JP2001296631A - Heat-developable image-recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-developable image-recording material for a scanner and an image setter, suitable particularly for photoengraving, which are free of surface swelling and crackling and superior in adhesiveness of an image to the base. SOLUTION: In the heat-developable image-recording material, having an image-forming layer containing at least (a) an organic silver salt, (b) a reducing agent and (c) photosensitive silver halide and at least one protective layer disposed on the image forming layer on the base and using a polymer latex as a binder of the image-forming layer and the protective layer, at lest one of the image-forming layer and the protective layer contains a thickener, which increases the viscosity of its aqueous solution at above a certain transition temperature in heating, and the thickener is a polymer containing 50 mass % or higher (meth)acrylamide derivative as constituent units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable image recording material, and more particularly to a heat-developable image recording material for a scanner and an image setter suitable for photolithography.
For more details, "wrinkles" on the surface of the image recording material
The present invention relates to a heat-developable image recording material which is free from cracks, has excellent adhesion between an image and a support, and is suitable for color lithography.

[0002]

2. Description of the Related Art One of the methods of exposing a photographic light-sensitive material is to scan an original drawing, perform exposure on a silver halide photographic material based on the image signal, and form a negative image or a positive image corresponding to the image of the original drawing. There is known an image forming method using a so-called scanner method for forming. Further, there is a demand for a scanner photosensitive material having a super-high contrast characteristic for a case of printing directly on a printing plate without passing through a turning process after being output from a scanner to a film or a scanner light source having a soft beam profile.

There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image.
Among them, there is a technique of forming an image by thermal development as a system that contributes to image preservation and can simplify the image forming means. 2. Description of the Related Art In recent years, in the field of photolithography, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there has been a need to develop a technology relating to photothermographic materials for photolithography, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a clear black image having high resolution and sharpness. is needed. According to such a photothermographic material, it is possible to supply a simpler and less environmentally harmful heat development processing system to a customer, which does not require a solution processing chemical.

A method of forming an image by thermal development is described in, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075, and D.C. Crosta Bohr (DK
“Thermally Processed Silver Systems A” by Loserboer (Imaging Processes and Materials (Imag)
ing Processes and Materials) Neblette 8th edition, J.M.
Sturge, V.S. Walworth
h), A. Edited by Shepp, Chapter 9, 279
1989). The light-sensitive materials described therein include a non-photosensitive reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, a light-sensitive silver halide), and a silver reducing agent, usually an organic binder. It is contained in a dispersed state in the matrix. The photosensitive material is stable at room temperature, but high temperature (for example, 80 ° C. or higher)
When silver is heated, silver is generated by a redox reaction between a reducible silver source (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver produced by the reaction of the reducible silver salt in the exposed areas becomes black and forms an image because it contrasts with the unexposed areas.

Conventionally known photothermographic materials are:
In many cases, the image forming layer is formed by applying a coating solution using an organic solvent such as toluene, methyl ethyl ketone (MEK), or methanol as a solvent. The use of an organic solvent as a solvent not only adversely affects the human body in the manufacturing process, but also disadvantageous in cost because a solvent recovery and other steps are required. Then, a method of forming an image forming layer using a coating solution using water as a solvent has been proposed.
For example, JP-A-49-52626 and JP-A-53-11
JP-A-6144 and the like describe an image forming layer using gelatin as a binder. Japanese Patent Laid-Open No. 50-151
No. 138 describes an image forming layer using polyvinyl alcohol as a binder. Further, JP
JP-A-61747 describes an image forming layer using a combination of gelatin and polyvinyl alcohol. As another example, JP-A-58-28737 describes an image forming layer using a water-soluble polyvinyl acetal as a binder. If such a binder is used,
Since the image forming layer can be formed using a coating solution of a water solvent, there are great environmental and cost advantages.

However, when a polymer such as gelatin, polyvinyl alcohol, or water-soluble polyvinyl acetal is used as a binder, when the obtained photosensitive material is thermally developed, dehydration shrinkage of the binder and thermal expansion of the support occur at the same time. A problem of wrinkling occurs, and only an unsuitable film is obtained for color printing used in superposition. As a method for preventing generation of wrinkles due to thermal development, JP-A Nos. 11-84573 and 11-2
No. 95845, Japanese Patent Application Nos. 11-91359, 11-143058, and 11-187243 disclose techniques using a polymer latex as a binder. This method is an excellent method for preventing wrinkles from occurring. A coating solution using a polymer latex as a binder is forcibly heated and dried after coating. However, a coating solution using a latex which is an aqueous dispersion of a hydrophobic polymer as a binder is applied to the surface of the coating layer in a drying process after the coating. However, it has a serious problem that it is easy to skin and the internal drying is difficult to proceed. If the drying temperature is increased or the drying air volume is increased to promote the drying, the film may swell or crack. In order to prevent "swelling" and "cracking", it is necessary to lower the drying temperature and the amount of drying air and to suppress the drying speed to apply. Therefore, increasing speed to increase productivity and reducing energy costs are extremely important issues in this field.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a coating solution which is heated and dried so as to suppress skinning on the surface and to cause "swelling" or " An object of the present invention is to provide a heat-developable image recording material having no "crack" and having excellent adhesion between an image and a support.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve these problems, and as a result, the coating solution is thickened and gelled by drying and heating to suppress the leather tension phenomenon. However, they have found that an excellent heat-developable image recording material exhibiting desired effects can be provided, and the present invention has been completed. That is, in the invention, an image forming layer containing at least (a) an organic silver salt, (b) a reducing agent, and (c) photosensitive silver halide is provided on a support, and provided on the image forming layer. A heat-developable image recording material having at least one protective layer, wherein a polymer latex is used as a binder for the image-forming layer and the protective layer, wherein at least one of the image-forming layer and the protective layer is fixed with heating. A thickener that increases the viscosity of the aqueous solution when the temperature exceeds the transition temperature of the (meth) acrylamide derivative represented by the following general formula (1) or (2). An object of the present invention is to provide a heat-developable image recording material, characterized in that it is a polymer containing at least 10% by mass.

[0009]

Embedded image (In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 6 carbon atoms,
R ³ to R ⁶ each independently represent a hydrogen atom or a methyl group, X is -O -, - S -, - NH -, - N (R 7) -
(Where R ⁷ represents an alkyl group having 1 to 4 carbon atoms),
—CH ₂ — or a direct bond. )

[0010]

Embedded image (In the general formula (2), R ¹ and R ² are represented by the general formula (1)
And R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (provided that R ⁸ and R ⁹
Is 3 or more). )

Preferably, in the heat-developable image recording material of the present invention, the (meth) acrylamide derivative is N-morpholinoethyl (meth) acrylamide or N- (4-methylpiperazinoethyl) (meth) acrylamide. . Preferably, in the heat-developable image recording material of the present invention, the binder of the image forming layer is a styrene / butadiene latex, an acrylic latex, or a styrene / acrylic latex. Further, the glass transition temperature of the binder in the image forming layer is preferably from -30C to 80C. Further, the glass transition temperature of the binder of the protective layer is preferably from 25 ° C to 80 ° C. In addition, in this specification, “to” is a range including numerical values described before and after it as a minimum value and a maximum value.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments and methods of the heat-developable image recording material of the present invention will be described in detail. The heat-developable image recording material of the present invention comprises, on a support, an image forming layer containing at least (a) an organic silver salt, (b) a reducing agent, and (c) photosensitive silver halide; At least one protective layer provided on the substrate, wherein a polymer latex is used as a binder for the image forming layer and the protective layer, and at least one of the image forming layer and the protective layer has a constant transition temperature upon heating. A thickener that increases the viscosity of the aqueous solution when exceeded, wherein the thickener is
It is a polymer containing the (meth) acrylamide derivative represented by the general formula (1) or (2) as a constituent unit in an amount of 50% by mass or more.

Specific examples of the (meth) acrylamide derivative represented by the general formula (1), which is a component of the polymer of the thickener used in the present invention, include those having a (thio) morpholine ring [N -Morpholinoethyl (meth) acrylacrylamide, N-morpholinopropyl (meth) acrylamide, N-morpholinobutyl (meth) acrylamide, N- (3-methylmorpholino-4-ethyl) (meth) acrylacrylamide, N- (2, 6-dimethylmorpholino-4-ethyl) (meth) acrylamide, N
-Thiomorpholinoethyl (meth) acrylamide, N-
Thiomorpholinopropyl (meth) acrylamide, etc.],
Those having a piperidine ring [N-piperidinoethyl (meth) acrylamide, N- (2-methylpiperidinoethyl) (meth) acrylamide, N- (3,5-dimethylpiperidinoethyl) (meth) acrylamide, etc.], Having a pyrrolidine ring [N-pyrrolidinoethyl (meth)
Acrylamide, N-pyrrolidinopropyl (meth) acrylamide, etc.], those having a piperazine ring [N-piperazinoethyl (meth) acrylamide, N-piperazinopropyl (meth) acrylamide, N-piperazinobutyl (meth) acrylamide, N-pipe Radinopentyl (meth) acrylamide, N-piperazinohexyl (meth) acrylamide, N- (4-methylpiperazinoethyl) (meth) acrylamide, N- (4-ethylpiperazinoethyl) (meth) acrylamide N- (4-propylpiperazinoethyl) (meth) acrylamide, N-
(4-butylpiperazinoethyl) (meth) acrylamide and the like]. Among these, N-morpholinoethyl (meth) acrylamide or N- (4-methylpiperazinoethyl) (meth) acrylamide is particularly preferable because it shows a sharper temperature-sensitive viscosity increase.

In the (meth) acrylamide derivative represented by the general formula (2), which is a constituent component of the polymer of the thickener used in the present invention, the total number of carbon atoms of R ⁸ and R ⁹ is 3 or more. And preferably 5 to 8. If the total number of carbon atoms of R ⁸ and R ⁹ is less than 3, sufficient viscosity increase in temperature cannot be obtained. Specific examples of the (meth) acrylamide derivative represented by the general formula (2) include N- (propylaminoethyl) (meth) acrylamide, N- (propylaminopropyl) (meth) acrylamide, and N- (propylaminobutyl) (Meth) acrylamide, N- (propylaminopentyl) (meth) acrylamide, N- (propylaminohexyl) (meth) acrylamide, N- (butylaminoethyl) (meth) acrylamide, N- (hexylaminoethyl) (meth) ) Acrylamide, N-
(Isobutylaminoethyl) (meth) acrylamide,
N- (N'-methyl-N'-propylaminoethyl)
(Meth) acrylamide, N- (N'-methyl-N'-
Butylaminoethyl) (meth) acrylamide, N-
(N'-ethyl-N'-isopropylaminoethyl)
(Meth) acrylamide, N- (N ', N'-dipropylaminoethyl) (meth) acrylamide, N-
(N ′, N′-dibutylaminoethyl) (meth) acrylamide, N- (N ′, N′-dihexylaminoethyl) (meth) acrylamide and the like. Among these, N- (N'-ethyl-N'-isopropylaminoethyl) (meth) acrylamide and N- (N'-
Ethyl-N′-dipropylaminoethyl) (meth) acrylamide is particularly preferred because it shows a sharper temperature-sensitive viscosity increase.

The polymer used as a thickener in the present invention contains 50% by mass or more, preferably 70% by mass, of a (meth) acrylamide derivative represented by the general formula (1) or (2) as a constitutional unit. It contains above. The polymer may be one or more (co) polymers of the (meth) acrylamide derivative represented by the general formula (1) or (2), and may be a compound represented by the general formula (1) or (2). It may be a copolymer of one or more of the (meth) acrylamide derivatives represented and other vinyl monomers.

In the present invention, the polymer used as a thickener is at least one kind of the (meth) acrylamide derivative represented by the general formula (1) or (2) or one kind of the (meth) acrylamide derivative. It can be obtained by (co) polymerizing the above and other vinyl monomers by a known method (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.). The weight average molecular weight of the polymer used as a thickener in the present invention is usually 1,000 to 5,000,000.
And preferably 10,000 to 2,000,000
And particularly preferably 10,000 to 1,000,000.
00.

