JP2003057779A - Thermally developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally developable image recording material that undergoes little dimensional change with the lapse of time after thermal development and is free of wrinkling in thermal development. SOLUTION: When the thermally developable image recording material is thermally developed at 120 deg.C development temperature in an environment at 25 deg.C and 75% relative humidity and a dimension Y3 after the lapse of 3 min after the start of cooling and a dimension Y240 after the lapse of 240 min are measured, a rate of dimensional change T240 represented by the equation T240=[(Y240 -Y3 )/Y3 ]×100 is in the range of 0.00-0.03%.

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 used for photolithography. More about scanners,
The present invention relates to an image recording material for an imagesetter, and more particularly to a heat-developable image recording material suitable for color photoengraving which is excellent in dimensional stability without causing wrinkles on the film due to heat development.

[0002]

2. Description of the Related Art As one of the exposure methods for a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or a positive image corresponding to the image of the original image. There is known an image forming method using a so-called scanner method for forming an image. Further, there is a demand for a scanner light-sensitive material having super-high contrast characteristics for a case of printing on a film from a scanner and then directly printing it on a printing plate without passing through a returning step and a scanner light source having a soft beam profile.

A large number of photosensitive materials having a photosensitive layer on a support and forming an image by imagewise exposure are known.
Among them, as a system capable of environmental protection and easy image forming means, there is a technique of forming an image by thermal development. In recent years, it has been strongly desired to reduce the amount of processing waste liquid in the field of photoengraving from the viewpoint of environmental protection and space saving.
Therefore, there is a need for a technology related to a photosensitive heat-developable material for photolithography that can efficiently expose with a laser scanner or a laser imagesetter and form a clear black image with high resolution and sharpness. It is said that. With these photosensitive heat-developable materials,
Eliminating the use of solution-type processing chemicals, it is possible to provide customers with a heat development processing system that is simpler and does not damage the environment.

A method of forming an image by heat development is disclosed in, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075, and D.I. Morgan and B. “Thermally Processed Silver Systems” by Shely
(Imaging Processes and Materials) Neblette 8th Edition, Sturge, V. Walw
orth), A. Edited by Shepp, page 2, 196
9 years). Such a light-sensitive material has a reducible non-photosensitive silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a silver reducing agent usually dispersed in an organic binder matrix. Contained in. Photosensitive materials are stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. To generate. This redox reaction is promoted by the catalytic action of the latent image generated by exposure. The silver produced by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms the image.

Conventionally, this type of photothermographic material has been known, but most of these photothermographic materials use a stretched film-forming polyester as a support, and when heat-developed, the thermal dimension of the support is increased. There is an inconvenience that the image is deformed due to the change (mainly heat shrinkage). Further, the binder in the image forming layer also undergoes dehydration shrinkage and thermal expansion at the same time during thermal development, and the change thereof is different from the thermal dimensional change behavior of the support, so that there is a problem that wrinkles occur in the film. For this reason, only a film unsuitable for color printing to be used by overlapping is obtained.

As a technique for preventing the dimensional change and wrinkles due to the heat development, various heat treatment methods for relaxing the internal strain generated when the support is stretched to form a film have been disclosed. For example, JP-A-3-24936 and JP-A-64
-64833, JP-A-8-212547,
JP-A-3-97523 and JP-A-61-15482.
No. 9, JP-A-3-97523, JP-A-57-
Techniques disclosed in Japanese Patent Publication No. 109946 and the like can be mentioned. Certainly, according to the methods disclosed in these, the heat shrinkage amount of the biaxially stretched film-formed support can be reduced,
It is not possible to reduce the dimensional change over time after the heat development treatment.

Color photoengraving can be performed in Y, M, C, K
It is carried out using four films of plates. It would be nice if the exposure / heat development of these four plates were done simultaneously, but often
The exposure / heat development time may be shifted. In such a case, the size of each film did not match because the elapsed time after heat development of each film was different, which often caused color misregistration. Therefore, there has been a demand for a technique for providing a heat-developable image recording material excellent in dimensional stability under any handling condition.

[0008]

Therefore, according to the present invention, there is little dimensional change over time after heat development, no wrinkles occur during heat development, and less dimensional change before and after heat development. The object was to provide an image recording material. Then, it was an object to provide a heat-developable image recording material which gives an image excellent in photographic properties.

[0009]

As a result of intensive studies to solve the above problems, the present inventor has found that the dimensional change rate under a specific condition may be within a certain range, and the present invention can be achieved. It came to offer. That is, according to the present invention, in the environment of 25 ° C. and 75% relative humidity, the heat-developable image recording material is heat-developed at the development temperature of 120 ° C., and after cooling starts, the dimension Y ₃ is 3 minutes. Dimension Y after 240 minutes
_{When 240} is measured, the dimensional change rate T ₂₄₀ expressed by the following formula
Is 0.00 to 0.03%, preferably 0.00 to 0.0
Provided is a heat-developable image recording material characterized by being in the range of 1%. T ₂₄₀ = [(Y ₂₄₀ −Y ₃ ) / Y ₃ ] × 100 The heat-developable image recording material of the present invention has a temperature of 25 ° C. and a relative humidity of 75.
% Of the environment, the heat-developable image recording material was heat-developed at a development temperature of 120 ° C., and then the dimension Y ₃ after 3 minutes from the start of cooling and the dimension Y ₁₂₀ after 120 minutes were measured. At this time, the dimensional change rate T ₁₂₀ represented by the following formula is 0.00
It is preferably in the range of 0.01%. T ₁₂₀ = [(Y ₁₂₀ −Y ₃ ) / Y ₃ ] × 100

The present invention also provides a heat-developable image recording material having a dimension X of 120 in an environment of 25 ° C. and a relative humidity of 75%.
When the dimension Y ₂₄₀ after 240 minutes has passed from the start of cooling after the heat development treatment at the development temperature of ° C, the dimensional change rate H ₂₄₀ represented by the following formula is 0.00 to 0.05%. A heat-developable image recording material is provided. _H240 = [( _Y240− X) / X] × 100 Further, in the present invention, the heat development image recording material of dimension X is subjected to heat development treatment at a development temperature of 120 ° C. in an environment of 25 ° C. and relative humidity of 75%. After that, when the dimension Y ₁₂₀ after 120 minutes has elapsed from the start of cooling, the dimensional change rate H ₁₂₀ represented by the following formula is in the range of 0.00 to 0.05%. The heat-developable image recording material is also provided. H ₁₂₀ = [(Y ₁₂₀ −X) / X] × 100

The heat-developable image recording material of the present invention comprises a coating layer containing a vinylidene chloride copolymer containing at least 70% by mass of a vinylidene chloride monomer repeating unit at a thickness of 0.5 μm or more on each side. It is preferable to have a support provided in the. In addition, the support has an image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide, and at least one protective layer provided on the image forming layer. 70 to 99.9% by mass of repeating units of vinylidene chloride monomer and 0.1 to 5
It is preferable that the repeating unit of the carboxyl group-containing monomer is contained in an amount of mass%.

The support used in the heat-developable image recording material of the present invention is coated with a coating layer containing the above-mentioned vinylidene chloride copolymer, and then the carrier tension is 4 kg / cm ² at a temperature of 130 to 185 ° C. It is preferable that it is heat-treated below. The heat-treated support is 120
After heating for 30 seconds at 30 ° C., the thermal dimensional change rate after 3 minutes is −0.03 to 0.01% in the longitudinal (MD) direction and 0.00 to 0.04% in the transverse (TD) direction. Is preferred. Further, in the heat-developable image recording material of the present invention, it is preferable to use a polymer latex as a binder for the image forming layer and the protective layer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In addition, in this specification, "-" shows the range which includes the numerical value described before and after that as a minimum value and a maximum value, respectively. The heat-developable image recording material of the present invention forms an image by a heat development treatment, and the development temperature thereof is generally 8
It is 0 to 140 ° C. The heating in the heat development processing in this case includes not only heating for image formation but also preheating for the purpose of suppressing uneven processing. Therefore, the development may be carried out at a constant temperature, or may be multi-step heating in which heating at a constant temperature is followed by heating at a higher temperature.

The present invention provides a heat-developable image recording material in which the dimensional change after such heat-development treatment is within a certain range. That is, T ₂₄₀ calculated by the above equation is 0.00 to 0.03%, preferably 0.00 to 0.01
The heat-developable image recording material is provided within the range of%. T
The specific measurement method of ₂₄₀ can be referred to the description of Examples below. In the heat-developable image recording material of the present invention, T ₂₄₀ is preferably in the range of 0.00 to 0.03% and T ₁₂₀ is preferably in the range of 0.00 to 0.01%. In the conventional heat-developable image recording material, the dimensional change after the heat-development treatment was large. In many cases, the dimensions change with time, which causes the image shift. However, when the heat-developable image recording material of the present invention is used, such an image shift is not recognized and a good image can be formed.

The heat-developable image recording material of the present invention preferably has a relatively small dimensional change rate H _t before and after heat development, which is determined by the following equation. _{H t = [(Y t -X} ) / X] × 100 In the above formula, X is the size of the heat developable image recording material before thermal development, Y _t is t from the start of cooling after the heat development
It is a dimension at the time of minute. In the heat-developable image recording material of the present invention, H ₁₂₀ is preferably in the range of 0.00 to 0.05%, more preferably in the range of 0.00 to 0.03%. Further, H ₂₄₀ is 0.00-0.
It is preferably in the range of 0.05%, and 0.00 to 0.
It is more preferably within the range of 03%. By using a heat-developable image recording material having such a dimensional change rate H _t before and after heat development within a preferable range, it is possible to eliminate wrinkles. In addition, for example, when drawing with an imagesetter, the dimensional difference between the writing and the thermal development is sufficiently small, so that the image deviation (color deviation) is not recognized. Therefore, it is possible to form a good image.

The heat-developable image recording material of the present invention satisfying the above conditions can be produced by appropriately selecting the material applied to the support and the processing conditions. The material used as the base material of the support can be appropriately selected from various materials conventionally used for heat-developable image recording materials. Typical base materials include polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetals and polycarbonates. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferable from the viewpoint of strength, dimensional stability, chemical resistance and the like. The thickness of the base material constituting the support (base thickness excluding the undercoat layer) is 90 to 18
It is preferably 0 μm.

An undercoat layer is preferably coated on both sides of the base material to form a support. At this time, a layer containing a vinylidene chloride copolymer or polyphenylene sulfide, particularly a layer containing a vinylidene chloride copolymer is preferably formed as the undercoat layer. The undercoat layer is preferably applied on both sides of the base material, and the total thickness of one side is preferably 0.5 μm or more, more preferably 0.5 to 5 μm. By coating such an undercoat layer, it is possible to provide the heat-developable image recording material of the present invention having a small dimensional change. When a vinylidene chloride copolymer layer is applied as the undercoat layer, it is preferably provided as the first undercoat layer directly provided on the base material. Usually, one layer is provided on each side, but in some cases, two or more layers may be provided.
When a multi-layered structure having two or more layers is formed, the thickness of the vinylidene chloride copolymer layer may be 0.5 μm or more in total per one surface. The thickness of the vinylidene chloride copolymer layer per layer is preferably 0.3 to 4 μm, more preferably 0.6 to 3 μm in order to obtain a good coated surface state.
m, more preferably 1.0 to 2 μm.

Conventionally, for example, a styrene-butadiene-based copolymer has been used as an undercoat layer for coating both sides of a support, but a styrene-butadiene-based copolymer alone will cause a large dimensional change, and the dimensional change will be large. A heat developable image recording material satisfying the conditions of the invention cannot be provided. Even when a layer containing a vinylidene chloride copolymer or polyphenylene sulfide is formed as an undercoat layer, even if the total thickness is less than 0.5 μm per side,
A heat developable image recording material satisfying the conditions of the present invention cannot be provided.

