JP2002296731A - Heat developable color image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable color image recording material giving a high quality color image less liable to color development fogging only by heat development as a developing means without requiring an additional step such as peeling or transfer. SOLUTION: In the heat developable color image recording material containing photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material and an organic binder on the base, the color image forming material is a two-equivalent type coupler and a scavenger coupler which does not substantially form a color image is further contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable color image recording material and a heat-developable color image forming method. More specifically, the present invention relates to a heat-developable color image recording material and a heat-developable color image forming method capable of obtaining a high-quality color image by only heat development without requiring additional steps such as peeling and transfer. It is. The heat-developable color image recording material and the heat-developable color image forming method of the present invention can be used in various color photographic fields such as a color proof material, a color print material, a color transmission recording material, and a color microfilm used in the printing industry. .

[0002]

2. Description of the Related Art An image forming method using a heat-developable image recording material using an organic silver salt is disclosed, for example, in US Pat. No. 3,152,904.
No. 3,457,075, and "Thermally Processed Silver Systems" by J. Klosterboer
(Imaging Processes and Materials Neblette 8
Edition, J. Sturge, V.S. Wallwards
orth), A. Edited by Shepp, p. 279, 1989
Year). Such photosensitive materials are prepared by dispersing a non-photosensitive reducible 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.

In these photographic materials, an organic solvent solution of an organic binder is usually used, in which an organic silver salt and silver halide are dispersed, and a reducing agent dissolved in an organic solvent is added. It was a target. Also, silver halide is
It has been recognized that placement in contact with the surface of an organic silver salt crystal is an important requirement for image formation. These technologies are, for example, MRV Sahyun, Thermally Developable
Photographic Materials (TDPM): A Review of the Sta
te-of-the-Art in mechanistic Understanding, J. Imag
ing Sci. & Technology, 42, 23 (1998).

A heat-developable color image recording material using an organic silver salt is described in the above-mentioned book by J. Crostaver et al., P.
It is described in the section of LOR TPSM. As described therein, attempts have been made to create color images since the 1970s, but they have not yet been put to practical use. A color developing system that functions effectively in the organic silver salt heat development method has not been found. In addition, there is a problem that the color developing system is unstable and the performance is deteriorated before the coated film is used after it is manufactured. In addition, there is a problem that non-image-wise color development occurs during storage after thermal development, resulting in fogging and image damage. In addition, as a basic problem, there is a problem that the saturation of the developed hue is impaired because developed silver coexists. In order to separate the developed silver from the coloring dye, there is a method of transferring the coloring dye to another layer or another support. However, the dye transfer method has problems that the process operation becomes complicated, the processing speed is impaired, and the processing apparatus becomes complicated and expensive. Furthermore, there is a problem of increasing the burden on the environment due to the generation of waste materials.

[0005] For this reason, reducing agents and couplers having excellent storage stability in a film, high heat development activity and excellent color development are disclosed in Japanese Patent Application Nos. 2000-76173 and 2000-13.
No. 2270, No. 2000-76016,
And 2000-132181. In addition, an application related thereto is disclosed in Japanese Patent Application No. 2000-76.
053, 2000-83730, 2000-138148, 2000-857
No. 98, etc. The image recording materials described therein are excellent in storage stability, and after exposure, from 110 ° C.
Since a color image can be obtained at a relatively low developing temperature of 5 to 30 seconds at 125 ° C. in a short developing time, and a color image can be obtained effectively with a small amount of developed silver, the developed silver remains as it is. Also has a low density, so that it can be observed substantially as a color image.

However, as a problem of the above color image forming material, a problem of color fog has occurred. Color fogging is an adverse effect due to high activity and high efficiency, and is non-image-wise color development due to a small amount of fog development. If development is refrained from development in order to reduce the occurrence of fogging, the color image density will not be sufficient, and if an additive known as an antifogging agent for development is used until the fog is effectively reduced, the photographic sensitivity will decrease and the development speed will decrease. With a negative effect such as a decrease in It was necessary to develop a color image forming material that solved such a problem of color fog.

Further, in order to form a multicolor image, it is necessary to employ a multicolor developing unit comprising a combination of a plurality of silver halide grains having different color sensitivity and a color image forming material. is there. In such a multilayer configuration,
It is necessary to prevent the phenomenon of color mixing that causes unintended color formation when the oxidation product of the reducing agent from one image forming layer diffuses into other units. For this purpose, it is effective to include a material that captures the oxidation product of the reducing agent in the intermediate layer between these units, and such a functional material is well known in ordinary wet processing color photographic materials. Have been. However, such a functional material has never been known as a completely dry heat-developable image forming material.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art. That is, in the present invention, the developing means is only thermal development,
An object of the present invention is to provide a heat-developable color image recording material capable of obtaining a high-quality color image with little color fogging without requiring additional steps such as peeling and transfer. That is, the present invention has made one of the problems to be solved to solve the problem of color fogging. Another object of the present invention is to find a material that captures oxidation products of a reducing agent that is useful for preventing color mixing in a multilayer structure.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, on a support, a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, In a heat-developed color image recording material containing an organic binder, a two-equivalent coupler is used as a color image forming material,
Furthermore, they have found that by using a scavenger coupler that does not substantially form a color image, it is possible to provide an excellent heat-developable color image recording material having a desired effect, thereby completing the present invention.

That is, according to the present invention, in a heat-developable color image recording material containing a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, and an organic binder on a support, the color image A heat-developable color image recording material is provided, wherein the forming material is a two-equivalent coupler and further includes a scavenger coupler that does not substantially form a color image.

According to a preferred embodiment of the present invention, the reducing agent is a compound represented by the following general formula (D): General formula (D): Q ¹ -NHNH-Q ² (General formula (D) Wherein Q ¹ represents an aromatic group bonded to —NHNH—Q ² at a carbon atom, or a 5- to 7-membered unsaturated ring,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. ); The content of the scavenger coupler with respect to the color image forming material is 0.01 in a molar ratio.
An embodiment in which the scavenger coupler is a 4-equivalent coupler; an embodiment in which the scavenger coupler is a general formula (SC-I) to (S
An embodiment in which an organic binder is formed from a polymer latex dispersed in water; an embodiment in which a reducing agent is applied as a dispersion of fine particles solid-dispersed in water; An embodiment in which the color image forming material is applied as a dispersion of fine particles solid-dispersed in water; an embodiment in which the scavenger coupler is applied as a dispersion of fine particles solid-dispersed in water; containing a halogen precursor An embodiment in which the halogen precursor is applied as a dispersion of fine particles solid-dispersed in water; an embodiment in which the color image forming material and the scavenger coupler are contained in the same layer; and a layer containing the color image forming material An embodiment containing a scavenger coupler in a layer adjacent to the substrate.

According to another aspect of the invention, on a support,
Photosensitive silver halide having a sensitivity in the first wavelength region,
An organic silver salt, a reducing agent, a color image forming material, a first image forming layer containing an organic binder, and a photosensitive silver halide photosensitive to a second wavelength region, an organic silver salt, a reducing agent,
In a heat-developed color image recording material having at least two or more different photosensitive wavelength regions, including a color image forming material and a second image forming layer containing an organic binder, the color image forming material is a 2-equivalent coupler. And further comprising a scavenger coupler that does not substantially form a color image. According to a preferred embodiment of the present invention, an embodiment in which the scavenger coupler is contained in a layer between image forming layers having different photosensitive wavelength ranges; and an embodiment in which the reducing agent is a compound represented by the following general formula (D); General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. ): Is provided.

According to still another aspect of the present invention, there is provided a heat-developable color image forming method, comprising the steps of exposing and thermally developing the above-described heat-developable color image recording material of the present invention. According to still another aspect of the present invention, an image recording layer comprising a photosensitive silver halide, an organic silver salt, a reducing agent, a two-equivalent coupler, and an organic binder on a support, the image recording layer and And / or a heat-developable color image recording material having a scavenger coupler in an adjacent layer, wherein the photosensitive silver halide is contained in a ratio of 0.01 mol% to 200 mol% of the organic silver salt in the number of moles of silver. A heat-developed color image forming method is provided, wherein an image in which developed silver and a color-developed image coexist is formed by exposure and heat development, and the color image is observed without separating the images. .

In the above-described heat development color image forming method,
Preferably, the reducing agent is a compound represented by the following general formula (D). General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. )

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The heat-existing color image recording material of the present invention contains a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, and an organic binder on a support, and the color image forming material has 2 equivalents. And a scavenger coupler which does not substantially form a color image.
The exposed color image recording material of the present invention can provide a single color or multicolor image only by heating after exposure.

The organic silver salt that can be used in the present invention includes:
Relatively stable to light, but in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent,
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, especially
Silver salts of long chain fatty carboxylic acids (with 10-30, preferably 15-28 carbon atoms) are preferred. Also preferred are organic or inorganic silver salt complexes in which the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver donor can preferably comprise about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate,
Silver maleate, silver fumarate, silver tartrate, silver linoleate,
And silver butyrate and 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-
Silver salt of phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamide) benzothiazole, S-alkylthio Silver salts of thioglycolic acid, such as silver salts of glycolic 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 thioamide, Silver salt of carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt described in U.S. Pat.No.4,123,274, for example, 3-amino- Silver salts of 1,2,4-mercaptothiazole derivatives such as silver salts of 5-benzylthio-1,2,4-thiazole, 3- (3-carboxyethyl) -4- described in U.S. Pat.No.3,301,678. Silver salt of methyl-4-thiazoline-2-thione Includes silver salts of thione compounds. Further, 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, and US Pat. And silver salts of 1,2,4-triazole or 1-H-tetrazole, imidazole and silver salts of imidazole derivatives as described in US Pat. No. 4,220,709. For example, various silver acetylide compounds as described in U.S. Pat. Nos. 4,761,361 and 4,775,613 can also be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, and various shapes such as a needle shape, a scale shape, and a lump shape can be used. Particularly preferred are needles and scales. For needle-shaped crystals, short axis 0.01μ
m or more and 0.20 μm or less, major axis 0.10 μm or more and 5.0 μm or less, minor axis 0.01 μm or more and 0.15 μm or less, major axis 0.10 μm or more
4.0 μm or less is more preferable. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is the minor axis, the minor axis, the minor axis, the standard deviation of the length of each major axis divided by each major axis 100% is preferably 100% or less, more preferably 8% or less.
0% or less, more preferably 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 obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, the value divided by the volume-weighted average diameter of 100.
The fraction (coefficient of variation) is preferably 100% or less, more preferably 80% or less, and still more preferably 50% or less. As a measuring method, for example, irradiating a laser beam to an organic silver salt dispersed in a liquid, and obtaining the particle size (volume weight average diameter) obtained by obtaining an autocorrelation function for a time change of fluctuation of the scattered light. Can be.

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, and floc-forming water washing by a coagulation method can be preferably used. . In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, the organic silver salt which is an image forming medium is contained, and the photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which an aqueous dispersion is converted into a high-speed stream and then the pressure is reduced.

After passing through these 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 photothermographic material is prepared using such a coating liquid, a haze is low, and a low-fogging and high-sensitivity photothermographic material can be obtained. On the other hand, when converted to a high-pressure, high-speed flow and dispersed, the presence of a photosensitive silver salt causes fog to increase and the sensitivity to decrease significantly. 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 liquid into the photosensitive silver salt is used instead of the method of mixing the aqueous solution of the photosensitive silver salt, the sensitivity is lowered. In the above, the high-pressure, the aqueous dispersion is dispersed and converted to high speed, is substantially free of photosensitive silver salt, the water content is 0.1 mol% based on the non-photosensitive organic silver salt The following is the case where 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 and Hiroki Usui, 1991, Shinzansha Publishing Co., Ltd., p357
-P403), "Advances in Chemical Engineering, Vol. 24" (edited by the Society of Chemical Engineers, Tokai Chapter, 1990, Maki Shoten, p184-p185), and the like. Is pressurized with a high-pressure pump or the like and sent into the pipe, and then passed through a narrow slit provided in the pipe. How to do.

The high-pressure homogenizer to which the present invention relates is generally composed of (a) a "shear force" generated when the dispersoid passes through a narrow gap at a high pressure and at a high speed, and (b) a dispersoid is supplied from a high pressure to 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. An example of this type of dispersing device is a Gaulin homogenizer.In this device, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on the 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
0-600 kg / cm ² , the flow rate is in the range of several m-30 m / s. In order to increase the dispersion efficiency, the high flow rate part is made into a saw blade shape to increase the number of collisions. 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.).

The dispersion apparatus suitable for the present invention 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
0-Z 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, or the like, and a sudden pressure drop is caused in the dispersion to obtain an organic silver salt dispersion optimal for the present invention. .

In the dispersion of an organic silver salt, it is possible to obtain a desired particle size by adjusting the flow rate, the differential pressure at the time of pressure drop, and the number of treatments. / Sec to 600m / sec, differential pressure at pressure drop
Is preferably in the range of 900~3000kg / cm ^2, the flow rate is 300 meters / sec to 60
More preferably, the pressure difference at the time of the pressure drop is 0 to 3,000 kg / cm ² at 0 m / sec. The number of times of dispersion processing can be selected as needed, but usually 1 to 10 times is selected, but 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 characteristics.At a temperature higher than 90 ° C., the particle size tends to increase, and the fog tends to increase. is there. Therefore, in the present invention, the high pressure, the step before converting to a high flow rate, or
The step after the pressure is reduced, or both of these steps include a cooling step, and the temperature of such aqueous dispersion is preferably kept in the range of 5 to 90 ° C. by the cooling step, and more preferably 5 to 90 ° C. It is preferred that the temperature be kept in the range of 80 ° C, particularly in the range of 5 to 65 ° C. In particular, when dispersing under high pressure in the range of 1500 to 3000 kg / cm ² , it is effective to provide the above cooling step. As the cooler, a double tube, a double tube using a static mixer, a multi-tube heat exchanger, a coiled tube heat exchanger, or the like can be appropriately selected according to the required heat exchange amount. Also, to increase the efficiency of heat exchange,
Considering the working pressure, a suitable one such as the thickness, thickness and material of the pipe may be selected. The refrigerant used for the cooler is based on the amount of heat exchange, 20 ° C well water or 5-10 ° C cold water treated with a refrigerator,
If necessary, a refrigerant such as ethylene glycol / water at -30 ° C can be used.

In the dispersion operation in the present invention, it is preferable to disperse the organic silver salt in the presence of a dispersant (dispersion aid) soluble in an aqueous solvent. As a dispersing aid, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer,
Synthetic anionic polymers such as maleic acid monoester copolymer, acrylomethylpropanesulfonic acid copolymer,
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 the like Other polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, known polymers such as hydroxypropylmethylcellulose, or a polymer compound existing in nature such as gelatin can be appropriately selected and used, but polyvinyl alcohols, Water-soluble cellulose derivatives are particularly preferred.