The form of the thickener used in the present invention is not particularly limited.
It may be a solution of any concentration. Examples of the solvent in the case of a solution include water, acetone, methanol, and isopropyl alcohol. The thickener used in the present invention has a transition temperature at which the aqueous solution is reversibly thickened by heating. The transition temperature of the thickener used in the present invention changes depending on the hydrophilicity of the polymer, and the higher the hydrophilicity of the thickener, the higher the transition temperature, and the lower the hydrophilicity, the lower the transition temperature.

The thickener used in the present invention is mixed with the aqueous solution at a temperature lower than the transition temperature, and then used after being heated. The amount of the thickener used in the present invention varies depending on the type, viscosity, etc. of the aqueous solution to be mixed. 01 to 20 parts by mass. The thickener used in the present invention is mixed with an aqueous solution at a temperature equal to or lower than the transition temperature of the thickener, and the temperature varies depending on the types of components such as salts, surfactants, and solvents in the aqueous solution.

The image forming layer and the protective layer of the heat-developable image recording material of the present invention use a polymer latex as a binder. In the present invention, the “polymer latex” is obtained by dispersing a water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. The polymer latex used in the present invention is described in “Synthetic Resin Emulsion (Edited by Taira Okuda and Hiroshi Inagaki, published by Kobunshi Kankokai (197
3))), “Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara), Published by Polymer Publishing Association (19)
93)) "," Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is preferably 1 to 50,000 nm, more preferably about 5 to 1,000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution.

The polymer latex used in the present invention may be a so-called core / shell type latex other than a polymer latex having a normal uniform structure. in this case,
It may be desirable for the core and shell to have a different glass transition temperature. The preferable range of the glass transition temperature (Tg) of the polymer of the polymer latex used in the present invention is different for the image forming layer and the protective layer. The polymer latex for the image forming layer promotes diffusion of the photographic material at the time of thermal development, and in order to obtain good photographic properties such as high Dmax and low fog,
Those having a glass transition temperature of -30 to 80 ° C are preferable,
~ 40 ° C is more preferred. The polymer latex for the protective layer has a glass transition temperature of 25 to 25 from the viewpoint of film strength and prevention of adhesion failure since the protective layer comes into contact with various devices.
Those at 80 ° C. are preferred.

The polymer latex used in the present invention preferably has a minimum film formation temperature (MFT) of 0 to 90 ° C.
Those having a temperature of about 30 to 70 ° C are more preferable. A film-forming auxiliary may be added to control the minimum film-forming temperature.
The film-forming aid is also called a temporary plasticizer, and is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex. Issuance (1970)) ". Specific examples of the film-forming aid include the following compounds. K-1: benzyl alcohol K-2: 2-dimethylaminoethanol K-3: 2,2,4-trimethylpentanediol-
1,3-monoisobutyrate K-4: diacetone alcohol K-5: ethylene glycol monobutyl ether K-6: diethylene glycol monobutyl ether acetate K-7: dibutyl phthalate K-8: diethylene glycol

The polymer used in the polymer latex used in the present invention includes acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or a copolymer thereof. Coalescence and the like.
The polymer may be a linear polymer, a branched polymer, or a cross-linked polymer. Further, the polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. The molecular weight of the polymer is 5,0 by weight average molecular weight.
It is preferably about 00 to 5,000,000, and more preferably about 10,000 to 100,000. If the molecular weight is too small, the mechanical strength as a binder is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

In the present invention, specific examples of the polymer latex used as a binder for the image forming layer and the protective layer include the following. Methyl methacrylate / methyl acrylate copolymer latex, methyl acrylate / methyl methacrylate / styrene copolymer latex, methyl methacrylate / ethyl acrylate copolymer latex, methyl methacrylate / n-butyl acrylate copolymer latex, methyl methacrylate / tert-butyl Methacrylate copolymer latex, methyl methacrylate / tert
-Butyl methacrylate / acrylic acid copolymer latex, vinyl acetate / methyl methacrylate / acrylic acid copolymer latex, methyl methacrylate / n-butyl acrylate / acrylonitrile copolymer latex,
Methyl methacrylate / ethyl acrylate / acrylamide copolymer latex, methyl acrylate / methyl methacrylate / acrylic acid copolymer latex, methyl acrylate / ethyl acrylate / acrylic acid copolymer latex, methyl methacrylate / n-butyl acrylate / acrylic acid copolymer Combined latex, methyl acrylate / styrene / methyl methacrylate / acrylic acid copolymer latex, ethyl acrylate / styrene / methyl methacrylate / acrylic acid copolymer latex, methyl methacrylate / styrene / n-butyl acrylate / acrylic acid copolymer latex, Ethyl methacrylate / methyl acrylate / acrylic acid copolymer latex, methyl acrylate / tert-butyl methacrylate / Acrylic acid copolymer latex,
Methyl acrylate / methyl methacrylate / hydroxyethyl methacrylate copolymer latex, styrene / butadiene / acrylic acid copolymer latex, styrene / butadiene / divinylbenzene / methacrylic acid copolymer latex, methyl methacrylate / vinyl chloride /
Acrylic acid copolymer latex, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer latex, and the like. Such polymers are also commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635, 465
83, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), N
ipol LX811, 814, 821, 820, 85
7 (all made by Nippon Zeon Co., Ltd.), VONCORT-R3
As polyester resins such as 340, R3360, R3370 and R4280 (all manufactured by Dainippon Ink and Chemicals, Inc.), FINTEX ES650, 611, 675, 85
0 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-siz
e, WMS (all manufactured by Eastman Chemical Co., Ltd.), such as HYDRAN AP10, 20,
LACSTAR 7310K, 330 as rubber resins such as 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
7B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol LX410, 430, 43
5, 438C (all manufactured by Nippon Zeon Co., Ltd.) such as L502, L513 (all manufactured by Asahi Kasei Corporation), Alon D7020, D504, D5071
Examples of olefin resins include Chemipearl S-120 and SA100 (manufactured by Mitsui Petrochemical Co., Ltd.), etc. These polymers may be used alone or as necessary. If necessary, two or more kinds may be blended and used.

In the present invention, the binder for the image forming layer is preferably a styrene / butadiene latex, an acrylic latex, or a styrene / acrylic latex.

In the present invention, the polymer latex is preferably used in the image forming layer as 50% by mass or more of the total binder, and more preferably 70% by mass or more. The total binder amount of the image forming layer is preferably from 0.2 to 30 g / m ² , more preferably from 1.0 to 15 g / m ² . The total amount of the binder in the protective layer is 0.2 to 10 g /
m ² , more preferably 0.5 to 5.0 g / m ² . In the present invention, the image forming layer and the protective layer may each be provided in two or more layers. When the image forming layer has two or more layers, it is preferable to use a polymer latex as a binder for all the layers. The protective layer is a layer provided on the image forming layer, and when two or more layers are present, it is preferable that at least one layer, particularly the outermost protective layer, use a polymer latex.

In the present invention, each layer has a paragraph number [0023] to JP-A-2000-19678.
It is also possible to use a first polymer latex into which the functional group described in [0041] is introduced, a crosslinking agent having a functional group capable of reacting with the first polymer latex, and / or a second polymer latex. Specific examples of the above functional groups include a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, an oxazolinyl group, an amino group, and a vinylsulfonyl group. Examples of the crosslinking agent include an epoxy compound, an isocyanate compound, a blocked isocyanate compound, a methylol compound, a hydroxy compound, a carboxyl compound, an amino compound, an ethyleneimine compound, an aldehyde compound, and a halogen compound. Specific examples of the crosslinking agent include hexamethylene isocyanate, duranate WB40-80D, and WX-1 as isocyanate compounds.
741 (manufactured by Asahi Kasei Corporation), Baihijuru 310
0 (Sumitomo Bayer Urethane Co., Ltd.), Takenate WD
725 (manufactured by Takeda Pharmaceutical Co., Ltd.), Aquanate 10
0, 200 (manufactured by Nippon Polyurethane Co., Ltd.) and water-dispersible polyisocyanates described in JP-A-9-160172, and Sumitex Resin M- as an amino compound.
3 (manufactured by Sumitomo Chemical Co., Ltd.) as an epoxy compound
Dinacol EX-614B (Nagase Chemical Industry Co., Ltd.)
Manufactured), 2,4-dichloro-6- as a halogen compound
And hydroxy-1,3,5-triazine sodium.

The heat-developable image recording material of the present invention contains (a) an organic silver salt. The organic silver salt that can be used in the present invention is relatively stable to light, but at 80 ° C. or less in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. A silver salt that forms a silver image when heated as described above. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids,
Particularly (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms)
Silver salts of long chain fatty carboxylic acids are preferred. The ligand is 4.0
Complexes of organic or inorganic silver salts having a complex stability constant in the range of from 10.0 to 10.0 are also preferred. The silver donor can preferably comprise about 5 to 70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate,
Silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, it is preferable to use silver behenate having a silver behenate content of 75 mol% or more, more preferably 85 mol% or more, of the above-mentioned organic silver salts or a mixture of the organic silver salts. . Here, the content of silver behenate indicates the mole fraction of silver behenate with respect to the organic acid silver used. As the organic acid silver other than silver behenate contained in the organic acid silver used in the present invention, those mentioned above can be preferably used. The silver salt of an organic acid preferably used in the present invention is prepared by reacting a solution or suspension of an alkali metal salt (including a Na salt, a K salt, a Li salt and the like) of the organic acid described above with silver nitrate. . Regarding these preparation methods, the methods described in paragraphs [0019] to [0021] of Japanese Patent Application No. 11-104187 can be used.

In the present invention, a method of preparing an organic silver salt by adding an aqueous solution of silver nitrate and a solution of an alkali metal salt of an organic acid to a means for mixing a sealed liquid can be preferably used. Regarding these preparation methods, the method described in Japanese Patent Application No. 11-203413 can be used. In the present invention, a water-soluble dispersing agent can be added to the silver nitrate aqueous solution and the organic acid alkali metal salt solution or the reaction solution when preparing the organic acid silver. Specific examples of the type and amount of the dispersant used are described in paragraph [0052] of Japanese Patent Application No. 11-115457.

The organic acid silver used in the present invention is preferably prepared in the presence of a tertiary alcohol. The tertiary alcohol preferably has a total carbon number of 15 or less, and particularly preferably 10 or less. Preferred examples of the tertiary alcohol include tert-butanol, but the present invention is not limited to this. The tertiary alcohol used in the present invention may be added at any time during the preparation of the silver salt of an organic acid, but is preferably added during the preparation of the alkali metal salt of an organic acid to dissolve and use the alkali metal salt of the organic acid. . The amount of the tertiary alcohol to be used is 0.00 by mass ratio with respect to H ₂ O as a solvent at the time of preparing the organic acid silver.
It can be used arbitrarily in the range of 1 to 10,
The range of 03 to 1 is preferred.

The shape and size of the organic silver salt which can be used in the present invention are not particularly limited.
No. 87 described in paragraph [0024] can be used. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. Another method of measuring monodispersity is to determine the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) of the value divided by the volume-weighted average diameter is preferably 80% or less. It is preferably at most 50%, more preferably at most 30%. As a measuring method, for example, the organic silver salt dispersed in a liquid is irradiated with laser light, and the particle size (volume weighted average diameter) obtained by obtaining an autocorrelation function with respect to a time change of the fluctuation of the scattered light is obtained. Can be. A dispersion of solid fine particles having an average particle size of 0.05 μm to 10.0 μm in this measurement method is preferred. More preferably, the average particle size is 0.1 μm
~ 5.0 µm, more preferably 0.1 µm average particle size
m to 2.0 μm.

The organic silver salt that can be used in the present invention is
Preferably, desalting can be performed. The desalting method is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used. For the ultrafiltration method, see Japanese Patent Application No. 11-1.
No. 15,457, can be used. In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, the organic silver salt which is an image forming medium is contained and the photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which an aqueous dispersion is converted into a high-speed stream and then the pressure is reduced. As for these dispersing methods, the methods described in paragraphs [0027] to [0038] of Japanese Patent Application No. 11-104187 can be used.

