JP2000171937A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material which does not cause the problem of tendency to curl even when rolled and is excellent in development stability even in the case of a large development area. SOLUTION: The heat developable photosensitive material has a photosensitive layer containing a photosensitive silver halide, an organic silver salt, a reducing agent and a binder on the substrate and contains a matting agent having larger than 10 μm average particle diameter in a layer on the substrate opposite to the photosensitive layer. Preferably the photosensitive material has a matting agent even on the photosensitive layer side, has the relation of 0<(the average particle diameter of the matting agent on the photosensitive layer side)/(the average particle diameter of the matting agent in the layer opposite to the photosensitive layer)<2/3, satisfies the relation of 0<(the matting degree of the surface on the photosensitive layer side)/(the matting degree of the surface opposite to the photosensitive layer)<1/5 and contains a hydrazine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material suitable for use in printing and plate making as a roll.

[0002]

2. Description of the Related Art Conventionally, in the process of printing plate making and plate making or X-ray photosensitive material at a medical site, after exposure, using an automatic developing machine, immersing in order of developing solution → fixing solution → water or stabilizing solution, Further, what is called a wet process for further drying has been generally performed. However, since this method uses liquid, workability (heavy, dirty, requires inventory control, etc.),
Improvements have been desired from the viewpoint of environment (generation of waste liquid).

[0003] In order to improve these, studies have been made on dry silver halide photographic materials. A typical example is a heat-developable silver salt type described in U.S. Pat. No. 3,457,075 which uses an organic silver salt and forms an image by a reaction by heat. There are known those which form an image by transfer and those which form an image by melting, sublimation, ablation or the like by converting laser light into light and heat. Each of these technologies has not yet achieved the same performance and handleability as the current silver halide photographic materials, but some systems have achieved levels near practical use, and some There is also a system that has been put to practical use while leaving the technical problems described above. In particular, the development of photothermographic materials using organic silver salts has been actively developed, and many research results have been reported.

[0004]

When a photothermographic material using an organic silver salt is used for printing plate making, the screen size is large and a large number of sheets are required. Although practical, a roll shape has a problem that the film tends to be curled because the film thickness on the photosensitive layer side is large. Further, since a large developing size is developed by the zone heating method, heat transfer efficiency is deteriorated and development stability is deteriorated.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photothermographic material which is free from the problem of curling even in a roll shape and has excellent development stability even when the development area is large. Is to provide.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a photosensitive layer containing a photosensitive silver halide, an organic silver salt, a reducing agent and a binder on a support. A photothermographic material containing a matting agent having an average particle size of greater than 10 μm in the opposite layer, a matting agent also in the photosensitive layer side, and having the relationship of the following formula (1): (1) 0 <photosensitive (Average particle size of layer-side matting agent / Average particle size of matting agent in layer opposite to photosensitive layer <2/3) Further satisfying the following formula (2), and (2) 0 <the surface of photosensitive layer side Matting degree / matting degree on the surface on the side opposite to the photosensitive layer <1/5 It is achieved by containing a hydrazine compound.

Hereinafter, the present invention will be described in detail.

In the present invention, the layer on the side opposite to the photosensitive layer of the support of the photothermographic material (hereinafter also referred to as the back surface side) has an average particle size of more than 10 μm (preferably 10 to 30 μm).
Contains a matting agent, has a matting agent also on the photosensitive layer side, and the relationship of 0 <average particle size of the matting agent on the photosensitive layer side / average particle size of the matting agent on the layer opposite to the photosensitive layer <2/3. And the relationship 0 <mat degree on the photosensitive layer side surface / matte degree on the surface opposite to the photosensitive layer <1/5 is satisfied.

The matting agent may be either an organic substance or an inorganic substance. For example, as inorganic substances, Swiss Patent No. 330,1
No. 58, etc., French Patent No. 1,296,99
Glass powder described in No. 5, etc., British Patent No. 1,173,18
Alkaline earth metals or carbonates such as cadmium and zinc described in No. 1 and the like can be used as a matting agent.
Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol as described,
Polystyrene or polymethacrylate described in Swiss Patent No. 330,158 and the like, US Pat. No. 3,079,
Organic matting agents such as polyacrylonitrile described in US Pat. No. 257 and the like and polycarbonate described in US Pat. No. 3,022,169 and the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical.

