JP2001013620A - Heat-developable photographic sensitive material, image recording method, and image forming method by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-developable photosensitive material small in fluctuation of photographic performances such as sensitive and fog and almost restrained from occurrence of uneven development and high in quality and further, to provide method for recording and forming images. SOLUTION: In the heat-developable photographic sensitive material provided at least on one side of a support with a photosensitive layer containing a photosensitive layer and containing photosensitive silver halide and a layer containing a nonphotosensitive silver salt, and its reducing agent, a protective layer an intermediate layer, or a backcoat layer contains an inorganic laminar compound. The surface of the protective layer has a smooster value of 0-25 mm Hg and the backcoat layer has that of 50-300 mm Hg.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, an image recording method and an image forming method using the same.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, a waste liquid caused by wet processing of an image forming material has been a problem in terms of workability. Weight loss is strongly desired. Therefore, there has been a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As a technique for this, a heat-developable photographic light-sensitive material for forming a photographic image using a heat-development processing method is disclosed in, for example, US Pat. Nos. 3,152,904 and 3,457,07.
No. 5, and D.E. Morgan and B.A. Shelly Processed Si System by Shelly
Lever Systems) "(Imaging Processes and Materials (Imaging P
processes and Materials) N
Eblette Eighth Edition, Sturge,
V. Walworth, A .; Shepp, page 2, 1969).

[0004] As described in the above literature, heat-developable photographic materials differ from conventional wet-processed photographic materials in that a photographic material contains a developer, an inhibitor and other conventional photographic processing agents. It is characterized by containing a raw material. Compounds contained in the light-sensitive material such as a developer are diffused in the light-sensitive material by a heat development process and exhibit their respective functions to form a photographic image.

The photographically useful compound added to each layer of the photographic element by various methods as described above is usually used by being fixed in the photographic material. However, various problems such as the following problems have occurred during the thermal development process, although they are slightly diffused out of the layer.

(1) Additives that affect photographic properties, such as a development inhibitor, a development accelerator, a reducing agent, or a dye, diffuse out of the light-sensitive material and heat-process. Accumulates and accumulates on rollers and transport rollers,
The accumulated matter is transferred to a film to be processed later, causing a problem that the quality of the photosensitive material is deteriorated or unstable. Further, a sublimable compound in the photosensitive material precipitates in the automatic developing machine, causing a problem such as poor conveyance. To prevent this, measures such as increasing the molecular weight of the additive and increasing the thickness of the protective layer or the intermediate layer are taken. However, these countermeasures are accompanied by an adverse effect such that the effect of the additive is reduced or the curl is deteriorated by increasing the film thickness.

(2) During storage under high humidity, powder blowing failure occurs due to the additive diffusing in the layer and depositing on the surface. In order to solve this, a binder is usually selected or its amount is increased. However, these countermeasures are not sufficient, and an increase in film thickness causes adverse effects such as deterioration of curl.

Further, the following problems occur due to the diffusion of oxygen, water vapor, nitrogen oxides, sulfur oxides, and the like from the air into the layer.

(3) The contained compound is oxidized by oxygen to change its quality, or is irradiated with light in the presence of oxygen to promote photobleaching. In order to prevent this, an antioxidant or an ultraviolet absorber is added, or a protective layer or an intermediate layer of a polymer having a low oxygen permeability is provided, but the effect is not always sufficient and curling is also deteriorated.

(4) The added compound is altered under high humidity.

(5) A trace amount of nitrogen oxide or sulfur oxide in the air diffuses into the film and reacts with the compound in the photographic element to cause problems such as coloring, discoloration, and alteration.

There has been a demand for a solution to the above problems.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent the deposition of additives in an image forming apparatus by reducing the amount of leaching from a light-sensitive material, and to prevent various gases (atmospheres) in the atmosphere from being produced. A heat-developable photographic light-sensitive material capable of forming a good image with less uneven development and sensitivity fluctuation by suppressing diffusion of oxygen, water vapor, carbon dioxide, nitrogen oxide, sulfur oxide, etc. into the photographic layer; And an image recording method and an image forming method using the same.

[0014]

The object of the present invention has been attained by the following items 1 to 11.

1. A heat-developable photographic material having a photosensitive layer containing a photosensitive silver halide on at least one surface of a support and containing a non-photosensitive silver salt and a reducing agent for the non-photosensitive silver salt, wherein a protective layer, an intermediate A photothermographic material comprising a layer or a back coat layer containing an inorganic layered compound.

2. 2. The photothermographic material according to the above item 1, wherein the protective layer or the back coat layer contains an inorganic layered compound.

3. The smoother value of the protective layer surface is 0 to 2
3. The photothermographic material according to the above item 1 or 2, wherein the back coat layer has a smoother value of 50 to 300 mmHg at 5 mmHg.

4. 4. The photothermographic material according to any one of items 1 to 3, wherein the weight ratio of the inorganic layered compound to the binder in the layer containing the inorganic layered compound is 1/10 to 10/1.

5. The aspect ratio of the inorganic layered compound is 10
Any one of the above 1 to 4, which is 0 or more
4. The photothermographic material according to item 1.

6. 6. The photothermographic material according to any one of items 1 to 5, wherein the inorganic layered compound is synthetic mica.

7. 7. The photothermographic material according to any one of items 1 to 6, wherein the inorganic layered compound is bentonite.

8. 8. An image recording method, comprising exposing the photothermographic material according to any one of the above items 1 to 7 using a laser.

9. Using an exposure apparatus in which the angle between the exposure surface and the scanning laser light is not substantially perpendicular,
8. An image recording method, comprising exposing the photothermographic material according to any one of items 7 to 7.

10. 8. An image recording method, comprising exposing the photothermographic material according to any one of 1 to 7 above using a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi.

[11] 8. An image forming method, wherein the photothermographic material according to any one of the above items 1 to 7 is heat-developed in a state where the photothermographic material contains a solvent of 500 mg / m ² or less.

The details of the present invention will be described below.

Examples of the inorganic layered compound used in the present invention include clay minerals such as bentonite, hectonite and montmorillonite, synthetic mica, and synthetic smectite. These inorganic layered compounds have a laminated structure composed of a unit crystal lattice layer having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals. As a result, the lattice layer has a shortage of positive charges, and cations such as Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers to compensate for the shortage. The cations interposed between these layers are called exchangeable cations and exchange with various cations.

As synthetic mica used in the present invention, Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na
Alternatively, Li teniolite (NaLi) Mg ₂ Li (Si ₄
O ₁₀ ) F ₂ , Na or Li hextry (NaLi) _1/3
Mg _2/3 Li _1/3 (Si ₄ O ₁₀ ) F _{2 and the} like. The synthetic mica preferably used in the present invention has a thickness of 1 to 50 nm and a surface size of 1 to 20 μm. For diffusion control, the thinner the better, the better the flatness is, and the better the planar size is, as long as the smoothness and transparency of the coated surface are not deteriorated. Therefore, the aspect ratio is 100 or more, preferably 200 or more, and particularly preferably 500 or more.