The particle size (volume weight average diameter) of an organic silver salt solid fine particle dispersion is determined, for example, by irradiating a solid fine particle dispersion dispersed in a liquid with a laser beam, and changing the autocorrelation function with respect to the time change of the fluctuation of the scattered light. Can be determined from the particle size (volume under load average diameter) and transmission electron microscope image. Average particle size 0.0
A solid fine particle dispersion of 5 μm to 10.0 μm is preferred.
More preferably, the average particle size is from 0.1 μm to 5.0 μm.
m, more preferably an average particle size of 0.1 μm to 2.0
μm. The particle size distribution of the organic silver salt solid fine particle dispersion is preferably monodispersed. Specifically, the percentage (coefficient of variation) of the value obtained by dividing the standard deviation of the volume load average diameter by the volume load average diameter is 80% or less, more preferably 50%.
%, More preferably 30% or less.

The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio between the organic silver salt and water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass.
It is preferable to use the above-mentioned dispersing aid, but it is preferable to use the dispersing aid in a minimum amount within a range suitable for minimizing the particle size, and 0.5 to 30% by mass, especially 1 to 30% by mass based on the organic silver salt.
A range of 15% by mass is preferred. In the present invention, the organic silver salt can be used in a desired amount.
m ² is preferred, and more preferably 1 to 3 g / m ² .

In the present invention, it is preferable to add a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt. Regarding the addition of a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt, it is preferable to add it in the form of a water-soluble metal salt which is not a halide. It is preferably added in the form of a salt or the like. The addition of a halide is not preferable because it deteriorates the image preservability of the processed image recording material due to light (such as room light or sunlight), that is, the so-called printout property. For this reason, in the present invention, it is preferable to add in the form of a water-soluble metal salt which is not a halide. The addition time of the metal ion selected from Ca, Mg, Zn and Ag preferably used in the present invention is, for example, after the formation of the particles of the non-photosensitive organic silver salt, immediately before the formation of the particles, before the dispersion, after the dispersion and before and after the preparation of the coating solution. The timing may be any time as long as immediately before the coating, preferably after the dispersion and before and after the preparation of the coating solution. The addition amount of the metal ion selected from Ca, Mg, Zn and Ag in the present invention is preferably from 10 ^-3 to 10 ^-1 mol, particularly from 5 × 10 ^{-3 to} 5 ×, per mol of non-photosensitive organic silver.
10 ^-2 mol is preferred.

The heat-developable image recording material of the present invention contains (c) a photosensitive silver halide. The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition,
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. Regarding the grain formation of the photosensitive silver halide emulsion, grains can be formed by the methods described in paragraphs [0217] to [0224] of JP-A-11-119374, but the method is particularly limited. Not something. Examples of the shape of silver halide grains include cubic, octahedral, tetradecahedral, tabular, spherical, rod-like, potato-like and the like. In the present invention, cubic grains or tabular grains are particularly preferred. For the characteristics of the particle shape such as the particle aspect ratio and the surface index, see paragraph [02] of JP-A-11-119374.
25]. The distribution of the halogen composition may be uniform inside and on the surface of the silver halide grains, and the halogen composition may be changed stepwise or may be changed continuously. Further, silver halide grains having a core / shell structure can be preferably used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

In the particle size distribution of the silver halide grains used in the present invention, the value of the monodispersity is 30% or less, preferably 1%.
-20% or less, and further 5-15%. Here, the monodispersity is defined as a percentage (%) (coefficient of variation) of a value obtained by dividing the standard deviation of the particle size by the average particle size.
For convenience, the grain size of silver halide grains is represented by a ridge length in the case of cubic grains, and other grains (octahedral, tetradecahedral,
For example, a flat plate shape) is calculated by a projected area circle equivalent diameter.

The photosensitive silver halide grains used in the present invention contain a metal or a metal complex of Group VII or VIII of the periodic table. Group VII or VII of the periodic table
Rhodium, rhenium, ruthenium, osnium and iridium are preferred as the group I metal or the central metal of the metal complex. A particularly preferred metal complex is (NH ₄ ) ₃ Rh
(H ₂ O) Cl ₅ , K ₂ Ru (NO) Cl ₅ , K ₃ IrC
l ₆ and K ₄ Fe (CN) ₆ . One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is 1 × per mole of silver.
The range of 10 ^-9 mol to 1 × 10 ^-3 mol is preferable, and 1 × 1 mol
The range of 0 ^-8 mol to 1 × 10 ^-4 mol is more preferable. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used. The types and addition methods of these heavy metals are described in paragraphs [0227] to [0227] of JP-A-11-119374.
[0240].

The photosensitive silver halide grains can be desalted by washing with water by a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. . The photosensitive silver halide emulsion used in the present invention is preferably chemically sensitized. For the chemical sensitization, a method described in paragraphs [0242] to [0250] of JP-A-11-119374 is used. European Patent No. 293,91 discloses silver halide emulsions.
The thiosulfonic acid compound may be added according to the method described in the specification of JP-A No. 7 (1994).

The gelatin contained in the photosensitive silver halide used in the present invention is used in order to maintain a good dispersion state of the photosensitive silver halide emulsion in a coating solution containing an organic silver salt.
It is preferred to use low molecular weight gelatin. The low molecular weight gelatin has a molecular weight of 500 to 60,000, preferably 1,000 to 40,000. These low molecular weight gelatins may be used at the time of particle formation or at the time of dispersion after desalting treatment, but are preferably used at the time of dispersion after desalting treatment. When forming particles, use ordinary gelatin (molecular weight 1).
) And low-molecular-weight gelatin may be used at the time of dispersion after desalting. The concentration of the dispersion medium is 0.05 to 2
0% by mass can be used.
A concentration range of mass% is preferred. As a kind of gelatin,
Usually, alkali-treated gelatin is used, but other modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

The silver halide emulsion in the image recording material used in the present invention may be of one kind or two or more kinds (eg, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Those having different conditions of chemical sensitization) may be used in combination. The amount of the photosensitive silver halide used is 0.0 mol of the photosensitive silver halide to 1 mol of the organic silver salt.
1 mol to 0.5 mol is preferable, and 0.02 mol to 0.3 mol
Mole is more preferable, and 0.03 mole to 0.25 mole is particularly preferable. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. And the like, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt. There is no particular limitation as long as it appears in. In addition, mixing two or more aqueous dispersions of organic silver salts and two or more aqueous dispersions of photosensitive silver salts during mixing is a method preferably used for adjusting photographic characteristics.

The sensitizing dye applicable to the present invention is a sensitizing dye capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on the silver halide grains. The sensitizing dye to be used can be advantageously selected. For example, as a dye for spectrally sensitizing a wavelength region of 550 nm to 750 nm, JP-A-10-1865
No. 72, dyes represented by general formula (II), specifically, II-6, II-7, II-14, II-15, II-1
8, II-23 and II-25. Also, 750-
As a dye that spectrally sensitizes a wavelength region of 1400 nm,
JP-A-11-119374 discloses dyes represented by the general formula (I), specifically, (25), (26),
(30), (32), (36), (37), (41),
The dyes of (49) and (54). Furthermore, J-ban
US Pat. No. 5,510,236 as a dye forming d.
No. 3,871,887, Example 5
The dyes described in JP-A-2-96131 and JP-A-5-96131
And dyes disclosed in JP-A-9-48753. These sensitizing dyes may be used alone or in combination of two or more. The addition of these sensitizing dyes is described in paragraph [01] of JP-A-11-119374.
06], but the method is not particularly limited to this method. The addition amount of the sensitizing dye in the present invention may be a desired amount according to the sensitivity and the performance of fogging, but is preferably 10 ^-6 to 1 mol, more preferably 10 ^-6 mol, per mol of silver halide in the photosensitive layer. ^-4 to 10 ^-1 mol.

In the present invention, a supersensitizer can be used in order to improve the spectral sensitization efficiency. The supersensitizer used in the present invention is described in European Patent No. 587,338, US Pat. No. 3,877,943, and US Pat.
873, 184, compounds selected from heteroaromatic or aliphatic mercapto compounds, heteroaromatic disulfide compounds, stilbene, hydrazine, and triazine.

Particularly preferred supersensitizers are described in JP-A-5-3
Japanese Patent Application Laid-Open No. 4-43232 discloses a heteroaromatic mercapto compound, a heteroaromatic disulfide compound,
A compound represented by the general formula (I) or (II) in JP-A-182639; a stilbene compound represented by the general formula (I) in JP-A-10-111543;
It is a compound represented by the general formula (I) of JP-A-09947. Specifically, M-1 disclosed in JP-A-5-341432
-M-24, compounds d-1) to d-14) of JP-A-4-18239, JP-A-10-1115
No. 43, compounds of SS-01 to SS-07, JP-A No. 11-109547, 31, 32, 37, 38;
41 to 45 and 51 to 53. The addition amount of these supersensitizers is preferably in the range of 10 ^-4 to 1 mol per mol of silver halide in the emulsion layer, more preferably 0.001 to 0.3 per mol of silver halide. It is a molar amount.

The heat-developable image recording material of the present invention preferably contains a nucleating agent. The type of nucleating agent that can be used in the present invention is not particularly limited, but examples of preferred nucleating agents are shown below. Hydrazine derivatives represented by formula (H) described in Japanese Patent Application No. 11-87297, specifically, hydrazine derivatives described in Tables 1 to 4 of the same specification. JP 1
0-10672, JP-A-10-161270, JP-A-10-62898, JP-A-9-304
870, JP-A-9-304872, JP-A-9-304871, JP-A-10-31282, U.S. Pat. No. 5,496,695, and EP 741,320A. All hydrazine derivatives described. A substituted alkene derivative, a substituted isoxazole derivative and a specific acetal compound represented by formulas (1) to (3) described in Japanese Patent Application No. 11-87297;
More preferably, a cyclic compound represented by Formula (A) or Formula (B) described in the same specification, specifically, Compounds 1 to 72 described in Chemical Formulas 8 to 12 of the same specification. Further, a plurality of these nucleating agents may be used in combination.

The nucleating agent may be water or a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone. Then, an emulsified dispersion can be prepared and used mechanically. Alternatively, a nucleating agent powder can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleating agent may be added to the image forming layer or any other layer on the image forming layer side with respect to the support.
It is preferably added to the image forming layer or a layer adjacent thereto. The amount of the nucleating agent was 1 × 10
^-6 to 1 mol, preferably 1 × 10 ^{-5 to} 5 × 10 ^-1 mol, more preferably 2 × 10 ^-5 to 2 × 10 ^-1 mol.

In addition to the above compounds, US Pat.
545,515, 5,635,339 and 5,654,130, International Publication WO
97/34196, US Pat. No. 5,686,22.
No. 8 or the compound described in JP-A-11-1
19372, JP-A-11-133546,
JP-A-11-119373, JP-A-11-109
Compounds described in JP-A-546-546, JP-A-11-95365, JP-A-11-95366, and JP-A-11-149136 may be used.

In the present invention, in order to form a super-high contrast image, a high contrast accelerator can be used in combination with the nucleating agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5,
Hydroxamic acids described in U.S. Pat. No. 5,545,507, specifically HA-1 to HA-11, acrylonitriles described in U.S. Pat. No. 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in U.S. Pat. No. 5,558,983, specifically, CA-1 to CA-6, JP-A-9-297.
No. 368, onium salts, specifically, A-
1 to A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

In a photothermographic material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, formic acid or formate is a strong fogging substance. In the present invention,
The content of formic acid or formate on the side of the photothermographic material having the image forming layer containing the photosensitive silver halide is preferably 5 mmol or less, more preferably 1 mmol or less per mole of silver.