The matting agent contained in the photosensitive layer preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. Here, the particle size of the matting agent indicates a diameter when its volume is converted into a spherical shape. The polymer having a variation coefficient of the particle size distribution of 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 degree of matte in the present invention indicates the roughness of the surface. The measuring method is as follows. After the sample is conditioned at 23 ° C. and 50% RH for 2 hours, a metal cylinder capable of decompressing is placed on the measuring surface and the pump The pressure was forcibly reduced by using a pressure sensor, and the degree of vacuum at which the state of equilibrium was reached at that time was measured.
0 to 200 mmHg, preferably 30 to 100 mmHg
100-700 mmHg on the back side, preferably 40
0 to 700 mHg.

The matting agent on the photosensitive layer side can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer, and more preferably the outermost layer as viewed from the support.

The addition of the matting agent may be carried out by dispersing it in the coating solution in advance, or by spraying the matting agent after the coating solution is applied and before the drying is completed. When a plurality of types of matting agents are added, both methods may be used in combination.

For details of the photothermographic material, see, for example, US Pat. Nos. 3,152,904 and 3,457,075 and D.C. "Dry Silver Photograph" by Morgan
phy Materials) "(Handbook
of Imaging Materials, Mar
cel Dekker, Inc. 48, 1991)
And D. Morgan and B. "Silver System Treated by Heat (Thermall) by Shelly
y Proceded Silver System
s) "(Imaging Processes and
Materials, Neblette Eighth Edition, St
urge, V.E. Waleorth, A .; Shepp, 2nd page, 1969).

The photothermographic material is used to form a photographic image by a heat development process. The photothermographic material is capable of reducing a silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, a color tone of silver. It is preferable that the toning agent to be suppressed is usually contained in a dispersed state in an (organic) binder matrix. The photothermographic material is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. That is, heating produces silver 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. Silver produced by the reaction of the organic silver salt in the exposed area forms a black image,
This is in contrast to the unexposed areas, where the image is formed. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The silver halide grains function as an optical sensor. In order to suppress cloudiness after image formation and obtain good image quality, it is preferable that the average particle size is small.
Hereinafter, more preferably 0.01 to 0.1 μm, and particularly preferably 0.1 to 0.1 μm.
02 to 0.08 μm is preferred. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere having the same volume as the silver halide grains. Further, the silver halide grains are preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. The particle size is more preferably 30 or less, and particularly preferably 0.1 to 20.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is not particularly limited.
The ratio occupied by the Miller index (100) plane is preferably high, and this ratio is preferably at least 50%, more preferably at least 70%, particularly preferably at least 80%. Miller index (10
The ratio of the (0) plane is determined by the T.I. Tani,
J. Imaging Sci. , 29, 165 (198
5 years).

[0020] Tabular grains are also preferred. When tabular silver halide grains are used, the average aspect ratio is preferably from 2 to 100, more preferably from 3 to 50, and the grain size is from 0. 1 to 3.
1 μm or less, more preferably 0.01 to 0.08 μm
It is. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958, and can easily obtain target tabular grains.

The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide.

The photographic emulsion used in the present invention is described in P.I. Gl
Chimie et Physique by Afkids
e Photographique (Paul Mon
tel, 1967); F. By Duffin
Photographic Emulsion Chem
istry (published by The Focal Press, 19
66); L. M by Zelikman et al
aking andCoating Photogra
phi Emulsion (The Focal P
Ress, published in 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. May be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, 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 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 the transition metal complex ion are shown below, but the present invention is not limited to these.

[0029] 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) ClCN _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: [R (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 may be a metal complex or metal complex ions one type, the metal of the same kind of metal or different may be used alone or in combination. 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 before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably. It is added 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 to 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 are preferably chemically sensitized. Examples of the sensitization method include known sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization, and reduction sensitization. Can be used. In addition, these sensitization methods are 2
A combination of two or more species may be used. For sulfur sensitization, thiosulfates, thiourea compounds, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization include the compounds described in JP-A-9-230527. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate,
Gold sulfide, gold selenide, or US Patent 2,448,0
No. 60 and British Patent No. 618,061. As the shell-like compound in the reduction sensitization method, ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. Also,
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. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

Organic silver salts are reducible silver sources, silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10-30, preferably 15-25 carbon atoms). Aliphatic carboxylic acids and silver salts of nitrogen-containing heterocycles are preferred.