The vinylidene chloride copolymer preferably used in the present invention contains 70% by mass or more of repeating units of vinylidene chloride monomer (hereinafter referred to as "vinylidene chloride monomer"). 70% vinylidene chloride monomer
If it is less than mass%, sufficient moisture resistance cannot be obtained, and the dimensional change becomes large over time after thermal development.
Further, the vinylidene chloride copolymer preferably contains a repeating unit of a carboxyl group-containing vinyl monomer (hereinafter referred to as “carboxyl group-containing vinyl monomer”) as a constitutional repeating unit other than the vinylidene chloride monomer. The carboxyl group-containing vinyl monomer referred to here is 1 in the molecule.
Specific examples of the vinyl monomer having at least one carboxyl group include acrylic acid, methacrylic acid, itaconic acid, citraconic acid, and the like. The vinylidene chloride copolymer contains a carboxyl group-containing vinyl monomer as a constitutional repeating unit because the vinyl chloride monomer alone causes the polymer (polymer) to crystallize and is uniform when the moisture-proof layer is applied. This is because it is difficult to form a transparent film, and the carboxyl group-containing vinyl monomer is indispensable for stabilizing the polymer.

In the present invention, as a vinylidene chloride copolymer, 70 to 99.9% by mass, preferably 85 to 99% by mass of vinylidene chloride monomer and 0.1 to 5% by mass, preferably 0.2 It is desirable to use a copolymer containing ˜3% by weight of a carboxyl group-containing vinyl monomer.

The vinylidene chloride copolymer of the present invention may contain a repeating unit of a monomer copolymerizable therewith in addition to the vinylidene chloride monomer and the carboxyl group-containing monomer. Specific examples of these monomers include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene. These monomers may be used alone or in combination of two or more. The weight average molecular weight of the vinylidene chloride copolymer of the present invention is preferably 45,000 or less, more preferably 10,000 to 45,000. When the molecular weight is high, the adhesion between the vinylidene chloride copolymer layer and the support layer such as polyester tends to be deteriorated.

In the present invention, the vinylidene chloride copolymer may be used in the form of being dissolved in an organic solvent or in the form of an aqueous dispersion of latex. It is preferably used in the form of an aqueous dispersion of latex. In this case, a latex of polymer particles having a uniform structure may be used, or a latex of polymer particles having a so-called core-shell structure in which the core portion and the shell portion have different compositions. The particle size and the like of the polymer particles in the latex are the same as those used in the binder layer of the image forming layer or the protective layer described later. The arrangement of the monomer units of the vinylidene chloride copolymer is not limited and may be periodic, random, block or the like.

Specific examples of the vinylidene chloride copolymer preferably used in the present invention are listed below. Numbers in parentheses indicate mass ratios. The average molecular weight represents the weight average molecular weight. V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1) (average molecular weight 42,
000) V-2 vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (8
7: 4: 4: 4: 1) latex (average molecular weight 40,
000) V-3 vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90: 6: 2:
2) Latex (average molecular weight 38,000) V-4 Vinylidene chloride: ethyl methacrylate: 2-
Hydroxyethyl methacrylate: acrylic acid (90:
8: 1.5: 0.5) latex (average molecular weight 44,
000) V-5 core-shell type latex (core part 90 mass%, shell part 10 mass%) core part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (9
3: 3: 3: 0.9: 0.1) Shell part Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile: Acrylic acid (8
8: 3: 3: 3: 3) (Average molecular weight 38,000) V-6 core-shell type latex (70% by mass of core part, 30% by mass of shell part) Core part Vinylidene chloride: Methyl acrylate: Methyl methacrylate: Acrylonitrile: Methacrylic acid (9
2.5: 3: 3: 1: 0.5) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (average molecular weight 20,000)

The vinylidene chloride copolymer may be used alone or in combination of two or more kinds. In addition to the vinylidene chloride copolymer, the undercoat layer may contain a crosslinking agent or a matting agent. Furthermore, an undercoat layer containing no vinylidene chloride copolymer may also be applied to the base material.
For example, an undercoat layer using SBR, polyester, gelatin or the like as a binder can be applied. These undercoat layers may have a multi-layered structure and may be provided on one side or both sides of the base material. Further, at least one of these undercoat layers can be used as a conductive layer. The thickness (per layer) of these undercoat layers is generally 0.01 to 5 μm.
m, preferably 0.05 to 1 μm, and the thickness of the conductive layer is generally 0.01 to 1 μm, preferably 0.
It is from 03 to 0.8 μm.

The support used in the heat-developable image recording material of the present invention relaxes the internal strain remaining in the film during biaxial stretching, and causes the heat-shrinkage strain and stickiness of the support itself generated during heat development. In order to suppress it, it is preferable to perform heat treatment in the temperature range of 130 to 185 ° C. In particular, when polyester, particularly polyethylene terephthalate, is used as the base material, it is recommended to perform such heat treatment. The heat treatment may be carried out at a constant temperature within the temperature range, or may be carried out while raising the temperature. The heat treatment of the support may be carried out in the form of a roll or may be carried in the form of a web while being conveyed. When carrying out in the form of a web, it is preferred that the carrying tension of the support during the heat treatment is relatively low, and specifically, it is preferably 4 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is 0.01 k.
It is about g / cm ² , preferably about 0.5 kg / cm ² .

Such heat treatment is a treatment for improving the adhesiveness of the image forming layer or the back layer to the support,
It is preferably performed after applying an undercoat layer containing a vinylidene chloride copolymer. The support used in the heat-developable image recording material of the present invention has a heat shrinkage ratio of −0.03 to 3 in the machine direction (MD) after 3 minutes have elapsed after heating at 120 ° C. for 30 seconds.
It is preferably 0.01% and 0 to 0.04% in the lateral direction (TD). In particular, it is preferable that the support subjected to the above heat treatment has these heat shrinkage rates.

The heat-developable image recording material of the present invention preferably has an image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide on a support, and at least one layer is formed on the image forming layer. Is provided with a protective layer. It is particularly preferred that the support is a polyester coated on both sides with a subbing layer containing a vinylidene chloride copolymer. Further, the heat-developable image recording material of the present invention preferably has at least one back layer on the opposite side of the support from the image forming layer. When the image forming layer, the protective layer and the back layer are provided, As a binder for the back layer, a hydrophobic synthetic polymer or a hydrophobic natural polymer is used.

The use of these polymers or vinylidene chloride copolymers as the polymer latex is particularly preferable because it enables water-based coating using a solvent (dispersion medium) containing water as a main component, which is advantageous in terms of environment and cost. The vinylidene chloride copolymer preferably used here is as described above. However, even a heat-developable image recording material obtained by solution coating using a polymer dissolved in various organic solvents as a binder can obtain desired effects as long as the conditions of the present invention are satisfied.

Next, the binder for the image forming layer, the protective layer, the back layer and the like will be described. In the present invention, the polymer binder preferably used as the binder,
A water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. As the dispersed state, the polymer is emulsified in the dispersion medium, emulsion-polymerized, micelle-dispersed, or the polymer chain has a partially hydrophilic structure and the molecular chains themselves are molecularly dispersed. Any of these may be used. For the polymer binder preferably used in the present invention, "Synthetic resin emulsion (Okuda Taira, Hiroshi Inagaki, edited by Kobunshi Kogyokai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Edited by Keiji Kasahara, published by Kobunshi Kogakukai (1993)), "Chemistry of Synthetic Latex (Soichi Muroi, published by Kobunshi Kogakukai (1970))" and the like. The average particle size of the dispersed particles is 1 to 50,000n.
m, more preferably about 5 to 1,000 nm. The particle size distribution of the dispersed particles is not particularly limited, and it may have a wide particle size distribution or a monodisperse particle size distribution.

The polymer binder used in the present invention may be a so-called core / shell type polymer latex other than the polymer latex having a usual uniform structure. In this case, it may be preferable that the core and the shell have different glass transition temperatures. Regarding the glass transition temperature (Tg) of the polymer of the polymer latex used in the present invention, the preferable temperature range differs between the protective layer, the back layer and the image forming layer. Since the protective layer and the back layer are in contact with various devices, a glass transition temperature of 25 to 100 ° C. is particularly preferable from the viewpoint of film strength and prevention of adhesion failure, and the image forming layer promotes diffusion of photographically useful materials during heat development. In order to obtain good photographic properties such as high Dmax and low fog, a glass transition temperature of -30 to 40 ° C is preferable, and 0 to 40 ° C is particularly preferable. Further, the gel fraction of the polymer of the polymer latex used in the image forming layer is preferably 30 to 90% by mass for the same reason. The gel fraction in this case was 2 for a membrane sample formed by using polymer latex at a drying temperature of 70 ° C.
It was obtained by immersing in tetrahydrofuran (THF) at 5 ° C. for 24 hours, quantifying insoluble matter, and following the formula below. Gel fraction (mass%) = [mass of insoluble matter (g) / mass of film using polymer latex (g)] × 100

The minimum film forming temperature (MFT) of the polymer latex used in the present invention is preferably -30 to 90 ° C, more preferably 0 to 70 ° C. Here, a film forming auxiliary may be added to control the minimum film forming temperature. The film-forming auxiliary 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.
0)) ”.

Examples of the polymer used for the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked 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 kinds of monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The weight average molecular weight of the polymer is preferably 5,0.
00 to 1,000,000, more preferably 10,000
It is about 0 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 tends to be poor.

Specific examples of the polymer latex used as the binder of the heat-developable image recording material of the present invention include:
Methyl methacrylate / ethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / Vinyl chloride / acrylic acid copolymer,
Examples thereof include vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer. Such polymers are also commercially available, for example, as an example of acrylic resin, Sebian A-4635, 4
6583, 4601 (above Daicel Chemical Industries, Ltd.)
Manufactured), Nipol Lx811, 814, 821, 82
0,857,857x2 (all manufactured by Nippon Zeon Co., Ltd.),
VONCORT R3340, R3360, R337
0, 4280, 2830, 2210 (all manufactured by Dainippon Ink and Chemicals, Inc.), Julimer ET-410, 530, S
EK101-SEK301, FC30, FC35 (Nippon Pure Chemical Industries, Ltd.), Polysol F410, AM20
0, AP50 (all manufactured by Showa Highpolymer Co., Ltd.) and the like, as a polyester resin, FINETEX ES650, 6
11, 675, 850 (above Dainippon Ink and Chemicals, Inc.)
), WD-size, WMS (above Eastman Chemical) and HYDRAN as a polyurethane resin.
AP10, 20, 30, 40, VON DIC 132
0NS (manufactured by Dainippon Ink and Chemicals, Inc.) and other rubber-based resins LACSTAR 7310K, 3307
B, 4700H, 7132C, LQ-618-1 (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx41.
6,410,430,435,2507 (Nippon Zeon Co., Ltd.) and other vinyl chloride resins such as Nipol
As vinylidene chloride resin such as G351 and G576 (all manufactured by Nippon Zeon Co., Ltd.), L502 and L513.
(All manufactured by Asahi Kasei Corporation), Aron D7020, D5
040, D5071 (all manufactured by Toagosei Co., Ltd.) and other olefin resins such as Chemipearl S120 and SA100
(Above, manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone, or may be used by blending two or more kinds as necessary.

Among these polymer latexes, as the binder for the protective layer, acrylic, styrene, acrylic / styrene, vinyl chloride and vinylidene chloride polymer latexes are preferably used, and specifically acrylic resin VONCORTR3370. , 4280, N
Preferably used are ipol Lx857, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, vinyl chloride resin Nipol G576 and vinylidene chloride resin Aron D5071.