[0029] The addition amount of the inorganic layered compound used in the present invention, from the viewpoint of performing diffusion control using the intermediate layer or the protective layer is preferably from 50 to 500 mg / m ^2, more preferably 100 to 300 mg / m ² It is. In addition, from the viewpoint of improving the film quality, it can be arbitrarily selected in the range of 5 to 5000 mg / m ² according to the purpose.

The binder used in the layer containing the inorganic layered compound used in the present invention is transparent or translucent and generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other media for forming films are preferably used. For example, 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 (methyl methacrylic acid) Vinyl), poly (methacrylic acid), copoly (styrene-
Maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinylacetal) s (eg, poly (vinylformal) and poly (vinylbutyral)), poly (esters),
There are poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder used in the present invention may be hydrophilic or non-hydrophilic.

In the present invention, the binder amount of the photosensitive layer is preferably from 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² .

The amount of the binder in the inorganic layered compound-added layer used in the present invention is 1 to 2,000 parts by weight, preferably 10 to 1,000 parts by weight, particularly preferably 20 to 500 parts by weight, per 100 parts by weight of the inorganic layered compound. It is.

Next, a method for dispersing the inorganic layered compound used in the present invention will be described. 5 to 10 parts by weight of the inorganic stratiform compound is added to 100 parts by weight of the solvent, and dispersed by a dispersing machine. Examples of the dispersing machine used to carry out the present invention include various milling methods in which a direct mechanical force is applied to disperse, a high-speed stirring type dispersing machine having a large shearing force, and a dispersing machine for applying high-intensity ultrasonic energy. and so on. Specifically, a ball mill, a sand grinder mill, a biscomil, a colloid mill, a homogenizer, a dissolver, a polytron, a homomixer, a homoblender, a kedi mill, a jet agitator, a capillary emulsifier, a liquid siren, an electromagnetic strain type ultrasonic generator, There is an emulsifying device having a Paulman whistle. The dispersion of 5 to 10% by weight dispersed by the above method has a high viscosity or a gel state, and has extremely good storage stability. When it is added to the coating liquid, it is added after diluting with a solvent and sufficiently stirring.

Since the surface of the inorganic layered compound used in the present invention is negatively charged, the surface becomes hydrophobic when a cationic surfactant or the like is adsorbed on the surface. When using an inorganic layered compound whose surface is hydrophobized in this way,
After swelling with a solvent having a sufficient affinity for the hydrophobic part of the surfactant adsorbed on the surface, the mixture is dispersed and a binder solution is added to prepare a coating solution.

In the photothermographic material of the present invention described in the above item 1, the inorganic layered compound used in the present invention is contained in at least the outermost layer, and the inorganic layered compound is further contained in layers other than the outermost layer. It may be contained.

In the photothermographic material of the present invention described in the above item 2, the inorganic layered compound used in the present invention is contained in the protective layer (outermost layer), the intermediate layer or the back coat layer. May further contain an inorganic layered compound.

The inorganic layered compound used in the present invention can be applied to the heat-developable photographic material of the present invention using a photosensitive silver halide as an optical sensor, or various photographic elements used in combination therewith. it can.

In the present invention, from the viewpoint of improving the transportability of the photothermographic material in the image forming apparatus and reducing the sensitivity fluctuation and uneven development, the outermost layer (protective layer) on the photosensitive layer side is used. ) The surface smoother value is 23 ° C,
It is preferably 0 to 25 mmHg at 55% RH, more preferably 0 to 10 mmHg, and particularly preferably 0 to 5 mmHg.
Hg. The smoother value of the back coat surface is 50 to 500 mmHg at 23 ° C. and 55% RH, preferably 50 to 300 mmHg.

In the present invention, the smoother value indicates the smoothness of a surface, and specifically, JAPAN TAPPI
Paper pulp test method No. It is measured according to the method for measuring smoother smoothness described in 5A.

The degree of surface roughening of the light-sensitive material is determined by the smoother value described above. If the value of the smoother is too small, the transportability in the image forming apparatus (automatic processing machine) becomes poor. Conversely, if the value of the smoother is large, light diffusion occurs during exposure, and problems such as a decrease in sensitivity and a decrease in image quality tend to occur.

In order to adjust the smoother value of the outermost layer of the photothermographic material of the present invention to the above-mentioned value, it is preferable to use, for example, a matting agent, and more preferably to use an average particle size. It is preferable to use two or more different matting agents in combination.

By adjusting the outermost layer on the photosensitive layer side and the surface of the back coat layer to select different smoother values, excellent transportability in an automatic developing machine is achieved.
Further, it is possible to obtain a heat-developable photographic light-sensitive material with less deterioration in sensitivity and image quality.

In the present invention, it is preferable that a matting agent is contained in both the backing layer and the outermost layer (protective layer). In order to improve the dimensional repetition accuracy of the photothermographic material of the present invention, a polymer matting agent is required. Alternatively, an inorganic matting agent may be used in a weight ratio of 0.5 to 10 with respect to all binders on the emulsion layer side.
%.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance.

For example, as inorganic substances, Swiss Patent No. 3
Silica described in No. 30,158, French Patent No. 1,29
No. 6,995, etc., British Patent No. 1,17
Alkaline earth metals or carbonates such as cadmium and zinc described in 3,181 and the like can be used as a matting agent. As organic substances, US Pat. No. 2,322,03
7, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, and Swiss Patent No. 330,158. Polystyrene or polymethacrylate described in U.S. Pat.
Organic matting agents such as polyacrylonitrile described in No. 079,257 and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent refers to this spherical converted diameter.

The average particle size of the matting agent is 0.5 μm
To 15 μm, more preferably 1.0 μm to
10.0 μm. The variation coefficient of the particle size distribution is preferably 40% or less, more preferably 30% or less.
%, Particularly preferably 20% 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 Further, in the present invention, it is preferable to use a mixture of two types of matting agents having different average particle sizes. The addition amount and ratio of each of the two matting agents can be arbitrarily changed according to the balance of the smoother value, sensitivity, haze, etc., but the average particle size is 1.0 μm to 5.0 μm and 5.0 μm.
The effect of the present invention is best exhibited by using a matting agent having a size of μm to 10.0 μm in combination.

The matting agent used in the present invention can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer, and more preferably the outermost layer (outermost layer) as viewed from the support. ).

The method for adding the matting agent used in the present invention may be a method in which the matting agent is dispersed in a coating solution in advance, or the matting agent may be sprayed after the coating solution is applied and before the drying is completed. May be used. When a plurality of types of matting agents are added, both methods may be used in combination.