Organic or inorganic silver salt complexes whose ligands have a complex stability constant for silver ions of 4.0 to 10.0 are also useful. For example, silver salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, oleic acid, caproic acid, myristic acid, palmitic acid, maleic acid, linoleic acid, etc.), carboxyalkylthio Urea (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl)-
Silver salts of 3,3-dimethylthiourea, etc., polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (eg, silver complexes of aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, Silver salts or silver complexes of salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, etc., thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-) Silver salts or silver complexes of thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene, etc., imidazole, pyrazole, urazole, 1,2,4-thiazole or 1H-tetrazole, 3-amino- Selected from 5-benzylthio-1,2,4-triazole or benzotriazole Complexes or salts of periodate and silver;. Saccharin, a silver salt such as 5-chloro salicylaldoxime, or mercaptides silver examples of suitable silver salts, RD # 170
29 and 29996, and particularly preferred silver salts are silver behenate, silver arachidate and silver stearate.

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, an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate) is prepared by adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide) to an organic acid, and then controlled by a double jet method. The above-mentioned 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 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 having the same volume as the organic silver salt particles when the particles are spherical, rod-shaped, or flat. The average particle size is preferably 0.01
To 0.8 μm, particularly preferably 0.05 to 0.5 μm. The monodispersity is the same as described above, and is preferably 1 to 30. Further, tabular grains having an aspect ratio of 3 or more preferably account for 60% or more of the total organic silver salt. In order to adjust the shape of the organic silver salt, the organic silver salt crystal may be dispersed and pulverized with a binder, a surfactant or the like by a ball mill or the like.

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 to 2.2 g per m ² in terms of silver. With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total silver is 50% or less by weight, preferably 25% or less, and more preferably 0.1 to 15%.

As the reducing agent, US Pat. No. 3,770,
No. 448, No. 3,773, 512, No. 3,59
No. 3,863, and RD17029 and 29963, and include the following. Aminohydroxycycloalkenones (e.g., 2-hydroxypiperidino-2-cyclohexenone); Amino reductone esters (e.g., piperidinohexose reductone monoacetate) as precursors of reducing agents; N-hydroxyurea derivatives (E.g., Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (e.g., anthracenaldehyde phenylhydrazone);
Phosphoramidophenols; Phosphoramidoanilines; Polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., Sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, benzenesulfhydroxamic acid);
2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydroquinoxaline);
Amides (eg, combinations of aliphatic carboxylic acid arylhydrazides and ascorbic acid); polyhydroxybenzenes and hydroxylamines; reductones and / or hydrazines; hydroxanoic acids; azines and sulfonamide phenols Combination; α-cyanophenylacetic acid derivative; bis-β
A combination of -naphthol and a 1,3-dihydroxybenzene derivative; 5-pyrazolone; a sulfonamide phenol reducing agent; 2-phenylindane-1,3-dione and the like; chroman; 1,4-dihydropyridines (for example,
2,6-dimethoxy-3,5-dicarbethoxy-1,
4-dihydropyridine); bisphenols (for example,
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).

[0042]

Embedded image

In the formula, R represents a hydrogen atom or a group having 1 to 1 carbon atoms.
0 alkyl group (propyl group, butyl group, 2,4,4-
R ′ and R ″ each represent an alkyl group having 1 to 5 carbon atoms (a methyl group, an ethyl group,
Propyl, butyl, pentyl, etc.).

Specific examples of the compound represented by formula (A) are shown below.

[0045]

Embedded image

[0046]

Embedded image

The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mole of silver.
It is 10 ^-3 to 10 mol, especially 1 × 10 ^{-2 to} 1.5 mol.

The binder preferably used for the photothermographic material is transparent or translucent, generally colorless, and is a natural polymer synthetic resin, polymer or copolymer, or other film-forming medium, for example, gelatin, gum arabic, polyvinyl alcohol , Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer Coal, styrene-butadiene copolymer, polyvinyl acetal (eg, polyvinyl formal and polyvinyl butyral), polyester, polyurethane, phenoxy resin, polyvinyl chloride Den, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides. It may be hydrophilic or non-hydrophilic.

