JP2003131341A - Heat developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable image recording material having an excellent traveling property particularly for photographic plate making. SOLUTION: In the heat developable image recording material having at least one layer of an image forming layer on one surface of a supporting body, the outermost layer in the opposite side of the supporting body to the image forming layer shows 10 mJ/m<2> to 70 mJ/m<2> surface energy after the heat developing treatment.

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 having excellent transportability in the steps after the heat-development treatment. The present invention also relates to a method of processing a heat developable image recording material.

[0002]

2. Description of the Related Art There are many known image recording materials having a photosensitive layer on a support and capable of forming an image by imagewise exposure. However, in recent years, the waste liquid associated with the wet processing of the image recording material has been regarded as a problem in terms of workability, and it has been strongly desired to reduce the amount of the processing waste liquid from the viewpoint of environmental protection and space saving. ing. Therefore, it is possible to efficiently expose with a laser scanner or laser imagesetter,
Attention has been paid to a technique relating to a heat-developable image recording material for photolithography which can form a clear black image having high resolution and sharpness. Since the heat-developable image recording material does not require the conventional development, fixing and washing with a solution-type processing chemical, it is possible to provide a heat-development processing system which 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. Klostabour (Klos
terboer) "Heat treated silver system (T
hermally Processed SilverSystems A ”(Imaging Processes & Materials)
Processes and Materials) Neblette 8th edition, J. Sturge, V.I. Walworth,
A. Edited by Shepp, Chapter 9, 279, 1
989). Such a photosensitive material is
It contains a reducible non-photosensitive silver source (eg organic silver salt), a catalytically active amount of photocatalyst (eg silver halide), and a reducing agent of silver, usually dispersed in an organic binder matrix. The photosensitive material is stable at room temperature, but when it is heated to a high temperature (for example, 80 ° C. or higher) after exposure, it undergoes a redox reaction between a reducible silver source (which functions as an oxidant) 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 provided a black image, which contrasts with the unexposed areas,
An image is formed. The heat-developable image recording material based on such a method is expected to be applied in various fields because it has the advantage that it is a monosheet and an image is formed only by heat treatment.

When the heat-developable image recording material is used for printing, it is usually heat-developed at 80 to 150 ° C. to form an image. However, when processed at such a development temperature,
A heat-developable image recording material using gelatin as a binder like a conventional photographic light-sensitive material has a large change in dimension due to shrinkage of gelatin. Therefore, by using a polymer binder that does not shrink due to heating as a binder in the heat-developable image recording material, dimensional changes during heat development are avoided.

On the other hand, when the heat-developable image recording material is used for printing, it is general to mechanically convey the heat-developable image recording material after the heat-development treatment. The modes of mechanical conveyance are roughly classified into (1) the case where the heat-developable image recording material is held and conveyed, and (2) the case where the heat-developable image recording material is attached to a transparent base serving as a guide and conveyed. The holding of the heat-developable image recording material of (1) includes holding by suction and holding by an adhesive tape. In the case of (2), generally, the back surface of the heat-developable image recording material is attached to the guide base with a double-sided tape, and the guide base is conveyed together. As described above, the heat-developable image recording material is often held and conveyed by utilizing the adhesive force of the tape. However, when the heat-developable image recording material having the layer using the polymer binder on the back surface is stuck to the tape as described above, there is a problem that the adhesive strength of the tape is lowered under high humidity and a conveyance failure occurs. . Therefore, there has been a demand for the provision of a heat-developable image recording material that does not cause transport problems.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a heat developable image recording material excellent in transportability, especially for photolithography.

[0007]

As a result of intensive studies, the present inventor has found that an excellent heat-developable image recording material can be provided by adjusting the surface energy of the outermost layer of the back surface. Reached That is, the present invention is
In a heat-developable image recording material having at least one image forming layer on one side of a support, the outermost layer on the side opposite to the image forming layer with respect to the support has a surface energy after the heat development of 10 mJ / m ² to. 70 mJ / m ² , preferably 20 mJ /
There is provided a heat-developable image recording material having a m ^{2 to} 50 mJ / m ² . Further, the present invention has at least one image forming layer on one surface of the support, and the thermal development carried by a tape adhered to the outermost layer on the opposite side of the support from the image forming layer. In the image recording material, there is also provided a heat developable image recording material characterized in that the difference between the surface energy of the outermost layer and the surface energy of the tape is 30 mJ / m ² or less.

In the heat-developable image recording material of the present invention, it is preferable that at least one layer constituting the surface of the support opposite to the image forming layer contains a hydrophobic cellulose derivative as a binder. The layer containing the hydrophobic cellulose derivative can be formed by applying a coating liquid containing 20% by mass or more of an organic solvent. In the heat-developable image recording material of the present invention, the Beck second on the surface opposite to the image forming layer with respect to the support is preferably 1500 seconds or less, and the outermost layer on the opposite side from the image forming layer with respect to the support. It is preferable to include a fluorine-based surfactant having a molecular weight of 500 or more as the coating aid. Further, in the heat-developable image recording material of the present invention, the image forming layer preferably contains an organic silver salt and a reducing agent, and 750
It is preferable to contain an antihalation dye having an absorption maximum at ˜850 nm. The heat-developable image recording material of the present invention is in the form of a sheet having a width of 550 to 650 mm and a length of 1 to 65 m, and a part or the whole thereof is wound around a cylindrical core member with the image forming layer on the outside. May be.

The present invention is characterized in that the above heat-developable image recording material having recorded information is exposed to light having a wavelength of 750 to 800 nm and the recorded information is read with light having a wavelength of 600 to 700 nm. A method of processing the image recording material is also provided. A method of heat-development of the above heat-developable image recording material with a heat-development machine having a heat-development section, wherein the heat-development section comprises a heating member for heating the heat-development image-recording material from both sides, There is also provided a method for treating a heat-developable image recording material, characterized in that a carrier roller is provided only on the surface of the support of the heat-developable image recording material having an image forming layer. Further, the above heat-developable image recording material is used in an amount of 20 to 200
There is also provided a method of treating a heat-developable image recording material, which comprises performing heat development at a speed of mm / sec.

In the present specification, the surface of the support on which the image forming layer is formed may be referred to as the image forming surface, and the opposite surface may be referred to as the back surface.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-developable image recording material and the method for treating the heat-developable image recording material of the present invention will be 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 is a heat developable image recording material having at least one image forming layer on one surface of a support. The characteristic is that the surface energy of the outermost layer of the back surface after the heat development treatment is 10 mJ / m ^{2 to} 70 mJ.
/ Is is the point at m ^2. The surface energy as used herein is a numerical value calculated by the Forks equation based on the contact angle measured with water and methylene iodide (reference: FM Fowkes; Ind.Eng.Chem.56 (12 ) 40 ~ 52 (196
Four)). The contact angle can be measured by directly projecting the shape of a small droplet on the measurement surface onto the screen, and measuring the droplet volume, height, bottom circle radius, etc. There are a method of obtaining it as a part of a sphere by calculation, and a method of measuring an inclination angle when the measurement surface is inclined from the vertical position so that the curved portion of the liquid surface in contact with the measurement surface becomes a horizontal plane.

High surface energy means that the surface
Means that it is more hydrophilic,
In this case, the adhesive strength of the tape is lowered. Development image of the present invention
The surface energy of the outermost layer on the back surface of the image recording material is 10 m.
J / m²~ 70 mJ / m²And is 20 mJ / m²~ 60
mJ / m²Is preferred, 20 mJ / m²~ 50mJ / m²
Is more preferable because the stability of transportability is further increased.

In order to improve the transportability of the heat-developable image recording material, the difference between the surface energy of the outermost layer on the back surface of the heat-developable image recording material and the surface energy of the adhesive of the tape attached to the heat-developable image recording material is also required. is important. Generally, the adhesiveness of the adhesive tape is changed depending on the purpose of use. Its stickiness is also reflected in the surface energy,
The surface energy of adhesive tape is 20m depending on its type
J / m ^{2 to} 40 mJ / m ² and various. Further, the surface energy of the tape slightly changes with time. In the present invention, it is preferable that difference between the surface energy of the surface energy and the heat developable image recording material of the tape is less than 30 mJ / m ^2, if 20 mJ / m ² or less, since further increases the stability of the transportability More preferable.

The binder to be used is generally selected as a means for adjusting the surface energy of the outermost layer on the back surface of the heat-developable image recording material. In order to lower the surface energy, it is most advantageous to use a hydrophobic polymer. However, it is possible to reduce the surface energy even when a hydrophilic high molecular polymer is used.

When the outermost layer on the back surface of the heat-developable image recording material is formed by using a coating solution dissolved in a solvent, 100 ° C.
It is preferable to use a transparent hydrophobic polymer that is soluble in an organic solvent having the following boiling point. Specific examples thereof include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, and polyurethane. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are preferably used. Among them, hydrophobic cellulose derivatives such as cellulose acetate and cellulose acetate butyrate are particularly useful. When the outermost layer of the back surface of the heat-developable image recording material of the present invention is formed by applying a coating solution containing hydrophobic cellulose, the coating solution may contain an organic solvent in an amount of 20% by mass or more.

When the outermost layer on the back surface of the heat-developable image recording material is formed using an aqueous coating solution, it is preferable to use a water-soluble polymer rather than a polymer latex containing a surfactant for dispersion. Is also preferable. When a polymer latex is used, the amount of the high molecular polymer is 1 based on the total amount of the binder in the outermost layer of the back layer.
The surface energy can be reduced by adding 0% to 50%, and this method is the most preferable in order to obtain the desired film physical properties.

Specific examples of the water-soluble polymer mentioned here include gelatin and polyvinyl alcohol. Specific examples of the polymer latex mentioned here include latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / butadiene / itaconic acid copolymer, latex of copolymer of ethyl acrylate / methacrylic acid, methyl methacrylate / 2- Ethylhexyl acrylate / styrene / acrylic acid copolymer latex, styrene / butadiene / acrylic acid copolymer latex, styrene / butadiene / divinylbenzene / methacrylic acid copolymer latex, methyl methacrylate / vinyl chloride / acrylic acid copolymer latex, vinylidene chloride / ethyl Examples thereof include latex of acrylate / acrylonitrile / methacrylic acid copolymer. More specifically, methyl methacrylate / ethyl acrylate / methacrylic acid = 33.5 /
50 / 16.5 (mass%) copolymer latex, methyl methacrylate / butadiene / itaconic acid = 47.
5 / 47.5 / 5 (mass%) copolymer latex,
Examples thereof include a copolymer latex of ethyl acrylate / methacrylic acid = 95/5 (mass%). Also,
Such a polymer is also commercially available, and as an example of an acrylic resin, for example, Julimer ET-410 (Nippon Pure Chemical Industries, Ltd.) Sebian A-4635, 46583, 4
601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol
LX811, 814, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.), VONCORT-R3340,
As polyester resin such as R3360, R3370, 4280 (all manufactured by Dainippon Ink and Chemicals, Inc.), FI
NETEX ES650, 611, 675, 850 (manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, WM
HYDRAN AP10, 20, 30, 4 as polyurethane resin such as S (above Eastman Chemical)
0 (all manufactured by Dainippon Ink and Chemicals, Inc.) and other rubber-based resins are LACSTAR 7310K, 3307B, 4
700H, 7132C (above Dainippon Ink and Chemicals, Inc.)
Manufactured), Nipol LX410, 430, 435, 43
Vinyl chloride resins such as 8C (all manufactured by Nippon Zeon Co., Ltd.) are G351 and G576 (all manufactured by Nippon Zeon Co., Ltd.).
Made of vinylidene chloride resin, L502, L5
13 (all manufactured by Asahi Kasei Corporation), Aron D7020,
D504, D5071 (Mitsui Toatsu Co., Ltd.), etc.
Chemipearl S120, SA10 as olefin resin
0 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like.

It is not preferable to use a low-molecular-weight surfactant as a coating aid in the coating solution for the outermost layer on the back surface, because the surface energy of the outermost layer is increased. Therefore, it is desirable to refrain from using low molecular weight surfactants as much as possible. Surfactants that can be preferably used are compounds having a molecular weight of 500 or more. Particularly, a fluorine compound is effective as a coating aid. However, even if it is a fluorine compound, if a compound having a molecular weight of 500 or less is used, the surface energy is remarkably increased. Therefore, it is preferable to use a fluorine compound having a molecular weight of 500 or more. The following compounds can be illustrated as specific examples of the fluorine compound that can be preferably used. _{C 8 F 17 -C 6 H 4} -SO 3 Na C 8 F 17 - (CH 2 CH 2 O) 12 -C 8 F 17

The heat-developable image recording material of the present invention has a structure for achieving the main purpose such as copying an image on a PS plate, and recording such as a bar code for recording image information or a register mark for recording a position. It is preferable to also have information. In the automated process, it is necessary to automatically confirm the heat-developable image recording material, but at that time, the recorded information is read to confirm the heat-developable image recording material.
A bar code is preferably used as the recorded information because it is a commonly used format and is convenient. There are two types of bar code readers for reading the information recorded on the bar code: a model that reads at around 780 nm and a model that reads at around 670 nm. However, when a model that reads at around 780 nm is used, the reading of the light and shade difference often does not go well, so the heat-developable image recording material of the present invention is 60
Reading at 0-700 nm is preferred.

Further, the heat-developable image recording material of the present invention may be conveyed by a tape, or after being fixed on a guide base with a tape and then conveyed, alignment is performed by an image called a register mark. The detection wavelength at this time is 60
There are a wide variety within the range of 0 nm to 800 nm. 700n
When the detection wavelength of m to 800 nm is used, it takes time to perform the alignment. If it takes a long time to perform the alignment, there are more chances that the transport trouble occurs. For this reason,
In the case of the heat-developable image recording material of the present invention, 600 nm to 7 nm
Reading at 00 nm is preferred.

