JPH11305382A - Photosensitive heat developable recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive heat developable image recording material with low fogging, high contrast and high sensitivity. SOLUTION: This photosensitive heat developable image recording material is obtd. by using a nonphotosensitive silver salt prepared in thepresence of tertiary alcohols. In the image recording material, (i) a photosensitive layer containing photosensitive silver halide and/or adjacent layer contain a nuclear forming agent of (ii) the photosensitive layer contains a photosensitive silver halide prepared independently of a nonphotosensitive silver salt and added at the time of preparing a coating liquid. Further a polymer latex having >=-30 deg.C and <=40 deg.C Tg is used as the main binder of the photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive heat-developable image recording material, and more particularly to a photosensitive heat-developable image recording material used for photolithography, and more particularly to a photosensitive material for scanners and imagesetters. More specifically, the present invention relates to a photothermographic material having a low Dmin and high photographic characteristics.

[0002]

2. Description of the Related Art There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technique for forming an image by thermal development is a system that can simplify environmental preservation and image forming means.

In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of waste liquid from the viewpoint of environmental protection and space saving.
Therefore, there is a need for a technology relating to a photothermographic material for photoengraving, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a clear black image having high resolution and sharpness. It has been. In these photosensitive heat developing materials,
By eliminating the use of solution processing chemicals, it is possible to provide customers with a simpler and more environmentally friendly thermal development processing system.

[0004] Methods of forming an image by thermal development are described in, for example, US Pat.
Morgan and B.A. "Thermal Proces Silver System (Thermally Proces)" by Shely
sed Silver Systems) A "(Imaging Processes and M
aterials) Neblette 8th edition, Sturge,
V. Walworth, A .; Shep
p) Edit, page 2, 1969). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

As a method for preparing an organic acid silver which is preferably used among the organic silver salts, an organic acid such as an aliphatic carboxylic acid is treated with an alkali to form an organic acid alkali metal salt. A method for preparing an organic silver salt by an exchange reaction between a salt of an alkali metal and silver ions is widely known to those skilled in the art. In the case of this method, the organic acid alkali metal salt becomes a solid, and it is difficult to carry out the exchange reaction with silver ions uniformly, and it is difficult to obtain a homogeneous organic acid silver salt.

The use of alcohol and the use of a homogeneous solution of an alkali metal salt of an organic acid in the preparation of silver organic acid is described in, for example, Journal of the Photographic Society of Japan, Vol. 52, p. 21 (1989). The secondary alcohols used here, such as iso-propanol, are not sufficient in terms of fog, and when a primary alcohol such as ethanol is used, it reacts with silver ions to cause explosive thunderic acid. There was a problem that silver could be formed.

[0007] European Patent No. 762,196, JP-A-9-90550 and the like disclose photosensitive silver halide grains used in heat-developable image recording materials to groups VII or VIII of the periodic table (groups 7 to 1).
It is disclosed that a metal ion or a metal complex ion of Group 0) is contained, and that a hydrazine derivative can be contained in a photosensitive material to obtain high-contrast photographic characteristics. As silver bromide, and in order to use for plate making, Dmin in the UV region which is the wavelength of a light source when printing on a plate.
(Fog) was high. By high silver chloride, Dmin in the UV region can be reduced, but fogging is difficult, high contrast images are not obtained, and high Dmax is difficult to obtain.
And so on.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photographic plate, especially a scanner and an image setter, which provide photographic characteristics with high contrast and low Dmin (fog) and stable production. It is to provide a photosensitive heat-developable image recording material having a high property. First of all,
A second object of the present invention is to provide a photosensitive heat-developable image recording material having a low Dmin (fog).
Another object of the present invention is to provide a photosensitive heat-developable image recording material having high contrast and high sensitivity.

[0009]

This object has been achieved by the following means. (1) A photosensitive heat-developable image recording material having a non-photosensitive organic silver salt and a photosensitive silver halide on a support, wherein the non-photosensitive organic silver salt is formed in the presence of a tertiary alcohol; A photosensitive heat-developable image recording material, wherein the photosensitive layer containing the photosensitive silver halide and / or an adjacent layer contains a nucleating agent. (2) The nucleating agent is selected from a substituted alkene derivative represented by the following general formula (1), a substituted isoxazole derivative represented by the general formula (2), and an acetal compound represented by the general formula (3) The heat-developable photosensitive image recording material according to the above (1).

[0010]

Embedded image

[In the general formula (1), R ¹ , R ² and R
³ independently represent a hydrogen atom or a substituent;
Represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z
May be bonded to each other to form a cyclic structure. In the general formula (2), R ⁴ represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, Represents a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group. In the general formula (3), X and Y, and A and B may be mutually bonded to form a cyclic structure. (3) The photothermographic image recording material according to the above (1), wherein the nucleating agent is a hydrazine derivative. (4) having a non-photosensitive organic silver salt on a support and having a photosensitive layer containing a photosensitive silver halide formed independently of the non-photosensitive organic silver salt and added at the time of preparing a coating solution; In the photosensitive heat-developable image recording material, the glass transition temperature is -30 ° C or more and 40 ° C or more as 50% by weight or more of the binder of the photosensitive layer.
The latex of the following polymer is used, and the photosensitive layer is applied by using a coating solution in which 60% by weight or more of a solvent of the layer is water, and the non-photosensitive organic silver salt is
A photosensitive heat-developable image recording material, which is formed in the presence of an alcohol. (5) The photothermographic image recording material according to the above (4), which contains a nucleating agent in the photosensitive layer and / or a layer adjacent thereto. (6) The nucleating agent is selected from a substituted alkene derivative represented by the following general formula (1), a substituted isoxazole derivative represented by the general formula (2), and an acetal compound represented by the general formula (3) The photosensitive heat-developable image recording material as described in (5) above.

[0012]

Embedded image

[In the general formula (1), R ¹ , R ² and R
³ independently represent a hydrogen atom or a substituent;
Represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z
May be bonded to each other to form a cyclic structure. In the general formula (2), R ⁴ represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, Represents a heterocyclic oxy group, a heterocyclic thio group or a heterocyclic amino group. In the general formula (3), X and Y, and A and B may be mutually bonded to form a cyclic structure. ]
(7) The photothermographic image recording material according to the above (5), wherein the nucleating agent is a hydrazine derivative.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The photosensitive heat-developable image recording material of the present invention contains a non-photosensitive organic silver salt and a photosensitive silver halide, and the non-photosensitive organic silver salt is formed in the presence of a tertiary alcohol. .
In such a constitution, the photosensitive heat-developable image recording material of the present invention comprises i) a nucleating agent contained in the photosensitive layer containing photosensitive silver halide and / or a layer adjacent thereto, or ii. ) A photosensitive silver halide is formed independently of a non-photosensitive organic silver salt, is added during preparation of a coating solution for a photosensitive layer, and has a glass transition temperature (Tg) of -30 ° C as a main binder of the photosensitive layer. The polymer latex having a temperature of 40 ° C. or lower is used.

By forming the non-photosensitive organic silver salt in the presence of the tertiary alcohol, the fog (D
min) decreases. When a nucleating agent is used,
A high-contrast image is obtained while maintaining low fog and high sensitivity. On the other hand, by using a photosensitive silver halide formed independently of the non-photosensitive organic silver salt, and by adding the photosensitive silver halide at the time of preparing a coating solution for the photosensitive layer, and as a main binder of the photosensitive layer The use of the above polymer latex makes it possible to carry out an aqueous coating which is advantageous in terms of environment and cost.
In addition, photographic performance can be improved. Therefore, practically preferable as a recording material for photoengraving,
It has both the configurations of i) and ii). On the other hand, when a secondary alcohol is used in place of the tertiary alcohol, or when a non-photosensitive organic silver salt is formed in the absence of the alcohol, a high-contrast image is obtained particularly by using a nucleating agent. In such a case, the fog rises remarkably, and the tone tends to be rather soft.

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

Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used.
Preferred examples of these compounds include 3-mercapto-4
-Phenyl-1,2,4-triazole silver salt, 2-mercaptobenzimidazole silver salt, 2-mercapto-5-aminothiadiazole silver salt, 2- (ethylglycolamide) benzothiazole silver salt, S- Silver salts of thioglycolic acid such as silver salts of alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithiocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamides, 5 -Carboxyl-1-methyl-2-phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, silver salts described in U.S. Pat.No.4,123,274, for example, 3-amino-5 Silver salts of 1,2,4-mercaptothiazole derivatives such as -benzylthio-1,2,4-thiazole silver salt, 3- (3-carboxyethyl) -4- described in U.S. Pat.No. 3,301,678
Includes silver salts of thione compounds such as silver salt of methyl-4-thiazoline-2-thione. Furthermore, compounds containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof,
For example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, U.S. Pat.
0,709 1,2,4-triazole or 1-H-
Includes silver salts of tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, U.S. Pat.
Various silver acetylide compounds as described in No. 1 and 4,775,613 can also be used.

The shape of the organic silver salt which can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. In the present invention, the minor axis is 0.01 μm or more and 0.2 μm or more.
0 μm or less, major axis of 0.10 μm or more and 5.0 μm or less, minor axis of 0.01 μm or more and 0.15 μm or less, and major axis of 0.10 μm or more and 4.0 μm or less are more preferred. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by each minor axis, major axis is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of determining the standard deviation of the volume-weighted average diameter of the organic silver salt, the percentage of the value divided by the volume-weighted average diameter (coefficient of variation) is preferably 100% or less, more Preferably 80% or less,
More preferably, it is 50% or less. As a measuring method, for example, the particle size (volume weighted average diameter) obtained by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained. Can be.

The organic silver salt used in the present invention is prepared in the presence of a tertiary alcohol. The tertiary alcohols preferably have a total carbon number of 15 or less, particularly preferably 10 or less. Preferred examples of the tertiary alcohol include tert-butanol and the like, but the present invention is not limited thereto.

The tertiary alcohol used in the present invention may be added at any timing during the preparation of the silver salt of an organic acid, which is preferably used as an organic silver salt. It is preferable to dissolve and use the alkali metal salt of an organic acid during the preparation. The amount of the tertiary alcohol used in the present invention is 0.01 to 1 by weight based on H ₂ O as a solvent during the preparation of the organic silver salt.
Although it can be used arbitrarily in the range of 0, the range of 0.03 to 1 is preferable. The same applies to organic silver salts other than organic acid silver.

The organic silver salt that can be used in the present invention includes:
Preferably, desalting can be performed. The method for desalting is not particularly limited, and a known method can be used. However, a known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used.

In the present invention, in order to obtain a solid dispersion of an organic silver salt having a high S / N, a small particle size and no aggregation, an organic silver salt as an image forming medium and a photosensitive silver salt are substantially contained. It is preferable to use a dispersion method in which a water dispersion liquid which is not included in the liquid is converted into a high-speed flow and then the pressure is reduced.

After passing through such steps, the mixture is mixed with an aqueous solution of a photosensitive silver salt to prepare a coating solution for a photosensitive image forming medium. When a photosensitive heat-developable image recording material is prepared using such a coating solution, a photosensitive heat-developable image recording material having low haze, low fog and high sensitivity can be obtained. On the other hand, when the photosensitive silver salt is coexistent when the light is converted into a high-pressure, high-speed flow and dispersed, the fog increases and the sensitivity is remarkably lowered. When an organic solvent is used instead of water as a dispersion medium, haze increases, fog increases, and sensitivity tends to decrease. On the other hand, when a conversion method for converting a part of the organic silver salt in the dispersion to the photosensitive silver salt is used instead of the method of mixing the aqueous solution of the photosensitive silver salt, the sensitivity is reduced.

In the above, the aqueous dispersion which is converted to a high-pressure and high-speed and dispersed is substantially free of a photosensitive silver salt, and its content is based on the non-photosensitive organic silver salt. 0.
The content is 1 mol% or less, and the photosensitive silver salt is not positively added.

