JP2002318432A - Heat developable color image recording material and heat developed color image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable color image recording material which adopts only heat development as a developing means, does not require an additional step such as stripping or transfer, takes on particularly good cyan coloring and gives a high quality color image and to provide a heat developed color image recording method. SOLUTION: In the heat developable color image recording material containing 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 compound of formula (l) wherein R1 and R2 are each substituted or unsubstituted alkyl or the like; R3 and R4 are each H or the like; R2 and R4 , or R1 and R3 may link together to form a cyclic structure; L1 and L2 are each -N(R5 )- or the like, R5 is H or the like; and X is H or a group which can be released by oxidative coupling reaction with a developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color image recording material and a heat-developable color image recording method, and more particularly, to a color proof material, a color print material and a color transmission recording material used in the printing industry. A heat-developed color image recording material which is suitable for various color photographic fields such as color microfilms and the like, in which the developing means is only heat development and high-quality color images can be obtained without requiring additional steps such as peeling and transfer. And a heat development color image recording method.

[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.
2,904, 3,457,075,
And J. "Heat Treated Silver System (Therma) by Klosterboer
llly Processed Silver System
ems) "(Imaging Processors and
Materials (Imaging Processes)
and Materials) Neblette No. 8
Edition, J. Sturge, V.S. Walworth, A .; Shepp
Edited, p. 279, 1989). One of them is an image forming material of a system in which an image is formed by drawing an image with light and then heating the image uniformly, and includes a reducible non-photosensitive silver source (for example, an organic silver salt) and a catalytic activity amount. (For example, silver halide) and a reducing agent for silver are usually contained in a state dispersed in an organic binder matrix. This type of image forming material is stable at room temperature, but has a high temperature after exposure (for example, 80 ° C. or higher).
When heated to a low temperature, silver is produced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver 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. Another heat-developable image-forming material is of a type that is insensitive to ordinary light and is directly drawn with heat. this is,
This is a material which is drawn by a thermal head or drawn by light having an absorption wavelength of the dye which contains a photothermal conversion dye and generates heat, and is developed by the heat. High energy laser exposure is used to obtain the heat required for development using the photothermal conversion dye. Such a heat-developable heat-developable image recording material does not contain a photosensitive silver halide and supports an image recording layer containing a non-photosensitive silver source (for example, an organic silver salt) and a reducing agent in a binder. Have on the body.

A heat-developable color image recording material using an organic silver salt is disclosed in the aforementioned J. Org. Book by Crostaver et al., 290
Page COLOR 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. That is, there is a problem that a color developing system that effectively functions in the organic silver salt heat development method has not been found. For example, Japanese Patent Application No. 2000-132270, Japanese Patent Application No. 2
000-132181 and Japanese Patent Application No. 2000-279.
The 122 publication proposes a reducing agent and a coupler that form color effectively. However, the color development by these is U
Wavelengths up to V, yellow or magenta
There is a problem that it is not possible to develop a long wave in the cyan region. In addition, even if a cyan-colored coupler well-known in a color photograph using a normal alkaline developer is used in an organic silver salt heat development method, no color is formed, or even if a color is formed, the coupler remains in the yellow to magenta color wavelength range. . The reason is,
In the case of the organic silver salt thermal development method, since the alkali film is not used and the film is in a weakly acidic atmosphere, the situation is completely different from the color development system using the alkali developer, and the conventional coupler,
Alternatively, the analogy regarding the color tone does not work at all. Therefore, development of a cyan coloring coupler (color image forming material) and a reducing agent effective in the organic silver salt heat development system has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a heat-developable color image recording material capable of obtaining a high-quality color image exhibiting a good cyan color without using an additional process such as peeling or transfer as a developing means only by heat development. And a heat development color image recording method.

[0005]

Means for solving the above problems are as follows. <1> In a heat-developable color image recording material containing an organic silver salt, a reducing agent, a color image forming material, and an organic binder on a support, the color image forming material is a compound represented by the following general formula (1) The heat-developable color image recording material is characterized in that:

[0006]

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In the general formula (1), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ₃ and R ₄ are each independently
Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₂ and R ₄ , and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ are each independently —N (R
₅ ) represents-, -O-, or a single bond. R ₅ is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent.

<2> The reducing agent is represented by the following general formula (2)
The heat-developable color image recording material according to <1>, which is a compound represented by the formula:

[0009]

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In the general formula (2), Q ₁ represents an aromatic group bonded to —NHNH—Q ₂ via a carbon atom, or a 5- to 7-membered unsaturated ring. Q ₂ is a carbamoyl group,
Represents 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 <1> or <2>, wherein the color image forming material is a two-equivalent type color image forming material.

<4> The organic binder according to any one of <1> to <3>, wherein the organic binder contains a polymer latex dispersed in water.
<3> The heat-developable color image recording material described in any one of <1>

<5> The heat-developable color image recording material according to any one of <1> to <4>, wherein the reducing agent is fine particles solid-dispersed in water.

<6> The heat-developable color image recording material according to any one of <1> to <5>, wherein the color image forming material is fine particles dispersed solid in water.

<7> The heat-developable color image recording material according to any one of <1> to <6>, further comprising a halogen precursor.

<8> The heat-developable color image recording material according to <7>, wherein the halogen precursor is a compound represented by the following general formula (H).

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In the general formula (H), Q represents an aryl group or a heterocyclic group. Z ¹ and Z ² are each independently
Represents a halogen atom. A represents a hydrogen atom or an electron-withdrawing group.

<9> The above <7> or <8>, wherein the halogen precursor is fine particles solid-dispersed in water.
3. The heat-developable color image recording material described in 1. above.

<10> The heat-developable color image recording material according to any one of <1> to <9>, containing a photosensitive silver halide. <11> In a heat-developable color image recording material having an image recording layer 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 photosensitive material is exposed to the organic silver salt. A silver molar ratio of the reactive silver halide is 0.1 to 100 mol%, the color image forming material is a compound represented by the following general formula (1), and after exposure of the heat-developable color image recording material, A heat-developed color image forming method characterized by forming an image in which developed silver and a color image coexist by heat development, and observing the color image without separating the developed silver.

[0021]

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In the general formula (1), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ₃ and R ₄ are each independently
Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₂ and R ₄ , and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ are each independently —N (R
₅ ) represents-, -O-, or a single bond. R ₅ is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent.

<12> The method according to <11>, wherein the reducing agent is a compound represented by the following general formula (2).

[0024]

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In the general formula (2), Q ₁ represents an aromatic group bonded to —NHNH—Q ₂ via a carbon atom, or a 5- to 7-membered unsaturated ring. Q ₂ is a carbamoyl group,
Represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, or a sulfamoyl group.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The heat-developable color image recording material and the heat-developable color image recording method of the present invention will be described in detail below.

[1] Heat-Developable Color Image Recording Material The heat-developable color image-recording material of the present invention comprises a support, which contains an organic silver salt, a reducing agent, a color image-forming material, and an organic binder. The material is characterized in that the color image forming material is a compound represented by the following general formula (1).

[0028]

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In the general formula (1), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ₃ and R ₄ are each independently
Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₂ and R ₄ , and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ are each independently —N (R
₅ ) represents-, -O-, or a single bond. R ₅ is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent.

The heat-developable color image recording material of the present invention is an image recording material capable of forming a multicolor image only by heating. As a drawing means, a method using a thermal head,
A method of drawing with light using a photothermal conversion dye and generating heat can be applied. In particular, a photothermal development system in which photosensitive silver halide grains are added to an image recording layer, which is drawn with light, and which is uniformly heated to form an image is preferable because a high-sensitivity, high-definition image can be formed.

(A) Image Recording Layer The heat-developable color image recording material of the present invention preferably has an image recording layer containing a reducing agent, a color image forming material, an organic silver salt and an organic binder on a support. . It is preferable that the image recording layer further contains a halogen precursor.
The image recording layer preferably contains a photosensitive silver halide. The image recording layer may be a laminate of a plurality of layers, a reducing agent, a color image forming material, an organic silver salt, etc.
They may be included in the same layer or different layers. When the image recording layer is formed by a coating method, the pH of the coating solution is preferably adjusted to 5.5 to 7.8, and the acid used in the adjustment preferably contains no halogen. Hereinafter, each component and layer configuration of the image recording layer in the invention will be described in detail.

(1) Color Image Forming Material The color image forming material used in the present invention is a compound represented by the following general formula (1).

[0033]

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In the general formula (1), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ₃ and R ₄ are each independently
Represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₂ and R ₄ , and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ are each independently —N (R
₅ ) represents-, -O-, or a single bond. R ₅ is a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent.

Hereinafter, R ₁ to R ₁ in the general formula (1) will be described.
R ₅ , L ₁ , L ₂ and X will be described in detail.

R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. R ₁ and R ₂ may be the same or different from each other, and may be a chain or cyclic alkyl group having 1 to 32 carbon atoms (eg, a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, etc.), An aryl group (eg, phenyl group, naphthyl group, etc.), or a heterocyclic group (eg,
2-pyridyl group, 2-imidazolyl group, 2-furyl group,
6-quinolyl group) is preferable, and among these, an alkyl group and a heterocyclic group are more preferable. These may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group, a 2-methoxyethoxy group, etc.), a phenoxy group (for example, a 2-chlorophenoxy group), a carboxy group, a carbonyl group (for example, , Acetyl group, benzoyl group, etc.), ester group (for example, methoxycarbonyl group,
Phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group,
Ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.),
Sulfamide group (for example, dipropylsulfamoylamino group and the like), imide group (for example, succinimide group,
Hydantoinyl group, etc., ureido group (eg, phenylureido group, dimethylureide group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), hydroxy group, cyano group, nitro group, halogen atom, thio group (eg, ethylthio group) Phenylthio group) and the like, and among them, an alkoxy group, a phenoxy group, a sulfamide group, a sulfonyl group, and a halogen atom are more preferable.

R ₃ and R ₄ each independently represent a hydrogen atom,
Represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₃ and R ₄ may be the same or different from each other, and include a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a chain or cyclic alkyl group (eg, a methyl group, A butyl group, a dodecyl group, a cyclohexyl group, etc.), an alkoxy group (eg, methoxy group, butoxy group, tetradecyloxy group, etc.), a carbamoyl group (eg, diethylcarbamoyl group, phenylcarbamoyl group, etc.), or a nitrile group is preferable, Among these, a hydrogen atom and an alkyl group are more preferred. R ₁
And R ₃ , and R ₂ and R ₄ may be linked to each other to form a ring structure.

L ₁ and L ₂ are each independently —N
(R ₅ ) —, —O—, or a single bond. R ₅ represents a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. The alkyl group, aryl group, or heterocyclic group has the same meaning as the alkyl group, aryl group, or heterocyclic group represented by R ₁ and R ₂ .

X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent. As the group capable of leaving by the oxidative coupling reaction with the developing agent,
Halogen atoms (eg, fluorine, chlorine, bromine, iodine),
An alkoxy group (for example, ethoxy group, dodecyloxy group, methoxyethylcarbamoyl group, carboxymethoxy group, methylsulfonylethoxy group, etc.), an aryloxy group (for example, phenoxy group, naphthyloxy group,
-Carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g.,
Methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutyrylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, dodecyloxy Carbonyloxy group, hexadecyloxycarbonyloxy group, benzyloxycarbonyl group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), thio group (eg, phenylthio group, tetrazolylthio group, etc.), imide group (eg, Succinimide group, hydantoinyl group, etc.), azo group (eg, phenylazo group, etc.), aminocarbonyloxy group (eg, N, N-diethylaminocarbonyloxy group, N-methyl-N Octadecyl amino carbonyl group) and the like. Among them, a halogen atom, an alkoxycarbonyloxy group and an aminocarbonyloxy group are more preferred. These may contain photographically useful groups.

Next, specific examples (exemplary compounds No. 1 to No. 26) of the compound represented by the general formula (1) will be given, but the present invention is not limited to these.

[0041]

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[0042]

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[0043]

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The color image forming material of the present invention is preferably of a two-equivalent type, since a high color density can be obtained. Further, the two-equivalent color image forming material is also preferable in that it has excellent storage stability until the image recording material is used after it is manufactured. Here, the 2-equivalent type means a coupler that requires stoichiometric reduction of 2 moles of silver ions to form 1 mole of a coloring dye. Chemically, it is located at the coupling position of the coupler. A compound having a leaving group other than a hydrogen atom.
On the other hand, a coupler having a hydrogen atom at the coupling position is called a 4-equivalent coupler and forms 1 mol of a dye by reduction of 4 mol of silver ions.

The color image forming material of the present invention is preferably added to an image recording layer. The color image-forming material of the present invention is generally used in an amount of 0.001 to 1 mol, preferably 0.01 to 0.5 mol, more preferably 0.02 mol per total silver amount of the image recording layer.
０．２0.2 mol is used.

The color image forming material used in the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethylformamide, dimethylsulfoxide. , Methyl cellosolve and the like. Alternatively, according to an already well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, oils 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, a powder of a coupler compound can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves and used.

The color image forming material is preferably fine particles solid-dispersed in water. A preferred addition method is
This is a method of adding fine particles of 0.01 μm to 10 μm, preferably 0.05 μm to 1 μm by solid dispersion, and adding them.

(2) Reducing Agent The reducing agent used in the present invention is preferably a compound represented by the following general formula (2).

[0049]

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In the general formula (2), Q ₁ represents an aromatic group bonded to NHNH-Q ₂ at a carbon atom or a 5- to 7-membered unsaturated ring group. As the unsaturated ring group, a group containing a 5- to 6-membered ring is preferable. Q ₁ represents a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring,
2,4-triazine ring, 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, 1,2,2
4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring,
A thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a thiophene ring, or a group containing a condensed ring formed by condensing these rings is preferable, and a benzene ring, a pyrimidine ring, a 1,2,3-triazole ring, , 2,4
-A triazole ring, a tetrazole ring, a 1,3,4-thiadiazole ring, a 1,2,4-thiadiazole ring,
3,4-oxadiazole ring, 1,2,4-oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, or these rings condensed with a benzene ring or an unsaturated heterocycle Are more preferred.