A styrene / butadiene polymer latex is preferably used as the binder for the image forming layer. Specifically, LACSTAR33, which is a rubber resin, is used.
07B and Nipol Lx430 and 435 are preferably used. As the binder for the back layer, an acrylic, olefinic, or vinylidene chloride-based polymer latex is used, and specifically, acrylic resin-based Julimer ET-410, Sevian A-4635, and Polysol F.
Olefin resin type Chemipearl S120 such as 410,
Vinylidene chloride-based L502, Aron D7020 and the like are preferably used.

If desired, hydrophilic polymers such as polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and hydroxypropyl methyl cellulose may be added to the binder used in the present invention in the range of 20% by mass or less based on the total weight of the binder. Good. The addition amount of these hydrophilic polymers is preferably 10% by mass or less based on the total amount of binders in the protective layer and the image forming layer.

Each layer constituting the heat-developable image recording material of 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. As components other than water of the solvent of the coating liquid, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxy. A water-miscible organic solvent such as ethyl phenyl ether can be used.

The total amount of binder for the protective layer in the present invention is preferably 0.2 to 5.0 g / m ² ,
It is more preferably 0.5 to 3.0 g / m ² . The total amount of binder for the image forming layer in the present invention is 0.2.
-30 g / m ² is preferred, 1.0-15 g
/ M ² is more preferable. Total amount of binder for the back layer in the invention is preferably from 0.01 to 3 g / m ^2, and more preferably 0.05 to 1.5 g / m ^2. A cross-linking agent for cross-linking, a surfactant for improving coating property, and the like may be added to each layer.

Each of these layers may be provided in two or more layers. When the number of image forming layers is two or more, it is preferable to use polymer latex as a binder for all layers. The protective layer is a layer provided on the image forming layer and may be stored in two or more layers.
A polymer latex is preferably used for the layer, particularly the outermost protective layer. Further, the back layer is a layer provided on the undercoat layer on the back surface of the support, and there may be two or more layers, but it is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.

The back layer or undercoat layer adjacent to the support of the heat-developable image recording material of the present invention preferably contains a metal oxide in order to reduce adhesion of dust. At least one layer of the layers (those provided on both sides of the support) is preferably the conductive layer. However, it is preferable that the conductive layer is not the outermost back layer. The metal oxides used herein are particularly preferably those described in JP-A-61-20033 and JP-A-56-82504.

The amount of the conductive metal oxide used in the present invention is preferably 0.05 to ²⁰ g, and particularly preferably 0.1 to 10 g per 1 m ^{2 of} the image recording material. The surface resistivity of the metal oxide-containing layer is 1 in an atmosphere of 25 ° C and 25% relative humidity.
It is preferably 0 ¹² Ω or less, and more preferably 10 ¹¹ Ω or less. Thereby, good antistatic property can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually about 10 ⁷ Ω. In the present invention, a further good antistatic property can be obtained by using a fluorine-containing surfactant together with the above metal oxide.

The preferred fluorine-containing surfactant used in the present invention has a fluoroalkyl group, a fluoroalkenyl group or a fluoroaryl group having 4 or more carbon atoms (usually 15 or less), and an anionic group ( Sulfonic acid (salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cation group (amine group, ammonium salt,
Aromatic amine salt, sulfonium salt, phosphonium salt),
A surfactant having a betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) or a nonion group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue) Can be mentioned.

These fluorine-containing surfactants are disclosed in JP-A-49
-10722, British Patent 1,330,356, U.S. Patents 4,335,201, 4,347,308, British Patent 1,417,
915, JP-A-55-149938, JP-A-58-196544, and British Patent No. 1,439,4.
No. 02 specification and the like. Some of these specific examples are described below.

[0044]

[Chemical 1]

In the present invention, the layer to which the fluorine-containing surfactant is added is at least 1 layer constituting the heat-developable image recording material.
The layer is not particularly limited as long as it is a layer, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer and a back layer. Among them, a preferable addition layer is a surface protective layer,
Either the image forming layer side or the back layer side may be used, but it is particularly preferable to add it to at least the image forming layer side surface protective layer. When the surface protective layer is composed of two or more layers, any of these layers may be used, and the surface protective layer may be further overcoated and used. The amount of the fluorine-containing surfactant used in the present invention may be 0.0001 to 1 g per 1 m ² of the heat-developable image recording material, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003 to. It is 0.1 g. Further, two or more kinds of fluorine-containing surfactants may be mixed and used.

The Beck smoothness of the heat-developable image recording material of the present invention can be determined by the Japanese Industrial Standard (JIS) P8119 "Paper and paperboard Beck tester smoothness test method" and TAP.
It can be easily determined by the PI standard method T479.
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 surface of the outermost layer opposite thereto is preferably 2000 seconds or less, more preferably 10 to 2000 seconds. is there. The Beck smoothness of the outermost surface of the surface having the image forming layer and the outermost surface of the opposite surface of the heat-developable image recording material of the present invention is the average particle size of fine particles called a matting agent contained in the layers on both sides. It can be controlled by variously changing the diameter and the addition amount. The matting agent is preferably contained in the protective layer which is the outermost layer farthest from the support on the side having the image forming layer, and is preferably contained in the back layer which is not the outermost layer on the opposite side.

The average particle size of the matting agent preferably used in the present invention is in the range of 1 to 10 μm. The amount of the matting agent added is preferably 5 to 400 mg / m ² ,
A range of 200 mg / m ² is particularly preferred. The matting agent used in the present invention may be any solid particles as long as it does not adversely affect various photographic characteristics. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, and silicates of calcium and aluminum.
Included are organic polymeric matting agents such as cellulose esters, polymethylmethacrylate, polystyrene or polydivinylbenzene and copolymers thereof.

In the present invention, the porous matting agent described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, the Japanese Patent Application Laid-Open No. 4-127142, page 3, upper right column. A matting agent surface-modified with an alkali described in lines 7 to 5, lower right column, a matting agent of an organic polymer described in paragraph Nos. "0005" to "0026" of JP-A-6-118542. Is more preferably used. Also, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an irregularly shaped matting agent and a spherical matting agent, a mat having a different average particle size. There is a combined use of agents (for example, a combined use of a matting agent having an average particle size of 1.5 μm or more and a matting agent having an average particle size of 1 μm or less described in JP-A-6-118542).

In the present invention, it is preferable to add a slip agent to the outermost surface layer on the surface having the image forming layer and / or the surface opposite thereto. The slip agent in the present invention is not particularly limited, and may be any compound as long as the compound 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. Typical examples of the slip agent used in the present invention include US Pat. No. 3,042,522, British Patent No. 955,061 and US Pat. No. 3,080,317. Fourth 4,004,92
No. 7, No. 4,047,958, No. 3,489,567, and British Patent No. 1,143.
Silicone-based lubricants described in Japanese Patent No. 118, US Pat. Nos. 2,454,043 and 2,732,3
No. 05, No. 2,976,148, No. 3,206,311, German Patent No. 1,284,
295, 1,284,294 and the like, higher fatty acid-based, alcohol-based, acid amide-based lubricants, British Patent 1,263,722, US Patent 3,933,
516, etc., metal soaps, US Pat.
588,765, 3,121,060, British Patent 1,198,387, and other ester-based and ether-based lubricants, and U.S. Pat. No. 3,50.
There are taurine-based lubricants described in the specifications of 2,473 and 3,042,222.

Specific examples of slip agents that are preferably used include Cerosol 524 (main component carnauba wax), POLYLON A, 393, H-481 (main component polyethylene wax), Himicron G-110 (main component ethylenebisstearic acid). Amide), High Micron G-270
(Main component stearic acid amide) (above, Chukyo Yushi Co., Ltd. product) etc. The amount of the slip agent used is 0.1 to 50% by mass of the amount of the binder in the addition layer, and preferably 0.1.
It is 5 to 30 mass%.

The photosensitive silver halide used in the present invention may be any of silver chloride, silver chlorobromide and silver iodochlorobromide. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or the halogen composition may be continuously changed.
The method for forming the photosensitive silver halide in the present invention is well known in the art and described in, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458. Any method can be used. As a specific method which can be used in the present invention, a method of converting a part of silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin, Alternatively, a method in which a photosensitive silver halide grain is prepared by adding a silver-supplying compound and a halogen-supplying compound to another polymer solution and then mixed with an organic silver salt can be used.
In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or less.
To 0.15 μm, more preferably 0.02 to 0.12 μm
m is good. The term "grain size" as used herein means the length of the edges of silver halide grains when the silver halide grains are cubic or octahedral so-called normal crystals. Further, when the silver halide grains are tabular grains, it means the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other non-normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it means the diameter when considering a sphere equivalent to the volume of silver halide grains.

The image forming layer of the heat-developable image recording material of the present invention usually contains 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 higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated above. The organic silver salt may be any organic substance containing a source capable of reducing silver ions. Silver salts of organic acids, especially (having 10 to 30, preferably 15 to 30 carbon atoms)
Silver salts of long-chain fatty carboxylic acids (of 28) are preferred. Also preferred are complexes of organic or inorganic silver salts in which the ligand has a complex stability constant in the range 4.0 to 10.0. The silver-providing substance can preferably constitute about 5 to 70% by mass of the image forming 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, and fumarate. Included are silver citrate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, it is preferable to use organic acid silver having a silver behenate content of 75 mol% or more, and more preferably 85 mol% or more, among the above-mentioned organic acid silver or a mixture of organic acid silver. Here, the silver behenate content 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 listed above can be preferably used. The organic acid silver salt preferably used in the present invention is prepared by reacting a solution or suspension of the above-described organic acid alkali metal salt (including Na salt, K salt, Li salt, etc.) with silver nitrate. . As a method for preparing these, 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 acid silver salt can be preferably used by adding an aqueous silver nitrate solution and an organic acid alkali metal salt solution into a means for mixing a sealed liquid. The method described in Japanese Patent Application No. 11-203413 can be used for the preparation of these. In the present invention, a water-soluble dispersant can be added to the silver nitrate aqueous solution and the organic acid alkali metal salt solution used during the preparation of the organic silver salt, or the reaction solution. Specific examples of the type and amount of the dispersant used are described in Japanese Patent Application No. 11-115457, paragraph [0052].

The organic silver salt used in the present invention is preferably prepared in the presence of a tertiary alcohol. The tertiary alcohol preferably has 15 or less total carbon atoms, and particularly preferably 10 or less. Examples of preferable tertiary alcohols include tert-butanol and the like, but the present invention is not limited thereto. The third alcohol used in the present invention may be added at any time during the preparation of the organic acid silver salt, but it is preferably added during the preparation of the organic acid alkali metal salt and used by dissolving the organic acid alkali metal salt. . The amount of the tertiary alcohol used is 0.01 to 0.01 by mass ratio with respect to water as a solvent when preparing the organic acid silver salt.
It can be arbitrarily used in the range of 10, but 0.03
The range of -1 is preferable.

The shape and size of the organic silver salt that can be used in the present invention are not particularly limited, but Japanese Patent Application No. 11-1041.
Those described in paragraph No. [0024] of the No. 87 specification can be used. The shape of the organic silver salt can be measured by a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of obtaining the standard deviation of the volume weighted average diameter of the organic silver salt, and the percentage (variation coefficient) of the value divided by the volume weighted average diameter is preferably 80% or less, It is preferably 50% or less, more preferably 30% or less. As a measuring method, for example, the particle size (volume-weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with laser light and obtaining an autocorrelation function with respect to the time change of the fluctuation of scattered light You can A solid fine particle dispersion having an average particle size of 0.05 to 10.0 μm in this measuring method is preferable. More preferably, the average particle size is 0.1 to 5.0.
μm, more preferably average particle size 0.1 to 2.0 μm
m.