In the present invention, the solid dispersion apparatus and the technique used for carrying out the dispersion method as described above are described in, for example, "Dispersion Rheology and Dispersion Technology" (Toshio Kajiuchi, Hiroki Usui, 1991, Shinzansha Publishing Co., Ltd., p357
-P403), "The 24th Progress of Chemical Engineering", edited by The Society of Chemical Engineers, Tokai Branch, 1990, Maki Shoten, p184-p185),
Although detailed in the dispersing method of the present invention, the aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and sent into a pipe, and then passed through a narrow slit provided in the pipe, Thereafter, the dispersion is finely dispersed by causing an abrupt pressure drop in the dispersion.

The high-pressure homogenizer to which the present invention relates is generally composed of (a) a "shearing force" generated when the dispersoid passes through a narrow gap at a high pressure and a high speed, and (b) a dispersoid is generated under a high pressure and a normal pressure. It is considered that the particles are dispersed into fine particles by a dispersing force such as "cavitation force" generated when the particles are released. As an example of this type of dispersing apparatus, a Gaulin homogenizer is mentioned in the past.In this apparatus, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on a cylindrical surface, and the force is applied to the surrounding wall by the force. The particles collide and are emulsified and dispersed by the impact force. Working pressure is generally 10
0~600kg / cm ^2, the flow rate is in the range of a few M～30m / sec, be devised that the high flow rate portion was devised such increasing the number collisions in the saw-toothed in order to increase the dispersion efficiency I have. On the other hand, in recent years, apparatuses capable of dispersing at higher pressure and higher flow rate have been developed, and typical examples thereof include a microfluidizer (Microfluidex International Corporation) and a nanomizer (specialized machine). Industrial Co., Ltd.).

As a dispersion apparatus suitable for the present invention, there is a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation.
(With G10Z interaction chamber), M-
110Y (with H10Z interaction chamber), M-140K (with G10Z interaction chamber), HC-5000 (L30Z or H23
With 0Z interaction chamber), HC-80
00 (with an E230Z or L30Z interaction chamber) and the like.

Using these devices, an aqueous dispersion containing at least an organic silver salt is pressurized by a high-pressure pump or the like and fed into a pipe, and then passed through a narrow slit provided in the pipe to obtain a desired pressure. Is applied, and thereafter, the pressure in the pipe is rapidly returned to the atmospheric pressure, for example, by causing a rapid pressure drop in the dispersion liquid, thereby making it possible to obtain an optimal organic silver salt dispersion for the present invention. .

It is preferable that the raw material liquid is preliminarily dispersed before the dispersion operation. As means for preliminary dispersion, known dispersion means (for example, high-speed mixer, homogenizer, high-speed impact mill, Banbury mixer, homomixer, kneader, ball mill, vibration ball mill, planetary ball mill, attritor, sand mill, bead mill, colloid mill,
Jet mill, roller mill, tron mill, high-speed stone mill) can be used. Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing agent. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation.

In the organic silver salt dispersion of the present invention, the flow rate,
It is possible to disperse to the desired particle size by adjusting the pressure difference during pressure drop and the number of treatments.However, from the viewpoint of photographic characteristics and particle size, the flow rate is 200 m / sec to 600 m / sec, is preferably in the range pressure is 900~3000kg / cm ^2, flow rate 300
m / sec ～600M / sec, the pressure difference at the pressure drop 1500~3000kg / cm ²
More preferably, it is within the range. The number of times of dispersion processing can be selected as needed, but usually 1 to 10 times is selected. From the viewpoint of productivity, about 1 to 3 times is selected. It is not preferable to raise the temperature of such an aqueous dispersion under high pressure from the viewpoint of dispersibility and photographic properties.
If the temperature is higher than the above range, the particle size tends to increase and fog tends to increase. Therefore, in the present invention, the step before the conversion to the high pressure and high flow rate, the step after the pressure is reduced, or both of these steps include a cooling step, and the temperature of such water dispersion is reduced by the cooling step. It is preferably kept in the range of ~ 90 ° C,
More preferably, the temperature is maintained in the range of 5 to 80C, particularly preferably in the range of 5 to 65C. In particular, it is effective to provide the above cooling step at the time of high-pressure dispersion in the range of 1500 to 3000 kg / cm ² . The cooler, depending on its required heat exchange,
Double tube or double tube using static mixer,
A multi-tube heat exchanger, a coiled tube heat exchanger, and the like can be appropriately selected. Further, in order to increase the efficiency of heat exchange, it is sufficient to select a suitable one such as a pipe thickness, a wall thickness and a material in consideration of a working pressure. The refrigerant used for the cooler is based on the amount of heat exchange
It is possible to use well water at 20 ° C., cold water at 5 to 10 ° C. treated with a refrigerator, and if necessary, a refrigerant such as ethylene glycol / water at −30 ° C.

In the dispersion operation of the present invention, it is preferable to disperse the organic silver salt in the presence of an aqueous solvent-soluble dispersant (dispersion aid). Examples of the dispersing agent include polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, a maleic acid monoester copolymer, a synthetic anionic polymer such as an acrylomethylpropanesulfonic acid copolymer, and carboxymethyl. Starch, semi-synthetic anionic polymers such as carboxymethyl cellulose, alginic acid, anionic polymers such as pectic acid, the compounds described in JP-A-7-350753, or known anionic, nonionic, cationic surfactants and other polyvinyl Known polymers such as alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, and naturally occurring polymer compounds such as gelatin can be appropriately selected and used. Lumpur acids, particularly preferred water-soluble cellulose derivatives.

It is a general method to mix a dispersion aid with an organic silver salt powder or an organic silver salt in a wet cake state before dispersion and to send the mixture as a slurry to a dispersing machine. Heat treatment or treatment with a solvent may be performed in the combined state to obtain an organic silver salt powder or a wet cake. The pH may be controlled by a suitable pH adjuster before, during or after dispersion.

In addition to mechanical dispersion, the dispersion may be roughly dispersed in a solvent by controlling the pH, and then the pH may be changed in the presence of a dispersing agent to form fine particles. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation.

The prepared dispersion may be stored with stirring for the purpose of suppressing sedimentation of fine particles during storage, or stored in a highly viscous state (for example, in a jelly state using gelatin) with a hydrophilic colloid. You can also do.
Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

The particle size (volume-weighted average diameter) of the organic silver salt solid fine particle dispersion of the present invention is determined, for example, by irradiating a solid fine particle dispersion dispersed in a liquid with a laser beam and changing the scattered light fluctuation with time. It can be obtained from the particle size (volume weighted average diameter) obtained by obtaining the autocorrelation function. A solid fine particle dispersion having an average particle size of 0.05 μm or more and 10.0 μm or less is preferable. The average particle size is more preferably 0.1 μm or more and 5.0 μm or less, and still more preferably the average particle size is 0.1 μm or more and 2.0 μm or less.

The particle size distribution of the organic silver salt is preferably monodispersed. Specifically, the percentage of the standard deviation of the volume-weighted average diameter divided by the volume-weighted average diameter (coefficient of variation)
Is 80% or less, more preferably 50% or less, even more preferably 30%
% Or less.

The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion.

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 to water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by weight, and more preferably 10 to 30% by weight.
Although it is preferable to use the above-mentioned dispersing aid, it is preferable to use the dispersing aid in the minimum amount within a range suitable for minimizing the particle size.
A range of weight% is preferred.

In the present invention, it is possible to produce a recording material by mixing an aqueous dispersion of an organic silver salt and an aqueous dispersion of a photosensitive silver salt. The ratio of the photosensitive silver salt to the organic silver salt is 1 to 3
The range is preferably 0 mol%, more preferably 3 to 20 mol%, particularly preferably 5 to 15 mol%. Mixing two or more aqueous dispersions of organic silver salts with two or more aqueous dispersions of photosensitive silver salts during mixing is a method preferably used for adjusting photographic characteristics.

[0040] While the organic silver salt according to the invention can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably from 1 to 3 g / m ^2.

The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. . The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously.
Further, silver halide grains having a core / shell structure can be preferably used. The structure is preferably 2
Core / shell particles having a ５5-fold structure, more preferably a 2- to 4-fold structure, can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods for forming photosensitive silver halide are well known in the art, for example, Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458.
Can be used.Specifically, a photosensitive silver halide is prepared by adding a silver-supplying compound and a halogen-supplying compound to a gelatin or other polymer solution, and then the organic silver halide is added. A method of mixing with a silver salt is used. The grain size of the photosensitive silver halide is
For the purpose of suppressing white turbidity after image formation, it is preferably small, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.02 μm or more and 0.1 μm or more.
It is preferably 12 μm or less. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high.
The proportion occupied by the {100} plane is preferably high. The ratio is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. The Miller index ratio of {100} plane was determined by T. Tani; J. Imaging Sci., 29, 165 (1985) using the dependence of adsorption of sensitizing dyes on {111} and {100} planes. It can be determined by the method described.

The light-sensitive silver halide grains of the present invention can be prepared from Group VII or VIII (Groups 7 to 10) of the periodic table.
Of a metal or metal complex. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 nmol to 10 mmol, and more preferably in the range of 10 nmol to 100 μmol per 1 mol of silver. 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.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III)
Complex salts, pentachloroacolodium (III) complex salts, tetrachlorodiachodium (III) complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts are exemplified.
These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl, KBr, NaBr
Etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, and particularly preferably 5 × 10 ^-8 mol to 1 × 10 ^-6 mol, per mol of silver halide. Is a mole.

These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042, JP-A-1-285941,
It is added in the form of a water-soluble complex salt described in JP-A Nos. 2-20852 and 2-20855. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ⁿ -where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4.

In this case, the counter ion is not important, and an ammonium or alkali metal ion is used.

Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands and the like.
Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1- [RuCl ₅ (H ₂ O)] ^2- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) ₃ Cl ₃ ] ^2- [Ru (CO) Cl ₅ ] ^2- [Ru (CO) Br ₅ ] ^2- [OsCl ₆ ] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (O) ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
It is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol per mol, particularly preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol.

These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains.

In order to add these compounds into silver halide grains by adding them during silver halide grain formation, an aqueous solution of metal complex powder or an aqueous solution dissolved together with NaCl and KCl is added to the aqueous solution during grain formation. A method in which silver halide grains are added to a salt or a water-soluble halide solution, or as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-liquid simultaneous mixing method is used, Alternatively, there is a method in which a required amount of an aqueous solution of a metal complex is charged into a reaction vessel during particle formation. Especially powder or NaCl, KCl
Is preferable to add an aqueous solution dissolved together with the above to a water-soluble halide solution.

For the addition to the particle surface, a required amount of an aqueous solution of a metal complex can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

Various compounds can be used as the iridium compound used in the present invention, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, and pentachloronitrosyliridium. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used for stabilizing a solution of the iridium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or a method of adding an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain doped with iridium in advance during the preparation of silver halide.

Further, the silver halide grains used in the present invention may contain cobalt, iron, nickel, chromium, palladium,
It may contain metal atoms such as platinum, gold, thallium, copper and lead. For compounds of cobalt, iron, chromium and ruthenium, hexacyano metal complexes can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion,
Examples include, but are not limited to, hexacyanochromate ions and hexacyanoruthenate ions. The metal complex in the silver halide may be contained uniformly, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration, and there is no particular limitation.

The above metal is 1 × per mole of silver halide.
It is preferably from 10 ^-9 to 1 × 10 ^-4 mol. Further, in order to contain the above-mentioned metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added at the time of preparing particles.

The photosensitive silver halide grains can be desalted by washing with a method known in the art, such as a noodle method or flocculation method, but in the present invention, they may or may not be desalted. .

As the gold sensitizer used for sensitizing the silver halide emulsion of the present invention to gold, the oxidation number of gold may be +1 or +3 and is usually used as a gold sensitizer. Gold compounds can be used. Representative examples include chloroauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

[0061] The addition amount of the gold sensitizer may vary depending on various conditions, 10 ^-3 mol per mol of the silver halide 10 ^-7 mol or more as a guide, and more preferably 10 ^-6 mol to 5 × 10 ^- Not more than ⁴ moles.

The silver halide emulsion of the present invention is preferably used in combination with gold sensitization and another chemical sensitization. As other chemical sensitization methods, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used. When used in combination with the gold sensitization method,
For example, sulfur sensitization and gold sensitization, selenium sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization Preferred methods include sulfur sensitization, selenium sensitization, tellurium sensitization, and gold sensitization.