In the heat-developable image recording material of the present invention, it is preferable that the back surface has a Beck second of 1500 seconds or less. From the viewpoint of obtaining stable transportability, it is more preferably 10 to 1000 seconds. More preferably, it is 10 to 500 seconds. The Beck's smoothness in the present invention can be easily determined according to Japanese Industrial Standard (JIS) P8119 "Method for testing smoothness of paper and board by Beck tester" and TAPPI standard method T479.

Organic silver salts can be used in the heat-developable image recording material of the present invention. 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 of reducible 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. Specific examples thereof include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate,
Silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate,
Mention may be made of silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, the silver behenate content of the organic silver salt or the mixture of organic acid silver is 75 m.
It is preferable to use an organic acid silver of ol% or more, and it is more preferable to use an organic acid silver having a silver behenate content of 85 mol% or more. 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, the above exemplified organic acid silver can be preferably used.

The organic silver salt preferably used in the present invention is
It is prepared by reacting an alkali metal salt (Na salt, K salt, Li salt, etc.) solution or suspension of the above organic acid with silver nitrate. For the preparation method thereof, see paragraph No. 00 of JP-A No. 2000-292882.
The methods described in 19 to 0021 can be used.

In the present invention, a method of preparing an organic acid silver salt by adding an aqueous silver nitrate solution and an organic acid alkali metal salt solution into a sealing means for mixing liquids can be preferably used. Specifically, JP-A-200
The method described in JP-A-1-33907 can be used. 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 or the reaction solution when the organic silver salt is prepared.
Specific examples of the type and amount of the dispersant used here are described in paragraph No. 0052 of JP-A-2000-305214.

The organic silver salt used in the present invention is preferably prepared in the presence of a tertiary alcohol. As the tertiary alcohol, a compound having a total carbon number of 15 or less is preferable, and a compound having a total carbon number of 10 or less is particularly preferable. Examples of preferable tertiary alcohol include tert-butanol and the like, but the tertiary alcohol that can be used in the present invention is not limited thereto. The tertiary alcohol used in the present invention may be added at any time during the preparation of the organic acid silver salt, but it may be added during the preparation of the organic acid alkali metal salt.
It is preferable to dissolve the organic acid alkali metal salt before use. The tertiary alcohol used in the present invention has a mass ratio of 0.01 to 1 with respect to water as a solvent when preparing the organic silver salt.
It can be used in the range of 0, but it is preferably used in the range of 0.03 to 1.

The shape and size of the organic silver salt that can be used in the present invention are not particularly limited.
It is preferable to use the one described in paragraph No. 0024 of 2882 publication. The shape of the organic silver salt can be determined from 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, Preferably 50% or less, more preferably 30
% Or less. The measurement method is, for example, the particle size (volume-weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with a laser beam and obtaining an autocorrelation function with respect to the time change of the fluctuation of the scattered light. be able to. The average particle size in this measurement method is 0.
A solid fine particle dispersion having a particle diameter of 05 μm to 10.0 μm is preferable. A more preferable average particle size is 0.1 μm to 5.0.
μm, more preferably the average particle size is 0.1 μm
It is 2.0 μm.

The organic silver salt used in the present invention is preferably desalted. The desalting method is not particularly limited, and a known method can be used, but centrifugal filtration, suction filtration,
Known filtration methods such as ultrafiltration and washing with floc formation by a flocculation method can be preferably used. As a method of ultrafiltration, the method described in JP 2000-305214 A can be used.

In the present invention, for the purpose of obtaining an organic silver salt solid dispersion having a high S / N, a small particle size and no aggregation, an organic silver salt as an image forming medium is contained and a photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which an aqueous dispersion liquid that does not contain water is converted into a high-speed flow and then the pressure is dropped. For these dispersion methods, the methods described in paragraph Nos. 0027 to 0038 of JP-A-2000-292882 can be used.

The particle size distribution of the organic silver salt solid fine particle dispersion used in the present invention 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.

The organic silver salt used in the present invention can be used in a desired amount, but the amount of silver is preferably 0.1 to 5 g / m ² .
It is more preferably 1 to 3 g / m ² , and most preferably 1 to 1.6 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 the 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 that is not a halide, and more specifically, it is preferable to add it in the form of nitrate or sulfate. Addition with a halide deteriorates the image storability due to light (indoor light, sunlight, etc.) of the heat-developable image recording material after processing, that is, so-called print-out property, 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.

Ca, Mg, Zn preferably used in the present invention
The metal ion selected from Ag and Ag may be added at any time after particle formation of the non-photosensitive organic silver salt, immediately after particle formation, before dispersion, after dispersion and before and after coating such as before and after coating solution preparation. It may be carried out at any time, preferably after dispersion and before and after preparation of the coating solution.

Ca, Mg, Zn and A in the present invention
The addition amount of the metal ion selected from g is preferably 10 ⁻³ to 10 ⁻¹ mol, and particularly preferably 5 × 10 ^{−3 to} 5 × 10 ⁻² mol per mol of the non-photosensitive organic silver.

In the present invention, it is preferable to use 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, and preferably a salt. They are silver bromide, silver bromide and silver iodobromide. Regarding the grain formation of the photosensitive silver halide emulsion, paragraph Nos. 0217 to 0 of JP-A No. 11-119374.
Particles can be formed by the method described in No. 224, but the method is not particularly limited to this method. The shape of silver halide grains is cubic, octahedron, tetradecahedron,
Examples thereof include tabular, spherical, rod-shaped, potato-shaped, etc., but cubic particles or tabular particles are particularly preferable in the present invention. Regarding the characteristics of the particle shape such as the aspect ratio and surface index of the particles, Japanese Patent Laid-Open No. 11-119374.
It is the same as that described in paragraph No. 0225 of the publication. 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. When using a silver halide grain having a core / shell structure, it is preferably a core / shell grain having a 2- to 5-fold structure, more preferably a 2- to 4-fold structure. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be used. The distribution of the halogen composition is preferably uniform inside and on the surface of the grain.

The grain size of the silver halide grains of the photosensitive silver halide used in the present invention can be used without any particular limitation, but it is preferably 0.12 μm or less, and more preferably 0.
01 to 0.10 μm is preferable. The grain size distribution of silver halide grains used in the present invention has a monodispersity value of 30.
% Or less, preferably 1 to 20%, and further 5
~ 15%. Here, the monodispersity is defined as a percentage (%) (variation coefficient) of a value obtained by dividing the standard deviation of the particle size by the average particle size. For the sake of convenience, the grain size of the silver halide grains is represented by the edge length in the case of cubic grains, and the other grains (octahedral, tetradecahedral, tabular, etc.) are calculated by the diameter equivalent to the projected area circle.

The photosensitive silver halide grain used in the present invention contains a metal or metal complex of Group VII or VIII of the Periodic Table. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.
The central metal of the Group II or Group VIII metal or metal complex is preferably rhodium, rhenium, ruthenium, osmium, or iridium. Particularly preferred metal complexes are (NH ₄ ) ₃ Rh (H ₂ O) Cl ₅ , K ₂ Ru (N
O) Cl ₅ , K ₃ IrCl ₆ , and K ₄ Fe (CN) ₆ .
One of these metal complexes may be used, or two or more of the same metal complex and different metal complexes may be used in combination. The preferred content is 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ m for 1 mol of silver.
The range of ol is preferable and 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴
The range of mol is more preferable. The types and addition methods of these heavy metals are described in paragraph Nos. 0227 to 0240 of JP-A No. 11-119374.

The photosensitive silver halide grains can be desalted by a washing method known in the art such as a noodle method and a flocculation method. The photosensitive silver halide emulsion used in the present invention is preferably chemically sensitized. For chemical sensitization, it is preferable to use the method described in paragraph Nos. 0242 to 0250 of JP-A No. 11-119374. The silver halide emulsion used in the present invention includes
It is preferable to add the thiosulfonic acid compound by the method shown in European Patent Publication EP293,917A.

As the gelatin contained in the photosensitive silver halide used in the present invention, a low molecular weight gelatin is used in order to maintain a good dispersion state of the photosensitive silver halide emulsion in a coating solution containing an organic silver salt. Preferably. 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. Further, it is more preferable to use ordinary gelatin (molecular weight of about 100,000) at the time of grain formation and to use low molecular weight gelatin at the time of dispersion after desalting treatment.

The concentration of the dispersion medium can be 0.05 to 20% by mass, but a concentration range of 5 to 15% by mass is preferable for handling. As the type of gelatin, modified gelatin such as alkali-treated gelatin, acid-treated gelatin and phthalated gelatin is used, but modified gelatin such as alkali-treated gelatin and phthalated gelatin is preferable.

The silver halide emulsion in the heat-developable image recording material used in the present invention may be used alone or in combination of two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, and crystals). Those having different habits and different conditions for chemical sensitization) may be used in combination, but in the present invention, it is preferable to use one kind of silver halide emulsion.

The photosensitive silver halide used in the present invention is preferably used in an amount of 0.01 mol to 0.5 mol, preferably 0.02 mol, per 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 the organic silver salt, the prepared silver halide grains and the organic silver salt are respectively mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, There are a method of mixing with a homogenizer or the like, or a method of mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt to prepare the organic silver salt. In addition, 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 preferable method for controlling photographic characteristics. In the present invention, it is preferable to mix the separately prepared photosensitive silver halide and organic silver salt with a low speed (100 to 200 rpm) propeller stirrer.

The sensitizing dye that can be used in the present invention is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and is suitable for the spectral characteristics of an exposure light source. A sensitizing dye having a spectral sensitivity can be advantageously selected. For example, 550 nm to 750 n
As a dye for spectrally sensitizing the wavelength region of m, there is disclosed in Japanese Patent Laid-Open No.
Examples of the dyes represented by the general formula (II) of JP-A-186572 include II-6, II-7, and II-1.
4, II-15, II-18, II-23, II-25
The above dye can be exemplified as a preferable dye. Examples of dyes that spectrally sensitize the wavelength region of 750 to 1400 nm include dyes represented by the general formula (I) in JP-A No. 11-119374, and specifically (2
5), (26), (30), (32), (36), (3
The dyes of 7), (41), (49) and (54) can be exemplified as preferable dyes. Furthermore, J-ban
Examples of the dye forming d include US Pat. No. 5,510,23.
Preferred dyes are the dyes described in Example 5 of Japanese Patent No. 6 and 3,871,887, and the dyes disclosed in JP-A-2-96131 and JP-A-59-48753. It can be illustrated. These sensitizing dyes may be used alone or in combination of two or more, but in the present invention, they are preferably used alone.

The method of adding these sensitizing dyes is described in JP-A-11-1999.
The method described in paragraph No. 0106 of JP-A-119374 can be mentioned, but it is preferable to dissolve it in ethanol or methanol and add it. The addition amount of the sensitizing dye in the present invention can be a desired amount according to the sensitivity and fog performance, but is preferably 10 ^{−6 to} 1 mol per 1 mol of silver halide in the image forming layer (photosensitive layer), More preferably, it is 10 ⁻⁴ to 10 ⁻¹ mol.

In order to improve the spectral sensitization efficiency of the present invention,
It is preferable to use a supersensitizer. Examples of the supersensitizer used in the present invention include European Patent Publication EP587,338A.
Compounds disclosed in U.S. Pat. No. 3,877,943 and U.S. Pat. No. 4,873,184;
Examples thereof include compounds selected from heteroaromatic or aliphatic mercapto compounds, heteroaromatic disulfide compounds, stilbenes, hydrazines and triazines. Preferred supersensitizers are the heteroaromatic mercapto compounds and heteroaromatic disulfide compounds disclosed in JP-A-5-341432, and the general formula (I) or (II) of JP-A-4-182639. The compound represented by the formula (I) in JP-A-10-111543 and the compound represented by formula (I) in JP-A-11-109547. Particularly preferred supersensitizers are M-1 to JP-A-5-341432.
Compound of M-24, d of JP-A-4-182639
-1) to d-14), JP-A-10-11154
No. 3, compounds SS-01 to SS-07, JP-A-1
No. 31, 32, 37, 38, 4 of JP-A No. 1-109547.
1 to 45 and 51 to 53. The addition amount of these supersensitizers is preferably in the range of 10 ^{−4 to} 1 mol per mol of silver halide in the emulsion layer.
The range of 0.001 to 0.3 mol per mol is more preferable.

In the heat-developable image recording material of the present invention, it is particularly preferable to use an acid formed by hydration of diphosphorus pentaoxide or a salt thereof as a compound containing phosphorus. 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), hexametaline. Examples thereof include acids (salts). Particularly preferred acids or salts thereof formed by hydration of phosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate,
Examples include sodium hexametaphosphate and ammonium hexametaphosphate. The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent to the image forming layer from the viewpoint of exhibiting a desired effect in a small amount. The amount of the compound containing phosphorus and the acid formed by hydration of diphosphorus pentoxide or a salt thereof (coating 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. However, 0.1 to 500 mg / m ² is preferable,
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 image-forming surface of the support. When it is added to layers other than the image forming layer, it is 10 to 1 mol of silver.
It is preferable to use a large amount of 50 mol. Further, the reducing agent may be a so-called precursor which is derivatized so as to effectively function only during development.

A wide range of reducing agents can be used in the heat-developable image recording material (heat-developable photosensitive material) using an organic silver salt. For example, JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, JP-A-49-46427, and JP-A-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
The reducing agents disclosed in 4,738, German Patent 2,321,328, European Patent Publication EP692,732A and the like can be used. For example, amidoximes such as phenylamidoxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,
A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of 2'-bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid; of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine Combinations such as hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine; phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alininehydroxam. Hydroxamic acids such as acids; combinations of azine and sulfonamide phenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamide phenol); ethyl-α-cyano Α such as 2-methylphenylacetate and ethyl-α-cyanophenylacetate
-Cyanophenylacetic acid derivative; 2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,
Bis-β-naphthol as exemplified by 2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, , 2, 4
-Dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone, etc.); 3-methyl-
5-pyrazolone such as 1-phenyl-5-pyrazolone;
Reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4-benzenesulfonamidephenol and p-benzenesulfone Sulfonamide phenol reducing agents such as amidophenol; 2
-Phenylindane-1,3-dione and the like; 2,2-dimethyl-7-tert-butyl-6-hydroxychroman and other chromanes; 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine Such as 1,4
-Dihydropyridine; bisphenol (e.g. 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 and the like); ascorbic acid derivatives (for example,
1-ascorbyl palmitate, ascorbyl stearate and the like); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and some indane-1,3-diones; chromanol (such as tocopherol). 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 emulsified dispersion. Among them, it is added as a solid fine particle dispersion. It is preferable. Solid fine particle dispersion is carried out by a known refining means (for example, ball mill,
Vibration ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). Further, when dispersing solid fine particles, it is preferable to use a dispersion aid known in the art, and specifically, JP-A-2001-83657.
The water-soluble polymers described in paragraph Nos. 91 to 101 of the publication,
Surfactants are preferably used.