In the heat-developable image recording material of the present invention, an acid or a salt thereof formed by hydration of diphosphorus pentoxide is preferably used in combination with a nucleating agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline Acids (salts); Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide are orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, Examples include sodium hexametaphosphate and ammonium hexametaphosphate. The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto in that a desired effect is exhibited in a small amount. The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide (the amount of coating per m ^{2 of the} image recording material) may be a desired amount in accordance with the performance such as sensitivity and fog. 500m
g / m ² is preferred, and 0.5 to 100 mg / m ² is more preferred.

The heat-developable image recording material of the present invention contains (b) a reducing agent for an organic silver salt. The reducing agent for the organic silver salt is any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% based on 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable image recording material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, and JP-A-49-46427. 49-115540
JP-A-50-34334, JP-A-50-14361
Nos. 0, 50-147711 and 51-32
632, 51-1023721, 51
JP-A-32324, JP-A-51-51933, JP-A-5-51933
JP-A-2-84727, JP-A-55-108654,
JP-A-56-146133, JP-A-57-82828, JP-A-57-82829, JP-A-6-3793, U.S. Pat. Nos. 3,679,426 and 3,751,252 No. 3,751,255
No. 3,761,270, No. 3,
Nos. 782,949, 3,839,048, 3,928,686, and 5,46
No. 4,738, German Patent No. 2,321,328 and European Patent No. 692,732. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehydeazine; 2,2'-bis (hydroxymethyl) propionyl A combination of an aliphatic carboxylic acid aryl hydrazide such as a combination of β-phenylhydrazine and ascorbic acid with ascorbic acid; a combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (for example, hydroquinone, bis (ethoxy) Ethyl) hydroxylamine, a combination of piperidinohexose reductone or formyl-4-methylphenylhydrazine, etc.); phenylhydroxamic acid, p
Hydroxamic acids such as -hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano Α-cyanophenylacetic acid derivatives such as -2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-
Bis-β as exemplified by dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane -Naphthol; bis-β-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2 ′,
4′-dihydroxyacetophenone); 3
5-methyl-1-phenyl-5-pyrazolone and the like;
Pyrazolones; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4-benzenesulfonamidophenol and p- Sulfonamidophenol reducing agents such as benzenesulfonamidophenol; 2-phenylindane-1,3-dione; and chromanes such as 2,2-dimethyl-7-tert-butyl-6-hydroxychroman; 2,6-dimethoxy- 3,
1,4-dihydropyridines such as 5-dicarbethoxy-1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4- Hydroxy-
3-methylphenyl) propane, 4,4-ethylidene-
Bis (2-t-butyl-6-methylphenol), 1,
1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-
Bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain Species indane-1,3-dione; chromanol (such as tocopherol). Particularly preferred reducing agents are bisphenol and chromanol.

In the present invention, the reducing agent may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion, and an emulsified dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

In the present invention, as a development accelerator, Japanese Patent Application No. Hei 11
A phenol derivative represented by the formula (A) described in -73951 is preferably used. The phenol derivative represented by the formula (A) exhibits a strong development promoting effect when used in combination with the above reducing agent. Specifically, A-1 to A-54 described in the same specification are preferably used. The phenol derivative represented by the formula (A) is preferably used in a range of 0.01 mol% to 100 mol%, more preferably in a range of 0.1 mol% to 20 mol%, based on the reducing agent. Preferably.

The phenol derivative represented by the formula (A) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. It is preferably added to the containing layer. The phenol derivative represented by the formula (A) may be added by any method such as an aqueous solution, an organic solvent solution, powder, solid fine particle dispersion, and emulsified dispersion. Dispersion of solid fine particles can be performed by a known means for making fine (for example, a ball mill, a vibrating ball mill, a sand mill,
Colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

When an additive known as a "toning agent" for improving an image is included, the optical density may be increased. The toning agent may also be advantageous in forming a black silver image. The color tone agent is preferably contained in an amount of 0.1 to 50% mol, more preferably 0.5 to 20% mol, per mol of silver on the side having the image forming layer. Further, the color tone agent may be a so-called precursor which is derivatized so as to have a function effectively only during development. In a heat-developable image recording material using an organic silver salt, a wide range of toning agents are disclosed in JP-A-46-6077 and JP-A-47-10.
No. 282, No. 49-5019, No. 49-50
No. 20, JP-A-49-91215, JP-A-49-91
No. 215, No. 50-2524, No. 50-32
Nos. 927 and 50-67132 and 50-6
Nos. 7641, 50-114217, 51
No. 3223, No. 51-27923, No. 52
No. 14788, No. 52-99813, No. 5
Nos. 3-1020, 53-76020, 5
JP-A-4-156524, JP-A-54-156525, JP-A-61-183642, JP-A-4-5684
No. 8, JP-B-49-10727, JP-B-54-2
No. 3,333, U.S. Pat. Nos. 3,080,254, 3,446,648, and 3,783.
No. 2,941, 4,123,282, 4,510,236, British Patent 1,
380,795, Belgian Patent No. 841,91
No. 0 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides; naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4 N- (aminomethyl) aryldi-mercaptans exemplified by -dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole Carboximide, (for example, (N, N-dimethyl) Aminomethyl) phthalimide and N, N- (dimethylaminomethyl) - naphthalene-2,3-dicarboximide); and blocked pyrazole, isothiuronium derivatives and certain photobleaching agents (e.g., N,
N'-hexamethylenebis (1-carbamoyl-3,5
-Dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl-5-[(3 −
Ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthala Derivatives such as dinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetraphthalic acid) Phthalazine, phthalazine derivatives (eg, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-iso-butylphthalazine, 6
Derivatives such as -tert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid) Quinazolinedione, benzoxazine or naphthoxazine derivatives; not only as a color tone regulator but also as a source of halide ions for silver halide formation in situ. Functional rhodium complexes such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate and hexachlororhodium (III)
Potassium peroxide and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide;
3-benzoxazine-2,4-dione, 8-methyl-
1,3-benzoxazine-2,4-dione and 6-
Benzoxazine-2,4-dione such as nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric triazine (for example, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine and the like) ), Azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o -Chlorophenyl)-
3,6-dimercapto-1H, 4H-2,3a, 5,6
a-tetraazapentalene).

The toning agent used in the present invention is described in JP-A-20
A phthalazine derivative represented by the general formula (F) described in JP-A-00-35631 is preferably used. Specifically, A-1 to A-10 described in the same specification are preferably used. When a toning agent is used in the present invention, it may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. Dispersion of solid fine particles can be performed by a known means for fineness (for example, ball mill, vibrating ball mill, sand mill, colloid mill,
Jet mill, roller mill, etc.). Also,
When dispersing the solid fine particles, a dispersing aid may be used.

The film surface pH of the heat-developable image recording material of the present invention before the heat development treatment is preferably 6.0 or less, more preferably 5.5 or less. The lower limit is not particularly limited, but is about 3. The adjustment of the film surface pH is preferably performed using an organic acid such as a phthalic acid derivative, a nonvolatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is preferable in achieving a low film surface pH since ammonia is easily volatilized and can be removed before the application step and the heat development. The method of measuring the film surface pH is described in paragraph [0123] of Japanese Patent Application No. 11-87297.

In the heat-developable image recording material of the present invention, the silver halide emulsion and / or the organic silver salt are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors. In addition, it is possible to stabilize against a decrease in sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are described in US Pat. No. 2,131,0.
No. 38,2,694,716, the thiazonium salt described in U.S. Pat. No. 2,886,437.
No. 2,444,605, mercury salts described in U.S. Pat. No. 2,728,663, and mercury salts described in U.S. Pat. No. 3,287,135. Urazole, US Patent No. 3,235,65
No. 2, sulphocatechol, British Patent No. 62
Oxime, nitrone, nitroindazole described in US Pat. No. 3,448, polyvalent metal salt described in US Pat. No. 2,839,405, US Pat. No. 3,220,839.
No. 2,566,263 and U.S. Pat. No. 2,597,9.
15, palladium, platinum and gold salts described in US Pat. No. 4,108,665 and US Pat.
No. 4,128,557 and U.S. Pat. No. 4,137,079, U.S. Pat. No. 4,138,365 and U.S. Pat. And the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The heat-developable image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fogging. The benzoic acid used in the present invention may be any benzoic acid derivative. Examples of a preferred structure include those described in US Pat. Nos. 4,784,939 and 4,152,160.
Specification, JP-A-9-329863, JP-A-9-32
Compounds described in JP-A-9864 and JP-A-9-28637 are exemplified. The benzoic acid may be added to any layer of the image recording material, but is preferably added to the layer having the image forming layer, more preferably to the organic silver salt-containing layer. The benzoic acid may be added in any step of the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed. To just before application. The benzoic acid may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a color tone agent. The benzoic acid may be added in any amount, but 1 × 10 ⁻⁶ per mole of silver.
The mole is preferably from 2 to 2 mol, more preferably from 1 × 10 ^{−3 to} 0.5 mol.

Although not essential for practicing the present invention,
It may be advantageous to add mercury (II) salts as antifoggants to the image forming layer. Preferred mercury (I
I) The salts are mercury acetate and mercury bromide. The amount of mercury used in the present invention is preferably from 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol, more preferably from 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ per mol of the coated silver. Range of moles.

Fogging prevention particularly preferably used in the present invention
The terminating agent is an organic halide.
Nos. 119,624 and 50-120328,
JP-A-51-121332, JP-A-54-58022
Bulletin, JP-A-56-70543, JP-A-56-99335
Gazettes, JP-A-59-90842, JP-A-61-12964
No. 2, JP-A-62-129845, and JP-A-6-2
JP 08191, JP 7-5621, JP 7-27
No. 81, 8-15809, U.S. Pat.
No. 340,712, No. 5,369,000
No. 5,464,737.
Such compounds. Japanese Patent Application No. 11-87297
Organic halide represented by the formula (P) described in the specification
Is preferably used as an antifoggant. Concrete
Specifically, (P-1) to (P-118) described in the same specification
Is preferably used. The amount of organic halide added is
It is expressed in terms of mole amount per mole of Ag (mol / mol Ag).
And preferably 1 × 10^-Five~ 2 mol / mol Ag, more preferred
Preferably 5 × 10 ^-Five~ 1 mol / mol Ag, more preferred
1x10^-Four~ 5 × 10^-1Mol / mol Ag. This
These may be used alone or in combination of two or more.

A salicylic acid derivative represented by the formula (Z) described in Japanese Patent Application No. 11-87297 is preferably used as an antifoggant. Specifically, (A-1) to (A-60) described in the same specification are preferably used. The amount of the salicylic acid derivative represented by the formula (Z) is represented by a molar amount (mol / mol Ag) relative to 1 mol of Ag, and is preferably from 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol / mol A.
g, more preferably 5 × 10 ^-5 to 1 × 10 ^-1 mol / mol Ag, and still more preferably 1 × 10 ^{-4 to} 5 × 10 ^-2 mol / mol.
It is molar Ag. These may be used alone or in combination of two or more.

As a fogging inhibitor preferably used in the present invention, a formalin scavenger is effective.
And the exemplified compounds (S-1) to
(S-24). The antifoggant used in the present invention is water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Can be used by dissolving it. Also, by the well-known emulsification dispersion method,
An oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone can be used to dissolve and mechanically produce and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, the powder is placed in water using a ball mill, a colloid mill, a sand grinder mill,
It can be dispersed and used by a microfluidizer or ultrasonic waves.

The antifoggant used in the present invention may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on this layer side. It is preferable to add it to the layer adjacent thereto.
The image forming layer is a layer containing a reducible silver salt (organic silver salt), and is preferably an image forming layer further containing a photosensitive silver halide.

The heat-developable image recording material of the present invention may contain a mercapto compound, a disulfide compound or a thione compound in order to suppress or accelerate the development and control the development, or to improve the preservability before and after the development. . When a mercapto compound is used in the present invention, it may be of any structure, but may be Ar-SM, Ar-SS-
Those represented by Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, Ar is one or more nitrogen,
An aromatic or fused aromatic ring having sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is 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 can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy ( For example, it may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and aryl (which may have a substituent). Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, and 6-ethoxy-2.
-Mercaptobenzothiazole, 2,2'-dithiobis- (benzothiazole), 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-Hydrocyr-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,
2,4-triazole, 1-phenyl-5-mercaptotetrazole, 3- (5-mercaptotetrazole)-
Sodium benzenesulfonate, N-methyl-N'-
{3- (5-mercaptotetrazolyl) phenyl} urea, 2-mercapto-4-phenyloxazole, and the like, but are not limited thereto. The amount of the mercapto compound to be added is preferably in the range of 0.0001 to 1.0 mol per mol of silver in the image forming layer, more preferably 0.001 to 0.3 mol per mol of silver. It is.

