exposure surface when the laser beam is scanned onto the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. This is preferable in that the smaller the spot diameter, the smaller the angle of deviation of the laser incident angle from the vertical. 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 generation of interference fringe-like unevenness.

  As a second method, it is preferable to perform exposure using a laser scanning exposure machine that emits scanning laser light that is a vertical multi. Compared with a longitudinal single mode scanning laser beam, image quality degradation such as occurrence of interference fringe-like unevenness is reduced.

  In order to make it vertically multi-ply, methods such as using return light by multiplexing and applying high-frequency superposition are preferable. 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. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

In the image recording methods of the first and second aspects described above, the laser used for the scanning exposure is generally well-known solid laser such as ruby laser, YAG laser, glass laser; HeNe laser, Ar ion. Gas laser such as laser, Kr ion laser, CO ₂ laser, CO laser, HeCd laser, N ₂ laser, excimer laser; InGaP laser, AlGaAs laser, GaAsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, GaSb laser, etc. Semiconductor lasers; chemical lasers, dye lasers, and the like can be selected and used in a timely manner, but among these, it is preferable to use a semiconductor laser having a wavelength of 600 to 1200 nm from the viewpoint of maintenance and the size of the light source. However, a semiconductor laser having an emission peak intensity in the range of 390 nm to 430 nm can also be used when the present invention is applied to a photosensitive material that utilizes the inherent photosensitive characteristics of silver halide grains.

  In addition, in a laser used in a laser imager or a laser image setter, the beam spot diameter on the material exposure surface when scanned with a silver salt photothermographic dry imaging material is generally 5 to 75 μm as a minor axis diameter, The major axis diameter is in the range of 5 to 100 μm, and the laser beam scanning speed can be set to an optimum value for each photosensitive material depending on the sensitivity and laser power at the laser oscillation wavelength unique to the silver salt photothermographic dry imaging material.

[Development conditions]
In the present invention, the development conditions vary depending on the equipment, equipment, or means used, but typically involve heating the imagewise exposed silver salt photothermographic dry imaging material at a suitable high temperature. . The latent image obtained after exposure is obtained by heating the silver salt photothermographic dry imaging material at a moderately high temperature (eg, about 100-200 ° C.) for a sufficient time (generally about 1 second to about 2 minutes). It can be developed. When the heating temperature is 100 ° C. or lower, sufficient image density cannot be obtained in a short time, and when the heating temperature is 200 ° C. or higher, the binder melts, and not only the image itself, such as transfer to a roller, but also adversely affects the transportability and the developing machine. Effect. By heating, a silver image is generated by an oxidation-reduction reaction between silver ions (which function as an oxidizing agent) supplied from an aliphatic carboxylic acid silver salt or the like and a reducing agent. This reaction process proceeds without any supply of treatment liquid such as water from the outside.

  The heating device, apparatus, and means may be a heating means typical as a heat generator using a hot plate, iron, hot roller, carbon, white titanium, or the like. More preferably, in the silver salt photothermographic dry imaging material provided with the protective layer of the present invention, the surface on the side having the protective layer is brought into contact with the heating means, and the heat treatment is performed for uniform heating and thermal efficiency. From the viewpoint of workability and the like, it is preferable that the surface is conveyed while being brought into contact with a heat roller, heated and developed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
<< Preparation of undercoated photographic support >>
Corona discharge treatment of 8 W · min / m ^{2 was performed} on both sides of a biaxially stretched heat-fixed polyethylene terephthalate film with an optical density of 0.170 (measured with a Densitometer PDA-65 manufactured by Konica Corporation) in blue. The applied photographic support was subjected to subbing. That is, the undercoat coating liquid a-1 was applied to one surface of this photographic support so that the dry film thickness was 0.2 μm at 22 ° C. and 100 m / min, and dried at 140 ° C. to form an image. A layer side undercoat layer was formed (referred to as undercoat underlayer A-1). Moreover, the following undercoat coating liquid b-1 was applied to the opposite surface as a backing layer undercoat layer at 22 ° C. and 100 m / min so that the dry film thickness was 0.12 μm, and dried at 140 ° C. An undercoat conductive layer having an antistatic function (referred to as undercoat underlayer B-1) was applied on the backing layer side. A corona discharge of 8 W · min / m ² is applied to the upper surfaces of the subbing lower layer A-1 and the subbing lower layer B-1, and the following subbing coating solution a-2 is dried on the lower subbing layer A-1. It is coated at 33 ° C. and 100 m / min so as to have a film thickness of 0.03 μm, and dried at 140 ° C. to form an undercoat upper layer A-2. -2 was applied at 33 ° C. and 100 m / min to a dry film thickness of 0.2 μm, dried at 140 ° C. to form an undercoating upper layer B-2, and the support was further heat-treated at 123 ° C. for 2 minutes. The sample was wound up under the conditions of 50 ° C. and 50% RH to prepare a sample that had been subtracted.

[Preparation of aqueous polyester A-1 solution]
35.4 parts by weight of dimethyl terephthalate, 33.63 parts by weight of dimethyl isophthalate, 17.92 parts by weight of dimethyl sodium 5-sulfoisophthalate, 62 parts by weight of ethylene glycol, 0.065 parts by weight of calcium acetate / monohydrate, After transesterification of 0.022 parts by mass of manganese acetate tetrahydrate under a nitrogen stream while distilling off methanol at 170 to 220 ° C., 0.04 parts by mass of trimethyl phosphate and a polycondensation catalyst were used. 0.04 parts by mass of antimony oxide and 6.8 parts by mass of 1,4-cyclohexanedicarboxylic acid were added, and at a reaction temperature of 220 to 235 ° C., a theoretical amount of water was distilled off for esterification.

  Thereafter, the inside of the reaction system was further depressurized and heated over about 1 hour, and finally subjected to polycondensation at 280 ° C. and 133 Pa or less for about 1 hour to synthesize aqueous polyester A-1. The obtained aqueous polyester A-1 had an intrinsic viscosity of 0.33, an average particle size of 40 nm, and Mw = 80000 to 100,000.

  Next, 850 ml of pure water was put into a 2 L three-necked flask equipped with a stirring blade, a reflux condenser, and a thermometer, and 150 g of aqueous polyester A-1 was gradually added while rotating the stirring blade. After stirring for 30 minutes at room temperature, the mixture was heated to an internal temperature of 98 ° C. over 1.5 hours and dissolved at this temperature for 3 hours. After completion of the heating, the mixture was cooled to room temperature over 1 hour and allowed to stand overnight to prepare a 15% by mass aqueous polyester A-1 solution.

[Preparation of Modified Aqueous Polyester B-1-2 Solution]
Into a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel, 1900 ml of the 15% by mass aqueous polyester A-1 solution was placed, and the internal temperature was adjusted to 80 ° C. while rotating the stirring blade. Until heated. Into this, 6.52 ml of a 24% aqueous solution of ammonium peroxide was added, and a monomer mixture (28.5 g of glycidyl methacrylate, 21.4 g of ethyl acrylate, 21.4 g of methyl methacrylate) was dropped over 30 minutes, The reaction is continued for another 3 hours. Then, it cooled and filtered to 30 degrees C or less, and prepared the modified aqueous polyester B-1 solution (vinyl-type component modification | denaturation ratio 20 mass%) whose solid content concentration is 18 mass%.

  The solid content concentration was the same except that the vinyl modification ratio was 36% by mass and the modified components were styrene: glycidyl methacrylate: acetoacetoxyethyl methacrylate: n-butyl acrylate = 39.5: 40: 20: 0.5. An 18% by mass modified aqueous polyester B-2 solution (vinyl component modification ratio 20% by mass) was prepared.

[Production of Acrylic Polymer Latex C-1 to C-3]
Acrylic polymer latexes C-1 to C-3 having the monomer composition shown in the following table were synthesized by emulsion polymerization. The solid content concentration was 30% by mass.

<< Aqueous polymer containing polyvinyl alcohol unit >>
D-1: PVA-617 (Kuraray Co., Ltd. aqueous dispersion (solid content 5%): degree of saponification 95)
[Image forming layer side undercoat coating solution a-1]
Acrylic polymer latex C-3 (solid content 30%) 70.0 g
Water dispersion of ethoxylated alcohol and ethylene homopolymer (10% solids)
5.0g
Surfactant (A) 0.1g
Distilled water was added to make 1000 ml, and a coating solution was obtained.

<< Image Forming Layer Side Undercoat Layer Coating Solution a-2 >>
Modified aqueous polyester B-2 (18% by mass) 30.0 g
Surfactant (A) 0.1g
Spherical silica matting agent (Nippon Shokubai Co., Ltd. Sea Hoster KE-P50)
0.04g
Distilled water was added to make 1000 ml, and a coating solution was obtained.

[Backing layer side undercoat coating solution b-1]
Acrylic polymer latex C-1 (solid content 30%) 30.0 g
Acrylic polymer latex C-2 (solid content 30%) 7.6 g
SnO ₂ sol 180g
(SnO ₂ sol synthesized by the method described in Example 1 of Japanese Patent Publication No. 35-6616 was heated and concentrated so that the solid content concentration was 10% by mass, and then adjusted to pH = 10 with ammonia water)
Surfactant (A) 0.5g
PVA-613 (PVA manufactured by Kuraray Co., Ltd.) 5% by weight aqueous solution 0.4 g
Distilled water was added to make 1000 ml, and a coating solution was obtained.

[Backing layer side undercoat upper layer coating solution b-2]
Modified aqueous polyester B-1 (18% by mass) 145.0 g
Spherical silica matting agent (Nippon Shokubai Co., Ltd. Sea Hoster KE-P50)
0.2g
Surfactant (A) 0.1g
Distilled water was added to make 1000 ml, and a coating solution was obtained.