The sulfur sensitization preferably used in the present invention is
Usually, a sulfur sensitizer is added, and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Unstable selenium compounds include JP-B-44-15748, JP-B-43-13489, and JP-A-2-13097.
Compounds described in 2-229300, 3-21798 and the like can be used. In particular, the general formula (VIII) in JP-A-4-324855
It is preferable to use the compound represented by (IX).

The tellurium sensitizer used in the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in JP-A-5-3132.
It can be tested by the method described in No. 84. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals,
Tellurosulfonates, compounds having a P-Te bond, containing T
e Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, UK Patent 235,211 and 1,121,496,
No. 1,295,462, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-204640, JP-A-3-53693, JP-A-3-31598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibid 6
45 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.
Trans.) 1,2191 (1980), edited by S. Patai, The Chemistry of Organ, Selenium and Tellurium Campounds
ic Serenium and Tellunium Compounds), Vol 1 (1986),
The compounds described in Vol. 2 (1987) can be used.
In particular, the general formulas (II), (III) and (IV) in JP-A-5-313284
Are preferred.

[0066] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physical ripening.

In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also, when the pH of the emulsion is 7 or more or p
Reduction sensitization can be achieved by aging while keeping Ag at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in EP-A-293,917.

The silver halide emulsion in the recording material used in the present invention may be only one kind or two or more kinds (for example,
Those with different average grain sizes, different halogen compositions, different crystal habits, different chemical sensitization conditions)
You may use together.

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 mol to 0.5 mol, more preferably 0.02 mol to 0.3 mol, and more preferably 0.03 mol to 1 mol of the organic silver salt. It is particularly preferably at least 0.25 mol and not more than 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt are mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. There is a method of mixing, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt,
There is no particular limitation as long as the effects of the present invention are sufficiently exhibited.

The heat-developable image recording material of the present invention preferably contains a reducing agent for an organic silver salt. A reducing agent for an organic silver salt is any substance that reduces silver ions to metallic silver,
Preferably, it may be 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 used in an amount of 5 to 1 mol per mol of silver on the surface having the image forming layer.
It is preferably contained at 50 mol%, more preferably at 10 to 40 mol%. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable image recording material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
Nos. 47-33621, 49-46427, 49-115540, 5
0-14334, 50-36110, 50-147711, 51-32632
No. 51-10223721, No. 51-32324, No. 51-51933, No.
52-84727, 55-108654, 56-146133, 57-828
No. 28, No. 57-82829, JP-A-6-3793, U.S. Pat.
9586, 3,679,426, 3,751,252, 3,751,255
Nos. 3,761,270, 3,782,949, 3,839,048,
3,928,686, 5,464,738, German patent 2321328,
It is disclosed in European Patent No. 692732 and the like. For example, phenylamide oxime, 2-thienylamide oxime and
Amide oximes such as p-phenoxyphenylamide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; combinations of 2,2′-bis (hydroxymethyl) propionyl-β-phenylhydrazine with ascorbic acid A combination of such an aliphatic carboxylic acid aryl hydrazide and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone Or a combination of formyl-4-methylphenylhydrazine, etc.); phenylhydroxamic acid, p
Hydroxamic acids such as -hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano Α-cyanophenylacetic acid derivatives such as 2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy Bis-β-naphthol as exemplified by -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); 3-methyl-1-phenyl
5-pyrazolone, such as -5-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone;
Sulfonamidophenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-
Diones and the like; chromanes such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; Bisphenols (e.g., bis (2-hydroxy
-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene
-Bis (2-t-butyl-6-methylphenol), 1,1, -bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like); ascorbic acid derivatives (for example, palmitic acid 1 And aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones; chromanol (such as tocopherol). Particularly preferred reducing agents are bisphenol and chromanol.

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

When an additive known as a "toning agent" for improving an image is included, the optical density may be increased. The toning agent may also be advantageous in forming a black silver image. The toning agent is preferably contained in an amount of 0.1 to 50% (mole) per mole of silver on the surface having the image forming layer, and more preferably 0.5 to 20% (mole). Further, the toning agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable image recording material using an organic silver salt, a wide range of toning agents are disclosed in JP-A-46-6077 and JP-A-47-1028.
No. 2, No. 49-5019, No. 49-5020, No. 49-91215, No. 49-
No. 91215, No. 50-2524, No. 50-32927, No. 50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-279
No. 23, No. 52-14788, No. 52-99813, No. 53-1020, No. 5
3-76020, 54-156524, 54-156525, 61-1836
No. 42, JP-A-4-56848, JP-B-49-10727, 54-2033
No. 3, U.S. Pat.Nos. 3,080,254, 3,446,648, 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent 138079
No. 5, Belgian Patent No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimides (eg, N
-Hydroxy-1,8-naphthalimide); cobalt complexes (eg, 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-1,3,4-thiadiazole N- (aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide ); And blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, 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-1,4-phthalazinedione A combination of phthalazinone and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); phthalazine,
Phthalazine derivatives (e.g., 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine,
6-iso-butylphthalazine, 6-tert-butylphthalazine,
5,7-dimethylphthalazine, and derivatives such as 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and Quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes, such as hexachloro, which function not only as a color tone regulator but also in-situ as a source of halide ions for silver halide formation Ammonium rhodate (III), rhodium bromide, rhodium nitrate and hexachlororhodium (I
II) potassium acid and the like; inorganic peroxides and persulfates, such as ammonium peroxide and hydrogen peroxide;
Benzoxazine-2 such as 3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione Pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto-1) , 4-diphenyl-1
H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di
(o-chlorophenyl) -3,6-dimercapto-1H, 4H-2,3a, 5,6
a-tetraazapentalene).

The color-toning agent of the present invention may be added by any method such as a solution, a powder and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

At least one of the photosensitive layers of the present invention, that is, the image forming layer, is an image forming layer using the polymer latex described below in an amount of 50% by weight or more of the total binder. (Hereinafter, this image forming layer is referred to as "the image forming layer of the present invention",
The polymer latex used for the binder is referred to as “the polymer latex of the present invention”. In addition, the polymer latex may be used not only for the image forming layer but also for the protective layer and the back layer. It is necessary to use a polymer latex also for the back layer. However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. For the polymer latex of the present invention, `` Synthetic resin emulsion (Hiroshi Okuda, edited by Hiroshi Inagaki, published by the Society of Polymer Publishing (1978)) '', `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, edited by Keiji Kasahara, Polymer Chemistry Publishing Association (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, Published by Polymer Publishing Association (1970))" and the like. The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably
A range of about 5 to 1000 nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and those having a wide particle size distribution or those having a monodispersed particle size distribution may be used.

As the polymer latex of the present invention, other than a polymer latex having a normal uniform structure, a so-called core / polymer latex may be used.
Shell type latex may be used. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

The preferable range of the polymer glass transition temperature (Tg) of the polymer latex used in the binder of the present invention differs between the protective layer, the back layer and the image forming layer. In the image forming layer, a material having a temperature of -30 to 40 [deg.] C. is used in order to promote diffusion of a photographically useful material during thermal development. When used for protective layer or back layer, 25-70 to contact with various devices
A glass transition temperature of ° C. is preferred.

The minimum film forming temperature (MFT) of the polymer latex of the present invention is preferably -30 ° C to 90 ° C, more preferably about 0 ° C to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex, also called a plasticizer. )"It is described in.

Examples of the polymer used in the polymer latex of the present invention include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. There is. 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 monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is preferably from 5000 to 100000, more preferably from about 10,000 to 100,000 in number average molecular weight. 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-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder for the image forming layer of the heat-developable image recording material of the present invention include the following. Latex of methyl methacrylate / 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 Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like. Such polymers are also commercially available, and the following polymers can be used. For example, as examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,8
Polyester resins include FINETEX ES650, 611, 675, and 850 (all manufactured by Dainippon Ink and Chemicals), WD-size, WMS (all manufactured by Eastman Chemical), etc. , HYDRAN AP1 as polyurethane resin
0, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
LACSTAR 7310K, 3307B, 4700H, 713 as rubber resin
2C (Dai Nippon Ink Chemical Co., Ltd.), Nipol Lx410, 43
0, 435, 438C, 2507, (all manufactured by Nippon Zeon Co., Ltd.)
Examples of vinyl chloride resins include G351 and G576 (all manufactured by Nippon Zeon Co., Ltd.). Examples of vinylidene chloride resins include L502 and L51.
3 (all manufactured by Asahi Kasei Corporation), Aron D7020, D504, D507
Examples of olefin resins include Chemipearl S120 and SA100 (both manufactured by Mitsui Petrochemical Co., Ltd.). These polymers may be used alone or as a blend of two or more as necessary.

In the image forming layer of the present invention, the above polymer latex is used in an amount of 50% by weight or more of the total binder.
It is preferable to use the above polymer latex in an amount of at least% by weight.

In the image forming layer of the present invention, if necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose or the like is added in an amount of 50% by weight or less of the whole binder. May be. The amount of the hydrophilic polymer to be added is preferably 30% by weight or less, more preferably 15% by weight or less of the total binder in the image forming layer.

The image forming layer of the present invention is preferably prepared by applying an aqueous coating solution and then drying it. However, the term "aqueous" as used herein means that 60% by weight or more of the solvent (dispersion medium) of the coating liquid is water. As components other than water of the coating solution, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used. Specific examples of the solvent composition include the following in addition to water. Water / methanol = 90
/ 10, water / methanol = 70/30, water / ethanol = 90/1
0, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide
= 80/15/5, water / methanol / dimethylformamide = 9
0/5/5. (However, the numbers represent weight%.)

The total amount of the binder in the image forming layer of the present invention is 0.1.
The range is preferably ^{2 to} 30 g / m ² , more preferably 1 to 15 g / m ² . A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer of the invention.

The photosensitive heat-developable image recording material of the present invention preferably contains a nucleating agent in the photosensitive layer or in the layer adjacent thereto in order to obtain a high-contrast image. As the nucleating agent used in the present invention, a compound selected from a substituted alkene derivative, a substituted isoxazole derivative, a specific acetal compound, and a hydrazine derivative is preferably used.

The substituted alkene derivative used in the present invention,
The substituted isoxazole derivative and the specific acetal compound will be described. As these compounds, compounds represented by the general formulas (1), (2) and (3) are preferable.

[0090]

Embedded image

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹
And Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure. General formula (2)
In the above, R ⁴ represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent,
A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the general formula (3), X and Y or A and B may be bonded to each other to form a cyclic structure.

The compound represented by formula (1) will be described in detail. In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹
And Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure.

When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group). An alkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including an N-substituted nitrogen-containing heterocyclic group) and a heterocyclic group containing a quaternized nitrogen atom ( For example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an imino group substituted by an N atom, a thiocarbonyl group, a sulfonylcarbamoyl group, an acylcarbamoyl group, Famoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, A droxy group or a salt thereof, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, and a carbamoyloxy group , Sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle)
Thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoryl group, phosphorus Examples thereof include a group having an acid amide or phosphate structure, a silyl group and a stannyl group.

These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the general formula (1) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxy group, Carbonyl group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom, perfluoroalkyl group, perfluoroalkyl Alkanamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group (or salt thereof), sulfo group (or salt thereof), heterocyclic group, alkenyl group, alkynyl group, acyloxy group, acylthio group, sulfonyl An oxy group, or an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is a saturated or unsaturated heterocyclic group, such as a pyridyl group, a quinolyl group, a pyrazinyl group, a quinoxalinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, and a hydantoin-1-yl group. , A succinimide group, a phthalimide group and the like.

The electron-withdrawing group represented by Z in the general formula (1) may further have a substituent, and the substituent includes R ¹ , R ² , R ^The same substituents as may be possessed when ³ represents a substituent are exemplified.

In the general formula (1), R ¹ and Z, R ² and R ³ ,
R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure, and the cyclic structure formed at this time is a non-aromatic carbon ring or a non-aromatic heterocycle. It is a ring.

Next, a preferred range of the compound represented by the formula (1) will be described. Preferable examples of the silyl group represented by Z in the general formula (1) specifically include a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a trimethylsilyldimethylsilyl group, and the like. is there.