The aforementioned Q ₁ may have a substituent,
When it has two or more substituents, those substituents may be the same or different. Examples of the substituent on Q ₁ 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,
Examples include an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyl group. Among them, a cyano group, an alkylsulfonyl group, a carbamoyl group, and an arylsulfonyl group are more preferable. The Q
The substituent on ₁ may further have a substituent, such as a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryl group. An oxy group,
Alkylthio, arylthio, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, cyano, sulfamoyl, alkylsulfonyl, arylsulfonyl, or acyloxy are preferred, and halogen, alkylsulfonamide, cyano Groups are more preferred.

In the general formula (2), Q ₂ represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group, preferably a carbamoyl group, and a hydrogen atom on a nitrogen atom. Is particularly preferred.

When Q ₂ is a carbamoyl group, it preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. Examples thereof include an unsubstituted carbamoyl group, methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-sec-butylcarbamoyl group, N-octylcarbamoyl group, N-cyclohexylcarbamoyl group, N-tert- Butylcarbamoyl group, N-dodecylcarbamoyl group, N- (3-dodecyloxypropyl) carbamoyl group, N-octadecylcarbamoyl group, N- {3- (2,4-tert-pentylphenoxy) propyl} carbamoyl group, N- (2-
Hexyldecyl) carbamoyl group, N-phenylcarbamoyl group, N- (4-dodecyloxyphenyl) carbamoyl group, N- (2-chloro-5-dodecyloxycarbonylphenyl) carbamoyl group, N-naphthylcarbamoyl group, N-3 -Pyridylcarbamoyl group, N-benzylcarbamoyl group and the like.

When Q ₂ is an acyl group, it preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. Examples thereof include formyl group, acetyl group, 2-methylpropanoyl group, cyclohexylcarbonyl group, octanoyl group, 2-hexyldecanoyl group, dodecanoyl group,
Examples thereof include a chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and the like.

When Q ₂ is an alkoxycarbonyl group, it preferably has 2 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. Examples thereof include a methoxycarbonyl group,
Examples include an ethoxycarbonyl group, an isobutyloxycarbonyl group, a cyclohexyloxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, and the like.

When Q ₂ is an aryloxycarbonyl group, it preferably has 6 to 50 carbon atoms, and 6 to 40 carbon atoms.
Is more preferred. Examples thereof include a phenoxycarbonyl group, a 4-octyloxyphenoxycarbonyl group,
-Hydroxymethylphenoxycarbonyl group, 4-dodecyloxyphenoxycarbonyl group and the like.

When Q ₂ is a sulfonyl group, it preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms. Examples thereof include a methylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a 2-hexadecylsulfonyl group, a 3-dodecyloxypropylsulfonyl group, a 2-octyloxy-5-tert-octylphenylsulfonyl group, and a 4-dodecyloxy group. And a phenylsulfonyl group.

When Q ₂ is a sulfamoyl group,
The carbon number is preferably from 0 to 50, more preferably from 6 to 40. Examples thereof include an unsubstituted sulfamoyl group, N-
Ethylsulfamoyl group, N- (2-ethylhexyl)
Sulfamoyl group, N-decylsulfamoyl group, N-
Hexadecylsulfamoyl group, N- {3- (2-ethylhexyloxy) propyl} sulfamoyl group, N-
(2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl group, N- (2-tetradecyloxyphenyl) sulfamoyl group and the like.

The aforementioned Q ₂ may have a substituent,
When it has two or more substituents, those substituents may be the same or different. The substituent on Q ₂ is
It may be the same as the substituent on Q ₁ described above.

The reducing agents represented by the general formula (2) are described in JP-A-9-152702 and JP-A-8-28634.
No. 0, No. 9-152700, No. 9-1527
No. 01, No. 9-152703, No. 9-152
The compound can be synthesized according to the method described in JP-A-704-704. Hereinafter, specific examples (exemplary compounds D-101 to D-154) of the reducing agent represented by the general formula (2) are shown, but the present invention is not limited thereto.

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[0062]

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[0065]

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[0067]

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The reducing agent may be added to the image recording layer in any state, such as a solution, a powder, a dispersion of solid fine particles, an emulsion, and an oil protect dispersion, but is added as fine particles solid-dispersed in water. Is preferred. Dispersion of solid fine particles can be performed by a known fine means (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. The addition amount of the reducing agent can be selected from a wide range, but based on the total silver amount of the image recording layer,
Preferably it is 0.01 to 100 mole times, more preferably 0.1 to 10 mole times.

In the present invention, another reducing agent (hereinafter referred to as an auxiliary reducing agent) may be used in addition to the reducing agent represented by the general formula (2). The auxiliary reducing agent can be appropriately selected from those known as a reducing agent for an organic silver salt, and examples thereof include a photographic developer such as phenidone, hydroquinone, and catechol, and a hindered phenol reducing agent. In particular, polyhindered phenols having two or more hindered phenol groups can be preferably used. The auxiliary reducing agent is 1 mol of the above general formula (1)
Is preferably used in an amount of 0.1 to 100 mol%, more preferably 1 to 10 mol%, based on the reducing agent represented by

As the auxiliary reducing agent, JP-A-46-6
Nos. 074, 47-1238 and 47-33
No. 621, No. 49-46427, No. 49-1
Nos. 15540, 50-14334, 50
-36110, 50-147711, 51-32632, 51-103721, 51-32424, 51-51933, 52-84727, and 55-. 10865
No. 4, No. 56-146133, No. 57-82
828, 57-82829, and JP-A-6-62829.
No. 3,793, U.S. Pat. Nos. 3,667,9586, 3,679,426, and 3,751,2.
No. 52, 3,751, 255, 3,
761,270, 3,782,949, 3,839,048, 3,928,6
Nos. 86, 5,464, 738, German Patent 231,328, European Patent 692732, and the like can also be used.

Specifically, amide oxime (phenylamide oxime, 2-thienyl amide oxime, p-phenoxyphenyl amide oxime, etc.); azine (4-hydroxy-3,5-dimethoxybenzaldehyde azine, etc.); aliphatic carboxylic acid Combination of arylhydrazide and ascorbic acid (such as combination of 2,2'-bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid); Combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (Such as a combination of hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); hydroxamic acid (phenylhydroxamic acid, p-hydrido) Hydroxyphenyl hydroxamic acid,
combination of azine and sulfonamidophenol (phenothiazine and 2,2)
Α-cyanophenylacetic acid derivatives (such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate); bis-β-naphthol (2,2′-dihydroxy-1,1 ′
-Binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, etc.); bis-β-naphthol and 1,3-dihydroxybenzene Combinations of derivatives (such as 2,4-dihydroxybenzophenone, 2 ′, 4′-dihydroxyacetophenone); 5-pyrazolone (such as 3-methyl-1-phenyl-5-pyrazolone); reductone (dimethylaminohexose reductone, Hydrodihydroaminohexose reductone, anhydrodihydropiperidone hexose reductone, etc.); sulfonamide phenol reducing agents (2,6-dichloro-4-benzenesulfonamidophenol, p-benzenesulfonamidophenol, etc.); 2- Phenylindane-1,3-dione; chroman (2,2- Dimethyl-7-t-butyl-
1,4-dihydropyridine (2,6-dimethoxy-3,5-dicarbethoxy)
Bisphenol (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, 2,2-bis (3,
5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (1-ascorbyl palmitate, ascorbyl stearate, etc.); aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone; indane-1,3-dione; Chromanol (such as tocopherol) can be used.

The reducing agent represented by the general formula (2) may be added not only to the image recording layer but also to a protective layer and the like. The reducing agent may be a so-called precursor which is derivatized so as to function effectively only during development.

(3) Organic Silver Salt The organic silver salt used in the present invention is generally relatively stable to light, and can be used in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) or a reducing agent. When heated to about 80 ° C. or higher in the presence, a silver image is formed. The organic silver salt is not particularly limited as long as it is an organic substance containing a source capable of reducing silver ions, but is preferably a silver salt of an organic acid, and more preferably a silver salt of an organic compound having a carboxyl group. Also,
A complex of an organic or inorganic silver salt whose ligand has a complex stability constant of 4.0 to 10.0 can also be preferably used.

As the silver salt of the organic compound having a carboxyl group, a silver salt of an aliphatic carboxylic acid, a silver salt of an aromatic carboxylic acid and the like can be used. The silver aliphatic carboxylate is
Preferably it has 10 to 30 carbon atoms, more preferably 1 carbon atom
5-28. Preferred examples thereof include silver behenate, silver arachidate, silver stearate, silver oleate,
Examples thereof include silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

As the organic silver salt, a silver salt of a compound containing a mercapto group or a thione group and derivatives thereof can also be used. Preferred examples of such silver salts include silver salts of 3-mercapto-4-phenyl-1,2,4-triazole, silver salts of 2-mercaptobenzimidazole, and silver salts of 2-mercapto-5-aminothiadiazole. Silver salts of thioglycolic acid, such as silver salts of 2-, (ethyl glycolamido) benzothiazole, silver salts of S-alkylthioglycolic acid (the alkyl group preferably has 12 to 22 carbon atoms), silver salts of dithioacetic acid, etc. Silver salt of dithiocarboxylic acid, silver salt of thioamide, silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, U.S. Pat. No. 4,123,274 (for example, 3-amino-5-benzylthio-).
Silver salts of 1,2,4-mercaptothiazole derivatives such as silver salts of 1,2,4-thiazole), U.S. Pat.
And silver salts of thione compounds such as silver salt of 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione described in 1,678.

As the organic silver salt, a compound containing an imino group can be used. Preferred examples thereof include silver salts of benzotriazole and derivatives thereof, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, and US Pat. No. 4,220. , 7
No. 09, silver salts of 1,2,4-triazole or 1H-tetrazole, and silver salts of imidazole and imidazole derivatives. Also, U.S. Pat.
Silver acetylide compounds described in 1,361 and 4,775,613 can also be used.

The shape of the organic silver salt is not particularly limited, and may be various shapes such as a needle shape, a flake shape and a lump shape, but it is preferably a needle shape or a flake shape. The shape of the organic silver salt can be determined from a transmission electron microscope image or the like of the organic silver salt dispersion. In the case of a needle-shaped crystal, its size is from 0.01 to
Preferably, the major axis is 0.10 to 5.0 μm, the minor axis is 0.01 to 0.15 μm, and the major axis is 0.10 μm.
More preferably, it is 10 to 4.0 μm. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is preferably 100% of the value obtained by dividing the standard deviation of the length of each of the short axis and long axis by each of the short axis and long axis.
Or less, more preferably 80% or less, particularly preferably 50% or less.
% Or less. As another method for evaluating the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the standard deviation divided by the volume-weighted average diameter is preferably 100% (coefficient of variation). Is 100% or less, more preferably 80% or less, particularly preferably 50% or less.
It is as follows. The volume-weighted average diameter can be obtained, for example, by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light.

The organic silver salt is preferably used after desalting. The method for desalting is not particularly limited, and 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, an aqueous dispersion containing an organic silver salt which is an image forming medium and containing substantially no photosensitive silver salt is converted into a high-pressure, high-speed stream to be dispersed and reduced in pressure. It is preferable to use an organic silver salt solid dispersion having a small S / N and a small particle size and no aggregation. Usually, the obtained organic silver salt solid dispersion is mixed with a photosensitive silver salt aqueous solution to prepare a photosensitive image forming medium coating solution. When such a coating liquid is used, a heat-developable color image recording material having low haze, low fog and high sensitivity can be obtained. On the other hand, when a photosensitive silver salt is allowed to coexist with an organic silver salt during dispersion, fog increases and sensitivity is significantly reduced. When an organic solvent is used instead of water as the dispersion medium, haze increases, fog increases, and sensitivity tends to decrease. If a conversion method for converting a part of the organic silver salt in the dispersion liquid to the photosensitive silver salt is used instead of mixing the photosensitive silver salt aqueous solution, the sensitivity is reduced. The water content of the above aqueous dispersion is usually 0.1 mol% or less based on the non-photosensitive organic silver salt.

In the present invention, regarding the solid dispersion apparatus used to carry out the dispersion method as described above and the technology thereof, “Dispersion Rheology and Dispersion Technology” (Toshio Kajiuchi and Hiroki Usui, 1991, Nobuyama) Publishing Co., Ltd., 357-40
3), "Progress in Chemical Engineering, Vol. 24," edited by The Society of Chemical Engineers, Tokai Branch, 1990, Maki Shoten, 184-185
Page) and the like. In the present invention, at least an aqueous dispersion containing 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 apply a desired pressure. It is preferable to perform fine dispersion by rapidly reducing the pressure in the dispersion later.

In the above-mentioned dispersion method, generally, (a) “shearing force” generated when the dispersoid passes through a narrow gap at high pressure and high speed, and (b) when the dispersoid is released from high pressure to normal pressure. Dispersion into fine particles is performed by a dispersing force such as "cavitation force" generated in the process. In such a dispersion method, a dispersing device such as a Gaulin homogenizer is used in the old days. 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 a cylindrical surface, and the force is used. It collides with the surrounding wall, and is emulsified and dispersed by the impact force. At this time, the pressure is generally 1 to 6 MPa (100 to 600 k
g / cm ² ), and the flow rate is several m to 30 m / sec. There is also known a method of increasing the number of collisions by making the high flow velocity portion into a saw blade shape in order to increase the dispersion efficiency. Further, in recent years, devices capable of dispersing at high pressure and high flow rate, such as a microfluidizer (Microfluidics International Corporation) and a nanomizer (Special Kika Kogyo Co., Ltd.), have been developed. Can also be suitably used in the present invention.

A dispersion apparatus particularly suitable for the present invention is a microfluidizer M-110SE-E manufactured by Microfluidics International Corporation.
H (with G10Z interaction chamber), M
-110Y (with H10Z interaction chamber), M-140K (with G10Z interaction chamber), HC-5000 (L30Z or H230
With Z interaction chamber), HC-800
0 (with an E230Z or L30Z interaction chamber).