  An antihalation layer having the following composition was coated on the undercoat layer A-2 of the support to which the undercoat layer had been applied.

(Anti-halation layer coating composition)
PVB-1 (binder) 0.8 g / m ²
C1 (dye) 1.2 × 10 ⁻⁵ mol / m ²
On the other hand, on the back surface side, the BC layer prepared so as to have the following weight (per 1 m ² ) and each coating liquid for the protective layer are sequentially applied and dried on the undercoat upper layer B-2. A BC layer and a protective layer were formed.

(BC layer composition)
PVB-1 (binder) 1.8g
C1 (dye) 1.2 × 10 ⁻⁵ mol (BC layer protective layer coating solution)
Cellulose acetate butyrate 1.1g
Matting agent (polymethyl methacrylate: average particle size 5 μm) 0.12 g
Antistatic agent: F-EO 250mg
Antistatic agent: F-DS1 30mg

<< Preparation of photosensitive silver halide emulsion >>
[Preparation of photosensitive silver halide emulsion 1]
(Solution A1)
Phenylcarbamoylated gelatin 88.3g
Compound A (* 1) (10% aqueous methanol solution) 10 ml
Potassium bromide 0.32g
Finish to 5429 ml with water (Solution B1)
0.67 mol / L silver nitrate aqueous solution 2635 ml
(Solution C1)
Potassium bromide 51.55g
Potassium iodide 1.47g
Finish to 660 ml with water (Solution D1)
Potassium bromide 154.9g
4.41 g of potassium iodide
K ₃ IrCl ₆ (equivalent to 4 × 10 ⁻⁵ mol / Ag) 50.0 ml
Finish to 1982 ml with water (Solution E1)
0.4 mol / L potassium bromide aqueous solution The following silver potential control amount (Solution F1)
Potassium hydroxide 0.71g
Finish to 20 ml with water (Solution G1)
56% acetic acid aqueous solution 18.0 ml
(Solution H1)
Anhydrous sodium carbonate 1.72 g
Finish to 151 ml with water (* 1) Compound A:
_{HO (CH 2 CH 2 O)} n (CH (CH 3) CH 2 O) 17 (CH 2 CH 2 O) m H
(M + n = 5-7)
Using a mixing stirrer described in Japanese Patent Publication No. 58-58288, the solution A1 was adjusted to 4 by simultaneous mixing while controlling the 1/4 amount of the solution B1 and the total amount of the solution C1 to 32 ° C. and pAg 8.09. Addition took 45 minutes to nucleate. After 1 minute, the entire amount of solution F1 was added. During this time, the pAg was adjusted as appropriate using the solution E1. After 6 minutes, 3/4 amount of the solution B1 and the total amount of the solution D1 were added over 14 minutes and 15 seconds by the simultaneous mixing method while controlling the temperature at 32 ° C. and pAg 8.09. After stirring for 5 minutes, the temperature was raised to 40 ° C., and the entire amount of the solution G1 was added to precipitate the silver halide emulsion. The supernatant was removed leaving 2000 ml of the sedimented portion, 10 L of water was added, and after stirring, the silver halide emulsion was sedimented again. The remaining portion of 1500 ml was left, the supernatant was removed, 10 L of water was further added, and after stirring, the silver halide emulsion was allowed to settle. After leaving 1500 ml of the sedimented portion and 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, the pH was adjusted to 5.8, and water was added so that the amount was 1161 g per mole of silver to obtain an emulsion.

  This emulsion was monodispersed cubic silver iodobromide grains having an average grain size of 0.040 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 92%.

[Preparation of photosensitive silver halide emulsion 2]
Photosensitive silver halide emulsion 2 was prepared in the same manner as in the preparation of photosensitive silver halide emulsion 1 except that 5 ml of a 0.4% aqueous solution of lead bromide was added to solution D1.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.042 μm, a grain size variation coefficient of 13%, and a [100] face ratio of 94%.

[Preparation of photosensitive silver halide emulsion 3]
In the preparation of the photosensitive silver halide emulsion 1, after addition of the entire amount of the solution F1 after nucleation, 40 ml of a 5% aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added. A photosensitive silver halide emulsion 3 was prepared in the same manner as described above.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.041 μm, a grain size variation coefficient of 14%, and a [100] face ratio of 93%.

[Preparation of photosensitive silver halide emulsion 4]
In the preparation of the photosensitive silver halide emulsion 1, the photosensitive halogenation was similarly carried out except that 4 ml of a 0.1% ethanol solution of the following compound (ETTU) was added after the entire amount of the solution F1 was added after nucleation. Silver emulsion 4 was prepared.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.042 μm, a grain size variation coefficient of 10%, and a [100] face ratio of 94%.

[Preparation of photosensitive silver halide emulsion 5]
In the preparation of the above photosensitive silver halide emulsion 1, the same procedure was followed except that 4 ml of a 0.1% ethanol solution of 1,2-benzisothiazolin-3-one was added after addition of the entire amount of solution F1 after nucleation. Photosensitive silver halide emulsion 5 was prepared.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.041 μm, a grain size variation coefficient of 11%, and a [100] face ratio of 93%.

<< Preparation of photosensitive layer coating solution >>
(Preparation of powdered aliphatic carboxylic acid silver salt A)
In 4720 ml of pure water, 117.7 g of behenic acid, 60.9 g of arachidic acid, 39.2 g of stearic acid and 2.1 g of palmitic acid were dissolved at 80 ° C. Next, 486.2 ml of a 1.5 mol / L potassium hydroxide aqueous solution was added, and 6.2 ml of concentrated nitric acid was added, followed by cooling to 55 ° C. to obtain a fatty acid potassium solution. While maintaining the temperature of the fatty acid potassium solution at 55 ° C., 347 ml of t-butyl alcohol was added and stirred for 20 minutes, and then 45.3 g of the above photosensitive silver halide emulsion 1 and 450 ml of pure water were added, Stir for 5 minutes.

  Next, 702.6 ml of a 1 mol / L silver nitrate solution was added over 2 minutes and stirred for 10 minutes to obtain an aliphatic carboxylic acid silver salt dispersion. Thereafter, the obtained aliphatic carboxylic acid silver salt dispersion was transferred to a water-washing vessel, deionized water was added and stirred, and then allowed to stand to float and separate the aliphatic carboxylic acid silver salt dispersion. Was removed. Thereafter, washing with deionized water and drainage were repeated until the electrical conductivity of the drainage reached 50 μS / cm, and centrifugal dehydration was carried out. Using a dryer (manufactured by Seishin Enterprise Co., Ltd.), drying is performed until the water content becomes 0.1% according to the operating conditions of the nitrogen gas atmosphere and the hot air temperature at the dryer entrance, to obtain a powdered aliphatic carboxylic acid silver salt A It was. An infrared moisture meter was used to measure the water content of the aliphatic carboxylic acid silver salt composition. The silveration rate of the aliphatic carboxylic acid silver was confirmed to be about 95% by the method described above.

(Preparation of preliminary dispersion A)
14.57 g of polyvinyl butyral resin P-9 was dissolved in 1457 g of methyl ethyl ketone (hereinafter abbreviated as MEK), and the powdered aliphatic carboxylic acid silver salt A was stirred with a dissolver DISPERMAT CA-40M manufactured by VMA-GETZMANN. Preliminary dispersion A was prepared by gradually adding 500 g and mixing well.

(Preparation of photosensitive emulsion dispersion A)
Media type dispersion filled with 80% of the internal volume of 0.5 mm diameter zirconia beads (Toreceram manufactured by Toray Industries, Inc.) using the prepared preliminary dispersion A so that the residence time in the mill is 1.5 minutes using a pump. A photosensitive emulsion dispersion A was prepared by supplying to a machine DISPERMAT SL-C12EX type (manufactured by VMA-GETZMANN) and dispersing at a mill peripheral speed of 8 m / s.

(Preparation of stabilizer solution)
A stabilizer solution was prepared by dissolving 1.0 g of Stabilizer 1 and 0.31 g of potassium acetate in 4.97 g of methanol.

(Preparation of infrared sensitizing dye liquid A)
19.2 mg of infrared sensitizing dye 1, 10 mg of infrared sensitizing dye 2, 1.48 g of 2-chloro-benzoic acid, 2.78 g of stabilizer 2 and 365 mg of 5-methyl-2-mercaptobenzimidazole Was dissolved in 31.3 ml of MEK in the dark to prepare an infrared sensitizing dye solution A.

(Preparation of additive solution a)
27.98 g and 1.54 g of 4-methylphthalic acid as 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (developer A) as a developer, 0 20 g of the infrared dye 1 was dissolved in 110 g of MEK to obtain an additive solution a.

  In this experiment, depending on the sample for evaluation, in addition to the developer A described above as a developer, the compounds shown in Table 3 from the exemplary compound group represented by the general formula (RED) as the developer (developer) A mole equivalent to A) or a development accelerator (10 mol% based on the total amount of developer) was selected and used. 150 mg of the leuco dye shown in Table 3 was added to the additive solution a.

(Preparation of additive liquid b)
3.56 g of antifoggant 2 and 3.43 g of phthalazine were dissolved in 40.9 g of MEK to obtain additive solution b.

(Preparation of photosensitive layer coating liquid A)
In an inert gas atmosphere (97% nitrogen), the photosensitive emulsion dispersion A (50 g) and 15.11 g of MEK were kept at 21 ° C. with stirring, and 390 μl of antifoggant 1 (10% methanol solution) was added, Stir for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added and 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 A was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C. and further stirred for 30 minutes. While keeping the temperature at 13 ° C., 13.31 g of polyvinyl acetal resin P-1 as a binder resin was added and stirred for 30 minutes, and then 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added thereto. Stir for minutes. Further, while continuing stirring, 12.43 g of additive solution a, 1.6 ml of Desmodur N3300 / Mobey aliphatic isocyanate (10% MEK solution), and 4.27 g of additive solution b were sequentially added and stirred for photosensitivity. An aqueous layer coating solution A1 was obtained.