The electron-withdrawing group represented by Z in the general formula (1) is preferably a group having a total number of carbon atoms of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, A thiocarbonyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a perfluoroalkyl group, an acyl group, a formyl group, a phosphoryl group, an acyloxy group, an acylthio group, or A phenyl group or the like substituted with any electron-withdrawing group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
An acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group, and particularly preferably a cyano group, a formyl group,
An acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group.

The group represented by Z in the general formula (1) is more preferably an electron-withdrawing group.

In the general formula (1), R ¹ , R ² and R ³
The substituent represented by is preferably a total of 0 to 3 carbon atoms.
A group of 0, specifically, a group having the same meaning as the electron-withdrawing group represented by Z in the general formula (1), and an alkyl group, a hydroxy group (or a salt thereof), and a mercapto group (or a salt thereof) An alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, an acylamino group, a sulfonamide group, Or a substituted or unsubstituted aryl group.

In the general formula (1), R ¹ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom, or a silyl group.

When R ¹ represents an electron-withdrawing group, preferably the following groups having a total of 0 to 30 carbon atoms, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), Or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, a carboxy group (or a salt thereof) Or a saturated or unsaturated heterocyclic group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a saturated or unsaturated heterocyclic group.

When R ¹ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms in total, and the substituent may be any substituent. Is preferred.

In formula (1), R ¹ is more preferably an electron-withdrawing group or an aryl group.

In the general formula (1), the substituents represented by R ² and R ³ are preferably specific examples of the above-mentioned general formula
(1) a group having the same meaning as the electron-withdrawing group represented by Z, an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group; Group, arylthio group, heterocyclic thio group, amino group, alkylamino group, anilino group,
Examples include a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group.

In the general formula (1), R ² and R ³ are more preferably when either one is a hydrogen atom and the other is a substituent. Preferably as the substituent, an alkyl group, a hydroxy group (or a salt thereof), a mercapto group
(Or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly perfluoro Alkanamide group), a sulfonamide group, a substituted or unsubstituted phenyl group, or a heterocyclic group,
More preferably a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group, Preferably a hydroxy group (or a salt thereof), an alkoxy group,
Or a heterocyclic group.

In the general formula (1), it is also preferable that Z and R ¹ , or R ² and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number of 1 including a substituent.
To 40, more preferably 3 to 30.

[0109] Among the compounds represented by the general formula (1), more One of preferred, Z represents a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group,, R ¹ Represents an electron-withdrawing group or an aryl group, one of R ^{2 and} R ³ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof) or a mercapto group
(Or its salt), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group.
Furthermore, one of the particularly preferable compounds represented by the general formula (1) is that Z and R ^{1 form a} non-aromatic 5- to 7-membered cyclic structure, and R ² or R ^{2 One of the three} is a hydrogen atom, the other is a hydroxy group (or a salt thereof),
It is a compound that represents a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group. At this time, Z which forms a non-aromatic cyclic structure together with R ¹ is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group and the like, and R ¹ is an acyl group, a carbamoyl group , An oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted by an N atom, an acylamino group, and a carbonylthio group.

Next, the compound represented by formula (2) will be described. In the general formula (2), R ⁴ represents a substituent. R ⁴
Examples of the substituent represented by are the same as those described for the substituents of R ^{1 to} R ^{3 in} the general formula (1).

The substituent represented by R ⁴ is preferably an electron-withdrawing group or an aryl group. When R ⁴ represents an electron-withdrawing group, preferably the following groups having a total carbon number of 0 to 30,
That is, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group,
A phosphoryl group, an imino group, or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic group. preferable. Particularly preferably, a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group,
It is a carbamoyl group or a heterocyclic group.

[0112] When R ⁴ represents an aryl group, preferably a total carbon number of 0 to 30, a substituted or unsubstituted phenyl group, the substituent of the general formula ^{(1) R 1, R 2} , R ^{When 3} represents a substituent, the same as those described as the substituent can be mentioned.

R ⁴ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group or a substituted or unsubstituted phenyl group, and most preferably a cyano group, a heterocyclic group or an alkoxycarbonyl group. is there.

Next, the compound represented by formula (3) will be described in detail. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, Represents a ring thio group, a heterocyclic oxy group, or a heterocyclic amino group. X and Y or A and B may be bonded to each other to form a cyclic structure.

The substituents represented by X and Y in the general formula (3) are the same as those described for the substituents R ^{1 to} R ^{3 in} the general formula (1). Specifically, an alkyl group (including a perfluoroalkyl group, a trichloromethyl group, etc.), an aryl group, a heterocyclic group, a halogen atom,
Cyano group, nitro group, alkenyl group, alkynyl group, acyl group, formyl group, alkoxycarbonyl group, aryloxycarbonyl group, imino group, imino group substituted by N atom, carbamoyl group, thiocarbonyl group, acyloxy group, acylthio group An acylamino group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group,
A phosphoryl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), a hydroxy group (or a salt thereof),
A mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, a silyl group, etc. No.

These groups may further have a substituent. X and Y may be bonded to each other to form a cyclic structure, and the cyclic structure formed in this case may be a non-aromatic carbon ring or a non-aromatic hetero ring. .

The substituents represented by X and Y in the general formula (3) are preferably groups having 1 to 40 carbon atoms in total, more preferably 1 to 30 carbon atoms in total, and include a cyano group and an alkoxycarbonyl group. , Aryloxycarbonyl, carbamoyl, imino, imino substituted with an N atom, thiocarbonyl, sulfamoyl, alkylsulfonyl, arylsulfonyl, nitro, perfluoroalkyl, acyl, formyl, phosphoryl Groups, acylamino groups, acyloxy groups, acylthio groups, heterocyclic groups, alkylthio groups, alkoxy groups, and aryl groups.

In the general formula (3), X and Y are more preferably a cyano group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a formyl group, an acylthio group,
Acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, imino group, imino group substituted with N atom, phosphoryl group, trifluoromethyl group, heterocyclic group, substituted phenyl group, etc. Particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylthio group,
Examples include an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, and a phenyl group substituted with any electron-withdrawing group.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the formed cyclic structure is preferably a 5- to 7-membered ring, and has a total carbon number of 1 to 40, and more preferably 3 to 7 members.
30 is preferred. X and Y forming a cyclic structure include an acyl group, a carbamoyl group, an oxycarbonyl group,
Preferred are a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like.

In the general formula (3), A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group, which may be bonded to each other to form a cyclic structure. The group represented by A or B in the general formula (3) is preferably a group having a total carbon number of 1 to 40, more preferably a group having a total carbon number of 1 to 30, and may further have a substituent. .

In the general formula (3), A and B are more preferably bonded to each other to form a cyclic structure. The cyclic structure formed at this time is preferably a 5- to 7-membered non-aromatic hetero ring, and preferably has a total carbon number of 1 to 40, and more preferably 3 to 30. In this case, an example in which A and B are linked (-AB-) is, for example, -O- (C
_{H 2) 2 -O -, -} O- (CH 2) 3 -O -, - S- (CH
_{2) 2 -S -, - S-} (CH 2) 3 -S -, - S-ph-S
_{-, - N (CH 3)} - (CH 2) 2 -O -, - N (CH 3)
_{- (CH 2) 2 -S -} , - O- (CH 2) 2 -S -, - O-
_{(CH 2) 3 -S -,} - N (CH 3) -ph-O -, - N
(CH ₃ ) -ph-S-, -N (ph)-(CH ₂ ) _2-
S- and so on.

The compounds represented by the general formulas (1) to (3) of the present invention may have incorporated therein an adsorptive group that adsorbs to silver halide. Such adsorbing groups include:
U.S. Pat. Nos. 4,385,108 and 4,459,347 such as alkylthio group, arylthio group, thiourea group, thioamide group, mercapto heterocyclic group and triazole group.
And JP-A-59-195233 and JP-A-59-20023.
No. 1, No. 59-201045, No. 59-201046
Nos. 59-201047 and 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
The group described in 3-234246 is mentioned. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

The compounds represented by the general formulas (1) to (3) of the present invention incorporate therein a ballast group or a polymer commonly used in immobile photographic additives such as couplers. It may be something. Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy group, alkylphenoxy group and the like. Examples of the polymer include, for example,
No. 100530.

The compounds represented by the general formulas (1) to (3) of the present invention contain a cationic group (specifically, a group containing a quaternary ammonium group, or a quaternized group). A nitrogen-containing heterocyclic group containing a nitrogen atom, a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy) dissociable by a base. Group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.). In particular, a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, or (alkyl, aryl, or heterocycle)
Those containing a thio group are one of the preferred examples of the present invention.
One. Specific examples of these groups include, for example, JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Pat. The compounds described in U.S. Pat. No. 4,988,604, JP-A-3-259240, JP-A-7-5610, JP-A-7-244348, German Patent 4006032, and the like can be mentioned.

Next, specific examples of the compounds represented by formulas (1) to (3) of the present invention are shown below. However, the present invention is not limited to the following compounds.

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

The compounds represented by the general formulas (1) to (3) of the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol) and ketones (acetone). , Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve mechanically. An emulsified dispersion can be prepared and used. Alternatively, a compound powder can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

The compounds represented by formulas (1) to (3) of the present invention can be added to a layer on the photosensitive layer side of the support, that is, to the photosensitive layer or any other layer. However, it is preferable to add it to the photosensitive layer or a layer adjacent thereto.

The addition amount of the compounds represented by formulas (1) to (3) of the present invention is preferably 1 × 10 ^-6 to 1 mol per 1 mol of silver, and more preferably 1 × 10 ^{-5 to} 5 mol. × 10 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is most preferred.

The compounds represented by formulas (1) to (3) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515 and US Pat.
No. 39, US Pat. No. 5,654,130, International Patent WO-9
7/34196 or Japanese Patent Application No. 9-354107.
, Japanese Patent Application No. 9-309813, Japanese Patent Application No. 9-27200
The compound can be synthesized with reference to the method described in No. 2.

The compounds represented by formulas (1) to (3) of the present invention may be used alone or in combination of two or more. Also, in addition to the above, US Pat.
No. 5,635,339, U.S. Pat.
0, International Patent WO-97 / 34196, U.S. Pat.
No. 686228;
No. 279962, Japanese Patent Application No. 9-228885, Japanese Patent Application No. 9-273935, Japanese Patent Application No. 9-354107, Japanese Patent Application No. 9-309913, Japanese Patent Application No. 9-296174, Japanese Patent Application No. 9-282564. No., Japanese Patent Application No. 9-272002,
Compounds described in Japanese Patent Application Nos. 9-272003 and 9-332388 may be used in combination.

The hydrazine derivative used in the present invention is
Compounds represented by the following general formula (H) are preferred.

[0142]

Embedded image

In the formula, R ¹² represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹¹ represents a hydrogen atom or a block group, and G ¹ represents —CO—, —COCO—, —C (= S)-, -SO-, -SO-, -PO
(R ^{1 3)} - group (. R ¹³ is selected from the same range as the groups defined in R ^11, may be different from R ^11), or an iminomethylene group. A ¹ and A ^{2 each} represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. m1 is 0 or 1, when m1 is 0, R ¹¹ represents an aliphatic group, an aromatic group or a heterocyclic group.

In the general formula (H), the aliphatic group represented by R ¹² is preferably a substituted or unsubstituted, straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. .

In the general formula (H), the aromatic group represented by R ¹² is a monocyclic or condensed-ring aryl group such as a phenyl group and a naphthyl group. The heterocyclic group represented by R ¹² is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group,
Examples of the hetero ring in these groups include, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring, a triazine ring, a morpholino ring, Examples include a piperidine ring and a piperazine ring.

Preferred as R ¹² is an aryl group or an alkyl group.

R ¹² may be substituted. Representative examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, and an active methine group). Group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group ( (Including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, (Alkyl, aryl, or heterocyclic) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) Ruboniruamino group, a sulfamoylamino group, semicarbazide group, thiosemicarbazide group,
Hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl,
Or heterocycle) thio group, (alkyl or aryl)
A sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric amide or a phosphoric ester structure, and the like. Can be

These substituents may be further substituted with these substituents.