The image forming layer in the present invention is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating liquid is water.

The lubricant in the present invention is not particularly limited, and any compound may be used as long as it reduces the friction coefficient of the surface of the object when it is present on the surface of the object as compared with the case where it is not present. The slipping agent may be any layer as long as it can reduce the coefficient of friction, but is preferably added to the outermost layer on the side having the image forming layer and / or the opposite side. The slip agent used in the present invention is disclosed in
-84573, paragraph numbers [0061] to [006]
4], compounds described in paragraphs [0049] to [0062] of Japanese Patent Application No. 11-106881. Specific examples of preferred slip agents include Cellsol 524 (main component carnauba wax), polysiloxane, Polylon A, 393, H-481 (main component polyethylene wax), and Himicron G-110 (main component ethylene bisstearic acid amide). , High Micron G-270 (main component stearic acid amide) (above, Chukyo Yushi Co., Ltd.)
_{Ltd.), W-1: C 16} H 33 -O-SO 3 Na W-2: and the like _{C 18 H 37 -O-SO 3} Na. The amount of the slipping agent used is 0.1 to 50% by mass, preferably 0.5 to 30% by mass of the binder amount of the additive layer.

In the present invention, Japanese Patent Application No. 10-34656 is disclosed.
No. 1, specification, Japanese Patent Application No. 11-196276, the pre-heating unit is conveyed by an opposing roller, and the heat development processing unit drives the roller on the side having the image forming layer by driving the roller.
In the case of using a heat development processing apparatus which conveys the opposite back surface by sliding it to a smooth surface, the outermost surface layer on the side having the image forming layer of the heat development image recording material at the development processing temperature and the outermost surface layer on the back surface Is 1.5 or more, and the upper limit thereof is not particularly limited, but is about 30. Further, μb is 1.0 or less, preferably 0.8 to 0.05. This value is obtained by the following equation. Ratio of friction coefficient = dynamic friction coefficient (μe) between roller member of heat developing machine and surface having image forming layer / dynamic friction coefficient (μb) of smooth surface member and back surface of heat developing machine (heat) Of the outermost surface layer on the surface having the heat development processing machine member and the image forming layer and / or the opposite surface can be adjusted by adding a slipping agent to the outermost surface layer and changing the amount of addition. .

On both sides of the support, JP-A-64-2054
No. 4, JP-A-1-180537, JP-A-1-18037
No. 209443, JP-A-1-285939,
JP-A-1-296243, JP-A-2-24649
JP, JP-A-2-24648, JP-A-2-18
4844, JP-A-3-109545, JP-A-3-137637, JP-A-3-141346, JP-A-3-141347, JP-A-4-96
No. 055, U.S. Pat. No. 4,645,731, Japanese Patent Application Laid-Open No. 4-68344, Registration No. 2,557,
No. 641, P2 right column, line 20 to P3 right column, line 30;
Paragraph number [002] of JP-A-2000-39684
0] to [0037] and vinylidene chloride copolymers containing 70% by mass or more of vinylidene chloride monomer repeating units described in paragraphs [0063] to [0080] of Japanese Patent Application No. 11-106881. It is preferable to provide an undercoat layer containing the undercoat layer.

When the amount of the vinylidene chloride monomer is less than 70% by mass, sufficient moisture-proof properties cannot be obtained, and the dimensional change over time after thermal development becomes large. The vinylidene chloride copolymer preferably contains a repeating unit of a carboxyl group-containing vinylidene monomer as another constituent repeating unit of the vinylidene chloride monomer. The polymer (polymer) is crystallized with only the vinylidene chloride monomer to include such a constitutional repeating unit,
This is because it becomes difficult to form a uniform film when the moisture-proof layer is provided, and a carboxyl group-containing vinylidene monomer is indispensable for stabilizing the polymer. The molecular weight of the vinylidene chloride copolymer is 450 by weight average molecular weight.
00 or less, more preferably 10,000 to 45000. When the molecular weight is large, the adhesiveness between the vinylidene chloride copolymer layer and the support layer such as polyester is deteriorated.

The content of the vinylidene chloride copolymer is 0.3 μm or more as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer, and is preferably at least 0.1 μm.
It is in the range of 3 μm to 4 μm. The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support. Usually, one layer is provided on each side, but in some cases, two layers are provided. The above may be provided. When a multi-layer structure of two or more layers is used, the total amount of the vinylidene chloride copolymer may fall within the range of the present invention. Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer. The support may be coated, if necessary, with an undercoat layer using SBR, polyester, gelatin or the like as a binder, in addition to the vinylidene chloride copolymer layer. These undercoat layers may have a multilayer structure or may be provided on one side or both sides of the support. The general thickness (per layer) of the undercoat layer is 0.01 to 5 μm, more preferably 0.05 to 1 μm.
μm.

Various supports can be used for the heat-developable image recording material of the present invention. Typical supports include polyesters such as polyethylene terephthalate, polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetal, syndiotactic polystyrene, polycarbonate, paper supports coated on both sides with polyethylene, and the like. Among them, biaxially stretched polyester, especially polyethylene terephthalate (PET)
Is preferred in terms of strength, dimensional stability, chemical resistance and the like.
The thickness of the support is 50 to 2 as the base thickness excluding the undercoat layer.
It is preferably 00 μm.

The support used in the heat-developable image recording material of the present invention is described in JP-A-10-48772 and JP-A-10-1.
0676, JP-A-10-10677, JP-A-11-65025, JP-A-11-138648
In order to alleviate the internal strain remaining in the film at the time of biaxial stretching described in Japanese Patent Application Laid-Open Publication No. H10-260, and to eliminate the heat shrinkage strain generated during the heat development processing, 130 to 210 ° C., more preferably 13 to 210 ° C.
Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of 0 to 185 ° C is preferably used. The temperature of the support at 120 ° C.
The dimensional change rate by heating for 0 seconds is -0.0 in the vertical direction (MD).
3% to + 0.01%, lateral direction (TD) 0 to 0.04%
It is preferred that

The heat-developable image recording material of the present invention has
Reduces wear, prevents static marks, and uses automatic transfer
Japanese Patent Application Laid-Open No. 11-84573
Nos. [0040] to [0051] of Japanese Patent Publication No.
Use conductive metal oxide and / or fluorine-based surfactant
To prevent static charge. Conductive metal oxide
No. 5,575,957, U.S. Pat.
Paragraph Nos. [0012] to 11-223901
Antimony-doped needle according to [0020]
Conductive tin oxide described in JP-A-4-29134
Fibrous tin oxide doped with antimony is preferred
Used. Surface resistivity (surface resistance) of the metal oxide-containing layer
Rate) is 10 in an atmosphere of 25 ° C and 20% relative humidity.¹²Ω or less
Below, preferably 10¹¹Ω or less is good. This is good
An antistatic property is obtained. The lower limit of the surface resistivity at this time is
Although not particularly limited, usually 10 ⁷About Ω.

The Beck smoothness of at least one of the surface having the image forming layer of the heat-developable image recording material of the present invention and the outermost layer surface opposite thereto, preferably both, is 2,000 seconds or less, more preferably 10 seconds or less. ~ 2000 seconds.
The Beck smoothness in the present invention is determined by the Japanese Industrial Standards (JI
S) It can be easily obtained according to P8119 “Smoothness test method of paper and paperboard with Beck tester” and TAPPI standard method T479. The Beck smoothness of the outermost layer having the image forming layer of the heat-developable image recording material and the outermost layer on the opposite side thereof are as described in paragraphs [0052] to [0059] of JP-A-11-84573. It can be controlled by appropriately changing the particle size and amount of the matting agent contained in the layers on both surfaces.

The surfactant used in the present invention will be described below. Surfactants are classified into dispersants, coating agents, wetting agents, antistatic agents, photographic control agents, and the like, depending on the purpose of use, but the purpose is achieved by appropriately using the surfactants described below. it can. The surfactant used in the present invention may be nonionic or ionic (anion, cation, betaine). Further, a fluorine-based surfactant is also preferably used. Preferred nonionic surfactants include polyoxyethylene, polyoxypropylene, polyoxybutylene, a surfactant having a nonionic hydrophilic group of polyglycidyl or sorbitan, and specifically, polyoxyethylene alkyl ether, Polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanol Amine fatty acid partial esters may be mentioned.

The anionic surfactants include carboxylate, sulfate, sulfonate and phosphate salt.
Representative examples include fatty acid salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates, α-olefin sulfonates, dialkyl sulfosuccinates, α-sulfonated fatty acid salts, N-methyl-N oleyl Taurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene Alkyl ether phosphate, naphthalene sulfonate formaldehyde condensate and the like.

As the cationic surfactant, an amine salt,
Examples thereof include quaternary ammonium salts and pyridium salts, and include primary to tertiary fatty amine salts and quaternary ammonium salts (tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridium salts, alkylimidazolium salts and the like). ). Examples of betaine-based surfactants include carboxybetaine and sulfobetaine, such as N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-N-sulfoalkyleneammonium betaine. These surfactants are described in "Applications of Surfactants (written by Koshobo and Takao Karimei, published on September 1, 1980)". In the present invention, the preferred surfactant is not particularly limited in the amount used, and may be any amount as long as the desired surfactant properties can be obtained. In addition, the application amount of the fluorine-containing surfactant is preferably 0.01 mg to 250 mg per 1 m ² .

Specific examples of the surfactant are described below, but are not limited thereto (here, -C ₆ H _4- represents a phenylene group). _{WA-1: C 16 H 33} (OCH 2 CH 2) 10 OH WA-2: C 9 H 19 -C 6 H 4 - (OCH 2 CH 2) 12 OH WA-3: sodium dodecylbenzene sulfonate WA-4 : Sodium tri (isopropyl) naphthalenesulfonate WA-5: sodium tri (isobutyl) naphthalenesulfonate WA-6: sodium dodecyl sulfate WA-7: α-sulfosuccinic acid di (2-ethylhexyl) ester sodium salt WA-8: C _{8 H 17 -C 6 H 4 -} (CH 2 CH 2 O) 3 (CH
₂ ) ₂ SO ₃ K

WA-10: Cetyltrimethylammonium
Mu chloride WA-11: C₁₁H_{twenty three}CONHCH_TwoCH_TwoN⁺(CH_Three)
_Two-CH_TwoCOO^- WA-12: C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_TwoCH
_TwoO)₁₆H WA-13: C₈F₁₇SO_TwoN (C_ThreeH₇) CH_TwoCOOK WA-14: C₈F₁₇SO_ThreeK WA-15: C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_TwoCH_TwoO)
_Four(CH_Two)_FourSO_ThreeNa WA-16: C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_Two)_ThreeOCH_Two
CH_TwoN⁺(CH_Three)_Three-CH _Three-C₆H_Four-SO_Three ^- WA-17: C₈F₁₇SO_TwoN (C_ThreeH₇) CH_TwoCH_TwoCH_Two
N⁺(CH_Three)_Two-CH_TwoCOO^-

In a preferred embodiment of the present invention, an intermediate layer may be provided, if necessary, in addition to the image forming layer and the protective layer. At the same time. The coating method includes extrusion coating, slide bead coating, curtain coating and the like, and the slide bead coating method disclosed in FIG. 1 in the specification of JP-A-2000-2964 is particularly preferable.