<Surface protective layer>
A coating solution having the following composition was prepared in the same manner as the photosensitive layer coating solution, and coated and dried on the photosensitive layer so as to have the following weight (per 1 m ² ) to form a photosensitive layer protective layer.

Cellulose acetate propionate 2.0g
4-methylphthalic acid 0.7g
Tetrachlorophthalic acid 0.2g
Tetrachlorophthalic anhydride 0.5g
Silica matting agent (average particle size 5μm) 0.5g
1,3-bis (vinylsulfonyl) -2-propanol 50mg
Benzotriazole 30mg
Antistatic agent: F-EO 20mg
Antistatic agent: F-DS1 3mg
The binder used was polyacetal, and methyl ethyl ketone (MEK) was used as the organic solvent. Polyacetal is obtained by saponifying 98% of polyvinyl acetate having a polymerization degree of 500 and then converting 86% of the remaining hydroxyl groups into butyral, which is referred to as PVB-1.
《Preparation of silver salt photothermographic dry imaging material sample》
The sample 101 is prepared by simultaneously applying the photosensitive layer coating solution A and the surface protective layer coating solution prepared above on the undercoat layer of the prepared support at the same time using a known extrusion coater. did. The coating was carried out so that the photosensitive layer had an applied silver amount of 1.5 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 75 ° C. and a dew point temperature of 10 ° C., and a sample 101 was manufactured.

  Next, Table 3 shows the types of the photosensitive silver halide emulsion in the photosensitive layer coating solution A, the developer (comparative developer in the additive solution a), and the silver behenate ratio among the aliphatic carboxylic acid silver. Samples 102 to 119 were produced in the same manner as the sample 101 except that the samples were changed to those. The relative ratio of the three content ratios of silver arachidate, silver stearate and silver palmitate when the ratio of silver behenate was changed was constant.

<< Evaluation of each characteristic value >>
(Exposure and development processing)
From the photosensitive layer coating surface side of each sample produced as described above, exposure by laser scanning is given by an exposure machine using a semiconductor laser having a longitudinal multimode wavelength of 800 to 820 nm by high frequency superposition as an exposure source. It was. At this time, an image was formed by setting the angle of the exposure surface of the sample and the exposure laser beam to 75 degrees. In this method, an image with less unevenness and unexpectedly good sharpness or the like was obtained compared to the case where the angle was 90 degrees.

  Thereafter, using an automatic developing machine having a heat drum, the surface protective layer of the sample and the drum surface were in contact with each other, and heat development was performed at 123 ° C. for 15 seconds. At that time, exposure and development were performed in a room adjusted to 23 ° C. and 50% RH.

(Measurement of sensitivity, fog density and maximum density)
The density of the formed image obtained as described above was measured using a densitometer, and a characteristic curve consisting of a horizontal axis—exposure amount and a vertical axis—density was created. In the characteristic curve, the sensitivity is defined as the reciprocal of the exposure amount giving a density 1.0 higher than that of the unexposed area, and the minimum density fog density (minimum density) and the maximum density were measured. Note that the sensitivity and the maximum density are expressed as relative values with each of the samples 101 as 100.

(Evaluation of image storage stability after development)
<Measurement of change rate of minimum density (Dmin)>
For each of the heat-developed samples prepared by the same method as the sensitivity measurement, a commercially available white fluorescent lamp is placed in an environment of 45 ° C. and 55% RH so that the illuminance on the sample surface is 500 lux for 3 days. Continuous irradiation was applied. The minimum concentration (D ₂ ) of the sample irradiated with the fluorescent lamp and the minimum concentration (D ₁ ) of the sample not irradiated with the fluorescent lamp were measured, respectively, and the minimum concentration change rate (%) was calculated from the following equation.

Minimum density change rate = D ₂ / D ₁ × 100 (%)
<Measurement of change rate of maximum density (Dmax)>
Each heat-developed sample prepared by the same method as the measurement of the minimum density change rate is allowed to stand for 3 days in an environment of 25 ° C. and 45 ° C., and then the maximum density of each sample is measured. The rate of change was measured and used as a measure of image preservation.
Maximum concentration change rate = maximum concentration of sample stored at 45 ° C./maximum concentration of sample stored at 25 ° C. × 100 (%)
(Image tone evaluation: measurement of u ^* , v ^* and a ^* , b ^* in CIE 1976 color space)
A four-stage wedge sample including an unexposed portion and optical densities of 0.5, 1.0, and 1.5 was prepared using a heat development apparatus. Each wedge concentration part thus produced was measured with CM-3600d (manufactured by Minolta Co., Ltd.) to calculate u ^* , v ^* or a ^* , b ^* . The measurement conditions at that time were F7 light source as the light source, the viewing angle was 10 °, and the measurement was performed in the transmission measurement mode. Plotting u ^* , v ^* or a ^* , b ^* measured on a graph with u ^* or a ^{* on} the horizontal axis and v ^* or b ^{* on the} vertical axis to obtain a linear regression line, multiple determination R ² , intercept and The slope was determined.

Note: In the above table, K100 means that the alkali metal of the aliphatic alkali metal salt is 100% potassium in the aliphatic carboxylate silver preparation step. B ^* means the following development accelerator. Note that the developer RED-13 includes 90% or more of the cis body.

  Note: Figures in parentheses in the Relative Sensitivity column indicate that the photosensitive material was heat-treated at the heat development temperature before the light-sensitive material was exposed to white light, and then was exposed to white light through an optical wedge (4874K, 30 seconds) and thermally developed. The sensitivity relative value of the former when the sensitivity of the latter is assumed to be 100 is shown in the comparison between the sensitivity of the case and the sensitivity when heat development is performed by exposure to white light under the same conditions as above without heat treatment before exposure. It was. In this relative comparison, the main cause of the decrease in the relative sensitivity of the sample obtained by heat-treating the photosensitive material at the heat development temperature before exposing the photosensitive material to white light is the surface sensitivity of the silver halide grains due to the disappearance or reduction of the spectral sensitization effect. It was confirmed by observation / measurement of changes in the spectral sensitivity spectrum that the relative relationship between the internal sensitivity and the internal sensitivity was changed.

  As is apparent from Table 3, the silver salt photothermographic dry imaging material of the present invention has a fog (minimum density) equal to or lower than that of the comparison, and has a sensitivity and a maximum density equal to or higher. It turns out that it is excellent in image storability later.

Further, in the color tone evaluation of the sample according to the present invention, the linear regression line determination coefficient (multiple determination) R ² is 0.998 or more and 1.000 or less, and the b ^* value of the intersection with the vertical axis of the linear regression line. Is -5 or more and 5 or less and the slope (b ^* / a ^* ) is 0.7 or more and 2.5 or less, it can be said that the color tone is better.

Example 2
The following various silver halide emulsions were prepared in the same manner as in Example 1.

[Preparation of photosensitive silver halide emulsion 6]
In the preparation of the photosensitive silver halide emulsion 1, the temperature before the addition of the solution (G1) was set to 25 ° C., and the total amount of the solution F1 was added after the nucleation. Photosensitive silver halide emulsion 6 was prepared in the same manner except that 4 ml of 1% ethanol solution was added.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.035 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 93%.

[Preparation of photosensitive silver halide emulsion 7]
In the preparation of the photosensitive silver halide emulsion 1, the temperature before the addition of the solution (G1) was set to 45 ° C., and the total amount of the solution F1 was added after the nucleation. Photosensitive silver halide emulsion 7 was prepared in the same manner except that 4 ml of 1% ethanol solution was added.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.060 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 93%.

[Preparation of photosensitive silver halide emulsion 8]
In the preparation of the photosensitive silver halide emulsion 1, the temperature before the addition of the solution (G1) was set to 60 ° C., and the total amount of the solution F1 was added after the nucleation. Photosensitive silver halide emulsion 8 was prepared in the same manner except that 4 ml of 1% ethanol solution was added.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.080 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 93%.

[Preparation of photosensitive silver halide emulsion 9]
In the preparation of the photosensitive silver halide emulsion 6, a photosensitive silver halide emulsion 9 was prepared in the same manner except that 4 ml of the compound (ETTU) was not added after adding the whole amount of the solution F1 after nucleation.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.035 μm, a grain size variation coefficient of 13%, and a [100] face ratio of 94%.

[Preparation of photosensitive silver halide emulsion 10]
A photosensitive silver halide emulsion 10 was prepared in the same manner as in the preparation of the photosensitive silver halide emulsion 7 except that 4 ml of the compound (ETTU) was not added after adding the entire amount of the solution F1 after nucleation.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.060 μm, a grain size variation coefficient of 14%, and a [100] face ratio of 93%.

[Preparation of photosensitive silver halide emulsion 11]
In the preparation of the photosensitive silver halide emulsion 8, the photosensitive silver halide emulsion 11 was prepared in the same manner except that the compound (ETTU) was not added after adding the whole amount of the solution F1 after nucleation.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.082 μm, a grain size variation coefficient of 14%, and a [100] face ratio of 91%.

  Next, the above-described silver halide emulsion was prepared using an alkali metal salt of an aliphatic carboxylic acid having the composition shown in Table 4 by a method according to the method for preparing powdered aliphatic carboxylic acid silver salt A in Example 1. Aliphatic carboxylic acid silver salts were prepared in the presence of any of 6 to 11 and silver halide emulsion 4, and various samples as shown in the table were prepared in the same manner as in Example 1. However, in each sample, the developer and leuco dye were the same as the sample 113 in Example 1.

  The sample was evaluated in the same manner as in Example 1.