[0149] Preferred examples of the substituent which may be R ¹² optionally has, when R ¹² represents an aromatic group or a heterocyclic group, (including an active methylene group) alkyl group, an aralkyl group, a heterocyclic group, Substituted amino group, acylamino group, sulfonamide group, ureido group, sulfamoylamino group,
Imide group, thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl , Aryl, or heterocycle)
Examples thereof include a thio group, a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group, and a nitro group.

When R ¹² represents an aliphatic group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide group, a thioureido group, Phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group,
Acyloxy group, acyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocycle) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group, etc. Is preferred.

In the general formula (H), R ¹¹ represents a hydrogen atom or a block group, and the block group is specifically an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group. Group (monocyclic or condensed-ring aryl group), heterocyclic group, alkoxy group, aryloxy group,
Represents an amino group or a hydrazino group.

The alkyl group represented by R ¹¹ is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, trifluoromethyl, difluoromethyl, 2-carboxytetra. Fluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group,
Phenylsulfonylmethyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxymethyl group, 4-ethylphenoxymethyl group, phenylthiomethyl group, t-butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, methoxy Examples thereof include a carbonyldiphenylmethyl group, a cyanodiphenylmethyl group, and a methylthiodiphenylmethyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, for example, a vinyl group, a 2-ethoxycarbonylvinyl group, a 2-trifluoro-2.
-Methoxycarbonylvinyl group and the like. The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, phenyl, perfluorophenyl, 3,5-dichlorophenyl, 2-methanesulfonamidophenyl, 2-carbamoylphenyl, 4,5
-Dicyanophenyl group, 2-hydroxymethylphenyl group, 2,6-dichloro-4-cyanophenyl group, 2-chloro-5-
An octylsulfamoylphenyl group;

The heterocyclic group is preferably at least
5- to 6-membered, saturated or unsaturated, monocyclic or fused-ring heterocyclic group containing one nitrogen, oxygen, and sulfur atom, such as morpholino group, piperidino group (N-substituted), imidazolyl group, indazolyl Groups (such as 4-nitroindazolyl group), pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group, pyridyl group, pyridinio group (such as N-methyl-3-pyridinio group), quinolinio group, and quinolyl group.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, such as methoxy, 2-hydroxyethoxy, benzyloxy and t-butoxy. As the aryloxy group, a substituted or unsubstituted phenoxy group is preferable, and as the amino group, an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group ( (Including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom). Examples of amino groups are 2,2,
6,6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino And the like. As the hydrazino group, a substituted or unsubstituted hydrazino group, or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

The group represented by R ¹¹ may be substituted, and examples of the substituent include those exemplified as the substituent of R ¹² .

In the general formula (H), R ¹¹ cleaves the G ¹ -R ¹¹ moiety from the residual molecule and causes a cyclization reaction to form a cyclic structure containing atoms of the -G ¹ -R ¹¹ moiety. May be used. Examples thereof include, for example,
9751 and the like.

The hydrazine derivative represented by the general formula (H) may have a built-in adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio, arylthio, thiourea, thioamide,
U.S. Patent Nos. Such as mercapto heterocyclic groups and triazole groups
Nos. 4,385,108 and 4,459,347, JP-A-59-195233
No., 59-200231, 59-201045, 59-201046,
59-201047, 59-201048, 59-201049, JP-A-61-170733, 61-270744, 62-948, 63-234
The groups described in Nos. 244, 63-234245 and 63-234246 are exemplified. The adsorbing groups to these silver halides are
It may be a precursor. Examples of such a precursor include groups described in JP-A-2-285344.

R ¹¹ or R ^{12 in} the formula (H) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group has a carbon number of 8 or more and is a group relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ¹¹ or R ¹² in the general formula (H) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (H) is a polymer having a hydrazino group. Represents, for example, JP-A-64-86134
No., JP-A-4-16938, JP-A-5-97091, WO95-32452
No., WO95-32453, Japanese Patent Application No. 7-351132, Japanese Patent Application No. 7-351269
No., Japanese Patent Application No. 7-351168, Japanese Patent Application No. 7-351287, Japanese Patent Application No. 7-35
Compounds described in No. 1279 and the like can be mentioned.

In formula (H), R ¹¹ or R ¹² represents a cationic group (specifically, a group containing a quaternary ammonium group or a nitrogen-containing hetero atom containing a quaternized nitrogen atom). Ring group), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy group, sulfo group, acylsulfa Moyl group, carbamoylsulfamoyl group, etc.). Examples of these groups include, for example, JP-A-7-234471, JP-A-5-333466, JP-A-6-19032
No., JP-A-6-19301, JP-A-5-45761, U.S. Pat.
No. 4,365, U.S. Pat.No.4,988,604, JP-A-3-259240, JP-A-7-5610, JP-A-7-244348, German Patent 4,006,032
And the like.

In the general formula (H), A ¹ and A ² represent a hydrogen atom,
An alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more), an acyl group having 20 or less carbon atoms (Preferably, a benzoyl group, a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group.

A ¹ and A ² are most preferably hydrogen atoms.

Next, particularly preferred hydrazine derivatives in the present invention will be described.

R ¹² is preferably a phenyl group or a substituted alkyl group having 1 to 3 carbon atoms.

When R ¹² represents a phenyl group, preferred substituents are a nitro group, an alkoxy group, an alkyl group, an acylamino group, a ureido group, a sulfonamide group,
Thioureido group, carbamoyl group, sulfamoyl group,
Examples include a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), an alkoxycarbonyl group, or a chloro atom.

When R ¹² represents a substituted phenyl group, the substituent may be, directly or via a linking group, a ballast group, an adsorptive group to silver halide, a group containing a quaternary ammonium group, or a quaternized group. A nitrogen-containing heterocyclic group containing a nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, (alkyl, aryl,
Or heterocycle) to form a thio group, nitro group, alkoxy group, acylamino group, sulfonamide group, dissociative group (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.), or a multimer More preferably, at least one of the resulting hydrazino groups (the group represented by -NHNH-G ¹ -R ¹¹ ) is substituted.

[0167] When R ¹² represents a substituted alkyl group having 1 to 3 carbon atoms, R ¹² is more preferably a substituted methyl group, more preferably a disubstituted methyl group or trisubstituted methyl group, as a substituent Are specifically a methyl group, a phenyl group, a cyano group, an (alkyl, aryl or heterocycle) thio group, an alkoxy group, an aryloxy group, a chloro atom, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl A group, a sulfamoyl group, an amino group, an acylamino group, or a sulfonamide group is preferred, and a substituted or unsubstituted phenyl group is particularly preferred.

When R ¹² represents a substituted methyl group, more preferred examples are t-butyl group, dicyanomethyl group, dicyanophenylmethyl group, triphenylmethyl group (trityl group), diphenylmethyl group, methoxycarbonyldiphenyl Examples include a methyl group, a cyanodiphenylmethyl group, a methylthiodiphenylmethyl group, a cyclopropyldiphenylmethyl group, and among them, a trityl group is most preferred.

In the general formula (H), R ¹² is most preferably a substituted phenyl group.

[0170] While in m1 general formula (H) represents 1 or 0, when m1 is 0, R ¹¹ represents an aliphatic group, an aromatic group or a heterocyclic group. When m1 is 0, R ¹¹ is particularly preferably a substituted alkyl group of the phenyl group or 1 to 3 carbon atoms, which is the same as the preferable ranges of R ¹² described above.

M1 is preferably 1.

Among the groups represented by R ¹¹ , when R ¹² represents a phenyl group and G ¹ is —CO—, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and most preferably a hydrogen atom or an alkyl group. Where R
^{When 11} represents an alkyl group, the substituent is particularly preferably a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a carboxy group.

R ¹² represents a substituted methyl group, and G ¹ represents —CO
In the case of-, R ¹¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group
(Unsubstituted amino group, alkylamino group, arylamino group, heterocyclic amino group), more preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, alkylamino group, arylamino group, hetero It is a ring amino group. When G ¹ is —COCO—, regardless of R ¹² , R ¹¹ is preferably an alkoxy group, an aryloxy group, or an amino group, particularly a substituted amino group, specifically an alkylamino group, an arylamino group, or a saturated or Unsaturated heterocyclic amino groups are preferred. When G ¹ is —SO ₂ —, R ¹¹ is preferably an alkyl group, an aryl group or a substituted amino group, regardless of R ¹² .

In the general formula (H), G ¹ is preferably -CO-
Or -COCO-, particularly preferably -CO-.

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

[0176]

[Table 1]

[0177]

[Table 2]

[0178]

[Table 3]

[0179]

[Table 4]

[0180]

[Table 5]

[0181]

[Table 6]

[0182]

[Table 7]

[0183]

[Table 8]

[0184]

[Table 9]

[0185]

[Table 10]

[0186]

[Table 11]

[0187]

[Table 12]

[0188]

[Table 13]

[0189]

[Table 14]

[0190]

[Table 15]

[0191]

[Table 16]

[0192]

[Table 17]

[0193]

[Table 18]

[0194]

[Table 19]

[0195]

[Table 20]

[0196]

[Table 21]

[0197]

[Table 22]

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. (In some cases, they can be used in combination.) The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized.

Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. Compounds represented by formulas (4), (5) and (6) described in JP-A-6-230497, specifically, compound 4- described on pages 25 and 26 of the same publication. 1 to compound 4-1
0, compounds 5-1 to 5-42 on pages 28 to 36, and page 39,
Compounds 6-1 to 6-7 described on page 40. Compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compound 1-1 described on pages 5 to 7 of the same publication)
~ 1-17) and 2-1). JP-A-6-313936 describes the
Compounds represented by 2) and (Formula 3), specifically, the compounds described on pages 6 to 19 of the same publication. A compound represented by (Chemical Formula 1) described in JP-A-6-313951, specifically from page 3 to
Compounds described on page 5. A compound represented by the general formula (I) described in JP-A-7-5610.
Compounds I-1 to I-38 described on page. A compound represented by the general formula (II) described in JP-A-7-77783;
Compounds II-1 to II-102 described on pages 10 to 27. JP 7-1044A
Compounds represented by formulas (H) and (Ha) described in No. 26, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in Japanese Patent Application No. Hei 7-110007 characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. ), A compound represented by the general formula (B), a general formula (C), a general formula (D), a general formula (E), or a general formula (F). 1 to N-30. Compounds represented by the general formula (1) described in Japanese Patent Application No. 7-191007, specifically, compounds D-1 to D-55 described in the same gazette.

Further, “Known techniques (1 to
207) ”(published by Aztec) on pages 25 to 34. Compounds D-2 and D-39 of JP-A-62-86354 (pages 6 to 7).

The hydrazine-based nucleating agent of the present invention can be used in a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve. It can be used by dissolving it in such as.

Further, by using a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsified dispersion can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention may be added to the layer on the side of the photosensitive layer with respect to the support, that is, to any layer of the photosensitive layer or another layer. Preferably, it is added to the layer.

The nucleating agent added amount of the present invention is 1 to 1 mol of silver.
× preferably 10 ^-6 to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-5 ~5 × 10 ^{-3 mol, 2 × 10 -5 ~5 × 10} -3 mol and most preferred.

In the present invention, for forming a high contrast image, a high contrast accelerator can be used in combination with the nucleating agent (high contrast agent). For example, the amine compounds described in U.S. Patent No. 5,545,505, specifically AM-1 to AM-5,
Hydroxamic acids described in 5,507, specifically HA-1 to
HA-11, acrylonitriles described in 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in 5,558,983, specifically CA-1 to CA-6, Japanese Patent Application No. 8 Onium salts described in -132836, specifically A-1 to
A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

The nucleating agent (high contrast agent) and the method for synthesizing, adding, and the amount of the high contrast accelerator can be carried out as described in each of the cited patents.

As the sensitizing dye in the present invention, any dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17
Item 643IV-A (p.23, December 1978), Item 1831X (August 1979)
p.437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate making cameras can be advantageously selected.