In the present invention, a desired particle size can be obtained by adjusting the flow rate, the pressure difference at the time of pressure drop, and the number of treatments in the dispersion of the organic silver salt. From the viewpoint of photographic characteristics and particle size, the flow velocity should be 200 to 600 m /
Second, the differential pressure at the time of pressure drop is 900 to 3000 kg / cm ²
The flow rate is preferably 300 to 600 m / sec, and the pressure difference at the time of pressure drop is more preferably 1500 to 3000 kg / cm ² . The number of treatments may be generally 1 to 10 times, but is preferably about 1 to 3 times from the viewpoint of productivity.

It is not preferable to raise the temperature of the aqueous dispersion under high pressure from the viewpoint of dispersibility and photographic characteristics. For example, at a high temperature exceeding 90 ° C., the particle size tends to increase, and the fog tends to increase. Therefore, in the present invention, a cooling step is performed before converting to a high pressure / high flow rate and / or after the pressure is reduced, and the temperature of the aqueous dispersion is set to 5 to 5.
Preferably, it is kept at 90 ° C. The temperature is more preferably 5
-80 ° C, particularly preferably 5-65 ° C. 1500
When dispersing under a high pressure of up to 3000 kg / cm ² , performing this cooling step is particularly effective. The cooler used in the cooling step is appropriately selected from a double pipe or a pipe using a static mixer for the double pipe, a multi-tube heat exchanger, a coiled pipe heat exchanger, etc., according to the required heat exchange amount. be able to. Further, in order to increase the efficiency of heat exchange, the thickness, wall thickness, material and the like of the tube of the cooler may be appropriately selected according to the working pressure. As the refrigerant used for the cooler, well water at 20 ° C, cold water at 5 to 10 ° C treated with a refrigerator, ethylene glycol / water at -30 ° C, or the like can be used.

The organic silver salt is preferably dispersed in the presence of an aqueous solvent-soluble dispersant (dispersion aid). Polyacrylic acid, a copolymer of acrylic acid,
Maleic acid copolymer, maleic acid monoester copolymer, synthetic anionic polymer such as acrylomethylpropanesulfonic acid copolymer, carboxymethyl starch, semi-synthetic anionic polymer such as carboxymethylcellulose,
Alginic acid, anionic polymers such as pectic acid, compounds described in JP-A-7-350753, known anionic, nonionic or cationic surfactants, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, Natural polymer compounds such as hydroxypropylmethylcellulose and gelatin can be used, and among them, polyvinyl alcohols and water-soluble cellulose derivatives are particularly preferable. The dispersing aid is generally mixed with a powdery or wet cake-like organic silver salt before dispersion and sent to a dispersing machine as a slurry.However, it is preliminarily mixed with the organic silver salt and treated with a heat treatment or a solvent. , Powder or wet cake. PH before and after dispersion or during dispersion using a pH adjuster
May be controlled. Alternatively, the particles may be roughly dispersed in a solvent by controlling the pH, and the pH may be changed in the presence of a dispersing agent to form fine particles. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and this organic solvent is usually removed after the completion of fine particle formation.

The prepared dispersion is stored with stirring to prevent sedimentation of the fine particles during storage, or stored in a highly viscous state by a hydrophilic colloid (for example, in a jelly state using gelatin). be able to. Further, a preservative may be added for the purpose of preventing germs and the like from growing during storage.

[0089] The amount of the organic silver salt, to the area of the image recording layer may preferably be 0.1 to 5.0 g / m ² as silver amount, 0.3~2.5g / m ² More preferably,

(4) Organic Binder The organic binder used in the present invention is preferably a hydrophobic thermoplastic organic polymer. The term `` thermoplastic '' as used herein is broader than the strict definition of thermoplasticity in physicochemical terms, and refers to the property of a polymer being softened or melted by the properties of the polymer when heated above a certain temperature. means. This is similar to the fact that "plastic" meaning a thermoplastic resin is practically used not only for linear polymers but also for three-dimensionally crosslinked rubber elastic polymers. Therefore, for example, an SBR polymer having rubber elasticity depending on the degree of cross-linking, which softens or melts when heated to a heat development temperature, forms a state in which transfer and diffusion of a substance is facilitated and a development reaction can occur, Can be used as an organic binder.

Specifically, the organic binder usually comprises a natural polymer, a synthetic resin polymer, a copolymer, and other film-forming media, such as hydrophobically modified gelatin, modified polyvinyl alcohol, and the like.
Cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl chloride, polyacrylates, polymethyl methacrylates, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-
Butadiene), polyvinyl acetals (eg, polyvinyl formal, polyvinyl butyral, etc.), polyesters, polyurethanes, phenoxy resins, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, polyamides and the like. The organic binder may be coated from a solution of water or an organic solvent, or an emulsion.

The organic binder preferably contains a polymer latex, particularly preferably a polymer latex dispersed in water. Since polymer latex can be applied without using an organic solvent, it has the advantage of not harming the organic solvent gas into the atmosphere when drying the coating film, or gasifying and scattering during thermal development. is there. The content of the polymer latex in the organic binder is preferably 50% by mass or more based on the whole organic binder. Further, the polymer latex may be added not only to the image recording layer but also to 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 preferable to use a polymer latex for the protective layer and the back layer. In the present invention, the “polymer latex” refers to a polymer in which a hydrophobic polymer insoluble in water is dispersed as fine particles in a water-soluble dispersion medium.

The above-mentioned polymer latex is obtained by emulsifying the above-mentioned hydrophobic polymer in a dispersion medium, emulsion-polymerized or micellar-dispersed one, and wherein the hydrophobic polymer has a partially hydrophilic structure and the molecular chain itself has a molecular structure. They may be dispersed. For polymer latex, see "Synthetic Resin Emulsion" (edited by Tadashi Okuda and Hiroshi Inagaki, published by the Polymer Publishing Association (1978)), "Application of Synthetic Latex" (edited by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Polymer) Published by the Japan Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex" (Souichi Muroi, published by the Society of Polymer Publishing (1970)).

In the polymer latex, the average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

The polymer latex may be an ordinary polymer latex having a uniform structure or a so-called core / shell type latex. In the latter case, it is preferable to change the glass transition temperature of the core and the shell as necessary.

In the present invention, the glass transition temperature (TG) of the polymer of the polymer latex used for the image recording layer
In order to promote the diffusion of useful photographic materials during thermal development,
The temperature is preferably 0 ° C. or lower, more preferably −30 to 40 ° C. The minimum film forming temperature (MFT) of the polymer latex is preferably from -30 to 90C, more preferably from 0 to 70C. A film-forming auxiliary (plasticizer) may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex.
970)).

Specific examples of the polymer used in the polymer latex include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. No. This polymer may be a linear polymer or a branched polymer,
Further, it may be 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. When it is a copolymer, it may be a random copolymer or a block copolymer. Examples of copolymers include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl Examples include methacrylate / vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like. These polymers may be used alone or as a mixture of two or more as necessary.

A commercially available polymer may be used as the polymer. Examples of the commercially available polymer include Sebian A46.
35, 46583 and 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 82
Acrylic resins such as 1, 820 and 857 (all manufactured by Nippon Zeon Co., Ltd.); FINITEX ES650, 611;
675 and 850 (all manufactured by Dainippon Ink and Chemicals, Inc.),
Polyester resins such as WD-size and WMS (all manufactured by Eastman Chemical); HYDRAN AP10;
20, 30, and 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
Polyurethane resin such as LACSTAR 7310K;
3307B, 4700H and 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.); Nipol Lx416, 41
0, 438C and 2507 (all manufactured by Nippon Zeon Co., Ltd.)
Rubber resins such as G351 and G576 (all manufactured by Zeon Corporation); L502 and L51
3 (all manufactured by Asahi Kasei Corporation), Aron D7020, D
Vinylidene chloride resins such as 504 and D5071 (all manufactured by Mitsui Toatsu Co., Ltd.); Chemipearl S120 and SA100
(Above, manufactured by Mitsui Petrochemical Co., Ltd.).

The number average molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 1,000.
0 to 100,000. When the number average molecular weight is less than 5,000, the mechanical strength of the image recording layer is insufficient, and
If it exceeds 0000, the film-forming properties are poor, which is not preferable.

The amount of the organic binder is preferably from 0.2 to 30 g / m ² , more preferably from 1 to 15 g / m ² , based on the area of the image recording layer.

(5) Halogen Precursor The heat-developable color image recording material of the present invention preferably contains a halogen precursor. The halogen precursor used in the present invention is a compound capable of releasing a halogen by heat, light or the like. The halogen precursor is preferably an organic polyhalogen compound having two or more halogen atoms on the same carbon atom.
JP-A-119624, JP-A-50-120328,
Nos. 51-121332, 54-58022, 56-70543, 56-99335, 59-90842, and 61-12964.
No. 2, JP-A-62-129845, and JP-A-6-2
08191, 6-208193, 7-
Nos. 5621, 7-2781, 8-158
09, U.S. Pat. No. 5,340,712,
5,369,000 and 5,464,737
And those disclosed in the specification. Two or more halogen precursors may be used in combination. The halogen precursor is preferably represented by the following general formula (H).

[0102]

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In the general formula (H), Q represents an aryl group or a heterocyclic group. When the Q is an aryl group, the number of carbon atoms is preferably from 6 to 30, more preferably from 6 to 20. The aryl group may be a single ring or form a condensed ring. Specific examples include a phenyl group and a naphthyl group, and a phenyl group is preferable.

When Q is a heterocyclic group, N, O,
Alternatively, it is preferable to have a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one S atom. The hetero ring may be a single ring or may form a condensed ring with another ring. Specific examples of the heterocyclic group include thienyl, furyl, pyrrolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinidyl, isoindolinidyl, 3H-indolyl, indolyl 1, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, β-carbonylyl group, phenanthridinyl Group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, fenaldazinyl group, phenothiazinyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazo Dinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, triazolyl group, tetrazolyl group, thiadiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group Group, benzotriazolyl group, triazinyl group, uracil group, triazopyrimidinyl group and the like. Among them, a thienyl group, a pyridyl group, an isoquinolyl group, a quinolyl group, a triazolyl group, a benzimidazolyl group, and a benzthiazolyl group are preferable.

The above Q is -SO ₂ -C (Z ¹ ) (Z ² )-
It may have a substituent other than the A group. The substituent may be any group as long as it does not adversely affect photographic performance. Examples thereof include a linear, branched, or cyclic alkyl group or a combination thereof (preferably having 1 carbon atom).
-20, more preferably 1-12, particularly preferably 1-4, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl,
a tert-amyl group, a cyclohexyl group, etc., an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, for example, a vinyl group, an allyl group, Butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, a propargyl group, a 3-pentynyl group and the like, and an aryl group (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms). , Particularly preferably a carbon number of 6 to
12, for example, a phenyl group, a p-methylphenyl group, a naphthyl group, etc.) and an amino group (preferably having 0 to 0 carbon atoms).
20, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, etc., and an alkoxy group (preferably Number 1-2
0, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methoxy group, an ethoxy group, a butoxy group, etc., and an aryloxy group (preferably 6 carbon atoms).
-20, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms.
-Naphthyloxy group, etc.), acyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, for example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group Etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group), and an aryloxycarbonyl group (Preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as a phenoxycarbonyl group), an acyloxy group (preferably having 1 to 2 carbon atoms).
0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetoxy group, benzoyloxy group and the like, acylamino group (preferably 1 to carbon atom)
20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetylamino group, benzoylamino group and the like, alkoxycarbonylamino group (preferably 2 to 20 carbon atoms, more preferably Number 2
To 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group, and an aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably carbon atoms). 7-12
And a sulfonylamino group (preferably having 1 to 2 carbon atoms).
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, a methanesulfonylamino group, a benzenesulfonylamino group and the like, a sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably A number of 0 to 16, particularly preferably a carbon number of 0 to 12, for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.),
A carbamoyl group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 16 carbon atoms, and particularly preferably having 0 to 12 carbon atoms;
And, for example, a carbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group and the like, a ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms,
Particularly preferably, it has 1 to 12 carbon atoms, for example, a ureido group, a methylureide group, a phenylureido group, etc., and an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon number). 1-12, for example, a methylthio group, an ethylthio group, etc.), an arylthio group (preferably having 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms,
A phenylthio group, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, for example, a mesyl group, a benzenesulfonyl group, a tosyl group, etc.), Sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 carbon atom
To 16, particularly preferably having 1 to 12 carbon atoms, such as a methanesulfinyl group and a benzenesulfinyl group),
Phosphoric acid amide group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms)
For example, a diethylphosphoramide group, a phenylphosphoramide group, etc.), a hydroxyl group, a mercapto group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, a sulfo group or a salt thereof, Carboxyl group or a salt thereof, nitro group, hydroxam group, sulfino group, hydrazino group, sulfonylthio group, thiosulfonyl group, heterocyclic group (for example, imidazolyl group, pyridyl group,
Furyl group, piperidyl group, morpholinyl group, etc.), disulfide group, polyethyleneoxy group, quaternary ammonium group and the like. These may be further substituted.

In the formula (H), Z ¹ and Z ² each independently represent a halogen atom, preferably a bromine atom. In the general formula (H), A represents a hydrogen atom or an electron-withdrawing group, preferably a hydrogen atom or a bromine atom, and particularly preferably a bromine atom.

Specific examples (exemplary compounds H-1 to H-39) of the halogen precursor which can be preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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The halogen precursor used in the present invention is
It may be dissolved in water or a suitable organic solvent, added to the coating solution, dried, and allowed to exist in a microcrystalline state in the film. Organic solvents include alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like.
Further, according to an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, and diethyl phthalate, and an ethyl acetate, an auxiliary solvent such as cyclohexanone, and the halogen precursor are dissolved, An emulsified dispersion may be prepared and used. Alternatively, using a known dispersing machine such as a ball mill, a colloid mill, or a sand mill, or a dispersing machine using ultrasonic waves, using a dispersing medium such as glass beads, zirconia beads, zircon silicate beads, etc., and converting the halogen precursor into water or the like. It may be dispersed in a suitable solvent to form a fine solid dispersion and added to the coating solution.