Inclusion of additives known as "toning agents" to improve the image may increase the optical density.
Further, the toning agent may be advantageous in forming a black silver image. The color toning agent is preferably contained in the layer on the image forming surface of the support in an amount of 0.1 to 50 mol, and more preferably 0.5 to 20 mol, based on 1 mol of silver. Further, the toning agent is more preferably a so-called precursor which is derivatized so as to effectively function only during development. A wide variety of toning agents can be used in the heat-developable image recording material using an organic silver salt.
For example, JP-A-46-6077 and 47-102.
82, 49-5019, 49-502.
No. 0, 49-91215 and 49-912.
No. 15, gazette 50-2524, gazette 50-329.
27, 50-67132, 50-67.
No. 641, No. 50-114217, No. 51-
No. 3223, No. 51-27923, and No. 52-
14788, 52-99813, 53.
-1020 gazette, the same 53-76020 gazette, the same 54.
No. 156524, No. 54-156525,
61-183642, JP-A-4-56848, JP-B-49-10727 and 54-203.
33, U.S. Pat. No. 3,080,254,
No. 3,446,648 and No. 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent No. 1,380,
The toning agents disclosed in, for example, Specification No. 795 and Belgian Patent No. 841,910 can be used. Specific examples of the toning agent include phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-. Cyclic imides such as thiazolidinediones; naphthalimides (eg N-hydroxy-1,8
-Naphthalimide); cobalt complex (for example, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,
2,4-triazole and 2,5-dimercapto-
Mercaptans exemplified by 1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximide, (for example, (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene- 2,3-dicarboximide); and blocked pyrazoles, 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, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-
Dimethoxyphthalazinone and 2,3-dihydro-1,
Derivatives such as 4-phthalazinedione; a combination of phthalazinone and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); phthalazine, a phthalazine derivative (for example, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-
Derivatives such as isobutylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; halide ions for in situ silver halide formation as well as toning agents Complexes that also serve as a source of, for example, ammonium hexachlororhodium (III), rhodium bromide, rhodium nitrate and potassium hexachlororhodium (III); inorganic peroxides and persulfates such as ammonium peroxydisulfide. And peroxide water ; 1,3 benzoxazine -2,
4-dione, 8-methyl-1,3-benzoxazine-
Benzoxazine-2, such as 2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione,
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-1
H, 4H-2,3a, 5,6a-tetraazapentalene) and the like are preferably used. Particularly, phthalazine derivatives and phthalic acid derivatives are preferably used. In the present invention, the phthalazine derivative represented by the general formula (F) described in JP-A 2000-35631 is most preferably used as the color toning agent. Specifically, A-1 to A described in the publication
-10 is preferably used

The color toning agent is preferably used by dissolving it in water or a suitable organic solvent. It is preferable to add it by making it into an aqueous solution using a solubilizing agent well known in the art, and specifically, paragraph No. 91 of JP-A-2001-83657.
The water-soluble polymers and surfactants described in Nos. 101 to 101 are preferably used. When dissolved in an appropriate organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve It is preferable to use it after dissolving it. Further, in the case of a compound having an acidic group bonded, it is preferably neutralized with an equivalent amount of alkali and used as a salt.

When the solubility in water is low, an emulsion dispersion method,
It is preferable to disperse and use the solid dispersion method. When performing emulsification dispersion, by emulsion dispersion method well known in the art, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, It is preferable to mechanically prepare an emulsified dispersion and use it in the heat-developable image recording material.
When performing solid dispersion, the powder may be ball milled, colloid milled, or submerged in water by a solid dispersion method well known in the art.
It is preferably dispersed in a sand grinder mill, manton-goulin, microfluidizer or ultrasonic waves and used in a heat-developable image recording material. Further, in order to carry out emulsification dispersion and solid dispersion, it is preferable to use a dispersion aid known in the art, and specifically, JP-A-2001-83.
The water-soluble polymers and surfactants described in paragraphs Nos. 91 to 101 of 657 publication are preferably used.

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 preferable to stabilize against the 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.
Thiazonium salts described in 1,038 and 2,694,716, US Pat.
Azaindene, U.S. Pat. No. 2,728,663 described in U.S. Pat. No. 437 and No. 2,444,605.
Salt described in U.S. Pat. No. 3,287,13
Urazol as described in US Pat.
5,652, sulfocatechol, British Patent 623,448, oxime, nitrone, nitroindazole, U.S. Pat. No. 2,839,40.
Polyvalent metal salts described in US Pat.
No. 0,839, and thiuronium salts, and US Pat. Nos. 2,566,263 and 2,
597,915, palladium, platinum and gold salts, halogen-substituted organic compounds described in US Pat. Nos. 4,108,665 and 4,442,202, US Pat. , 128,557 and 4,137,079, 4,13.
Triazines described in US Pat. No. 8,365 and 4,459,350 and US Pat. No. 4,41.
1, 985 and the like.

The heat-developable image recording material of the present invention preferably contains 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 preferred examples thereof 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 on the image forming surface of the support, and more preferably to the organic silver salt-containing layer. The benzoic acids may be added at any step in the preparation of the coating solution, and when added to the organic silver salt-containing layer, it may be added at any step from the preparation of the organic silver salt to the preparation of the coating solution. Just before is preferred. 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 1 × 10 1 per mol of silver
^-6 mol to 2 mol is preferable, 1 x 10 ^-3 mol 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 added amount of mercury used in the present invention is as follows.
Preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ per mol
mol, more preferably 1 × 10 ⁻⁸ mol to 1 × 10
^-4 mol range.

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 publication are preferably used. The addition amount of the salicylic acid derivative represented by the formula (Z) is
Mol amount per mol of Ag (mol / mol Ag)
, Preferably 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol /
molAg, more preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻¹ m
ol / molAg, more preferably 1 × 10 ^{−4 to} 5 ×
It is 10 ^-2 mol / mol Ag. These may be used alone or in combination of two or more.

Formalin scavenger is effective as an antifoggant preferably used in the present invention. For example, the compound represented by the formula (S) described in JP-A-2000-221634 and its exemplified compound (S-
1) to (S-24).

The antifoggant used in the present invention can be used by dissolving it in water or a suitable organic solvent. When added as an aqueous solution, a solubilizer known in the art can be used, and specifically, JP-A 2001-836 can be used.
The water-soluble polymers and surfactants described in paragraph Nos. 91 to 101 of 57 publication are preferably used. When used by dissolving in an organic solvent, for example, alcohols (methanol,
It is preferable to use it after dissolving it in ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Further, in the case of a compound having an acidic group bonded, it is preferably neutralized with an equivalent amount of alkali and used as a salt.
When the solubility in water is low, it is preferable to use by dispersing by an emulsion dispersion method or a solid dispersion method. When performing emulsification dispersion, by emulsion dispersion method well known in the art, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, It is preferable to mechanically prepare an emulsified dispersion and use it in the heat-developable image recording material. When performing solid dispersion, the powder is dispersed in water by a ball mill, colloid mill, sand grinder mill, manton-goulin, microfluidizer, or ultrasonic wave by a solid dispersion method well known in the art, and heat development image recording is performed. It is preferably used in the material. In addition, it is preferable to use a dispersion aid known in the art for emulsification dispersion and solid dispersion, and specifically, the water-soluble polymer and the interface described in paragraphs 91 to 101 of JP 2001-83657 A. Activators are preferably used.

The antifoggant used in the present invention may be added to a layer on the image forming surface of the support, that is, the image forming layer or any other layer on the side of the image forming layer. Is preferably added to the layer. 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 contains a mercapto compound, a disulfide compound and a thione compound for the purpose of suppressing or accelerating the development to control the development and improving the storage stability before and after the development. It is preferable. When the mercapto compound is used in the present invention, it may have any structure, but Ar-SM, A
Those represented by r-S-S-Ar are preferable. In the formula, M
Is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, 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-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2- Mercaptoquinoline, 8-mercaptopurine,
2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5
6-Tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto- 1, 2,
4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-
Methylpyrimidine hydrochloride, 3-mercapto-5
-Phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, 3- (5-mercaptotetrazole) -sodium benzenesulfonate, N-
Methyl-N '-{3- (5-mercaptotetrazolyl)
Phenyl} urea and 2-mercapto-4-phenyloxazole are preferably used. The addition amount of these mercapto compounds is preferably 0.001 to 1.0 mol per 1 mol of silver in the image forming layer, and more preferably 0.001 to 0.3 per 1 mol of silver.
The amount is mol.

In the heat-developable image recording material of the present invention, a volatile base such as ammonia is liable to volatilize and volatilizes not only during the coating step and heat development but also during storage, so that it should be present in the film. Is not preferable, and the NH ₄ ⁺ content is preferably 0.06 mmol or less in terms of coating amount per 1 m ² of the support. More preferably, it is 0.03 mmol or less. The amount of NH ₄ ⁺ in the film was determined by Tosoh Corporation 800
As a 0 type ion chromatograph (electrical conductivity method) and a separation column, TSKgel IC-C manufactured by Tosoh Corporation
ation, as a guard column, TSK guard
It measured using column IC-C. A 2 mM nitric acid aqueous solution was used as an eluent, and the flow rate was 1.2 mL / min. The column constant temperature bath temperature was 40 ° C. To extract NH ₄ ⁺ from the heat-developable image recording material, an acetic acid: ion-exchanged water = 1: 148 mixed solution was used as an extract solution, and 5 mL of the extract solution was used to extract 1 × 3.5 of the heat-developable image recording material.
A heat-developable image recording material having a size of cm ² was soaked for 2 hours, and after extraction, a solution filtered with a 0.45 μm filter was measured. For the adjustment of 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 non-volatile base. The film surface pH of the heat-developable image recording material of the present invention before the heat-development treatment is preferably 6.0 or less, more preferably 5.5 or less. The lower limit is not particularly limited, but is about 3. The method for measuring the film surface pH is described in paragraph No. 0123 of JP-A 2000-284339.

The heat-developable image recording material of the present invention 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 protective layer is provided on the image forming layer. Layers are preferably provided. The heat-developable image recording material of the present invention preferably has at least one layer on the back surface.

As the binder used in the present invention, natural polymer synthetic resins, polymers and copolymers, and other mediums for forming films such as: gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate. , Poly (vinylpyrrolidone), casein,
Starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid),
Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg poly (vinyl formal) and poly (vinyl butyral)),
Poly (ester) s, poly (urethane) s, phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, poly (amides).

It may be hydrophilic or hydrophobic, but in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after heat development. Preferable binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate and cellulose acetate butyrate are particularly preferably used.

In order to protect the surface of the heat-developable image recording material and prevent scratches, it is preferable to have a protective layer outside the image forming layer. The binder used in these protective layers may be the same or different from the binder used in the image forming layer. A polymer having a softening point higher than that of the binder polymer forming the image forming layer is preferably used in order to prevent scratches and phase deformation, and cellulose acetate, cellulose acetate butyrate, etc. serve this purpose.

When coating using a solvent (dispersion medium) containing water as the main component as the binder used in the present invention, the polymer latex described below is preferably used. At least one layer of the image-forming layers containing the photosensitive silver halide of the heat-developable image recording material of the present invention is preferably an image-forming layer in which the polymer latex described below is used in an amount of 50% by mass or more based on all binders. Further, the polymer latex may be used not only in the image forming layer but also in a protective layer or a layer on the back surface. In particular, when the heat-developable image recording material of the present invention is used for a printing application in which dimensional change is a problem, protection is required. It is preferable to use the polymer latex for the layer and the layer on the back surface. However, the "polymer latex" referred to herein is a polymer in which 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. You can use any one.
Regarding the polymer latex used in the present invention, "Synthetic Resin Emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Kobunshi Kogyokai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara) , Published by Kobunshi Shuppankai (1993)), "Chemistry of Synthetic Latex (Souichi Muroi, published by Kobunshi Shuppankai (1970))" and the like. The average particle size of dispersed particles is 1 to 5
The range is preferably 0000 nm, more preferably about 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may be a wide distribution or a monodisperse particle.

The polymer latex used in the present invention may be a so-called core / shell type latex other than the ordinary polymer latex having a uniform structure. In this case, it may be preferable that the core and the shell have different glass transition temperatures.

The glass transition temperature (Tg) of the polymer latex preferably used in the binder used in the present invention differs between the protective layer, the back surface layer and the image forming layer. In the image forming layer, the temperature is preferably -30 to 40 ° C. in order to promote diffusion of the photographically useful material during heat development. When used as a protective layer or a layer on the back surface, a glass transition temperature of 25 to 70 ° C. is preferable because it comes into contact with various devices.

The minimum film forming temperature (MFT) of the polymer latex used in the present invention is preferably -30 ° C to 90 ° C, more preferably about 0 ° C to 70 ° C. It is preferable to add a film-forming auxiliary for controlling the minimum film-forming temperature.
A film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of polymer latex, also called a plasticizer.
For example, it is described in the above-mentioned “Chemistry of Synthetic Latex (Souichi Muroi, published by Kobunshi Kogakukai (1970))”.

The polymer species used in the polymer latex used in the present invention include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or copolymers thereof. And so on.
The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. 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 preferred polymer is a linear random copolymer. The number average molecular weight of the polymer is about 5,000 to 1,000,000, preferably about 10,000 to 100,000. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film formability is poor, which is not preferable.