Examples of spectral sensitization to red light include He-Ne
For lasers, so-called red light sources such as red semiconductor lasers and LEDs, I-1 to I-1 described in JP-A-54-18726.
-38, the compound of I-1 to I-35 described in JP-A-6-75322 and the compound of I-1 to I-34 described in JP-A-7-287338, JP-B-55-39818 Dyes 1 to 20 described, compounds of I-1 to I-37 described in JP-A-62-284343 and compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected. Is done.

For a semiconductor laser light source in the wavelength region of 750 to 1400 nm, cyanine, merocyanine, styryl,
Various known dyes, including hemicyanines, oxonols, hemioxonols and xanthene dyes, can be spectrally sensitized favorably. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Pat.
3,719,495, 3,877,943, UK Patent 1,466,201,
No. 1,469,117, No. 1,422,057, No. 3-10391, No. 6
-52387, JP-A-5-341432, JP-A-6-94781, JP-A-6-3011
The dye may be appropriately selected from known dyes as described in No. 41.

Particularly preferred structures of the dyes used in the present invention are cyanine dyes having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
72661, 6-222491, 2-230506, 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-301
No. 141, dyes described in U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524, JP-A-51-127719,
No. 52-80829, No. 54-61517, No. 59-214846, No. 60-67
No. 50, 63-159841, JP-A-6-35109, 6-59381
No., 77-146537, 77-146537, Tokuyohei 55-50111,
Dyes described in British Patent 1,467,638 and US Patent 5,281,515).

Further, dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887 as dyes forming J-band,
JP-A-2-96131 and JP-A-59-48753 are disclosed and can be preferably used in the present invention.

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are
Research Disclosure Volume 176, 17643 (December 1978) No. 23
Section IV of Page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2, 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy
It may be added to the emulsion by dissolving it in a solvent such as 1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, alone or in a mixed solvent.

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid. Method of adding to Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and this solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or base. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in U.S. Patent Nos. 3,822,135 and 4,006,025, JP-A-51-746, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion as disclosed in JP-A-51-746.
As disclosed in JP-A No. 24, a method of dissolving a dye using a compound that causes a red shift and adding this solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any stage of the emulsion preparation which has been found to be useful. For example, U.S. Patents 2,735,766 and 3,628,960,
4,183,756, 4,225,666, JP-A-58-184142,
As disclosed in the specification of JP-A-60-196749 and the like, the timing before silver halide grain forming step and / or desalting, during and / or after desalting and before the start of chemical ripening. As disclosed in the specification such as JP-A-58-113920, any time immediately before chemical ripening or during the process, after chemical ripening, and before coating the emulsion before coating It may be added at the time and in the process.
Further, as disclosed in the specification of U.S. Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step. The compound may be divided and added during the ripening step or after the completion of the chemical ripening, or may be added separately before or during the chemical ripening or after the completion of the chemical ripening. May be added.

The amount of the sensitizing dye used in the present invention may be a desired amount in accordance with the performance such as sensitivity and fog.
The amount is preferably from 10 ^-6 to 1 mol, more preferably from 10 ^-4 to 10 ^-1 mol, per mol of silver halide in the photosensitive layer.

The silver halide emulsion or //
And the organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and can be stabilized against reduced sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716; U.S. Pat.Nos. 2,886,437 and 2,444,605. Azaindene, U.S. Pat.
8,663 mercury salt, U.S. Pat.No. 3,287,135 urazole, U.S. Pat.No. 3,235,652 sulfocatechol, British Patent 623,448 Oxime,
Nitrone, nitroindazole, U.S. Patent No. 2,839,405
No. 3,220,839, thiuronium salts, and U.S. Pat.Nos. 2,566,263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.Nos. 4,108,665 and 4,442,202 No. 4,128,557
Nos. 4,137,079 and 4,138,365 and 4,
No. 4,59,350 and U.S. Pat.
And the phosphorus compounds described in No. 1,985.

The antifoggant preferably used in the present invention is an organic halide, for example, as described in JP-A-50-119624.
No. 50-120328, No. 51-121332, No. 54-58022, No.
56-70543, 56-99335, 59-90842, 61-12964
No. 2, 62-129845, JP-A-6-208191, 7-5621,
Nos. 7-2781, 8-15809, U.S. Pat.No. 5,340,712,
Compounds such as those disclosed in US Pat. Nos. 5,369,000 and 5,464,737 can be mentioned.

The antifoggant of the present invention may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

Although not required to practice the present invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the emulsion layer (photosensitive layer). Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The amount of mercury used in the present invention is preferably 1 nmol to 1 mmol, more preferably 10 nmol, per 1 mol of coated silver.
The range is from mol to 100 μmol.

The heat-developable image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acids of the present invention may be any benzoic acid derivative, but examples of preferred structures include those described in U.S. Pat.
No. 939, No. 4,152,160, Japanese Patent Application No. 8-151242, No. 8-151241
And the compounds described in JP-A-8-98051 and the like. The benzoic acid of the present invention may be added to any part of the recording material, but is preferably added to the layer having the photosensitive layer as the additional layer, and more preferably to the organic silver salt-containing layer. . The benzoic acid of the present invention may be added at any time during the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be added at any time from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable after salt preparation and immediately before application. The benzoic acid of the present invention may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent. The addition amount of the benzoic acids of the present invention may be any amount, but is preferably 1 μmol or more and 2 mol or less per 1 mol of silver, and 1 mmol or more.
More preferably, it is 5 mol or less.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like. be able to.

When a mercapto compound is used in the present invention, it may have any structure, but may be any of Ar-SM, Ar-SSA
Those represented by r are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogens (e.g., Br and Cl), hydroxy, amino, carboxy,
Alkyl (e.g. one or more carbon atoms, preferably 1-4
Having one carbon atom), alkoxy (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and aryl (optionally having substituents)
And a substituent selected from the group consisting of:
As mercapto-substituted heteroaromatic compounds, 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-Hydrocyr-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2
-Mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1-phenyl
-5-mercaptotetrazole, 3- (5-mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N'-
Examples thereof include {3- (5-mercaptotetrazolyl) phenyl} urea and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is preferably in the range of 0.0001 to 1.0 mol per mol of silver in the emulsion layer, and more preferably 0.001 to 0.1 mol per mol of silver.
3 moles.

In the photosensitive layer according to the invention, a polyhydric alcohol (for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. No. 60,404), fatty acids or esters described in U.S. Pat. Nos. 2,588,765 and 3,121,060, and silicone resins described in British Patent No. 955,061.

The image recording material of the present invention may have a surface protective layer for the purpose of preventing the photosensitive layer (image forming layer) from adhering.

Although any polymer may be used as the binder for the surface protective layer of the present invention, the binder preferably contains a polymer having a carboxylic acid residue in an amount of from 100 mg / m ^{2 to} 5 g / m ² . Examples of the polymer having a carboxyl residue include natural polymers (gelatin, alginic acid, etc.), modified natural polymers (carboxymethylcellulose, phthalated gelatin, etc.), and synthetic polymers (polymethacrylate, polyacrylate, polyalkylmethacrylate / acrylate). Copolymer, polystyrene / polymethacrylate copolymer, etc.). The carboxy residue content of such a polymer should be 10 mmol or more per 100 g of the polymer.
It is preferably at most 1.4 mol. Further, the carboxylic acid residue may form a salt with an alkali metal ion, an alkaline earth metal ion, an organic cation, or the like.

As the surface protective layer of the present invention, any anti-adhesion material may be used. Examples of anti-adhesion materials include waxes, silica particles, styrene-containing elastomeric block copolymers (e.g., styrene-butadiene-
Styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and mixtures thereof. Further, a crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the surface protective layer.

In the photosensitive layer or the protective layer of the photosensitive layer in the invention, US Pat. Nos. 3,253,921 and 2,274,782
No. 2,527,583 and No. 2,956,879, light absorbing substances and filter dyes can be used. Also, dyes can be mordanted, for example, as described in US Pat. No. 3,282,699. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3, and particularly preferably 0.2 to 1.5.

In the photosensitive layer of the present invention, various dyes and pigments can be used from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer of the present invention may be any, for example, there are pigments and dyes described in the color index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye,
Oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments including phthalocyanine, and inorganic pigments. Preferred dyes used in the present invention include anthraquinone dyes (e.g., compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), azomethine Dyes (e.g., compounds 17 to 47 described in JP-A-5-341441) and indoaniline dyes (e.g., compound 11 described in JP-A-5-289227).
To 19, compound 47 described in JP-A-5-341441, JP-A-5-1651
No. 47, compounds 2-10 to 11) and azo dyes (JP
Compounds 10 to 16) described in 5-341441 are exemplified. As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds used is determined depending on the desired absorption amount, but it is generally preferable to use them in an amount of 1 μg or more and 1 g or less per 1 m ² .

The heat-developable image recording material of the present invention is a so-called single-sided recording material having at least one photosensitive layer containing a silver halide emulsion on one side of a support and a back layer on the other side. It is preferred that

In the present invention, the back layer preferably has a maximum absorption in a desired range of about 0.3 or more and 2.0 or less.
750-360nm if the desired range is 750-1400nm
Is preferably 0.005 or more and less than 0.5, more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3. When the desired range is 750 nm or less, the halation is such that the maximum absorption in the desired range before image formation is 0.3 or more and 2.0 or less, and the optical density at 360-750 nm after image formation is 0.005 or more and less than 0.3. Preferably, it is a prevention layer. The method for lowering the optical density after image formation to the above range is not particularly limited. For example, as described in Belgian Patent No. 733,706, a method in which the density of a dye is reduced by decolorization by heating, And a method of decreasing the density by decoloring by light irradiation described in JP-A-17833.

When antihalation dyes are used in the present invention, these dyes have the desired absorption in the desired range,
Any compound may be used as long as it has a sufficiently low absorption in the visible region after the treatment and a desirable absorbance spectrum shape of the back layer is obtained. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458, JP-A-2-216140,
No. 7-13295, No. 7-11432, U.S. Pat.No.5,380,635, JP-A-2-688539, page 13, lower left column, line 1 to line 14,
The lower left column of the page, line 9, from the lower left column of page 14 of JP-A-3-24539
There are compounds described in the lower right column of page 16, and as dyes which can be decolorized by treatment, JP-A Nos. 52-139136, 53-132334, 56-50148.
No. 0, No. 57-16060, No. 57-68831, No. 57-101835, No.
59-182436, JP-A-7-36145, JP-A-7-199409, Tokubo Akira
No. 48-33692, No. 50-16648, Japanese Patent Publication No. 2-41734, U.S. Pat.Nos. 4,088,497, 4,283,487, 4,548,896, 5,1
There is 87,049.

In the present invention, suitable binders for the back layer are transparent or translucent, generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (vinyl) (Alcohol), hydroxyethylcellulose, 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 (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal))
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the single-sided recording material of the invention, a matting agent may be added to the surface protective layer of the photosensitive emulsion layer and / or the back layer or the surface protective layer of the back layer in order to improve the transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Patent Nos. 1,939,213 and 2,70
1,245, 2,322,037, 3,262,782, 3,539,344
No. 3,767,448 No., organic matting agents described in each specification such as No. 1,260,772, No. 2,192,241, No. 3,257,206,
Inorganic matting agents well-known in the art, such as inorganic matting agents described in the specifications of JP-A Nos. 3,370,951, 3,523,022, and 3,769,020 can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of water-dispersible vinyl polymers, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, and starch derivatives such as carboxy starch, carboxynitrophenyl Gelatin hardened with a known hardener such as starch, urea-formaldehyde-starch reactant, and hardened gelatin formed into microcapsule hollow granules by coacervate hardening are preferably used. Can be. As examples of the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth can be preferably used. The above matting agents can be used by mixing different types of substances as necessary.
The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In carrying out the present invention
It is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the coating film and the surface gloss, the particle size, shape, and particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, it is a preferred embodiment to add a matting agent to the backing layer. The matting degree of the backing layer is preferably Beck smoothness of 1200 seconds or less and 10 seconds or more, more preferably 700 seconds or less and 50 seconds or more. It is.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the recording material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferable to be contained. Further, the matte degree of the emulsion surface protective layer may be any value as long as stardust failure does not occur, but the Beck smoothness is 500 seconds or more.
It is preferably at most 000 seconds, particularly preferably at least 500 seconds and at most 2,000 seconds.