The organic silver salt that can be used in the present invention is
Preferably desalting can be carried out. The desalting method is not particularly limited, and a known method can be used, but 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
The method described in the specification of 15457 can be used. In the present invention, for the purpose of obtaining a solid dispersion of an organic silver salt having a high S / N, a small particle size and no aggregation, the organic silver salt as an image forming medium is contained and the photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which a non-aqueous dispersion liquid is converted into a high-speed flow and then the pressure is dropped. As the dispersing method, the methods described in Japanese Patent Application No. 11-104187, paragraphs [0027] to [0038] can be used.

The particle size (volume-weighted average diameter) of the organic silver salt solid fine particle dispersion is determined, for example, by irradiating the solid fine particle dispersion dispersed in a liquid with a laser beam, and the autocorrelation function with respect to the time change of the fluctuation of the scattered light. Can be determined from the particle size (volume-weighted average diameter) and transmission electron microscope image obtained by determining Average particle size 0.0
A solid fine particle dispersion of 5 to 10.0 μm is preferable. The average particle size is more preferably 0.1 to 5.0 μm, still more preferably the average particle size is 0.1 to 2.0 μm. The particle size distribution of the organic silver salt solid fine particle dispersion is preferably monodisperse. Specifically, the percentage (variation coefficient) of the value obtained by dividing the standard deviation of the volume-loaded average diameter by the volume-loaded average diameter is 80% or less, more preferably 50% or less, and further 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 of the organic silver salt and water is not particularly limited, but the ratio of the organic silver salt in 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 dispersion aid, but it is preferable to use the minimum amount within a range suitable for minimizing the grain size, and 0.5 to 30% by mass, particularly 1 to 30% by mass based on the organic silver salt.
The range of 15 mass% is preferable. In the present invention, the organic silver salt can be used in a desired amount, but the silver amount is 0.1 to 5 g /
m ² is preferable, 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, specifically, a nitrate or a sulfuric acid. It is preferably added in the form of salt or the like. The addition of halide is the image storability due to the light (indoor light, sunlight, etc.) of the processed light-sensitive material,
The so-called print-out property is deteriorated, which is not preferable. Therefore, in the present invention, it is preferable to add in the form of a water-soluble metal salt that is not a halide. The timing of addition of the metal ion selected from Ca, Mg, Zn and Ag preferably used in the present invention is, after the formation of the particles of the non-photosensitive organic silver salt, immediately after the formation of the particles, before the dispersion, after the dispersion and before and after the preparation of the coating solution. It may be at any time up to immediately before coating, preferably after dispersion and before and after preparation of coating solution. The addition amount of the metal ion selected from Ca, Mg, Zn and Ag in the present invention is preferably 10 ^-3 to 10 ^-1 mol, and particularly 5 × 10 ^{-3 to} 5 per ¹ mol of the non-photosensitive organic silver.
× 10 ^-2 mol is preferable.

The heat-developable image recording material of the present invention preferably contains a photosensitive silver halide. The photosensitive silver halide used in the present invention is not particularly limited in halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide can be used. Regarding the grain formation of the photosensitive silver halide emulsion, the grain formation can be performed by the method described in paragraph Nos. [0217] to [0224] of JP-A No. 11-119374, but the method is not particularly limited to this method. Not something. Examples of the shape of silver halide grains include cubic, octahedral, tetradecahedral, tabular, spherical, rod-shaped, and potato-shaped grains, but in the present invention, cubic grains or tabular grains are particularly preferable. The characteristics of the particle shape such as the aspect ratio and surface index of the particles are the same as those described in paragraph No. [0225] of JP-A No. 11-119374. The distribution of the halogen composition may be uniform inside and on the surface of the silver halide grain, the halogen composition may be changed stepwise, or may be continuously changed. 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-fold structure, more preferably a 2- to 4-fold structure, can be used. Further, a technique of localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

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

Photosensitive silver halide grains used in the present invention
Is a metal of Group VII or VIII of the Periodic Table
Alternatively, it contains a metal complex. There is Group VII of the Periodic Table
Or a central metal of a Group VIII metal or metal complex
Preferably rhodium, rhenium, ruthenium, osni
Um and iridium. A particularly preferred metal complex is
(NH_Four)₃Rh (H₂O) Cl_Five, K₂Ru (NO) C
l_Five, K₃IrCl₆, K_FourFe (CN)₆Is. these
The metal complex may be of one kind, or of the same kind of metal or different kind of metal.
You may use 2 or more types of complexes together. Preferred content is silver 1
1 x 10 for mol ^-9mol ~ 1 x 10^-3range of mol
Surrounding is preferable, 1 × 10^-8mol ~ 1 x 10^-Fourmol
A range is more preferable. Specific metal complex structure
Gold having a structure described in JP-A-7-225449
A genus complex can be used. Types of these heavy metals,
Regarding the addition method, see Japanese Patent Laid-Open No. 11-119374.
Paragraph numbers [0227] to [0240]
It

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

The gelatin contained in the photosensitive silver halide used in the present invention is contained in order to maintain a good dispersion state of the photosensitive silver halide emulsion in the organic silver salt-containing coating solution.
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 during grain formation or dispersion after desalting treatment, but are preferably used during dispersion after desalting treatment. Ordinary gelatin (molecular weight of about 100,000) may be used at the time of grain formation, and low molecular weight gelatin may be used at the time of dispersion after desalting treatment.
The concentration of the dispersion medium may be 0.05 to 20% by mass, but a concentration range of 5 to 15% by mass is preferable in terms of handling. Alkali-treated gelatin is usually used as the type of gelatin, but modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

The silver halide emulsion used in the heat-developable image recording material of the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, and those having crystal habits). Different ones, different chemical sensitization conditions) may be used together. The amount of the photosensitive silver halide used is preferably 0.01 mol to 0.5 mol, and 0.02 to 1 mol of the organic silver salt.
mol-0.3 mol is more preferable, 0.03 mol
~ 0.25 mol is particularly preferred. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide grains and organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer. Method of mixing with etc.,
Alternatively, there is 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, but it is not particularly limited as long as the effect of the present invention is sufficiently exhibited. There is no. Further, mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions at the time of mixing is a method preferably used for controlling photographic characteristics.

The sensitizing dye applicable to the present invention is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for spectral characteristics of an exposure light source. The sensitizing dye having can be advantageously selected. For example, as a dye that spectrally sensitizes a wavelength region of 550 to 750 nm, there is disclosed in Japanese Patent Laid-Open No. 10-186572.
The dyes represented by the general formula (II) can be mentioned, and specifically, II-6, II-7, II-14, II-15,
II-18, II-23, and II-25 dyes. Examples of dyes that spectrally sensitize the wavelength region of 750 to 1400 nm include dyes represented by the general formula (I) of JP-A No. 11-119374, and specifically (2
5), (26), (30), (32), (36), (3
7), (41), (49), and (54). Further, as a dye forming J-band, US Pat. No. 5,510,236 and U.S. Pat. No. 3,871,887 are cited.
Dye described in Example 5 of JP-A-2-9613.
Examples thereof include dyes disclosed in JP-A No. 1 and JP-A-59-48753. These sensitizing dyes may be used alone or in combination of two or more. The addition of these sensitizing dyes can be carried out by the method described in paragraph No. [0106] of JP-A No. 11-119374, but it is not particularly limited to this method. The addition amount of the sensitizing dye in the present invention,
The desired amount may be selected depending on the sensitivity and fog performance, but it is preferably 10 ^-6 to ¹ mol, and more preferably 10 ^-4 to 10 ^-1 mol per mol of silver halide in the photosensitive layer.

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

A particularly preferred supersensitizer is disclosed in JP-A-5-3.
Heteroaromatic mercapto compounds and heteroaromatic disulfide compounds disclosed in Japanese Patent No. 41432/1992.
Compounds represented by the general formula (I) or (II) of 182639 gazette, stilbene compound represented by the general formula (I) of JP-A-10-111543, JP-A-11-
It is a compound represented by the general formula (I) in Japanese Patent Publication No. 109547. Specifically, M- in JP-A-5-341432
Compounds 1 to M-24, compounds d-1) to d-14) in JP-A-4-182639, JP-A-10-111
Compounds SS-01 to SS-07 in JP-A No. 543, 31, 32, 37, 3 in JP-A No. 11-109547.
8, 41-45, 51-53. The amount of these supersensitizers added is 1 in the emulsion layer.
The range is preferably from 10 ^{−4 to} 1 mol per mol, and more preferably 0.001 per mol of silver halide.
~ 0.3 mol.

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 preferable nucleating agents are shown below. Hydrazine derivatives represented by the formula (H) described in JP-A-2000-284399, specifically the hydrazine derivatives described in Tables 1 to 4 of the same specification. JP-A-10-10672, JP-A-10-161270, JP-A-10-62898, JP-A-9-30
No. 4870, No. 9-304872, No. 9-304871, No. 10-31282, US Pat. No. 5,496,695, European Patent No. 741,320A. All hydrazine derivatives mentioned. Substituted alkene derivatives represented by formulas (1) to (3), substituted isoxazole derivatives and specific acetal compounds described in JP-A-2000-284399, more preferably formula (A) or A cyclic compound represented by the formula (B), specifically, Compounds 1 to 72 described in Chemical formulas 8 to 12 of the same specification. Also, a plurality of these nucleating agents may be used in combination.

The nucleating agent is water or a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used after dissolving. Further, by well-known emulsification and dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone. However, an emulsified dispersion can be mechanically prepared and used. Alternatively, the 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 then used.

The nucleating agent may be added to the image forming layer on the side of the image forming layer with respect to the support or any other layer.
It is preferably added to the image forming layer or a layer adjacent thereto. Addition amount of nucleating agent is 1 × 1 for 1 mol of silver
0 ^{-6 to} 1 mol is preferable, 1 x 10 ^{-5 to} 5 x 10 ^-1 m
is more preferable, and 2 × 10 ⁻⁵ to 2 × 10 ⁻¹ mol is most preferable.

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

In the present invention, in order to form a super-high contrast image, a contrast enhancing agent may be used in combination with the nucleating agent. For example, amine compounds described in US Pat. No. 5,545,505, specifically AM-1 to AM-5,
Hydroxamic acids described in US Pat. No. 5,545,507, specifically HA-1 to HA-11, acrylonitriles described in US 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.
Onium salts described in Japanese Patent No. 368, specifically A-
1 to A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

In a heat-developable image recording material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, formic acid or formic acid salt is a strong fogging substance. In the present invention, the content of formic acid or formate on the side of the heat-developable image recording material having the image forming layer containing photosensitive silver halide is 5 mmol or less, and further 1 mmo per mol of silver.
It is preferably 1 or less.

In the heat-developable image recording material of the present invention, it is preferable to use an acid formed by hydration of diphosphorus pentoxide or a salt thereof together with a nucleating agent. Examples of the acid formed by hydration of diphosphorus pentoxide or a salt thereof include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt) and hexametaline. Examples include acids (salts). Particularly preferably used acids formed by hydration of diphosphorus pentaoxide or salts thereof are orthophosphoric acid (salt) and hexametaphosphoric acid (salt), and 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 to the image forming layer from the viewpoint of exhibiting a desired effect in a small amount. The amount of the acid formed by hydration of diphosphorus pentoxide or a salt thereof (application amount per 1 m ^{2 of the} heat-developable image recording material) may be a desired amount according to the performance such as sensitivity and fog, but is 1-5
00 mg / m ² is preferable, and 0.5 to 100 mg / m ² is more preferable.