Specific examples of the polymer latex used as the binder of the image forming layer of the heat-developable image recording material of the present invention include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex and methyl methacrylate / butadiene / itaconic acid copolymer latex. Latex of ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, Methyl methacrylate / vinyl chloride / acrylic acid copolymer latex, vinylidene chloride / ethyl acrylate / acrylonitri / Such as latex of methacrylic acid copolymers. More specifically, methyl methacrylate / ethyl acrylate / methacrylic acid = 3
Copolymer latex of 3.5 / 50 / 16.5 (mass%), methyl methacrylate / butadiene / itaconic acid = 47.5 / 47.5 / 5 (mass%) copolymer latex, ethyl acrylate / methacrylic acid = 95 / 5
(Mass%) copolymer latex and the like.
Moreover, such a polymer is also commercially available, for example, as an example of an acrylic resin, Sebian A-4635,46.
583, 4601 (all manufactured by Daicel Chemical Industries, Ltd.),
Nipol LX811, 814, 821, 820, 8
57 (Nippon Zeon Co., Ltd.), VONCORT-R
As polyester resins such as 3340, R3360, R3370, and 4280 (all manufactured by Dainippon Ink and Chemicals, Inc.), FINETEX ES650, 611, 675,
850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-si
ZEDR, WMS (above Eastman Chemical), etc., as a polyurethane resin, HYDRAN AP10, 2
0, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) and other rubber-based resins such as LACSTAR 7310K,
3307B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol LX410, 430,
435, 438C (all manufactured by Nippon Zeon Co., Ltd.), vinyl chloride resin as G351, G576 (all manufactured by Nippon Zeon Co., Ltd.), vinylidene chloride resin as L5.
02, L513 (all manufactured by Asahi Kasei Corporation), Aron D
7020, D504, D5071 (above Mitsui Toatsu Co., Ltd.)
Chemipearl S12 as an olefin resin
0, SA100 (all 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, but it is preferable to use them alone.

The image forming layer contains 50% by mass of all binders.
The above-mentioned polymer latex is preferably used as described above, and more preferably 70% by mass or more is used as the polymer latex.

If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose or hydroxypropyl methyl cellulose may be added to the image forming layer in a range of 50% by mass or less based on the total binder. . The amount of these hydrophilic polymers added is preferably 30% by mass or less, more preferably 15% by mass or less, based on the total amount of the binder in the image forming layer.

The image forming layer is preferably prepared by applying an aqueous coating solution and then drying. However, the term “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating liquid is water. The components other than water of the coating liquid are methyl alcohol, ethyl alcohol, isopropyl alcohol,
Water-miscible organic solvents such as methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate can be used. The following are examples of specific solvent compositions. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10,
Water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the numbers represent mass%.)

The total amount of binder in the image forming layer is 0.2 to 3
0 g / m ^2, more preferably in the range of 1 to 15 g / m ^2. It is preferable to add a cross-linking agent for cross-linking, a surfactant for improving coatability, etc. to the image forming layer.

Further, as a binder for the protective layer, paragraph Nos. 0025 to JP-A-2000-267226 are used.
A combination of polymer latexes having different I / O values obtained by dividing the inorganic value based on the organic conceptual diagram described in 0029 by the organic value can be preferably used.

In the present invention, if necessary, JP-A-20
Paragraph Nos. 0021 to 002 of Japanese Patent Publication No. 00-267226
5 plasticizers (eg, benzyl alcohol, 2, 2,
4-trimethylpentanediol-1,3-monoisobutyrate, etc.) can be added to control the film forming temperature. Further, as described in paragraph Nos. 0027 to 0028 of JP-A-2000-267226, a hydrophilic polymer can be added to the polymer binder and a water-miscible organic solvent can be added to the coating solution.

Each layer is provided with Japanese Patent Laid-Open No. 2000-196.
Use of a first polymer latex having functional groups introduced in paragraph Nos. 0023 to 0041 of Japanese Patent No. 783 and a crosslinking agent having a functional group capable of reacting with the first polymer latex and / or a second polymer latex. Can also The above-mentioned functional groups include a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, an oxazolinyl group, and the like, as a crosslinking agent, an epoxy compound, an isocyanate compound, a blocked isocyanate compound, a methylol compound, a hydroxy compound, It is selected from carboxyl compounds, amino compounds, ethyleneimine compounds, aldehyde compounds, halogen compounds and the like. Specific examples of the cross-linking agent include hexamethylene isocyanate as an isocyanate compound and duranate WB4.
0-80D, WX-1741 (manufactured by Asahi Chemical Industry Co., Ltd.),
Bayhijour 3100 (Sumitomo Bayer Urethane Co., Ltd.)
Manufactured by Takeda Pharmaceutical Co., Ltd., Takenate WD725
Manufactured by Sumitomo Chemical Co., Ltd.), Aquanate 100, 200 (manufactured by Nippon Polyurethane Co., Ltd.), water-dispersed polyisocyanate described in JP-A 9-160172; Denacol EX-614B (manufactured by Nagase Kasei Co., Ltd.) as an epoxy compound; 2,4 dichloro- as a halogen compound
Examples thereof include 6-hydroxy-1,3,5-triazine sodium.

The total amount of binder for the image forming layer is 0.2 to
30 g / m ^2, more preferably in the range of 1.0~15g / m ^2. The total amount of the binder for the protective layer is 1 to 10.0 g / m ² , more preferably ² as the amount necessary for achieving the film thickness of 3 μm or more preferably used in the present invention.
The range of up to 6.0 g / m ² is preferred. The thickness of the protective layer preferably used in the present invention is 3 μm or more and 4
More preferably, it is at least μm. The upper limit of the protective layer film thickness is not particularly limited, but in consideration of coating and drying, it is 10 μm.
Hereafter, it is more preferably 8 μm or less. The total amount of binder for the back surface layer is preferably 0.01 to 10.0 g / m ² , and more preferably 0.05 to 5.0 g / m ² .

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 there may be two or more layers, but at least one protective layer is provided.
A polymer latex is preferably used for the layer, particularly the outermost protective layer. Further, the back surface layer is a layer provided on the undercoat layer of the support back surface, and there may be two or more layers, but it is preferable to use a polymer latex for at least one layer, particularly for the outermost layer.

In the present specification, the slip agent means a compound which, when present on the surface of an object, reduces the coefficient of friction of the surface of the object as compared with the case where it is not present. The type is not particularly limited.

As the slipping agent used in the present invention, Japanese Patent Laid-Open No.
Paragraph Nos. 0061 to 0064 of 1-84573 gazette,
Paragraph Nos. 0049 to JP-A-2000-47083
The compounds described in 0062 can be mentioned. Specific examples of preferable slip agents include Cerosol 524 (main component carnauba wax), Polylon A, 393, H-481.
(Main component polyethylene wax), High Micron G-1
10 (main component ethylene bis-stearic acid amide), Himicron G-270 (main component stearic acid amide)
(Above, Chukyo Yushi Co.), etc. _{W-1 C 16 H 33 -O} -SO 3 Na W-2 C 18 H 37 -O-SO 3 Na and the like. The amount of the slipping agent used is 0.1 to 50% by mass of the amount of the binder in the addition layer, and preferably 0.5 to
It is 30% by mass.

In the present invention, Japanese Patent Laid-Open No. 2000-1719.
No. 35, JP-A-2000-47083, the preheating unit is conveyed by a counter roller, and the heat development processing unit drives the roller to drive the side having the image forming layer so that the back surface on the opposite side is moved. In the case of using a heat development processing apparatus which slides and conveys on a smooth surface, the ratio of the friction coefficient between the outermost layer of the image forming surface and the outermost layer of the back surface of the heat developable image recording material at the development processing temperature is 1.5 or more. , Preferably 1.5 to 3
It is 0. Further, μb is 1.0 or less, preferably 0.0
5 to 0.8. This value is calculated by the following formula. Ratio of friction coefficient = coefficient of dynamic friction between roller member of heat developing machine and image forming surface (μe) / coefficient of dynamic friction between smooth surface member of heat developing machine and back surface (μb) Heat at heat development processing temperature in the present invention The slidability between the developing processor member and the outermost layer on the image forming surface and / or the back surface can be adjusted by incorporating a slipping agent in the outermost layer and changing the addition amount thereof.

On both sides of the support, there are JP-A-64-2054.
No. 4, JP-A-1-180537, and JP-A-1-180537.
209443, JP-A 1-285939,
JP-A-1-296243, JP-A-2-24649
Japanese Patent Application Laid-Open No. 24-48648, Japanese Patent Application Laid-Open No. 2-18
No. 4844, No. 3-109545, No. 3-137637, No. 3-141346, No. 3-141347, No. 4-96.
055, U.S. Pat. No. 4,645,731, Japanese Patent Laid-Open No. 4-68344, and Japanese Patent No. 2,557,
No. 641, page 2, right column, line 20 to page 3, right column, line 30,
Paragraph Nos. 0020 to JP-A-2000-39684
It is preferable to provide an undercoat layer containing a vinylidene chloride copolymer containing 70% by mass or more of repeating units of the vinylidene chloride monomer described in paragraph Nos. 0063 to 0080 of JP-A-2000-47083.

If the vinylidene chloride monomer content is less than 70% by mass, sufficient moisture resistance cannot be obtained, and the dimensional change over time after thermal development becomes large. Further, the vinylidene chloride copolymer preferably contains a repeating unit of a carboxyl group-containing vinyl monomer as a constituent repeating unit other than the vinylidene chloride monomer. The vinyl chloride monomer alone contains such a repeating unit,
The polymer will crystallize, making it difficult to form a uniform film when applying the moisture-proof layer. In addition, a carboxyl group-containing vinyl monomer is indispensable for stabilizing the polymer. Because there is. The vinylidene chloride copolymer used in the present invention has a weight average molecular weight of 45,0.
00 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.

The content of the vinylidene chloride copolymer used in the present invention is 0.3 μm or more as the total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer,
The range is preferably 0.3 μm to 4 μm.

The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer layer directly provided on the support. Usually, one layer is provided on each side. May be provided in two or more layers.
When a multi-layered structure having two or more layers is used, the total amount of vinylidene chloride copolymer may be within the range of the present invention.
In addition to the vinylidene chloride copolymer, such a layer preferably contains a crosslinking agent, a matting agent and the like.

The support is preferably coated with a vinylidene chloride copolymer layer and, if necessary, an undercoat layer containing polyester or gelatin as a binder. These undercoat layers preferably have a multi-layered structure and are preferably provided on both sides of the support. Undercoat thickness (1
Per layer) is generally from 0.01 to 5 μm, more preferably from 0.05 to 1 μm.

Various supports can be used in the heat-developable image recording material of the present invention. Typical supports include polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetals, syndiotactic polystyrenes, polycarbonates, paper supports coated on both sides with polyethylene, and the like. 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 support is preferably 90 to 180 μm in terms of the base thickness excluding the undercoat layer.

The support used in the heat-developable image recording material of the present invention is disclosed in JP-A-10-48772 and JP-A-1.
0-10676, JP-A-10-10677, JP-A-11-65025, and JP-A-11-13.
Polyester heat-treated in the temperature range of 130 to 185 ° C. in order to alleviate internal strain remaining in the film during biaxial stretching described in Japanese Patent No. 8648 and eliminate the heat shrinkage strain generated during the heat development treatment, Particularly, polyethylene terephthalate is preferably used.

12 of the support after such heat treatment
The dimensional change rate by heating at 0 ° C. for 30 seconds is −0.03% to + 0.01% in the machine direction (MD) and 0 in the transverse direction (TD).
It is preferably 0.04%.

The heat-developable image recording material of the present invention has the purpose of reducing dust adhesion, preventing the occurrence of static marks, and preventing conveyance defects in the automatic conveyance process.
It is preferable to use a conductive metal oxide and / or a fluorinated surfactant described in paragraphs 0040 to 0051 of the publication to prevent electrification. Examples of the conductive metal oxide include US Pat. No. 5,575,957 and JP-A-1
Paragraph Nos. 0012 to 0020 of JP-A 1-223901
The needle-shaped conductive tin oxide doped with antimony described in JP-A-4-29134 and the fibrous tin oxide doped with antimony described in JP-A-4-29134 are preferably used.

The surface specific resistance (surface resistivity) of the metal oxide-containing layer is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less in an atmosphere of 25 ° C. and 20% relative humidity. 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.

The Beck smoothness of the image forming surface of the heat-developable image recording material of the present invention is 2000 seconds or less, more preferably 10 seconds to 2000 seconds. The Beck's smoothness in the present invention refers to Japanese Industrial Standards (JIS) P8119 "Smoothness test method for Beck's tester for paper and board" and T.
It can be easily determined by the APPI standard method T479. The Beck smoothness of the outermost layer on the image forming surface and the outermost layer on the opposite surface of the heat-developable image recording material are described in JP-A-11-84.
As described in paragraph Nos. 0052 to 0059 of Japanese Patent No. 573, it can be controlled by appropriately changing the particle size and the addition amount of the matting agent contained in the layers on both sides.

In the present invention, a water-soluble polymer is preferably used as a thickener for imparting coatability, and it may be a natural product or a synthetic polymer, and its kind is not particularly limited. Specifically, starches (corn starch,
Starch, etc.), seaweed (agar, sodium alginate, etc.), vegetable stickies (eg gum arabic), animal proteins (such as glue, casein, gelatin, egg white etc.), fermented stickies (pullulan, dextrin etc.), etc. Semi-synthetic polymers such as starch (soluble starch, carboxyl starch, dextran, etc.), celluloses (viscose, methyl cellulose, ethyl cellulose,
Carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, etc.), and synthetic polymers (polyvinyl alcohol, polyacrylamide,
Polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl ether, polyethyleneimine, polystyrenesulfonic acid or its copolymer, polyvinylsulfinic acid or its copolymer, polyacrylic acid or its copolymer, acrylic acid or its copolymer, etc. , Maleic acid copolymer, maleic acid monoester copolymer, acryloylmethyl propane sulfonic acid or its copolymer, etc.).