The halogen precursor is preferably added as fine particles solid-dispersed in water. If a fine solid dispersion is prepared and added in advance, it can be stably added with a uniform particle size, so that aggregation does not occur in the coating solution and performance does not fluctuate. When an aqueous dispersion of a thermoplastic resin is used as a binder, it is particularly preferable to add it as a solid dispersion. The average particle size of the halogen precursor particles in the solid dispersion is preferably 0.05 to 5 μm, and more preferably 0.1 to 5 μm.
1 to 1 μm.

The halogen precursor may be added not only to the image recording layer but also to an intermediate layer and a protective layer described later.

[0116] The amount of the halogen precursor may be appropriately selected according to the property such as sensitivity and fog, is preferably from 10 ^-4 to 1 mol of the organic silver salt to 1 mole of the image recording layer, 10 ^{- 3} to 5 × 10 ^-1 mol is more preferable.

(6) Photosensitive silver halide In the present invention, the image recording layer preferably contains photosensitive silver halide. The photosensitive silver halide used in the present invention is not particularly limited, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide and the like can be used. When the photosensitive silver halide grains are used, the distribution of the halogen composition in the grains may be uniform or may be changed stepwise or continuously. Further, photosensitive silver halide grains having a core / shell structure can be preferably used. In this case, the structure of the particles is preferably a 2- to 5-fold structure, and more preferably a 2- to 4-fold structure. It is also preferable to localize silver bromide on the surface of silver chloride or silver chlorobromide grains.

The method for forming the photosensitive silver halide is described in Research Disclosure, June 1978, June,
No. 17029 and U.S. Pat. No. 3,700,458. Specifically, a method of adding a halogen-containing compound to the prepared organic silver salt to convert a part of the silver of the organic silver salt into photosensitive silver halide, a silver supply compound in gelatin or other polymer solution. And a method of preparing a photosensitive silver halide grain by adding a halogen-supplying compound and mixing with an organic silver salt. In the present invention, the latter method is preferably used.

The shape of the photosensitive silver halide grains may be cubic, octahedral, tabular, spherical, rod-like, potato-like, or the like, but is preferably cubic or tabular. . Also, photosensitive silver halide grains having rounded corners can be preferably used. When the tabular photosensitive silver halide grains are used, the average aspect ratio is preferably from 100: 1 to 2: 1, more preferably from 50: 1 to 3: 1. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited, and it is preferable that the {100} plane occupying a high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed is high. The ratio is preferably 50% or more, more preferably 65% or more, and particularly preferably 80% or more.

In order to keep the cloudiness after image formation low,
The grain size of the photosensitive silver halide is preferably 0.2
0 μm or less, more preferably 0.01 to 0.15 μm,
Particularly preferably, the thickness is 0.02 to 0.12 μm. In addition,
Here, the `` grain size '' refers to the length of the edge of the photosensitive silver halide grains when the grains are cubic or octahedral so-called normal crystals, and when the silver halide grains are tabular grains. Means the diameter when converted into a circular image having the same area as the projected area of the main surface. In addition, in the case of non-normal crystals, for example, in the case of spherical particles, rod-shaped particles, etc., it refers to the diameter of a sphere equivalent to the volume of the photosensitive silver halide particles.

Photosensitive silver halide grains used in the present invention
Contains a metal of Group VII or VIII of the Periodic Table
Is preferred. Among these metals, rhodium,
Rhenium, ruthenium, osmium and iridium are preferred.
Good. These may be used alone or in combination of two or more.
You may use together. The metal is a metal compound or metal complex, or
Is a photosensitive halide as a metal salt in the form of a single salt, a double salt or a complex salt.
May be added to silver halide grains. Photosensitive halogenation of the metal
The amount of silver used per mole of silver is preferably 10 ^-9~ 1
0^-2Mole, more preferably 10^-8-10^-FourIs a mole.
A metal complex containing a metal as described above is disclosed in JP-A-7-225.
No. 449, for example. Also rhenium, lute
And osmium are added in the form of water-soluble complex salts
Preferably, the water-soluble complex salt is described in JP-A-63-2
042, JP-A-1-285941, JP-A-2-285941
Nos. 20852, 2-20855, etc.
Have been. The ruthenium is a hexacyano metal complex
It is preferred to add. The rhodium is a water-soluble rhodium
It is preferably added as a compound.
Rhodium (III) compound, halogenated as ligand
Rhodium complex salt containing amines, amines, oxalato, etc.
Sachlororhodium (III) complex salt, pentachloroacolodi
(III) complex salt, tetrachlorodiachodium (III)
Complex salt, hexabromorhodium (III) complex salt, hexaan
Minrhodium (III) complex salt, trizalatrodium (III)
Complex salts). Exposure of these rhodium compounds
The amount of the neutral silver halide used per mole of silver is preferably
Is 1 × 10^-8~ 5 × 10^-6Mole, more preferably 5 × 1
0^-8Mol ~ 1 x 10^-6Is a mole.

The photosensitive silver halide is cobalt,
It may contain metal atoms such as iron, nickel, chromium, palladium, platinum, gold, thallium, copper and lead. These metals can be added as a metal compound or a metal complex, or a metal salt in the form of a single salt, a double salt or a complex salt when preparing the photosensitive silver halide grains. The cobalt, iron, and chromium are preferably contained as a hexacyano metal complex.
Specific examples thereof include a ferricyanate ion, a ferrocyanate ion, a hexacyanocobaltate ion, a complex containing a hexacyanochromate ion or a hexacyanoruthenate ion, and the like. These metals are preferably used in an amount of 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of the photosensitive silver halide.

The above-mentioned metal may be contained uniformly in the photosensitive silver halide, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration.

The light-sensitive silver halide may be prepared by a noodle method,
Desalting may be performed by a flocculation method or the like.

The photosensitive silver halide is preferably used after being 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, and sulfur sensitization It is preferable to combine sensitization, selenium sensitization, tellurium sensitization, gold sensitization and the like. The conditions for the chemical sensitization are not particularly limited, but the pH is preferably 5 to 8, and the pAg is preferably 6 to 11, and more preferably 7 to 10. The temperature is preferably from 40 to 95 ° C, more preferably from 45 to 85 ° C. The amounts of the selenium sensitizer and the tellurium sensitizer used in the selenium sensitization method and the tellurium sensitization method can be appropriately selected according to photosensitive silver halide grains, chemical ripening conditions, and the like. It can be used in an amount of about 10 ^-8 to 10 ^-2 mol, preferably about 10 ^-7 to 10 ^-3 mol, per 1 mol. Examples of the noble metal sensitizer used in the noble metal sensitization method include a gold sensitizer, a platinum sensitizer, a palladium sensitizer, and an iridium sensitizer. Among them, a gold sensitizer is particularly preferable. Specific examples of the gold sensitizer include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide. Gold sensitizer is generally silver halide 1
About 10 ^-7 to 10 ^-2 mol can be used per mol.

The photosensitive silver halide may be used after reduction sensitization. Specific examples of compounds used for reduction sensitization include ascorbic acid, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, and polyamine compounds. In addition, the pH of the photosensitive silver halide emulsion
The reduction sensitization can be achieved by maintaining the pAg at 7 or more, or keeping the pAg at 8.3 or less for ripening. Furthermore, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

Cadmium salts, sulfites, lead salts, thallium salts and the like may be allowed to coexist with the photosensitive silver halide during the formation or physical ripening of silver halide grains. Further, a thiosulfonic acid compound may be added by a method described in European Patent Publication No. EP293,917.

In the present invention, the photosensitive silver halide may be used alone or in combination of two or more (for example, those having different average grain sizes, those having different halogen compositions,
Those having different crystal habits or different chemical sensitization conditions) may be used in combination. The amount of the photosensitive silver halide used is:
0.1-100 mol% is preferable with respect to the organic silver salt,
0.5 to 50 mol% is more preferable, and 1.0 to 30 mol% is particularly preferable.

(7) Development Accelerator The heat-developable color image recording material of the present invention accelerates development, which is conventionally called a "toning agent" in the field of a heat-developable image recording system called a dry silver system. (Development accelerator) is preferred. The development accelerator is added to the layer on the side of the support having the image recording layer, preferably in an amount of 0.1 to 50 mol%, more preferably 0.5 to 20 mol%, per mol of silver. Further, such a development accelerator may be added as a precursor which is derivatized so as to have a function effectively only during development. The development accelerator is
JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, JP-A-49-5020, JP-A-49-91215, JP-A-50-2524, and JP-A-50-32927. No. 50-67132, No. 50-67641, No. 50-11421
No. 7, No. 51-3223, No. 51-2792
No. 3, No. 52-14788, No. 52-998
No. 13, No. 53-1020, No. 53-760
No. 20, No. 54-156524, No. 54-1
Nos. 56525, 61-183642, JP-A-4-56848, JP-B-49-10727, JP-A-54-20333, U.S. Pat.
0,254, 3,446,648, 3,782,941, 4,12
No. 3,282, 4,510,236, British Patent No. 1,380,795, Belgian Patent No. 841,910 and the like are disclosed as toning agents.

Specific examples of the development accelerator include phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, Cyclic imides such as 2,4-thiazolidinedione; naphthalimides such as N-hydroxy-1,8-naphthalimide; cobalt complexes such as cobalt hexamine trifluoroacetate; 3-mercapto-1,2,4
-Triazole, 2,4-dimercaptopyrimidine, 3
Mercaptans such as -mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; (N, N-dimethylaminomethyl) phthalimide, N, N- ( N such as dimethylaminomethyl) -naphthalene-2,3-dicarboximide
-(Aminomethyl) aryldicarboximide; photobleaching agents such as blocked pyrazoles and isothiuronium derivatives (N, N'-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3, 6-
Diazaoctane) bis (isothiuronium trifluoroacetate), 2- (tribromomethylsulfonyl)-
Benzothiazole and the like); 3-ethyl-5-[(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-2,4-oxazolidinedione; 4- (1
-Naphthyl) phthalazinone, 6-chlorophthalazinone,
5,7-dimethoxyphthalazinone, 2,3-dihydro-
1,4-phthalazine dione. Phthalazinone such as a derivative thereof and a derivative thereof or a metal salt; a combination of phthalazinone and a phthalic acid derivative (phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, tetrachlorophthalic anhydride, etc.); 4- (1-naphthyl) Phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-isopropylphthalazine, 6-isobutylphthalazine, 6-t
phthalazine such as tert-butylphthalazine, 5,7-dimethylphthalazine, 2,3-dihydrophthalazine and derivatives or metal salts thereof; phthalazine or its derivatives and phthalic acid derivatives (phthalic acid, 4-methylphthalic acid, Nitrophthalic acid, tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine and naphthoxazine derivatives; Rhodium complex which functions not only as a regulator but also as a halide ion source for silver halide formation; inorganic peroxides and persulfates such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine- 2,4-dione, 8-
Methyl-1,3-benzoxazine-2,4-dione,
Benzoxazine-2,4-dione such as 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric triazine such as 2,4-dihydroxypyrimidine and 2-hydroxy-4-aminopyrimidine; 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,
3a, 5,6a-tetraazapentalene, 1,4-di (o-chlorophenyl) -3,6-dimercapto-1
Examples include azauracil and tetraazapentalene derivatives such as H, 4H-2,3a, 5,6a-tetraazapentalene.

The above-mentioned development accelerator is preferably added as an aqueous solution, but when it is insoluble in water, it may be added in any state, such as a methanol solution, powder, or solid fine particle dispersion. The dispersion of the solid fine particles can be carried out by a known finely-refining means (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.

(8) Layer Structure The heat-developable color image recording material of the present invention may have a plurality of image recording layers. Yellow, magenta and cyan 3
In order to obtain a wide range of colors on the chromaticity diagram using the primary colors, it is preferable to use a combination of at least three image recording layers containing silver halide having photosensitivity in different spectral regions. Examples of this combination include 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 image recording layer can adopt various arrangement orders known for ordinary color light-sensitive materials.

The heat-developable color image recording material of the present invention has at least one image recording layer containing a plurality of silver halides having substantially the same color sensitivity but different sensitivities on a support. May be. In this case, the image recording layer is blue light,
It has color sensitivity to either green light or red light.

In the case where a plurality of image recording layers are used, the order of installation is not particularly limited. When the heat-developable color image recording material of the present invention is used as a multicolor heat-developable color image recording material, generally, the image recording layer is arranged in order from the support side in a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. Install in order. The color-sensitive layers may be provided in the reverse order, or the order in which different color-sensitive layers are sandwiched between the same color-sensitive layers is also possible. A non-photosensitive layer may be provided between the image recording layers, above the uppermost layer or below the lowermost layer. The non-photosensitive layer is a coupler, a reducing agent, D
It may contain IR compounds, color mixture inhibitors, dyes and the like. Also,
As described in German Patent No. 1,121,470 and British Patent No. 923,045, two layers of a high-sensitivity image recording layer and a low-sensitivity image recording layer are sequentially formed on a support. It is preferable to arrange them so that the sensitivity is low. JP-A-57-112751, JP-A-62-20
As described in JP-A Nos. 0350, 62-206541 and 62-206543, a low-sensitivity image recording layer is provided on a side away from the support, and a high-sensitivity image recording layer is provided on the side near the support. An image recording layer may be provided. Specifically, from the side farthest from the support, the low-sensitivity blue-sensitive layer (B
L) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer ( RL), BH / B
L / GL / GH / RH / RL, BH / BL / GH /
They can be installed in the order of GL / RL / RH. As described in JP-B-55-34932, a blue-sensitive layer / GH / RH / GL / R is used from the side far from the support.
They can be arranged in the order of L. Japanese Patent Application Laid-Open No. 56-25 / 1981
As described in JP-A-738 and JP-A-62-63936, the blue-sensitive layer / G
They may be arranged in the order of L / RL / GH / RH.