  In Table 4, Na100, Na75, Na50, Na25, and Na0 are 100% and 75%, respectively, in the alkali metal salt of the fatty acid in the aliphatic carboxylate preparation step. , 50%, 25%, 0%. Similarly, K100 to K0 represent that the percentage of potassium is 100%, 75%, 50%, 25%, and 0%, respectively.

  Note: Figures in parentheses in the Relative Sensitivity column indicate that the photosensitive material was heat-treated at the heat development temperature before the light-sensitive material was exposed to white light, and then was exposed to white light through an optical wedge (4874K, 30 seconds) and thermally developed. The sensitivity relative value of the former when the sensitivity of the latter is assumed to be 100 is shown in the comparison between the sensitivity of the case and the sensitivity when heat development is performed by exposure to white light under the same conditions as above without heat treatment before exposure. It was. In this relative comparison, the main cause of the decrease in the relative sensitivity of the sample obtained by heat-treating the photosensitive material at the heat development temperature before the photosensitive material is exposed to white light is due to the disappearance or reduction of the spectral sensitization effect and the chemical sensitization effect. It was confirmed by observation / measurement such as a change in spectral sensitivity spectrum that the relative relationship between the surface sensitivity and the internal sensitivity of the silver halide grains was changed.

  As is clear from Table 4, the silver salt photothermographic dry imaging material of the present invention has a fog (minimum density) equal to or lower than that of the comparison, and has a sensitivity and maximum density equal to or higher. It turns out that it is excellent in image storability later. It can also be seen that the alkali metal salt used in the aliphatic carboxylate preparation step has a higher maximum concentration and relative sensitivity as the ratio of potassium salt is higher and the average grain size of the coexisting silver halide is smaller.

In the color tone evaluation of the sample according to the present invention, the linear regression line determination coefficient (multiple determination) R ² is 0.998 or more and 1.000 or less, and the b ^* value of the intersection with the vertical axis of the linear regression line. Is from −5 to 5, and the gradient (b ^* / a ^* ) is from 0.7 to 2.5.

Example 3
Using silver halide emulsions 1 and 4 in Example 1, according to the same method as in Example 1, as shown in Table 5, compounds represented by general formula (ST), compounds represented by general formula (CV), and halogen radicals Various samples containing a polymer having a releasing group were prepared, and the effects of each sample were examined.

  The addition amount and addition method of the compound represented by the general formula (ST), the compound represented by the general formula (CV), and the polymer having a halogen radical releasing group are as follows.

The compound represented by the general formula (ST) was added to the photosensitive coating solution immediately before coating so that the coating weight (per 1 m ² ) was 0.015 g. The compound represented by the general formula (CV) was added to the protective layer coating solution immediately before coating so that the coating weight (per 1 m ² ) was 0.135 g. The polymer having a halogen radical releasing group was added to the photosensitive coating solution immediately before coating so that the coating weight (per 1 m ² ) was 0.45 g.

  For the preparation of the silver salt photothermographic dry imaging material sample, various samples shown in Table 5 were prepared in the same manner as in Example 1. However, in each sample, the developer and leuco dye were the same as the sample 113 in Example 1. The sample was evaluated in the same manner as in Example 1.

  The storage stability before development was evaluated by the following method.

(Evaluation of storage stability before development)
After each sample is stored for 10 days under the following two conditions, exposure and development are performed in the same manner as each sensitivity measurement, and then the sensitivity and minimum density of the obtained image are measured. The minimum density (Dmin) of Condition B with respect to A and the rate of change in sensitivity were obtained from the following formulas and used as a measure of storage stability before development.

In addition, the obtained sample was cut into half-cut size, and the packaging material (PET 10 μm / PE 12 μm / Aluminum foil 9 μm / Ny 15 μm / Polyethylene 50% containing 3% carbon, oxygen permeability: 0 ml / 1 ×) 10 ⁵ Pa · m ² · 25 ° C · day, moisture permeability: 0 g / 1 × 10 ⁵ Pa · m ² · 25 ° C · day), and stored under the following conditions.

Condition A: 25 ° C., 55% RH
Condition B: 40 ° C., 80% RH
Rate of change = minimum density or sensitivity in condition B / minimum density or sensitivity in condition A × 100 (%)

  Note: The values in parentheses in the relative sensitivity column indicate that the photosensitive material was heat-treated at the heat development temperature before the light-sensitive material was exposed to white light, and then exposed to white light through an optical wedge (4874K, 30 seconds) and heat-developed. The sensitivity relative value of the former when the sensitivity of the latter is assumed to be 100 is shown in the comparison between the sensitivity of the case and the sensitivity when heat development is performed by exposure to white light under the same conditions as above without heat treatment before exposure. It was. In this relative comparison, the main cause of the decrease in the relative sensitivity of the sample obtained by heat-treating the photosensitive material at the heat development temperature before the photosensitive material is exposed to white light is due to the disappearance or reduction of the spectral sensitization effect and the chemical sensitization effect. It was confirmed by observation / measurement such as a change in spectral sensitivity spectrum that the relative relationship between the surface sensitivity and the internal sensitivity of the silver halide grains was changed.

As is apparent from Table 5, the silver salt photothermographic dry imaging material of the present invention has a fog (minimum density) equivalent or lower than that of the comparison, but has a sensitivity and maximum density equivalent or higher, and is stored before development. It can be seen that it is excellent in property (raw preservation) and in particular, image preservation after development processing. Further, in the color tone evaluation of the sample according to the present invention, the linear regression line determination coefficient (multiple determination) R ² is 0.998 or more and 1.000 or less, and the b ^* value of the intersection with the vertical axis of the linear regression line. Is -5 or more and 5 or less and the slope (b ^* / a ^* ) is 0.7 or more and 2.5 or less, it can be said that the color tone is better.

Example 4
Using the silver halide emulsions 1 to 5 in Example 1, each silver halide emulsion was chemically sensitized by the following method.

(Preparation of photosensitive layer coating liquid A4)
In an inert gas atmosphere (97% nitrogen), the photosensitive emulsion dispersion A (50 g) and 15.11 g of MEK were kept at 21 ° C. with stirring, and 390 μl of antifoggant 1 (10% methanol solution) was added, Stir for 1 hour. Next, 240 ml of sulfur sensitizer S-5 (0.5% methanol solution) was added and stirred at 21 ° C. for 1 hour for chemical sensitization. Further, 494 μl of calcium bromide (10% methanol solution) was added and 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 A was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C. and further stirred for 30 minutes. While keeping the temperature at 13 ° C., 13.31 g of polyvinyl acetal resin P-1 as a binder resin was added and stirred for 30 minutes, and then 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added thereto. Stir for minutes. Further, while continuing stirring, 12.43 g of additive solution a, 1.6 ml of Desmodur N3300 / Mobey aliphatic isocyanate (10% MEK solution), and 4.27 g of additive solution b were sequentially added and stirred for photosensitivity. An aqueous layer coating solution A4 was obtained.

  Various photosensitive layer coating solutions were prepared in the same manner as described above, and various samples as shown in Table 6 were prepared and evaluated in the same manner as in Example 1.

  Note: The values in parentheses in the relative sensitivity column indicate that the photosensitive material was heat-treated at the heat development temperature before the light-sensitive material was exposed to white light, and then exposed to white light through an optical wedge (4874K, 30 seconds) and heat-developed. The sensitivity relative value of the former when the sensitivity of the latter is assumed to be 100 is shown in the comparison between the sensitivity of the case and the sensitivity when heat development is performed by exposure to white light under the same conditions as above without heat treatment before exposure. It was. In this relative comparison, the main cause of the decrease in the relative sensitivity of the sample obtained by heat-treating the photosensitive material at the heat development temperature before the photosensitive material is exposed to white light is due to the disappearance or reduction of the spectral sensitization effect and the chemical sensitization effect. It was confirmed by observation / measurement such as a change in spectral sensitivity spectrum that the relative relationship between the surface sensitivity and the internal sensitivity of the silver halide grains was changed.

As is clear from Table 6, the silver salt photothermographic dry imaging material of the present invention has a fog (minimum density) equal to or lower than that of the comparison, and the sensitivity and the maximum density are substantially equal to or higher, in particular, It can be seen that the image storability after development processing is excellent. Further, in the color tone evaluation of the sample according to the present invention, the linear regression line determination coefficient (multiple determination) R ² is 0.998 or more and 1.000 or less, and the b ^* value of the intersection with the vertical axis of the linear regression line. Is -5 or more and 5 or less and the slope (b ^* / a ^* ) is 0.7 or more and 2.5 or less, it can be said that the color tone is better.

  In addition, after completion of the final stage (hydrolysis) of each preparation step of silver halide emulsions 1 to 5, 240 ml of sulfur sensitizer S-5 (0.5% methanol solution) was added and stirred at 55 ° C. for 120 minutes. The same results were obtained qualitatively for samples prepared by chemical sensitization and adding the silver halide emulsion to a separately prepared coating solution containing an aliphatic carboxylic acid silver salt.