Among these, water-soluble polymers preferably used are sodium alginate, gelatin, dextran, dextrin, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, Polystyrene sulfonic acid or its copolymer, polyacrylic acid or its copolymer, maleic acid monoester copolymer, acryloylmethyl propane sulfonic acid or its copolymer, etc. are particularly preferably used as a thickener.

Among these, particularly preferable thickeners include
Examples thereof include gelatin, dextran, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, polystyrene sulfonic acid or its copolymer, polyacrylic acid or its copolymer, and maleic acid monoester copolymer. These compounds are
It is described in detail in "Applications and Markets of New Water-Soluble Polymers" (published by CMC, edited by Shinji Nagatomo, published on November 4, 1988).

The amount of the water-soluble polymer used as the thickener is not particularly limited as long as the viscosity increases when added to the coating solution. Generally, the concentration in the liquid is 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 0.1 to 10% by mass. The viscosity obtained by these is 1 to 200 mPas as an increase from the initial viscosity.
・ S is preferable, and more preferably 5 to 100 mPa · s.
Is. The viscosity is a value measured with a B-type rotational viscometer at 25 ° C. In addition to the coating liquid, it is generally desirable to add the thickener in a dilute solution as much as possible. In addition, it is preferable to perform sufficient stirring during the addition.

The surfactant used in the present invention is described below. The surfactant used in the present invention is classified into a dispersant, a coating agent, a wetting agent, an antistatic agent, a photographic control agent and the like according to the purpose of use, and the surfactant described below is appropriately selected and used. By doing so, those goals can be achieved. The surfactant used in the present invention may be nonionic or ionic (anion, cation, betaine). Further, a fluorine-based surfactant is also preferably used.

Preferred nonionic surfactants include:
Examples thereof include surfactants having polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl or sorbitan as a nonionic hydrophilic group, and specific examples thereof include polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether. , Polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid partial ester be able to.

Examples of the anionic surfactants include carboxylates, sulfates, sulfonates and phosphates, of which fatty acid salts, alkylbenzene sulfonates and alkylnaphthalene sulfonates are typical. Salt, alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxy Examples include ethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, naphthalene sulfonate formaldehyde condensate, etc. You can

As the cationic surfactant, an amine salt,
Examples thereof include quaternary ammonium salts and pyridinium salts. First to third fatty amine salts, quaternary ammonium salts (tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, alkylimidazolium salts, etc.) ) Can be mentioned.

Examples of betaine-based surfactants include carboxybetaine and sulfobetaine.
-Trialkyl-N-carboxymethylammonium betaine, N-trialkyl-N-sulfoalkylene ammonium betaine and the like can be mentioned.

These surface active agents are described in "Application of surface active agents" (Koshobo, Takao Karime, published September 1, 1980).
It is described in. In the present invention, the preferred amount of the surfactant is not particularly limited as long as it is used, as long as the desired surfactant properties are obtained. The coating amount of the fluorine-containing surfactant is 0.01 mg / m ^{2 or} more.
250 mg is preferred.

Specific examples of the surfactant will be described below.
Is not limited to (where -C₆H_Four− Is fe
Represents a nylene group). WA-1: C₁₆H₃₃(OCH₂CH₂)_TenOH WA-2: C₉H₁₉-C₆H_Four-(OCH₂CH₂)₁₂OH WA-3: Sodium dodecylbenzene sulfonate WA-4: Sodium tri (isopropyl) naphthalene sulfonate WA-5: Sodium tri (isobutyl) naphthalene sulfonate WA-6: Sodium dodecyl sulfate WA-7: α-sulfa-succinic acid di (2-ethylhexyl) ester Natri Umm salt WA-8: C₈H₁₇-C₆H_Four-(CH₂CH₂O)₃(CH₂)₂SO₃K WA-10: Cetyltrimethylammonium chloride WA-11: C₁₁H_{twenty three}CONHCH₂CH₂N⁽⁺⁾(CH₃)₂-CH₂COO^(-) WA-12: C₈F₁₇SO₂N (C₃H₇) (CH₂CH₂O)₁₆H WA-13: C₈F₁₇SO₂N (C₃H₇) CH₂COOK WA-14: C₈F₁₇SO₃K WA-15: C₈F₁₇SO₂N (C₃H₇) (CH₂CH₂O)_Four(CH₂)_FourSO₃N a WA-16: C₈F₁₇SO₂N (C₃H₇) (CH₂)₃OCH₂CH₂N⁽⁺⁾(CH₃ )₃-CH₃・ C₆H_Four-SO₃ ^(-) WA-17: C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂N⁽⁺⁾(CH₃)₂-C H₂COO^(-)

In a preferred embodiment of the present invention, an intermediate layer may be provided, if necessary, in addition to the image forming layer and the protective layer. For the purpose of improving productivity and the like, it is preferable that these plural layers are simultaneously multilayer coated in an aqueous system. The coating method includes extrusion coating, slide bead coating, curtain coating, and the like.
The slide bead coating method shown in FIG. 1 of Japanese Patent No. 964 is particularly preferable.

In the case of a silver halide photographic light-sensitive material using gelatin as a main binder, it is rapidly cooled in the first drying zone provided downstream of the coating die, resulting in gelatinization of gelatin and cooling of the coating film. Solidified. The coating film which has been solidified by cooling and stopped flowing is guided to the subsequent second drying zone, and the solvent in the coating liquid is volatilized in the subsequent drying zone to form a film. As the drying method after the second drying zone, an air loop method in which a jet is blown from a U-shaped duct onto a roller-supported support body, or a support body is wound around a cylindrical duct in a spiral shape, and is dried. A firewood method (air floating method) and the like can be mentioned.

When a layer is formed using a coating solution whose main component of the binder is a polymer latex, rapid cooling cannot stop the flow of the coating solution, so that preliminary drying is insufficient only in the first drying zone. In some cases.
In this case, a drying method such as that used in silver halide photographic light-sensitive materials causes unevenness in flow and unevenness in drying, and serious defects are likely to occur on the coated surface.

A preferable drying method in the present invention is horizontal regardless of the first drying zone and the second drying zone as described in JP-A-2000-002964. This is a method of drying in a drying zone. The support may be conveyed immediately after coating until it is guided to the horizontal drying zone, either horizontally or not, and the rising angle of the coating machine with respect to the horizontal direction may be in the range of 0 to 70 °. Further, the horizontal drying zone in the present invention does not mean horizontal transportation as long as the support is vertically transported within ± 15 ° with respect to the horizontal direction of the coating machine.

The constant rate drying in the present invention means a drying process in which the liquid film temperature is constant and all of the inflowing heat quantity is used for evaporation of the solvent. Decreasing rate drying means that at the end of drying, the drying rate decreases due to various factors (moisture transfer inside the material is rate-determining, evaporation surface receding, etc.), and the applied heat is also used to raise the liquid film temperature. Means the drying process performed. The critical moisture content in transition from the constant rate process to the decreasing process is 200-3
It is 00%. When the constant rate drying is completed, the drying can be carried out sufficiently until the flow stops, so that a drying method such as a silver halide photographic light-sensitive material can also be adopted. It is preferable to dry in a horizontal drying zone up to the drying point.

The drying conditions for forming the image forming layer and / or the protective layer are such that the liquid film surface temperature during constant rate drying is 3 to the minimum film forming temperature (MTF; usually glass transition temperature Tg of polymer) of the polymer latex. It is preferably 5 ° C higher) or higher. Normally, 25 ℃ -40 ℃ due to the limitation of manufacturing equipment
Often. Further, the dry-bulb temperature during the rate-decreasing drying is preferably a temperature lower than the Tg of the support (usually 80 ° C. or lower in the case of PET). The liquid film surface temperature in this specification refers to the solvent liquid film surface temperature of the coating liquid film applied to the support, and the dry bulb temperature refers to the temperature of the dry air in the drying zone.

When drying is performed under the condition that the temperature of the liquid film surface during constant rate drying becomes low, the drying tends to be insufficient. For this reason, the film-forming property of the protective layer is remarkably reduced, and cracks are likely to occur on the film surface. In addition, the film strength becomes weak, and serious problems such as scratches are likely to occur during conveyance by an exposure machine or a heat development machine.

On the other hand, when dried under the condition that the surface temperature of the liquid film becomes high, the protective layer mainly composed of polymer latex forms a film promptly, while the lower layer such as the image forming layer has low fluidity. Since it is not stopped, unevenness is likely to occur on the surface. Further, when excessive heat higher than Tg is applied to the support (base), the dimensional stability and curl resistance of the heat-developable image recording material tend to be deteriorated.

The same applies to the sequential coating in which the lower layer is applied and dried, and then the upper layer is applied. In particular, the simultaneous upper layer application in which the upper layer is applied before the lower layer is dried and both layers are simultaneously dried is applied. As for liquid properties, the pH difference between the coating liquid for the image forming layer and the coating liquid for the protective layer is preferably 2.5 or less, and the smaller the pH difference, the more preferable. PH of coating liquid
If the difference becomes large, microscopic aggregation easily occurs at the interface of the coating liquid, and serious surface defects such as coating streaks are likely to occur during long continuous coating.

The viscosity of the coating liquid of the image forming layer is 15 to 25 ° C.
100 mPa · s is preferable, and more preferably 30 to
It is 70 mPa · s. On the other hand, the coating liquid viscosity of the protective layer is 2
It is preferably 5 to 75 mPa · s at 5 ° C., and more preferably 20 to 50 mPa · s. These viscosities are measured with a B type viscometer.

The winding after drying is preferably carried out under the conditions of a temperature of 20 to 30 ° C. and a relative humidity of 45 ± 20%, and the winding form may be such that the image forming surface is on the outside depending on the subsequent processing form. It may be inside. Further, in the case where the processed form is a roll product, it is also preferable to use a roll form wound on the side opposite to the wound form at the time of processing in order to remove curl generated in the wound form. The relative humidity of the heat-developable image recording material is 2
It is preferably controlled in the range of 0 to 55% (measured at 25 ° C).

In the conventional photographic emulsion coating solution, which is a viscous liquid containing silver halide and containing gelatin as a base, bubbles are usually dissolved in the solution and disappeared only by feeding under pressure. Even if it is returned, air bubbles rarely precipitate. However, in the case of the image forming layer coating solution containing the organic silver salt dispersion and the polymer latex, which are preferably used in the present invention, defoaming tends to be insufficient only by pressure feeding, so that a gas-liquid interface does not occur. It is preferable to defoam by applying ultrasonic vibration while feeding the solution.

In the present invention, defoaming of the coating solution is carried out by degassing under reduced pressure before applying the coating solution, and further 1.5 kg / cm ²
It is preferable to use a system in which ultrasonic vibration is applied while continuously feeding the liquid while maintaining the above pressurized state and preventing the gas-liquid interface from occurring. Specifically, Japanese Examined Patent Publication No. 55-6405 (4
The method described on page 20, line 7 to page 7, line 11) is preferred. As an apparatus for performing such defoaming, Japanese Patent Laid-Open No. 2000-
The apparatus shown in the embodiment of Japanese Patent Publication No. 98534 and shown in FIG. 3 can be preferably used.

The pressurizing condition is preferably 1.5 kg / cm ² or more, more preferably 1.8 kg / cm ² or more. The upper limit is not particularly limited, but usually 5 kg / cm ²
It is a degree. The sound pressure of ultrasonic waves given is 0.2 V or more,
The sound pressure is preferably 0.5 V to 3.0 V, and it is generally preferable that the sound pressure is high. However, if the sound pressure is too high, the temperature becomes partially high due to capitation, which causes fog. The frequency is not particularly limited, but usually 10 kHz or more,
It is preferably 20 kHz to 200 kHz. Note that the depressurization degassing refers to hermetically depressurizing the inside of the tank (usually the preparation tank or the storage tank) to increase the diameter of bubbles in the coating liquid, depressurizing the buoyancy and degassing. Pressure reduction conditions are -200 mmHg or lower pressure conditions,
The pressure condition is preferably -250 mmHg or lower, and the lowest pressure condition is not particularly limited but is usually about -800 mmHg. Decompression time is 30 minutes or more,
It is preferably 45 minutes or longer, and the upper limit thereof is not particularly limited.

In the present invention, the image forming layer, the protective layer for the image forming layer, the undercoat layer and the back surface layer are described in JP-A No. 11-
Paragraph numbers 0204 to 0208 of Japanese Patent No. 84573 and paragraph numbers 0240 to 02 of Japanese Patent Laid-Open No. 2000-47083.
As described in 41, it is preferable to add a dye for the purpose of preventing halation.

From the viewpoint of improving color tone and preventing irradiation, various dyes and pigments are preferably used in the image forming layer. Any dye and pigment may be used in the image forming layer, but for example, compounds described in paragraph No. 0297 of JP-A No. 11-119374 are preferably used. Examples of the method for adding these dyes include solutions, emulsions, solid fine particle dispersions, and a state in which they are mordanted with a polymer mordant, and it is preferable to add an aqueous gelatin solution. The amount of these compounds used is determined depending on the intended absorption amount, but is generally 1 × 10 ⁻⁶ g to 1 per 1 m ^2.
It is preferably used in the range of g.

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 surface layer. Any compound may be used as long as it is obtained. Particularly, an antihalation dye having an absorption maximum at 750 to 850 nm can be preferably used. Examples of the antihalation dye that can be used in the present invention include the compounds described in paragraph No. 0300 of JP-A No. 11-119374. Further, as described in Belgian Patent No. 733,706, a method of decreasing the density of a dye by erasing by heating, and erasing by light irradiation as described in JP-A-54-17833. A method of decreasing the concentration can also be used. In the present invention, JP-A-11
It is preferable to use the compound described in paragraph No. 0297 of JP-A-119374.