The amount of the binder in the photosensitive layer is preferably from 1.5 to 10 g / m ² from the viewpoint of the heat development rate. More preferably, it is 1.7 to 8 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In order to control the amount or wavelength distribution of light passing through the photosensitive layer of the photothermographic material, a dye or pigment is added to the protective layer, a filter layer is formed on the side opposite to the photosensitive layer, or the photosensitive layer May contain a dye or a pigment. Dyes or pigments used are described in JP-A-59-6481, 5
No. 9-182436, U.S. Pat. No. 4,271,263
No. 4,594,321, European Patent Publication No. 53
No. 3,008, No. 652,473, JP-A-2-21
No. 6140, No. 4-348339, No. 7-19143
Compounds described in Nos. 2, 7-301890 and 8-201959 are preferred. The photosensitive layer may have a plurality of layers, and the sensitivity may be a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

It is preferable to add a toning agent to the photothermographic material for the purpose of improving the silver tone after development. Examples of suitable toning agents are disclosed in RD 17029 and include:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 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 photobleaching combinations (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 Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The photothermographic material may be a mercapto compound, a disulfide compound, a thione compound or the like for controlling development such as suppressing or accelerating development, improving spectral sensitization efficiency or improving storage stability before and after development. Can be contained. When a mercapto compound is used, it may have any structure, but it may be Ar-SM, Ar-S-
Those represented by S-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is a heteroaromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms.

Preferred heteroaromatic rings are benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine. , Pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy,
Amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms)
And alkoxy (for example, those having one or more carbon atoms, preferably 1 to 4 carbon atoms).

The mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole,
-Mercapto-1,2,4-triazole, 2-mercaptoquinoline, 8-mercaptopurine, 2,3,5,6
-Tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine, 2-mercapto-4-
Phenyloxazole and the like.

The photothermographic material can contain an antifoggant. What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Non-mercury antifoggants include, for example, US Pat.
No. 075 and 4,452,885 and JP-A-59
Preferred are antifoggants such as those disclosed in US Pat.

Particularly preferred non-mercury antifoggants are US Pat. Nos. 3,874,946 and 4,756,993.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036], and compounds described in paragraphs [0062] to [0063] of JP-A-9-90550. Still other suitable antifoggants include U.S. Pat. No. 5,028,523 and British Patent No. 92221.
No. 383.4, No. 9300147.7, No. 931
1790.1 and the like.

The photothermographic materials include, for example, those described in
No. 159841, No. 60-140335, No. 63-2
No. 31437, No. 63-259651, No. 63-30
Nos. 4242 and 63-15245, U.S. Pat.
Nos. 39,414, 4,740,455, 4,
Nos. 741,966, 4,751,175, 4,835,096 and RD17643 IV-A (19)
December 1978 p. 23), and sensitizing dyes described in the literature described or cited in section 1831X (p. 437, August 1978) can be used. In particular, spectral sensitizing dyes having spectral sensitivity suitable for the spectral characteristics of the light source of various scanners can be advantageously selected. For example, JP-A-9-340
Compounds described in Nos. 78, 9-54409 and 9-80679 are preferably used.

Examples of the photothermographic material include a surfactant,
Antioxidants, stabilizers, plasticizers, ultraviolet absorbers, coating aids and the like may be used.

The support used for the photothermographic material is preferably a plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate) in order to prevent deformation of the image after the development processing. .

Among them, preferred supports include a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene-based polymer having a syndiotactic structure. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

It is also possible to use a heat-treated plastic support. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is applied, at a temperature 30 ° C. or more higher than the glass transition point of the support,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
Heating at a temperature higher than ℃.

For the photothermographic material, a conductive compound described in, for example, US Pat. No. 5,244,773 can be used to adjust the chargeability.

In the case of printing plate making, it is preferable to contain a hydrazine compound in order to obtain a high contrast image. Preferred hydrazine compounds include the following general formula (1):
The compound represented by (2) or (3) is used.

[0065]

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[Wherein, R ₁ represents a hydrogen atom or a block group, R ₂ represents an aliphatic group or a heterocyclic group, and G ₁ represents CO
Group, COCO group, CS group, SO ₂ group, SO group, PO
It represents an (R ₃ ) group (R ₃ has the same meaning as R ₁ and may be the same or different) or an iminomethylene group. A ₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an alkylsulfonyl group, an arylsulfonyl group, or a substituted or unsubstituted acyl group. m ₁ is 0 or 1, and m ₁ is 0
In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group. ]

[0067]

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[Wherein, R ₂₃ is a substituted or unsubstituted hydrazino group, alkylamino group, sulfonylamino group,
Represents a ureido group, an oxycarbonylamino group, an alkynyl group or an unsubstituted amino group. ]