The heat-developable image recording material of the present invention preferably contains a reducing agent for the 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 5 to 5 with respect to 1 mol of silver on the surface having the image forming layer.
The content is preferably 0 mol, more preferably 10 to 40 mol. The reducing agent-containing layer may be any layer on the side having the image forming layer. When added to a layer other than the image forming layer, it is 10 to 50 with respect to 1 mol of silver.
It is preferable to use a large amount of mol. Further, the reducing agent may be a so-called precursor that is derivatized so as to have an effective function only during development.

In the heat-developable image recording material utilizing 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. , Ibid. 49-115540
No. 50-14334, No. 50-3611.
No. 0, No. 50-147711, No. 51-32
No. 632, No. 51-1023721, No. 51
No. 32324, No. 51-51933, and No. 5
No. 2-84727, No. 55-108654,
No. 56-146133, No. 57-82828, No. 57-82829, JP-A-6-3793, U.S. Pat. No. 3,679,426, and Nos. 3,751,252. Calligraphy, No. 3,751,255
No. 3,761,270, No. 3,3
782,949, 3,839,048, 3,928,686, 5,46
4, 738, German Patent 2,321,328, European Patent 692,732 and the like. For example, amidoximes such as phenylamidoxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2'-bis (hydroxymethyl) propionyl. A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid such as a combination of -β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (e.g. hydroquinone and bis (ethoxy). Ethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine combination); phenylhydroxamic acid, p
Hydroxamic acids such as hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; Combinations of azines with sulfonamide phenols (eg phenothiazine and 2,6-dichloro-4-benzenesulfonamidephenol); ethyl-α-cyano 2-Methylphenylacetate, α-cyanophenylacetic acid derivatives such as 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, etc.); 3
5-methyl-1-phenyl-5-pyrazolone, such as 5-
Pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and reductone as exemplified by anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4-benzenesulfonamidephenol and p- Sulfonamide phenol reducing agents such as benzenesulfonamide phenol; 2-phenylindane-1,3-dione and the like; Chroman such as 2,2-dimethyl-7-tert-butyl-6-hydroxychroman; 2,6-dimethoxy- 1,4-dihydropyridines such as 3,5-dicarboethoxy-1,4-dihydropyridine; bisphenols (eg bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 2,2-bis ( 4-
Hydroxy-3-methylphenyl) propane, 4,4-
Ethylidene-bis (2-tert-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); ascorbic acid derivatives (eg 1-ascorbyl palmitate, stearic acid) Ascorbyl); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones; chromanols (such as tocopherols). Particularly preferred reducing agents are bisphenol and chromanol.

When the reducing agent is used in the present invention, it may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion and an emulsion dispersion. Dispersion of solid fine particles is performed by a known refining means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). Further, a dispersion aid may be used when dispersing the solid fine particles.

In the present invention, as the development accelerator, Japanese Patent Application No.
A phenol derivative represented by the formula (A) described in JP-A-73951 is preferably used. The phenol derivative represented by the formula (A) exhibits a strong development promoting effect when used in combination with the 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 0.01 m with respect to the reducing agent.
It is preferably used in the range of ol% to 100 mol%, and more preferably in the range of 0.1 to 20 mol%.

The phenol derivative represented by the formula (A) may be added to the layer on the image forming layer side of the support, that is, the image forming layer or any other layer on this layer side. It is preferably added to the contained layer. The phenol derivative represented by the formula (A) may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion, or an emulsion dispersion. The solid fine particles are dispersed by a known refining means (for example, ball mill, vibrating ball mill, sand mill,
Colloid mill, jet mill, roller mill, etc.). Further, a dispersion aid may be used when dispersing the solid fine particles.

Inclusion of additives known as "toning agents" for improving the image may increase the optical density. Further, the toning agent may be advantageous in forming a black silver image. Toning agent is 1 m silver on the side with the image forming layer
The amount is preferably 0.1 to 50 mol, and more preferably 0.5 to 20 mol per ol. Further, the toning agent may be a so-called precursor which is derivatized so as to have an effective function only during development.
In a heat-developable image recording material using an organic silver salt, a wide range of color tones are disclosed in JP-A-46-6077 and JP-A-47-1.
No. 0282, No. 49-5019, No. 49-5.
020, 49-91215 and 49-9.
No. 1215, No. 50-2524, No. 50-3.
No. 2927, No. 50-67132, No. 50-67132
No. 67641, No. 50-114217, No. 5
No. 1-3223, No. 51-27923, and No. 5
No. 2-14788, No. 52-99813, No. 53-1020, No. 53-76020, No. 54-156524, No. 54-156525, No. 61-183642. 4-5684
No. 8, Japanese Patent Publication No. 49-10727, No. 54-2.
0333, U.S. Pat. No. 3,080,254, No. 3,446,648, and No. 3,78.
No. 2,941, No. 4,123,282, No. 4,510,236, British Patent No. 1,
380,795, Belgian Patent No. 841,91
No. 0 specification 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 such as; naphthalimide (eg N-hydroxy-1,8-naphthalimide); cobalt complex (eg cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4 -Mercaptans exemplified by dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldi 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 a 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 (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetra A phthalazine, a phthalazine derivative (eg, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-isobutylphthalazine, 6-t).
derivatives such as ert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-dihydrophthalazine)
Or a metal salt; phthalazine and a derivative thereof and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid,
4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; function not only as a color-modifying agent but also as a source of halide ions for in situ silver halide formation Rhodium complexes such as ammonium hexachlororhodium (III), rhodium bromide, rhodium nitrate and hexachlororhodium (II
I) Potassium acid and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide;
Benzoxazines such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione -2,4-dione; pyrimidine and asymmetric-triazine (for example, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine and the like), azauracil, and tetraazapentalene derivative (for example, 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
6a-tetraazapentalene) and the like.

As the color toning agent used in the present invention, there is disclosed in Japanese Patent Application Laid-Open No. 20
The 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 the toning agent is used in the present invention, it may be added by any method such as solution, powder and solid fine particle dispersion. Solid fine particle dispersion can be achieved by a known refining means (for example, ball mill, vibrating ball mill, sand mill, colloid mill,
Jet mill, roller mill, etc.). Also,
A dispersion aid may be used when dispersing the solid fine particles.

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. From the viewpoint of reducing the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia for adjusting the film surface pH. Ammonia is particularly volatile so that it can be removed before the coating step or heat development, which is preferable for achieving a low film surface pH. The method for measuring the film surface pH is described in paragraph No. [0123] of JP-A No. 2000-284399.

In the heat-developable image recording material of the present invention, the silver halide emulsion and / or the organic silver salt is further protected against the formation of additional fog by the antifoggant, the stabilizer and the stabilizer precursor. In addition, it is possible to stabilize against a decrease in sensitivity during stock storage. Suitable antifoggants, stabilizers and stabilizer precursors which may be used alone or in combination are described in US Pat. No. 2,131,0.
Thiazonium salts described in US Pat. No. 38 and 2,694,716, US Pat. No. 2,886,437.
And Azaindene described in U.S. Pat. No. 2,444,605, mercury salts described in U.S. Pat. No. 2,728,663, and U.S. Pat. No. 3,287,135. Urazol, US Pat. No. 3,235,65
2, sulfocatechol, British Patent No. 62
Oxime, nitrone, nitroindazole described in US Pat. No. 3,448, polyvalent metal salts described in US Pat. No. 2,839,405, US Pat. No. 3,220,839.
Salts described in U.S. Pat. No. 2,566,263 and U.S. Pat. Nos. 2,566,263 and 2,597,9.
Palladium, platinum and gold salts described in No. 15, U.S. Pat. Nos. 4,108,665 and 4,4.
42,202, halogen-substituted organic compounds, U.S. Pat. Nos. 4,128,557 and 4,137,079, 4,138,365, and 4 , 459,350 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 sensitivity and preventing fog. The benzoic acid used in the present invention may be any benzoic acid derivative, but examples of preferable structures include US Pat. Nos. 4,784,939 and 4,152,160.
Specification, JP-A-9-329863, and JP-A-9-32.
The compounds described in 9864, 9-281637 and the like can be mentioned. The benzoic acid may be added to any layer of the heat-developable image recording material, but it is preferably added to the layer having the image forming layer, and more preferably to the organic silver salt-containing layer. The benzoic acid may be added at any step of the coating solution preparation, and when it is added to the organic silver salt-containing layer, it may be any step from the preparation of the organic silver salt to the preparation of the coating solution, but after the preparation of the organic silver salt. Therefore, immediately before coating is preferable. The benzoic acid may be added by any method such as powder, solution and fine particle dispersion. Also, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a toning agent. Any amount of benzoic acid may be added, but it is 1 per 1 mol of silver.
× 10 ⁻⁶ mol to 2 mol is preferable, and 1 × 10 ⁻³ mo is preferred.
1 to 0.5 mol is more preferable.

Although not essential to the practice of the invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the imaging layer. Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The addition amount of mercury used in the present invention is 1 mol of coated silver.
Preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mo per liter
1, more preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ m
It is in the range of ol.

The antifoggant which is particularly preferably used in the present invention is an organic halide, for example, JP-A-50-
No. 119624, No. 50-120328, No. 51-121332, No. 54-58022, No. 56-70543, No. 56-99335, No. 59-90842, No. 61-12964.
No. 2, JP-A No. 62-129845 and JP-A No. 6-2.
No. 08191, No. 7-5621, No. 7-27
No. 81, No. 8-15809, US Pat. No. 5,
Compounds such as those disclosed in 340,712, 5,369,000 and 5,464,737 are mentioned. JP 2000-2843
A hydrophilic organic halide represented by the formula (P) described in JP-A-99 is preferably used as an antifoggant. Specifically, (P-1) to (P-11) described in the same specification.
8) is preferably used. The addition amount of the organic halide is a mol amount (mol / molA per 1 mol of Ag).
g), preferably 1 × 10 ^{−5 to 2} mol / mo
lAg, more preferably 5 × 10 ^{−5 to} 1 mol / mol
Ag, more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol
/ MolAg. These may be used alone or in combination of two or more.

A salicylic acid derivative represented by the formula (Z) described in JP-A-2000-284399 is preferably used as an antifoggant. Specifically, (A-1) to (A-60) described in the specification are preferably used. The addition amount of the salicylic acid derivative represented by the formula (Z) is a mol amount (mol / molA per 1 mol of Ag).
g), preferably 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mo
1 / molAg, more preferably 5 × 10 ⁻⁵ to 1 × 10
^-1 mol / mol Ag, more preferably 1 x 10 ^-4 ~
It is 5 × 10 ^-2 mol / mol Ag. These may be used alone or in combination of two or more.

As an antifoggant preferably used in the present invention, formalin scavenger is effective. For example, the formula (S) described in Japanese Patent Application No. 11-23995 is used.
And the exemplified compounds (S-1) represented by
(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, etc. It can be dissolved in and used. In addition, by the well-known emulsion 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 dissolved to mechanically prepare an emulsified dispersion for use. Alternatively, by a method known as a solid dispersion method, the powder is ball milled in water, a colloid mill, a sand grinder mill, a manton-goulin,
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 of the support, that is, the image forming layer or any other layer on this layer side. It is preferably added to the layer adjacent thereto.
The image forming layer is a layer containing a reducible silver salt (organic silver salt), and 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 for the purpose of suppressing or accelerating the development and controlling the development, and improving the preservability before and after the development. . When the mercapto compound is used in the present invention, it may have any structure, but Ar-SM, Ar-SS-
Those represented by Ar are preferable. In the formula, M is a hydrogen atom or an alkali metal atom, Ar is at least one nitrogen,
An aromatic ring or condensed aromatic ring having a sulfur, oxygen, selenium or tellurium atom. Preferably, the heteroaromatic ring is benzimidazole, nafusuimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine. , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring may be, for example, halogen (eg Br and Cl), hydroxy, amino, carboxy, alkyl (eg having 1 or more carbon atoms, preferably 1 to 4 carbon atoms), alkoxy ( For example, having one or more carbon atoms, preferably having 1 to 4 carbon atoms) and aryl (which may have a substituent) selected from the group of substituents. Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis- (benzothiazole), 3-mercapto-1,2,
4-triazole, 4,5-diphenyl-2-imidazolthiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-
4 (3H) -quinazolinone, 7-trifluoromethyl-
4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4 -Thiadiazole, 3
-Amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 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-
Examples thereof include N ′-{3- (5-mercaptotetrazolyl) phenyl} urea and 2-mercapto-4-phenyloxazole, but are not limited thereto. The addition amount of these mercapto compounds is preferably in the range of 0.0001 to 1.0 mol per 1 mol of silver in the image forming layer, more preferably 0.0 to 1 mol per 1 mol of silver.
The amount is from 01 to 0.3 mol.