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 with a suitable pH adjuster before, during or after dispersion.

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 completion of the fine particle formation.

The prepared dispersion is 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) by means of 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 organic silver salt can be used in a desired amount, but the silver amount is preferably 0.1 to 5.0 g / m ² , more preferably 0.3 to 2.5 g / m ² .

Next, the color image forming material used in the present invention will be described. The color image forming material used in the present invention is a two-equivalent coupler. Specific examples of the color image forming material include those represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0031]

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[0032]

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[0033]

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. In the general formulas (1) to (3), R ¹⁵ is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent.

Examples of the substituent which R ¹⁴ , R ¹⁵ and R ¹⁶ may have include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl,
Methyl, ethyl, propyl, heptafluoropropyl,
Isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like, a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (for example, vinyl,
1-methylvinyl, cyclohexen-1-yl and the like, an alkynyl group having a total of 2 to 50 carbon atoms (for example, ethynyl,
-Propynyl, etc.), an aryl group having 6 to 50 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.),
50 acyloxy groups (eg, acetoxy, tetradecanoyloxy, benzoyloxy, etc.), having 1 to 5 carbon atoms
0 carbamoyloxy group (for example, N, N-dimethylcarbamoyloxy and the like), a carbonamide group having 1 to 50 carbon atoms (for example, formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide and the like), carbon Number 1 to 50 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 50 carbon atoms (for example, N-
Methylcarbamoyl, N, N-diethylcarbamoyl,
N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 50 carbon atoms (for example, N-butylsulfamoyl, N,
N-diethylsulfamoyl, N-methyl-N- (4-
Methoxyphenyl) sulfamoyl etc.), having 1 to 5 carbon atoms
An alkoxy group of 0 (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy,
Dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy, etc.), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy,
Naphthoxy, etc.), an aryloxycarbonyl group having 7 to 50 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), an alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), carbon number 1 to 50 N-acylsulfamoyl groups (for example, N-tetradecanoylsulfamoyl,
N-benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (for example, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2
-Hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (for example, benzenesulfonyl, p
-Toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl and the like), an alkoxycarbonylamino group having 2 to 50 carbon atoms (such as ethoxycarbonylamino), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (such as phenoxycarbonylamino, Naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl group, hydroxy group, sulfo group, mercapto group An alkylsulfinyl group having 1 to 50 carbon atoms (e.g., methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 50 carbon atoms (e.g., benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluene) C1 to C50 alkylthio group (for example, methylthio, octylthio, cyclohexylthio, etc.), C6 to C50 arylthio group (for example, phenylthio, naphthylthio, etc.), and C1 to C50 ureido group (For example, 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide and the like), a heterocyclic group having 2 to 50 carbon atoms (for example, at least one heteroatom such as nitrogen, oxygen and sulfur) Above, preferably includes 1 to 9
And a 12-membered monocyclic or condensed ring such as 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
Imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc., an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), 0 carbon atoms To 50 sulfamoylamino groups (for example, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), and a silyl group having 3 to 50 carbon atoms (for example, trimethylsilyl, dimethyl-t-butylsilyl, triphenyl) Silyl, etc.), and a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.). The above-mentioned substituent may further have a substituent, and examples of the substituent include the substituents mentioned here. The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable.

In the general formulas (1) to (4), Y is a group capable of leaving by a coupling reaction with an oxidized developing agent. Examples of Y include a heterocyclic group (a saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one nitrogen, oxygen, sulfur or the like as a hetero atom;
Examples include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole,
Imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione, thiazolidine-
2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrroline- 5-one,
2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,2
4-triazolidine-3,5-dione, 2-pyridone,
4-pyridone, 2-pyrimidone, 6-pyridazone, 2-
Pyrazone, 2-amino-1,3,4-thiazolidine, 2
-Imino-1,3,4-thiazolidine-4-one and the like),
Halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), acyloxy group (eg, acetoxy, benzoyloxy) Etc.), alkoxy groups (for example,
Methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.),
An alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylthio group (eg, phenylthio, naphthylthio, etc.),
Heterocyclic thio groups (eg, tetrazolylthio, 1,3,
4-thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio groups (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy groups (eg, methanesulfonyloxy, etc.), Arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl Group (eg, methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, methanesulfinyl, etc.), arylsulfinyl group (eg, benzenesulfinyl, etc.) Le etc.), an arylazo group (e.g., phenylazo, naphthylazo etc.), carbamoylamino group (e.g., N- methylcarbamoyl amino, etc.) and the like.

Y may be substituted by a substituent,
Examples of the substituent that substitutes for Y include those described as examples of the substituent that R ¹⁴ , R ¹⁵ , and R ¹⁶ may have. Y is preferably a halogen atom, an aryloxy group,
A heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, and a carbamoyloxy group. In the general formulas (1) to (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring.

Formula (5) represents a coupler called a 5-pyrazolone coupler, wherein R ¹⁷ is an alkyl group,
Represents an aryl group, an acyl group or a carbamoyl group. R
¹⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups.
Among the 5-pyrazolone couplers represented by the general formula (5), those in which R ¹⁷ is an aryl group or an acyl group and R ¹⁸ is a phenyl group substituted by one or more halogen atoms are preferable.

More specifically, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
An aryl group such as an octadecylsulfonamidophenyl group or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di-t) -Pentylphenoxy) butanoyl group, benzoyl group, 3- (2,
Acyl groups such as 4-di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these groups are organic groups linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom. Y has the same meaning as described above. R ¹⁸ is a 2,4,6-trichlorophenyl group, 2,5
Preferred are substituted phenyl groups such as -dichlorophenyl group and 2-chlorophenyl group.

The general formula (6) represents a coupler called a pyrazoloazole-based coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-
b] pyrazoles, pyrazolo [1,5-b] -1,2,4-triazoles described in U.S. Pat. No. 4,500,654, and pyrazolo [5 described in U.S. Pat. No. 3,725,067. , 1-c] -1,2,4-triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
22279 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

Formulas (7) and (8) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ^{22
_{R 23, -SO 2 NR 22 R}} 23, -NHCOR 22, -NHC
ONR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In the general formulas (7) and (8), R ²¹ represents a substituent;
Represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. As the substituent of R ^{21 to} R ²³ , X ¹
Those mentioned above as examples for to X ⁵ may be mentioned. Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
No. 166,956 and the like, 2,5-diacylaminophenols, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like. Y is the same as described above.

The general formulas (9) to (12) represent pyrrolotriazo
Is a coupler called R ³², R³³, R³⁴Is water
Represents an atom or a substituent. As for Y
It is. R³², R³³, R³⁴Is a substituent of R¹⁴,
R¹⁵, R¹⁶Described as examples of the substituent which may be possessed
Is mentioned. Pyro represented by general formulas (9) to (12)
Preferred examples of rotriazole couplers include European
Patent Nos. 488,248A1 and 491,197A1
No. 545,300.³², R³³Less of
One of them is a coupler in which one is an electron-withdrawing group.
Y is the same as described above.

In addition, couplers having structures such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle can be used. U.S. Pat. No. 4,327,173 discloses fused ring phenolic couplers.
No. 4,564,586 and 4,904,57
The couplers described in No. 5, etc. can be used. U.S. Pat. No. 4,818,672, as imidazole couplers,
The couplers described in JP-A-5,051,347 and the like can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,16.
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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Formula (1) preferably used in the present invention
The color image forming materials represented by (12) can be easily synthesized by a method known in the photographic industry. The amount of the color image forming material used in the present invention is 0.01 to 0.01 mol per mol of silver.
To 1 mol, more preferably 0.02 to 0.5
Mol, more preferably 0.05 to 0.2 mol. One color image forming material may be used alone, or two or more color image forming materials may be used in combination.

The color image forming material used in the present invention may be water or a suitable organic solvent such as alcohols (eg, methanol, ethanol, propanol, fluorinated alcohol), ketones (eg, acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. , Methyl cellosolve and the like. Alternatively, according to the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, oil such as diethyl phthalate, ethyl acetate, dissolved using an auxiliary solvent such as cyclohexanone,
An emulsified dispersion can be prepared and used mechanically. Alternatively, according to a well-known solid dispersion method, the powder of the coupler compound can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or ultrasonic waves, and used. A preferred method of adding the color image forming material is 0.01 μm to 10 μm, preferably 0.0 μm, depending on solid dispersion.
This is a method of adding fine particles of 5 μm to 1 μm.

Next, the scavenger coupler used in the present invention will be described. One group of scavenger couplers used in the present invention is a group of couplers called 4-equivalent couplers. The 4-equivalent coupler has the following general formula [2]-
In [13], Y is represented by a hydrogen atom.

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Formulas [2] to [5] represent couplers referred to as active methylene couplers, wherein R ₂₄ represents an optionally substituted acyl group, cyano group, nitro group or aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas [2] to [5], R ₂₅ is an alkyl group, an aryl group or a heterocyclic group which may have a substituent. In the general formula [5], R ₂₆ is an aryl group or a heterocyclic group which may have a substituent. R ₂₄ ,
Examples of the substituent which R ₂₅ and R ₂₆ may have include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, a halogen atom, an acylamino group, a sulfone Various substituents such as an amide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group and a sulfo group can be exemplified. Preferred examples of R ₂₄ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group. In the general formulas [2] to [5], R ₂₄ and R ₂₅ , and R ₂₄ and R ₂₆ may be bonded to each other to form a ring.

The general formula [6] represents a coupler called a 5-pyrazolone-based magenta coupler, wherein R ₂₇ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ₂₈ is a phenyl group or one or more halogen atoms,
Represents a phenyl group substituted by an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group.

Among the 5-pyrazolone magenta couplers represented by the general formula [6], those wherein R ₂₇ is an aryl group or an acyl group and R ₂₈ is a phenyl group substituted by one or more halogen atoms are preferred.

To describe these preferred groups in detail, R ₂₇ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2-
(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-di-t-pentylphenoxy) acetyl, 2- (2 , 4-
Acyl groups such as di-t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl; these groups may further have a substituent; Is an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ₂₈ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The general formula [7] represents a coupler called a pyrazoloazole-based coupler, wherein R ₂₉ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

For details of the substituent R ₂₉ and the substituent of the azole ring represented by Z, see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-6
Pyrazoloazole couplers in which a branched alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole group as described in JP-A-5245, and a sulfonamide group in the molecule described in JP-A-61-65245 A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
No. 457 or 63-307453, pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, and Japanese Patent Application No. 1-222279.
(1) pyrazolotriazole couplers having a carboxamide group in the molecule described in (1).

The general formula [8],

[9] is a coupler called a phenol-based coupler or a naphthol-based coupler, wherein R ₃₀ is a hydrogen atom or —NHCOR ₃₂ ,
_{-SO 2 NR 32 R 33, -NHSO} 2 R 32, -NHCOR
₃₂ , —NHCONR ₃₂ R ₃₃ , and —NHSO ₂ NR ₃₂ R ₃₃ . R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. General formula [8],

In [9], R ₃₁ represents a substituent, p represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. As R _{31 to} R ₃₃ , R _{24 to} R
The substituents described for ₂₆ are mentioned.

Formulas [10] to [13] are couplers called pyrrolotriazole, and R ₄₂ , R ₄₃ and R ₄₄ each represent a hydrogen atom or a substituent. As the substituents for R ₄₂ , R ₄₃ and R ₄₄ , those described above as the substituents for R _{24 to} R ₂₆ can be mentioned.

Others, fused phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

Specific examples of the scavenger coupler which can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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Another group of scavenger couplers that can be used in the present invention is represented by the following general formula (SC-
1) to (SC-V).

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The compound represented by formula (SC-I) will be described. In the general formula (SC-I), Y represents a carbonyl group or a sulfonyl group. In the general formula (SC-I),
The non-metallic atomic group forming a 5- or 6-membered ring represented by Q ₁ will be described in detail. Q ₁ may be any nonmetallic atom, preferably a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, more preferably a carbon atom and an oxygen atom. The ring formed by Q ₁ together with —CO—C (Y) H—X— is a 5-membered or 6-membered ring, and the atoms forming the ring are an aliphatic group, an alkoxy group, an alkoxy group. It may be substituted with any one of a carbonyl group and a carbamoyl group. This ring may contain a multiple bond. Further, another ring may be condensed with this ring. Another condensed ring may be further substituted with any one of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.

The number of ring members formed by Q ₁ together with --CO--C (Y) H--X-- is more preferably a 5-membered ring. Specifically, from the side closer to the carbonyl group, --O -C-
Or the case of -CC- is preferable. At this time, Q
_The carbon atom corresponding to ₁ may be unsubstituted, an aliphatic group,
It may be substituted with any of the substituents of an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group, but a case where a carbon atom is unsubstituted is more preferable. In the general formula (SC-I), the non-metallic atomic group forming a 5- or 6-membered ring represented by Q ₂ will be described in detail. Q ₂ may be any non-metallic atom, but is preferably a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a carbon atom and an oxygen atom. Q ₂ is -X-CH (CO
-) The ring formed together with -Y- has a 5-membered or 6-membered ring, and the atoms forming this ring are any of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group. It may be substituted with a substituent. This ring may contain a multiple bond. Further, another ring may be condensed with this ring. Another condensed ring may be further substituted with any one of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.

The number of ring members of the ring formed by Q ₂ together with -X-CH (CO-)-Y- is more preferably a 6-membered ring. Specifically, from the side closer to X, -C- C--C-- is preferred. At this time, the carbon atom corresponding to Q ₂ may be unsubstituted or may be substituted with any of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group. This is the case where the atom is unsubstituted or substituted with an aliphatic group.

In the general formula (SC-I), C- represented by X
The _RX or N atom will be described in detail. R _X represents a hydrogen atom or a substituent. Examples of the substituent at this time include an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group. Most preferred as X is C
-H. Hereinafter, specific examples of the compound represented by the general formula (SC-I) are shown, but the present invention is not limited to these specific examples.

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The compound represented by formula (SC-II) will be described. In the general formula (SC-II), the non-metallic atomic group forming a 5- or 6-membered ring represented by Q ₃ will be described in detail. Q ₃ may be any nonmetallic atom, but is preferably a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a carbon atom and an oxygen atom. Q
_The ring formed by ₃ with --CO--C (R ₁ ) H-- has a 5-membered or 6-membered ring, and the atoms forming the ring are an aliphatic group, an alkoxy group, or an alkoxycarbonyl group. ,
It may be substituted with any substituent of the carbamoyl group. This ring may contain a multiple bond.
Further, another ring may be condensed with this ring. Another condensed ring may be further substituted with any one of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.

The number of ring members formed by Q ₃ together with —CO—C (R ₁ ) H— is preferably a 5-membered ring.
Specifically, from the side close to the carbonyl group, -OCC-
Or the case of -CCCC- is preferable. At this time, the carbon atom corresponding to Q ₃ may be unsubstituted or may be substituted with any of an aliphatic group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group.
Another ring may be fused, but more preferred is a case where a carbon atom is fused with a benzene ring, or a case where the carbon atom is unsubstituted.