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

The organic silver salt used in the present invention preferably has an average particle size of 1 μm or less and is monodispersed.
The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.01 μm to 0.8 μm, especially 0.0 μm.
5 μm to 0.5 μm is preferred. The term “monodisperse” is synonymous with silver halide, and preferably has a coefficient of variation of 1
３０30%.

The organic silver salt used in the present invention has an average particle size of 1
It is more preferable that the particles are monodisperse particles having a particle size of not more than μm.

Further, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystal is obtained by dispersing and pulverizing the organic silver crystal together with a binder, a surfactant and the like by a ball mill or the like. Can be

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

The organic silver salt used in the present invention is a reducible silver source, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10 to 30, preferably 15 to 15). Aliphatic carboxylic acids having up to 25 carbon atoms) and nitrogen-containing heterocycles are preferred. The ligand is 4.0 to 10.0
Also useful are organic or inorganic silver salt complexes having a total stability constant for silver ions of. An example of a suitable silver salt is Rese
arch Disclosure Nos. 17029 and 29
963, and include: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, arachidic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthioureas Salt (for example, 1
-(3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.);
Silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) , 5,5-thiodisalicylic acid), silver salts or complexes of thiones (e.g., 3
-(2-carboxyethyl) -4-hydroxymethyl-
4- (thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione), imidazole,
Pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-
A complex or salt of silver and a nitrogen acid selected from 1,2,4-triazole and benzotriazole; saccharin,
Silver salts such as 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate and silver stearate. The organic silver salt is preferably contained at a silver amount of 4 g / m ² or less. More preferably, it is 3 g / m ² or less.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and includes a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
The controlled double jet method described in No. 3 is preferably used.

The photosensitive silver halide used in the present invention will be described.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. The above metals include W, Fe, Co, N
i, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

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

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

Specific examples of transition metal complex ions are shown below, but the present invention is not limited to these.

[0066] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^{2 -} 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl ₅ ] ^2-27 : [Ir (NS) Cl ₅ ] ^2- These metal ions, metal complexes or metal complex ions may be of one kind, or two or more of the same kind and different kinds of metals may be used in combination. Good. The content of these metal ions, metal complexes or metal complex ions, generally is suitably ¹ × 10 -9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

The compounds providing these metals are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical ripening are carried out. Although it may be added at any stage, such as before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening.
It is preferably added at the stage of growth, most preferably at the stage of nucleation.

In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added uniformly to the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are used. When they are mixed simultaneously, they are added as a third aqueous solution to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method in which halogen is added. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation of silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution.

When adding to the surface of the particles, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by a known desalting method such as a noodle method, flocculation method, ultrafiltration method, and electrodialysis method.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Examples of the sensitization method include known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization and reduction sensitization. A sensitization method can be used. These sensitization methods can be used in combination of two or more. For sulfur sensitization, thiosulfates, thiourea compounds, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization are described in JP-A-9-2.
No. 30527 can be mentioned. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent 618,06.
Compounds described in No. 1 and the like can be mentioned.
Specific compounds used in the reduction sensitization method include ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less.

The heat-developable photographic light-sensitive material of the present invention contains, as spectral sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxonol dyes. Dyes and the like can be used. For example, JP-A-63-1598
No. 41, No. 60-140335, No. 63-23143
No. 7, 63-259,651 and 63-304242
No. 63-15245, U.S. Pat. No. 4,639,4
No. 14, No. 4,740,455, No. 4,741,
No. 966, No. 4,751,175, No. 4,83
Sensitizing dyes described in U.S. Pat. No. 5,096 can be used.

Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
17643 IV-A (p. 23, December 1978), and Item 18431 (p. 437, August 1979), etc. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers and scanners can be advantageously selected. For example, JP-A-9-34078 and JP-A-9-5440
Compounds described in Nos. 9 and 9-80679 are preferably used.

The cyanine dye useful in the present invention is, for example, a cyanine dye having a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including.

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, (A) For an argon laser light source,
JP-A-60-162247, JP-A-2-48653
No. 2,161,331, West German Patent No. 93
(B) Helium-neon laser light sources such as simple merocyanines described in Japanese Patent Application No. 6,071 and Japanese Patent Application No. 3-189532 are disclosed in JP-A-50-62425 and JP-A-50-62425.
(C) LED light sources and red semiconductor lasers such as trinuclear cyanine dyes described in JP-A Nos. 4-18726 and 59-102229 and merocyanines described in Japanese Patent Application No. 6-103272. 48-42172, 5
Nos. 1-9609 and 55-39818.
(D) infrared semiconductor laser light sources such as thiacarbocyanines described in JP-A-284343 and JP-A-2-105135;
Tricarbocyanines described in JP-A-80841, and dicarbocyanines containing a 4-quinoline nucleus described in the general formulas (IIIa) and (IIIb) of JP-A-59-192242 and JP-A-3-67242. The above (A) ~
The sensitizing dyes described in (D) and the like are advantageously selected. Further, when the wavelength of the infrared laser light source is 750 nm or more, and more preferably 800 nm or more, in order to cope with a laser in such a wavelength range, Japanese Patent Application Laid-Open Nos. 4-18239, 5-341432, and 6-52387. 3-10
931; U.S. Pat. No. 5,441,866;
Sensitizing dyes described in 13295 and the like are preferably used. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The exposure of the photothermographic material of the present invention is carried out by A
r laser (488 nm), He-Ne laser (633 n
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 820 nm) and the like are preferably used. However, from the viewpoint of high laser power and transparency of the photosensitive material, infrared semiconductor lasers are used. Lasers are more preferably used.

In the present invention, it is particularly preferred to use a sensitizing dye having a spectral sensitivity in the infrared, but the sensitizing dye having a spectral sensitivity in the infrared is preferably represented by the following general formula (1-a):
It is preferable to contain at least one compound represented by (1-d).

[0079]