In the case of a silver halide photographic material using gelatin as a main binder, the material is rapidly cooled in a first drying zone provided downstream of a coating die, and as a result, gelatinization of gelatin occurs and the coating film is cooled. Is solidified. The coating film that has been cooled and solidified and has stopped flowing is guided to the subsequent second drying zone, where the solvent in the coating solution is volatilized and formed into a film in the subsequent drying zone. As a drying method after the second drying zone, an air loop method in which a jet is blown from a U-shaped duct to a roller-supported support, or a support in which the support is wound around a cylindrical duct in a helical shape, and conveyed and dried. A fire method (air floating method) and the like can be mentioned.

In the case of a coating liquid in which the main component of the binder is a polymer latex, the flow of the coating liquid cannot be stopped by rapid cooling, so that the preliminary drying may be insufficient only in the first drying zone. In this case, in a drying method such as a silver halide photographic light-sensitive material, flow unevenness and drying unevenness occur, and serious defects are likely to occur on the coated surface.

[0086] A preferable drying method in the present invention is that at least one-fourth or more of the constant-rate drying period is used regardless of the first drying zone or the second drying zone as described in JP-A-2000-2964. Is preferably a method of drying in a horizontal drying zone. The transport of the support immediately after the application until it is led to the horizontal drying zone may or may not be a horizontal transport, and the rising angle with respect to the horizontal direction of the coating machine may be between 0 and 70 °. . In addition, the horizontal drying zone may be such that the support is transported within ± 15 ° vertically with respect to the horizontal direction of the coating machine,
It does not mean horizontal conveyance. The drying air in the constant-rate drying period is preferably dried at an air velocity of 1 to 30 m / s, preferably 2 to 20 m / s, on the coating liquid film surface. More preferably, the first drying zone is a low-speed air-drying zone, and in this area, the time within 1/2 of the constant-rate drying period, the wind speed is:
10 m / s or less, preferably 2 to 8 m / s on the support surface
Then, the subsequent second drying zone is a high-speed air drying region, and the wind speed is 5 to 25 m / s, preferably 10 to 20 m / s, without drying unevenness and the like, and productivity can be improved.

The constant-rate drying in the present invention means a drying process in which the liquid film temperature is constant and all the heat flowing in is used for evaporating the solvent. At the end of drying, the rate of drying decreases at the end of drying due to various factors (such as the rate of diffusion of moisture inside the material and the evaporation surface receding), and the applied heat is also used to raise the liquid film temperature. Drying process. When the constant-rate drying is completed, the drying proceeds sufficiently until the flow stops, so that a drying method such as a silver halide photographic light-sensitive material can be employed.

The preferred drying conditions in the present invention are as follows: the drying conditions for forming the image forming layer and / or the protective layer are the minimum film forming temperature (MFT) of the polymer latex using the liquid film surface temperature during constant rate drying. As described above, in many cases, the temperature is usually 25 ° C. to 45 ° C. due to the limitation of the manufacturing equipment. Further, the dry-bulb temperature during the rate-decreasing drying is preferably a temperature lower than the Tg of the support to be used (usually 80 ° C. or lower in the case of PET). The liquid film surface temperature in the present invention refers to the surface temperature of the coating liquid film applied to the support, and the dry bulb temperature refers to the temperature of the drying air in the drying zone.

When drying is performed under the condition that the liquid film surface temperature during constant-rate drying is low, the drying tends to be insufficient. For this reason, particularly, the film forming property of the protective layer is significantly reduced, and cracks are easily generated on the film surface. In addition, the film strength is weakened, and serious problems such as susceptibility to damage during transport in an exposure machine or a heat developing machine are likely to occur. When an excessive heat higher than the Tg of the support (base) is applied, the dimensional stability, the curl resistance and the like of the photosensitive material are deteriorated.

The winding after drying is preferably carried out under the conditions of a temperature of 20 to 30 ° C. and a relative humidity of 45 ± 20%. Good or inside. Further, when the processing form is a roll product, it is also preferable to use a roll form wound on the side opposite to the winding form at the time of processing in order to remove the curl generated in the winding form. The environmental conditions at the time of packaging the photosensitive material are preferably in the range of 20 to 30 ° C. and a relative humidity of 20 to 65%.
It is preferable to control within the range of (measured at 25 ° C.).

The photographic emulsion coating solution which is a viscous solution containing silver halide and containing gelatin as a base, which has been conventionally used, usually dissolves and disappears in the solution simply by sending the solution under pressure. Even when the pressure is returned to the atmospheric pressure, bubbles hardly precipitate. However, in the case of an image forming layer coating solution containing an organic silver salt dispersion and a polymer latex which are preferably used in the present invention, defoaming tends to be insufficient only by pressurized liquid feeding, so that a gas-liquid interface does not occur. It is preferable to remove the bubbles by applying ultrasonic vibration while feeding the liquid.

In the present invention, the defoaming of the coating solution is performed by deaeration under reduced pressure before the coating solution is applied, further maintaining the pressurized state at 1.5 kg / cm ² or more and preventing the gas-liquid interface from being generated. It is preferable to apply ultrasonic vibration while continuously feeding liquid. Specifically, the method described in JP-B-55-6405 (page 4, line 20 to page 7, line 11) is preferable. As an apparatus for performing such defoaming, Japanese Patent Application No. Hei 10-2
Example of the specification of Japanese Patent No. 90003 The structure shown in FIG. 3 can be preferably used.

The pressing condition is 1.5 kg / cm ² or more,
It is preferably at least 1.8 kg / cm ² . The upper limit is not particularly limited, but is usually about 5 kg / cm ² . The sound pressure of the applied ultrasonic waves is 0.2 V or more, preferably 0.1 V or more.
In general, it is preferable that the sound pressure is high. However, if the sound pressure is too high, the temperature becomes partially high due to capitation, which causes fog. The frequency is not particularly limited, but is usually 10 kHz or more, preferably 20 kHz or more.
kHz to 200 kHz. In addition, decompression degassing refers to deaeration by increasing the air bubble diameter in the coating solution, increasing the buoyancy, and degassing the inside of the tank (usually, a liquid preparation tank or a storage tank). Decompression condition is -200
mmHg or lower pressure conditions, preferably -2
The pressure condition is 50 mmHg or lower, and the lowest pressure condition is not particularly limited, but is usually -800 mmHg.
g. The decompression time is 30 minutes or more, preferably 45 minutes.
There is no particular upper limit for minutes or more.

In the present invention, the image forming layer, the protective layer of the image forming layer, the undercoat layer and the back layer are described in JP-A-11-845.
No. 73, paragraph numbers [0204] to [0208], and Japanese Patent Application No. 11-106881, paragraph number [024]
0] to [0241], a dye can be contained for the purpose of preventing halation and the like. Various dyes and pigments can be used in the image forming layer of the heat-developable image recording material of the present invention from the viewpoint of improving color tone and preventing irradiation. Although any dyes and pigments can be used for the image forming layer, for example, compounds described in paragraph [0297] of JP-A-11-119374 can be used. As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds to be used is determined depending on the desired absorption amount, but it is generally preferable to use them in the range of 1 × 10 ⁻⁶ g to 1 g per 1 m ² .

When an antihalation dye is used in the present invention, the dye has the desired absorption in the desired range, has a sufficiently low absorption in the visible region after the treatment, and has a desirable absorbance spectrum shape of the back layer. Any compound can be used, if possible. For example, the compound described in paragraph [0300] of JP-A-11-119374 can be used. Further, as described in Belgian Patent No. 733,706, a method in which the concentration by a dye is reduced by discoloration by heating, and the concentration is reduced by decolorization by light irradiation described in JP-A-54-17833. And the like.

When the heat-developable image-recording material of the present invention is used as a mask when preparing a printing plate using a PS plate after heat-development, the heat-developable image-recording material after heat development is applied to a PS plate in a plate making machine. Information for setting exposure conditions and information for setting plate making conditions such as mask original and PS plate transfer conditions are carried as image information. Therefore, the concentration (use amount) of the irradiation dye, the halation dye, and the filter dye is limited in order to read them. Since such information is read by an LED or a laser, Dmin (minimum concentration) in the wavelength range of the sensor needs to be low, and the absorbance needs to be 0.3 or less. For example, a plate making machine S-FNRIII manufactured by Fuji Photo Film Co., Ltd. uses a light source having a wavelength of 670 nm as a detector and a bar code reader for detecting a register mark. The bar code reader of the plate making machine APML series manufactured by Shimizu Seisakusho Co., Ltd.
nm light source is used. That is, when Dmin (minimum density) around 670 nm is high, information on the film cannot be detected accurately, and a work error such as a transport failure or an exposure failure occurs in a plate making machine. Therefore, in order to read information with a 670 nm light source, Dmin around 670 nm needs to be low, and the absorbance at 660 to 680 nm after thermal development needs to be 0.3 or less. More preferably 0.25
It is as follows. Although the lower limit is not particularly limited, it is usually 0.
It is about 10.

In the present invention, the exposure apparatus used for imagewise exposure may be any apparatus capable of performing exposure with an exposure time of less than 10 ^-7 seconds.
mode (LD), Light Emitting Di
An exposure apparatus using an OLED (LED) as a light source is preferably used. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

The exposure is performed by overlapping the light beams of the light source, and the overlap means that the sub-scanning pitch width is smaller than the beam diameter. For example, the overlap can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient) when the beam diameter is represented by a half width of beam intensity (FWHM). In the present invention, the overlap coefficient is preferably 0.2 or more.
The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. Also, the light source channel may be single channel or multi channel,
In the case of a cylindrical outer surface type, a multi-channel is preferably used.

The heat-developable image recording material of the present invention has a low haze at the time of exposure, and tends to cause interference fringes. Examples of the technology for preventing the occurrence of interference fringes include a technology disclosed in Japanese Patent Application Laid-Open No. Hei 5-113548 in which a laser beam is obliquely incident on an image recording material, and a technology disclosed in International Publication WO 95/3.
A method using a multi-mode laser disclosed in, for example, Japanese Patent No. 1754 is known, and it is preferable to use these techniques. The heat development step of the image forming method used in the present invention may be any method, and usually, the heat development image recording material exposed imagewise is heated and developed. A preferred embodiment of the heat developing machine used is a type in which the heat-developable image recording material is brought into contact with a heat source such as a heat roller or a heat drum.
No. 6499, Japanese Patent Application Laid-Open No. 9-292695, Japanese Patent Application Laid-Open No. 9-297385 and International Publication WO95 / 3.
Japanese Patent Application Laid-Open No. Hei 7-13294 as a non-contact type heat developing machine described in Japanese Patent Application Laid-open No.
JP-A-28489, JP-A-97 / 28488 and JP-A-97 / 28487 disclose a thermal developing machine. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250C, more preferably 100 to 140C. The development time is 1
The time is preferably 180 to 180 seconds, more preferably 10 to 90 seconds.

As a method for preventing processing unevenness due to a dimensional change during the heat development of the heat-developable image recording material of the present invention, a temperature of 80 ° C.
A method of heating at a temperature lower than 115 ° C. for 5 seconds or more so as not to form an image and then thermally developing at 110 ° C. to 140 ° C. to form an image (a so-called multi-stage heating method) is effective. The heat development of the heat-developable image recording material of the invention is described in Japanese Patent Application No. 10-346561 and Japanese Patent Application No. 11-1430.
No. 58, Japanese Patent Application No. 11-196276, etc., the preheating is carried by a facing roller, and the heat development processing section is driven by the roller on the side having the image forming layer, and the back surface on the opposite side is driven by the roller. Is preferably used. When the heat-developable image recording material of the present invention is subjected to a heat development process, it is exposed to a high temperature of 110 ° C. or more, so that a part of the components contained in the material or a part of the decomposed components by the heat development are volatilized. Come. These volatile components may cause uneven development, corrode the components of the heat developing machine, precipitate at low temperatures, cause deformation of the screen as foreign matter, and adhere to the screen and become dirty. Is known to have a bad effect. In order to eliminate these effects, it is known to install a filter in the heat developing machine and to optimally adjust the flow of air in the heat developing machine. These can be effectively used in combination.