In the formula (SC-II), the substituted or unsubstituted aryl group or substituted carbonyl group represented by R ₁ will be described in detail. Examples of the substituent of the substituted aryl group and the substituted carbonyl group represented by R ₁ include various substituents as described above for R ₁₃ . Among them, preferred substituents are a halogen atom, an aliphatic group, an aryl group,
Examples include a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, and an alkoxycarbonyl group. Of these substituents, those that can be substituted are
It may be further substituted with substituents such as those mentioned in R _13.

As the substituent for the substituted aryl group represented by R ₁ , more preferred are a hydrogen atom, a halogen atom, an aliphatic group (for example, a linear or branched alkyl group having 1 to 80 carbon atoms, an aralkyl group). Alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group), hydroxyl group and alkoxycarbonyl group. More preferred substituents of the substituted carbonyl group represented by R ₁ are a substituted or unsubstituted anilino group, an alkoxy group, and an aryloxy group. Hereinafter, the general formula (SC
Specific examples of the compound represented by -II) will be given below, but the present invention is not limited to these specific examples.

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The compound represented by formula (SC-III) will be described. In the general formula (SC-III), the non-metallic atomic group forming a 5- or 6-membered ring represented by Q ₄ will be described in detail. Q ₄ may be any non-metallic atom, but is preferably a carbon atom, a nitrogen atom, an oxygen atom,
Sulfur atom, more preferably carbon atom, nitrogen atom and oxygen atom. The ring formed by Q ₄ together with the pyrrole ring has a 5-membered or 6-membered ring, and the atoms forming this ring may be substituted with the substituents as mentioned above for R _13. . When this substituent can be further substituted, it may be substituted with a substituent such as those described above for R ₁₃ .

The number of members of the ring formed by Q ₄ together with the pyrrole ring is more preferably a 5-membered ring. Specifically, from the N atom side of pyrrole, -N （C (R ₄₁ ) -NH- Or those in which -C (R ₄₁ ) = N-NH- are preferred.
At this time, R ₄₁ represents a substituent. In this case, the substituent R ₄₁ is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted aliphatic group.

In the general formula (SC-III), R ₂ and R ₃
The substituent represented by is described in detail. R ₂ and R ₃
Examples of the substituent represented by R ₁₃ include the substituents described above for R ₁₃ , and particularly preferable are those having an Hammett's substituent constant σp value of 0.20 or more and 1.0 or less. It is. R ₂ is preferably a cyano group, an aliphatic oxycarbonyl group (a linear or branched alkoxycarbonyl group having 2 to 36 carbon atoms, an aralkyloxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, a cycloalkoxycarbonyl group, An alkenyloxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl, oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyl Oxycarbonyl, cyclohexyloxycarbonyl,
2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), a dialkylphosphono group (2 to 2 carbon atoms)
A dialkylphosphono group of 36, for example, diethylphosphono, dimethylphosphono), an alkyl or arylsulfonyl group (an alkyl having 1 to 36 carbon atoms or an arylsulfonyl group having 6 to 36 carbon atoms, for example, a methanesulfonyl group) A butanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group), a fluorinated alkyl group (a fluorinated alkyl group having 1 to 36 carbon atoms,
For example, trifluoromethyl). R ₂ is particularly preferably a cyano group, an aliphatic oxycarbonyl group or a fluorinated alkyl group, and a cyano group is most preferred.

R ₃ is preferably an aliphatic oxycarbonyl group or a carbamoyl group (having 1 carbon atom) as described for R _2.
A carbamoyl group to 36, for example, di-phenylcarbamoyl, dioctylcarbamoyl), a sulfamoyl group sulfamoyl group (1 to 36 carbon atoms, for example, dimethylsulfamoyl, dibutylsulfamoyl), as mentioned in R ₂ Dialkylphosphono groups and diarylphosphono groups (diarylphosphono groups having 12 to 50 carbon atoms, such as diphenylphosphono and di (p-tolyl) phosphono). R ₃ is particularly preferably an aliphatic oxycarbonyl group or a heterocyclic oxycarbonyl group.

Next, the group represented by L ₁ in formula (SC-III) will be described in detail. L ₁ represents a group which does not leave by the reaction with the reducing agent. Preferred examples of L ₁ include:
Substituted or unsubstituted aliphatic group, substituted or unsubstituted aryl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group and substituted or unsubstituted heterocyclic group (pyrazole group, imidazole group, pyrrole And a particularly preferable one is an unsubstituted aliphatic group. The general formula (SC-
Specific examples of the compound represented by III) will be given below, but the present invention is not limited to these specific examples.

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The compound represented by formula (SC-IV) will be described. In the general formula (SC-IV), a non-metallic atomic group forming a 5- or 6-membered ring represented by Q ₅ will be described in detail. Q ₅ may be any nonmetallic atom, but is preferably a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a carbon atom, a nitrogen atom, and an oxygen atom. The ring formed by Q ₅ together with the pyrazole ring has a 5-membered or 6-membered ring, and the atoms forming this ring may be substituted by the substituents as described above for R _13. . When this substituent can be further substituted, it may be substituted with a substituent such as those described above for R ₁₃ . Q
More preferably 5-membered ring as ring members _{rings 5} form together with the pyrazole ring, and specifically from the N atom side of the _{pyrazole, -N = C (R 51)} -NH- or -C
Those in which (R ₅₁ ) = N—NH— are preferred. At this time, R ₅₁ represents a substituent. At this time, the substituent R ₅₁ is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted aliphatic group.

The substituent represented by R ₄ in formula (SC-IV) will be described in detail. Examples of the substituent represented by R ₄ include the substituents described above for R ₁₃ , and preferred are an aliphatic group and an alkoxy group,
Particularly preferred is an aliphatic group. Next, the general formula (SC-
In IV), the group represented by L ₂ will be described in detail. L ₂
Represents a group which does not leave during the reaction with the reducing agent. Preferred examples of L ₂ include a substituted or unsubstituted aliphatic group and a substituted or unsubstituted aryl group, and particularly preferred is an unsubstituted aliphatic group. Hereinafter, specific examples of the compound represented by the general formula (SC-IV) will be given, but the present invention is not limited to these specific examples.

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The compound represented by formula (SC-V) will be described. In the general formula (SC-V), the substituents represented by R ₅ and R ₆ will be described in detail. Examples of the substituent represented by R ₅ and R ₆ include the substituents described above for R _13. Particularly preferred are a substituted or unsubstituted aliphatic group and a substituted or unsubstituted alkoxy group. Or a substituted or unsubstituted aryl group. Next, the group represented by L ₃ in formula (SC-V) will be described in detail. L ₃ represents a group which does not leave upon reaction with the reducing agent.
Preferred examples of L ₃ include a substituted or unsubstituted aliphatic group and a substituted or unsubstituted aryl group, and particularly preferred is an unsubstituted aliphatic group. Hereinafter, the general formula (S
Specific examples of the compound represented by CV) will be given, but the present invention is not limited to these specific examples.

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The amount of the scavenger coupler used in the present invention is from 0.01 mol% to 1 mol of the color image forming material.
200 mol% is preferable, and 0.1 mol% is more preferable.
To 100 mol% mol, more preferably 0.5 to 100 mol%.
50 mol%. One scavenger coupler may be used alone, or two or more scavenger couplers may be used in combination. The scavenger coupler used in the present invention may be water or a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. Alternatively, according to an already 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 dissolved and mechanically emulsified and dispersed. A product can be prepared and used. Alternatively, according to a well-known solid dispersion method, the powder of the coupler compound can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or ultrasonic waves, and used. The preferred method of adding the scavenger coupler is 0.01 μm to 10 μm, preferably 0.05 μm, depending on the solid dispersion.
This is a method in which fine particles of m to 1 μm are added.

In the present invention, the following functional couplers may be used. Examples of couplers in which a color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent Publication EP 96,873B, and German Patent No. 3 ,
Those described in JP-A-234,533 are preferred. As a coupler for correcting unnecessary absorption of coloring dyes,
Yellow colored cyan couplers described in European Patent Publication EP 456,257 A1; yellow colored magenta couplers described in the European Patent Publication, and magenta colored cyan couplers described in U.S. Pat. No. 4,833,069. .

Compounds (including couplers) which react with oxidized reducing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: European Patent Publication EP 378,23
Compounds represented by formulas (I) to (IV) described on page 11 of JP 6A1, EP 436,938 A2
The compound represented by the formula (I) described on page 7 of the publication, the compound represented by the formula (1) of the European Patent Publication EP 568,037A, the European Patent Publication EP 440,195A
The formulas (I), (II) and (I) described on pages 5 to 6 of JP-A-2
A compound represented by II). Bleach accelerator releasing compound: European Patent Publication EP 310,12
Compounds represented by formulas (I) and (I ') on page 5 of 5A2 and compounds represented by formula (I) of claim 1 of JP-A-6-59411. Ligand releasing compound: a compound represented by LIG-X described in claim 1 of U.S. Pat. No. 4,555,478.

Leuco dye releasing compounds: US Pat. No. 4,7
Compounds 1 to 6 in columns 3 to 8 of 49,641; Fluorescent dye-releasing compound: a compound represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181. Development accelerator or fogging agent releasing compound: Formula (1) in column 3 of US Pat. No. 4,656,123;
Compounds represented by (2) and (3) and ExZK-2 on page 75, lines 36 to 38 of EP450,637A2.

Compounds which release a group which becomes a dye only after leaving: Compounds represented by formula (I) in claim 1 of US Pat. No. 4,857,447, JP-A-5-307
No. 248 (Patent No. 2835665), a compound represented by the formula (1), European Patent Publication EP440,
Formulas (I) and (I) described on pages 5 and 6 of 195A2
Compounds represented by I) and (III), JP-A-6-59
411, the compound of formula (I) -ligand releasing compound of claim 1, U.S. Pat. No. 4,555,478
A compound represented by LIG-X described in claim 1 of the specification. Such a functional coupler is preferably used in an amount of 0.05 to 10 times, preferably 0.1 to 5 times the mole of the color image forming material that contributes to the color development described above.

Next, the reducing agent used in the present invention will be described. As the reducing agent used in the present invention, a compound represented by formula (D) is preferable. General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. )

In the formula (D), preferred examples of the group represented by Q ¹ include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring, a 1,3 , 5-triazine ring, pyrrole ring, imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring,
1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4
-Oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring, thiazole ring,
An oxazole ring, an isothiazole ring, an isoxazole ring, a thiophene ring and the like are preferable, and a condensed ring in which these rings are condensed with each other is also preferable.

These rings may have a substituent,
When it has two or more substituents, those substituents may be the same or different. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, and a cyano group. Groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyl groups. When these substituents are substitutable groups, they may further have a substituent, and examples of preferred substituents include:
Halogen atom, alkyl group, aryl group, carbonamide group, alkylsulfonamide group, arylsulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group ,
Cyano group, sulfamoyl group, alkylsulfonyl group,
An arylsulfonyl group and an acyloxy group can be mentioned.

In formula (D), the carbamoyl group represented by Q ² has 1 to 50 carbon atoms, more preferably 6 to 50 carbon atoms.
40 carbamoyl groups, for example, unsubstituted carbamoyl, methylcarbamoyl, N-ethylcarbamoyl,
N-propylcarbamoyl, N-sec-butylcarbamoyl, N-octylcarbamoyl, N-cyclohexylcarbamoyl, N-tert-butylcarbamoyl,
N-dodecylcarbamoyl, N- (3-dodecyloxypropyl) carbamoyl, N-octadecylcarbamoyl, N- {3- (2,4-tert-pentylphenoxy) propyl} carbamoyl, N- (2-hexyldecyl) carbamoyl, N-phenylcarbamoyl, N-
(4-dodecyloxyphenyl) carbamoyl, N-
(2-chloro-5-dodecyloxycarbonylphenyl) carbamoyl, N-naphthylcarbamoyl, N-3
-Pyridylcarbamoyl, N-benzylcarbamoyl.

In the general formula (D), the acyl group represented by Q ² is an acyl group having 1 to 50 carbon atoms, preferably 6 to 40 carbon atoms, and is, for example, formyl, acetyl, 2-methylpropanoyl. , Cyclohexylcarbonyl, octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl, and 2-hydroxymethylbenzoyl. In Formula (D), the alkoxycarbonyl group represented by Q ² is an alkoxycarbonyl group having 2 to 50 carbon atoms, preferably 6 to 40 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, Cyclohexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl.

In formula (D), the aryloxycarbonyl group represented by Q ² is an aryloxycarbonyl group having 6 to 50 carbon atoms, preferably 6 to 40 carbon atoms, such as phenoxycarbonyl and 4-octyl. Oxyphenoxycarbonyl, 2-hydroxymethylphenoxycarbonyl, 4-dodecyloxyphenoxycarbonyl are exemplified. In the general formula (D), the sulfonyl group represented by Q ² is a sulfonyl group having 1 to 50 carbon atoms, preferably 6 to 40 carbon atoms, for example, methylsulfonyl, butylsulfonyl, octylsulfonyl, 2-hexadecyl Sulfonyl, 3-dodecyloxypropylsulfonyl, 2-octyloxy-5-tert-octylphenylsulfonyl, 4-dodecyloxyphenylsulfonyl are exemplified.

In formula (D), the sulfamoyl group represented by Q ² has 0 to 50 carbon atoms, preferably 6 to 4 carbon atoms.
0, for example, unsubstituted sulfamoyl, N-ethylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N-decylsulfamoyl,
N-hexadecylsulfamoyl, N- {3- (2-ethylhexyloxy) propyl} sulfamoyl, N-
(2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl and N- (2-tetradecyloxyphenyl) sulfamoyl. The group represented by Q ² may further have, at a substitutable position, the group exemplified as the substituent for the 5- to 7-membered unsaturated ring represented by Q ¹ above. When it has two or more substituents, those substituents may be the same or different.

Next, the preferred range of the compound represented by formula (D) will be described. The unsaturated ring represented by Q ¹ is preferably a 5- to 6-membered ring, and a benzene ring, a pyrimidine ring,
1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,3,4-oxadiazole ring, A 1,2,4-oxadiazole ring, a thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, and a ring obtained by condensing these rings with a benzene ring or an unsaturated hetero ring are more preferable. Also,
Q ² is preferably a carbamoyl group, particularly preferably a carbamoyl group having a hydrogen atom on a nitrogen atom.

The synthesis of the compound represented by the general formula (D)
JP-A-9-152702, JP-A-8-286340, JP-A-9-152700, and JP-A-9-152701
Gazette, JP-A-9-152703 and JP-A-9-15
It can be carried out according to the method described in JP-A No. 2704 or the like. Hereinafter, specific examples of the compound represented by Formula (D) are shown, but the compounds used in the present invention are not limited to these specific examples.