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Where Z₁₁, Z₁₂, Z_{twenty one}, Z_{twenty two}, Z₃₁, Z
₄₁And Z₄₂Is a monocyclic or fused 5-membered or
Is the nonmetallic atom required to complete the 6-membered nitrogen-containing heterocycle
Represents a group, Q₃₁, Q₃₂And Q₄₁Are oxygen atom, sulfur
Represents a yellow atom, a selenium atom or -N (R)-
And R represents an alkyl group, an aryl group or a heterocyclic group.
You. R₁₁, R₁₂, R_{twenty one}, R_{twenty two}, R₃₁, R₄₁And R₄₃Is
Each represents an aliphatic group; ₃₂, R₃₃And R₄₂Are
Represents an alkyl group, an aryl group or a heterocyclic group. R₁₃,
R₁₄, R_Fifteen, R₁₆, R₁₇, R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, R
₂₇, R₂₈, R₂₉, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈,
R₃₉, R₄₄, R₄₅, R₄₆, R₄₇, R₄₈And R₄₉Is each
Hydrogen, alkyl, alkoxyl, aryl
An oxy group, an aryl group, -N (W₁, W_Two)-, -SR or
Or a heterocyclic group. Where R is an alkyl group, aryl
A group or a heterocyclic group;₁And W_TwoIs an alkyl group
Or an aryl group;₁And W_TwoIs connected to each other
It can also form a 5- or 6-membered nitrogen-containing heterocycle.
You. R₁₁And R₁₃, R₁₄And R₁₆, R₁₇And R₁₂, R_{twenty one}When
R_{twenty three}, R_{twenty four}And R₂₆, R_{twenty five}And R₂₇, R₂₆And R₂₈, R_{twenty two}And R
₂₉, R₃₁And R₃₄, R₃₅And R₃₇, R₄₁And R₄₄, R₄₅And R₄₇
And R₄₉And R₄₃Are connected to each other to form a 5- or 6-membered ring
Can be achieved. X₁₁, X_{twenty one}And X₄₁Are the molecules
Represents the ions necessary to neutralize the charge in
21 and m41 are each required to neutralize intramolecular charge.
Indicates the number of important ions. n11, n12, n21, n2
2, n31, n41 and n42 each represent 0 or 1.
And k31, k32, k33, k41, k42 and k4
3 represents 0 or 1, respectively.

The compound represented by the general formula (1-a) is preferably a compound represented by the following general formula (1-e) or (1-f).

[0082]

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Wherein Y ₅₁ , Y ₅₂ , Y ₆₁ and Y ₆₂ are each
Oxygen atom, sulfur atom, selenium atom or-(NR ₀ )-
Wherein R ₀ represents an aliphatic group. R ₅₁ and R ₅₂ each represent an aliphatic group, and R ₆₁ represents a non-metal atom group necessary for forming a 5- or 6-membered condensed ring by bonding to the aliphatic group or R ₆₅ . R ₅₃ and R ₅₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₅₅ and R ₆₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxyl group, Represents an aryloxy group, an alkylthio group, an arylthio group or an amino group, and R ₆₃ and R ₆₄ are each bonded to a hydrogen atom, an alkyl group or R ₆₃ and R ₆₄ to form a 5- or 6-membered ring; Represents a group of nonmetallic atoms necessary for R ₆₅ represents a hydrogen atom or a bond to R ₆₁ . A _{51 to} A ₅₈ and A _{61 to} A ₆₈
Each represents a hydrogen atom or a substituent (substitutable group), and A ₅₁ and A ₅₂ , A ₅₂ and A ₅₃ , A ₅₃ and A ₅₄ , A ₅₅ and A ₅₆ , A ₅₆ and A ₅₇ , A ₅₇ and _A58 and _A61 and _A62 , A
₆₂ and A ₆₃ , A ₆₃ and A ₆₄ , A ₆₅ and A ₆₆ , A ₆₆ and A ₆₇ , A ₆₇
And at least one pair of A ₆₈ can be linked to each other to form a fused naphthol ring. M ₅₁ and M ₆₁ each represent an ion required to neutralize the intramolecular charge, and m ₅₁ and m ₆₁ each represent the number of ions required to neutralize the intramolecular charge. p represents 2 or 3.

As the compound represented by the above general formula (1-b), the following general formula (1-g), (1-h) or (1-h)
It is preferably a compound represented by -i).

[0085]

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In the formula, Y ₇₁ , Y ₇₂ , Y ₈₁ , Y ₈₂ , Y ₉₁ and Y ₉₂ each represent an oxygen atom, a sulfur atom, a selenium atom or
(NR ₀ ) —, where R ₀ represents an aliphatic group.
R ₇₁ , R ₇₂ , R ₈₁ , R ₈₂ , R ₉₁ and R ₉₂ each represent an aliphatic group. R ₇₃ and R ₇₄ and R ₉₃ and R ₉₄ each represent a nonmetallic atom group necessary to form a 5- or 6-membered ring, and R ₇₅ and R ₉₅ each represent a hydrogen atom , An alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group or an amino group. A _{71 to} A ₇₈ , A _{81 to} A
₈₈ and A _{91 to} A ₉₈ each represent a hydrogen atom or a substitutable group, and A ₇₁ and A ₇₂ , A ₇₂ and A ₇₃ , A ₇₃ and A ₇₄ , A ₇₅ and A ₇₆ , A ₇₅ and A ₇₆ , A ₇₆ and A ₇₇ , A ₇₇ and A ₇₈ and A ₈₁ and A _82, A ₈₂ and A _83, A ₈₃ and A _84, A ₈₅ and A _86, A ₈₆ and A _87, A ₈₇ and A
₈₈ and A ₉₁ and A ₉₂ , A ₉₂ and A ₉₃ , A ₉₃ and A ₉₄ , A ₉₅ and A
_96, A ₉₆ and A _97, A ₉₇ and at least one pair of A ₉₈ may be linked to form a fused naphthol ring. M
₇₁ , M ₈₁ and M ₉₁ each represent an ion required to neutralize an intramolecular charge, and m ₇₁ , m ₈₁ and m ₉₁ each represent the number of ions required to neutralize an intramolecular charge. Represents

Hereinafter, the sensitizing dyes represented by formulas (1-a) to (1-d) and (1-e) or (1-i) will be described in detail.

In the above general formulas (1-a) to (1-d), a 5- or 6-membered group represented by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ , respectively. Examples of the nitrogen-containing heterocyclic ring include an oxazole nucleus (for example, an oxazolidine ring, an oxazoline ring, a benzoxazole ring, a tetrahydrobenzoxazole ring, a naphthoxazole ring, a benzonaphthoxazole ring, and the like), and an imidazole nucleus (for example, an imidazolidine ring, an imidazoline ring, An imidazole ring, a tetrahydrobenzimidazole ring, a naphthoimidazole ring, a benzonaphthoimidazole ring, etc.), a thiazole nucleus (for example, a thiazolidine ring, a thiazoline ring, a benzothiazole ring, a tetrahydrobenzothiazole ring, a naphthothiazole ring, a benzonaphthothiazole ring, etc.), Selenazole nucleus (for example, Renazorijin ring, selenazoline ring,
Benzoselenazole ring, tetrahydrobenzoselenazole ring, naphthoselenazole ring, benzonaphthoselenazole ring, etc., tellurazole nucleus (for example, tellurazolidine ring, tellurazoline ring, benzotellurazole ring, etc.), pyridine nucleus (for example, pyridine, quinoline) Etc.), pyrrole nucleus (for example, pyrrolidine ring, pyrroline ring, pyrrole ring,
3,3-dialkylindolenin ring), and on these rings, any group described as a substitutable group represented by A _{1 to} A ₉₈ described below can be substituted.