[0069]

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[Wherein, R ₃₃ represents an aliphatic group, an aromatic group, a heterocyclic group, a group bonded with a nitrogen atom or a group bonded with an oxygen atom, and G ₃ represents a COCO group, a CS group, or a SO ₂ group. , SO
Represents a group, a PO (R ₃₅ ) group (R ₃₅ has the same meaning as R _33, and may be the same or different) or an iminomethylene group. n ₃
Is 0 or 1, and when n ₃ is 0, R ₃₃ represents a heterocyclic group. In the general formula (1), the aliphatic group represented by R ₂ is preferably a substituted or unsubstituted C 1-30 aliphatic group.
It is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ₂ is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group such as a pyridine ring, a pyrimidine ring, an imidazole ring, and a pyrazole ring. Quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring, morpholino ring, piperidine ring, piperazine ring and the like.

Preferred as R ₂ is an aryl group or an alkyl group.

R ₂ may be substituted. Representative examples of the substituent include a halogen atom, an alkyl group (an alkyl group,
A cycloalkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (for example, a pyridinio group), an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group ( Ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide Group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group,
Semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl Or heterocycle) thio, (alkyl or aryl) sulfonyl,
(Alkyl or aryl) sulfinyl groups, sulfo groups or salts thereof, sulfamoyl groups, acylsulfamoyl groups, sulfonylsulfamoyl groups or salts thereof, groups having a phosphoric acid amide or phosphate ester structure, and the like. These substituents may be further substituted with the same substituent.

When R ₂ is an aromatic group or a heterocyclic group, preferred examples of the substituent which R ₂ may have include an alkyl group (including an active methylene group), an aralkyl group, a heterocyclic group and a substituted amino group. Group, acylamino group, sulfonamide group, ureido group, sulfamoylamino group, imide group,
Thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl, aryl, Or heterocycle) thio group,
Examples include a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group, and a nitro group. When R ₂ represents an aliphatic group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide group,
Thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl or (Heterocycle) A thio group, a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group, and a nitro group are preferred.

In the general formula (1), the block group represented by R ₁ is specifically an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group (single ring or condensed group). An aryl group), a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a trifluoromethyl group, a difluoromethyl group,
-Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxy Methyl group, 4-ethylphenoxymethyl group, phenylthiomethyl group, t-butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, methoxycarbonyldiphenylmethyl group, cyanodiphenylmethyl group, methylthiodiphenylmethyl group, etc. No. The alkenyl group preferably has 1 to 10 carbon atoms, and examples thereof include a vinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. The alkynyl group preferably has 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. The aryl group is preferably a single ring or a condensed ring, and particularly includes a benzene ring, and includes a phenyl group, a perfluorophenyl group, a 3,5-dichlorophenyl group, a 2-methanesulfonamidophenyl group, and a 2-carbamoyl group. Phenyl group,
4,5-dicyanophenyl group, 2-hydroxymethylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2-chloro-5-octylsulfamoylphenyl group and the like.

The heterocyclic group is preferably a 5- or 6-membered, saturated or unsaturated, monocyclic or condensed ring containing at least one nitrogen, oxygen or sulfur atom, and is preferably a morpholino group, a piperidino group (N- Substitution), imidazolyl group, indazolyl group (4-nitroindazolyl group), pyrazolyl group, triazolyl group, benzimidazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinio group (such as an N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group. The alkoxy group preferably has 1 to 8 carbon atoms, and examples thereof include a methoxy group, a 2-hydroxyethoxy group, a benzyloxy group, and a t-butoxy group. As the aryloxy group, a substituted or unsubstituted phenoxy group is preferable, and as the amino group, an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group ( (Including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom). Examples of amino groups include 2, 2, 6,
6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc. Is mentioned. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

The group represented by R ₁ may be substituted, and the substituent is the same as that of R ₂ .

In the general formula (1), R ₁ causes a cyclization reaction that cleaves the G ₁ -R ₁ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₁ moiety. Such an example may be used.
And those described in US Pat.