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The amount of the reducing agent (preferably, the reducing agent represented by the general formula (D)) has a wide range, but is preferably 0.01 to 100 times, more preferably 0.1 to 100 times, silver ion. 10 molar times is appropriate. The reducing agent (preferably, the reducing agent of the general formula (D)) may be added by any method such as a solution, a powder, a solid fine particle dispersion, an emulsion, and an oil protection dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

In the present invention, other reducing agents may be used together with the reducing agent of the formula (D). It can be selected from known reducing agents for organic silver salts. For example, there are photographic developers such as phenidone, hydroquinone and catechol, and hindered phenol reducing agents. Among these, preferred reducing agents are polyhindered phenols having two or more hindered phenol groups in one molecule. The auxiliary reducing agent is a reducing agent 1 of the general formula (D)
It is preferably contained in an amount of 0.1 to 100% by mole, more preferably 1 to 10% by mole, based on the mole.

As other auxiliary reducing agents, JP-A-46-6
No. 074, No. 47-1238, No. 47-33621, No. 49-46427, No.
No. 49-115540, No. 50-14334, No. 50-36110, No. 50-1477
No. 11, No. 51-32632, No. 51-1023721, No. 51-32324,
No. 51-51933, No. 52-84727, No. 55-108654, No. 56-14
No. 6133, No. 57-82828, No. 57-82829, JP-A-6-3793
No. 3,667,9586, 3,679,426, 3,751,2
No. 52, No. 3,751,255, No. 3,761,270, No. 3,782,949
No. 3,839,048, 3,928,686, 5,464,738,
It is disclosed in German Patent No. 2321328, European Patent No. 692732 and the like. Amide oximes such as, for example, phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; for example 4-hydroxy-3,5-
Azines such as dimethoxybenzaldehyde azine; 2,2 '
A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of -bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid; polyhydroxybenzene, hydroxylamine,
Combinations of reductone and / or hydrazine (such as a combination of hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid And hydroxamic acids such as β-alinine hydroxamic acid; combinations of azine and sulfonamidophenol
(Eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate, ethyl-α-cyanophenylacetate; 2'-dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl and bis (2-hydroxy-
Bis-β-naphthol as exemplified by 1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (such as 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxyacetophenone) Combination of 3
5-pyrazolone, such as -methyl-1-phenyl-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-dione; 2,2-dimethyl-7-t-butyl Chromans such as -6-hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarbethoxy-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, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl;
Pyrazolidone and certain indan-1,3-diones; chromanol (such as tocopherol).

The layer to which the reducing agent is added may be any layer on the side having the image forming layer. Preferably, it is added to the image forming layer, the protective layer and the undercoat layer. Particularly preferred is an image forming layer. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

The heat-developable color image recording material of the present invention may contain a halogen precursor. Next, the halogen precursor that can be used in the present invention will be described. The halogen precursor used in the present invention is heat,
Alternatively, it is a compound capable of releasing halogen by light. The compound having such a function is an organic polyhalide in which two or more halogen atoms are substituted with the same carbon atom.
No. 51-121332, No. 54-58022, No. 56-
No. 70543, No. 56-99335, No. 59-90842,
JP 61-129642 JP, JP 62-129845 JP, JP-A-6-2081
No. 91, No. 6-208193, No. 7-5621, No. 7-27
Nos. 81, 8-15809, U.S. Pat. Nos. 5,340,712, 5,369,000, and 5,464,737.

Next, the photosensitive silver halide used in the present invention will be described in detail. The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition,
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide can be used. The distribution of the halogen composition in the grains may be uniform, the halogen composition may change stepwise, or may change continuously. Further, silver halide grains having a core / shell structure can be preferably used. As a structure,
Preferably, core / shell particles having a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

Methods for forming photosensitive silver halide which can be used in the present invention are well known in the art, for example, Research Disclosure No. 17029, June 1978.
And US Pat. No. 3,700,458. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method of preparing a photosensitive silver halide grain by adding a silver supply compound and a halogen supply compound to another polymer solution and mixing the resultant with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation, 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.
12 μm or less is preferred. The grain size as used herein refers to 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-like 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 from 100: 1 to 2: 1, and more preferably from 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 grains is not particularly limited, but the spectral sensitizing efficiency when a 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 photosensitive silver halide grains used in the present invention preferably contain a metal or a metal complex of Group VII or VIII of the periodic table. VI of the Periodic Table
Rhodium, rhenium, ruthenium, osnium and iridium are preferred as the Group I or Group VIII metal or the central metal of the metal complex. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is 10 ^-9 per mole of silver.
The range is preferably from mol to 10 ^-2 mol, more preferably from 10 ^-8 mol to 10 ^-4 mol. 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 a rhodium compound preferably used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalates and the like as ligands, for example, hexachlororhodium (III) complex salt, pentachloroacolodium (III) complex salt, tetrachlorodia Examples thereof include a cholium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaamminerhodium (III) complex salt, and a trizalatrodium (III) complex salt.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁶ mol per mol of silver halide, particularly preferably 5 × 10 ⁻⁸ mol to 1 × 1 mol.
0 ^-6 mol. Rhenium, ruthenium and osmium preferably used in the present invention are disclosed in JP-A-63-2042,
It is added in the form of a water-soluble complex salt described in JP-A-1-285941, JP-A-2-20852, JP-A-2-20855 and the like.

The silver halide grains used in the present invention may further include 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, hexacyanoruthenate ions, and the like. The phase containing the metal complex in the silver halide may be uniform, may be contained in the core at a high concentration, or may be contained in the shell at a high concentration, and there is no particular limitation. The metal is 1 × 10 ^-9 to 1 × 10 per mol of silver halide.
^-4 mol is preferred. In addition, in order to incorporate the 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, it may or may not be desalted.

The silver halide emulsion used in the present invention is preferably chemically sensitized. As the method of chemical sensitization, 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, and these are used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, Sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization and the like are preferred. The amount of the selenium and tellurium sensitizers varies depending on the silver halide grains used, the conditions of chemical ripening, and the like.
^-8 to 10 ^-2 mol, preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8 and the pAg is 6 to
11, preferably 7 to 10, and the temperature is 40 to
The temperature is 95C, preferably 45-85C.

The noble metal sensitizer used in the present invention includes gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. 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. The silver halide emulsion used in the present invention includes
By the method shown in EP 293,917,
A thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (e.g., those having different average grain sizes, different halogen compositions, different crystal habits, different chemical habits, Those with different conditions) may be used in combination. The photosensitive silver halide is 0.1 mol% to 100 mol
Mol%, preferably 0.5 mol% to 50 mol%, more preferably 1.0 mol% to 30 mol%.

The heat-developable color image recording material of the present invention may be used for either a monochromatic light-sensitive material or a multi-color light-sensitive material. In order to obtain color, at least three silver halide emulsion layers having sensitivity to different spectral regions are used in combination. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. Photosensitive materials include protective layers, undercoat layers, intermediate layers,
Various auxiliary layers such as an antihalation layer and a back layer can be provided. Further, various filter dyes can be added to improve color separation.

The heat-developable color image recording material of the present invention may be provided with at least one photosensitive layer on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side.
However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain the aforementioned couplers, reducing agents, DIR compounds, color mixture inhibitors, dyes and the like. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer may be composed of a high-sensitivity emulsion layer as described in German Patent 1,121,470 or British Patent 923,045. It is preferred that the two low-sensitivity emulsion layers are arranged so that the sensitivity gradually decreases toward the support. Also, JP-A-57-112751 and JP-A-62-200.
Nos. 350, 62-206541, 62-
As described in JP-A-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on. In addition, Japanese Patent Publication 55-34
As described in JP-A No. 932/1992, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / GL / RL is selected from the side farthest from the support.
The sequence may be arranged in the order of / GH / RH.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a middle layer. In addition, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer is arranged from the side farther from the support in the same color-sensitive layer. It may be arranged in the order of / high-speed emulsion layer / low-speed emulsion layer. In addition, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

In order to improve the color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436, and JP-A-62-26764.
A donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in the specifications of JP-A-160448 and JP-A-63-89850 is adjacent to or adjacent to the main photosensitive layer. It is preferable to arrange them.
In the present invention, the silver halide, the coupler and the reducing agent may be contained in the same layer, but may be separately added to another layer as long as they can react. For example, when a layer containing a reducing agent and a layer containing silver halide are formed as separate layers, the raw storability of the light-sensitive material can be improved.

The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary. However, when a cyan coupler is used for a red photosensitive layer, a magenta coupler is used for a green photosensitive layer, and a yellow coupler is used for a blue photosensitive layer, a conventional color paper can be used. Etc. can be directly projected and exposed. In the photosensitive member, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layer and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer constitution as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-1677838, JP-A-61-20
No. 943, an intermediate layer having a solid pigment,
Reducing agents and D as described in JP-A-1-120553, JP-A-5-34884 and JP-A-2-64634.
Interlayer with IR compound, US Pat. No. 5,017,4
No. 54, 5,139,919, and an intermediate layer having an electron transfer agent as described in JP-A-2-235444 and a reducing agent as described in JP-A-4-249245. A protective layer or a combination thereof.

As the dye which can be used in the yellow filter layer and the antihalation layer, those which are decolored or removed at the time of heat development and do not contribute to the density after the processing are preferred. Decoloring or removing the dye in the yellow filter layer and the antihalation layer during development means that the amount of the dye remaining after the processing becomes 1/3 or less, preferably 1/10 or less immediately before coating.

More specifically, European Patent Publication EP549,4
No. 89A, JP-A-7-152129
Dyes ExF2 to Ex6 described in Japanese Patent Application Laid-Open Publication No. HEI 6-202, pp. 1 to 6. JP-A-8-
Dyes dispersed in a solid as described in JP 101487B can also be used. Further, the mordant and the binder may be dyed with a mordant. In this case, as the mordant and the dye, those known in the field of photography can be used, and US Pat.
Column 59 and 32-41 of JP-A-61-88256.
Pp. 62-244043, 62-24403
The mordants described in JP-A No. 6 and the like can be used. It can also be decolorized by reacting with a reducing agent. Specifically, U.S. Pat. Nos. 4,559,290 and 4,459,290.
No. 783,396, European Patent Publication EP 220,7
No. 46A2, JP-A-87-6119, and paragraph 0 of JP-A-8-101487.
080-0081.

A decolorizable leuco dye or the like can also be used. Specifically, a silver halide photosensitive material containing a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid described in JP-A-1-150132 can be used. Materials are disclosed.
The leuco dye and the developer complex decolor by reaction with heat or an alkali agent. Known leuco dyes can be used,
Moriga, Yoshida, "Dyes and Chemicals", 9, 84 pages (Chemical Products Industry Association), "New Edition Dye Handbook", 242 pages (Maruzen, 1970),
R. Garner "Reports on the Progress of Appl. Chem"
56, 199 (1971), "Dyes and Chemicals", 19, 2
30 (Chemical Products Association, 1974), "Coloring Materials" 62,
288 (1989), “Dyeing Industry”, 32, 208 and the like.

As a color developer, a metal salt of an organic acid is preferably used in addition to an acid clay-based color developer, a phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodanes, metal salts of xanthogenates, and the like are useful, and zinc is particularly preferable as the metal. Among the above developers, oil-soluble zinc salicylate is described in U.S. Pat. Nos. 3,864,146 and 4,046,941 and JP-B-52-13.
No. 27 can be used.

In the present invention, the following various additives can be used in combination. Dispersion medium of oil-soluble organic compound: P-3, 5, 16, 1 of JP-A-62-215272
9, 25, 30, 42, 49, 54, 55, 66, 8
1, 85, 86, 93 (pp. 140-144); Latex for impregnation of oil-soluble organic compounds: U.S. Pat. No. 4,199,
No. 363; oxidized developing agent scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of U.S. Pat. No. 4,978,606 (particularly I-, (1 ), (2), (6), (12)
(Columns 4 to 5), the formulas in columns 5 to 10 of column 2 of U.S. Pat. No. 4,923,787 (especially compound 1 (column 3), stain inhibitor: European Patent Publication EP29832)
Formulas (I) to (III) on page 4, lines 30 to 33 of 1A, especially I-47, 72, III-1, 27 (24 to 48)
Page); Anti-fading agent: A-6, 7, 20, 21, 23, 24, 25, 2 of European Patent Publication EP 298321A.
6, 30, 37, 40, 42, 48, 63, 90, 9
2, 94, 164 (pp. 69-118); U.S. Pat.
II-1 of columns 25 to 38 of JP-A-122,444.
~ III-23, especially III-10, European Patent Publication EP
I-1 to III-4 on pages 8 to 12 of 471347A,
Particularly II-2, A-1 to 48 of columns 32 to 40 of U.S. Pat. No. 5,139,931, especially A-39,4.
2; Material for reducing the amount of a color-enhancing agent or color-mixing inhibitor used: I-5 to I-15 on pages 5 to 24 of European Patent Publication EP 411324A, particularly I-46; Formalin scavenger: 24- to I-4 of European Patent Publication EP477932A
SCV-1 to 28 on page 29, especially SCV-8; Hardener: H-1 on page 17 of JP-A-1-214845,
4, 6, 8, 14, compounds (H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of U.S. Pat. No. 4,618,573;
No. 852, page 8, lower right compound (H-1 to 76) represented by formula (6), particularly H-14, U.S. Pat.
Compound described in claim 1 of 5,287; Development inhibitor precursor: P-24, 37, 39 of JP-A-62-168139 (pages 6 to 7); U.S. Pat.
No. 019,492, Claim 1;
In particular, 28 and 29 of column 7; preservatives and fungicides: I of columns 3 to 15 of U.S. Pat. No. 4,923,790
-1 to III-43, especially II-1, 9, 10, 18,
III-25; stabilizer, antifoggant: U.S. Pat.
No. 923,793, columns 6 to 16, I-1 to
(14), especially I-1, 60, (2), (13), columns 25 to 32 of U.S. Pat. No. 4,952,483.
Compounds 1 to 65, especially 36; Chemical sensitizer: triphenylphosphine selenide, Compound 50 in JP-A-5-40324; Dye: 1 in JP-A-3-156450
A-1 to b-20 on pages 5 to 18, especially a-1, 12;
18, 27, 35, 36, b-5, pages 27-29 V-
1 to 23, especially V-1, European Patent Publication EP 445627.
No. A, F-I-1 to F-II-4 on pages 33 to 55
3, especially FI-11, F-II-8, European Patent Publication E
III-36 on pages 17-28 of P457153A,
In particular, III-1, 3, microcrystalline dispersions of Dye-1 to 124 of International Publication No. WO88 / 04794, 8-26,
Compounds 1 to 22 on page 6 to 11 of European Patent Publication EP 319999 A, in particular Compound 1, EP 51
No. 9306A, compounds D-1 to 87 (pages 3 to 28) represented by formulas (1) to (3), U.S. Pat.
Compound 1 represented by Formula (I) of JP-A-68,622
-22 (columns 3-10), U.S. Patent No. 4,923,7
No. 88, compounds represented by formula (I):
(31) (Columns 2 to 9); UV absorber: JP-A-46-
No. 3335, the compound represented by the formula (1) (18)
b) to (18r), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) and formulas (III) represented by formula (I) in EP520938A. Compounds HBT-1 to 10 (14
Page), and the compounds (1) to (31) represented by the formula (1) in EP 521823A (column 2).
9).