R ₀ , R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R
₄₁ , R ₄₃ , R ₅₁ , R ₅₂ , R ₆₁ , R ₇₁ , R ₇₂ , R ₈₁ ,
Examples of the aliphatic group represented by R ₈₂ , R ₉₁ and R ₉₂ include, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, Pentyl group, iso-pentyl group, 2-ethylhexyl group, octyl group, decyl group, etc., alkenyl group having 3 to 10 carbon atoms (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group) , A 3-pentenyl group, a 1-methyl-3-butenyl group, a 4-hexenyl group, etc.) and an aralkyl group having 7 to 10 carbon atoms (eg, a benzyl group, a phenethyl group, etc.).

The above-mentioned groups further include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Vinyl group, aryl group (eg, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoromethyl group, alkoxyl group (eg, methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group ( For example, phenoxy group, p-tolyloxy group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group) Etc.), an amino group (for example, an amino group, a biscarboxymethylamino group, etc.),
Aryl group (for example, phenyl group, carboxyphenyl group, etc.), heterocyclic group (for example, tetrahydrofurfuryl,
2-pyrrolidinone-1-yl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ureido group (eg, ureido group, 3-methylureido group, 3-phenylureido group, etc.), thioureido group (eg, Thioureido group, 3-methylthioureido group, etc., alkylthio group (eg, methylthio, ethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic thio group (eg, 2-thienylthio group, 3-thienylthio group) etc),
Carbonyloxy group (eg, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetylamino, benzoylamino group, etc.), thioamide group (eg, thioacetamido group, thiobenzoylamino group, etc.) Groups, or, for example,
Sulfo group, carboxy group, phosphono group, sulfate group, hydroxy group, mercapto group, sulfino group, carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (for example, , A sulfamoyl group,
N, N-3-oxpentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide, butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.) ), An acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), an acylamicarbonyl group (eg, acetamidocarbonyl, methoxyacetamidocarbonyl group, etc.), a sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl, ethanesulfinyl) And a hydrophilic group such as aminocarbonyl group). Specific examples of the aliphatic group substituted with these hydrophilic groups include carboxymethyl, carboxyethyl, carboxybutyl, carboxypentyl, 3-sulfatobutyl,
-Sulfopropyl, 2-hydroxy-3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3-sulfinobutyl, 3-phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, 2 -Carboxy-2-propenyl, o
-Sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like.

R, R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ ,
_{R 23, R 24, R 25} , R 26, R 27, R 28, R 29, R 32, R
₃₃ , _R34 , _R35 , _R36 , _R37 , _R38 , _R39 , _R42 ,
_R44 , _R45 , _R46 , _R47 , _R48 , _R49 , _R53 , _R54 , R
Examples of the alkyl group represented by ₅₅ , R ₆₂ , R ₆₃ , R ₆₄ , R ₇₅ and R ₉₅ include, for example, a methyl group, an ethyl group, a butyl group, an iso-butyl group, and the like. Including monocyclic and polycyclic groups, examples include groups such as phenyl group and naphthyl group, and examples of the heterocyclic group include groups such as thienyl, furyl, pyridyl, carbazolyl, pyrrolyl, and indolyl.

These groups can be substituted by the groups described in the description of the aliphatic groups represented by R ₀ , R _{11 and} R _92. Specific examples of the substituted alkyl group include 2-methoxyethyl , 2-hydroxyethyl, 3-ethoxycarbonylpropyl, 2-carbamoylethyl, 2-methanesulfonylethyl, 3-methanesulfonylaminopropyl, benzyl, phenethyl, carboxymethyl, carboxyethyl, allyl, 2-furylethyl, etc. And specific examples of the substituted aryl group include, for example,
p-carboxyphenyl, pN, N-dimethylaminophenyl, p-morpholinophenyl, p-methoxyphenyl, 3,4-dimethoxyphenyl, 3,4-methylenedioxyphenyl, 3-chlorophenyl, p-nitrophenyl And specific examples of the substituted heterocyclic group include, for example, 5-chloro-2-pyridyl, 5
-Ethoxycarbonyl-2-pyridyl, 5-carbamoyl-2-pyridyl and the like.

As the alkyl group and the aryl group represented by W ₁ and W ₂ , the groups described above for R and the like can be mentioned.

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₂₃ , R
_{24, R 25, R 26,} R 27, R 28, R 29, R 34, R 35,
_R36 , _R37 , _R38 , _R39 , _R44 , _R45 , _R46 , _R47 , R
Examples of the alkoxyl group represented by each of ₄₈ , R ₄₉ , R ₅₅ , R ₆₂ , R ₇₅ and R ₉₅ include, for example, a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-hydroxyethoxy group and the like, Examples of the aryloxy group include a phenoxy group, a 2-naphthoxy group, a 1-naphthoxy group, a p-tolyloxy group, a p-methoxyphenyl group and the like.

Examples of the halogen atom represented by R ₅₅ , R ₆₂ , R ₇₅ and R ₉₅ include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and examples of the alkylthio group include a methylthio group and an ethylthio group. And the like,
Examples of the arylthio group include a phenylthio group and m-
Examples of the amino group include substituted and unsubstituted groups, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a diphenylamino group, an N, N-tetramethyleneamino group, N,
And an N-pentamethyleneamino group.

R ₁₄ and R ₁₆ , R ₂₄ and R ₂₆ , R ₂₅ and R ₂₇ , R
₂₆ and R ₂₈ , R ₃₅ and R ₃₇ , R ₄₅ and R ₄₇ , R ₄₉ and R ₄₃ , R ₆₃
And R ₆₄ , R ₇₃ and R _74, and R ₉₃ and R ₉₄ may be each connected to each other to form a condensed ring, for example, 5
And 6-membered saturated or unsaturated fused carbocycles. Any of these condensed rings can be substituted at any position, and examples of these substituted groups include the groups described above as the groups that can be substituted with the aliphatic group.

R ₁₁ and R ₁₃ , R ₁₇ and R ₁₂ , R ₂₁ and R ₂₃ , R
Examples of the condensed ring which can be formed by connecting ₂₂ and R ₂₉ , R ₃₁ and R ₃₄ , and R ₄₁ and R ₄₄ to each other include, for example, 5
And 6-membered saturated or unsaturated nitrogen-containing condensed rings. Examples of the 5- or 6-membered nitrogen-containing heterocyclic ring formed by connecting W ₁ and W ₂ together with a nitrogen atom include a pyrrolidine ring, a morpholine ring, and a piperidine ring.