The hydrazine compound represented by the general formula (1) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include U.S. Pat. Nos. 4,477,086 such as alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercapto heterocyclic groups, and triazole groups.
385,108 and 4,459,347, JP-A-5
Nos. 9-195233, 59-200231 and 59
No.-201045, No.59-201046, No.59-
No. 201047, No. 59-201048, No. 59-2
No. 01049, No. 61-170733, No. 61-27
Nos. 0744, 62-948 and 63-234244
And groups described in JP-A-63-234245 and JP-A-63-234246. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

R ₁ or R _{2 in} the general formula (1) may contain a ballast group or a polymer commonly used in immobile photographic additives such as couplers. The ballast group has a carbon number of 8 or more and is relatively inert to photographic properties, and includes an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy groups, alkylphenoxy groups and the like. As the polymer, for example,
No. 100530.

R ₁ or R ₂ in the general formula (1) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (1) becomes a polymer with respect to the hydrazino group, Specifically, JP-A-64-86134, JP-A-4-16938, and 5-97091, WO9
Compounds described in 5-32452, 95-32453 and the like are specific examples.

R ₁ or R _{2 in} the general formula (1) represents a cationic group (a group containing a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, etc.), A group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfur) dissociable by a base A famoyl group, etc.). Examples of these groups include JP-A-3-259240,
5-45761, 5-333466, 6-1
No. 9031, No. 6-19032, No. 7-5610,
7-234471, 7-244348, U.S. Pat. Nos. 4,988,604, 4,994,365,
Compounds described in German Patent No. 4,006,032 and the like can be mentioned.

A ₁ and A _{2 in} the general formula (1) are preferably a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a Hammett having a sum of substituent constants of -0.1. A phenylsulfonyl group substituted so as to have 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of the defined number of Hammett substitutions becomes -0.5 or more) Or a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (where the substituent is a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, a sulfo group, or the like. )), And a hydrogen atom is most preferred.

Specific examples of the hydrazine compound represented by the general formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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These compounds are described in JP-B-6-77138.
JP-A-6-93082, JP-A-6-23049, JP-A-6-289520, JP-A-6-313936 and JP-A-6-3
No. 13951, No. 7-5610, No. 7-77783
No. 7-104426, and the like.

In the general formula (2), the alkyl group of the alkylamino group represented by R ₂₃ has 1 to 16 carbon atoms.
Linear, branched or cyclic, methyl, ethyl, propyl, isopropyl, n-butyl, t-
Butyl, 2,4,4-trimethylpentyl, 2-butenyl, 2-hydroxyethyl, benzyl, 4-
Examples include a methylbenzyl group, a 2-methoxyethyl group, a cyclopentyl group, and a 2-acetamidoethyl group. R
_The alkynyl group represented by ₂₃ has 2 to 18 carbon atoms,
Preferably it is 2-10, and includes an ethynyl group, a phenylethynyl group and the like.

Examples of the substituent which the group represented by R ₂₃ may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxy group, a mercapto group, a nitro group, a carboxy group,
A cyano group, a halogen atom, an aryl group, a heterocyclic group (including those having a quaternized nitrogen atom), a mercapto-substituted heterocyclic group, an alkoxy group (including a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit) ), An aryloxy group, an acylamino group, an alkylamino group,
Anilino group, quaternary ammonium group, ureido group, sulfamoylamino group, alkylthio group, arylthio group,
Tertiary sulfonium group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl Group,
Examples include a sulfonyl group, an aryloxycarbonyl group, an acyl group, and a group consisting of a combination thereof, preferably an alkyl group, an aryl group, an alkoxy group, an acyl group, an acyloxy group, an acylamino group, a sulfonamide group, a halogen atom, and a ureide group. It is.

The group represented by R ₂₃ is preferably a hydrazino group or an amino group, particularly preferably an N ′, N′-disubstituted hydrazine group, an N′-acylhydrazine group or an N′-carbamoylhydrazine group.

Specific examples of the compound represented by formula (2) are shown below, but it should not be construed that the invention is limited thereto.

[0109]

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[0110]

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[0111]

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[0112]

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In the general formula (3), examples of the aliphatic group represented by R ₃₃ include an alkyl group, an alkenyl group and an alkynyl group. Examples of the alkyl group and the alkynyl group include those represented by R _{23 in} the general formula (2). Similarly, examples of the alkenyl group include a vinyl group and a 2-styryl group having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms.