As described in JP-B-49-15495, a structure in which three image recording layers having different sensitivities are used, and these are arranged so that the sensitivities are successively reduced toward the support. Is also possible. That is, the upper layer can be an image recording layer having the highest sensitivity, the middle layer can be an image recording layer having a lower sensitivity, and the lower layer can be an image recording layer having a lower sensitivity than the middle layer. 3
When an image recording layer of two layers is used, JP-A-59-20246
As described in Japanese Patent Application Laid-Open No. 4 (1999) -2004, the medium-sensitivity image recording layer / the high-sensitivity image recording layer / the low-sensitivity image recording layer may be arranged in this order from the side away from the support. In addition, a high-sensitivity image recording layer / low-sensitivity image recording layer / medium-sensitivity image recording layer, or a low-sensitivity image recording layer / medium-sensitivity image recording layer / high-sensitivity image recording layer may be arranged in this order. When four or more image recording layers are used, the order of installation can be similarly selected.

In order to improve the color reproducibility of the heat-developable color image recording material, US Pat. Nos. 4,663,271, 4,705,744, and 4,707,4
As described in JP-A-36-160, JP-A-62-160448 and JP-A-63-89850, B
It is preferable that a donor layer (CL) having a spectral sensitivity distribution different from that of the image recording layer such as L, GL, and RL is disposed adjacent to or close to the image recording layer.

In the present invention, in the image recording layer, the photosensitive silver halide, the color image forming material and the reducing agent may be contained in the same layer, but they are contained in different layers as long as they can react. It may be. For example, when a layer containing a reducing agent and a layer containing photosensitive silver halide are separately provided, the raw storage stability of the heat-developable color image recording material can be improved.

The relationship between the spectral sensitivity of each layer and the hue of the color image forming material is arbitrary. When a color image forming material is used, a natural multicolor image can be obtained by ordinary light exposure.

In the present invention, a plurality of image recording layers are
Spectral sensitization can be performed in various wavelength regions such as blue, green, red, and near infrared. It is not always necessary to make the light-absorbing characteristics of the photosensitive region and the color-forming dye correspond to each other. Various layer configurations can be designed as needed, such as a two-color, three-color or four-color coloring system. These multiple layers may be applied sequentially or simultaneously.

(9) Additives The image recording layer in the invention may contain the additives described below. These additives may be added to a layer other than the image recording layer, for example, an intermediate layer or a protective layer.

(A) Dispersion Stabilizer The image recording layer in the invention preferably contains a dispersion stabilizer. Usually, the dispersion stabilizer is added at the time of preparing a dispersion, and is additionally added at the time of preparing a coating solution. As the dispersion stabilizer, a hydrophilic polymer can be used. Preferred examples of the hydrophilic polymer include polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and hydroxypropyl methyl cellulose. The amount of the hydrophilic polymer to be added is preferably 30% by mass or less, more preferably 10% by mass or less, based on all binders in the image recording layer. Although the lower limit of the amount is not particularly limited, it is usually 0.1% by mass.
It is about.

A surfactant may be used as the dispersion stabilizer. The amount of the surfactant to be added is preferably 5% by mass or less, more preferably 2% by mass or less, based on all binders in the image recording layer. Although the lower limit of the addition amount is not particularly limited, it is usually about 0.1% by mass. Specific examples of the surfactant that can be used as the dispersion stabilizer are shown below, but the present invention is not limited thereto.

[0143]

Embedded image

(B) Crosslinking Agent and Surfactant for Improving Coatability The image recording layer in the invention may contain a crosslinker for crosslinking, a surfactant for improving coatability, and the like. The surfactant may be any of a nonionic surfactant, an anionic surfactant, a fluorine-based surfactant and the like. Specifically, fluorinated polymer surfactants described in JP-A-62-170950, U.S. Pat. No. 5,380,644, etc., JP-A-60-244945 and JP-A-63-244945. No. 188135, a fluorine-based surfactant described in U.S. Pat. No. 3,885,965, a polysiloxane-based surfactant described in JP-A-6-301140, and the like. An anionic surfactant or the like can be used.

(C) Fluorinated Surfactant It is preferred to add a fluorinated surfactant to the image recording layer in the present invention, since good antistatic properties can be obtained. Examples of preferred fluorine-containing surfactants include 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 group, sulfate group, A carboxylic acid group, a phosphoric acid group, a salt derived therefrom, etc.), a cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt, etc.), a betaine group (carboxyamine salt, carboxyammonium salt, A surfactant having a sulfoamine salt, a sulfoammonium salt, a phosphoammonium salt, or the like or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group, sorbitan residue, or the like) is included. About the fluorine-containing surfactant,
JP-A-49-10722, British Patent No. 1,33
No. 0,356, U.S. Pat. No. 4,335,201, U.S. Pat. No. 4,347,308, British Patent No. 1,417,915, JP-A-55-14993.
No. 8, No. 58-196544, and British Patent No. 1,439,402.

The fluorine-containing surfactants may be used as a mixture of two or more kinds. The amount of the fluorinated surfactant to be used is preferably 0.0001 to 1 g, more preferably 0.0002 to 0.25 g, per m ^{2 of} the image recording material.
0.0003 to 0.1 g is particularly preferred.

(D) Light Absorbing Substance and Filter Dye In the image recording layer of the present invention, US Pat. No. 3,253,921 and US Pat. Specification, No. 5,527,583
And light-absorbing substances and filter dyes as described in US Pat. No. 2,956,879. No. 3,282,69.
The dye can be mordanted as described in US Pat. The amount of the filter dye used is selected such that the absorbance at the exposure wavelength is preferably 0.1 to 3, more preferably 0.2 to 1.5.

(E) Dyes and Pigments Various dyes and pigments may be added to the image recording layer of the invention for the purpose of improving color tone and preventing radiation.
These dyes and pigments are not particularly limited, and for example, those described in Color Index can be used, and specific examples thereof include pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, carbocyanine dyes, and styryl dyes. And organic pigments such as triphenylmethane dyes, indoaniline dyes, indophenol dyes, and phthalocyanines, and inorganic pigments. Among them, anthraquinone dyes (Japanese Unexamined Patent Publication No.
Compounds 1 to 9 described in JP-A-41441, JP-A-5-1
Compounds 3-6 to 18 and 3- described in No. 65147
23-38 etc.), azomethine dyes (JP-A-5-3414)
Nos. 41 to 47 described in JP-A No. 41, and indaniline dyes (Compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441, and JP-A-5-165147). And azo dyes (JP-A-5-34).
Compounds 10 to 16) described in No. 1441 can be preferably used.

The amounts of the dyes and pigments to be used may be selected according to the desired absorption amount.
¹ μg to 1 g per ² is preferred. The dye and pigment may be added in any state, such as a solution, an emulsion, a solid fine particle dispersion, and a mordant in a high-molecular mordant. It is preferable to add a water-insoluble substance as a solid fine particle dispersion using water as a dispersion medium.

(F) Sensitizing dye A sensitizing dye may be used in the image recording layer in the invention. When the sensitizing dye is adsorbed on the photosensitive silver halide grains,
Any material can be used as long as it can spectrally sensitize photosensitive silver halide grains in a desired wavelength region, and a cyanine dye, a merocyanine dye, a complex cyanine dye,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. RES
EARCH DISCLOSUREItem17643
Section IVA (December 1978, p. 23), Item 1
Sensitizing dyes described in section 831X (August 1979, page 437) and references cited therein can also be preferably used in the present invention. In particular, various laser imagers,
It is preferable to select a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of a light source such as a scanner, an image setter, and a plate making camera.

Examples of sensitizing dyes used for spectral sensitization of red light by a so-called red light source such as a He-Ne laser, a red semiconductor laser, and an LED are described in JP-A-54-187.
No. 26, compounds I-1 to I-38,
Compounds I-1 to I-35 described in -75322,
Compounds 1-1 to 1 described in JP-A-7-287338.
I-34, Dyes 1 to 20 described in JP-B-55-39818, compounds I-1 to I-37 described in JP-A-62-284343, and compounds described in JP-A-7-287338. I-1 to I-34 and the like.

Examples of sensitizing dyes used for spectral sensitization of light with a semiconductor laser light source in the wavelength range of 750 to 1400 nm include cyanine dyes, merocyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, xanthene dyes and the like. Various known dyes can be used. Among cyanine dyes, thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus,
Those having a basic nucleus such as a thiazole nucleus, a selenazole nucleus, and an imidazole nucleus can be preferably used. Of the merocyanine dyes, those having an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus, and a pyrazolone nucleus in addition to the basic nucleus are preferably used. it can. In the present invention, it is particularly preferable that the cyanine dye and the merocyanine dye have an imino group or a carboxyl group. Such dyes are described in U.S. Pat. Nos. 3,761,279 and 3,719,
No. 495, 3,877,943, British Patent No. 1,466,201, No. 1,46.
Nos. 9,117, 1,422,057, JP-B-3-10391, JP-A-6-52387, JP-A-5-341432, and JP-A-6-1947.
No. 81 and 6-301141.

Examples of sensitizing dyes that can be particularly preferably used in the present invention include cyanine dyes having a thioether bond-containing substituent (JP-A-62-58239, JP-A-3-13838, and JP-A-3-138642). ,
JP-A-4-255840, JP-A-5-72659,
JP-A-5-72661, JP-A-6-222491,
JP-A-2-230506, JP-A-6-258775, JP-A-6-317868, JP-A-6-324425, JP-T-7-500926 and U.S. Pat. No. 5,541,054. Dyes having a carboxylic acid group (JP-A-3-163440,
6-301141 and U.S. Pat.
899, etc.); merocyanine dyes,
Polynuclear merocyanine dyes and polynuclear cyanine dyes (Japanese Unexamined Patent Application Publication No.
Nos. 7-6329, 49-105524, 51-127719, 52-80829, 54-61517, and 59-21846.
Gazette, JP-A-60-6750, and 63-15984
No. 1, JP-A-6-35109, and JP-A-6-593
No. 81, No. 7-146537, No. 7-146
No. 537, British Patent No. 1,467,638 and U.S. Pat. No. 5,281,515). Also, dyes forming J-band (US Pat. Nos. 5,510,236, 3,871,887, JP-A-2-96131, JP-A-59-48753, etc.) ) Can also be preferably used in the present invention.

The sensitizing dyes may be used alone or in combination of two or more. The combination of sensitizing dyes
Particularly, it is often used for supersensitization. That is, together with the sensitizing dye, a dye having no spectral sensitizing action itself,
Alternatively, a substance which does not substantially absorb visible light and exhibits supersensitization may be used. For such combinations and dyes or supersensitizers used with sensitizing dyes, Research Disclosur
e 176, 17643, page 23, IV, J (1
Published in December 978), JP-B-49-25500, JP-B-43-4933, and JP-A-59-19032.
And JP-A-59-192242.

The sensitizing dye may be directly dispersed in the image recording layer, or may be water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,
3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2
-Propanol, N, N-dimethylformamide, a mixed solvent thereof or the like may be added after being dissolved.

[0156] The amount of the sensitizing dye may be desired amount depending on the performance of such sensitivity and fogging, image recording layer (photosensitive layer) The photosensitive silver halide per mole of 10 ^-6 in 1
Mole is preferable, and 10 ^-4 to 10 ^-1 mole is more preferable.

(G) Antifoggant, stabilizer and stabilizer precursor In the present invention, the formation of fog can be further suppressed by adding an antifoggant, stabilizer or stabilizer precursor to the image recording layer. This makes it possible to stabilize the heat-developable color image recording material and suppress a decrease in sensitivity during storage in inventory. Antifoggants, stabilizers and stabilizer precursors may be used alone or in combination, examples of which are described in U.S. Pat. Nos. 2,131,038 and 2,694, No. 716; 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; Oximes, nitrones and nitroindazoles described in GB 623,448; polyvalent metal salts described in U.S. Pat. No. 2,839,405; U.S. Pat. No. 3,220,839. Palladium, platinum and gold salts described in U.S. Pat. Nos. 2,566,263 and 2,597,915; U.S. Pat. No. 4,108,6
Halogen-substituted organic compounds described in US Pat. Nos. 65,652 and 4,442,202; US Pat. No. 4,128,5.
No. 57, No. 4,137,079, No. 4,
138,365 and 4,459,350 triazines; and US Pat. No. 4,41.
The phosphorus compounds described in the specification of Japanese Patent No. 1,985 are exemplified.

(H) Mercapto compound, disulfide compound and thione compound The image recording layer in the present invention controls the development by suppressing or accelerating the development, improves the spectral sensitization efficiency, and has the preservability before and after the development. A mercapto compound, a disulfide compound, or a thione compound may be added for the purpose of improvement. The mercapto compound is A
Those represented by r-SM or Ar-SS-Ar are preferred. Here, M represents a hydrogen atom or an alkali metal atom. Ar represents a group containing an aromatic ring or a condensed aromatic ring having at least one nitrogen atom, sulfur atom, oxygen atom, selenium atom or tellurium atom. Ar is preferably a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring, a naphthoxazole ring, a benzoselenazole ring, a benzotellurazole ring, an imidazole ring, an oxazole ring, a pyrazole ring, or a triazole ring. , Thiadiazole ring, tetrazole ring, triazine ring, pyrimidine ring,
It contains a pyridazine ring, a pyrazine ring, a pyridine ring, a purine ring, a quinoline ring or a quinazolinone ring. These rings include a halogen atom (Br, C1, etc.), a hydroxyl group, an amino group, a carboxyl group, an alkyl group (preferably having 1 to 4 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms). It may have a substituent selected from the group consisting of those having an atom) and an aryl group (which may further have a substituent). Specific examples of the mercapto 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 invention is not limited thereto. .
The amount of these mercapto compounds to be used is preferably 0.0001 to 1.0 mol, more preferably 0.001 to 0.3 mol, per 1 mol of silver in the image recording layer.