Example 5
<< Preparation of PET support >>
Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained according to a conventional method. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled to produce an unstretched film having a thickness of 175 μm after heat setting.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds and then stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. Thereafter, the chuck portion of the tenter was slit and then knurled at both ends, and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

[Surface corona treatment]
Using a solid state corona treatment machine 6KVA model manufactured by Pillar, both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, it was found that the support was processed at 0.375 kV · A · min / m ² . The treatment frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[Preparation of a sublimed support]
(1) Preparation formulation of undercoat layer coating solution (for photosensitive layer side undercoat layer)
59 g of pesresin A-520 (30% by mass solution) manufactured by Takamatsu Yushi Co., Ltd.
Polyethylene glycol monononyl phenyl ether (average ethylene oxide number = 8.5) 10% by mass solution 5.4 g
MP-1000 manufactured by Soken Chemical Co., Ltd. (polymer fine particles, average particle size 0.4 μm)
0.91g
935 ml of distilled water
(For back layer 1st layer)
Styrene-butadiene copolymer latex (solid content 40% by mass, styrene / butadiene mass ratio = 68/32) 158 g
8 mass% aqueous solution of 2,4-dichloro-6-hydroxy-S-triazine sodium salt
20g
10% 1% by weight aqueous solution of sodium laurylbenzenesulfonate
854 ml of distilled water
(For back side second layer)
SnO ₂ / SbO (9/1 mass ratio, average particle size 0.038 μm, 17 mass% dispersion)
84g
Gelatin (10 mass% aqueous solution) 89.2g
8.6 g of Metroise TC-5 (2% by mass aqueous solution) manufactured by Shin-Etsu Chemical Co., Ltd.
MP-1000 0.01g manufactured by Soken Chemical Co., Ltd.
10% 1% by weight aqueous solution of sodium dodecylbenzenesulfonate
NaOH (1% by mass) 6 ml
Proxel (ICI) 1ml
805 ml of distilled water
After the corona discharge treatment is performed on both surfaces of the biaxially stretched polyethylene terephthalate support having a thickness of 175 μm, the undercoating liquid formulation is applied to one surface (photosensitive layer surface) with a wire bar and the wet coating amount is 6.6 ml. / M ² (per one side) and dried at 180 ° C. for 5 minutes, and then the undercoat coating liquid formulation is applied to this back side (back side) with a wire bar at a wet coating amount of 5.7 ml / m ^2. And then dried at 180 ° C. for 5 minutes, and further, the above-mentioned undercoat coating liquid formulation is applied to the back surface (back surface) with a wire bar so that the wet coating amount is 7.7 ml / m ² . The substrate was dried at 6 ° C. for 6 minutes to prepare an underdrawn support.

<Preparation of back surface coating solution>
(Preparation of solid fine particle dispersion (a) of base precursor)
1.5 kg of base precursor compound-1 and 225 g of a surfactant (trade name: Demol N, manufactured by Kao Corporation), 937.5 g of diphenyl sulfone, butyl ester of parahydroxybenzoate (trade name: Plating: Ueno Pharmaceutical Co., Ltd.) 15 g and distilled water were added and the total amount was adjusted to 5.0 kg and mixed, and the mixture was dispersed with beads using a horizontal sand mill (UVM-2: manufactured by Imex Corporation). In the dispersion method, the mixed solution was fed to UVM-2 filled with zirconia beads having an average diameter of 0.5 mm by a diaphragm pump, and dispersed in a state where the internal pressure was 50 hPa or more until a desired average particle size was obtained.

  The dispersion was subjected to spectral absorption measurement and dispersed until the ratio of the absorbance at 450 nm to the absorbance at 650 nm (D450 / D650) in the spectral absorption of the dispersion was 2.2 or more. The obtained dispersion was diluted with distilled water so that the concentration of the base precursor was 20% by mass, and filtered for removing dust (filter made of polypropylene having an average pore size of 3 μm) for practical use.

(Preparation of dye solid fine particle dispersion)
6.0 kg of cyanine dye compound-1 and 3.0 kg of sodium p-dodecylbenzenesulfonate, 0.6 kg of surfactant Demol SNB manufactured by Kao Corporation, and antifoaming agent (trade name: Surfynol 104E, Nissin) 0.15 kg of Chemical Co., Ltd. was mixed with distilled water to make a total liquid volume of 60 kg.

  The mixed solution was dispersed with 0.5 mm zirconia beads using a horizontal sand mill (UVM-2: manufactured by Imex Corporation). The dispersion was subjected to spectral absorption measurement and dispersed until the ratio of the absorbance at 650 nm to the absorbance at 750 nm (D650 / D750) in the spectral absorption of the dispersion was 5.0 or more. The obtained dispersion was diluted with distilled water so that the concentration of the cyanine dye was 6% by mass, and subjected to filter filtration (average pore size: 1 μm) for removing dust.

(Preparation of antihalation layer coating solution)
30 g of gelatin, 24.5 g of polyacrylamide, 2.2 g of 1 mol / l caustic, 2.4 g of monodisperse polymethyl methacrylate fine particles (average particle size 8 μm, particle size standard deviation 0.4), benzoisothiazolinone 0.08 g, 35.9 g of the dye solid fine particle dispersion, 74.2 g of the solid fine particle dispersion (a) of the base precursor, 0.6 g of sodium polyethylene sulfonate, 0.21 g of blue dye compound-1 and yellow dye compound-1 0.15 g and 8.3 g of acrylic acid / ethyl acrylate copolymer latex (copolymerization ratio 5/95) were mixed, and the whole was made up to 8183 ml with water to prepare an antihalation layer coating solution.

(Preparation of back surface protective layer coating solution)
The container was kept at 40 ° C., 40 g of gelatin, 1.5 g of liquid paraffin emulsion as liquid paraffin, benzoisothiazolinone 35 mg, 1 mol / l caustic 6.8 g, sodium t-octylphenoxyethoxyethanesulfonate 0.5 g , 0.27 g of sodium polystyrene sulfonate, 37 mg of fluorosurfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt), fluorosurfactant (F-2: polyethylene glycol mono (N -Perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [ethylene oxide average polymerization degree 15]) 150 mg, fluorosurfactant (F-3) 64 mg, fluorosurfactant (F-4) 32 mg , Acrylic acid / ethyl acrylate copolymer ( The polymerization mass ratio 5/95) 6.0g, N, N- ethylenebis (vinylsulfone acetamide) was mixed 2.0 g, was the back surface protective layer coating solution of 10 liters of water.

<< Preparation of silver halide emulsion >>
[Preparation of silver halide emulsion 5-1]
A solution containing 3.1 ml of 1% by weight potassium bromide solution in 1421 ml of distilled water, 3.5 ml of 0.5 mol / L sulfuric acid, and 31.7 g of phthalated gelatin was stirred in a stainless steel reaction vessel. While maintaining the liquid temperature at 30 ° C., the solution A diluted with 95.4 ml of distilled water added to 22.22 g of silver nitrate, 15.3 g of potassium bromide and 0.8 g of potassium iodide in a distilled water volume of 97.4 ml. The whole amount of the solution B diluted to 1 was added at a constant flow rate over 45 seconds. Thereafter, 10 ml of a 3.5% by mass aqueous hydrogen peroxide solution was added, and 4 ml of a 0.1% ethanol solution of the above compound (ETTU) was further added. Further, a solution C in which distilled water was added to 51.86 g of silver nitrate to be diluted to 317.5 ml, a solution D in which 44.2 g of potassium bromide and 2.2 g of potassium iodide were diluted with distilled water to a volume of 400 ml was added to solution C. Was added at a constant flow rate over 20 minutes, and solution D was added by the controlled double jet method while maintaining pAg at 8.1. The total amount of potassium hexachloroiridium (III) was added 10 minutes after the start of the addition of Solution C and Solution D so that it would be 1 × 10 ⁻⁴ mole per mole of silver. Further, 5 seconds after the completion of the addition of the solution C, an aqueous solution of potassium iron (II) hexacyanide was added in an amount of 3 × 10 ⁻⁴ mol per mol of silver. The pH was adjusted to 3.8 using 0.5 mol / L sulfuric acid, stirring was stopped, and precipitation / desalting / water washing steps were performed. The pH was adjusted to 5.9 with 1 mol / L sodium hydroxide to prepare a silver halide dispersion having a pAg of 8.0.

While maintaining the silver halide dispersion at 38 ° C. with stirring, 5 ml of a methanol solution of 0.34% by mass of 1,2-benzisothiazolin-3-one was added, and after 40 minutes, the sensitizing dye A and the sensitizing dye A were increased. A methanol solution of 1: 1 in the molar ratio of dye B was added 1.2 × 10 ⁻³ mol of sensitizing dyes A and B per mol of silver, and the temperature was raised to 47 ° C. after 1 minute. 20 minutes after the temperature increase, sodium benzenethiosulfonate was added in a methanol solution to 7.6 × 10 ⁻⁵ mol per 1 mol of silver, and 5 minutes later, tellurium sensitizer C was added in a methanol solution to a ratio of 2. 9 × 10 −4 mol was added and aged for 91 minutes. 1.3 ml of a 0.8 mass% methanol solution of N, N′-dihydroxy-N ″ -diethylmelamine was added, and after 4 minutes, 5-methyl-2-mercaptobenzimidazole was added to the methanol solution in an amount of 4. Halogenation by adding 5.4 × 10 ⁻³ mol of 8 × 10 ⁻³ mol and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole to 1 mol of silver with methanol solution Silver emulsion 1 was prepared.

  The grains in the prepared silver halide emulsion were silver iodobromide grains containing 3.5 mol% of iodine having an average sphere equivalent diameter of 0.042 μm and a sphere equivalent diameter variation coefficient of 20%. The particle size and the like were determined from an average of 1000 particles using an electron microscope. The [100] face ratio of the particles was determined to be 80% using the Kubelka-Munk method.

[Preparation of silver halide emulsion 5-2]
In preparation of silver halide emulsion 5-1, the liquid temperature at the time of grain formation was changed from 30 ° C. to 47 ° C., and solution B was changed to dilute 15.9 g of potassium bromide with distilled water to a volume of 97.4 ml. Solution D was the same except that 45.8 g of potassium bromide was diluted with distilled water to a volume of 400 ml, and the addition time of solution C was changed to 30 minutes to remove potassium hexacyanoiron (II). Thus, silver halide emulsion 2 was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as silver halide emulsion 5-1. Further, the addition amount of a methanol solution of 1: 1 in the molar ratio of the spectral sensitizing dye A and the spectral sensitizing dye B is 7.5 × 10 ⁻ as the total of the spectral sensitizing dye A and the spectral sensitizing dye B per mole of silver. ⁴ mol, the addition amount of tellurium sensitizer C is 1.1 × 10 ⁻⁴ mol per mol of silver, and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole is added to 1 mol of silver. Except for changing to 3.3 × 10 ⁻³ mol, spectral sensitization, chemical sensitization, 5-methyl-2-mercaptobenzimidazole, 1-phenyl-2-heptyl-5-mercapto- 1,3,4-Triazole was added to obtain a silver halide emulsion 5-2. The emulsion grains of the silver halide emulsion 5-2 were pure silver bromide cubic grains having an average sphere equivalent diameter of 0.080 μm and a sphere equivalent diameter variation coefficient of 20%.