In general, a base is required in the processing of a photographic light-sensitive material. In the heat-developable color image recording material of the present invention, various base supply methods can be adopted. For example, when a base generating function is given to the photosensitive material side, it can be introduced into the photosensitive material as a base precursor. Such base precursors include, for example, salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution, Lossen rearrangement or Beckmann rearrangement, and the like. No. 4,514,493, and US Pat. No. 4,657,
No. 848, etc.

The heat-developable color image recording material of the present invention has an organic binder in the image forming layer. The organic binder used in the present invention is a hydrophobic and thermoplastic organic polymer. Thermoplastic, as defined herein, is broader than the strict definition of thermoplastic in the physicochemical term. "Plastic" which means thermoplasticity is used as a practical term for not only linear polymers but also polymers which are three-dimensionally crosslinked and have rubber elasticity.
In the present invention, when heated to a certain temperature or higher, it means that the polymer can be softened or melted depending on the properties of the polymer. Therefore, SBR polymers and the like also have rubber elasticity depending on the degree of crosslinking, but according to the gist of the present invention, when heated to the heat development temperature, they are softened or melted to facilitate the transfer and diffusion of the substance, and the development reaction occurs. The present invention is included in the present invention as long as the obtained state is formed. The same applies to other three-dimensional crosslinked polymers. Specifically, it is a medium for forming a natural polymer, a synthetic resin polymer, a copolymer, or another film, for example, hydrophobically modified gelatin, modified polyvinyl alcohol, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone) ), Poly (vinyl acetate), poly (vinyl chloride), poly (acrylate) s, poly (methyl methacrylate)
, Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrenebutadiene), poly (vinylacetal) s (eg, poly (vinylformal), and poly (vinylbutyral)), poly (ester) ), Poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide), poly (carbonate), poly (vinyl acetate), poly (amide) and the like. The binder may be coated from water or an organic solvent, or an emulsion.

As the organic binder used in the present invention,
Particularly, polymer latex is preferred. Since polymer latex can be applied without using an organic solvent, the organic solvent gas must not be released into the air when the coated film is dried, or the organic solvent does not remain in the film. It is preferable because it has no harm such as gasification and scattering. Polymer latex is 50% by mass of all binders
It is preferable that it is above. Further, the polymer latex may be used not only for the image forming layer but also for the protective layer and the back layer. In particular, when the heat-developable color image recording material of the present invention is used for printing in which dimensional change is a problem, it is necessary to use a polymer latex for the protective layer and 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. The polymer latex used in the present invention is described in "Synthetic Resin Emulsion (edited by Hira Okuda and Hiroshi Inagaki, published by Kobunshi Kanko (1978))" and "Application of Synthetic Latex (Edited by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara) , Published by The Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, Published by the Society of Polymer Publishing (1
970))). The average particle size of the dispersed particles is 1 to 50000 nm, more preferably 5 to 1000 nm.
A range of about nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a broad particle size distribution or a monodispersed particle size distribution.

The polymer latex used in the present invention may be a so-called core / shell type latex other than the usual polymer latex having a uniform structure. In this case the core and shell may be preferred when different glass transition temperature. The preferable range of the glass transition temperature (Tg) of the polymer of the polymer latex used for the binder differs between the protective layer, the back layer and the image forming layer. The temperature of the image forming layer is preferably 40 ° C. or lower, and more preferably −30 ° C. to 40 ° C., in order to promote diffusion of the photographically useful material during thermal development. When used as a protective layer or a back layer (especially the outermost layer), the glass transition temperature is 25 to 1 due to contact with various devices.
Preferably it is 00 ° C.

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

Examples of the polymer used for the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. 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 500 in number average molecular weight.
0 to 1,000,000, preferably 10,000 to 1000
About 00 is preferable. 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 property is poor, which is not preferable.

In the present invention, specific examples of the polymer latex used as the organic binder 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. Moreover, such polymers are also commercially available, it can be a polymer such as is available below. For example, examples of acrylic resin include Sebian A4635, 46583, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814,
Polyester resins such as 821, 820, and 857 (all manufactured by Nippon Zeon Co., Ltd.) include FINITEX ES
Examples of polyurethane resins such as 650, 611, 675, and 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, and WMS (all manufactured by Eastman Chemical) include HY.
Rubber-based resins such as DRAN AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) are LACS
TAR 7310K, 3307B, 4700H, 713
2C (Dai Nippon Ink Chemical Co., Ltd.), Nipol
G35 as a vinyl chloride resin such as Lx416, 410, 438C, 2507 (all manufactured by Nippon Zeon Co., Ltd.)
Examples of vinylidene chloride resins include L502 and L513 (all manufactured by Asahi Kasei Kogyo Co., Ltd.), and Alon D7020, D504, and D50.
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 mixture of two or more as necessary.

In the present invention, an acetal resin such as polyvinyl butyral and polyvinyl formal, particularly polyvinyl butyral is used as an organic binder.
It is preferable to apply by dissolving in an organic solvent.

In the present invention, it is preferable to provide an intermediate layer. In particular, when a plurality of layers having different color sensitivities are provided, they are provided between them for the purpose of preventing color mixing. Generally, 0.
01 μm to 30 μm, preferably 0.05 μm to 10 μm
m. Preferably, the intermediate layer comprises a scavenger of the oxidation product of the reducing agent. The scavenger is desirably diffusion resistant and fixed to the intermediate layer. Oxidation products of the reducing agent generated by thermal development diffuse in the layer and move to another adjacent color-sensitive layer, which hinders color reproduction. Scavengers can prevent this harmful reductant oxidation product from diffusing into adjacent layers and improve color turbidity.

As the scavenger, a reducing agent which is resistant to diffusion in the above-mentioned group of reducing agents and which can cross-oxidize with an oxidation product of the reducing agent is usually used.
Particularly effective in the present invention are the scavenger couplers described herein above. The addition amount of the scavenger coupler used in the present invention is preferably 0.01 mol% to 200 mol%, more preferably 0.1 mol% to 100 mol%, and further preferably 0 mol%, per mol of the color image forming material. 0.5 to 50 mol%. One scavenger coupler may be used alone, or two or more scavenger couplers may be used in combination. Additionally, sulfonamidophenol compounds and sulfonamidonaphthol compounds described in JP-A-8-220717, for example, compound numbers I- (1) to I-I
-(53), II- (1) to II- (39), JP-A-2-1
Compound Nos. 1 to 21 in JP-A-83246,
The immobile hydroquinone derivatives and resorcin derivatives described in JP-119555-A, for example, the compound numbers (1) to (12), the hydrazine derivatives described in JP-A-8-286340, preferably the compound number (C- 1) to (C-80), or JP-A-2000-2
A sulfonamide phenol compound described in JP-A-92886, for example, compounds D-1 to D-8 may be used in combination with the scavenger coupler described above.

The intermediate layer may contain a light absorbing agent. As the light absorber, colloidal silver or a diffusion-resistant dye is preferable. The dye may be decolorized by heating. Colloidal silver has yellow or magenta light absorption properties depending on its particle size. By including colloidal silver in the intermediate layer between the image forming layers having different color sensitivities, unnecessary light components can be removed, and preferable color reproduction can be provided. The amount of colloidal silver or dye added is such that the absorbance is 0.1-2.0, preferably 0.3-1.0.

The heat-developable color image recording material of the present invention is preferably provided with a protective layer. The protective layer is provided on the outer layer of the support having the image recording layer. Generally, 0.01μ
m to 30 μm, preferably 0.05 μm to 10 μm. As the binder for the intermediate layer and the protective layer, gelatin, polyvinyl alcohol, and other synthetic polymers can be used in addition to the polymer latex described above. In particular, gelatin is preferable in order to maintain a good coated surface state.

In the present invention, a plurality of image forming layers having different color sensitivity can be spectrally sensitized in various wavelength regions such as ultraviolet, blue, green, red, and near infrared. The color of the dye that develops can also develop due to these various light reductions. It is not always necessary to make the light-absorbing characteristics of the photosensitive region and the color-forming dye correspond to each other. In particular, in the case where color separation is performed in recent years and exposure with a laser is performed, any convenient combination can be selected. Various layer configurations can be designed as needed, such as a two-color system, a three-color system, or a four-color system. These plural layers may be applied sequentially or simultaneously.

The image recording layer, the intermediate layer and the protective layer in the heat-developable color image recording material of the present invention contain a dispersion stabilizer of various material dispersions. These dispersion stabilizers are added at the time of preparing a dispersion, and are additionally used at the time of preparing a coating solution. As the hydrophilic polymer used as the dispersion stabilizer, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and the like are preferable. The amount of the hydrophilic polymer to be added is preferably 30% by mass or less, more preferably 10% by mass or less of the total binder in these layers. The lower limit in this case is not particularly limited, but is about 0.1% by mass. In the protective layer, the amount of the hydrophilic polymer to be added is preferably 3% by mass or less, more preferably 1% by mass or less of the total binder in the protective layer. There is no particular lower limit in this case,
It is about 0.1% by mass.

Alternatively, a surfactant can be used as a dispersion stabilizer. As the surfactant, a known anionic surfactant can be used. Specific examples of the surfactant used as a dispersion stabilizer are shown below, but the present invention is not limited to the following compounds.

[0197]

Embedded image

The addition amount of these surfactants is preferably 5% by mass or less, more preferably 3% by mass or less of the whole binder. There is no particular lower limit in this case,
It is about 0.1% by mass.

In the heat-developable color image recording material of the present invention, the total amount of binder in the image recording layer is 0.2 to 30 g / m 2.
² , more preferably 1 to 15 g /
m ² . The total binder amount per one layer of the intermediate layer is
It is preferably 0.1 to 5 g / m ² , and more preferably 0.3 to 3 g / m ² . Total amount of binder per one layer of the protective layer is preferably 0.2 to 10 g / m ^2, more preferably 1 to 5 g / m ^2. When two or more protective layers are provided, the pH of the protective layer coating solution is preferably 5 to 8 for the lower layer and 2 to 7 for the upper layer.

In the present invention, a crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer, intermediate layer or protective layer. Examples of the surfactant used in the present invention include nonionic, anionic,
Any material such as a fluorine-based material is appropriately used. Specifically, Japanese Patent Application Laid-Open No. Sho 62-170950, U.S. Pat.
Fluoropolymer surfactants described in JP-A-80-644, JP-A-60-244945, JP-A-63
-188135, a fluorine-based surfactant described in U.S. Pat. No. 3,885,965, a polysiloxane-based surfactant described in JP-A-6-301140, a polyalkylene oxide described in JP-A-6-301140, and the like. Examples include anionic surfactants.

In the present invention, good antistatic properties can be obtained by including a fluorine-containing surfactant. The preferred fluorine-containing surfactant used in the present invention has a fluoroalkyl group, a fluoroalkenyl group, or a fluoroaryl group having 4 or more (usually 15 or less) carbon atoms and an anionic group (sulfonic acid ( Salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyamine) Surfactants having an ammonium salt, a sulfoamine salt, a sulfoammonium salt, a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue).

[0202] The fluorine-containing surfactant is disclosed in
9-10722, British Patent 1,330,356
No. 4,335,201, U.S. Pat. No. 4,347,308, British Patent 1,417,
No. 915, JP-A-55-149938 and JP-A-58-196544, British Patent 1,439,4.
No. 02 and the like. Two or more fluorine-containing surfactants may be mixed. The amount of the fluorinated surfactant to be used is 0.0001 to 1 per m ^{2 of} the image recording material.
1 g, more preferably 0.000 g
2 to 0.25 g, more preferably 0.0003
０．１0.1 g.

The layer to which the fluorinated surfactant is added is not particularly limited as long as it is at least one layer of the image recording material. Examples thereof include a surface protective layer, an image forming layer, an intermediate layer, an undercoat layer, and a back layer. it can. Among them, a preferable addition site is the surface protective layer, and either one of the image forming layer side and the back layer side may be used. More preferably, it is added to at least the surface protective layer on the image forming layer side.
When the surface protective layer is composed of two or more layers, any of the layers may be used, or the surface protective layer may be further overcoated on the surface protective layer.

Various supports can be used for the heat-developable image recording material of the present invention. Typical supports include polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetal, polycarbonate and the like. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferred in terms of strength, dimensional stability, chemical resistance and the like. The thickness of the support is 90 to 500 as a base thickness excluding the undercoat layer.
μm is preferred. The support may be a transparent, translucent or white reflective support. As the white reflective support, a polyester film into which a white inorganic pigment is kneaded can be used.

It is preferable to provide an undercoat layer containing a vinylidene chloride copolymer or a moisture-proof layer on both sides of the support. The vinylidene chloride copolymer may be used alone or in combination of two or more. The content of vinylidene chloride copolymer is
The total thickness per one side of the undercoat layer containing the vinylidene chloride copolymer is 0.3 μm or more, preferably 0.3 to 4 μm. Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer. The support may be coated, if necessary, with an undercoat layer using SBR, polyester, gelatin or the like as a binder, in addition to the vinylidene chloride copolymer layer. The general thickness (per layer) of the undercoat layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 1 μm.

The support used in the present invention is subjected to a heat treatment at a temperature in the range of 130 to 185 ° C. in order to alleviate the internal strain remaining in the film at the time of biaxial stretching and to eliminate the heat shrinkage strain generated during thermal development. The applied polyester, particularly polyethylene terephthalate, is preferably used. Such a thermal relaxation treatment may be performed at a constant temperature within a temperature range,
It may be carried out while raising the temperature. The heat treatment of the support may be performed in a roll form or may be performed while transporting the support in a web form. When carrying out while transporting in a web form, the transport tension of the support during the heat treatment is preferably relatively low,
Specifically, 7 kg / cm ² or less, particularly 4.2 kg / cm ²
It is preferable to set the following. The lower limit of the transport tension at this time is not particularly limited, but is about 0.5 kg / cm ² .

Such heat treatment is preferably carried out after the treatment for improving the adhesion of the image forming layer and the back layer to the support, the formation of the undercoat layer containing the vinylidene chloride copolymer, and the like. . The heat shrinkage of the support after heating at 120 ° C. for 30 seconds after the heat treatment is −0.03% to + 0.01% in the machine direction (MD) and 0 to 0.04% in the transverse direction (TD). Preferably, there is.