(I) Plasticizer Polyhydric alcohol (such as glycerin and diol described in US Pat. No. 2,960,404) may be added as a plasticizer to the image recording layer in the present invention. .

(J) Hardener The image recording layer in the invention may contain a hardener.
The hardener may be added to a protective layer, a back layer, and the like described below. Examples of hardeners include US Pat. No. 4,281,060.
Polyisocyanates described in JP-A-6-208193, epoxy compounds described in U.S. Pat. No. 4,791,042, etc .;
No. 048, vinyl sulfone compounds and oxazoline compounds.

(K) Benzoic Acids The image recording layer in the invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acid may be added to any layer of the heat-developable color image recording material of the present invention, but is preferably added to a layer provided on the image recording layer side of the support, and may be added to the image recording layer, the intermediate layer or the protective layer. It is more preferably added to the layer, particularly preferably to the intermediate layer or the protective layer. The benzoic acids used in the present invention are not particularly limited, but preferred examples include U.S. Pat. Nos. 4,784,939 and 4,152,160, JP-A-9-329865, and 9-329.
No. 864, 9-291637 and the like.

The benzoic acids may be added in any step of preparing a coating solution. When adding to the image recording layer,
The organic silver salt may be added in any of the steps from the organic silver salt preparation step to the coating liquid preparation step, and is preferably added after the organic silver salt preparation to immediately before coating. The benzoic acids may be added in any state such as a powder, a solution, and a fine particle dispersion. The benzoic acids may be added as a solution mixed with additives such as a sensitizing dye, a reducing agent, and a color tone agent. The amount of benzoic acid added is
The amount is preferably 1 μmol to 2 mol, more preferably 1 mmol to 0.5 mol, per 1 mol of the total silver in the image recording layer.

(B) Support The material of the support used in the present invention is not particularly limited, and typical examples thereof include polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), cellulose nitrate, cellulose ester, polyvinyl acetal, and the like. Polycarbonate and the like. Among these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferred from the viewpoint of strength, dimensional stability, chemical resistance and the like.

The thickness of the support is preferably 90 to 500 μm as a base thickness excluding an undercoat layer described later. The support may be transparent or translucent or a white reflective support. As the white reflective support, those made of a polyester film into which a white inorganic pigment is kneaded can be used.

It is preferable to provide an undercoat layer made of 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 undercoat layer may contain a cross-linking agent, a matting agent, and the like. If necessary, SBR, polyester, gelatin, or the like may be added as a binder.
Further, the undercoat layer may contain the above-mentioned fluorine-containing surfactant. The thickness of the undercoat layer is preferably 0.01 to 5 μm,
0.05 to 1 μm is more preferable. The thickness of the vinylidene chloride copolymer in the undercoat layer is preferably at least 0.3 μm, more preferably 0.3 to 4 μm.

When the above-described biaxially stretched polyester is used as a support, the polyester is preferably used in an amount of 130 to 130 to reduce internal strain remaining in the film during biaxial stretching and eliminate heat shrinkage distortion generated during thermal development. Preferably, a heat treatment at 185 ° C. is performed. The heat treatment may be performed at a constant temperature or while increasing the temperature, or may be performed in a roll shape or while being transported in a web shape. In the case of performing heat treatment while transporting in the form of a web, the transport tension of the support during processing is preferably relatively low, specifically, 7 kg / c.
m ² or less, more preferably 4.2 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is usually about 0.5 kg / cm ² . The heat treatment is preferably carried out after the support has been subjected to a treatment for improving the adhesion to the image recording layer or the back layer, or to the provision of an undercoat layer. The heat shrinkage of the support after the heat treatment is −0.03 to + 0.01% in the longitudinal direction (MD) and transverse direction (TD) in the case of heating conditions of 120 ° C. and 30 seconds.
Is preferably 0 to 0.04%.

(C) Others The heat-developable color image recording material of the present invention may have a non-photosensitive layer such as an intermediate layer and a protective layer between, above and / or below the above-mentioned image recording layers. Further, various auxiliary layers such as a back layer may be provided on the side of the support opposite to the image recording layer.

(1) Intermediate Layer When the heat-developable color image recording material of the present invention has a plurality of layers having different color sensitivity, it is preferable to provide an intermediate layer between them for the purpose of preventing color mixing. Preferably, the intermediate layer includes a capture agent for oxidation products of the reducing agent. It is desirable that the capture agent is fixed to the intermediate layer with diffusion resistance. 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. The scavenger can prevent this harmful reductant oxidation product from diffusing into adjacent layers and improve color turbidity.

As the above-mentioned trapping agent, any of the above-mentioned reducing agents having diffusion resistance can be used. In addition, JP-A-8-2
No. 20717, sulfonamidophenol compounds and sulfonamidonaphthol compounds (for example, compounds I- (1) to I- (53) and II- (1) to II)
(39)), compounds 1-21 described in JP-A-2-183246, immobile hydroquinone derivatives and resorcinol derivatives described in JP-A-60-119555 (for example, compounds (1) to (12)), Kaihei 8-28634
Hydrazine derivatives (preferably compounds (C-1) to (C-80)) described in Japanese Patent Application Publication No.
Sulfonamide phenol compounds described in Japanese Patent Publication No. 2 (for example, compounds D-1 to D-8) and the like can be used as the capturing agent.

[0170] The amount of the capture agent to be added may be an amount capable of effectively capturing the component of the oxidation product of the reducing agent that diffuses into the adjacent layer, and is appropriately selected according to the reaction activity of the capture agent used. Although it is possible, usually, 1/100 to 10
Mole, preferably 0.1 to 1 mole.

The intermediate layer may contain a light absorbing agent. It is preferable to use colloidal silver or a diffusion-resistant dye as the light absorber. Colloidal silver has yellow or magenta light absorption properties depending on its particle size. By adding colloidal silver to the intermediate layer, it is possible to remove unnecessary light components and to give preferable color reproduction. The diffusion-resistant dye may be decolorized by heating. The amount of colloidal silver or diffusion-resistant dye added is preferably such that the absorbance is 0.1 to
2.0, more preferably 0.3 to 1.0.

The intermediate layer may further contain the above-mentioned additives such as a halogen precursor, a dispersion stabilizer, a crosslinking agent, a surfactant for improving coating properties, and a fluorine-containing surfactant. Preferred embodiments of these additives are basically the same as those of the image recording layer. Further, the intermediate layer usually contains a binder, in addition to the polymer latex used in the image recording layer, gelatin,
Polyvinyl alcohol, other synthetic polymers and the like can be used. Among them, gelatin is preferable from the viewpoint of maintaining a good coated surface state. The thickness of the intermediate layer is 0.01 to 30 μ
m is preferable, and 0.05 to 10 μm is more preferable.

Intermediate layers containing solid pigments described in JP-A-1-167838 and JP-A-61-20943, JP-A-1-120553 and JP-A-5-34884.
And reducing agents described in JP-A-2-64634 and JP-A-2-64634.
An intermediate layer comprising an IR compound, and US Pat.
Nos. 454 and 5,139,919;
An intermediate layer containing an electron transfer agent described in JP-A-235044 can also be applied to the present invention.

(2) Protective Layer The heat-developable color image recording material of the present invention is preferably provided with a protective layer comprising a polymer binder or the like for protecting the surface. The protective layer is provided on the outer layer of the support having the image recording layer. The protective layer having a reducing agent described in JP-A-4-249245 is also applicable to the present invention.

As the polymer binder, the polymer latex used in the image recording layer can be used.
The glass transition temperature of the polymer of the polymer latex used for the protective layer is preferably 25 to 100 ° C. In addition to the polymer latex, gelatin, polyvinyl alcohol, other synthetic polymers and the like can be used as a binder for the protective layer. Among them, gelatin is preferable from the viewpoint of maintaining a good coated surface state. The addition amount of the binder is preferably the area of the protective layer is 0.2 to 10 g / m ^2, more preferably 1 to 5 g / m ^2.

The protective layer may further comprise the above-mentioned general formula (1)
, A halogen precursor, a dispersion stabilizer, a crosslinking agent, a surfactant for improving coating properties, benzoic acids, a hardener, a slipping agent, and the like.
Preferred embodiments of these additives are basically the same as those of the image recording layer. However, in the protective layer, when a hydrophilic polymer is used as the dispersion stabilizer, the amount of the hydrophilic polymer to be added is preferably 3% by mass or less, preferably 1% by mass or less based on all binders in the protective layer. More preferably, Protective layer thickness 0.01 to 30μ
m is preferable, and 0.05 to 10 μm is more preferable.

It is desirable to add a matting agent to the protective layer in order to prevent adhesion failure when the heat-developable color image recording materials are superposed. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Examples of the matting agent include U.S. Pat. Nos. 1,939,213, 2,701,245, and 2,322,0.
No. 37, No. 3,262,782, No. 3,
Organic matting agents described in JP-A-539,344, JP-A-3,767,448, etc., and JP-A-1,260,772, JP-A-2,192,241 and JP-A-3,25.
No. 7,206, 3,370,951,
3,523,022 and 3,769,020
And the like. Specifically, water-dispersible vinyl polymers (polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer,
Polystyrene, styrene-divinylbenzene copolymer,
Polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc.), cellulose derivatives (methyl cellulose, cellulose acetate, cellulose acetate propionate, etc.), starch derivatives (carboxy starch, carboxynitrophenyl starch, urea-formaldehyde-starch reactant, etc.), Organic compounds such as gelatin hardened with a known hardener and hardened gelatin that has been coacervated and hardened into microcapsule hollow granules, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, known methods Inorganic compounds such as silver chloride, silver bromide, glass, and diatomaceous earth desensitized by the above method can be preferably used as a matting agent. The matting agent may be used alone or in combination.

The matting agent has the effect of forming irregularities on the surface of the protective layer to reduce the contact area and prevent adhesion failure. Accordingly, the average particle size is preferably larger than the thickness of the protective layer. The average particle size of the matting agent is preferably from 1 to 10 μm. When the average particle size is less than 1 μm, it is not practical. The particle size distribution of the matting agent is preferably narrow, and the monodispersity is preferably 10% or less. When there are a plurality of protective layers, the matting agent is preferably added to the outermost surface layer or a layer as close as possible to the outer surface.

The protective layer preferably contains the above-mentioned fluorine-containing surfactant. The fluorinated surfactant may be added to one or both of the image recording layer side and the back layer side of the protective layer, but is preferably added at least to the image recording layer side. A fluorine-containing surfactant may be overcoated on the protective layer.

The pH of the protective layer varies depending on the additive, but is relatively low at 2 to 7. When a plurality of protective layers are formed, a layer close to the image recording layer has a pH of 4 to 7, and a layer far from the image recording layer has a pH of 2
It is preferable that the number be from 5 to 5. The protective layer may be composed of a plurality of layers. For example, a protective lower layer for protecting an image mainly composed of an organic polymer, and a protective upper layer for preventing adhesion including a matting agent, a slipping agent, a fluorine-containing surfactant, etc. and for improving the surface slipperiness. May do it.

(3) Undercoat Layer The heat-developable color image recording material of the present invention is described in US Pat.
It may have an undercoat layer described in JP-A-051,335 and the like.

(4) Yellow Filter Layer and Antihalation Layer A yellow filter layer or an antihalation layer may be provided between the image recording layer and the support of the heat-developable color image recording material of the present invention. The antihalation layer may be provided on the back layer. It is preferable that the dye used in the yellow filter layer and the antihalation layer is decolored or removed at the time of heat development and does not contribute to the density after the processing. Here, "the dye is decolored or removed at the time of 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. Specific examples of the dye include European Patent Publication EP 549,489A.
And dyes ExF2 to Ex6 described in JP-A-7-152129. JP-A-8-1
The solid-dispersed dye described in 01487 can also be used. The mordant and the binder may be dyed with a mordant. In this case, columns 58 to 59 of U.S. Pat. No. 4,500,626, pages 32 to 41 of JP-A-61-88256, JP-A-62-244043, and JP-A-62-24043.
A mordant described in JP-A-244036 can be used.
Further, the color can also be erased by reacting the dye with a reducing agent. Specifically, U.S. Pat. Nos. 4,559,290 and 4,783,396, European Patent Publication EP
220,746A2, Published Technical Report 87-6119
No., paragraph number 0080 of JP-A-8-101487
To 0081.

As the dye, a decolorizable leuco dye may be used. For example, JP-A-1-150132 discloses 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. The leuco dye and the developer complex decolor by reacting with heat or an alkaline agent. The leuco dye is Moriga,
Yoshida, "Dyes and Chemicals", 9, 84 pages (Japan Chemical Industry Association),
"Handbook of New Edition Dyes", p. 242 (Maruzen, 1970); G
arner "Reports on the Prog
less of Appl. Chem "56, 199
Page (1971), "Dyes and Chemicals", pages 19 and 230 (Keisei Kogyo Kyokai, 1974), "Colorants", pages 62 and 288 (1
989), “Dyeing industry” 32, 208 and the like. As the developer, an acid clay-based developer, phenol formaldehyde resin, a metal salt of an organic acid and the like are preferably used. As organic acid metal salts, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodanes, metal salts of xanthogenates, and the like are useful. It is particularly preferred that the metal is zinc.
U.S. Pat. Nos. 3,864,146 and 4,042
Oil-soluble zinc salicylate described in JP-A-6,941 and JP-B-52-1327 can also be used as a color developer.

(5) Back Layer The back layer of the heat-developable color image recording material of the present invention is obtained by adding the following additives to a polymer binder as needed. The back layer may contain the fluorine-containing surfactant.