When the heat-developable image recording material of the present invention is used as a mask when a printing plate is prepared by PS plate after heat development, the heat-developable image recording material after heat development is used for a 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, a plate-making machine S-FNRIII manufactured by Fuji Photo Film Co., Ltd. is used as a detector and bar code reader for detecting registration marks 670n.
A light source with a wavelength of m is used. Also, manufactured by Shimizu Manufacturing,
6 as bar code reader for plate making machine APML series
A 70 nm light source is used. That is, when Dmin (minimum density) near 670 nm is high, the information on the film cannot be accurately detected, and a work 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 needs to be 0.3 or less. More preferably 0.2
It is 5 or less. The lower limit is not particularly limited, but is usually about 0.10.

The size and shape of the heat-developable image recording material of the present invention are not particularly limited. For example, width 550 to 650 mm
And a sheet-like heat-developable image recording material having a length of 1 to 65 m. Further, this kind of sheet-shaped heat-developable image recording material can be partially or wholly wound around a cylindrical core member with the image forming surface facing outside.

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 10 ^-6 seconds or less. Generally, a laser diode (LD) or a light emitting diode is used. An exposure device using (LED) as a light source is preferably used. In particular, LD has a high output,
It is more preferable in terms of 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 of the present invention, the light beams of the light source are overlapped and exposed. The overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap refers to, for example, the beam diameter and the full width at half maximum (FW) of the beam intensity.
HM), it can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient).
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 and the like can be used. Also,
The channel of the light source may be a single channel or a multi-channel, but a multi-channel equipped with two or more laser heads is preferable in that high output can be obtained and the writing time can be shortened. Particularly, in the case of the cylindrical outer surface type, a multi-channel in which several to several tens or more laser heads are mounted 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. As a technique for preventing the generation of the interference fringes, Japanese Patent Laid-Open No. 5-113548
Disclosed in Japanese Patent Publication No. JP-A No. 2003-242242, a technique for obliquely entering laser light into a heat-developable image recording material, and international publication WO
Methods using a multimode laser disclosed in Japanese Patent Publication No. 95/31754 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 and 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- 29
7385 and International Publication WO95 / 30934, the thermal developing machine described in JP-A-7-13294 and International Publication WO97 / 28489 as a non-contact type.
No. 97/28488 and No. 97/28
There is a thermal developing machine described in Japanese Patent No. 487. A particularly preferred embodiment is a non-contact type heat developing machine. The preferred developing temperature is 80 to 250 ° C., more preferably 1
It is 00-140 degreeC. The developing time is preferably 1 to 180 seconds, more preferably 5 to 90 seconds. Line speed is 20 mm / sec or more, further 20-200 mm /
Seconds are preferred.

As a method for preventing uneven processing due to dimensional changes of the heat-developable image recording material during heat development, heating is carried out at a temperature of 80 ° C. or higher and lower than 115 ° C. for 5 seconds or longer, and then 110 ° C. A method of forming an image by thermal development at 140 ° C. (so-called multi-step heating method) is preferable.

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, and therefore, a part of the components contained in the material or a part of the decomposed components by the heat development. Will volatilize. 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. As a method for eliminating these influences, it is preferable to install a filter in the heat developing machine and optimally adjust the air flow in the heat developing machine. These methods can be effectively used in combination. International publication WO95 / 30933, ibid.
/ 21150 and Japanese Patent Publication No. 10-500946, a filter cartridge having a first opening having bound and absorbing particles and introducing a volatile component and a second opening discharging the volatile component is contacted with a film. It is described to be used in a heating device for heating by heating. In addition, international publication WO96 / 1
No. 2213 and Japanese Patent Publication No. 10-507403 describe using a filter in which a heat conductive condensing collector and a gas absorbing fine particle filter are combined. 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 the heat transfer member, and a heat transfer member are heated. And a device for doing so. In addition, International Publication WO98 / 27458 discloses that a component that increases volatilization fog from a film is removed from the film surface. These can also be preferably used in the present invention.

FIG. 1 shows an example of the constitution of a heat developing machine used for heat developing treatment of the heat developable image recording material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine of FIG. 1 carries in a heat developing image recording material 10 into a heating section while straightening and preheating the heat developing image recording material 10 (upper roller is a silicon rubber roller, lower roller is a heat roller made of aluminum). And a carry-out roller pair 12 for carrying out the heat-developed image recording material 10 after heat development from the heating section while straightening the heat-developed image recording material 10. 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 image forming surface is in contact, and a nonwoven fabric (for example, aromatic material) on the side where the back surface on the opposite side is in contact. A smooth surface 14 to which polyamide, Teflon (registered trademark) or the like is attached is provided. The heat-developable image recording material 10 is conveyed while the back surface slides on the smooth surface 14 by driving a plurality of rollers 13 that are in contact with the image forming surface. A heater 15 is installed above the roller 13 and below the smooth surface 14 so that both sides of the heat-developable image recording material 10 are heated. In this case, the heating means may be a plate heater or the like. Roller 13 and smooth surface 14
The clearance between and differs depending on the member having a smooth surface, but is appropriately adjusted to a clearance that allows the heat-developable image recording material 10 to be conveyed. It is preferably 0 to 1 mm.

Surface material of roller 13 and smooth surface 1
The member No. 4 has high temperature durability, and the heat-developable image recording material 1
Any material may be used as long as it does not hinder the transport of 0, but the material of the roller surface is preferably silicone rubber, and the member of the smooth surface is preferably a nonwoven fabric made of aromatic polyamide or Teflon (PTFE).
It is preferable to use a plurality of heaters as the heating means and set the heating temperature freely.

The heating section is composed of a preliminary heating section A having a carry-in roller pair 11 and a thermal development heating section B provided with a heater 15. The preliminary heating section upstream of the thermal development processing section B is used. A is lower than the heat development temperature (for example, 10 to 3).
It is desirable to set the temperature and time sufficient to evaporate the amount of water in the heat-developable image recording material 10 below the glass transition temperature (Tg) of the support of the heat-developable image recording material 10. It is preferable to set so that development unevenness does not occur even at a high temperature. The temperature distribution between the preheating section and the heat development processing section is preferably ± 1 ° C or less, more preferably ± 0.5 ° C or less. Further, a guide plate 16 is installed downstream of the heat development processing section B, and a slow cooling section C having a carry-out roller pair 12 and a guide plate 16 is installed. The guide plate 16 is preferably made of a material having a low heat conductivity, and it is preferable to gradually cool the heat-developable image recording material 10 so that the heat-developable image recording material 10 is not deformed.
10 ° C./second is preferable.

Although the above description has been made according to the illustrated example, the present invention is not limited to this, and the heat developing machine used in the present invention may have various structures such as the one described in JP-A-7-13294. Further, in the case of the multi-step heating method preferably used in the present invention, in the apparatus as described above,
Two or more heat sources having different heating temperatures may be installed to continuously heat at different temperatures. The heat-developable image recording material of the present invention is described by the packaging materials described in JP-A 2000-206653, paragraphs 0014 to 0026, or in JP-A 2001-13632, paragraphs 0020 to 0045. It is preferable that the packaging is performed according to the packaging method described below.

[0138]

EXAMPLES The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials shown in the following examples,
The usage amount, ratio, processing content, processing procedure, etc. can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

[0139]Example 1 <Polyethylene terephthalate with back / undercoat layer
Preparation of PET support> << Preparation of PET support >> Terephthalic acid and ethylene glycol
Intrinsic viscosity IV = 0.66 (Flu
2 in phenol / tetrachloroethane = 6/4 (mass ratio)
Polyethylene terephthalate (measured at 5 ° C.) was obtained. This
Pellet it and dry it at 130 ° C for 4 hours, then
After melting at 0 ° C, extruding from a T-die and further quenching, heat
An unstretched film having a thickness of 120 μm after fixing.
I made the film. Using the rolls with different peripheral speeds,
Vertical stretching to 3.3 times, then horizontal stretching to 4.5 times with a tenter
Was carried out. The temperatures at this time are 110 ° C and 1 respectively.
It was 30 ° C. After this, heat set at 240 ° C for 20 seconds
Later, at the same temperature as this, 4% was relaxed in the lateral direction. After this,
After slitting the chuck part of the tenter, knurl on both ends.
Processed to 4.8 kg / cm²I wound it up. This
Thus, width 2.4m, length 3500m, thickness 120μ
A m-rolled PET support was obtained.

<Formation of Undercoat Layer and Back Layer> First Undercoat Layer A coating solution having the composition shown below was applied on a support at a concentration of 9.7 mL / m ² and then at 125 ° C. for 30 seconds and 150 ° C. Thirty
Second, dried at 185 ° C. for 30 seconds. Latex-A 280 g KOH 0.5 g Polystyrene fine particles 0.03 g (average particle size 2 μm, variation coefficient of average particle size 7%) 2,4-dichloro-6-hydroxy-s-triazine 1.8 g Distilled water Total amount 1000 g Amount

Latex-A: core-shell type latex core portion having a core portion of 90% by weight and a shell portion of 10% by weight: 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 = 8
8/3/3/3/3 (mass%) mass average molecular weight 38,000

Undercoating second layer A coating solution having the composition shown below is applied onto the undercoating first layer so as to have a concentration of 8.3 mL / m ^2, and the mixture is heated 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 10 g (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) Acetic acid (20% aqueous solution) 10 g Compound-Bc-A 0.04 g Methylcellulose (2% aqueous solution) 25 g Emarex 710 (Japan emulsion ( Co., Ltd.) 0.3g Distilled water Total amount is 1000g

Back first layer 0.375 kV · on the surface opposite to the surface coated with the undercoat layer.
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. Pethresin A520 (30% aqueous dispersion, manufactured by KK) 46 g Alkali-treated gelatin 4.44 g (molecular weight about 10,000, Ca ²⁺ content 30 ppm) Deionized gelatin (Ca ²⁺ content 0.6 ppm) 0.84 g Compound- Bc-A 0.02 g Dye-Bc-A (adjusted so that the optical density at 783 nm is 1.3 to 1.4) As a guideline 0.88 g Polyoxyethylene phenyl ether 1.7 g Sumitex Resin M- 3 (8% aqueous solution) 15 g (water-soluble melamine compound, manufactured by Sumitomo Chemical Co., Ltd.) FS-10D 24 g (aqueous dispersion of needle-shaped particles of Sb-doped SnO ₂ , manufactured by Ishihara Sangyo Co., Ltd.) Polystyrene fine particles 0.03g (Average particle size 2μm, coefficient of variation of average particle size 7%) Distilled water Total amount of 1000g Bag Second layer Below The coating liquid was applied to the back first layer on to a 9.7mL / m ^2, 30 seconds at 125 ° C., 0.99
It was dried at 30 ° C. for 30 seconds and at 170 ° C. for 30 seconds.

[0144]     Latex-A 280g     KOH 0.5g     Polystyrene fine particles 0.03g     (Average particle size 2 μm, coefficient of variation of average particle size 7%)     1.8 g of 2,4-dichloro-6-hydroxy-s-triazine     Distilled water amount of 1000g

Back third layer A coating solution having the composition shown below was applied on the back second layer so as to have a concentration of 8.3 mL / m ^2, and the mixture was kept 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 10 g (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) Acetic acid (20% aqueous solution) 10 g Compound-Bc-A 0.04 g Methylcellulose (2% aqueous solution) 25 g Emalex 710 (Nippon Emulsion (stock) )) 0.3 g Potassium chloride 1.0 g Potassium bromide 1.0 g Distilled water Total amount of 1000 g

Back fourth layer A coating solution having the composition shown below was applied on the back third layer so that the concentration was 13.8 mL / m ^2, and the temperature was set 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. Coating liquid B-1
Was applied to sample 101, B-2 was applied to sample 102, and B-3 was applied to sample 103. Coating liquid B-1 Chemipearl S120 73.1 g (27% water dispersion, manufactured by Mitsui Chemicals, Inc.) Pethresin A615G 78.9 g (25% water dispersion, manufactured by Takamatsu Yushi Co., Ltd.) Compound-Bc-B 2. 7 g Compound-Bc-C 0.3 g Compound-Bc-D 0.25 g Denacol EX521 3.4 g (water-soluble epoxy compound, manufactured by Nagase Kasei Co., Ltd.) Polymethyl methacrylate 7.7 g (10% aqueous dispersion, average) Particle size 5 μm, coefficient of variation of average particle 7%) Distilled water Total amount is 1000 g

[0147]   Coating liquid B-2     Latex-B 286g     Compound-Bc-B 1.5 g     Compound-Bc-C 0.6 g     Compound-Bc-D 0.5 g     Sumitex Resin M-3 (8% aqueous solution) 195g     (Water-soluble melamine compound, Sumitomo Chemical Co., Ltd.)     Polymethylmethacrylate 7.7g     (10% aqueous dispersion, average particle size 5 μm)     Distilled water amount of 1000g

Latex-B: methyl methacrylate /
Styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9 /
26/5/1 (mass% copolymer)

Coating liquid B-3 Jurima-ET410 23 g (30% water dispersion, manufactured by Nippon Pure Chemical Co., Ltd.) Chemipearl S120 135 g (27% water dispersion, manufactured by Mitsui Petrochemical Co., Ltd.) Alkali-treated gelatin 12. 7 g (molecular weight about 10,000, Ca ²⁺ content 30 ppm) Compound-Bc-D 0.25 g Cerosol 524 (30% aqueous solution, manufactured by Chukyo Yushi Co., Ltd.) 12 g Denacol EX521 1.8 g (water-soluble epoxy compound, Nagase Chemical Industries ( Manufactured by KK) Polymethylmethacrylate 7.7 g (10% aqueous dispersion, average particle size 5 μm, coefficient of variation of average particles 7%) Distilled water Total amount of 1000 g

<Preparation of Material for Coating Solution><< Preparation of Silver Halide Emulsion A '>> 11 g of alkali-processed gelatin (calcium content: 2700 ppm or less), 30 mg of potassium bromide, and 1-sodium 4-methylbenzenesulfonate in 700 mL of water. Dissolve 0.3 g and temperature 4
After adjusting the pH to 6.5 at 5 ° C, 18.6 g of silver nitrate
Containing 159 mL of an aqueous solution containing 1 mol / 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 of K ₃ IrCl ₆ were added.
While maintaining the pAg at 7.7, the aqueous solution of halogen salt contained in the amount of / L was added over 28 minutes and 30 seconds by the control double jet method. After that, the pH was lowered to cause aggregation 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,
It was adjusted to pH 5.9 and pAg 8.0. The obtained particles have an average particle size of 0.11 μm, a projected area variation coefficient of 9%,
It was a cubic grain having a (100) plane ratio of 90%. To the silver halide grains thus obtained, 76 μmol of sodium benzenethiosulfonate and 71 μmol of triethylthiourea were added per 1 mol of silver, followed by ripening to give 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. After adding 5 × 10 ⁻⁴ mol and 0.17 g of Compound A, 4.7 × 10 ⁻² mo was added to 1 mol of silver halide.
l potassium bromide (added as an aqueous solution), 12.8 x 1
0 ^-4 mol of the following sensitizing dyes A, B or C (added as an ethanol solution), 6.4 × 10 ^-3 mol of compound B
(Added as a methanol solution) with stirring,
After 20 minutes, it was rapidly cooled to 30 ° C. to complete the preparation of silver halide emulsion A ′. The obtained silver halide emulsion A'was used for the preparation of the following coating solution.