The heat-developable color image recording material of the present invention includes
U.S. Pat. Nos. 3,253,921 and 2,274,
Light absorbing substances and filter dyes such as those described in 782, 2,527,583 and 2,956,879 can be used. Further, a dye can be mordanted as described in, for example, US Pat. No. 3,282,699. As the amount of the filter dye used, the absorbance at the exposure wavelength is 0.1 to 0.1.
3 is preferable, and 0.2 to 1.5 is particularly preferable.

In the image forming layer of the heat-developable color image recording material of the present invention, various dyes and pigments can be used from the viewpoint of improving color tone and preventing irradiation. These dyes and pigments may be any, for example, pigments and dyes described in the color index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, carbocyanine dye,
Examples thereof include styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments including phthalocyanine, and inorganic pigments. Preferred dyes include anthraquinone dyes (for example, see
Compounds 1 to 9 described in JP-A-341441, JP-A-5-1
Compounds 3-6 to 18 and 3- described in No. 65147
23-38), azomethine dyes (JP-A-5-341)
No. 441, compounds 17 to 47), indoaniline dyes (for example, compounds 11 to 19 described in JP-A-5-289227, compounds 47 described in JP-A-5-341441, and JP-A-5-165147). Compounds 2-10 to 11 described above) and azo dyes (Japanese Unexamined Patent Application Publication No.
Compounds 10 to 16) described in JP-A-341441. The amounts of dyes and pigments used are determined according to the desired absorption amount, but are generally preferably in the range of 1 μg to 1 g per 1 m ² of the image recording material. As a method for adding the dye and the pigment, 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.
If it is a water-soluble substance, it is preferable to add it in an aqueous solution,
If it is a water-insoluble substance, it is preferably added as a solid fine particle dispersion using water as a dispersion medium.

[0210] It is desirable to use certain additives to promote development. This additive is an additive which was conventionally called a "color tone agent" in the field of a heat development image recording system called a dry silver system. This additive is added to the layer on the side of the support having the photosensitive layer in an amount of 0.1 to 50 per mole of silver.
% (Mol), more preferably 0.5 to 20% (mol). Further, a so-called precursor which is derivatized so as to have a function effectively only at the time of development may be used. Many compounds are known as such additives. For example, JP-A-46-6077
JP-A-47-10282 and JP-A-49-5019
JP-A-49-5020 and JP-A-49-91215
JP, 50-5024, and 50-32927
JP, 50-67132, and 50-6764
No. 1, No. 50-114217, No. 51-32
No. 23, No. 51-27923, No. 52-14
No. 788, No. 52-99813, No. 53-1
No. 020, 53-76020, 54-1
Nos. 56524, 54-156525, 6
1-1183624, JP-A-4-56848, JP-B-49-10727, and 54-2033.
3, U.S. Pat. Nos. 3,080,254, 3,446,648, and 3,782,94.
No. 1, No. 4,123,282, No. 4,510,236, British Patent No. 1,380,
No. 795, Belgian Patent No. 841,910 and the like are disclosed as toning agents. Specific examples include phthalimide and N-hydroxyphthalimide;
Succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one,
Cyclic imides such as 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); -Mercapto-1,2,4-
Triazole, 2,4-dimercaptopyrimidine, 3-
Mercaptans exemplified by mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides; 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, a phthalazinone derivative or a metal salt, or 4- (1-naphthyl) phthalazinone, 6
Derivatives such as -chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid) Acid and tetrachlorophthalic anhydride, etc.);
Phthalazine, phthalazine derivatives (eg, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-
Dimethoxyphthalazine, 6-isopropylphthalazine,
6-isobutylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-
Derivatives such as dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; for silver halide formation in situ as well as color tone regulators Rhodium complexes that also function as sources of halide ions of, for example, hexachlororhodium (II)
I) ammonium acid, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2 Benzoxazine-2,4-dione, such as 1,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine And asymmetric-triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil,
And tetraazapentalene derivatives (for example, 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,
3a, 5,6a-tetraazapentalene, and 1,4
-Di (o-chlorophenyl) -3,6-dimercapto-
1H, 4H-2, 3a, 5, 6a-tetraazapentalene) and the like.

[0211] These additives are preferably added in the form of an aqueous solution.
It may be added by any method such as a solid fine particle dispersion.
The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

As the sensitizing dye that can be used in the present invention, any sensitizing dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength range when adsorbed on silver halide grains. For example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, and the like can be used. Useful sensitizing dyes that can be used in the present invention include, for example, RESEAR
CH DISCLOSURE Item17643IV
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in section 1X (August 1979, p. 437). 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.

As an example of spectral sensitization to red light, He-
For a so-called red light source such as a Ne laser, a red semiconductor laser or an LED, the compounds of I-1 to I-38 described in JP-A-54-18726,
Compounds I-1 to I-35 described in JP-A-5322 and compounds I-1 to I-34 described in JP-A-7-287338, and dyes 1 to 20 described in JP-B-55-39818. And compounds of I-1 to I-37 described in JP-A-62-284343 and JP-A-7-284.
The compounds of I-1 to I-34 described in JP-A-287338 are advantageously selected.

For a semiconductor laser light source in the wavelength range of 750 to 1400 nm, various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes are spectrally advantageously sensitized. Can be done. 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, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus,
Also includes acidic nuclei such as thiazolinone nuclei, malononitrile nuclei and pyrazolone nuclei. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, US Pat.
1,279, 3,719,495,
No. 3,877,943, British Patent No. 1,466,
No. 201, No. 1,469,117, No. 1,422,057, JP-B-3-10391, JP-A-6-52387, JP-A-5-341432
Gazette, JP-A-6-194787, JP-A-6-30114
The dyes may be appropriately selected from known dyes as described in JP-A-1.

Particularly preferred structures of the sensitizing dye which can be used in the present invention are cyanine dyes having a thioether bond-containing substituent (for example, see JP-A-62-5).
No. 8239, No. 3-138538, No. 3-1
38642, 4-255840, 5-
Nos. 72659, 5-72661 and 6-2
22491, 2-230506, 6-
Nos. 258,575 and 6-317868, 6
JP-A-324425, JP-A-7-500926, dyes described in U.S. Pat. No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440), JP-A-6-301141,
Dyes described in U.S. Pat. No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329 and JP-A-49-32949).
No. 105524, No. 51-127719, No. 52-80829, No. 54-61517,
JP-A 59-214846, JP-A 60-6750, JP-A 63-159841, JP-A-6-3510
No. 9, No. 6-59381, No. 7-14653
No. 7, No. 7-146537, British Patent No. 1,
No. 467,638, US Pat. No. 5,281,515.
And the dyes described in JP-A No. 7-1270). Also, J-b
US Pat. No. 5,510,236 as a dye forming and
Nos. 3,871,887, JP-A-2-96131 and JP-A-59-88131.
No. 48753 is 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 176, 17643 (Issued December 1978), page 23, IV, J.
Nos. -25500, 43-4933, JP-A-59-19032, and 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, or 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. The amount of the sensitizing dye may be desired amount depending on the performance such as sensitivity and fog, per mol of silver halide 10 ^-6 to 1 mole of the image forming layer (photosensitive layer) is preferably, 10 ^- More preferably, it is ⁴ to 10 ^-1 mol.

In the present invention, silver halide emulsions and / or organic silver salts are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and are sensitive during storage in stock. Can be stabilized. Suitable antifoggants, stabilizers and stabilizer precursors which can be used alone or in combination include the thiazoniums described in U.S. Pat. Nos. 2,131,038 and 2,694,716. Salts, azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605;
Mercury salts described in U.S. Pat. No. 2,728,663, urazoles described in U.S. Pat. No. 3,287,135, sulfocatechol described in U.S. Pat. No. 3,235,652, Oxime, nitrone, nitroindazole described in British Patent No. 623,448, polyvalent metal salt described in U.S. Pat. No. 2,839,405, and U.S. Pat. No. 3,220,839. Thiuronium salts as well as U.S. Pat.
No. 263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.
Halogen-substituted organic compounds described in U.S. Pat.
128,557, 4,137,079, 4,138,365 and 4,45
9,350, and the phosphorus compound described in U.S. Pat. No. 4,411,985.

The heat-developable color image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acid used in the present invention may be any benzoic acid derivative.
784,939, 4,152,160, JP-A-9-329865, and 9-32986.
No. 4, JP-A-9-291637 and the like. The benzoic acid may be added to any layer of the heat-developable color image recording material, but is preferably added to the layer on the image forming layer (photosensitive layer) side with respect to the support, and the organic silver salt layer and the intermediate layer Is preferably added to the protective layer. Particularly preferred is an intermediate layer or a protective layer.
The benzoic acid may be added in any step of the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed. To just before application. The benzoic acid may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a color tone agent. The benzoic acid may be added in any amount, but is preferably from 1 μmol to 2 mol, more preferably from 1 mmol to 0.5 mol, per mol of silver.

The heat-developable color image recording material of the present invention includes
A mercapto compound, a disulfide compound, and a thione compound can be contained for the purpose of suppressing or promoting the development to control the development, improving the spectral sensitization efficiency, and improving the storage stability before and after the development. In the present invention, when a mercapto compound is used, any structure may be used, but Ar-SM, Ar
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy ( For example, it may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and aryl (which may have a substituent). Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole,
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-hydrokilocy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-
Methyl pyrimidine hydrochloride, 3-mercapto-5
-Phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, sodium 3- (5-mercaptotetrazole) -benzenesulfonate, N-
Methyl-N '-{3- (5-mercaptotetrazolyl)
Examples include phenyl diurea, 2-mercapto-4-phenyloxazole, 2- [3- (9-carbazolyl) propylimino] -3- (2-mercaptoethyl) benzothiazoline, but the present invention is not limited thereto. . The use amount of these mercapto compounds is preferably in the range of 0.0001 to 1.0 mol per mol of silver in the image forming layer, and more preferably 0.0001 per mol of silver.
量 0.3 mol.

The heat-developable color image recording material of the present invention includes
Polyhydric alcohols as plasticizers (eg, US Pat.
Glycerin and diols of the type described in US Pat. No. 960,404) and the like can be used.

In the heat-developable color image recording material of the present invention, it is desirable to add a matting agent to the surface protective layer in order to prevent adhesion failure when superposed. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water.
Any matting agent can be used, for example, US Pat. Nos. 1,939,213 and 2,701,24.
5, 5,322,037, 3,2
Organic matting agents described in 62,782, 3,539,344, 3,767,448, etc .; 1,260,772, 2,192;
No. 241, 3,257, 206, 3,370,951, 3,523,022, 3,769,020 and the like. Agents well known in the art such as agents can be used. Specific 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, polystyrene, styrene-divinyl Examples of cellulose derivatives such as benzene copolymer, polyvinyl acetate, polyethylene carbonate, and polytetrafluoroethylene, such as methylcellulose, cellulose acetate, and cellulose acetate propionate; and examples of starch derivatives such as carboxy starch, carboxynitrophenyl starch, and urea- Gelatin hardened with a known hardener such as a formaldehyde-starch reactant and hardened gelatin formed into microcapsule hollow granules by coacervate hardening are preferably used. Door 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 agent may be used as a mixture of different types of materials as required.

The matting agent has the effect of forming irregularities on the surface of the protective layer and reducing the contact area, thereby preventing adhesion failure. Therefore, the average particle size is preferably larger than the thickness of the protective layer. However, even if the average particle size is small, it may form aggregates and protrude from the surface. Practically 1 μm
The above is the useful range. On the other hand, if the particle size is too large, there is a high risk that the particles will sink into the image forming layer, hinder image formation, and cause pinholes. Practically 10 μm
The following are useful ranges. Therefore, in the present invention,
The average particle size of the matting agent is preferably from 1 to 10 μm.
The particle size distribution of the matting agent is preferably narrow, and the monodispersity is preferably 10% or less. The average particle size, shape, and particle size distribution can be adjusted as needed when preparing the matting agent or by mixing a plurality of matting agents.

When there are a plurality of protective layers, the effect of the matting agent can be obtained by adding to any of the protective layers, since the protective layer is generally a thin layer, but preferably the outermost surface layer or the outer surface is as close as possible. It is good to add to the layer. In the present invention, the pH of the coating solution for the image forming layer is adjusted to 5.5 to 7.8, and the acid used for the adjustment is preferably an acid containing no halogen. Although the pH of the protective layer varies depending on the chemical added, it is relatively low at 2 to 7, but in the case of a plurality of protective layers, the layer closer to the photosensitive layer is 4 to 7, and the layer farther is 2 to 7.
It is preferable to make it as low as ~ 5.

In the present invention, in the case of a transparent support, the back layer preferably has a maximum absorption in a desired range of about 0.3 to 2.0. Desired range is 750 to 1400 nm
In this case, the optical density at 650 to 360 nm is preferably 0.001 or more and less than 0.5, and more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3. . Desired range is 7
When the thickness is 50 nm or less, the maximum absorption in a desired range before image formation is 0.3 or more and 2.0 or less, and the optical density at 360 to 650 nm after image formation is 0.005 or more and 0.005 or less.
It is preferable that the antihalation layer be less than 3. The method for lowering the optical density after image formation to the above range is not particularly limited. For example, Belgian Patent No. 7
As described in JP-A-33-706, a method of lowering the concentration of a dye by decoloring by heating,
No. 17833, a method of decreasing the density by decoloring by light irradiation, and the like.

In the case of using an antihalation dye, such a dye may have any desired absorption in the desired range, may have a sufficiently low absorption in the visible region after the treatment, and may have the desired absorbance spectrum of the back layer. It may be a compound. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458 and JP-A-2-2580
Nos. 16140, 7-13295, and 7-1
No. 1432, U.S. Pat. No. 5,380,635, JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9, and JP-A-3-24539, line 14 There are compounds described in the lower left column of the page to the lower right column of the same page 16 as dyes which can be decolorized by the treatment.
No. 36, No. 53-132334, No. 56-5
Nos. 01480 and 57-16060 and 57
JP-A-68831, JP-A-57-101835, JP-A-59-182436, JP-A-7-36145, JP-A-7-199409, and JP-B-48-3369.
No. 2, No. 50-16648, Japanese Patent Publication No. 2-41
No. 734, U.S. Pat. Nos. 4,088,497, 4,283,487 and 4,548,8.
Nos. 96 and 5,187,049.

In the present invention, binders suitable for the back layer are transparent or translucent, generally colorless, and include natural polymers, synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, acacia, (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein,
Starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid),
Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)),
Poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or a solvent or emulsion. Total amount of binder for the back layer is preferably 0.01 to 10 g / m ^2, more preferably from 0.5 to 5 g / m ^2.

In the present invention, it is a preferred embodiment to add a matting agent to the back layer in order to reduce the Beck seconds. It can be adjusted by changing the particle size and the amount added. The Beck smoothness is obtained from JIS P8119 and TAPPIT479.