When a transparent support is used, the back layer preferably has a maximum absorption of about 0.3 to 2.0 for light having a desired wavelength. Desired wavelength is 750-1400nm
Is preferable, the optical density at 650 to 360 nm is preferably 0.001 or more and less than 0.5.
It is more preferably 001 or more and less than 0.3. When the desired wavelength is 750 nm or less, the maximum absorption before image formation is 0.3 to 2.0, and the maximum absorption after image formation is 36 to 2.0.
The optical density at 0 to 650 nm is preferably 0.005 or more and less than 0.3. As a method for lowering the optical density after image formation to the above range, Belgian Patent No. 733,7
JP-A-54-17833, which discloses a method of reducing the concentration of a dye by decoloring by heating, as described in JP-A No.
And a method of reducing the density by decoloring by light irradiation described in Japanese Unexamined Patent Publication (Kokai) Publication.

When an antihalation dye is used in the back layer, the antihalation dye has desired absorption characteristics in a desired range, has a sufficiently low absorption in the visible region after treatment, and has the above-mentioned maximum absorption of the preferred back layer. Is not particularly limited as long as it can obtain Specific examples of the antihalation dye include JP-A-59-56458,
JP-A-2-216140, JP-A-7-13295, JP-A-7-11432, U.S. Pat.
No. 635, JP-A-2-68539, JP-A-3-24539, etc., which can be used as a single dye; JP-A-52-139136 and JP-A-52-139136.
-132334, 56-501480,
JP-A-57-16060, JP-A-57-68831, JP-A-57-101835, and JP-A-59-18243.
No. 6, JP-A-7-36145, and JP-A-7-199.
409, JP-B-48-33692, and 50
No. 16648, Japanese Patent Publication No. 2-41734, U.S. Pat. Nos. 4,088,497 and 4,283.
No. 487, 4,548,896, 5,187,049, and the like, and dyes that can be decolorized by the treatment described in the specification, and the like, but the present invention is not limited thereto. Absent.

[0187] The back layer may contain a binder. The binder used for the back layer is preferably transparent or translucent and colorless. The binder may be a natural polymer, a synthetic resin, a synthetic polymer, a synthetic copolymer, a medium for forming a film, and the like. Rate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-
Butadiene), polyvinyl acetals (polyvinyl formal, polyvinyl butyral, etc.), polyesters, polyurethanes, phenoxy resins, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, polyamides and the like. The back layer may contain a polymer latex used for the image recording layer, and the polymer of the polymer latex used for the back layer (particularly, the outermost layer) preferably has a glass transition temperature of 25 to 100 ° C. The amount of the binder in the back layer is 0.01 to 10
preferably ^{g / m 2, 0.5~5g / m} 2 is more preferable.

To reduce the Beck second, it is preferable to add a matting agent to the back layer. Beck smoothness is preferably 10 to 2000 seconds, more preferably 50 to 15 seconds.
It is 00 seconds, and the particle size and amount of the matting agent may be changed in order to obtain such Beck smoothness. The Beck smoothness is determined according to JIS P8119 or TAPPIT479.

(6) Coating The heat-developable color image recording material of the present invention can be coated by coating operations such as dip coating, air knife coating, flow coating, and extrusion coating using a hopper described in US Pat. No. 2,681,294. May be coated. Two or more layers can be simultaneously coated by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

(7) Slip Agent In the present invention, a slip agent is preferably contained in the surface of the support having the image recording layer and / or the outermost surface layer opposite to the image recording layer. The slip agent used in the present invention is not particularly limited as long as it is a compound that reduces the friction coefficient of the surface when it is present on the surface of the object. Specific examples of the slip agent include U.S. Pat. No. 3,042,522 and British Patent No. 95.
5,061, U.S. Pat. Nos. 3,080,317, 4,004,927, and 4,044.
7,958, 3,489,567,
Silicone-based slip agents described in British Patent No. 1,143,118; U.S. Pat. Nos. 2,454,043, 2,732,305 and 2,976,1
48, 3,206,311, German Patent 1,284,295, 1,284,29
Patent No. 1,26; higher fatty acid-based slip agents, alcohol-based slip agents and acid amide-based slip agents described in JP-A-4
No. 3,722, U.S. Pat. No. 3,933,516; metal soaps described in U.S. Pat.
765, 3,121,060, British Patent No. 1,198,387, etc .; ester sliding agents and ether sliding agents; U.S. Pat. No. 3,50
And the taurine-based slip agents described in 2,473, 3,042,222 and the like. Specific examples of the slip agent preferably used include Cellolsol 524.
(Main component carnauba wax), Polylon A, 393 and H-481 (main component polyethylene wax), high micron G-110 (main component ethylene bisstearic acid amide), high micron G-270 (main component stearic acid amide) ( As described above, Chukyo Yushi Co., Ltd.) and the like. The amount of the slip agent used is preferably 0.1 to 50% by mass, more preferably 0.5 to 50% by mass of the binder amount in the layer to be added.
-30% by mass.

(8) Base A photographic photosensitive material generally requires a base. In the heat-developable color image recording material of the present invention, various base supply methods can be adopted. For example, a base precursor can be introduced into the antihalation layer or the back layer. As such a base precursor, for example, a salt comprising an organic acid and a base which are decarboxylated by heat, a compound which releases amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like are known. The base precursor is also described in U.S. Pat. Nos. 4,514,493 and 4,657,848.

(9) Others In the heat-developable color image recording material of the present invention, the following various additives can be used. Dispersion medium of oil-soluble organic compound (P-3,5, JP-A-62-215272)
16, 19, 25, 30, 42, 49, 54, 55, 6
6, 81, 85, 86 and 93 (pp. 140-144)
Latex for impregnating an oil-soluble organic compound (such as the latex described in U.S. Pat. No. 4,199,363); oxidized developing agent scavenger (US Pat. No. 4,199,363)
No. 978,606 and U.S. Pat. No. 4,923,7.
No. 87, etc.); a stain inhibitor (formula (I) described in EP 298321A)
To (III) (especially I-47 and 72 and I
II-1 and 27) etc.); Anti-fading agents (European Patent Publication E
A-6, 7, 20, 2 described in P298321A
1, 23, 24, 25, 26, 30, 37, 40, 4
2, 48, 63, 90, 92, 94 and 164 (69-
118), II-1 to III-23 (particularly III-10) described in U.S. Pat. No. 5,122,444,
I-1 described in European Patent Publication EP 471347A
To III-4 (particularly II-2), U.S. Pat.
Nos. 9,931 and A-1 to 48 (especially A-3)
9 and 42) etc.); materials which reduce the amount of the color-enhancing agent or color-mixing inhibitor (European Patent Publication EP 411324A, pages 5 to 24, pages I-1 to II-15 (particularly I-4)
6) etc.); Formalin scavenger (European Patent Publication E
P. 477932A, SCV-1 on page 24-29,
28 (especially SCV-8), etc.);
No. 4845, page 17, H-1, 4, 6, 8 and 1
4. Compounds H-1 to H-5 represented by formulas (VII) to (XII) described in U.S. Pat. No. 4,618,573.
4. Compounds H-1 to 76 (especially H-14) represented by the formula (6) described in JP-A-2-214852, and compounds described in claim 1 of US Pat. No. 3,325,287. Etc.); Development inhibitor precursor (Japanese Patent Application Laid-Open No. Sho 62-62)
Nos. 168,139, P-24, 37 and 39; U.S. Pat. No. 5,019,492, Claim 1 (especially 28 and 29 of column 7); preservatives and fungicides (US Pat. No. 4,923,790.
1-III-43, especially II-1, 9, 10 and 18 and III-25 and the like; stabilizers and antifoggants (I-1 to 14 of U.S. Pat. No. 4,923,793 (especially I-1 -1, 60, (2) and (13)), compounds 1 to 65 (especially 3) of U.S. Pat.
6) etc.); chemical sensitizers (triphenylphosphine selenide, compound 50 in JP-A-5-40324); dyes (a-1 to b-20 in JP-A-3-156450).
(Particularly a-1, 12, 18, 27, 35 and 36 and b-5), and V-1 to 23 (particularly V-1), FI-1 to F-II of EP 445627A.
-43 (especially FI-11 and F-II-8), II on pages 17 to 28 of EP 457153A.
I-1 to 36 (particularly III-1 and 3), International Publication WO
88/47794, Dye-1 to 124 microcrystal dispersion, European Patent Publication EP319999A, 6 to
Compounds 1 to 22 (especially compound 1) on page 11, compounds D-1 to 87 represented by formula (1) or (3) in EP 519306A, U.S. Pat. No. 4,268,
No. 622, compounds 1 to 22 represented by the formula (I),
Compounds (1) to (31) represented by formula (I) in U.S. Pat. No. 4,923,788); UV absorbers (compounds represented by formula (1) in JP-A-46-3335). (18-b) to (18r) and 101 to 427, compounds (3) to (66) represented by the formula (I) and compounds represented by the formula (III) in European Patent Publication No. EP520938A HBT-1-10, European Patent Publication EP521823
Compounds (1) to (31) represented by Formula (1) in A Publication
Etc.).

[2] Heat-Developable Color Image Forming Method In the heat-developing color image forming method of the present invention, a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, and an organic binder are provided on a carrier. In a heat-developable color image recording material having an image recording layer containing the organic silver salt, the silver molar ratio of the photosensitive silver halide to the organic silver salt is preferably 0.1 to 100 mol%, and the color image forming material is preferably A compound represented by the general formula (1), and after exposure of the heat-developable color image recording material, forms an image in which developed silver and a color image coexist by heat development, without separating the developed silver The color image can be observed.

[0194]

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In the heat-developable color image forming method of the present invention, the color-developed image and the developed silver are observed without any separation and coexistence after thermal development. Optical density as low as possible,
From the viewpoint of increasing the optical density of the coloring dye to obtain an image with high chroma, the silver molar ratio of the photosensitive silver halide to the organic silver salt is preferably 0.1 to 100 mol%, and 0 to 100 mol%. It is more preferably from 0.5 to 70 mol%, particularly preferably from 1.0 to 30 mol%.

The reducing agent used in the heat-developable color image forming method of the present invention is preferably represented by the following general formula (2).

[0197]

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That is, in the heat-developable color image recording method of the present invention, the heat-developable color recording material is preferably used.

In the heat-developable color image forming method of the present invention, usually, the heat-developable color image recording material exposed imagewise is heated and developed. Examples of the thermal developing machine include Japanese Patent Publication No. 5-56499, Japanese Patent No. 684453, Japanese Patent Application Laid-Open No. 9-292695, and Japanese Patent Application Laid-Open No. 9-297.
No. 385 and WO 95/30934, and a heat developing machine of the type in which a heat-developable color image recording material is brought into contact with a heat source such as a heat roller or a heat drum; /
Nos. 28489, 97/28488 and 9
A non-contact type heat developing machine described in JP-A-7 / 28487 can be preferably used. In the present invention, it is particularly preferable to use a non-contact heat developing machine. The development temperature is 80-2
50 ° C is preferred, and 100 to 140 ° C is more preferred.
The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

In the heat-developable color image forming method of the present invention, in order to prevent processing unevenness due to dimensional change during heat development of the image recording material and physical bumps, the temperature is 80 ° C. or more and 115 ° C.
A so-called multi-stage heating method of forming an image by heating at a temperature of less than (preferably 113 ° C. or less) for 5 seconds or more so as not to produce an image, and then thermally developing the image at 110 ° C. or more (preferably 130 ° C. or less). Preferably, it is used. Further, it is preferable that cooling after the thermal development is performed gradually.
The cooling rate is preferably 200 ° C./min or less, more preferably 50 to 150 ° C./min.

In the heat-developable color image forming method of the present invention, the image recording material may be exposed by any method, but it is preferable to use a laser beam as an exposure light source. Among laser beams, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a semiconductor laser, a second harmonic generation element, or the like can be used.

The heat-developable color image recording material of the present invention described above has a low haze at the time of exposure and is liable to cause interference fringes.
As a technique for preventing the occurrence of interference fringes, Japanese Patent Application Laid-Open No.
For example, a method of obliquely entering a laser beam into a heat-developable color image recording material disclosed in Japanese Patent Application Laid-Open No. 13548 or the like, and a method of using a multi-mode laser disclosed in International Publication WO 95/31754 or the like. It is known and it is preferred to use these techniques. When exposing the heat-developable color image recording material, SPIE,
Vol. 169, Laser Printing,
116-128 (1979), JP-A-4-51043
It is preferable to expose the laser beams so that they overlap each other so as to make the scanning lines invisible, as disclosed in Japanese Patent Application Laid-Open Publication No. Hei.

[0203]

EXAMPLES The present invention will be described more specifically with reference to the following 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 by the following examples.

1. Preparation of Support Having Undercoat Layer and Back Layer An undercoat layer and a back layer were provided on a PET base having a thickness of 100 μm as described below, and heat treatment was performed. Dye A, compound A and compound H used in the undercoat layer and the back layer are shown below.

[0205]

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(I) 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 dried at 180 ° C. for 4 minutes.

Undercoat layer (a): Polymer latex V-5 3.0 g / m ² (solid content) 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

The polymer latex V-5 is a core-shell type latex having a core portion of 90% by mass and a shell portion of 10% by mass. /3/3/0.9/0.1
(Mass%), and the shell part is composed of vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (mass%). The weight average molecular weight is 38,000.

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 Methyl cellulose 4 mg / m ² Polyoxyethylene 3 mg / m ^Two

[0210] As the polyoxyethylene, "Emarex 710" manufactured by Nippon Emulsion Co., Ltd. was used.

(Ii) Application of Back Layer The following back layer (a) and back layer (b) were successively applied to the other side of the PET base, and dried at 180 ° C. for 4 minutes.

Back layer (a): Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 38 mg / m ² SnO ₂ / Sb (mass ratio 9/1) 200 mg / m ² Dye A 20 mg / m ² matting agent ( Polymethyl methacrylate particles) 10 mg / m ² Crosslinking agent (Denacol EX-614B, manufactured by Nagase Kasei Kogyo Co., Ltd.) 3 mg / m ²

For SnO ₂ / Sb, needle-like particles “FS-10D” manufactured by Ishihara Sangyo Co., Ltd. were used, and the average particle size of the matting agent was 5 μm.