[0151]

[Chemical 1]

[Chemical 2]

<< Preparation of Silver Behenate Dispersion A >> Behenic acid (produced by Henkel, product name Edenor C22-85R)
87.6 g of 5 mol / L NaOH aqueous solution 49.2
mL and tert-butyl alcohol 120 mL were mixed and reacted at 75 ° C. to obtain a sodium behenate solution. This sodium behenate solution and an aqueous solution of silver nitrate were added to a stirring reaction vessel containing 635 mL of distilled water and 30 mL of tert-butyl alcohol.
At this time, the temperature in the reaction vessel was set to 30 ° C. and controlled so that the liquid temperature did not rise. After the addition was completed, the solid content was separated by suction filtration and washed with water. Next, 7.4 g of polyvinyl alcohol (trade name: PVA-217, average degree of polymerization: about 1700) and water were added to the obtained wet cake having a solid content of 100 g of silver behenate, and the mixture was preliminary prepared with a homomixer. After dispersion, a disperser (manufactured by Microfluidex International Corporation, trade name: Microfluidizer M-110S-EH, G1
It was dispersed in a 0Z interaction chamber) to obtain a behenic acid dispersion A. The obtained behenic acid dispersion A was used for preparing the coating liquid described below.

<< 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 denatured polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 20 mass% aqueous solution 10 kg, Surfynol 104E (Nissin Chemical Co., Ltd.) 400 g,
640 g of methanol and 16 kg of water were added and mixed well to form a slurry. This slurry was dispersed by a horizontal bead mill (UVM-2, manufactured by IMEX Co., Ltd.), and then 4 g of benzoisothiazolinone sodium salt and water were added to obtain a solid fine particle dispersion of a reducing agent. The reducing agent particles contained in the thus obtained dispersion have a median diameter of 0.44 μm,
The maximum particle size was 2.0 μm or less, and the average particle size variation coefficient was 19%. The obtained solid fine particle dispersion of the reducing agent was used for the preparation of the coating liquid described below.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound A >> 10 kg of polyhalogen compound A and modified polyvinyl alcohol (Poval M manufactured by Kuraray Co., Ltd.)
P203) 20 mass% aqueous solution 10 kg, sodium triisopropylnaphthalene sulfonate 20 mass% aqueous solution 639 g, Surfynol 104E (manufactured by Nisshin Chemical Co., Ltd.) 400 g, methanol 640 g, and water 16
It was thoroughly mixed with kg to obtain a slurry. A horizontal bead mill (UVM-, manufactured by AIMEX Co., Ltd.)
After dispersing in 2), water is added to polyhalogen compound A.
Was adjusted to a concentration of 25% by mass to obtain a solid fine particle dispersion of organic polyhalogen compound A. The organic polyhalogen compound particles contained in the thus-obtained dispersion had a median particle size of 0.36 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 18%. The obtained solid fine particle dispersion of the organic polyhalogen compound A was used for the preparation of the following coating solution.

<< Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound B >> 5 kg of polyhalogen compound B and denatured polyvinyl alcohol (Poval MP2 manufactured by Kuraray Co., Ltd.)
2.5 kg of a 20 mass% aqueous solution of No. 03), 213 g of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate, and 10 kg of water were thoroughly mixed to form a slurry. This slurry was dispersed in a horizontal bead mill (UVM-2, manufactured by Aimex Co., Ltd.), and then 2.5 g of benzoisothiazolinone sodium salt and water were added to the mixture so that the concentration of the polyhalogen compound B was 23.5% 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 size of 2.0 μm or less, and a variation coefficient of the average particle size of 20%. The obtained solid fine particle dispersion of the organic polyhalogen compound B was used for the preparation of the following coating liquid.

<< Preparation of Organic Polyhalogen Compound C Aqueous Solution >> While stirring at room temperature, 75.0 mL of water and sodium tripropylnaphthalenesulfonate (20% aqueous solution)
8.6 mL, sodium dihydrogen orthophosphate dihydrate (5% aqueous solution) 6.8 mL, and potassium hydroxide 1
A mol / L aqueous solution (9.5 mL) was sequentially stirred and mixed. Further, 4.0 g of powder of the polyhalogen compound C was added while stirring, and 100 m of the organic polyhalogen compound C aqueous solution was added.
L was obtained. The obtained aqueous solution of the organic polyhalogen compound C was used for the preparation of the coating liquid described below.

<< Preparation of Emulsified Dispersion of Compound Z >> Compound Z
R-054 containing 85% by mass of Sanko Co., Ltd.
After mixing g with MIBK (11.66 kg), the mixture was replaced with nitrogen and dissolved at 80 ° C. for 1 hour. 25.52k of water in this liquid
12.76 kg of 20% by mass aqueous solution of g and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203)
And 0.44 kg of a 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate are added to the mixture to give 20 to 20.
It was emulsified and dispersed at 40 ° C. and 3600 rpm for 60 minutes. Furthermore, Surfynol 104E (Nisshin Chemical Co., Ltd.)
0.08 kg of water and 47.94 kg of water were added and distilled under reduced pressure to remove MIBK.
It was prepared to be 0% by mass. The obtained emulsified dispersion of compound Z was used for preparation of the following coating liquid.

<< Preparation of 6-Isopropylphthalazine Compound Dispersion >> While stirring 62.35 g of water at room temperature, modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval M) was used.
P203) (2.0 g) and stirred and mixed for 10 minutes,
It heated and was made to melt | dissolve uniformly in the range of internal temperature 50-60 degreeC.
The inner temperature was lowered to 40 ° C. or lower, and polyvinyl alcohol (Kuraray Co., Ltd., PVA-217, 10 mass% aqueous solution) 2
5.5 g, sodium tripropylnaphthalene sulfonate (20% by mass aqueous solution) 3.0 g, and 6-isopropylphthalazine (70% by mass aqueous solution) 7.15 g were added and mixed with stirring to obtain 100 g of a transparent dispersion liquid. It was The obtained dispersion liquid of 6-isopropylphthalazine compound was used for preparation of the following coating liquid.

<< Preparation of Solid Fine Particle Dispersion of Development Accelerator W >> 10 kg of the development accelerator W, 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), and 20 kg of water are added. Mix well to form a slurry. This slurry was applied to a horizontal bead mill (U
VM-2: manufactured by IMEX Co., Ltd., and then dispersed by adding water so that the concentration of the development accelerator W was adjusted to 20% by mass to obtain a solid fine particle dispersion of the development accelerator W. The obtained solid fine particle dispersion of the development accelerator W was used for preparation of the following coating liquid.

<Preparation of heat-developable image recording material> Sample 101
The coating solution for the image forming layer and the coating solution for the protective layer were applied to Nos. 103 to 103 to prepare a heat developable image recording material.

<< Preparation of Coating Solution for Image Forming Layer >> To 1 mol of silver of the 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. This coating solution contains 10% methanol and ethanol as organic solvents.
The coating liquid contained mass%. After completion, vacuum degassing was performed for 45 minutes at a pressure of 0.54 atm. The coating solution had a pH of 7.7 and a viscosity of 50 mPa · s at 25 ° C.

Binder; SBR latex Solid content 397 g (St / Bu / AA = 68/29/3 (mass%), Na ₂ S ₂ O ₈ is used as a polymerization initiator) 1,1-bis (2-hydroxy) -3,5-Dimethylphenyl) -3,5,5-trimethylhexane Solid content 149.5 g Polyhalogen compound B Solid content 36.3 g Polyhalogen compound C Solid content 2.34 g Sodium ethylthiosulfonate 47 g Benzotriazole 1.02 g Polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 10.8 g 6-Isopropylphthalazine 15.0 g Compound Z Solid content 9.7 g Compound X 7.7 g Dye A (with an average molecular weight of 10.5000) Added as a mixture with low molecular weight gelatin) The optical density at 783 nm becomes 0.3 The coating amount as the silver halide emulsion A Ag amount 40ppm Compound A coating solution as 0.06mol preservative as (2.5 mg / m ² as coated amount) pH adjusting agent (solid 0.40g as a guide), the NaOH Adjusted using. (The glass transition temperature of the coating film was 17 ° C.)

<< Preparation of Coating Solution for Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2
-Hydroxyethyl methacrylate / acrylic acid = 5
8.9 / 8.6 / 25.4 / 5.1 / 2 (mass%) polymer latex solution (copolymer glass transition temperature 46
C. (calculated value), solid content concentration of 21.5% by mass, compound A of 100 ppm, and compounding agent of compound D of 15% by mass relative to latex solid content, glass transition temperature of coating liquid Water was added to 943 g of an average particle size of 116 nm) at 24 ° C. to obtain an aqueous solution of polyhalogen compound C of 114.8 g, polyhalogen compound A as a solid content of 17.0 g, and sodium dihydrogen orthophosphate dihydrate. 0.69 g as solid content, development accelerator W
As solids, 11.55 g, matting agent (polystyrene particles, average particle size 7 μm, variation coefficient of average particle size 8%) 1.58 g, polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 29.3 g and compound E
Was added and water was further added to prepare a coating liquid (containing 0.8% by mass of a methanol solvent). After completion, vacuum degassing was performed for 60 minutes at a pressure of 0.47 atm. The coating solution had a pH of 5.5 and a viscosity of 45 mPa · s at 25 ° C.

[0164]

[Chemical 3]

<< Preparation of Coating Solution for Lower Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) polymer latex solution (copolymer glass transition temperature 46 ° C. (calculated value), solid content concentration 21.
5% by mass, 100 ppm of compound A was added, and compound D was added to the latex solid content as a film-forming auxiliary at 1%.
Water was added to 625 g of an average particle size of 74 nm, in which the coating liquid had a glass transition temperature of 24 ° C.
10.3 g of compound C, 0.13 g of compound E, 11.7 g of compound F, 2.7 g of compound H and polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 11.
5 g was added, and water was further added to prepare a coating solution (containing 0.1% by mass of a methanol solvent). After completion, vacuum degassing was performed for 60 minutes at a pressure of 0.47 atm. The coating solution had a pH of 2.6 and a viscosity of 30 mPa · s at 25 ° C.

<< Preparation of Coating Solution for Upper Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) polymer latex solution (copolymer glass transition temperature 46 ° C. (calculated value), solid content concentration 21.
5% by mass, 100 ppm of compound A was added, and compound D was added to the latex solid content as a film-forming auxiliary at 1%.
Water was added to 649 g of 5% by mass and the coating solution having a glass transition temperature of 24 ° C. and an average particle size of 116 nm), and carnauba wax (Cherosol 524, manufactured by Chukyo Yushi Co., Ltd .: silicone content less than 5 ppm) 30 mass%
Solution 18.4 g, compound C 0.23 g, compound E 1.85 g, compound G 1.0 g, matting agent (polystyrene particles, average particle size 7 μm, average particle size variation coefficient 8%) 3.45 g and 26.5 g of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.) was added, and water was further added to the coating solution (methanol solvent was 1.1%).
Mass% content) was prepared. After completion, vacuum degassing was performed at a pressure of 0.
It was carried out at 47 atm for 60 minutes. The pH of the coating solution is 5.3,
The viscosity was 25 mPa · s at 25 ° C.

[0167]

[Chemical 4]

From the above, samples 101 to 103 were obtained.

<Evaluation of Sample> Sample 10 obtained as described above.
Each of Nos. 1 to 103 was formed into a sheet having a width of 610 mm and a length of 59 m, which was wound around a cylindrical core member with the image forming layer surface facing outward to obtain a roll-shaped sample. This roll-shaped sample was set on FT-286R manufactured by NEC having a semiconductor laser of 785 nm. This exposure device (plotter) and automatic thermal processor FDS-610
Dock 0X (Fuji Photo Film Co., Ltd.),
It was exposed and heat-developed. Thermal development temperature during thermal development is 1
The processing was performed at 21 ° C. and a line speed of 25 mm / sec.

<Measurement of Beck's smoothness> The Beck's smoothness of the back surface of each sample was measured by the Japanese Industrial Standard (JIS) P8119.
"Smoothness test method for paper and board by Beck tester"
And TAPPI standard method T479. The results are shown in Table 1.

<< Measurement of Surface Energy >> A sample subjected to heat development was measured by an automatic contact angle measuring instrument (Kyowa Interface Science Co., Ltd .: C).
AZ) and the contact angle of water and methylene iodide to 2
The measurement was performed at 5 ° C. and a relative humidity of 50%, and the surface energy was calculated from the value using the Forks equation. The results are shown in Table 1.