In the present invention, it is preferable to include a slipping agent in the surface having the image forming layer and / or the outermost surface layer opposite to the surface. There is no particular limitation on the slip agent used in the present invention, and any compound may be used as long as it reduces the friction coefficient of the object surface when it is present on the object surface as compared to when it is not present.

Representative examples of the slip agent used in the present invention include, for example, US Pat. No. 3,042,522, British Patent No. 955,061 and US Pat. No. 3,080,317. Specification, JP-A-4,004,927, JP-A-4,047,958, JP-A-3,48
No. 9,567, British Patent No. 1,143,118, and the like.
454,043, 2,732,305, 2,976,148, 3,206,3
No. 11, higher fatty acid-based, alcohol-based, acid amide-based slip agents described in German Patent Nos. 1,284,295 and 1,284,294, and British Patent No. 1,263. U.S. Pat. No. 3,933,722.
No. 516, and the like.
Ester and ether slip agents described in 588,765 and 3,121,060, British Patent No. 1,198,387, and the like, US Pat. No. 3,50
And the taurine-based slip agents described in 2,473 and 3,042,222.

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

As one of applications of the present invention, the formed dye image may be diffused by heating and transferred to a fixed layer.
The fixing layer may be on the same support as the image forming layer (photosensitive layer) or on another support. When it is on another support, in a state where the sheet having the image forming layer and the sheet having the fixing layer are superimposed on each other, the dye generated by heat moves to the fixing layer by diffusion and is fixed. Thereafter, by peeling off both sheets, a transfer image of the dye separated from the image forming layer is obtained.

In the heat-developable color image recording material of the present invention, a hardener may be used for each layer such as an image forming layer (photosensitive layer), a protective layer and a back layer. Examples of the hardener include U.S. Pat. No. 4,281,060 and JP-A-6-2081.
No. 93, etc., polyisocyanates described in U.S. Pat. No. 4,791,042, etc., and vinylsulfones described in JP-A No. 62-89048, etc. Compounds or oxazoline compounds are used. In the present invention, the photothermographic emulsion is coated by various coating operations, including dip coating, air knife coating, flow coating, or extrusion coating using a hopper of the type described in U.S. Pat. No. 2,681,294. be able to. Optionally, U.S. Pat. No. 2,761,791 and British Patent 837,0
Two or more layers can be coated simultaneously by the method described in US Pat.

The heat-developable color image recording material of the present invention may be developed by any method. Usually, the image recording material exposed imagewise is heated and developed. As a preferred embodiment of the thermal developing machine to be used, a type in which the image recording material is brought into contact with a heat source such as a heat roller or a heat drum is disclosed in Japanese Patent Publication No. 5-56499 and Japanese Patent No. 684.
No. 453, JP-A-9-292695, JP-A-9-297385 and International Publication WO95 / 3
No. 0934, the thermal developing machine described in JP-A-7-13294 as a non-contact type.
JP-A-28489, JP-A-97 / 28488 and JP-A-97 / 28487 disclose a thermal developing machine. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is from 80 to 250C, more preferably from 100 to 140C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

In the present invention, as a method for preventing processing unevenness and physical unevenness due to a dimensional change during thermal development of an image recording material, 80 ° C. or more and less than 115 ° C. (preferably 113 ° C.)
(5 ° C. or lower) so that an image is not formed, and after heating for 5 seconds or more, heat developing at 110 ° C. or higher (preferably 130 ° C. or lower) to form an image (so-called multi-step heating method). Is valid. Cooling after thermal development is preferably performed gradually, and the cooling rate from the development temperature to 70 ° C. is 200 ° C./min or less, preferably 50 ° C./min.
１５０150 ° C./min.

The image recording material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source. As laser light according to the present invention, gas lasers,
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 image recording material of the present invention has a low haze at the time of exposure and tends to cause interference fringes. As a technique for preventing the occurrence of interference fringes, Japanese Patent Laid-Open No.
No. 3548, which discloses a technique for obliquely entering a laser beam into an image recording material,
Methods using multi-mode lasers disclosed in O95 / 31754 and the like are known, and it is preferable to use these techniques.

To expose the image recording material of the present invention, SPIE
vol.169 Laser Printing 116-128 pages (19
79), JP-A-4-51043, International Publication WO9
It is preferable to expose the laser beams so as to overlap each other so as to make the scanning lines invisible, as disclosed in Japanese Patent Publication No. 5/31754. Hereinafter, the present invention will be described more specifically with reference to examples. Materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[0238]

EXAMPLES {Description of Materials} <Preparation of heat-treated support having back layer> The following layers were provided on a PET base having a thickness of 125 μm. (Application of Undercoat Layer) The following undercoat layer (a) and undercoat layer (b) were applied to one surface of the PET base, and each was coated with 18
Dry at 0 ° C. for 4 minutes. [Undercoat layer (a)] Polymer latex V-5 A core-shell type latex having a core of 90% by mass and a shell of 10% by mass. /3/0.9/0.1 (% by mass) Shell part Vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3/3 (% by mass) Weight average molecular weight 38000, solid Quantity 3.0 g / m ² 2,4-Dichloro-6-hydroxy-s-triazine 23 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ²

[Undercoat layer (b)] Alkali-treated gelatin (Ca ²⁺ content 30 ppm, jelly strength 230 g) 83 mg / m ² Compound A 1 mg / m ² Compound H 2 mg / m ² Methylcellulose 4 mg / m ² Emalex 710 3 mg / m ² (trade name of Nippon Emulsion Co., Ltd., polyoxyethylene)

(Application of Back Layer) On the other side of the PET base, the following first back layer and second back layer were successively applied and dried at 180 ° C. for 4 minutes. [Back first layer] Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 38 mg / m ² SnO ₂ / Sb (mass ratio 9/1, needle-shaped particles manufactured by Ishihara Sangyo Co., Ltd., trade name: FS- 10D) 200 mg / m ² Dye A 20 mg / m ² Matting agent (polymethyl methacrylate particles, average particle size 5 μm) 10 mg / m ² Cross-linking agent (Denacol EX-614B, manufactured by Nagase Kasei Kogyo Co., Ltd.) 13 mg / m ²

[Back second layer] Latex binder (Chemipearl S-120, manufactured by Mitsui Petrochemical Co., Ltd.) 500 mg / m ² colloidal silica (Snowtex-C, Nissan Chemical Co., Ltd.) 40 mg / m ² crosslinked (Denacol EX-614B, manufactured by Nagase Kasei Kogyo Co., Ltd.) 30 mg / m ²

[0242]

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(Heat treatment of support) An undercoat layer and a back layer were applied, and a 5 kg / c tension was applied to a dried PET base.
A first heat treatment at m ² and a temperature of 130 ° C. for 10 minutes is performed, followed by a second heat treatment at a tension of 10 kg / cm ² and a temperature of 40 ° C. for 15 seconds to prepare a heat-treated support having a back layer. did.

<Preparation of photosensitive silver halide emulsion>
0 ml, phthalated gelatin 11 g, potassium bromide 30 m
g, and 10 mg of sodium thiosulfonate, and the temperature was adjusted to 35 ° C. to adjust the pH to 5.0. Then, 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 ml of potassium bromide were added.
The aqueous solution containing mol / liter was added over 6.5 minutes by the control double jet method while maintaining the pAg at 7.7. Then, 476 m of an aqueous solution containing 55.4 g of silver nitrate
solution containing 1 mol / l of potassium bromide and 1 mol / l
After adding over a period of 30 minutes by the control double jet method while maintaining the g at 7.7, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was further lowered to cause coagulation sedimentation. And desalted.
Thereafter, 0.1 g of phenoxyethanol was added, and the pH was adjusted.
5.9, pAg 8.2, and silver bromide particles (average particle size 0.12 μm, projected area diameter variation coefficient 8%, (1
00) cubic particles having an area ratio of 88%).

The silver halide grains thus obtained were heated to 60 ° C., and 8.5 × 10 ^-4 mol of sodium thiosulfonate per mol of silver was added.
After quenching to 0 ° C., 1 × 10 ⁻⁵ mol of sensitizing dye A and 5 × 10
^-5 mol of compound B and 5 × 10 ^-5 mol of N-methyl-N ′-{3- (mercaptotetrazolyl) phenyl}
100 ppm of urea and Compound A were added, and the mixture was rapidly cooled to 30 ° C. to obtain a silver halide emulsion A.

[0246]

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<Preparation of Dispersion A of Organic Acid Silver> 4.4 g of stearic acid, 39.4 g of behenic acid and 770 ml of distilled water were added to 9 parts each.
While stirring at 0 ° C., a 1 mol / L NaOH aqueous solution 103
Then, the mixture was reacted for 240 minutes and then cooled to 75 ° C. Then, an aqueous solution containing 19.2 g of silver nitrate 112.5 g
ml over 45 seconds and leave for 20 minutes.
The temperature was lowered to 30 ° C. Next, the solid content was separated by suction filtration and washed with water until the electric conductivity of the filtrate became 30 μS / cm. Polyvinyl alcohol 1 is added to the solid content thus obtained.
100 ml of a 0% by weight aqueous solution was added, and the total mass was 2
Water was added to 70 g. Next, after roughly dispersing in an automatic mortar, the pressure at the time of collision was 1000 kg / cm ² using a dispersing machine “Nanomizer” (manufactured by Nanomizer).
, Average minor axis 0.04μm, average major axis 0.8μ
m, a needle-shaped particle dispersion having a variation coefficient of 30% was obtained.

<Preparation of Reducing Agent Dispersion A> Reducing Agent A100
g and 125 g of polyvinyl alcohol were added with 600 g of water and mixed well to prepare a slurry. The slurry is dispersed with beads (zirconia grains having an average diameter of 0.5 mm) 840.
g in a vessel with a disperser sand mill (1/4
The mixture was dispersed and dispersed for 5 hours with a G sand grinder mill (manufactured by Imex Co., Ltd.), and 175 g of water was added and taken out of the vessel. Thus, a reducing agent dispersion A having an average particle size of 0.4 μm was obtained.

[0249]

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<Preparation of phthalazine derivative solubilizing solution> The following phthalazine derivative A solubilizing solution A was prepared by mixing and stirring at the following ratio. Phthalazine derivative A 25 g Leopol BX 2.1 g (trade name of Takemoto Yushi Co., Ltd., triisopropylnaphthalene sulfone sunsoda) Polyvinyl alcohol 100 g (Kuraray PVA-217) (20% aqueous solution) Water 373 g

[0251]

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<Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound> To 30 g of organic polyhalogen compound A, 0.5 g of hydroxypropylmethylcellulose, 0.5 g of compound C and 88.5 g of water were added and stirred well to form a slurry. Left for 3 hours. Thereafter, a solid fine particle dispersion was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80% by mass of the particles was 0.3 to 1.0 μm.

[0253]

[Of 75]

<Preparation of Dispersion A of Color Image Forming Material> 100 g of 2-equivalent coupler A and 125 g of polyvinyl alcohol
Was added and mixed well to prepare a slurry. This slurry was placed in a vessel together with 840 g of dispersed beads (zirconia particles having an average diameter of 0.5 mm) and dispersed in a sand mill (1 / 4G sand grinder mill, manufactured by IMEX Co., Ltd.) for 5 hours, and 175 g of water was added. Removed from the vessel. Average particle size 0.7
A μm color image forming material dispersion A was obtained.

[0255]

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<Preparation of Dispersion A of Scavenger Coupler> In Dispersion A of a color image forming material, Scavenger Coupler SC-4 was used in place of 2-equivalent coupler A, and Dispersion A of the color image forming material was used for the others. In the same manner as described above, a dispersion A of a scavenger coupler was prepared. The average particle size was 0.3 μm.

[0257]

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Example 1 <Preparation of Comparative Sample> The following image forming layer A coating solution was provided on the side of the PET support provided with the backing / undercoating layer with the undercoating layers (a) and (b). , And a protective layer coating solution were simultaneously layer-coated. (Preparation and Coating of Coating Solution for Image Forming Layer A) A photosensitive silver halide emulsion A was mixed with 85 g of the above-mentioned organic acid silver dispersion so that the silver amount was 5 mol%, and the reducing agent dispersion A was mixed. 20
g, 31 g of color image forming material dispersion A, Lacstar #
3307B (manufactured by Dainippon Ink and Chemicals, Inc., SBR latex; Tg 13 ° C., 49% by mass), 46 g, 10% by mass aqueous solution of Kuraray Povar MP-203, 6 g, phthalazine derivative solubilizing solution A, 13 g, organic polyhalide Dispersion 10 g, 5-methylbenzotriazole 0.07
g, 6 mg of Dye A and 25 g of water were added and mixed well. Coating was performed so that the coated silver amount was 0.8 g / m ² .

(Preparation and Application of Protective Layer Coating Solution) Solid Content 2
7.5% polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate methacrylic acid = 59 /
(9/26/5/1 copolymer with a glass transition temperature of 55 ° C)
To 109 g, 3.75 g of water was added, and 4.5 g of benzyl alcohol, 0.45 g of compound-2, 0.125 g of compound-3, 0.0125 mol of compound-4, and polyvinyl alcohol (Kuraray Co., Ltd., PVA-
217) Add 2.25 g, add water and add 150
g and the coating liquid. On the photosensitive layer, the coating amount of the polymer latex was applied so as to 2.0 g / m ^2.

[0260]

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The two layers were simultaneously coated by multi-layer coating, and after coating, dried at 60 ° C. for 2 minutes to obtain a heat-developable color photographic material. This is designated as Comparative Sample 1.

<Preparation of Sample of the Present Invention> In preparing the above comparative sample, the scavenger coupler dispersion A was added to the color image forming material dispersion A in the image forming layer.
Samples 1-1, 1-2, 1-3, 1-4 of the present invention were prepared in the same manner except that mol%, 4 mol%, 8 mol%, 12 mol%, 16 mol%, and 20 mol% were added. 1-5, 1-
No. 6 was created.

<Formation of Dye Image by Thermal Development> Samples 1-1 to 1-6 and Comparative Sample 1 were illuminated for 10 minutes through an interference filter having a peak at 780 nm and a step density wedge having a density difference of 0.1. ^{The substrate} was exposed to xenon flash light for ^-6 seconds, and subjected to a heat development treatment at 115 ° C. for 10 seconds. A magenta color image was obtained. The maximum density (Dmax) and the fog density (Fog) were measured with a Macbeth densitometer. As shown in Table 1, Fog decreased with the amount of scavenger coupler added. For example, the addition of a scavenger coupler of 8 mol%, the loss of Dmax was as small as 0.03, but the Fog was greatly reduced to 0.04. In the photographic art, a decrease of 0.04 in the Fog value is a very significant effect.