International Publication Nos. WO95 / 30933, WO97 / 21150, and JP-T10-500496 disclose a first opening for introducing volatile components and having a binding absorbing particle and a second opening for discharging. International Publication WO96 / 12213 discloses that a filter cartridge having an opening of
Japanese Patent Publication No. Hei 10-507403 describes the use of a filter in which a heat-conductive condensation collector and a gas-absorbing particulate filter are combined. In the present invention, these can be preferably used. U.S. Pat. No. 4,518,845 and Japanese Patent Publication No. 3-54331 disclose a device for removing vapor from a film, a pressurizing device for pressing the film against a heat transfer member, and heating of the heat transfer member. And a device having an apparatus for performing the operation described in
Japanese Patent Application Laid-Open No. 8/27458 describes that a component which increases fog volatilized from a film is removed from the film surface. These can also be preferably used in the present invention. Hereinafter, the present invention will be described more specifically with reference to Examples. The materials, usage amounts, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[0102]

EXAMPLES <Synthesis Example 1 of Thickener / Polymer> 100 parts of N-morpholinoethylacrylamide and 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule and freeze-dried. The mixture was air-tightly closed, and polymerized at 50 ° C. for 8 hours to obtain a polymer (P-1). <Synthesis Example 2 of Thickener / Polymer> 100 parts of N- (propylaminopropyl) acrylamide and 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) were added to an ampoule and frozen and degassed. Thereafter, the mixture was sealed and polymerized at 50 ° C. for 8 hours to obtain a polymer (P-2). <Synthesis example 3 of thickener / polymer> 100 parts of N- (4-methylpiperazinoethyl) methacrylamide and 2,2′-
1 part of azobis (2,4-dimethylvaleronitrile) was added to the ampoule, frozen, degassed, sealed, and polymerized at 50 ° C. for 8 hours to obtain a polymer (P-3).

<< Preparation of Silver Halide Emulsion A >> Water 700m
l is alkali-treated gelatin (calcium content of 2
700 g or less) 11 g and potassium bromide 30 m
g, 1.3 g of sodium 4-methylbenzenesulfonate
Is dissolved and the pH is adjusted to 6.5 at a temperature of 40 ° C.,
159 ml of an aqueous solution containing 18.6 g of silver nitrate, 1 mol / l of potassium bromide (NH ₄ ) ₂ RhCl ₅ (H ₂ O) 5 × 10 ^-6 mol / l and K ₃ IrCl ₆ of 2 × 10
^An aqueous solution containing ^-5 mol / liter was added over 6 minutes and 30 seconds by a control double jet method while maintaining the pAg at 7.7. Then, an aqueous solution 4 containing 55.5 g of silver nitrate 4
76 ml, 1 mol / l of potassium bromide and K ₃ I
An aqueous solution of a halogen salt containing 2 × 10 ^-5 mol / l of rCl ₆ was added by a control double jet method over 28 minutes and 30 seconds while maintaining the pAg at 7.7. Then p
H is lowered to cause coagulation and sedimentation, and desalting is carried out.
15,000 low molecular weight gelatin (calcium content of 2
0 ppm or less) 51.1 g, pH 5.9, pAg
It was adjusted to 8.0. The obtained particles have an average particle size of 0.1.
08 μm, projection area variation coefficient 9%, (100) plane ratio 9
It was 0% cubic particles.

The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and after 3 minutes, 71 μmol of triethylthiourea was added, followed by aging for 100 minutes. After adding 5 × 10 ^-4 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 0.17 g of compound A, the mixture was cooled to 40 ° C. Thereafter, the temperature was maintained at 40 ° C., and 4.7 × 10 ⁻² mol of potassium bromide (added as an aqueous solution) and 12.8 × 10 ^{−4 with} respect to 1 mol of silver halide.
Moles of the following sensitizing dye A (added as an ethanol solution),
6.4 × 10 ⁻³ mol of compound B (added as a methanol solution) was added with stirring, and after 20 minutes, the mixture was rapidly cooled to 30 ° C. to complete the preparation of silver halide emulsion A.

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<< Preparation of Silver Behenate Dispersion A >> Behenic acid (product name: Edenor C22-85R) 8 manufactured by Henkel Co.
7.6 kg, 423 liters of distilled water, 49.2 liters of a 5 mol / l NaOH aqueous solution, and 120 liters of tert-butyl alcohol were mixed, stirred at 75 ° C. for 1 hour, and reacted to obtain a sodium behenate solution. Separately, 206.2 liters of an aqueous solution of 40.4 kg of silver nitrate was prepared and kept at 10 ° C. A reaction vessel containing 635 liters of distilled water and 30 liters of tert-butyl alcohol was kept at 30 ° C., and while stirring, the entire amount of the sodium behenate solution and the entire amount of the silver nitrate aqueous solution were each kept at a constant flow rate for 62 minutes 10 seconds And over 60 minutes. At this time, only the aqueous silver nitrate solution was added for 7 minutes and 20 seconds after the addition of the aqueous silver nitrate solution was started, and then the addition of the sodium behenate solution was started.
During 0 seconds, only the sodium behenate solution was added. At this time, the temperature in the reaction vessel was set to 30 ° C., and the temperature was controlled so as not to rise. In addition, the piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the liquid temperature at the outlet of the addition nozzle tip was 75%.
The steam amount was controlled so as to reach ℃. Also,
The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Then, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. The morphology of the obtained silver behenate grains was evaluated by electron microscopy. Was.

Next, a dispersion of silver behenate was prepared by the following method. For a wet cake having a dry solid content of 100 g, polyvinyl alcohol (trade name: PVA-21)
(7, average degree of polymerization: about 1700) 7.4 g and water were added to make the total amount 385 g, and the mixture was preliminarily dispersed with a homomixer. Next, the pre-dispersed undiluted solution is dispersed in a disperser (trade name:
The pressure of a microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber) was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain silver behenate dispersion A. Obtained. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. The silver behenate particles contained in the silver behenate dispersion A thus obtained were particles having a volume-weighted average diameter of 0.52 μm and a coefficient of variation of 15%. Particle size measurements are available from Malvern
Instruments Ltd. MasterSi
Performed at zerX. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.5, and the particle thickness was 0.14 μm.
m, and the average aspect ratio (ratio of the circle equivalent diameter of the projected area of the particle to the particle thickness) was 5.1.

<< 1,1-bis (2-hydroxy-3,5)
-Dimethylphenyl) -3,5,5-trimethylhexane: Preparation of solid fine particle dispersion of reducing agent >> 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,
To 10 kg of 5,5-trimethylhexane and 10 kg of a 20% by mass aqueous solution of a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203), 16 kg of water was added.
The slurry was mixed well. The slurry was fed by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone By adding 4 g of sodium salt and water, the concentration of the reducing agent was adjusted to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the dispersion thus obtained have a median diameter of 0.44 μm and a maximum particle diameter of 2.
The average particle diameter was 0% or less, and the coefficient of variation was 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound A >> Organic polyhalogen compound A: tribromomethyl (4-
10 kg of (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone, 10 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), and 639 g of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate , 400 g of Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.), 640 g of methanol and 16 kg of water were added and mixed well to form a slurry. This slurry is fed by a diaphragm pump, and a horizontal sand mill (UVM-2: IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm.
) For 5 hours, and water was added to adjust the concentration of the organic polyhalogen compound A to 25% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound A. The organic polyhalogen compound particles contained in the dispersion thus obtained had a median diameter of 0.36 μm, a maximum particle diameter of 2.0 μm or less, and an average particle diameter variation coefficient of 18%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound B >> Organic Polyhalogen Compound B: A 20% by mass aqueous solution of 5 kg of tribromomethylnaphthyl sulfone and modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.)
5 kg, 213 g of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate and 10 kg of water were added and mixed well to form a slurry. The slurry was sent by a diaphragm pump, and the slurry was filled with a horizontal sand mill (UVM-
2: Imex Co., Ltd.) for 5 hours.
By adding 2.5 g of sodium benzoisothiazolinone and water, the concentration of the organic polyhalogen compound B was adjusted to be 20% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound B. The organic polyhalogen compound particles contained in the dispersion thus obtained have a median diameter of 0.38 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of the average particle diameter of 20%.
Met. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Compound Z >> MP 3.5 of Kuraray Co., Ltd.
1 kg of -203 and 15 kg of water were added and mixed well to form a slurry. The slurry was fed by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm in a horizontal sand mill (UVM-2: IMEX Co., Ltd.).
), Water was added thereto to adjust the concentration of compound Z to 10% by mass, and a solid fine particle dispersion of compound Z was obtained. The particles of compound Z contained in the dispersion thus obtained had a median diameter of 0.45 μm and a maximum particle diameter of 4.0.
μm or less, and the variation coefficient of the particle diameter was 17%. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of 6-iso-propylphthalazine Compound Dispersion >> Preparation Formula (Rate per 100 g of Finished Dispersion) and Preparation Procedure. (1) 87.9 g of water (2) Modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.) 2.0 g (3) 20% aqueous solution of sodium tripropylnaphthalenesulfonate 3.0 g (4) 6.14 g of 6-iso-propylphthalazine (70% aqueous solution) A dispersion was prepared by the following steps. 1. While stirring (1) at room temperature, (2) was added so as not to form a lump, and mixed by stirring for 10 minutes. 2. Thereafter, the mixture was heated to raise the internal temperature to 50 ° C., and then stirred for 1 hour to be uniformly dissolved. 3. The internal temperature was lowered to 40 ° C. or lower, (3) and (4) were added, and the mixture was stirred for 30 minutes to obtain a transparent dispersion. 4. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Solid Fine Particle Dispersion of Nucleating Agent A >> Poval PVA- manufactured by Kuraray Co., Ltd.
217 and 1 kg of water were added and mixed well to form a slurry. This slurry is fed by a diaphragm pump, and a horizontal sand mill (UVM-2: IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm.
), And 4 g of benzoisothiazolinone sodium salt and water were added to adjust the nucleating agent concentration to 10% by mass to obtain a solid fine particle dispersion of the nucleating agent. The particles of the nucleating agent contained in the dispersion thus obtained had a median diameter of 0.34 μm, a maximum particle diameter of 3.0 μm or less, and a coefficient of variation of the particle diameter of 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.

<< Preparation of Image Forming Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of silver behenate dispersion A prepared above.
Water was added to obtain an image forming layer coating solution. After completion, degassing under reduced pressure was performed at -350 mmHg for 60 minutes. The polymer latex concentration of the coating solution is 10.3% by mass, p
H was 7.7.

Binder-Luck Star 3307B 397 g as solids (manufactured by Dainippon Ink and Chemicals, Incorporated; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 149 g as solids Organic polyhalogen compound A 43.5 g as solids Organic polyhalogen compound B 13.5 g as solids Sodium ethylthiosulfonate 0.30 g Benzotriazole 1.04 g Table Polymer species shown in -1 12.0 g 6-iso-propylphthalazine 12.8 g as solid content Sodium dihydrogen orthophosphate dihydrate 0.37 g Compound Z 9.7 g as solid content Nucleating agent A Solid content Dye A (added as a mixture with low molecular weight gelatin having an average molecular weight of 15,000) 783n Amount (0.37 g as a guide) of silver halide emulsion A Ag amount 0.06 mol Compound C 2.0 g Compound A as a preservative 40 ppm in coating solution (2 g 0.5 mg / m ² ) 2% by mass as total solvent in methanol coating solution 1% by mass as total solvent in ethanol coating solution

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<< Preparation of Coating Solution for Lower Protective Layer >> H ₂ O was added to 203 g of a solid content of methyl methacrylate / methyl acrylate = 30/70 copolymer latex (containing 100 ppm of compound A), and an aqueous solution of compound E was added to the solid content. 1.62 g, and 29.4g of polymer species of the aqueous solution shown in Table 1 as a solid content was added as a further H ₂ O
Was added to prepare a coating solution (containing 2% by mass of a methanol solvent). After completion, degassing under reduced pressure was performed at -400 mmHg for 60 minutes. The polymer latex concentration of the coating solution was 11% by mass, and the pH was 5.5.