<< Transportability Test >> An automatic plate making machine S-FNR-IV (manufactured by Fuji Photo Film Co., Ltd.) was used for heat-developed samples.
Was placed in a thermostatic chamber, and a relative humidity was set to 60% or 75% to carry out a transportation test. The surface energy of the tape A (standard specification tape) used for transportation was 30 mJ / m ² . The sample size used was 610 mm × 450 mm. The wavelength of the position reading sensor is 670.
nm was used. After carrying out a 200-sheet carrying test by a normal use method, two sheets of each sample were overlaid with double-sided tape to increase the mass than usual, and a 200-sheet carrying test was carried out.
Further, the same experiment as above was conducted using a tape B having a surface energy of 40 mJ / m ² as a tape used for transportation. The above results are shown in Table 1. It is apparent that the heat developable image recording material of the present invention has improved transportability under high humidity.

[0173]

[Table 1]

[0174]Example 2 <Preparation of support> << Preparation of subbed support >> Commercially available biaxially stretched and heat-fixed
8 W / m on both sides of PET film (thickness 120 μm)
²・ A corona discharge treatment for minutes is applied to one surface
Apply cloth liquid a to a dry film thickness of 0.8 μm and dry
To form the undercoat layer A, and to the surface on the opposite side,
The prepared subbing coating solution b is adjusted to have a dry film thickness of 0.8 μm.
It was applied to and dried to obtain an antistatic-treated subbing layer B.

[0175]   Subbing coating liquid a     270 g of copolymer latex liquid having a solid content of 30%     (Butyl acrylate / tert-butyl acrylate /       Styrene / 2-hydroxyethyl acrylate = 30 /       20/25/25 (mass%))     Hexamethylene-1,6-bis (ethylene urea) 0.8 g     Polystyrene fine particles (average particle size 3 μm) 0.05 g     Colloidal silica (average particle size 90 μm) 0.1 g     Amount of water that totals 1 liter

Subbing coating liquid b SnO ₂ / Sb (9/1 (mass ratio)) (average particle size 0.18 μm) 200 mg / m ² amount A copolymer latex liquid having a solid content of 30% 270 g (butyl acrylate) / Styrene / Glycidyl acrylate = 30/20/40 (mass%)) Hexamethylene-1,6-bis (ethylene urea) 0.8 g Water Amount that makes the total amount 1 liter

<< Heat Treatment of Support >> In the undercoat drying step of the above-mentioned undercoated support, the support is heated at 140 ° C.,
Then, it was gradually cooled.

<Preparation of Material for Coating Solution><< Preparation of Silver Halide Emulsion A >> 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 mL of water to adjust the temperature to 35 ° C. and pH to 3.0. After that, silver nitrate 7
An aqueous solution containing 4 g of 370 mL, an aqueous solution containing sodium chloride, potassium bromide and potassium iodide in a molar ratio of 60/38/2, and 1 × 10 ⁻⁶ mol of [Ir (NO) Cl ₅ ] salt per mol of silver. , 1 × 10 per mol of silver
^-6 mol of rhodium chloride salt was added by the controlled double jet method while keeping the pAg at 7.7. Then 4-hydroxy-6-methyl-1,3,3a, 7-
Add tetrazaindene and adjust pH to 8 with NaOH, pAg
Reduction sensitization was performed by adjusting to 6.5, and cubic silver iodobromide grains having an average grain size of 0.06 μm, a monodispersity of 10%, a variation coefficient of the projected diameter area of 8%, and a [100] plane ratio of 87%. Got This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment to obtain a silver halide emulsion A.
The obtained silver halide emulsion A was used for the preparation of the following coating solution.

<< Preparation of Sodium Behenate Solution >> 945
32.4 g of behenic acid and 9.9 arachidic acid in mL of pure water.
g and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at high speed, 98 mL of a 1.5 mol / L sodium hydroxide aqueous solution was added. Further concentrated nitric acid 0.93
After adding mL, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution. The obtained sodium behenate solution was used for preparation of the following coating solution.

<< Preparation of Preform Emulsion A >> 15.1 of the above silver halide emulsion A was added to the above sodium behenate solution.
After adding g and adjusting the pH to 8.1 with a sodium hydroxide solution, 147 mL of a 1 mol / L silver nitrate solution was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The obtained silver behenate was particles having an average particle size of 0.8 μm and a monodispersity of 8%. After forming a floc in the dispersion, water was removed, and after washing with water 6 times and water removal, the product was dried to obtain Preform Emulsion A. The obtained preform emulsion A was used for the preparation of the following coating solution.

<< Preparation of Photosensitive Emulsion A >> To the obtained preform emulsion A, 544 g of a methyl ethyl ketone solution (17% by mass) of polyvinyl butyral (average molecular weight 3,000) and 107 g of toluene were gradually added. After mixing, the mixture was dispersed at 4000 psi with a media disperser using a 0.5 mm size ZrO ₂ bead mill to prepare a photosensitive emulsion A. The resulting photosensitive emulsion A was used for preparing the coating solution described below.

<Preparation of heat-developable image recording material> Coating solutions for the following layers were simultaneously coated on both sides of the support to prepare a sample of the heat-developable image recording material. In addition, each is dried at 60 ℃
Then, it took 15 minutes.

<< Coating on Back Side >> Undercoat layer B of support
A coating liquid having the following composition was applied onto A sample coated with the coating liquid C-1 was designated as a sample 201, a sample coated with the coating liquid C-2 was designated as a sample 202, and a sample coated with the coating liquid C-3 was designated as a sample 203.

[0184]   Coating liquid C-1     Cellulose cellulose acetate butyrate 15mL / m²     (10% methyl ethyl ketone solution)     Polyester (Byron 200 (manufactured by Toyobo Co., Ltd.)) 2.5 mL / m²     (10% methyl ethyl ketone solution)     Dye 7g / m²     Dye 7 mg / m²     Monodisperse silica matting agent 5mg / m²     (Monodispersion degree 15%, average particle size 8 μm monodisperse silica)     Compound-Bc-B 30 mg / m²     Compound-Bc-C 40 mg / m²     Compound-Bc-D 20 mg / m²

[0185]   Coating liquid C-2     Cellulose cellulose acetate butyrate 15mL / m²     (10% methyl ethyl ketone solution)     Polyester (Byron 200 (manufactured by Toyobo Co., Ltd.)) 2.5 mL / m²     (10% methyl ethyl ketone solution)     Dye 7 mg / m²     Dye 7 mg / m²     Monodisperse silica matting agent 10 mg / m²     (Monodispersion degree 15%, average particle size 8 μm monodisperse silica)     Compound-Bc-C 40 mg / m²     Compound-Bc-D 20 mg / m²

[0186]   Coating liquid C-3     Cellulose Cellulose Acetate Butyrate     (10% methyl ethyl ketone solution)     Dye 7g / m²     Dye 7 mg / m²     Monodisperse silica matting agent 30 mg / m²     (Monodispersion degree 15%, average particle size 8 μm monodisperse silica)     C₈F₁₇(CH₂CH₂O)₁₂C₈F₁₇                      50 mg / m²     C₈F₁₇-C₆H_Four-SO₃Na 10 mg / m²

<< Coating on Image Forming Side >> On the undercoat layer A of the support, an image forming layer coating solution having the following composition and a protective layer coating solution were simultaneously coated in a multilayer and dried. The image forming layer was coated such that the coated silver amount was 2.4 g / m ² . The image forming layer coating liquid contains 50 mass% of methyl ethyl ketone, toluene, methanol and acetone as organic solvents.
The coating liquid was contained.

[0188]   Image forming layer coating liquid     Photosensitive emulsion A 240g     Sensitizing dye (0.1% methanol solution) 1.7 mL     Pyridinium bromide perbromide (6% methanol solution) 3 mL     Calcium bromide (0.1% methanol solution) 1.7 mL     Oxidizing agent (10% methanol solution) 1.2mL     2,4-Dichlorobenzoylbenzoic acid 9.2 mL     (12% methanol solution)     2-mercaptobenzimidazole 11mL     (1% methanol solution)     Oxidizing agent 17mL   (Tribromomethylsulfoquinoline (5% methanol solution))     Phthalazine 0.6g     Hydrazine derivative 0.3g     Hydrazine derivative 0.3g     N-methylfurohydroxamic acid 0.3 g     4-methylphthalic acid 0.25g     Tetrachlorophthalic acid 0.2g     Developer (20% methanol solution) 29.5mL     Isocyanate compound     (Desmodur N3300 manufactured by Mobay) 0.5 g     Ethyl 1-cyano-2-hydroxyacrylate 0.2 g

[0189]   Surface protective layer coating liquid     Acetone 5mL / m²     Methyl ethyl ketone 21mL / m²     Cellulose acetate butyrate 2.3 g / m²     Methanol 7mL / m²     Phthalazine 250 mg / m²     Monodisperse silica matting agent 70mg / m²     (Monodispersity 10%, average particle size 4 μm)     CH₂= CHSO₂CH₂CH₂OCH₂CH₂SO₂CH = CH₂                                                       35 mg / m²     C₈F₁₇(CH₂CH₂O)₁₂C₈F₁₇                  100 mg / m²     C₈F₁₇-C₆H_Four-SO₃Na 10 mg / m²

[0190]

[Chemical 5]

[0191]

[Chemical 6]

From the above, samples 201 to 203 were obtained.

<Evaluation of Sample> Sample 20 obtained as described above.
Sheets Nos. 1 to 203 each having a width of 610 mm and a length of 59 m were wound on a cylindrical core member with the image forming surface facing outward to form a roll sample. This roll-shaped sample was set on FT-286R manufactured by NEC having a semiconductor laser of 785 nm. This exposure device (plotter) and automatic thermal processor FDS-6100
X (manufactured by Fuji Photo Film Co., Ltd.) was docked, and exposed and heat-developed. The heat development temperature during heat development is 121
C., and the line speed was 29 mm / sec.

By the same method as in Example 1, the Bekk smoothness and the surface energy of the back surface of each sample were measured, and the transportability test was conducted. The results are shown in Table 2. It is apparent that the heat developable image recording material of the present invention has improved transportability under high humidity.

[0195]

[Table 2]

[0196]Comparative Example 1 An experiment similar to the transportability test of Example 1 was performed using the position reading session.
Change the wavelength of the sensor from 670 nm to 780 nm.
It was. However, the number of transported sheets is 50, and the relative humidity is 75.
Set to%. The results are shown in Table 3. Position reading sensor
670nm as the wavelength
Confirmed that the transportability is significantly improved by
Was done.

[0197]

[Table 3]

[0198]

According to the present invention, it is possible to provide a heat-developable image recording material excellent in transportability, especially for photolithography.

[Brief description of drawings]

FIG. 1 is a side view showing an example of the configuration of a heat developing machine used for heat developing treatment of a heat developable image recording material of the present invention.

[Explanation of symbols]

10 Thermal development image recording material 11 Carry-in roller pair 12 Delivery roller pair 13 roller 14 smooth surface 15 heating heater 16 Guide plate A Preheating section B heat development processing section C slow cooling section

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) G03C 5/08 351 G03C 5/08 351 G03D 13/00 G03D 13/00 A EU F term (reference) 2H112 AA03 BA08 BA17 BA23 BC02 BC08 BC41 2H123 AB00 AB03 AB23 AB28 BA00 BA14 BA48 BA64 BB00 BB17 BC00 BC01 BC06 CA00 CA16 CA20 CB00 CB03

Claims (13)

[Claims] 1. A heat-developable image recording material having at least one image-forming layer on one side of a support, wherein the surface energy of the outermost layer on the opposite side of the support after the heat-development treatment is heat-developable image recording material which is a ^{10mJ / m 2 ~70mJ / m 2} . 2. A heat-developable image having at least one image-forming layer on one side of a support and conveyed by a tape adhered to an outermost layer on the opposite side of the support from the image-forming layer. A heat-developable image recording material, wherein the difference between the surface energy of the outermost layer and the surface energy of the tape is 30 mJ / m ² or less. 3. The surface energy of the outermost layer on the side opposite to the image forming layer with respect to the support after the heat development treatment is 20 mJ / m ^2.
The heat-developable image recording material according to claim 1 or 2, wherein the heat-developable image recording material has a density of -50 mJ / m ² . 4. A hydrophobic cellulose derivative as a binder, wherein at least one layer constituting the surface of the support on the side opposite to the image forming layer contains a hydrophobic cellulose derivative as a binder.
4. The heat-developable image recording material according to any one of 3 to 3. 5. The heat-developable image recording material according to claim 4, wherein the layer containing the hydrophobic cellulose derivative is a layer formed by applying a coating liquid containing 20% by mass or more of an organic solvent. 6. The heat-developable image recording material according to claim 1, wherein the Beck second of the surface of the support opposite to the image forming layer is 1500 seconds or less. . 7. A fluorosurfactant having a molecular weight of 500 or more is contained as a coating aid for the outermost layer on the side opposite to the image forming layer with respect to the support. The heat-developable image recording material as described in 1. 8. The heat-developable image recording material according to claim 1, wherein the image forming layer contains an organic silver salt and a reducing agent. 9. The heat-developable image recording material according to claim 1, further comprising an antihalation dye having an absorption maximum at 750 to 850 nm. 10. The heat-developable image recording material has a width of 550 to 65.
A sheet-like member having a length of 0 mm and a length of 1 to 65 m, and a part or all of the sheet member is wound around a cylindrical core member with the image forming layer facing outside. The heat-developable image recording material as described in 1) above. 11. The heat-developable image recording material according to claim 1, which has recording information, is exposed with light having a wavelength of 750 to 800 nm, and the wavelength is 600 to 7.
A method of processing a heat-developable image recording material, which comprises reading recorded information with light of 00 nm. 12. A heat developing machine having a heat developing section.
10. The method for heat-developing the heat-developable image recording material according to any one of 10 to 10, wherein the heat-development section includes a heating member for heating the heat-developable image recording material from both sides, and The method for treating a heat-developable image recording material, wherein a conveying roller is provided only on the surface having the image forming layer with respect to the support. 13. A method for treating a heat-developable image recording material, which comprises thermally developing the heat-developable image recording material according to claim 1 at a speed of 20 to 200 mm / sec.