Examples of the aromatic group represented by R ₃₃ include a monocyclic or condensed-ring aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, such as a phenyl group, a naphthyl group and a p-methoxyphenyl group. And the heterocyclic group is a saturated or unsaturated monocyclic or condensed ring having 1 to 5 carbon atoms.
Is a 5- or 6-membered member containing at least one oxygen atom, nitrogen atom or sulfur atom, and the number of hetero atoms constituting the ring and the kind of element may be one or more, and 2-furyl, 2 -Thienyl, 4-pyridyl, imidazolyl, quinolyl, isoquinolyl, benzimidazolyl, thiazolyl, benzothiazolyl, triazolyl, morpholino, piperidino, piperazinyl and the like.

Examples of the group bonded by a nitrogen atom represented by R ₃₃ include an acylamino group, an alkylamino group, an arylamino group and a heterocyclic amino group. The acylamino group has 1 to 16 carbon atoms, preferably 1 to 16 carbon atoms. And an alkylamino group having 1 to 16 carbon atoms, preferably 1 to
An N, N-dimethylamino group of 0, an arylamino group such as an anilino group having 6 to 24 carbon atoms, and a heterocyclic amino group having an oxygen atom, a nitrogen atom or a sulfur atom having 1 to 5 carbon atoms. Examples thereof include a 5- or 6-membered, saturated or unsaturated 2-oxazolylamino group, 2-tetrahydroalanylamino group, 4-pyridylamino group and the like containing one or more.

Examples of the group bonded by an oxygen atom represented by R ₃₃ include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, and a carbamoyloxy group. Here, the alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group and a 2-methoxyethoxy group. The aryloxy group includes a phenoxy group, 6 to 24 carbon atoms, -Methoxyphenoxy group and the like, and the heterocyclic oxy group has 1 carbon atom.
To 5, a 5- or 6-membered saturated or unsaturated 2-thiazolyloxy group, 2-tetrahydropyranyloxy group containing at least one oxygen atom, nitrogen atom or sulfur atom, 2
-Pyridyloxy group and the like, an acyloxy group having 1 to 16, preferably 1 to 10 carbon atoms, an acetoxy group, a benzoyloxy group and the like, and a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 10
N, N-dimethylcarbamoyloxy group, N-hexylcarbamoyloxy group, and N-phenylcarbamoyloxy group.

Specific examples of the compound represented by formula (3) are shown below, but it should not be construed that the invention is limited thereto.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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The compound represented by formula (2) or (3) may incorporate a so-called ballast group or polymer. These compounds are also available from S.A. R. Sandle
r, W.S. Karo, “Organic Funccio
nal Group Preparations "Vo
lume I, Academic Press, NY,
(1968), pages 363 to 386, or the literature described therein.

When these hydrazine compounds are used in the photothermographic material of the present invention, the amount used is 5 × 10 ^{−7 to} 5 ×.
10 ^-1 mol / mol Ag, especially 5 × 10 ^{-6 to} 5 × 10
^-2 mol / mol Ag is preferred.

[0125]

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

Example 1 (Preparation of silver halide grains) In 900 ml of pure water, 7.5 g of gelatin and 10 mg of potassium bromide were dissolved and the temperature was adjusted to 3
After adjusting to pH 3.0 at 5 ° C., 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide at a molar ratio of 96/4 were maintained at pH 7.7 for 10 minutes by a controlled double jet method. Was added. 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 projected diameter area was 8%. An emulsion comprising cubic silver iodobromide grains having a {100} face ratio of 86% was obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added, pH 5.9 and pAg7.
Adjusted to 5. Thereafter, sensitizing dyes SD-1 and SD-2 were added in an amount of 5 × 10 ⁻⁵ mol per mol of silver halide. Thereafter, the temperature was raised to 60 ° C., and 2 m
After ripening for 100 minutes and cooling to 38 ° C., chemical sensitization was completed to obtain silver halide grains.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
Into 10.6 g of behenic acid, heat and dissolve at 90 ° C., and with sufficient stirring, 31.1 ml of 1N sodium hydroxide
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared in advance are heated at 40 ° C. so that the silver amount becomes 10 mol% based on behenic acid.
The mixture was added while stirring while heating. Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

To the emulsion, polyvinyl butyral dissolved in ethyl acetate was added, stirred sufficiently, and allowed to stand to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite (A-3 to spherical, manufactured by Tosoh Corporation)
And 22 cc of isopropyl alcohol, left for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 cc of isopropyl alcohol were added, and the mixture was sufficiently stirred at 35 ° C. at a high speed for dispersion to complete the preparation of the organic fatty acid silver emulsion.