[Preparation of silver halide emulsion 5-3]
In the preparation of silver halide emulsion 5-1, silver halide emulsion 5-3 was prepared in the same manner except that the liquid temperature at the time of grain formation was changed from 30 ° C. to 27 ° C. Further, precipitation / desalting / washing / dispersion was performed in the same manner as silver halide emulsion 1. The molar ratio of spectral sensitizing dye A and spectral sensitizing dye B is 1: 1 as a solid dispersion (gelatin aqueous solution), and the addition amount is 6 × 10 ⁻ as the total of sensitizing dye A and sensitizing dye B per mole of silver. ³ moles, the amount of tellurium sensitizer C added was changed to 5.2 × 10 ⁻⁴ moles per mole of silver, and bromoauric acid was changed to 5 × 10 ⁻⁴ moles of silver 3 minutes after the addition of tellurium sensitizers. A silver halide emulsion 5-3 was obtained in the same manner as Emulsion 1 except that 2 × 10 ⁻³ mol of mol and potassium thiocyanate were added per mol of silver. The emulsion grains of the silver halide emulsion 5-3 were silver iodobromide grains uniformly containing 3.5 mol% of iodine having an average sphere equivalent diameter of 0.034 μm and a sphere equivalent diameter variation coefficient of 20%.

[Preparation of silver halide emulsion 5-4]
A silver halide emulsion 5-4 was prepared in the same manner as in the preparation of the silver halide emulsion 5-1, except that the compound (ETTU) was not added during grain formation. The grains in the prepared silver halide emulsion were silver iodobromide grains uniformly containing 3.5 mol% of iodine having an average sphere equivalent diameter of 0.044 μm and a sphere equivalent diameter variation coefficient of 19%. The [100] face ratio of the particles was determined to be 82%.

[Preparation of silver halide emulsion 5-5]
In the preparation of silver halide emulsion 5-1, silver halide emulsion 5-5 was prepared in the same manner except that the compound (ETTU) was not added during grain formation. The emulsion grains of the silver halide emulsion 5-6 were pure silver bromide cubic grains having an average sphere equivalent diameter of 0.081 μm and a sphere equivalent diameter variation coefficient of 17%.

[Preparation of silver halide emulsion 5-6]
In the preparation of silver halide emulsion 5-1, silver halide emulsion 5-6 was prepared in the same manner except that no compound (ETTU) was added during grain formation. The emulsion grains of the silver halide emulsion 5-6 were silver iodobromide grains uniformly containing 3.5 mol% of iodine having an average equivalent sphere diameter of 0.032 μm and a sphere equivalent diameter variation coefficient of 18%.

<< Preparation of mixed emulsion A for coating solution >>
70% by weight of silver halide emulsion 5-1, 15% by weight of silver halide emulsion 5-2, and 15% by weight of silver halide emulsion 5-3 are dissolved in a 1% by weight aqueous solution of benzothiazolium iodide. 7 × 10 ⁻³ mol was added per mol of silver. Further, water was added so that the content of silver halide per 1 kg of the mixed emulsion for coating solution was 38.2 g as silver.

<< Preparation of mixed emulsion B for coating solution >>
70% by mass of silver halide emulsion 5-4, 15% by mass of silver halide emulsion 5-5, and 15% by mass of silver halide emulsion 5-6 are dissolved in a 1% by mass aqueous solution of benzothiazolium iodide. 7 × 10 ⁻³ mol was added per mol of silver. Further, water was added so that the content of silver halide per 1 kg of the mixed emulsion for coating solution was 38.2 g as silver.

<< Preparation of fatty acid silver dispersion >>
[Preparation of recrystallized behenic acid]
100 kg of Henkel behenic acid (product name Edenor C22-85R) was mixed in 1200 kg of isopropyl alcohol, dissolved at 50 ° C., filtered through a 10 μm filter, cooled to 30 ° C., and recrystallized. The cooling speed during recrystallization was controlled at 3 ° C./hour. The obtained crystals were centrifugally filtered, washed with 100 kg of isopropyl alcohol, and then dried. When the obtained crystals were esterified and subjected to GC-FID measurement, the silver behenate content was 99%, and in addition, 0.5% lignoceric acid and 0.5% arachidic acid were contained.

[Preparation of fatty acid silver dispersion]
88 kg of recrystallized behenic acid, 422 L of distilled water, 49.2 L of 5 mol / L NaOH aqueous solution and 120 L of t-butyl alcohol were mixed and stirred at 75 ° C. for 1 hour to obtain a sodium behenate solution. Separately, 206.2 L (pH 4.0) of an aqueous solution containing 40.4 kg of silver nitrate was prepared and kept warm at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of t-butyl alcohol was kept at 30 ° C., and with sufficient agitation, the total amount of the previous sodium behenate solution and the total amount of silver nitrate aqueous solution were kept at a constant flow rate of 93 minutes and 15 seconds, respectively. And added over 90 minutes. At this time, only the silver nitrate aqueous solution is added for 11 minutes after the start of the addition of the silver nitrate aqueous solution, and then the addition of the sodium behenate solution B is started. After the addition of the silver nitrate aqueous solution, only the sodium behenate solution B is added for 14 minutes and 15 seconds Was added. At this time, the temperature in the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The pipe of the addition system for the sodium behenate solution was kept warm by circulating hot water outside the double pipe so that the liquid temperature at the outlet at the tip of the addition nozzle was 75 ° C. Moreover, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically around the stirring axis, and were adjusted so as not to contact the reaction solution.

  After completion of the addition of the sodium behenate solution, the mixture was left stirring for 20 minutes at the same temperature, heated to 35 ° C. over 30 minutes, and then aged for 210 minutes. Immediately after completion of the aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtrate water reached 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying.

  When the morphology of the obtained silver behenate particles was evaluated by electron microscope photography, it was a crystal having an average aspect ratio of 2.1, an average sphere equivalent diameter of 0.51 μm, and a sphere equivalent diameter variation coefficient of 11%.

  19.3 kg of polyvinyl alcohol (trade name: PVA-217) and water are added to a wet cake corresponding to a dry solid content of 260 kg. Co., Ltd .: PM-10 type).

Next, the pre-dispersed stock solution is subjected to a pressure of 1.13 × 10 ⁵ kPa (1150 kg / cm) using a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidics International Corporation, using a Z-type interaction chamber). ^The mixture was adjusted to ² ) and processed three times to obtain a silver behenate dispersion. The cooling operation was carried out by installing a serpentine heat exchanger before and after the interaction chamber, and adjusting the temperature of the refrigerant to a dispersion temperature of 18 ° C.

<< Preparation of reducing agent dispersion >>
[Preparation of Reducing Agent-1 Dispersion]
10 kg of 1: 1 complex of reducing agent-1 (6,6′-di-t-butyl-4,4′-dimethyl-2,2′-butylidenediphenol) and triphenylphosphine oxide; 10 kg of water was added to 12 kg and 16 kg of a 10 wt% aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 4 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a reducing agent complex concentration of 22% by mass to obtain a reducing agent-1 dispersion. The reducing agent complex particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.45 μm and a maximum particle diameter of 1.4 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

[Preparation of Reducing Agent-2 Dispersion]
10 masses of reducing agent-2 (6,6′-di-t-butyl-4,4′-dimethyl-2,2′-butylidenediphenol) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10 kg of water was added to 16 kg of% aqueous solution and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump, dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours 30 minutes, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a reducing agent concentration of 25% by mass to obtain a reducing agent-2 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

[Preparation of hydrogen bonding compound-1 dispersion]
Add 10 kg of water to 10 kg of 10% aqueous solution of hydrogen bonding compound-1 (tri (4-t-butylphenyl) phosphine oxide) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203). Mix to make a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a hydrogen bonding compound concentration of 25% by mass to obtain a hydrogen bonding compound-1 dispersion. The hydrogen bonding compound particles contained in the hydrogen bonding compound dispersion thus obtained had a median diameter of 0.35 μm and a maximum particle diameter of 1.5 μm or less. The obtained hydrogen bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

[Preparation of Development Accelerator-1 Dispersion]
10 kg of development accelerator-1 and 20 kg of 10% by weight aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) were added to 10 kg of water and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to adjust the concentration of the development accelerator to 20% by mass to obtain a development accelerator-1 dispersion. The development accelerator particles contained in the development accelerator dispersion thus obtained had a median diameter of 0.48 μm and a maximum particle diameter of 1.4 μm or less. The obtained development accelerator dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored. The solid dispersion of Development Accelerator-2, Development Accelerator-3, and Color Tone Modifier-1 was also dispersed by the same method as Development Accelerator-1, and a 20% by mass dispersion was obtained.

<Preparation of polyhalogen compound>
[Preparation of organic polyhalogen compound-1 dispersion]
10 kg of organic polyhalogen compound-1 (tribromomethanesulfonylbenzene), 10 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), 0.4 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate, Then, 14 kg of water was added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm. 2 g and water were added to prepare an organic polyhalogen compound concentration of 26% by mass to obtain an organic polyhalogen compound-1 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.41 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust and stored.