The heat-developable photographic emulsion of the present invention is a constituent of one or more layers on a support. One layer construction must include optional additional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is that the first emulsion layer (usually the layer adjacent to the support) contains an organic silver salt and silver halide, and the second layer or both layers do not contain some other components. No. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, and may include all components in a single layer as described in U.S. Pat.No. 4,708,928. Is also good. In the case of multi-dye, multi-color photothermographic materials, each emulsion layer generally has a functional or non-functional layer between the emulsion layers (photosensitive layers), as described in U.S. Pat. Are kept distinct from each other by using the barrier layer.

US Pat. Nos. 4,460,681 and 4,374,9
Backside resistive heating layer as shown in No. 21
stive heating layer) can also be used in a photosensitive heat developed photographic image system.

A hardener may be used for each layer such as the photosensitive layer, the protective layer and the back layer of the present invention. Examples of hardeners include:
U.S. Pat.
Vinyl sulfone compounds described in No. 48 and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically,
No. 62-170950, Fluoropolymer surfactants described in U.S. Pat.No. 5,380,644, JP-A-60-244945, JP-A-63-18
8135 No. fluorinated surfactants described in U.S. Pat.
Examples thereof include polysiloxane surfactants described in JP-A-5,965 and the like, polyalkylene oxides and anionic surfactants described in JP-A-6-301140 and the like.

The photographic emulsion for heat development of the present invention can be generally coated on various supports. Typical supports include polyester films, primed polyester films, poly (ethylene terephthalate) films, polyethylene naphthalate films, cellulose nitrate films, cellulose ester films, poly (vinyl acetal) films, polycarbonate films and related or resinous Materials, as well as glass,
Including paper, metal, etc. Flexible substrates, particularly coated with baryta and / or partially acetylated α-olefin polymers, especially polymers of C 2-10 α-olefins such as polyethylene, polypropylene, ethylene-butene copolymers A paper support is typically used. The support may be transparent or opaque, but is preferably transparent. 75 of these
Biaxially stretched polyethylene terephthalate (PET) of about 200 μm is particularly preferred.

On the other hand, when the plastic film is passed through a heat developing machine at a temperature of 80 ° C. or more, the dimensions of the film generally expand and contract. If the processed material is used for printing plate making,
This expansion and contraction is a serious problem when performing precision multicolor printing.
Therefore, in the present invention, it is preferable to use a film having a small dimensional change, which is designed to reduce internal strain remaining in the film at the time of biaxial stretching and eliminate thermal shrinkage distortion generated during thermal development. For example, polyethylene terephthalate, which is heat-treated at 100 to 210 ° C. before coating the photographic emulsion for thermal development, is preferably used. Those having a high glass transition temperature are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyethersulfone, polyarylate, polycarbonate and the like can be used.

The heat-developable image recording material of the present invention may be prepared, for example, as described in US Pat. Nos. 2,861,056 and 3,206,312, in order to prevent static charge, for example, soluble salts (eg, chlorides and nitrates), deposited metal layers. An ionic polymer or an insoluble inorganic salt as described in U.S. Pat.No. 3,428,451,
It may have a layer containing tin oxide fine particles described in JP-A-60-252349 and JP-A-57-104931.

As a method for obtaining a color image using the heat-developable image recording material in the present invention, there is a method described in JP-A-7-13295, page 10, left column, line 43 to 11 left column, line 40. Also, as a stabilizer for color dye images, UK Patent No. 1,326,
No. 889, U.S. Pat. Nos. 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337 and 4,042,394.

The photothermographic emulsion of the present invention can be coated by various coating operations including dip coating, air knife coating, flow coating or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

Additional layers in the heat-developable image recording material of the present invention, such as a dye-receiving layer for receiving a moving dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques And a known primer layer. It is preferable that the recording material of the present invention can form an image with only one recording material, and it is preferable that a functional layer required for image formation such as an image receiving layer does not become another material.

The heat-developable image-recording material of the present invention may be developed by any method, but is usually developed by elevating the temperature of the image-wise exposed recording material. As a preferred embodiment of the heat developing machine used, as a type in which the heat-developable image recording material is brought into contact with a heat source such as a heat roller or a heat drum, Japanese Patent Publication No. 5-56499, Patent Publication No. 684453,
-292695, JP-A-9-297385 and International Patent WO95 / 30
As the non-contact type, there is a heat developing machine described in JP-A-7-13294, International Patent Nos. WO97 / 28489, 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C., more preferably 1 to 250 ° C.
00-140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

As a method for preventing the uneven processing due to the dimensional change during the heat development of the heat-developable image recording material of the present invention,
A method of forming an image by heating at a temperature of 80 ° C. or more and less than 115 ° C. (preferably 113 ° C. or less) for 5 seconds or more so that an image is not formed, and then thermally developing the image at 110 ° C. or more (preferably 130 ° C. or less) ( A so-called multi-stage heating method) is effective.

The recording material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source.
As the laser beam according to the present invention, gas laser, YAG
Lasers, dye lasers, semiconductor lasers and the like are preferred. Further, a semiconductor laser and a second harmonic generation element can be used.

The recording material of the present invention has a low haze upon exposure and tends to cause interference fringes. Examples of the interference fringe prevention technology include a technology for obliquely entering a laser beam into a recording material as disclosed in JP-A-5-113548 and a multi-mode laser disclosed in WO95 / 31754 and the like. There is known a method of utilizing these techniques, and it is preferable to use these techniques.

For exposing the recording material of the present invention, SPIE vo
l.169 Laser Printing 116-128 (1979), JP-A-4-5104
No. 3, WO95 / 31754, etc., it is preferable to expose the laser beams so that they overlap each other so that the scanning lines are not visible.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process of the heat-developable image recording material of the present invention. FIG. 1 is a side view of the heat developing machine. A transfer endless belt 4 suspended by a plurality of feed rollers 3 is pressed against the peripheral surface of a cylindrical heat drum 2 containing a halogen lamp 1 as a heat source therein as a heat source of the heating means, and the endless belt 4 and the heat drum The heat-developable image recording material 5 is conveyed by being sandwiched therebetween. While being transported, the heat-developable image recording material 5 is heated to a development temperature, and is subjected to heat development. In this case, the orientation of the lamp is optimized, and the temperature control in the width direction is performed accurately.

Near the exit 6 from which the heat-developed image recording material 5 is sent out between the heat drum 2 and the endless belt 4, the heat-developed recording material 5 released from the curvature of the peripheral surface of the heat drum 2 is flattened. A correction guide plate 7 is provided. In the vicinity of the correction guide plate 7, the ambient temperature is adjusted so that the temperature of the heat development recording material 5 does not fall below a predetermined temperature.

A pair of feed rollers 8 for feeding the heat-developable image recording material 5 is installed downstream of the outlet 6, and the heat-developable image recording material 5 is maintained in a flat state downstream of the roller pair 8 adjacent to the roller pair 8. A pair of flat guide plates 9 for guiding in a state where the flat guide plates 9 are guided is installed, and further downstream thereof, another pair of feed rollers 10 is installed adjacent to the flat guide plates 9. The flat guide plate 9 has a length sufficient to cool the heat-developable recording material 5 while the heat-developable image recording material 5 is being conveyed therebetween. That is, the heat development recording material 5 is cooled until the temperature of the heat development recording material 5 becomes 30 ° C. or less. As this cooling means, a cooling fan 11 is provided.

Although the above has been described with reference to the drawings, the present invention is not limited to this. For example, the thermal developing machine used in the present invention, such as that described in JP-A-7-13294, may have various structures. In the case of the multi-stage heating method preferably used in the present invention, two or more heat sources having different heating temperatures may be provided in the above-described apparatus, and heating may be performed continuously at different temperatures.

[0257]

EXAMPLES The effects of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. <Example 1><< Preparation of silver halide emulsion >> (Emulsion A) 11 g of phthalated gelatin, 30 mg of potassium bromide and 10 mg of sodium benzenethiosulfonate were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at a temperature of 55 ° C. After that, silver nitrate 18.
An aqueous solution containing 159 ml of an aqueous solution containing 6 g and an aqueous solution containing potassium bromide at 1 mol / liter were added by a control double jet method over 6 minutes and 30 seconds while keeping the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate and an aqueous solution of a halogen salt containing 1 mol / l of potassium bromide were added by a control double jet method over 28 minutes and 30 seconds while keeping the pAg at 7.7. Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, and 0.17 g of compound A and 23.7 g of deionized gelatin (calculated as 20 ppm or less) were added to adjust the pH to 5.9 and pAg 8.0. The obtained particles were cubic particles having an average particle size of 0.11 μm, a projection area variation coefficient of 8%, and a (100) plane ratio of 93%.

The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and 3 minutes later, 154 μm of sodium thiosulfate was added.
Mole was added and aged for 100 minutes.

Thereafter, the temperature was maintained at 40 ° C.
6.4 × 10 ^-4 mol of sensitizing dye A per mol, 6.4 × 1
0 ^-3 added with stirring mole of compound B, 30 after 20 minutes
The mixture was rapidly cooled to ° C. to complete the preparation of silver halide emulsion A.

[0260]

Embedded image

<< Preparation of Organic Acid Silver Dispersion >><Organic acid silver A> While stirring 4.4 g of arachidic acid, 39.4 g of behenic acid, and 770 ml of distilled water at 85 ° C., 103 ml of an aqueous 1N-NaOH solution was added to 60 parts of the mixture.
The reaction was carried out for 240 minutes, and the temperature was lowered to 75 ° C. Then, 112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and the temperature was lowered to 30 ° C. afterwards,
The solid content is separated by suction filtration, and the solid content is 30%.
Washed with water until it reached μS / cm. The solid content thus obtained was treated as a wet cake without drying, and 5 g of polyvinyl alcohol (trade name: PVA-205) and water were added to a wet cake equivalent to 100 g of dry solid content,
After the total amount was 500 g, the mixture was preliminarily dispersed with a homomixer.

Next, the pre-dispersed stock solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain an organic acid silver dispersion A. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.04 μm and an average major axis of 0.8 μm.
m, needle-like particles having a variation coefficient of 30%. The measurement of the particle size was performed by MasterSizerX manufactured by Malvern Instruments Ltd. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature.

<Organic acid silver B> Arachiic acid 4.4 g, behenic acid
39.4 g, distilled water (700 ml) and sec-butanol (70 ml) were stirred at 85 ° C. while adding 1N-NaOH aqueous solution (103 ml) over 60 minutes, reacted for 240 minutes, and cooled to 75 ° C. Then, 112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and the temperature was lowered to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. Thereafter, the dispersion was carried out in the same manner as the organic acid silver A to obtain an organic acid silver dispersion B. The organic acid silver particles contained in the organic acid silver dispersion thus obtained were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%.

<Silver Organic Acid C> 4.4 g of arachidic acid, behenic acid
39.4 g, distilled water 700 ml, 1N-NaOH aqueous solution 103 ml was added over 60 minutes while stirring tert-butanol 70 ml at 85 ° C. 240
The reaction was allowed to proceed for 75 minutes, and the temperature was lowered to 75 ° C. Then, 112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and the temperature was lowered to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. Thereafter, the dispersion was carried out in the same manner as in the case of the organic acid silver A, whereby an organic acid silver dispersion C was obtained. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.04 μm and an average major axis of 0.8 μm.
m, needle-like particles having a variation coefficient of 30%.

<Organic acid silver D> Arachiic acid 4.4 g, behenic acid
39.4 g, distilled water 700 ml, tert-butanol 70 ml, 1N-NaOH aqueous solution 123 ml were mixed, stirred at 75 ° C. for 1 hour and reacted at 65 ° C.
The temperature dropped. Then, 112.5 ml of an aqueous solution of 22 g of silver nitrate was added to 45
The mixture was added over seconds, left as it was for 5 minutes, and cooled to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. Thereafter, the dispersion was performed in the same manner as in the case of the organic acid silver A, to obtain an organic acid silver dispersion D.
The organic acid silver particles contained in the organic acid silver dispersion thus obtained were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%.