<< Preparation of Coating Solution for Upper Protective Layer >> H ₂ O was added to 140 g of methyl methacrylate / methyl acrylate = 30/70 copolymer latex (containing 100 ppm of compound A) as a solid content, and carnava wax (Chukyo Yushi ( Cellosol 524: less than 5 ppm as a silicone content) 6.30 g of a 30% by mass solution, 0.23 g of compound C, 7.95 g of compound F, and 0.93 g of compound E
g, compound G1.8 g, aqueous dispersion of matting agent (polystyrene particles, average particle diameter 7 μm, coefficient of variation of average particle diameter 8%, dispersant: 100 g of polystyrene particles, compound E0.
3g, Kuraray Co., Ltd., PVA-235 6.3g) as a solid content of 1.18 g and an aqueous solution of the polymer species shown in Table 1 as a solid content of 12.1 g were added.
₂ O was added to prepare a coating solution (containing 1.5% by mass of a methanol solvent). After completion, vacuum degassing is -400mmHg
For 60 minutes. The coating solution had a polymer latex concentration of 8% by mass and a pH of 2.2.

[0119]

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<< Preparation of Polyethylene Terephthalate (PET) Support with Backing / Undercoat Layer >> (1) Preparation of PET Support Using terephthalic acid and ethylene glycol, the intrinsic viscosity IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained. This was pelletized, dried at 130 ° C. for 4 hours, and then melted at 300 ° C.
After being extruded from the mold die, it is quenched and the film thickness after heat setting is 12
An unstretched film having a thickness of 0 μm was produced.
This is longitudinally stretched 3.3 times using rolls having different peripheral speeds.
Then, the film was stretched by a factor of 4.5 with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Then, after heat-setting at 240 ° C. for 20 seconds, it was relaxed by 4% in the lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling is performed on both ends to perform 4.8 k.
g / cm ² . Thus, the width 2.4
m, length 3500 m, thickness 120 μm, roll-shaped PE
A T support was obtained.

(2) Preparation of Undercoat Layer and Back Layer (2-1) Undercoat First Layer A coating solution having the following composition was applied on a support so as to be 6.2 ml / m ² , 30 seconds, 30 minutes at 150 ° C
And dried at 185 ° C. for 30 seconds. Latex-A 280 g Core / shell type latex having a core / shell ratio of 90/10% by mass (weight average molecular weight: 38,000) Core: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93 / 3/3 / 0.9 / 0.1 (% by mass) Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (% by mass) ) KOH 0.5 g Polystyrene fine particles (average particle size: 2 μm, coefficient of variation of average particle size 7%) 0.03 g 2,4-Dichloro-6-hydroxy-s-triazine 1.8 g Distilled water Amount that becomes 1000 g in total amount

(2-2) Second layer of undercoat A coating solution having the composition shown below was applied on the first layer of undercoat so as to have a concentration of 5.5 ml / m ^2.
It dried at 30 degreeC for 30 second and 170 degreeC for 30 second. Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) 10 g Acetic acid (20% aqueous solution) 10 g Compound-Bc-A 0.04 g Methylcellulose (2% aqueous solution) 25 g Polyethyleneoxy compound 0.3 g Distillation Water Amount of 1000g in total

(2-3) Back first layer: 0.375 kV ·
A · min / m ² of a corona discharge treatment, and a coating solution having the following composition was applied to the surface so as to have a composition of 13.8 ml / m ^2. Dry at 30 ° C. for 30 seconds.

23 g of Julima-ET410 (30% aqueous dispersion, manufactured by Nippon Pure Chemical Co., Ltd.) 23 g of alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 4.44 g deionized gelatin (Ca ²⁺ content: 0.4%) 0.84 g Compound-Bc-A 0.02 g Dye-Bc-A 0.88 g as a guide (adjusted to an optical density at 783 nm of 1.3 to 1.4) Polyoxyethylene phenyl ether 1 0.7 g Sumitex Resin M-3 (8% aqueous solution) 15 g (water-soluble melamine compound, manufactured by Sumitomo Chemical Co., Ltd.) FS-10D (water dispersion of needle-like particles of Sb-doped SnO2, Ishihara Sangyo Co., Ltd.) 24 g of polystyrene fine particles (average particle size: 2 μm, coefficient of variation of average particle size: 7%) 0.03 g distilled water: amount to be 1000 g in total amount

(2-4) Back second layer A coating solution having the composition shown below was applied onto the first back layer so as to have a concentration of 5.5 ml / m ^2, and was applied at 125 ° C. for 30 seconds at 150 ° C.
For 30 seconds and 170 ° C. for 30 seconds.

Julima-ET410 (30% aqueous dispersion, manufactured by Nippon Pure Chemical Co., Ltd.) 57.5 g Polyoxyethylene phenyl ether 1.7 g Sumitex Resin M-3 (8% aqueous solution) 15 g (water-soluble melamine Compound, manufactured by Sumitomo Chemical Co., Ltd.) Cellosol 524 (30% aqueous solution, manufactured by Chukyo Yushi Co., Ltd.) 6.6 g Distilled water Total amount of 1000 g

(2-5) Back Third Layer The same coating solution as that for the first undercoat layer was applied onto the second back layer so as to have a concentration of 6.2 ml / m ^2.
C. for 30 seconds and 185.degree. C. for 30 seconds.

(2-6) Fourth Back Layer A coating solution having the composition shown below was applied onto the third back layer so as to have a concentration of 13.8 ml / m ^2.
It dried at 30 degreeC for 30 second and 170 degreeC for 30 second. Latex: Chemipearl S120 (manufactured by Mitsui Petrochemical Co., Ltd.) 77.22 g as solids Compound-Bc-B 2.7 g Compound-Bc-C 0.6 g Compound-Bc-D 0.5 g 2,4-dichloro-6 -Hydroxy-s-triazine 0.8 g Polymethyl methacrylate (10% aqueous dispersion, average particle diameter 5 μm, coefficient of variation of average particle 7%) 7.7 g Distilled water Amount that totals 1000 g

[0129]

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(3) Heat treatment for transport (3-1) Heat treatment PE thus prepared with a back / undercoat layer
The T support was placed in a heat treatment zone with a total length of 200 m set at 160 ° C. and transported at a tension of 2 kg / cm ² and a transport speed of 20 m / min. (3-2) Post-heat treatment Following the heat treatment, post-heat treatment was carried out by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time was 10 kg / cm ² .

<< Preparation of Photothermographic Material >> On the undercoat layer of the PET support on which the first undercoat layer and the second undercoat layer were coated, the film shown in FIG. 1 in JP-A-2000-2964 was used. The above-mentioned coating solution for the image forming layer was coated with a silver coating amount of 1.5 g / m ² by using the slide beam coating method disclosed in
The lower protective layer coating solution is further coated with the upper protective layer coating solution such that the solid content of the polymer latex is 0.8 g / m ² . The coating solution for the image forming layer and the lower and upper layers of the protective layer were simultaneously coated so as to have a solid content of 1.0 g / m ² . The drying conditions at the time of coating are as follows: the first drying zone (low-speed air drying area) has a dry bulb temperature of 75 ° C, a dew point of 22 to 25 ° C, an air velocity of 4 to 6 m / s on the support surface, and a liquid film surface temperature of 40 ° C. The second drying zone (high-speed air drying zone) was dried at a dry bulb temperature of 48 to 53 ° C., a dew point of 5 to 10 ° C., and a wind speed on the support surface of 20 to 25 m / s. The residence time in the first drying zone was 1/3 of the constant rate drying period (20 to 25 seconds) in this zone, and the zone was moved to the second drying zone and dried. The first drying zone is a horizontal drying zone (the support is at an angle of 1.5 ° to 3 ° with respect to the horizontal direction of the coating machine). The coating speed was 60 m / min. The shear viscosity of the coating solution was measured at 40 ° C. using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. By drying only the first drying zone,
With respect to the polymer latex in which the film formation failure of the protective layer occurred, a coating solution was prepared by adding 10% by mass of Compound Example K-3 to the polymer latex solid content as a film forming aid. The following evaluation was performed about the obtained sample.

<Evaluation> (1) Occurrence of Cracking of the Coating Film The coating film of the obtained sample was visually observed to evaluate the state of the cracking of the coating film. “4” is an intermediate level between “5” and “3”, and “2”
Is an intermediate level between “3” and “1”.

(2) Evaluation of Adhesion between Image Forming Layer and Protective Layer An adhesive tape was stuck on the surface of the protective layer of the obtained sample, and the adhesive tape was peeled off at a constant speed. Was evaluated by a five-point method. Practically, it needs to be "5" or "4". 5 ... no peeling 4 ... 1/4 peeling 3 ... 2/4 peeling 2 ... 3/4 peeling 1 ... whole peeling

(3) Evaluation of photographic properties The obtained sample was exposed to xenon flash light having an emission time of 10 ^-6 seconds through an interference filter having a peak at 780 nm and a continuous wedge. The logarithmic value of the exposure amount giving a density of 1.5 was determined. γ: The point of fog (fog density) + density 0.3 on the characteristic curve was connected to a point of fog + density 0.3 by a straight line, and the gamma value was determined by the slope of this straight line. Dmax: highest concentration of characteristic curve The obtained results are shown in Table 1. As is evident from the results in Table 1, the samples of the present invention have significantly improved cracking and adhesion of the coating film. The photographic properties were all the same and good performance was obtained.

[0135]

[Table 1]

<Example 2> The binder of the lower layer of the protective layer and the upper layer of the protective layer in Example 1 was changed to methyl methacrylate / methyl acrylate = 43/57 copolymer latex, and the binder of the image forming layer was HYDRAN AP10.
A sample was prepared in the same manner as in Example 1 except that the sample was changed to Dainippon Ink and Chemicals, Inc. Next, the obtained photothermographic material was evaluated in the same manner as in Example 1. The result is
It is shown in Table 2. As is evident from the results in Table 2, the samples of the present invention have significantly improved coating film cracking and adhesiveness. The photographic properties were all the same and good performance was obtained.

[0137]

[Table 2]

[0138]

According to the heat-developable image recording material of the present invention, skinning of the surface is suppressed by heating and drying after applying the coating solution, and the image recording material has no swelling or cracks on the surface, and the image recording Excellent support adhesion.

Claims (5)

[Claims] 1. An image forming layer comprising at least (a) an organic silver salt, (b) a reducing agent, and (c) photosensitive silver halide on a support, and at least one provided on the image forming layer. A heat-developable image recording material having one protective layer, wherein a polymer latex is used as a binder for the image-forming layer and the protective layer, wherein at least one of the image-forming layer and the protective layer has a constant level upon heating. A thickening agent that increases the viscosity of the aqueous solution when the temperature exceeds the transition temperature, wherein the thickening agent is composed of a (meth) acrylamide derivative represented by the following general formula (1) or (2) as a constituent unit;
A heat-developable image recording material comprising a polymer containing 0% by mass or more. Embedded image (In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 6 carbon atoms,
R ³ to R ⁶ each independently represent a hydrogen atom or a methyl group, X is -O -, - S -, - NH -, - N (R 7) -
(Where R ⁷ represents an alkyl group having 1 to 4 carbon atoms),
—CH ₂ — or a direct bond. ) (In the general formula (2), R ¹ and R ² are represented by the general formula (1)
And R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (provided that R ⁸ and R ⁹
Is 3 or more). ) 2. The method according to claim 1, wherein the (meth) acrylamide derivative is
N-morpholinoethyl (meth) acrylamide or N
The heat-developable image recording material according to claim 1, which is-(4-methylpiperazinoethyl) (meth) acrylamide. 3. The image forming layer according to claim 1, wherein the binder is a styrene / butadiene latex, an acrylic latex,
Or a styrene / acrylic latex.
Or the heat-developable image recording material according to 2. 4. The heat-developable image recording material according to claim 1, wherein the binder of the image forming layer has a glass transition temperature of −30 ° C. to 80 ° C. 5. The heat-developable image recording material according to claim 1, wherein the binder of the protective layer has a glass transition temperature of 25 ° C. to 80 ° C.