A _{51 to} A ₅₈ , A _{61 to} A ₆₈ , A _{71 to} A ₇₈ , A
Each Examples of the group can be substituted represented by ₈₁ to A ₈₈ and A ₉₁ to A _98, a lower alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), a halogen atom (e.g., fluorine atom, chlorine atom, bromine Atom), vinyl group, styryl group,
Aryl group (for example, phenyl group, p-tolyl group, p-
Bromophenyl group, etc.), trifluoromethyl group, alkoxyl group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), carbonyloxy group (eg, acetyloxy group, A propanoyloxy group, a benzoyloxy group, etc.), an amino group (eg, amino, dimethylamino, anilino, etc.), a heterocyclic group (eg, pyridyl group, pyrrolyl group, furyl group, thienyl group, imidazolyl group, thiazolyl) Group, pyrimidinyl group, etc.), acyl group (for example,
Acetyl group, benzoyl group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), carbamoyl group (eg, carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N-phenylsulfamoyl group, morpholinosulfonyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino, an ortho-hydroxybenzoylamino group, a sulfonylamino group (e.g., a methanesulfonylamino group, a benzenesulfonylamino group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a trifluoroethoxycarbonyl group, etc.), It is arbitrarily selected from a hydroxyl group, a carboxyl group and the like.

In the compounds represented by the above general formulas (1-a) to (1-i), when a group having a cationic or anionic charge is substituted, each of the compounds is designed to neutralize the intramolecular charge. A counter ion is formed with an equivalent amount of an anion or cation. For example, X ₁₁ , X ₂₁ , X ₄₁ , M ₅₁ ,
Specific examples of the cation required for neutralizing the intramolecular charge represented by M ₆₁ , M ₇₁ , M ₈₁ and M ₉₁ include a proton and an organic ammonium ion (for example, triethylammonium, triethylammonium). Specific examples of the acid anion include halogen ions (eg, chloride ion, bromide ion, iodine ion, etc.), and inorganic cations (eg, cations such as lithium, sodium, and potassium). ,
Examples include p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion and the like.

In the sensitizing dyes represented by formulas (1-a) to (1-d), the sensitizing dyes represented by formulas (1-e) and (1-d)
The sensitizing dye represented by f) is preferably used, and the sensitizing dyes represented by the general formulas (1-g) to (1-i) are more preferably used.

The following formulas (1-a) to (1-a)
Representative sensitizing dyes (compounds) shown in i) are shown below, but the present invention is not limited to these compounds.

[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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The above-mentioned infrared-sensitive sensitizing dye is described, for example, in FM Chemer's The Chemistry.
of Heterocyclic Compounds, Vol. 18, The Cyanine Dyes and
Related Compounds (A. Weiss
Herger ed. Published by Interscience,
New York 1964).

The sensitizing dyes used in the present invention may be used alone or in combination of two or more. When two or more sensitizing dyes (photosensitive dyes) of the present invention are used in combination, the photosensitive dyes can be dispersed in a silver halide emulsion independently or in a premixed manner by the method described above. A dye having absorption in the visible region for the purpose of supersensitization, a dye having no spectral sensitization itself, or a substance which does not substantially absorb visible light together with the photosensitive dye of the present invention, A substance exhibiting a feeling may be contained in the emulsion.

Useful photosensitive dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure.
176, 17643 (published December 1978), page 23
Section J of IV or JP-B-49-25500, 43-
No. 4933, JP-A-59-19032 and JP-A-59-19.
Nos. 2242 and 62-123454, JP-A-3-15
Nos. 049 and 7-146527.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to. When a mercapto compound is used in the present invention, it may be of any structure, but may be ArSM, Ar-
Those represented by SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzoterzole, imidazole, oxazole,
Pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is, for example, a halogen (for example,
Br and Cl), hydroxy, amino, carboxy,
Alkyl (eg one or more carbon atoms, preferably 1
May have a substituent selected from the group consisting of those having from 1 to 4 carbon atoms) and alkoxyl (for example, having 1 or more carbon atoms, preferably having from 1 to 4 carbon atoms). Good mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobisbenzothiazole, 3-mercapto-1,2,4 -Triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine,
2-mercapto-4- (3H) quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5
6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto- 1,2,
4-triazole, 4-hydroxy-2-mercaptopyrimidine, 21-mercaptopyrimidine, 4,6-diamino-2mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5
Examples thereof include phenyl-1,2,4-triazole and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto. The addition amount of these mercapto compounds is 0.001 per mole of silver in the emulsion layer.
The range is preferably from 1.0 to 1.0 mol, more preferably from 0.01 to 0.3 mol per mol of silver.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of the reducing agent suitable for the photothermographic material of the present invention are described in US Pat. No. 3,770,44.
No. 8, 3,773, 512, 3,593, 8
No. 63 and Research Disclosure
Nos. 17029 and 29996, and include the following.

Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (for example, benzenesulfhydroxamic acid); sulfonamidoanilines (for example, 4- (N-methanesulfonamido) aniline); 2-tetrazoli Ruthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydroquinoxaline); Synths; Azines (for example, a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid); Polyhydroxybenzene and hydroxylamine; reductone and / or hydrazine; Hydroxanoic acids; Azines and sulfonamidophenols Α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0118]

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In the formula, R is a hydrogen atom or a group having 1 carbon atom.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, t-
Butyl).

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

[0121]

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[0122]

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The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mole of silver.
10 ^-2 to 10 mol, particularly preferably 1 × 10 ^{-2 to} 1.5
Is a mole.

It is preferable to add a color tone agent to the photothermographic material of the present invention. Examples of suitable toning agents are Res
No. 17029, and includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2 , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Combinations of acids; phthalazine (including adducts of phthalazine) and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example,
A combination with at least one compound selected from phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine, naphthoxazine derivatives; benzoxazine-2,4-dione (Eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg,
3,6-dimercapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The photothermographic material of the present invention is particularly preferably 600
When applied to a photothermographic material for output of a printing image setter having an oscillation wavelength of up to 800 nm, a hydrazine compound is preferably contained in the photosensitive material. Preferred hydrazine compounds used in the present invention include R
search Disclosure Item23
516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4,269,929 and 4,276,36
No. 4, No. 4,278,748, No. 4,385,1
No. 08, No. 4,459, 347, No. 4,478,
No. 928, No. 4,560,638, No. 4,68
Nos. 6,167, 4,912,016 and 4,9
Nos. 88,604, 4,994,365 and 5,
041,355, 5,104,769, British Patent 2,011,391B, European Patent 217,31
No. 0, No. 301,799, No. 356,898,
JP-A-60-179733 and JP-A-61-170733.
Nos. 61-270744 and 62-178246
No. 62-270948, No. 63-29751,
No. 63-32538, No. 63-104047, No. 6
Nos. 3-121838, 63-129337, 63
-223744, 63-234244, 63-
No. 234245, No. 63-234246, No. 63-2
No. 94552, No. 63-306438, No. 64-10
No. 233, JP-A-1-90439 and 1-10053
No. 0, No. 1-1055941, No. 1-105943,
No. 1-276128, No. 1-280747, No. 1-
Nos. 283548, 1-283549, 1-285
No. 940, No. 2-2541, No. 2-77057, No. 2-139538, No. 2-196234, and No. 2-1
No. 96235, No. 2-198440, No. 2-1984
No. 41, 2-198442, 2-2-20042
Nos. 2-221953, 2-221954, 2-285342, 2-285343, and 2-2
No. 89843, No. 2-302750, No. 2-30445
Nos. 50, 3-37642, 3-54549, 3-125134, 3-184039, 3-2
No. 40036, No. 3-240037, No. 3-2592
No. 40, No. 3-2820038, No. 3-282536
Nos. 4-51143, 4-56842, 4-
Nos. 84134, 2-230233, 4-9605
No. 3, 4-216544, 5-45761, 5-45762, 5-45763, 5-457
No. 64, No. 5-45765, No. 6-289524,
No. 9-160164 and the like.