The image forming layer in the present invention is preferably prepared by applying an aqueous coating solution and then drying it. 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.

In the present invention, the image forming layer, the protective layer for the image forming layer, the undercoat layer and the back layer are described in JP-A No. 11-845.
No. 73, paragraph numbers [0204] to [0208], and Japanese Patent Application No. 11-106881 paragraph number [024
[0] to [0241], a dye may 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. Any dyes and pigments may be used in the image forming layer. For example, the compounds described in paragraph No. [0297] of JP-A No. 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, or a state of being mordanted with a polymer mordant may be used. The amount of these compounds used is determined depending on the desired absorption amount, but it is generally preferable to use it in the range of 1 × 10 ⁻⁶ g to 1 g per 1 m ² .

When the antihalation dye is used in the present invention, the dye has a desired absorption in a desired range, has a sufficiently small absorption in the visible region after the treatment, and has a preferable absorbance spectrum shape of the back layer. Any compound may be used as long as it is possible. For example, the compounds described in paragraph No. [0300] of JP-A No. 11-119374 can be used. Further, as described in Belgian Patent No. 733,706, a method of decreasing the density by a dye by heat erasing, and the density is decreased by light erasing as described in JP-A-54-17833. It is possible to use such a method.

When the heat-developable image recording material of the present invention is used as a mask after the heat development for producing a printing plate with a PS plate, the heat-developable image recording material after the heat development is applied to the PS plate in a plate making machine. Information for setting exposure conditions and information for setting plate-making conditions such as transport conditions for mask originals and PS plates are carried as image information. Therefore, the concentration (use amount) of the above-mentioned irradiation dye, halation dye, and filter dye is limited to read them. Since this information is read by the LED or laser, the 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, Fuji Photo Film Co., Ltd.'s plate-making machine S-FNRIII uses a light source with a wavelength of 670 nm as a detector and a barcode reader for register mark detection. Also, as a bar code reader for the plate making machine APML series manufactured by Shimizu Seisakusho 670n
m light source is used. That is, D near 670 nm
If the min (minimum density) is high, the information on the film cannot be accurately detected, and an operation error occurs in the plate making machine such as conveyance failure or exposure failure. Therefore, in order to read information with a light source of 670 nm, Dmin near 670 nm needs to be low, and the absorbance at 660 to 680 nm after thermal development is 0.
Must be 3 or less. It is more preferably 0.25 or less. The lower limit is not particularly limited, but is usually 0.10.
It is a degree.

In the present invention, the exposure device used for imagewise exposure may be any device as long as it can perform exposure with an exposure time of less than 10 ⁻⁷ seconds, but in general, Laser Diode (L
An exposure apparatus that uses D) or Light Emitting Diode (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 having an electromagnetic wave spectrum in a target wavelength range. For example, as the LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

In the exposure, the light beams of the light source are overlapped and exposed, and the overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient) when the beam diameter is expressed by the full width at half maximum (FWHM) of the beam intensity. In the present invention, this 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 flat surface scanning method or the like can be used. Also, the channel of the light source may be single channel or multi-channel,
In the case of the cylindrical outer surface type, multi-channel is preferably used.

The heat-developable image recording material of the present invention has a low haze upon exposure and tends to cause interference fringes. Examples of the technology for preventing the generation of interference fringes include a technology disclosed in Japanese Patent Laid-Open No. 5-113548 and the like in which laser light is obliquely incident on a heat-developable image recording material, and International Publication WO9.
Methods using a multimode laser disclosed in, for example, Japanese Patent Publication No. 5/31754 are 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, but usually, the heat development image recording material exposed imagewise is heated to be developed. As a preferred embodiment of the heat developing machine used, as a type in which the heat developing image recording material is brought into contact with a heat source such as a heat roller or a heat drum, JP-B-5-56499, JP-A-9-292695, and JP-A-9- 297385 gazette and international publication WO
As a non-contact type thermal developing machine described in Japanese Patent Laid-Open No. 95/30934, Japanese Patent Laid-Open No. 13294/1995, International Publication W
There are thermal developing machines described in O97 / 28489, 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type heat developing machine. The preferred developing temperature is 80 to 250 ° C.,
More preferably, it is 100-140 degreeC. The developing time is preferably 1 to 180 seconds, more preferably 10 to 90 seconds.

As a method for preventing uneven processing due to dimensional change during heat development of the heat-developable image recording material of the present invention,
A method (so-called multi-step heating method) in which an image is formed by heating at 110 to 140 ° C. after heating for 5 seconds or more so that an image does not appear at a temperature of less than 115 ° C. is effective. The heat-development treatment of the heat-developable image-recording material of the present invention is described in JP-A No. 20-1999
No. 00-171935, Japanese Patent Application No. 11-143058
The preheating described in Japanese Patent Application No. 11-196276 and the like is conveyed by a counter roller, and the heat development processing section drives the roller to drive the side having the image forming layer to the back surface on the opposite side. A heat development processing apparatus which slides on a smooth surface and conveys is preferably used. When the heat-developable image-recording material of the present invention is subjected to a heat-development treatment, it is exposed to a high temperature of 110 ° C. or higher, 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 on. These volatile components cause uneven development, corrode the components of the thermal processor, deposit in low temperature places to cause deformation of the screen as foreign matter, and adhere to the screen to cause stains. 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 optimally adjust the air flow in the heat developing machine. These can be effectively combined and used.

In International Publication Nos. WO95 / 30933, 97/21150, and Japanese Patent Publication No. 10-500946, there is disclosed a first opening having bound absorbent particles and a second opening for introducing volatile matter. The use of a filter cartridge having an opening of the above in a heating device for heating by contacting with a film is disclosed in International Publication WO96 / 12213.
In Japanese Patent Publication No. 10-507403, it is described to use a filter that is a combination of a heat conductive condensing collector and a gas absorbing fine particle filter. In the present invention, these can be preferably used. Further, in U.S. Pat. No. 4,518,845 and Japanese Patent Publication No. 3-54331, a device for removing vapor from a film, a pressure device for pressing the film against a heat transfer member, and a heat transfer member are heated. There is described a configuration having a device for
8/27458 describes removing from the film surface components that increase the fog that volatilizes from the film. These can also be preferably used in the present invention. The effects of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

[0102]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Materials, usage amount, ratio, and
The processing content, processing procedure, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Example 1><< Preparation of silver halide emulsion A >> 700 ml of water was treated with alkali-treated gelatin (calcium content was 2700 ppm).
11 g), potassium bromide 30 mg, and sodium 4-methylbenzenesulfonate (1.3 g) were dissolved to adjust the pH to 6.5 at a temperature of 40 ° C., and then silver nitrate 18.6.
159 ml of an aqueous solution containing 1 g of potassium bromide
L, (NH ₄ ) ₂ RhCl ₅ (H ₂ O) 5 × 10 ⁻⁶ mol
/ L and an aqueous solution containing K ₃ IrCl ₆ at 2 × 10 ⁻⁵ mol / L were added by the control double jet method over 6 minutes and 30 seconds while keeping pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / L of potassium bromide and 2 × 10 ⁻⁵ mol / L of K ₃ IrCl ₆ were added.
While maintaining the pAg at 7.7, the halogen salt aqueous solution containing the above was added by the control double jet method over 28 minutes and 30 seconds. After that, the pH was lowered to cause coagulation and sedimentation, desalting treatment, and 51.1 g of low-molecular weight gelatin having an average molecular weight of 15,000 (calcium content of 20 ppm or less) was added,
The pH was adjusted to 5.9 and pAg 8.0. The obtained particles have an average particle size of 0.08 μm, a projected area variation coefficient of 9%
It was a cubic grain having a (100) plane ratio of 90%.

The silver halide grains thus obtained were heated to 60 ° C., 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and after 3 minutes, 71 μmol of triethylthiourea was added, followed by ripening for 100 minutes and 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 5x10 ^-4 mol, compound A 0.17 g
After the addition, the temperature was lowered to 40 ° C. Then, the temperature was kept at 40 ° C., and 4.7 × 10 ⁻² for 1 mol of silver halide.
mol potassium bromide (added as an aqueous solution), 12.8
^{X10 -4} mol of the following sensitizing dye A (added as an ethanol solution) and 6.4 x 10 ^-3 mol of compound B (methanoe).
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.

[0105]

[Chemical 2]

<< Preparation of Silver Behenate Dispersion A >> Behenic acid (produced by Henkel, product name Edenor C22-85R)
87.6 kg, distilled water 423 L, 5 mol / L NaO
H aqueous solution 49.2L, tert-butyl alcohol 12
0 L was mixed and stirred at 75 ° C. for 1 hour for reaction to obtain a sodium behenate solution. Separately, 40.4 kg of silver nitrate
An aqueous solution of 206.2 L was prepared and kept at 10 ° C.
635 L of distilled water and 30 L of tert-butyl alcohol
The temperature of the reaction vessel containing the solvent was kept at 30 ° C., and while stirring, the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution were added at a constant flow rate over 62 minutes, 10 seconds and 60 minutes, respectively. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the addition of the silver nitrate aqueous solution was started, and then the sodium behenate solution was started to be added. After the addition of the silver nitrate aqueous solution was completed, only the sodium behenate solution was added for 9 minutes and 30 seconds. To be added. At this time, the temperature in the reaction vessel is 30
The temperature was set to ℃ and the temperature was controlled so that the liquid temperature did not rise.
The piping of the sodium behenate solution addition system was kept warm by a steam trace, and the steam amount was controlled so that the liquid temperature at the outlet of the addition nozzle tip was 75 ° C. Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The position of addition of the sodium behenate solution and the position of addition of the aqueous silver nitrate solution were symmetrically arranged around the stirring axis, and the height was adjusted so as not to come into contact with the reaction solution. After the addition of the sodium behenate solution was completed, the mixture was left stirring at the same temperature for 20 minutes,
The temperature was lowered to 25 ° C. Then, the solid content was filtered off by suction filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. The solid content thus obtained was stored as a wet cake without being dried. The morphology of the obtained silver behenate particles was evaluated by an electron microscopic photography. As a result, the average projected area diameter was 0.52 μm and the average grain thickness was 0.14 μm.
m, a scaly crystal having a variation coefficient of 15% of the average equivalent spherical diameter.