<< Preparation of Solid Fine Particle Dispersion of 1,1-Bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane >> 1,1-bis (2-hydroxy-3, 5-dimethylphenyl) -3,5,5-trimethylhexane 20 g for Kuraray Co., Ltd.
3.0 g of MP-203 made of MP polymer and 77 ml of water were added, and the mixture was stirred well and left as a slurry for 3 hours. afterwards,
360 g of 0.5 mm zirconia beads were prepared, placed in a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 3 hours to prepare a solid dispersion of reducing agent solid particles. Particle size is 80 wt% of particles
Was 0.3 μm or more and 1.0 μm or less.

<< Preparation of Solid Fine Particle Dispersion of Tribromomethylphenylsulfone >> Hydroxypropylmethylcellulose was added to 30 g of tribromomethylphenylsulfone.
0.5 g, 0.5 g of compound C and 88.5 g of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the antifoggant was prepared in the same manner as the preparation of the reducing agent solid fine particle dispersion. Particle size is 80μ% of particles 0.3μm
It was 1.0 μm or less.

<< Preparation of Emulsion Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Thus, an emulsion layer coating solution was obtained. Binder; Luck Star 3307B 470 g as solids (manufactured by Dainippon Ink and Chemicals, Inc .; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5 , 5-Trimethylhexane 110g as solid content Tribromomethylphenylsulfone 25g as solid content Sodium benzenethiosulfonate 0.25g Polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) 46g 6-iso-butylphthalazine 0.12mol Table 23 Nucleating agent described Amount shown in Table 23 Dye A 0.62 g Silver halide emulsion A 0.05 mol as Ag amount

[0269]

Embedded image

<< Preparation of Coating Solution for Emulsion Surface Protective Layer >> Solid Content 27.5
3.75 g of polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 copolymer having a glass transition temperature of 55 ° C.) and 3.75 H ₂ O g, 4.5 g of benzyl alcohol as a film-forming aid, Compound D
0.45 g, Compound E 0.125 g, Compound F 0.0125 mol,
And polyvinyl alcohol (Kuraray Co., Ltd., PVA-21
7) 0.225 g was added, and H ₂ O was further added to make 150 g, thereby obtaining a coating solution.

[0271]

Embedded image

<< Preparation of PET Support with Back / Undercoat Layer >> (1) Support Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6 / 4 (measured at 25 ° C. in weight ratio). This is pelletized and dried at 130 ° C. for 4 hours.
After being melted at 00 ° C., it was extruded from a T-die and then rapidly cooled to prepare an unstretched film having a thickness of 120 μm after heat setting.

Using a roll having a different peripheral speed, the film was longitudinally stretched 3.3 times and then stretched 4.5 times by a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the lateral direction at the same temperature. Then, after slitting the chuck part of the tenter, knurling is performed on both ends, and 4.8 kg / cm ²
Rolled up. In this way, width 2.4m, length 3500m,
A roll having a thickness of 120 μm was obtained.

(2) Undercoat Layer Undercoat Layer (a) Polymer Latex Styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (% by weight) 160 mg / m ² 2,4-dichloro- 6-Hydroxy-s-triazine 4mg / m ² Matting agent (polystyrene, average particle size 2.4μm) 3mg / m ²・ Undercoat layer (b) Alkali-treated gelatin (Ca ²⁺ content 30ppm, jelly strength 230g) 50mg / m ² Dye A Coating amount at which optical density of 780nm becomes 0.7

(3) Conductive Layer Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 38 mg / m ² SnO2 / Sb (9/1 weight ratio, average particle diameter 0.25 μm 120 mg / m ² matting agent (polymethyl methacrylate) , Average particle size 5 μm) 7 mg / m ² melamine 13 mg / m ²

(4) Protective layer Chemipearl S-120 (manufactured by Mitsui Petrochemical Co., Ltd.) 500 mg / m ² Snowtex-C (manufactured by Nissan Chemical Co., Ltd.) 40 mg / m ² Denacol EX-614B (Nagase Chemical Industries, Ltd.) 30mg / m ²

Undercoat layer (a) and undercoat layer (b) on both sides of the support
Were sequentially applied and dried at 180 ° C. for 4 minutes. Next, the undercoat layer (a) and the undercoat layer (b) are applied, and then a conductive layer and a protective layer are sequentially applied to one surface, and dried at 180 ° C. for 4 minutes, respectively, for PET support having a back / undercoat layer. Created body.

The PET support provided with the backing / undercoat layer thus prepared was placed in a heat treatment zone having a total length of 200 m set at 200 ° C., and was conveyed at a tension of 3 kg / m ² and a conveying speed of 20 m / min.
Thereafter, the film was passed through a zone at 40 ° C. for 15 seconds, and wound up at a winding tension of 10 kg / cm ² .

<< Preparation of heat-developable image recording material >> On the undercoat layer of the PET support provided with the back / undercoat layer, the above-mentioned emulsion layer coating solution was applied so as to have a coating silver amount of 1.6 g / m ² . . Further, the coating solution for the emulsion surface protective layer was applied thereon so that the coating amount of the solid content of the polymer latex was 2.0 g / m ² , to obtain a sample of the heat-developable image recording material.

<< Evaluation of Photographic Performance >> (Exposure Processing) The obtained coated sample was passed through an interference filter having a peak at 780 nm and a step wedge.
Exposure was performed with xenon flash light having an emission time of 10 ⁻⁶ seconds.

(Heat Developing Process) The exposed sample was subjected to a heat developing process at 115 ° C. for 15 seconds using the heat developing machine shown in FIG. In the drum type heat developing machine of FIG. 1, the light distribution of the lamp was optimized, and the temperature accuracy in the width direction was set at ± 1 ° C. Further, the temperature of the heat-developable image recording material near the correction guide plate 7 is 90 °.
The ambient temperature was adjusted so that the temperature did not fall below ℃.

(Evaluation of photographic performance) The obtained images were evaluated using a Macbeth TD904 densitometer (visible density). The results of the measurement were evaluated in terms of Dmin, sensitivity (the reciprocal of the ratio of the exposure amount giving a density higher than Dmin by 1.0), and contrast. Regarding the sensitivity, sample No. of the recording material was used. The sensitivity of 1 was set to 100. Contrast is expressed as logarithm of exposure amount on the horizontal axis, density 0.3 and 3.0
It was expressed by the slope of a straight line connecting the points. Table 23 shows the results of the above-described evaluation performed on each sample.

[0283]

[Table 23]

It can be seen that the sample of the present invention, in particular, a sample to which a nucleating agent is added, has low fog, high contrast, and high sensitivity.

<Example 2> A sample was prepared using the following silver halide emulsion B in place of the silver halide emulsion A of Example 1, and evaluation was performed in the same manner as in Example 1.

(Emulsion B) Phthalated gelatin 27 in 1000 ml of water
g and 1.8 g of sodium chloride, 10 mg of sodium thiosulfonate, and adjusted to pH 5.0 at a temperature of 40 ° C.
120 ml of an aqueous solution containing 60 g of silver nitrate and 120 ml of an aqueous solution of a halogen salt A containing 21.6 g of sodium chloride were prepared by the double jet method.
It was added over a minute. Then, an aqueous solution 3 containing 15 g of silver nitrate
K ₂ Rh equivalent to 1 × 10 ⁻⁶ mol per mol of silver nitrate containing 0 ml, 4.35 g of sodium chloride and 2.13 g of potassium bromide
30 ml of an aqueous solution of (H ₂ O) Cl ₅ halogen salt B was added over 2 minutes. Thereafter, 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was further lowered to cause coagulation and sedimentation for desalination. Thereafter, 0.1 g of phenoxyethanol was added, and the pH was adjusted to 5.9 and pAg7.6 to prepare silver chlorobromide particles (silver bromide content: 6 mol%, average size: 0.12 μm, projection area variation coefficient: 8%, cubic particles). finished.

The silver halide grains thus obtained were heated to 60 ° C., and 85 μmol of sodium thiosulfonate and 11 μmol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide per mol of silver were obtained. After adding 15 μmol of tellurium compound, 120 μmol of chloroauric acid and aging for 120 minutes, 40
After quenching to ℃, 100 μmol of sensitizing dye A, 500 μmol of 2-mercapto-5-methylbenzimidazole and 500 μmol
μmol N-methyl-N ′-{3- (5-mercaptotetrazolyl)
Phenyl} urea, 500 μmol of compound A, and 500 μmol of compound B were added and rapidly cooled to 30 ° C. to obtain a silver halide emulsion B.

In the samples in which Emulsion A was replaced with Emulsion B, the samples of the present invention, particularly the samples to which a nucleating agent was added, showed good results.

Example 3 The heat developing machine used in Example 1 has the same structure as the heat developing machine shown in FIG. 3 of JP-A-7-13294, and has a structure in which two types of heat sources are arranged. It was made to be able to perform two stages of heating continuously. When the following thermal development treatment was performed using this thermal developing machine, good results were obtained with the sample of the present invention, particularly with the sample to which the nucleating agent was added.

(1) Treatment (a): After treatment at 70 ° C. for 10 seconds, 1
15 ° C. for 30 seconds treatment (2) Treatment (b): After treatment at 90 ° C. for 10 seconds, treatment at 115 ° C. for 30 seconds (3) Treatment (c); Second processing (4) Processing (d): After processing at 105 ° C. for 2 seconds, processing at 115 ° C. for 30 seconds (5) Processing (e); After processing at 115 ° C. for 15 seconds (an image has already appeared), processing at 115 ° C. for 15 seconds

[0291]

According to the present invention, low fog is obtained. In addition, a high-contrast image is obtained and the sensitivity is high.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration example of a heat developing machine used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 halogen lamp 2 heat drum 3 feed roller 4 endless belt 5 heat-developed image recording material 6 outlet 7 guide plate 8 feed roller pair 9 flat guide plate 10 feed roller pair 11 cooling fan

Claims (7)

[Claims] 1. A photosensitive heat-developable image recording material having a non-photosensitive organic silver salt and a photosensitive silver halide on a support, wherein the non-photosensitive organic silver salt is formed in the presence of a tertiary alcohol. And a photosensitive layer containing the photosensitive silver halide and / or a layer adjacent thereto contains a nucleating agent. 2. A nucleating agent comprising a substituted alkene derivative represented by the following general formula (1), a substituted isoxazole derivative represented by the general formula (2), and an acetal compound represented by the following general formula (3): 2. The photosensitive heat-developable image recording material according to claim 1, which is selected. Embedded image [In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. General formula
In (2), R ⁴ represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group,
Alkylthio group, alkylamino group, aryloxy group, arylthio group, anilino group, heterocyclic oxy group,
Represents a heterocyclic thio group or a heterocyclic amino group. General formula
In (3), X and Y, and A and B may be bonded to each other to form a cyclic structure. ] 3. The photothermographic image recording material according to claim 1, wherein the nucleating agent is a hydrazine derivative. 4. A photosensitive layer comprising a non-photosensitive organic silver salt on a support and containing a photosensitive silver halide formed independently of the non-photosensitive organic silver salt and added at the time of preparing a coating solution. In the photosensitive heat-developable image recording material having a binder, the latex of a polymer having a glass transition temperature of -30 ° C or more and 40 ° C or less is used as 50% by weight or more of the binder of the photosensitive layer, and the photosensitive layer is formed of the layer. Wherein the non-photosensitive organic silver salt is formed in the presence of a tertiary alcohol. Image recording material. 5. The photosensitive heat-developable image recording material according to claim 4, wherein a nucleating agent is contained in the photosensitive layer and / or a layer adjacent thereto. 6. A nucleating agent comprising a substituted alkene derivative represented by the following general formula (1), a substituted isoxazole derivative represented by the following general formula (2), and an acetal compound represented by the following general formula (3): 6. The photothermographic image recording material according to claim 5, which is selected. Embedded image [In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. General formula
In (2), R ⁴ represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group,
Alkylthio group, alkylamino group, aryloxy group, arylthio group, anilino group, heterocyclic oxy group,
Represents a heterocyclic thio group or a heterocyclic amino group. General formula
In (3), X and Y, and A and B may be bonded to each other to form a cyclic structure. ] 7. The photothermographic image recording material according to claim 5, wherein the nucleating agent is a hydrazine derivative.