[0264]

[Table 1]

Example 2 A scavenger coupler S was used instead of the scavenger coupler SC-4 of Example 1.
C-38, SC-II-4, SC-16, SC-V-4,
Samples 2-1 and 2 of the present invention were prepared in the same manner as in Example 1 except that 4 mol% of SC-III-1 and SC-34 were used.
-2, 2-3, 2-4, 2-5, and 2-6 were prepared. Table 2 shows the results of the evaluation performed in the same manner as in Example 1.

[0266]

[Table 2]

Similarly to the sample of the present invention of Example 1, also in Example 2, the loss of Dmax was minimized, and
A color image with little og was obtained.

Example 3 <Preparation of Photosensitive Silver Halide Emulsion B> 11 g of phthalated gelatin, 30 mg of potassium bromide, and 10 mg of sodium thiosulfonate were dissolved in 700 ml of water, and the temperature was adjusted to 35.
° C and adjusted to pH 5.0, and 18.6 g of silver nitrate
159 ml of an aqueous solution containing 1 mol / l of potassium bromide and an aqueous solution containing 1 mol / l of potassium bromide were added over 6.5 minutes by a control double jet method while maintaining the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and an aqueous solution containing 1 mol / l of potassium bromide were added over 30 minutes by a control double jet method while keeping the pAg at 7.7, and then 4-hydroxy-6-methyl-1,
1 g of 3,3a, 7-tetrazaindene was added, and the pH was further lowered to cause coagulation and sedimentation, followed by desalting. Thereafter, phenoxyethanol 0.1g was added, pH 5.9, pA
g8.2, and silver bromide particles (average particle size 0.1
Adjustment of 2 μm, a projection area diameter variation coefficient of 8%, and a (100) plane ratio of 88% (cubic grains) was completed.

The silver halide grains thus obtained were heated to 60 ° C., and 8.5 × 10 −4 mol of sodium thiosulfonate per mol of silver was added.
After quenching to 0 ° C., 1 × 10 ⁻⁵ mol of spectral sensitizing dye B and 5 ×
10 ⁻⁵ mol of the following compound B and 5 × 10 ⁻⁵ mol of N
-Methyl-N '-{3- (mercaptotetrazolyl) phenyl} urea, 100 ppm of the following compound A was added,
The mixture was rapidly cooled to 30 ° C. to obtain a silver halide emulsion B.

[0270]

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<Preparation of Scavenger Coupler Dispersion B> 100 g of scavenger coupler SC-38 and 600 g of water were added to 125 g of polyvinyl alcohol and mixed well to prepare a slurry. This slurry was placed in a vessel together with 840 g of dispersed beads (zirconia particles having an average diameter of 0.5 mm) and dispersed for 5 hours with a dispersing machine sand mill (1 / 4G sand grinder mill, manufactured by Imex Co., Ltd.) to obtain an average particle size of 0.3 μm. Was obtained as a scavenger coupler dispersion B.

[0272]

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<Preparation of Dispersion B of Color Image Forming Material> 100 g of the following color image forming material C-62 and 600 g of water were added to 125 g of polyvinyl alcohol and mixed well to prepare a slurry. This slurry is dispersed with beads (average diameter of 0.1 mm).
840 g of 5 mm zirconia particles) was placed in a vessel and dispersed with a disperser sand mill (1 / 4G sand grinder mill, manufactured by IMEX Co., Ltd.) for 5 hours to obtain a color image forming material dispersion B having an average particle size of 0.7 μm. Was.

[0274]

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<Preparation of Dispersion C of Color Image Forming Material> Prepared in the same manner as Dispersion B of the color image forming material except that the following color image forming material C-53 was used. did. The average particle size was 0.3 μm.

[0276]

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<Preparation of Coated Sample> The following organic silver salt layer, photosensitive layer and protective layer were simultaneously formed on the side of the undercoat layer (a) or (b) of the PET support having the back / undercoat layer. Multi-layer coating was performed. (Preparation and Coating of Photosensitive Layer A) Organic acid silver dispersion A 85 g,
Photosensitive silver halide emulsion A18g Reducing agent dispersion A24
g, color image forming material dispersion B 45 g, Lacstar #
3307B (manufactured by Dainippon Ink and Chemicals, Inc., SBR latex; Tg 13 ° C., 49 mass%) 46 g, Kuraray Povar MP-203 10 mass% 6 g, phthalazine derivative solubilizing solution A 13 g, organic polyhalide dispersion 10 g, 5-methylbenzotriazole 0.07 g,
6 mg of Dye A and 25 g of water were added and mixed well. Coating was performed so that the coated silver amount was 1.2 g / m ² .

(Preparation and Coating of Intermediate Layer Coating Solution) Scavenger Coupler Dispersion B 15 g, Lacstar # 330
23 g of 7B (manufactured by Dainippon Ink and Chemicals, Inc., SBR latex; Tg 13 ° C., 49% by mass), 10 g of 10% by mass of Kuraray Povar MP-203, and 10 g of water
Was added and mixed well. The coating was applied onto the photosensitive layer A so that the scavenger coupler B was 0.5 g / m ² .

(Preparation and Coating of Photosensitive Layer B) The above-mentioned organic acid silver dispersion A (85 g), photosensitive silver halide emulsion B (18 g),
24 g of a reducing agent dispersion A, 29 g of a color image forming material dispersion C,
46 g of Lacstar # 3307B (manufactured by Dainippon Ink and Chemicals, Inc., SBR latex; Tg 13 ° C., 49% by mass), 6 g of Kuraray Povar MP-203 10% by mass, 13 g of phthalazine derivative solubilizing solution A, 13 g of organic polyhalide 10 g of dispersion, 0.07 g of 5-methylbenzotriazole, 6 mg of dye B, and 25 g of water
Was added and mixed well. Coating was performed so that the coated silver amount was 1.6 g / m2.

(Preparation and application of protective lower layer)
59% 20% aqueous solution of coal, 27.5% solids polymer latte
Box (methyl methacrylate / styrene / 2-ethyl
Xyl acrylate / 2-hydroxyethyl methacrylate
Tomethacrylic acid = 59/9/26/5/1 copolymer
Transition temperature 55 ° C) 51 g, benzyl alcohol as a film-forming aid
4.5 g of compound 2, 0.45 g of compound 2, 0.125 g of compound 3,
0.0125 mol of compound 4 and H_TwoAdd O to make 150g,
A coating solution was used. On the photosensitive layer B, a polymer latex
0.7 g / m ^TwoIt was applied so that

[0281]

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(Preparation and Coating of Protective Upper Layer) 71 g of 14% aqueous solution of acid-treated gelatin, polymer latex having a solid content of 27.5% (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate methacrylic acid = 59 / 18 g of a copolymer of 9/26/5/1 with a glass transition temperature of 55 ° C, and a polymer matting agent (average particle size of 5μ)
1.4 g of a 15% dispersion of m), 0.45 g of compound 2, compound 3
0.125 g and further added with H ₂ O to make 150 g, thereby obtaining a coating solution. The coating was performed on the protective lower layer so that the coating amount of gelatin was 0.6 g / m ² on the photosensitive layer. These five layers
Coating was performed by simultaneous multi-layer coating, and after coating, drying was performed at 60 ° C. for 2 minutes. The obtained sample is referred to as Sample 3-1 of the present invention. On the other hand, a sample was prepared in the same manner as Sample 3 except that the scavenger coupler B in the intermediate layer was excluded, and this was designated as Comparative Sample 3-2.

(Formation of Dye Image by Thermal Development) The sample 3-1 of the present invention was passed through an interference filter having a peak at 780 nm and a step density wedge having a density difference of 0.1, and a xenon flash having a light emission time of 10 ^-6 seconds was used. Exposure to light, 115
A heat development process was performed at 20 ° C. for 20 seconds. A good magenta color image was obtained. On the other hand, Comparative Sample 3-2 had a yellow color mixture and a reddish color tone. Next, the sample 3-1 of the present invention was exposed to xenon flash light having an emission time of 10 ^-6 seconds through an interference filter having a peak at 670 nm and a step density wedge having a density difference of 0.1.
A heat development process was performed at 20 ° C. for 20 seconds. A yellow image was obtained. Comparative Sample 3-2 had a magenta color mixture and thus had a reddish color tone, but Sample 3-1 of the present invention provided a color image with a good magenta color tone without color mixture.

As described above, the sample 3-1 of the present invention was used.
Is to provide a color image with less color mixture in both 780 nm exposure and 670 nm exposure, that is,
It was shown that the interference between the two photosensitive layers was well eliminated by the scavenger coupler.

[0285]

According to the present invention, a heat-developed color image can be obtained in which the developing means is only thermal development and a high-quality color image with little color fog is obtained without requiring additional steps such as peeling and transfer. It has become possible to provide recording materials.

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[Procedure amendment]

[Submission date] June 6, 2001 (2001.6.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (In the general formula (SC-I), Y represents a carbonyl group or a sulfonyl group, Q ₁ and Q ₂ each independently represent an form a 5- or 6-membered ring substituted or unsubstituted non-metallic atomic group, X represents a C—R ^X or N atom, wherein R ^X
Represents a hydrogen atom or a substituent. )

Embedded image (In formula (SC-II), Q ₃ represents a substituted or unsubstituted non-metallic atomic group forming a 5- or 6-membered ring, R ₁ represents a substituted or unsubstituted aryl group or a substituted carbonyl group. )

Embedded image(In the general formula (SC-III), Q_FourIs 5 or 6
Represents a group of substituted or unsubstituted nonmetallic atoms that form
Then R_TwoAnd R_ThreeEach independently represents a substituent; ₁Is return
Represents a group that does not leave during the reaction with the base agent. )

Embedded image (In the general formula (SC-IV), Q ₅ represents a substituted or unsubstituted nonmetallic atom group forming a 5- or 6-membered ring, R ₄ represents a substituent, and L ₂ represents a reaction with a reducing agent. Represents a group which does not leave.)

Embedded image (In the general formula (SC-V), R ₅ and R ₆ each independently represent a substituent, and L ₃ represents a group that does not leave upon reaction with a reducing agent.)

Claims (19)

[Claims] 1. A heat-developable color image recording material comprising a support and a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, and an organic binder, wherein the color image forming material is a 2-equivalent type. A heat-developable color image recording material, which is a coupler and further comprises a scavenger coupler that does not substantially form a color image. 2. The heat-developable color image recording material according to claim 1, wherein the reducing agent is a compound represented by the following general formula (D). General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. ) 3. The heat-developable color image recording material according to claim 1, wherein the content of the scavenger coupler with respect to the color image forming material is from 0.01 mol% to 200 mol% in a molar ratio. 4. The heat-developable color image recording material according to claim 1, wherein the scavenger coupler is a 4-equivalent coupler. 5. A scavenger coupler represented by the following general formula:
It is a coupler represented by (SC-I) to (SC-V)
4. The thermoelectric generator according to claim 1, wherein
Image color image recording material. Embedded image(In the general formula (SC-I), Y represents a carbonyl group or
Represents a sulfonyl group;₁And Q_TwoAre 5
Substituted or unsubstituted nonmetallic atom forming a 6-membered or 6-membered ring
X represents C—R^XOr N, where R^X
Represents a hydrogen atom or a substituent. )(In the general formula (SC-II), Q_ThreeMeans 5 or 6 members
Represents a group of substituted or unsubstituted nonmetallic atoms forming a ring of
Then R₁Is a substituted or unsubstituted aryl group or substituted
Represents a bonyl group. )(In the general formula (SC-III), Q_FourIs 5 or 6
Represents a group of substituted or unsubstituted nonmetallic atoms that form
Then R_TwoAnd R_ThreeEach independently represents a substituent; ₁Is return
Represents a group that does not leave during the reaction with the base agent. )(In the general formula (SC-IV), Q_FiveMeans 5 or 6 members
Represents a group of substituted or unsubstituted nonmetallic atoms forming a ring of
Then R_FourRepresents a substituent;_TwoIs released by the reaction with the reducing agent
Represents no group. )(In the general formula (SC-V), R_FiveAnd R₆Is German
Stands for a substituent;_ThreeDoes not leave by reaction with reducing agent
Represents a group. ) 6. The method according to claim 1, wherein the organic binder is formed from a polymer latex dispersed in water.
6. The heat-developable color image recording material according to any one of items 1 to 5. 7. The method according to claim 1, wherein the reducing agent is applied as a dispersion of fine particles solid-dispersed in water.
The heat-developable color image recording material according to claim 1. 8. The heat-developable color image recording material according to claim 1, wherein the color image forming material is applied as a dispersion of fine particles solid-dispersed in water. . 9. The heat-developable color image recording material according to claim 1, wherein the scavenger coupler is applied as a dispersion of fine particles solid-dispersed in water. 10. The heat-developable color image recording material according to claim 1, further comprising a halogen precursor. 11. The heat-developable color image recording material according to claim 10, wherein the halogen precursor is applied as a dispersion of fine particles solid-dispersed in water. 12. The color image forming material and a scavenger coupler are contained in the same layer.
12. The heat-developable color image recording material according to any one of items 1 to 11. 13. A layer adjacent to a layer containing a color image forming material, comprising a scavenger coupler.
The heat-developable color image recording material according to claim 1. 14. A first image-forming layer comprising, on a support, a photosensitive silver halide photosensitive to a first wavelength region, an organic silver salt, a reducing agent, a color image-forming material, and an organic binder; And at least two or more different photosensitive wavelengths, including a photosensitive silver halide having sensitivity in the second wavelength region, an organic silver salt, a reducing agent, a color image forming material, and a second image forming layer containing an organic binder. Heat-developable color image recording material having an image forming layer in a region, wherein the color image-forming material is a two-equivalent coupler and further contains a scavenger coupler that does not substantially form a color image. Recording material. 15. The heat-developable color image recording material according to claim 14, wherein said scavenger coupler is contained in a layer between image forming layers having different photosensitive wavelength ranges. 16. The heat-developable color image recording material according to claim 14, wherein the reducing agent is a compound represented by the following general formula (D). General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. ) 17. A heat-developable color image forming method, comprising a step of exposing and heat-developing the heat-developable color image recording material according to any one of claims 1 to 16. 18. An image recording layer comprising a photosensitive silver halide, an organic silver salt, a reducing agent, a two-equivalent coupler, and an organic binder on a support, and a scavenger in the image recording layer and / or an adjacent layer. Exposure and heat development of a heat-developable color image recording material having a coupler, wherein the photosensitive silver halide is contained in a ratio of 0.01 mol% to 200 mol% of the organic silver salt in the number of moles of silver. A method of forming a heat-developable color image, comprising forming an image in which developed silver and a color-developed image coexist, and observing the color image without separating them. 19. The heat-developable color image forming method according to claim 18, wherein the reducing agent is a compound represented by the following general formula (D). General formula (D): Q ¹ -NHNH-Q ² (In general formula (D), Q ¹ represents an aromatic group bonded to -NHNH-Q ² by a carbon atom, or a 5- to 7-membered unsaturated ring. ,
Q ² represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group. )