[Preparation of organic polyhalogen compound-2 dispersion]
10 kg of Yuki polyhalogen compound-2 (N-butyl-3-tribromomethanesulfonylbenzoamide), 20 kg of 10% by weight aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), and 20 of sodium triisopropylnaphthalenesulfonate 0.4 kg of a mass% aqueous solution was added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm. 2 g and water were added to prepare an organic polyhalogen compound concentration of 30% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-2 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 1.3 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.

[Preparation of Phthalazine Compound-1 Solution]
8 kg of Kuraray Co., Ltd. modified polyvinyl alcohol MP203 was dissolved in 174.57 kg of water, and then 3.15 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate and 70 mass of phthalazine compound-1 (6-isopropylphthalazine). 14.28 kg of a% aqueous solution was added to prepare a 5 mass% solution of phthalazine compound-1.

<Preparation of mercapto compound>
[Preparation of Mercapto Compound-1 Aqueous Solution]
7 g of mercapto compound-1 (1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt) was dissolved in 993 g of water to obtain a 0.7% by mass aqueous solution.

[Preparation of Mercapto Compound-2 Aqueous Solution]
20 g of mercapto compound-2 (1- (3-methylureido) -5-mercaptotetrazole sodium salt) was dissolved in 980 g of water to obtain a 2.0 mass% aqueous solution.

<< Preparation of Pigment-1 Dispersion >>
C. I. Pigment Blue 60 (64 g) and Kao Corp. Demol N (6.4 g) were added to 250 g of water and mixed well to obtain a slurry. Prepare 800 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and disperse with a disperser (1/4 G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours. Obtained. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

<< Preparation of SBR Latex Liquid >>
An SBR latex having a Tg of 22 ° C. was prepared as follows. Ammonium persulfate is used as a polymerization initiator, an anionic surfactant is used as an emulsifier, 70.0 mass of styrene, 27.0 mass of butadiene and 3.0 mass of acrylic acid are emulsion-polymerized, and then aging is performed at 80 ° C. for 8 hours. It was. Thereafter, the mixture was cooled to 40 ° C., adjusted to pH 7.0 with aqueous ammonia, and Sandet BL manufactured by Sanyo Chemical Co., Ltd. was further added to 0.22%. Next, 5% aqueous sodium hydroxide solution was added to adjust the pH to 8.3, and further adjusted to pH 8.4 with aqueous ammonia. The molar ratio of Na ⁺ ions and NH ₄ ⁺ ions used at this time was 1: 2.3. Further, 0.15 ml of a 7% aqueous solution of benzoisothiazoline non sodium salt was added to 1 kg of this liquid to prepare an SBR latex liquid.

  (SBR latex: Latex of -St (70.0) -Bu (27.0) -AA (3.0)-), Tg 22 ° C., average particle size 0.1 μm, concentration 43 mass%, 25 ° C. 60% RH Equilibrium water content of 0.6% by mass, ion conductivity of 4.2 mS / cm (Ion conductivity was measured using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd.), and latex stock solution (43% by mass) was 25 PH measured at ℃), pH 8.4.

  SBR latexes having different Tg can be prepared in the same manner by appropriately changing the ratio of styrene and butadiene.

<< Preparation of emulsion layer (photosensitive layer) coating solution-1 >>
1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, 33.2 g of pigment-1 dispersion, 21 g of organic polyhalogen compound-1 dispersion, 58 g of organic polyhalogen compound-2 dispersion, 173 g of phthalazine compound-1 solution, SBR 1082 g of latex (Tg: 22 ° C.) liquid, 299 g of reducing agent complex-1 dispersion, 6 g of development accelerator-1 dispersion, 9 ml of mercapto compound-1 aqueous solution, and 27 ml of mercapto compound-2 aqueous solution were sequentially added. The emulsion layer coating solution to which 117 g of silver halide mixed emulsion A was added and mixed well was fed to the coating die as it was and coated.

  The viscosity of the emulsion layer coating solution was 25 (mPa · s) at 40 ° C. (No. 1 rotor, 60 rpm) as measured with a B-type viscometer of Tokyo Keiki. The viscosity of the coating solution at 25 ° C. using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is 230, 60, 46, respectively at shear rates of 0.1, 1, 10, 100, and 1000 (1 / second). 24 and 18 (mPa · s).

  The amount of zirconium in the coating solution was 0.38 mg per 1 g of silver.

<< Preparation of emulsion layer (photosensitive layer) coating liquid-2 >>
1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, 32.8 g of pigment-1 dispersion, 21 g of organic polyhalogen compound-1 dispersion, 58 g of organic polyhalogen compound-2 dispersion, 173 g of phthalazine compound-1 solution, SBR 1082 g of latex (Tg: 20 ° C.) liquid, 155 g of reducing agent-2 dispersion, 55 g of hydrogen bonding compound-1 dispersion, 6 g of development accelerator-1 dispersion, 2 g of development accelerator-2 dispersion, development accelerator- 3 g of dispersion 3 g, 2 g of color adjusting agent-1 dispersion, 6 ml of mercapto compound-2 aqueous solution are added in order, and 117 g of silver halide mixed emulsion A 117 g is added just before coating, and the emulsion layer coating solution mixed well is directly applied to the coating die. The solution was fed and applied. The viscosity of the emulsion layer coating solution was 40 (mPa · s) at 40 ° C. (No. 1 rotor, 60 rpm) as measured with a B-type viscometer of Tokyo Keiki. The viscosity of the coating solution at 25 ° C using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is 530, 144, 96 at shear rates of 0.1, 1, 10, 100, and 1000 (1 / second), respectively. 51 and 28 (mPa · s).

  The amount of zirconium in the coating solution was 0.25 mg per 1 g of silver.

<Preparation of emulsion surface intermediate layer coating solution>
Polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) 1000 g, pigment 5 mass% dispersion 272 g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer mass ratio 64/9/20) / 5/2) 27% 5% aqueous solution of aerosol OT (manufactured by American Cyanamid Co., Ltd.) in 4200 ml of 19% by weight latex, 135 ml of 20% by weight aqueous solution of diammonium phthalate, total amount 10000g Water was added and adjusted with NaOH so that the pH was 7.5 to obtain an intermediate layer coating solution, which was then fed to the coating die so as to be 9.1 ml / m ² . The viscosity of the coating solution was 58 (mPa · s) at 40 ° C. (No. 1 rotor, 60 rpm) with a B-type viscometer.

<< Preparation of emulsion surface protective layer first layer coating solution >>
Inert gelatin (64 g) is dissolved in water, and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5/2) 27.5% by weight latex 80 g, 23 ml of a 10% by weight methanol solution of phthalic acid, 23 ml of a 10% by weight aqueous solution of 4-methylphthalic acid, 28 ml of sulfuric acid having a concentration of 0.5 mol / L, and a 5% by weight aqueous solution of Aerosol OT (American Cyanamid Co., Ltd.) Add 5 ml, 0.5 g phenoxyethanol, 0.1 g benzoisothiazolinone, add water to make a total amount of 750 g, and use 26 ml of 4% by weight chromium alum mixed with a static mixer just before coating. The solution was fed to the coating die so as to be 18.6 ml / m ² . The viscosity of the coating solution was 20 (mPa · s) at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).

<< Preparation of emulsion surface protective layer second layer coating solution >>
80 g of inert gelatin is dissolved in water, and a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5/2) latex 27.5% by mass solution 102 g, 3.2 ml of a 5% by mass solution of a fluorosurfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt), a fluorosurfactant (F-2: polyethylene glycol mono (N- Perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [ethylene oxide average polymerization degree = 15]) 2 mass% aqueous solution 32 ml, aerosol OT (manufactured by American Cyanamid Co., Ltd.) 5 mass% solution 23 ml , 4 g of polymethyl methacrylate fine particles (average particle size 0.7 μm), Water so that the total amount is 650 g in 21 g of dimethyl methacrylate fine particles (average particle size 4.5 μm), 1.6 g of 4-methylphthalic acid, 4.8 g of phthalic acid, 44 ml of 0.5 mol / L sulfuric acid, and 10 mg of benzoisothiazolinone. Was added with 445 ml of an aqueous solution containing 4% by weight of chromium alum and 0.67% by weight of phthalic acid using a static mixer immediately before coating, to obtain 8.3 ml / m ² as a surface protective layer coating solution. Then, the solution was fed to the coating die. The viscosity of the coating solution was 19 (mPa · s) at 40 ° C. (No. 1 rotor, 60 rpm) B-type viscometer.

<< Production of Photothermographic Dry Imaging Material-1 >>
On the back surface side of the undercoat support, the antihalation layer coating solution is applied so that the solid content coating amount of the solid fine particle dye is 0.04 g / m ^2, and the back surface protective layer coating solution is applied with a gelatin coating amount of 1 A simultaneous multilayer coating was applied so as to be 0.7 g / m ² , followed by drying to prepare a back layer.

A sample of a photothermographic material is prepared on the surface opposite to the back surface by simultaneous multi-layer coating using the slide bead coating method in the order of the emulsion layer, intermediate layer, protective layer first layer, and protective layer second layer from the undercoat surface. did. At this time, the emulsion layer and the intermediate layer were adjusted to 31 ° C., the protective layer first layer was adjusted to 36 ° C., and the protective layer first layer was adjusted to 37 ° C. The coating amount (g / m ² ) of each compound in the emulsion layer is as follows.

Silver behenate 5.55 pigment (CI Pigment Blue 60) 0.036, organic polyhalogen compound-1 0.12, organic polyhalogen compound-2 0.37, phthalazine compound-1 0.19, SBR latex 9.97, reducing agent complex-1 1.41, development accelerator-1 0.024, mercapto compound-1 0.002, mercapto compound-2 0.012, silver halide (as Ag) 0.091. The coating and drying conditions are as follows. The coating was performed at a speed of 160 m / min, the gap between the coating die tip and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set to be 196 to 882 Pa lower than the atmospheric pressure. The support was neutralized with an ion wind before coating. In the subsequent chilling zone, after cooling the coating solution with a wind at a dry bulb temperature of 10 to 20 ° C., it is transported in a non-contact type, and is dried at a dry bulb temperature of 23 to 45 ° C. It dried with the dry wind of the wet bulb temperature 15-21 degreeC. After drying, the humidity was adjusted at 25 ° C. and humidity of 40 to 60% RH, and then the film surface was heated to 70 to 90 ° C. After heating, the film surface was cooled to 25 ° C.