Next, a silver behenate dispersion was prepared by the following method. Polyvinyl alcohol (trade name: PVA-21) for wet cake equivalent to 100 g of dry solids
7. Average polymerization degree: about 1700) (7.4 g) and water were added to adjust the total amount to 385 g, and then predispersed with a homomixer. Then, the pre-dispersed stock solution is dispersed by a disperser (manufactured by Microfluidex International Corporation, trade name: Microfluidizer-M-110S-
The pressure of EH, G10Z interaction chamber (using) was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain silver behenate dispersion A. For the cooling operation, a spiral heat exchanger was installed in front of and behind the interaction chamber, and the desired dispersion temperature was set by adjusting the temperature of the refrigerant. The silver behenate particles contained in the thus-obtained silver behenate dispersion A were particles having a volume weighted average diameter of 0.52 μm and a coefficient of variation of 15%. Particle size is measured by Malvern Instrum
ents Ltd. It was performed with a MasterSizer X manufactured by. Also, when evaluated by electron microscopic photography, the ratio of the long side to the short side is 1.5, the particle thickness is 0.14 μm, and the average aspect ratio (the ratio of the equivalent circle diameter of the projected area of the particle to the particle thickness) is 5.1. It was

<< Preparation of Solid Fine Particle Dispersion of Reducing Agent >> Reducing agent [1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane] 10k
g and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) in a 20% by mass aqueous solution 10 kg, water 1
6 kg was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump to have an average diameter of 0.
3 hours 30 using a horizontal sand mill (UVM-2, manufactured by IMEX Co., Ltd.) filled with 5 mm zirconia beads.
After partial dispersion, 4 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the thus obtained dispersion have a median diameter of 0.44.
The maximum particle size was 2.0 μm or less, and the average particle size variation coefficient was 19%. The obtained dispersion was stored by filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound A >> 10 kg of organic polyhalogen compound A [tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone] and modified polyvinyl alcohol -R (Kuraray Co., Ltd., Poval MP203)
20% by weight aqueous solution of 10 kg and 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate 639
g and Surfynol 104E (manufactured by Nisshin Chemical Co., Ltd.) 4
00 g, 640 g of methanol and 16 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump, dispersed for 5 hours in a horizontal sand mill (UVM-2, manufactured by Aimex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and water was added to the organic polyhalogen. The concentration of the compound A was adjusted 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 thus obtained dispersion 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 stored by filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound B >> 5 kg of the organic polyhalogen compound B [tribromomethylnaphthylsulfone] and modified polyvinyl alcohol (Kuraray Co., Ltd., POVAL MP203) 20
2.5% by weight aqueous solution and 213 g of 20% by weight aqueous solution of sodium triisopropylnaphthalene sulfonate
Then, 10 kg of water was added and mixed well to obtain a slurry. This slurry was sent by a diaphragm pump and dispersed for 5 hours in a horizontal sand mill (UVM-2 manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium. 2.5 g of salt and water were added to adjust the concentration of the organic polyhalogen compound B 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 thus-obtained dispersion had a median diameter of 0.38 μm, a maximum particle diameter of 2.0 μm or less, and an average particle diameter variation coefficient of 20%. The resulting dispersion has a pore size of 3.
Filter with a polypropylene filter of 0 μm,
Foreign substances such as dust were removed and stored.

<< Preparation of Solid Fine Particle Dispersion of Compound Z >> 3.5 kg of Sanko Co., Ltd. R-054 containing 85% by mass of Compound Z was added to M of Kuraray Co., Ltd. MP polymer.
1 kg of P-203 and 15 kg of water were added and mixed well to prepare a slurry. A horizontal sand mill (manufactured by AIMEX Co., Ltd., UVM) filled with zirconia beads having an average diameter of 0.5 mm is prepared by sending the slurry with a diaphragm pump.
-2), the mixture was dispersed for 7 hours, and then water was added to adjust the concentration of the compound Z to 10% by mass to obtain a solid fine particle dispersion of the compound Z. 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.
The coefficient of variation in particle diameter was 0 μm or less and 17%. The obtained dispersion was stored by filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust.

<< Preparation of Dispersion of 6-Isopropylphthalazine Compound >> Modified polyvinyl alcohol (Kuraray Co., Ltd., POVAL MP2, stirred at room temperature with 87.9 g of water).
03) 2.0 g was added so as not to form a lump, and mixed by stirring for 10 minutes. After that, the mixture was heated to raise the internal temperature to 50 ° C., and then stirred for 1 hour to dissolve uniformly. Inner temperature is 40 ° C
The temperature was lowered to the following, 3.0 g of a 20% aqueous solution of sodium tripropylnaphthalenesulfonate and 7.14 g of 6-isopropylphthalazine (70% aqueous solution) were added, and stirred for 30 minutes to obtain 100 g of a transparent dispersion liquid. The resulting dispersion is
Filtration was performed with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Solid Fine Particle Dispersion of Nucleating Agent A >> For 4 kg of the nucleating agent A, PVA-PVA-produced by Kuraray Co., Ltd.
1 kg of 217 and 36 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and filled with zirconia beads with an average diameter of 0.5 mm.
After being dispersed for 12 hours in 2), 4 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the nucleating agent to 10% by mass to obtain a solid fine particle dispersion of the nucleating agent. The particles of the nucleating agent contained in the thus obtained dispersion had a median diameter of 0.34 μm, a maximum particle diameter of 3.0 μm or less, and a coefficient of variation of particle diameter of 19%. The obtained dispersion was stored by filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust.

<< Preparation of Coating Solution for Image Forming Layer >> To 1 mol of silver of silver behenate dispersion A prepared above, the following binder, materials and silver halide emulsion A were added, and water was added. To obtain an image forming layer coating solution. After completion, vacuum degassing was performed at -350 mmHg for 60 minutes. The polymer latex concentration of the coating liquid was 10.3% by mass, and the pH at 25 ° C was 7.7.

Binder: SBR latex (manufactured by Dainippon Ink and Chemicals, Inc., Luckster-3307B; glass transition temperature 17 ° C.) 397 g as solid content 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-Trimethylhexane Solid content 149 g Organic polyhalogen compound A Solid content 43.5 g Organic polyhalogen compound B Solid content 13.5 g Sodium ethylthiosulfonate 0.30 g Benzotriazol 1.04 g Polyvinyl Alcohol (PVA-235, manufactured by Kuraray Co., Ltd.) 12.0 g 6-isopropylphthalazine as a solid content 12.8 g Sodium dihydrogen orthophosphate dihydrate 0.37 g Compound Z as a solid content 9.7 g Nucleating agent A 0.03 mol as solid content Dye A (average molecular weight Added as a mixed solution with 15,000 low molecular weight gelatin) Coating amount at which optical density at 783 nm becomes 0.3 (0.37 g as a standard) Silver halide emulsion A Ag amount 0.06 mol Compound C 2.0 g Preservative Compound A as an agent 40 ppm in the coating liquid (2.5 mg / m ² as the coating amount) 2% by mass as the total amount of solvent in the coating liquid of methanol 1% by mass as the total amount of solvent in the coating liquid as ethanol

[0116]

[Chemical 3]

<< Preparation of Coating Solution for Lower Protective Layer >> Polymer latex solution of butyl acrylate / methyl butyrate = 42/58 (mass%) (100 pp of compound A)
(containing m) was added to 203 g as a solid content, water was added as a solid content of compound E of 1.62 g, and polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) aqueous solution as a solid content of 29.4 g. In addition, water was further added to prepare a coating liquid (containing 2% by mass of methanol solvent). After completion, vacuum degassing was performed at -400 mmHg for 60 minutes. The polymer latex concentration of the coating liquid is 11% by mass,
The pH was 5.5.

<< Preparation of coating solution for upper protective layer >> Polymer latex solution of methyl acrylate / methyl methacrylate = 42/58 (mass%) (100 pp of compound A)
Water was added to 140 g as a solid content of carnava wax (Chukyo Yushi Co., Ltd., Cellosol 524:
(Silicon content is less than 5 ppm) 30% by mass solution 6.30 g, compound C 0.23 g, compound F 7.95
g, compound E 0.93 g, compound G 1.8 g, water dispersion of matting agent (polystyrene particles, average particle size 7 μm, coefficient of variation of average particle size 8%, dispersant: polystyrene particles 100 g
On the other hand, compound E 0.3 g, manufactured by Kuraray Co., Ltd., PVA-
235 (6.3 g) as a solid content of 1.18 g and polyvinyl alcohol (Kuraray Co., Ltd., PVA-23).
5) 12.1 g of the aqueous solution was added as a solid content, and water was further added to prepare a coating solution (containing 1.5% by mass of methanol solvent). After completion, vacuum degassing is -400 mmHg
For 60 minutes. The coating solution had a polymer latex concentration of 8% by mass and a pH of 2.2.

[0119]

[Chemical 4]

<< Preparation of polyethylene terephthalate (PET) support with back / undercoat layer >> (1) Preparation of PET support Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = A polyethylene terephthalate of 0.66 (measured at 25 ° C. in phenol / tetrachloroethane = 6/4 (mass ratio)) was obtained. This was pelletized, dried at 130 ° C for 4 hours, melted at 300 ° C and
After extruding from the die, it is cooled rapidly and the film thickness after heat setting is 12
An unstretched film having a thickness of 0 μm was produced.
Using this roll with different peripheral speed, longitudinally stretching 3.3 times,
Then, transverse stretching was carried out 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, after heat setting at 240 ° C. for 20 seconds, 4% relaxation was carried out in the lateral direction at the same temperature. After this, after slitting the chuck part of the tenter, both ends are knurled and 4.8 k
It was wound up at g / cm ² . Thus, the width 2.4
m, length 3500 m, thickness 120 μm roll-shaped PE
A T support was obtained.

(2) Support I with Undercoat Layer and Back Layer
Preparation (2-1) Undercoating first layer A coating solution having the composition shown below is coated on a support so as to have a thickness shown in Table 1, and the temperature is 125 ° C. for 30 seconds and 150 ° C. for 3 seconds.
It was dried at 0 seconds and 185 ° C. for 30 seconds. Latex-A 280 g Core / shell ratio = 90/10% by mass Core-shell type latex Mass average molecular weight 38000 Core part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93/3/3 / 0.9 / 0.1 (mass%) Shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (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 Total amount of 1000 g

(2-2) Undercoating second layer A coating solution having the composition shown below was applied onto the undercoating first layer so as to have a concentration of 5.5 ml / m ^2, and the coating was carried out at 125 ° C. for 30 seconds for 150 seconds.
It was dried at 30 ° C. for 30 seconds and at 170 ° C. for 30 seconds. 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 Total amount of water is 1000g

(2-3) Back First Layer 0.375 kV ·
A · min / m ² corona discharge treatment was applied, and a coating solution having the composition shown below was applied to the surface so as to be 13.8 ml / m ^2, and the temperature was 125 ° C. for 30 seconds and 150 ° C. for 30 seconds. It was dried at 30 ° C. for 30 seconds.

30% aqueous dispersion (Nippon Pure Chemicals Co., Ltd., Jurima-ET410) 23 g Alkali-treated gelatin (molecular weight about 10,000, Ca ²⁺ content 30 ppm) 4.44 g Deionized gelatin (Ca ²⁺ content 0. 6 ppm) 0.84 g Compound-Bc-A 0.02 g Dye-Bc-A (adjusted to have an optical density of 783 nm of 1.3 to 1.4) 0.88 g Polyoxyethylene phenyl ether 1 Water-soluble melamine compound (8% aqueous solution) (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 15 g Sb-doped SnO ₂ needle-shaped aqueous dispersion of particles (manufactured by Ishihara Sangyo Co., Ltd., FS-10D) 24 g Polystyrene fine particles (average particle size: 2 μm, coefficient of variation of average particle size: 7%) 0.03 g Distilled water Total amount of 1000 g

(2-4) Back Second Layer A coating solution having the composition shown below was coated on the back first layer so as to have a concentration of 5.5 ml / m ^2, and the temperature was 125 ° C. for 30 seconds and 150 ° C.
And dried at 170 ° C. for 30 seconds.