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

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature after exposure. The heating temperature is preferably from 80 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C.

By heating, silver is produced through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. At least one non-photosensitive layer is formed on the photosensitive layer. A filter layer may be formed on the same side as the photosensitive layer or on the opposite side to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. . As the dye, compounds described in JP-A-8-201959 are preferred. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

[0131]

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

Example 1 (Preparation of support) 0.175 (densitometer PDA-65 manufactured by Konica Corp.) was colored blue and had a thickness of 175.
A corona discharge treatment of 8 W / m ² · min was applied to both sides of a μm PET film.

(Preparation of Photosensitive Silver Halide Emulsion A) Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, an aqueous solution containing 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide (equimolar to the above-mentioned silver nitrate) in a molar ratio of (98/2) was used.
0 ml and iridium chloride at 1 × 10 ^-4 per mole of silver.
Mole was added over 10 minutes by a controlled double jet method, keeping the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the particle size was 1
Cubic silver iodobromide grains of 2% and [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
5.9 and a pAg of 7.5 to obtain a photosensitive silver halide emulsion A.

(Preparation of Powdered Organic Silver Salt) In 9450 ml of pure water, 324 g of behenic acid, 99 g of arachidic acid and 56 g of stearic acid were dissolved at 80 ° C. Next, 980 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at a high speed. Next, 9.3 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. and stirred for 30 minutes.
(Containing 0.9 mole of silver and 1400 g of water) for 5 seconds and stirred for 5 minutes, and then 1M silver nitrate solution 1
Add 470 ml over 2 minutes and stir for another 20 minutes
Water-soluble salts were removed by filtration. After that, washing with deionized water and filtration are repeated until the conductivity of the filtrate becomes 2 μS / cm, centrifugal dehydration is performed, and then hot air drying is performed at 37 ° C. until the weight is reduced, and the powdered organic silver salt is removed. Obtained.

(Preparation of Photosensitive Emulsion Dispersion) Polyvinyl butyral powder (Butvar B manufactured by Monsanto)
-79) 14.57 g of methyl ethyl ketone 1457 g
And, while stirring with a dissolver-type homogenizer, 500 g of powdered organic silver salt was gradually added and mixed well. After that, 1mm diameter Zr beads (manufactured by Toray) are
The dispersion was carried out at a peripheral speed of 13 m and a residence time in the mill of 0.5 minute with a media-type disperser (manufactured by gettzmann) filled with% to prepare a photosensitive emulsion dispersion.

<< Preparation of Infrared Sensitizing Dye Liquid >> 350 mg of infrared sensitizing dye 1, 13.96 g of 2-chloro-benzoic acid,
And 2.14 g of 5-methyl-2-mercaptobenzimidazole were dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

<< Preparation of Stabilizer Liquid >> 1.0 g of stabilizer 1,
0.5 g of potassium acetate was dissolved in 8.5 g of methanol to prepare a stabilizer solution.

<< Preparation of Developer Solution >> 17.74 g of reducing agent A-3 was dissolved in methyl ethyl ketone (MEK),
Finished to 0 ml and used as developer solution.

<< Preparation of Antifoggant Solution >> 5.81 g of the antifoggant 2 was dissolved in MEK and finished to 100 ml.
An antifoggant solution was used.

<< Preparation of Coating Solution for Photosensitive Layer >> The above-mentioned photosensitive emulsion dispersion (50 g) and 15.11 g of MEK were kept at 21 ° C. while stirring, and 390 μl of antifoggant 1 (10% methanol solution) was added thereto for 1 hour. Stirred. Further, 889 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes. Next, infrared sensitizing dye solution 1.416
After stirring for 1 hour, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C, polyvinyl butyral (M
onsanto Butvar B-79) 13.31
g was added and stirred for 30 minutes, and then the following additives were added at 15-minute intervals while stirring was continued.

Phthalazine 305 mg Tetrachlorophthalic acid 102 mg 4-Methylphthalic acid 137 mg Infrared dye 1 37 mg After adding the above and stirring for 15 minutes, antifoggant solution 5.47 ml Developer solution 14.06 ml Desmodur N3300 (Mobay, Inc. Isocyanate) 10% MEK solution 1.60 ml The above-mentioned additives were sequentially added and stirred to obtain a photosensitive layer coating solution.

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[0143]

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<< Preparation of Protective Layer Coating Solution >> As shown below, a cellulose acetate butyrate premix solution and a calcium carbonate premix solution were prepared.

(1) Preparation of Cellulose Acetate Butyrate Premix Solution Cellulose Acetate Butyrate Premix Solution 10
A 00g batch was prepared as follows. 2-butanone 86
7.2 g of cellulose acetate butyrate (CAB)
171-15S Eastman Kodak Co., Ltd.) 9
5.67 g was added and stirred for 2 hours to completely dissolve.

(2) Preparation of Calcium Carbonate Premix Solution A 100 g batch of calcium carbonate premix solution was prepared as follows. 15.0 g of cellulose acetate butyrate (CAB 171-15S manufactured by Eastman Kodak Co., Ltd.) was added to 85.0 g of 2-butanone, and the mixture was stirred. The solution was further stirred for 2 hours to completely dissolve. This solution is added to Pitzer Superflex SF200CaC
O.Og was added, and the mixture was dispersed for 45 minutes while stirring at 8000 rpm using a dissolver-type homogenizer.

970.5 g of the cellulose acetate butyrate premix solution obtained above and 29.5 g of the calcium carbonate premix solution were stirred at 600 rpm. Further, 4.29 g of acryloid A-21 (manufactured by Rohm and Haas), 1.43 g of a non-uniformity inhibitor (KH40: nonionic type, a perfluoroalkylethylene oxide adduct manufactured by Asahi Glass Co., Ltd.), and 0.4% of compound (A). 8
94 g and 1.43 g of the compound (B) were added in this order, and the mixture was stirred for 2 hours to prepare a 1,000 g batch of the coating solution for the protective layer.

(Note: Compound (A) is a benzotriazole, compound (B) is a vinyl sulfone compound (HD-
1)) << Preparation of Coating Solution for Backcoat Layer >> A premix solution having the following composition was prepared.