  The resulting photothermographic imaging material had a Beck smoothness of 550 seconds on the photosensitive layer surface side and 130 seconds on the back surface. Further, the pH of the film surface on the photosensitive layer surface side was measured and found to be 6.0.

<< Production of Photothermographic Dry Imaging Material-2 >>
Photothermographic dry imaging material-2 was prepared in the same manner as in photothermographic dry imaging material-1, except that silver halide mixed emulsion B was used instead of silver halide mixed emulsion A in emulsion layer coating solution-1. did.

<< Production of Photothermographic Dry Imaging Material-3 >>
For the photothermographic dry imaging material-1, the emulsion layer coating solution-1 was changed to the emulsion layer coating solution-2, and the yellow dye compound-1 was removed from the halation preventing layer, and the back surface protective layer and the emulsion surface protective layer The photothermographic material-1 except that the fluorosurfactant was changed from F-1, F-2, F-3 and F-4 to F-5, F-6, F-7 and F-8, respectively. Photothermographic material-2 was produced in the same manner as described above. The coating amount (g / m ² ) of each compound in the emulsion layer at this time is as follows.

  Silver behenate 5.55, pigment (CI Pigment Blue 60) 0.036, organic polyhalogen compound-1 0.12, organic polyhalogen compound-2 0.37, phthalazine compound-1 0.19, SBR Latex 9.67, reducing agent-2 0.81, hydrogen bonding compound-1 0.30, development accelerator-1 0.024, development accelerator-2 0.010, development accelerator-3 0.015, Color tone adjuster-1 0.010, mercapto compound-2 0.002 silver halide (as Ag) 0.091.

<< Production of Photothermographic Dry Imaging Material-4 >>
Photothermographic dry imaging material-4 was prepared in the same manner as for photothermographic dry imaging material-3 except that silver halide mixed emulsion B was used instead of silver halide mixed emulsion A in emulsion layer coating solution-1. did.

  The chemical structure of the compound used in Example 5 is shown below.

  Samples were exposed and thermally developed with a medical dry laser imager (mounted with a 660 nm semiconductor laser with a maximum output of 60 mW (IIIB)) (photothermal photography with four panel heaters set at 112 ° C-119 ° C-121 ° C-121 ° C) The dry imaging materials-1 and 2 were 24 seconds in total, and the photothermographic dry imaging materials-3 and 4 were 14 seconds in total. The obtained samples were evaluated in the same manner as in Example 1, and the results shown in Table 7 were obtained. Obtained.

As is clear from Table 7, the silver salt photothermographic dry imaging material of the present invention has a fog (minimum density) equivalent to or lower than that of the comparison, while the sensitivity and the highest density are substantially the same or higher. It can be seen that the image storability after development processing is excellent. Further, in the color tone evaluation of the sample according to the present invention, the linear regression line determination coefficient (multiple determination) R ² is 0.998 or more and 1.000 or less, and the b ^* value of the intersection with the vertical axis of the linear regression line. Is -5 or more and 5 or less and the slope (b ^* / a ^* ) is 0.7 or more and 2.5 or less, it can be said that the color tone is better.

Claims (14)

In a silver salt photothermographic dry imaging material containing a non-photosensitive aliphatic carboxylic acid silver salt particle, a photosensitive silver halide particle, a silver ion reducing agent and a binder, the material has a sensitivity (2 ) Is 1/10 or less of the sensitivity (1), and each of the optical density 0.5, 1.0, 1.5 and the lowest optical density of the silver image obtained by thermally developing the dry imaging material to determine the concentration, the horizontal axis of the ^{CIE 1976 (L * a * b} *) color space a ^*, vertical axis in the two-dimensional coordinates to b ^*, a ^* in the above each optical density, placing the b ^* of determination R ² of the linear regression line that was created is 1.000 or less than 0.998, b ^* values of the intersection of the longitudinal axis is at -5 to 5, and gradient (b ^* / a ^*) is Silver salt photothermographic dry imageon characterized by being from 0.7 to 2.5 Material.
Sensitivity (1): Sensitivity of the material obtained based on a characteristic curve obtained by heat development under normal heat development conditions after exposure through an optical wedge. Note that exposure at this time is performed with light having spectral characteristics appropriate for exposing the material (specifically, white light or light in a specific spectral sensitization region). The normal heat development conditions refer to conditions in a range that is appropriate for heat development of the material and often used for heat development.
Sensitivity (2): After exposure under the same conditions as thermal development in sensitivity (1) before exposure, after exposure through an optical wedge under the same conditions as sensitivity (1), the same thermal development conditions as in sensitivity (1) Sensitivity obtained based on the characteristic curve obtained by heat development with. A silver salt photothermographic dry imaging material containing a non-photosensitive aliphatic carboxylic acid silver salt particle, a photosensitive silver halide particle, a silver ion reducing agent and a binder, wherein the photosensitive silver halide particle is subjected to a thermal development process. By converting from surface latent image type to internal latent image type, it is a silver halide grain whose surface sensitivity is lower than before thermal development, and contains at least one of yellow color developing leuco dye or cyan color developing leuco dye The silver salt photothermographic dry imaging material according to claim 1. The silver salt photothermographic dry imaging material according to claim 1 or 2, wherein at least one of the silver ion reducing agents is represented by the following general formula (RED).

[Wherein, X ₁ represents a chalcogen atom or CHR ₁ , and R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₂ represents an alkyl group. R ₃ represents a hydrogen atom or a group that can be substituted on a benzene ring. R ₄ represents a substitutable group on the benzene ring, and m and n each represents an integer of 0 to 2. ] The silver salt according to any one of claims 1 to 3, comprising at least two kinds of silver ion reducing agents having different chemical structures, or at least one kind of silver ion reducing agent and a development accelerator. Photothermographic dry imaging material. The silver salt according to any one of claims 1 to 4, wherein 50% or more of the total aliphatic carboxylate silver constituting the non-photosensitive aliphatic carboxylate silver salt particles is silver behenate. Photothermographic dry imaging material. A silver salt photothermographic dry imaging material containing non-photosensitive aliphatic carboxylic acid silver salt particles, photosensitive silver halide particles, a silver ion reducing agent and a binder, wherein the non-photosensitive aliphatic carboxylic acid silver salt particles are potassium Prepared in the presence of an alkali metal salt having a salt content of 50 mol% or more and that the photosensitive silver halide grains are converted from a surface latent image type to an internal latent image type in the heat development process, The silver salt photothermographic dry imaging material according to any one of claims 1 to 5, wherein the silver salt is a silver halide grain having a surface sensitivity lower than that before heat development. A silver salt photothermographic dry imaging material containing non-photosensitive aliphatic carboxylic acid silver salt particles, photosensitive silver halide particles, a silver ion reducing agent and a binder, wherein the non-photosensitive aliphatic carboxylic acid silver salt particles are potassium Prepared in the presence of an alkali metal salt having a salt content of 50 mol% or more and an average grain size of 0.07 to 0.02 μm silver halide grains, and the photosensitive silver halide grains were thermally developed. The silver halide grains according to any one of claims 1 to 6, wherein the surface sensitivity is a silver halide grain whose surface sensitivity is lower than that before heat development by converting from a surface latent image type to an internal latent image type in the process. Silver salt photothermographic dry imaging material. The silver salt photothermographic dry imaging material according to claim 1, comprising a compound represented by the following general formula (ST).
General formula (ST) Z-SO ₂ · SM
[Wherein, Z represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group, and M represents a metal atom or an organic cation. ] The silver salt photothermographic dry imaging material according to claim 1, comprising a compound represented by the following general formula (CV).

[Wherein, X represents an electron-withdrawing group, and W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, an acyl group, a thioacyl group, an oxalyl group, an oxy group. Oxalyl group, -S-oxalyl group, oxamoyl group, oxycarbonyl group, -S-carbonyl group, carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, -S-sulfonyl group, sulfamoyl group, oxysulfinyl Represents a group, -S-sulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, ammonium group, sulfonium group, phosphonium group, pyrylium group, or immonium group , R ₁ represents a hydroxyl group or a hydroxyl Represents salts, R ₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X and W each exclude a formyl group. X and W may combine with each other to form a cyclic structure. X and R ₁ are shown in cis form, but X and R ₁ include transformer form. ] The silver salt photothermographic dry imaging material according to any one of claims 1 to 9, comprising a polymer having at least one repeating unit of a monomer having a halogen radical releasing group. The silver salt photothermographic dry imaging according to any one of claims 1 to 10, wherein the photosensitive silver halide grains contain therein a dopant that functions as an electron trap after at least thermal development. material. Spectral sensitizing dye is adsorbed on the surface of the photosensitive silver halide grains to effect spectral sensitization, and the effect of spectral sensitization substantially disappears after the thermal development process. Item 12. The silver salt photothermographic dry imaging material according to any one of Items 1 to 11. The surface of the photosensitive silver halide grain is chemically sensitized, and the effect of the chemical sensitization substantially disappears after the thermal development process. The silver salt photothermographic dry imaging material according to claim 1. The surface of the photosensitive silver halide grain is chemically sensitized, spectrally sensitized by adsorbing a spectral sensitizing dye, and subjected to chemical sensitization and spectral sensitization after the thermal development process. The silver salt photothermographic dry imaging material according to any one of claims 1 to 13, wherein the effect is substantially lost.