[0126]   57.5 g of 30% aqueous dispersion (Jurima-ET410, manufactured by Nippon Pure Chemical Co., Ltd.)   Polyoxyethylene phenyl ether 1.7 g   Water-soluble melamine compound (8% aqueous solution)   (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 15 g   6.6 g of a 30% aqueous solution (Chukyo Yushi Co., Ltd., Cellosol 524)   Total amount of distilled water is 1000g

(2-5) Back Third Layer The same coating solution as the undercoat first layer was applied on the back second layer so as to have the thickness shown in Table 1, and the temperature was set at 125 ° C. for 30 seconds for 15 seconds.
It was dried at 0 ° C. for 30 seconds and at 185 ° C. for 30 seconds.

(2-6) Back Fourth Layer A coating solution having the composition shown below was coated on the back third layer so as to have a concentration of 13.8 ml / m ^2, and the coating was carried out at 125 ° C. for 30 seconds for 150 seconds.
It was dried at 30 ° C. for 30 seconds and at 170 ° C. for 30 seconds. Latex (Chemical Pearl S120, manufactured by Mitsui Petrochemical Co., Ltd.) 77.22 g as solid content 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 Polymethylmethacrylate (10% water dispersion, average particle size 5 μm, coefficient of variation of average particles 7%) 7.7 g Total amount of distilled water 1000 g

[0129]

[Chemical 5]

(3) Support I with Undercoat Layer and Back Layer
Preparation of I (2-1) The undercoat first layer and the back third layer (2-5) were replaced with coating solutions having the following compositions so that the thickness was 0.5 μm at 6.2 ml / m ^2. And applied and dried at the same drying temperature. Styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (mass%) 90 g 2,4-dichloro-6-hydroxy-S-triazine 2.4 g Polystyrene (average particle size 2. 4μm) 0.1g Distilled water 1000g in total amount

(4) Heat Treatment for Transporting (4-1) Heat Treatment PE thus prepared and having a back / undercoat layer
The T support was placed in a heat treatment zone having a total length of 200 m and set at 160 ° C., and the T support was transported at a transport speed of 20 m / min under the tensions shown in Table 1. However, the support No. No heat treatment was performed on II-5. (4-2) Post-Heat Treatment Subsequent to the above heat treatment, the steel sheet was passed through a zone of 40 ° C. for 15 seconds to be post-heat treated and wound. The winding tension at this time was 10 kg / cm ² .

<Preparation of heat-developable image recording material> The figure in the specification of JP-A-2000-2964 is formed on the undercoat layer of the PET support on the side coated with the first undercoat layer and the second undercoat layer. The slide beat coating method disclosed in No. 1 is used to apply the above-mentioned image forming layer coating solution to a coating silver amount of 1.5 g / m 2.
² so that the lower protective layer coating solution has a solid content of polymer latex of 0.8 g / m ² and the upper protective layer coating solution has a solid content of polymer latex. The coating solution for the image forming layer and the lower and upper layers of the protective layer were simultaneously coated in multiple layers so that the coating amount was 1.0 g / m ² . The drying conditions at the time of application are such that 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, a wind speed on the support surface of 4 to 6 m / s, and a liquid film surface temperature of 40 ° C. The second drying zone (high speed air drying area) 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 is 1/3 of the constant rate drying period in this zone (20 to 25 seconds), and the zone is moved to the second drying zone.
Dried. The first drying zone is a horizontal drying zone (the support has an angle of 1.5 ° to 3 ° with respect to the horizontal direction of the coating machine). The coating speed was 60 m / min.

<Evaluation> (1) Evaluation of Wrinkle Generation after Thermal Development Using the thermal developing machine shown in FIG. 1, a sample of size 60 cm × 75 cm was thermally developed and visually evaluated by reflected light from the surface.

(2) Evaluation of dimensional change due to heat development processing Samples (size 5 cm × 25 c, which has been exposed to the entire surface, before processing)
m) with 200 mm intervals and 2 holes with a diameter of 8 mm.
Individually open, using a pin gauge with a precision of 1/1000 mm,
The distance between the two holes was measured accurately. The dimension at this time is X (unit: mm). Then, heat development is carried out by the heat developing machine shown in FIG. 1 installed in a room controlled to a constant temperature and humidity,
The dimension after 3 minutes from the discharge from the heat developing machine (the dimension after 3 minutes from the heat development treatment) was measured with a pin gauge. The dimension at this time is Y ₃ (unit: mm). After heat development
The dimension at the time of minute is measured with a pin gauge, and the dimension at this time is defined as Y _t . Thermal dimensional change rate of the development before and after _{H t (%) H t =} [(Y t -X) / X] × 100 The dimensional change rate T _t (%) due to the time value in the heat developing T _t = [( _{Y t -Y 3) / Y 3} ] was evaluated by the value of × 100.

(3) Thermal Developing Machine The thermal developing machine used for the thermal developing treatment of the thermal developing image recording material (sample) is shown in FIG. FIG. 1 is a side view of the heat developing machine. The heat developing machine of FIG. 1 straightens and preheats the heat-developable image recording material 10 into the heating section while carrying in the heat-developable image recording material 10 and the heat-developable image recording material 10 after the heat development. It has a carry-out roller pair 12 for carrying out from the heating part while straightening the sheet. The heat-developable image recording material 10 is heat-developed while being conveyed from the carry-in roller pair 11 to the carry-out roller pair 12. The transporting means for transporting the heat-developable image recording material 10 during the heat development is provided with a plurality of rollers 13 on the side where the surface having the image forming layer is in contact, and the aromatic on the side where the back surface on the opposite side is in contact. A smooth surface 14 to which a polyamide nonwoven fabric is attached is installed. The back surface of the heat-developable image recording material 10 slides on the smooth surface 14 and is conveyed by the driving of a plurality of rollers 13 in contact with the surface having the image forming layer. As the heating means, a heater 15 is installed above the roller 13 and below the smooth surface 14 so as to heat both sides of the heat-developable image recording material 10. A plate heater was used as the heating means. The clearance between the roller 13 and the smooth surface 14 varies depending on the smooth surface member,
The clearance is adjusted so that the heat-developable image recording material 10 can be conveyed. It is preferably -0.5 to +0.5 mm, but in this example, it was 0 mm.

The heating section is composed of a preheating section A having a carry-in roller pair 11 and a heat development processing section B having a heating heater 15. The preheating section A upstream of the heat development processing section B has the following features. Is lower than the heat development temperature (for example, 10 to 50).
The temperature was set to be about 0 ° C. lower) and higher than the glass transition temperature (Tg) of the support of the heat-developable image recording material 10 so as to prevent uneven development. Further, in the downstream of the heat development processing section B,
The guide plate 16 was installed, and the slow cooling part C having the pair of carry-out rollers 12 (the lower roller is a heat roller) and the guide plate 16 was installed. A material having a low thermal conductivity was used for the guide plate, and cooling was gradually performed.

(4) Thermal Development Conditions The thermal development conditions in this example using the thermal developing machine of FIG. 1 are as follows. (I) Preheating section A (temperature of heat roller when the carry-in roller pair 11 is set to (1) to (6) from the upstream side) (Ii) Heat development processing section B (temperatures of upper and lower plate heaters when the heater 15 is set to (1) to (3) from the upstream side) Heater 15; (1) Upper / lower part = 122 ° C./122 C. (2) Upper / lower part = 122 ° C./122° C. (3) Upper / lower part = 122 ° C./122° C. The non-woven fabric made of aromatic polyamide having a smooth surface 14 was a non-mex aramid fiber (manufactured by DuPont). (Iii) Cooling part C Delivery roller pair 12 (heat roller temperature) 112 ° C. Cooling rate 120 ° C./min (iv) Line speed 20 mm / sec Table 1 shows the evaluation results.

[0138]

[Table 1]

[0139]

According to the present invention, it has photographic properties especially for photoengraving, has sufficient mechanical strength and brittleness for handling, does not cause wrinkles during development, and has dimensional stability. Is excellent.

[Brief description of drawings]

FIG. 1 is a side view showing the configuration of a thermal developing machine used in Examples.

[Explanation of symbols]

10 Thermal development image recording material 11 carry-in roller 12 unloading roller 13 roller 14 smooth surface 15 heating heater 16 Guide plate A Preheating section B heat development processing section C Slow cooling unit

Claims (10)

[Claims] 1. A dimension Y ₃ at 3 minutes after cooling is started after heat-development of a heat-developable image recording material at a development temperature of 120 ° C. in an environment of 25 ° C. and relative humidity of 75%.
And a dimension Y ₂₄₀ after 240 minutes, a dimensional change rate T ₂₄₀ represented by the following formula is within a range of 0.00 to 0.03%. T ₂₄₀ = [(Y ₂₄₀ −Y ₃ ) / Y ₃ ] × 100 2. The dimensional change rate T ₂₄₀ is 0.00-0.
The heat-developable image recording material according to claim 1, wherein the content is in the range of 01%. _3. A dimension Y ₃ after 3 minutes have elapsed from the start of cooling after heat-development of the heat-developable image recording material at a development temperature of 120 ° C. in an environment of 25 ° C. and relative humidity of 75%.
When the dimension Y ₁₂₀ after 120 minutes has elapsed is measured, the dimensional change rate T ₁₂₀ represented by the following formula is within the range of 0.00 to 0.01%. The heat-developable image recording material described. T ₁₂₀ = [(Y ₁₂₀ −Y ₃ ) / Y ₃ ] × 100 4. A dimension after 240 minutes have elapsed from the start of cooling after heat-developing the heat-developable image recording material of dimension X at a developing temperature of 120 ° C. in an environment of 25 ° C. and 75% relative humidity. A thermally developable image recording material having a dimensional change rate H ₂₄₀ represented by the following formula within a range of 0.00 to 0.05% when Y ₂₄₀ is measured. H ₂₄₀ = [(Y ₂₄₀ −X) / X] × 100 5. A dimension when 120 minutes have elapsed from the start of cooling after heat-development processing of the heat-developable image recording material of dimension X at a development temperature of 120 ° C. in an environment of 25 ° C. and relative humidity of 75%. A heat-developable image recording material having a dimensional change rate H ₁₂₀ represented by the following formula within a range of 0.00 to 0.05% when Y ₁₂₀ is measured. H ₁₂₀ = [(Y ₁₂₀ −X) / X] × 100 6. A support having a coating layer containing a vinylidene chloride copolymer containing at least 70% by mass of a vinylidene chloride monomer repeating unit on both sides with a thickness of 0.5 μm or more on each side. Claim 1 characterized by
5. The heat-developable image recording material according to any of 5. 7. An image forming layer containing an organic silver salt, a reducing agent and a photosensitive silver halide on the support, and at least one protective layer provided on the image forming layer, Vinylidene chloride copolymer is 70 to 99.9% by mass and repeating unit of vinylidene chloride monomer is 0.1 to 5% by mass.
7. The heat-developable image recording material according to claim 6, which contains the repeating unit of the carboxyl group-containing monomer. 8. The support, after being coated with a coating layer containing the vinylidene chloride copolymer, has a thickness of 130 to 185.
The heat-developable image recording material according to claim 6 or 7, wherein the heat-developable image recording material is heat-treated at a temperature of ° C at a transport tension of 4 kg / cm ² or less. 9. The heat-treated support is heated at 120 ° C. for 30 seconds, and the thermal dimensional change rate after 3 minutes elapses in the longitudinal direction (M
D-direction is -0.03 to 0.01%, and is transverse (T
The heat-developable image recording material according to claim 8, which is 0.00 to 0.04% in the D direction. 10. A polymer latex is used as a binder for the image forming layer and the protective layer.
9. The heat-developable image recording material according to any of 9.