(1) Preparation of Cellulose Acetate Butyrate Premix Solution A 1,000 g batch of the coating solution material was prepared as follows.
To 704.8 g of 2-butanone, 84.18 g of cellulose acetate butyrate (CAB 381-20 manufactured by Eastman Kodak Co., Ltd.) and 4.29 g of Vittel 2200B manufactured by Goodyear were added and stirred for 2 hours to completely dissolve.

(2) Preparation of Syloid X6000 Premix Solution A 200 g batch of the Syloid X6000 premix solution was prepared as follows. To 199.2 g of 2-butanone, 0.76 g of silica (Syloid 74-X6000 WR Grace) was added to form a slurry. The slurry was placed in a homogenizer at 280 kgf / cm ² (40
(00 psi) for one pass to homogenize.

To 789.0 g of the cellulose acetate butyrate premix solution described above, 0.314 g of infrared dye 1 and 197.0 g of a syloid X6000 / butanone premix solution were added and stirred well. Finally, an unevenness inhibitor (KH40: nonionic type perfluoroalkyl ethylene oxide adduct, manufactured by Asahi Glass Co., Ltd.) 9.3
7 g was added and stirred to completely dissolve the solution, thereby preparing a 1000 g batch of the back coat layer coating solution.

<< Coating Step and Preparation of Photothermographic Photosensitive Material >> The coating solution for the back coat layer described above was placed on an extrusion coater, and applied to the side of the support opposite to the side having the photosensitive layer. Coating was performed uniformly so that cellulose acetate butyrate as a binder was 3.71 g / m ² . The coating was performed using an extrusion coater. Thereafter, heating and drying were performed at 100 ° C. for 1 minute.

Subsequently, using an extrusion coater, a protective layer coating solution and a photosensitive layer coating solution were simultaneously coated on the support coated with the back coat layer under infrared safe light conditions. The photosensitive layer was coated with the liquid having the above composition so that the coating silver amount was 2.0 g / m ² and polyvinyl butyral as a binder was 8.5 g / m ² . Further, the protective layer was uniformly applied so that the cellulose acetate butyrate as a binder was 2.34 g / m ² . After the application, heating and drying were performed at 75 ° C. for 4 minutes. Thus, a photothermographic material was prepared.

As an inorganic layered compound, as synthetic mica, Na tetrathick mica (NaMg _2.5 (Si
₄ O ₁₀ ) F ₂ ) was added to the protective layer and the back coat layer as shown in Table 1. In addition, the addition of the inorganic layered compound is described in “Preparation of calcium carbonate premix solution” for the protective layer.
At this time, regarding the back coat layer, "Syloid X600
0 premix solution ". Thus, Sample 1 of the present invention was obtained.

Next, Samples 2 to 9 were prepared in the same manner as in Sample 1, except that the kind of the inorganic layered compound of the protective layer or the back coat layer was as shown in Table 1.

The smoother value of the protective layer was adjusted by increasing or decreasing the amount of calcium carbonate during the preparation of the calcium carbonate premix solution, and the smoother value of the back coat surface was adjusted by increasing or decreasing the amount of silica during the preparation of the Syloid X6000 premix solution.

<< Evaluation >><< Smoother smoothness >> JAPAN TAPPI N
o. The measurement was performed according to 5A. The smaller this value is, the higher the smoothness is.

<< Exposure and development treatment >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam. (Note that an image with less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.) Thereafter, protection of the photosensitive material was performed using an automatic developing machine having a heat drum. The film was thermally developed at 110 ° C. for 15 seconds so that the layer and the drum surface were in contact with each other. At that time, exposure and development were performed at 23 ° C and 50% R.
We went in a room conditioned to H. The obtained image was evaluated by a digital densitometer PDA-65 (manufactured by Konica Corporation). The above exposure and development are continuously performed on 2500 sheets, and the sensitivity of the 0th sheet and the 2500th sheet (1.0 times higher than the unexposed part)
The fluctuation (reciprocal of the ratio of the exposure amount giving a high density), the fog fluctuation and the development unevenness were evaluated. The sensitivity is 0 for photosensitive material 1.
The relative values are shown with the sensitivity at the time of processing the first sheet as 100. The practically acceptable levels of development unevenness are A and B.

<< Evaluation of Development Unevenness >> A: No development unevenness is observed. B: Development unevenness can be confirmed with a magnifying glass. C: Development unevenness can be visually confirmed. D: Development unevenness can be clearly confirmed.

<< Precipitation in Image Forming Apparatus >> The state of generation of precipitates in the image forming apparatus was visually evaluated. Acceptable levels are A and B.

A: Almost no occurrence B: Slight occurrence on a wall or the like but no problem C: Precipitation on roller portion and wall in image forming apparatus D: Driving in image forming apparatus Deposits on the part and causes problems.

[0163]

[Table 1]

[0164]

[Table 2]

From Table 2, it is clear that the sample of the present invention has little variation in photographic performance such as sensitivity and fog, and has little development unevenness.

[0166]

According to the present invention, a high-quality heat-developable photographic light-sensitive material which has little fluctuation in photographic performance such as sensitivity and fog and hardly shows development unevenness even after processing a large amount of photographic material. An image recording method and an image forming method to be used can be provided.

Claims (11)

[Claims] 1. A heat-developable photographic material having a photosensitive layer containing a photosensitive silver halide on at least one surface of a support, and containing a non-photosensitive silver salt and a reducing agent for the non-photosensitive silver salt. A heat-developable photographic material, wherein the protective layer, the intermediate layer or the back coat layer contains an inorganic layer compound. 2. The photothermographic material according to claim 1, wherein the protective layer or the backcoat layer contains an inorganic layered compound. 3. The protective layer surface has a smoother value of 0 to 25.
mmHg, smoother value of the surface of the back coat layer is 5
3. The photothermographic material according to claim 1, wherein the pressure is from 0 to 300 mmHg. 4. The heat according to claim 1, wherein the weight ratio of the inorganic layered compound to the binder in the layer containing the inorganic layered compound is 1/10 to 10/1. Developed photographic photosensitive material. 5. An inorganic layered compound having an aspect ratio of 100.
The method according to any one of claims 1 to 4, wherein
4. The photothermographic material according to item 1. 6. The photothermographic material according to claim 1, wherein the inorganic layered compound is synthetic mica. 7. The photothermographic material according to claim 1, wherein the inorganic layered compound is bentonite. 8. An image recording method comprising exposing the photothermographic material according to claim 1 using a laser. 9. An exposure apparatus using an exposure apparatus in which an angle between an exposure surface and a scanning laser beam does not become substantially vertical.
8. An image recording method, comprising exposing the photothermographic material according to any one of items 7 to 7. 10. An image recording method comprising exposing the photothermographic material according to claim 1 using a laser scanning exposure device that emits a scanning laser beam that is a vertical multi. 11. An image forming method, wherein the photothermographic material according to claim 1 is heat-developed in a state where the photothermographic material contains a solvent of 500 mg / m ² or less.