(Composition of photosensitive layer) Organic fatty acid silver emulsion 1.75 g / m ^{2 in} terms of silver pyridinium hydrobromide perbromide 1.5 × 10 ⁻⁴ mol / m ² Calcium bromide 1.8 × 10 ⁻⁴ mol / m ² 2- (4-chlorobenzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² Sensitizing dye SD-3 4.2 × 10 ⁻⁶ mol / m ² 2-mercaptobenzimidazole 3.2 × 10 ^{− 3} mol / m ² 2-tribromomethylsulfonylquinoline 6.0 × 10 ⁻⁴ mol / m ² hydrazine compound 1.5 × 10 ⁻³ mol / m ² shown in Table 1 1.5 × 10 ⁻³ mol / m ^{2 As a} solvent, methyl ethyl ketone, acetone and methanol are appropriately used. Was.

(Composition of surface protective layer) Cellulose acetate 4 g / m ² 1,1 bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 4.8 × 10 ^-3 mol / M ² phthalazine 3.2 × 10 ⁻³ mol / m ² 4-methylphthalic acid 1.6 × 10 ⁻³ mol / m ² tetrachlorophthalic acid 7.9 × 10 ⁻⁴ mol / m ² tetrachlorophthalic anhydride Compound 9.1 × 10 ⁻⁴ mol / m ² Silicon dioxide (particle size: 2 μm) 0.22 g / m ^{2 As a} solvent, methyl ethyl ketone, acetone and methanol were appropriately used.

(Backing Layer Composition) Cellulose Acetate 4 g / m ² Antihalation Dye A 0.06 g / m ² Antihalation Dye B 0.018 g / m ^{2 As a} solvent, methyl ethyl ketone, acetone and methanol were appropriately used.

(Non-photosensitive layer composed of water-soluble polymer) Polyvinyl alcohol 20 mg / m ² Ammonium sulfate 5 mg / m ² Silicon dioxide matting agent (particle size is shown in Table 1) 50 mg / m ²

[0133]

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Each of the above compositions was coated on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm and dried to obtain a coated sample. The layer of the water-soluble polymer was applied between the support and the backing layer.

<Evaluation of rise curl> The obtained sample was conditioned at 23 ° C. and 50% RH for 2 days, and then 440 × 6.
It was cut to 10 mm, wrapped around a 3.5-inch outside diameter ball core so that the emulsion side was in contact with the ball core, sealed in a barrier bag, and left at 40 ° C. for 2 days. Then, at 23 ° C, 20
The sample was unwound from the ball core under the condition of% RH and placed on a flat desk with the side in contact with the ball core facing up.
The height (mm) at which the corner was raised from the desk was measured, and the largest one was evaluated as rising curl.

<Evaluation of Development Stability> The obtained sample was exposed with a laser having an oscillation wavelength of 780 nm, and a Dry View film processor M-2 manufactured by Imation Co., Ltd. was used.
Using 771, thermal development was performed at a development temperature of 120 ° C., and the change in sensitivity at a density of 3 when the development was performed for 10 seconds, 15 seconds, and 20 seconds was evaluated as a relative value with that of Sample 1 being 100.

Table 1 shows the above results.

[0138]

[Table 1]

Example 2 Table 2 shows the results of evaluation in the same manner as in Example 1 by using a matting agent having a particle size of 20 μm and changing the addition amount to obtain a matte degree shown in Table 2.

[0140]

[Table 2]

[0141]

According to the present invention, a photothermographic material having excellent anti-curl properties and development stability can be obtained.

Claims (4)

[Claims] A photosensitive layer containing a photosensitive silver halide, an organic silver salt, a reducing agent and a binder is provided on a support, and a layer opposite to the photosensitive layer on the support has an average particle size of 10 μm or less. A photothermographic material comprising a large matting agent. 2. The photothermographic material according to claim 1, wherein the photothermographic material has a matting agent also on the photosensitive layer side and has a relationship represented by the following formula (1). (1) 0 <average particle size of matting agent on photosensitive layer side / average particle size of matting agent on layer opposite to photosensitive layer <2/3 3. The photothermographic material according to claim 1, further satisfying the following expression (2). (2) 0 <mat degree on the surface on the photosensitive layer side / mat degree on the surface on the side opposite to the photosensitive layer <1/5 4. The photothermographic material according to claim 1, further comprising a hydrazine compound.