Back layer (b): Latex binder 500 mg / m ² Colloidal silica 40 mg / m ² Crosslinking agent (Denacol EX-614B, manufactured by Nagase Kasei Kogyo Co., Ltd.) 30 mg / m ²

The latex binder used was Chemipearl S-120 manufactured by Mitsui Petrochemical Co., Ltd. The colloidal silica used was Snowtex-Made by Nissan Chemical Co.
C was used.

(Iii) Heat treatment After the undercoat layer and the back layer were applied and dried as described above, a tension of 5 kg / cm ² and a temperature of 130 ° C. were applied to a PET base.
The first heat treatment is performed for 10 minutes under the conditions of
A second heat treatment was performed for 15 seconds under the conditions of 0 kg / cm ² and a temperature of 40 ° C.

[0219] 2. Preparation of photosensitive silver halide emulsion A 11 g of phthalated gelatin, 30 mg in 700 ml of water
Of potassium bromide and 10 mg of sodium thiosulfonate were dissolved and heated to 35 ° C. to adjust the pH to 5.0.
159 ml of an aqueous solution containing 18.6 g of silver nitrate was added to this solution.
And an aqueous solution containing 1 mol / L of potassium bromide was added over 6.5 minutes by the control double jet method while maintaining the pAg at 7.7. Next, 5 was added to the resulting solution.
476 g of an aqueous solution containing 5.4 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 1 g of 4-hydroxy-6 was further added. -Methyl-1,
3,3a, 7-Tetrazaindene was added, and the pH was lowered to cause coagulation and sedimentation for desalting. Then, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9, the pAg to 8.2, and the silver bromide particles (average particle size was 0.1%).
Cubic grains having a projection area diameter variation coefficient of 8%, a (100) face ratio of 88%, and a projection area diameter of 2% were prepared.

The temperature of the obtained silver halide grains was raised to 60 ° C., and sodium thiosulfonate was added to 8.5 mol per mol of silver.
× 10 ^-4 mol was added, and the mixture was aged for 120 minutes. After aging, and quenching the silver halide grains 40 ° C., this 1 × 10 ^-5
Mol of the following sensitizing dye A and 5 × 10 ⁻⁵ mol of the following compound B, 5 × 10 ⁻⁵ mol of N-methyl-N ′-{3- (mercaptotetrazolyl) phenyl} urea, and 100 p
pm of Compound A was added, and the mixture was rapidly cooled to 30 ° C. to obtain a photosensitive silver halide emulsion A.

[0219]

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[0220] 3. Preparation of Organic Silver Salt Dispersion A 4.4 g of stearic acid, 39.4 g of behenic acid and 7
While stirring 70 ml of distilled water at 90 ° C., 103 ml of an aqueous solution of NaOH (1N) was added, reacted for 240 minutes, and cooled to 75 ° C. Then, 1 was added to the resulting mixture.
112.5 ml of an aqueous solution containing 9.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and then cooled to 30 ° C. Subsequently, the solid content was filtered off by suction filtration,
Washing with water was performed until the electric conductivity of the filtrate became 30 μS / cm. 100 ml of an aqueous solution of polyvinyl alcohol (polyvinyl alcohol: 10% by mass) was added to the obtained solid content, and water was further added so that the total mass became 270 g. This was roughly dispersed in an automatic mortar, and then subjected to a collision pressure of 100 using a nanomizer (manufactured by Nanomizer Co., Ltd.).
The dispersion was performed at 0 kg / cm ² to obtain an acicular particle dispersion (organic silver salt dispersion A) having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%.

4. Preparation of Reducing Agent Dispersion A 100 g of a reducing agent (Exemplary Compound D-119) and 125 g
Of polyvinyl alcohol was added and mixed well to prepare a slurry. 840 g of this slurry
In a vessel together with dispersed beads (zirconia grains having an average diameter of 0.5 mm) and dispersed with a disperser sand mill (1 / 4G sand grinder mill, manufactured by Imex Co., Ltd.) for 5 hours. Then, a reducing agent dispersion A having an average particle size of 0.4 μm was obtained.

5. Preparation of phthalazine derivative solubilizing solution A Using the following phthalazine derivative A, a phthalazine derivative solubilizing solution A having the following composition was prepared. Phthalazine derivative A 25 g Triisopropylnaphthalene sulfone sansoda 2.1 g Polyvinyl alcohol 100 g Water 373 g

The triisopropylnaphthalenesulfone soda used was “Leopol BX” manufactured by Takemoto Yushi Co., Ltd., and the polyvinyl alcohol was “PVA” manufactured by Kuraray Co., Ltd.
-217 (20% aqueous solution) ".

[0224]

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(6) Preparation of Organic Polyhalogen Compound Dispersion A To 30 g of the following organic polyhalogen compound A, 0.5 g of hydroxypropylmethylcellulose, 0.5 g of the following compound C, and 88.5 g of water were added, and the mixture was stirred well to form a slurry. Obtained. After leaving this slurry for 3 hours, an organic polyhalogen compound dispersion A was prepared in the same manner as in the case of the reducing agent dispersion A. 80% by mass of the particles is 0.3
It had a particle size of μ1.0 μm.

[0226]

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[0227] 7. Preparation of salicylic acid derivative dispersion A 30 g of the following salicylic acid derivative A, 30 g of modified polyvinyl alcohol (“MP-203” manufactured by Kuraray Co., Ltd.) and 0.6 g of sodium triisopropylnaphthalenesulfonate (manufactured by Takemoto Yushi Co., Ltd.) Leopold BX ")
g of water was added and mixed to form a slurry. This slurry was placed in a vessel together with 960 g of dispersed beads (zirconia particles having an average diameter of 0.5 mm) and dispersed for 5 hours by a sand mill (1 / 4G sand grinder mill manufactured by Imex Co., Ltd.). This was diluted with 105 g of water and the dispersion was taken out to obtain a salicylic acid derivative dispersion A having an average particle size of 0.4 μm.

[0228]

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[0229] 8. Preparation of Color Image Forming Material Dispersion A 600 g of water was added to a mixture of 100 g of the above color image forming material (exemplified compound No. 1) represented by the general formula (1) and 125 g of polyvinyl alcohol, and mixed well. Thus, a slurry was prepared. 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. In addition, the mixture was taken out of the vessel to obtain a color image forming material dispersion A having an average particle size of 0.5 μm.

9. Preparation of Color Image Forming Material Dispersion B for Comparison Except that the following color image forming material B for comparison was used in place of the color image forming material (exemplified compound No. 1) represented by the general formula (1). In the same manner as in the preparation method of the color image forming material dispersion A, the following color image forming material dispersion B for comparison was obtained.
The average particle size was 0.3 μm.

[0231]

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10. Heat-developable color image recording materials 1 and 2
Production and Evaluation of Heat-Developable Color Image Recording Material 1 of the Invention and Heat-Developable Color Image Recording Material 2 for Comparison were produced as follows.

(I) Preparation of the heat-developable color image recording material 1 of the present invention 85 g of the organic silver salt dispersion A, 18 g of a photosensitive silver halide emulsion A, 20 g of a reducing agent dispersion A, and 31 g of a color image Forming material dispersion A, 23.3 g of salicylic acid derivative dispersion A, 46 g of Lacstar # 3307B (manufactured by Dainippon Ink and Chemicals, SBR latex, Tg: 13)
C, 49% by mass), 6 g of Kuraray Povar MP-203
Aqueous solution (10% by mass), 13 g of phthalazine derivative solubilizing solution A, 10 g of organic polyhalide dispersion A, 0.1 g
25 g of water was added to 07 g of 5-methylbenzotriazole and 6 mg of Dye A and mixed well to obtain a coating solution for the image recording layer A. 109 g of a polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate methacrylic acid = 59/9/26/5/1 copolymer;
(Solid content: 27.5%, glass transition temperature: 55 ° C).
75 g of water was added, followed by 4.5 g of benzyl alcohol and 0.45 g of the following compound-2 as a film-forming aid.
125 g of the following compound-3, 0.0125 mol of the following compound-4, and 2.25 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-217) were added, and water was further added to make 150 g. I got

[0234]

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The coating solution for the image recording layer A and the coating solution for the protective layer thus obtained were simultaneously and multi-layer coated on the undercoat layer side of the support.
After drying at 0 ° C. for 2 minutes, a heat-developable color image recording material 1 of the present invention was obtained. The coating solution for the image recording layer A was applied so that the coating silver amount was 0.8 g / m ^2, and the coating solution for the protective layer was applied such that the coating amount of the polymer latex was 2.0 g on the image recording layer.
/ M ² .

(Ii) Preparation of heat-developable color image recording material 2 for comparison The heat-developable color image described above was used except that 24 g of color image forming material dispersion B was used in place of 31 g of color image forming material dispersion A. In the same manner as in the production method of the recording material 1, a heat-developable color image recording material 2 for comparison was obtained.

(Iii) Image formation by heat development and measurement of image density The heat-developable color image recording materials 1 and 2 were prepared at 780 nm.
Exposure with a xenon flash light with a light emission time of 10 ^-6 seconds through a step density wedge having a density difference of 0.1 and a heat development treatment at 115 ° C. for 10 seconds. In the color image recording material 1, a cyan image was obtained, and in the heat-developable color image recording material 2, a magenta image was obtained. In all samples, the developed silver density was lower than the color density at which the color was developed, and thus, despite the developed silver remaining, clear color images were obtained. Above all, the heat-developable color image recording material 1 of the present invention exhibited a vivid color tone with much less turbidity than the heat-developable color image recording material 2. As a result of measuring the spectral absorption spectrum of the color image, the heat-developable color image recording material 1 has an absorption maximum wavelength of 601 nm,
The heat-developable color image recording material 2 had a wavelength of 560 nm.

(Iv) Evaluation of Image Fastness The heat-developable color image recording materials 1 and 2 after image formation by heat development were subjected to 1000 Lu using a fluorescent lamp fading tester.
x light was irradiated for 2 weeks, and the fastness was evaluated by the change of the green density value at the initial density of 1.0. As a result, the heat-developable color image recording material 2 of the present invention faded to a green density of 0.52, whereas the heat-developable color image recording material 1 of the present invention exhibited a green density of 0.98, which was extremely excellent in image fastness. showed that.

[0239] 11. Preparation and evaluation of heat-developable color image recording materials 3 and 4 (i) Preparation of heat-developable color image recording materials 3 and 4 of the present invention In place of the color image forming material (exemplary compound No. 1), N
o. 10 and No. The heat-developable color image recording materials 3 and 4 of the present invention were produced in the same manner as in the method of producing the heat-developable color image recording material 1 except that No. 12 was used. (Ii) Evaluation of photographic performance and image fastness As a result of the evaluation in the same manner as in Example 1, both the heat-developable color image recording materials 3 and 4 produce a vivid cyan image similarly to the heat-developable color image recording material 1. Gave. The image fastness was 0.94 and 0.91, respectively, indicating high image fastness.

12. Preparation and Evaluation of Heat-Developable Color Image Recording Materials 5 to 9 Instead of the color image forming material (Exemplary Compound No. 1), Exemplified Compound No. 1 was used. 4, no. 5, no. 14, No. 1
9, and No. 9 Heat-developed color image recording materials 5 to 9 were produced in the same manner as in the method of producing heat-developed color image recording material 1 except that No. 20 was used. The performance was evaluated in the same manner as in the case of the heat-developable color image recording material 1. As a result, as in the case of the heat-developable color image recording material 1, a good cyan image was obtained. Similarly, the image fastness is also 0, respectively.
-96, 0.98, 0.92, 0.87, and 0.79 were good.

[0241]

According to the present invention, the developing means is only thermal development, and does not require additional steps such as peeling and transfer. A developed color image recording material and a thermally developed color image recording method can be provided.

Claims (12)

[Claims] 1. A heat-developable color image recording material comprising an organic silver salt, a reducing agent, a color image forming material, and an organic binder on a support, wherein the color image forming material is represented by the following general formula (1). A heat-developable color image recording material, Embedded image In the general formula (1), R ₁ and R ₂ are each independently
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. R ₃ and R ₄ are each independently a hydrogen atom,
Represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R
₂ and R ₄ , and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ each _{independently, -N (R 5) -,} -
Represents O- or a single bond. R ₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent. 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 (2). Embedded image In the general formula (2), Q ₁ represents — via a carbon atom.
Aromatic group binds to NHNH-Q _2, or represents a 5- to 7-membered unsaturated ring. Q ₂ is a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Represents a sulfonyl group or a sulfamoyl group. 3. The heat-developable color image recording material according to claim 1, wherein the color image forming material is a two-equivalent type color image forming material. 4. The heat-developable color image recording material according to claim 1, wherein the organic binder contains a polymer latex dispersed in water. 5. The heat-developable color image recording material according to claim 1, wherein the reducing agent is fine particles solid-dispersed in water. 6. The heat-developable color image recording material according to claim 1, wherein the color image forming material is fine particles solid-dispersed in water. 7. The heat-developable color image recording material according to claim 1, further comprising a halogen precursor. 8. The heat-developable color image recording material according to claim 7, wherein the halogen precursor is a compound represented by the following general formula (H). Embedded image In the general formula (H), Q represents an aryl group or a heterocyclic group. Z ¹ and Z ² each independently represent a halogen atom. A represents a hydrogen atom or an electron-withdrawing group. 9. The heat-developable color image recording material according to claim 7, wherein the halogen precursor is fine particles solid-dispersed in water. 10. The heat-developable color image recording material according to claim 1, which contains a photosensitive silver halide. 11. A heat-developable color image recording material having an image recording layer on a support, which comprises a photosensitive silver halide, an organic silver salt, a reducing agent, a color image forming material, and an organic binder. Wherein the molar ratio of the photosensitive silver halide to the photosensitive silver halide is 0.1 to 100 mol%, the color image forming material is a compound represented by the following general formula (1), Thereafter, an image in which the developed silver and the color-developed image coexist is formed by thermal development, and the color-developed image can be observed without separating the developed silver. Embedded image In the general formula (1), R ₁ and R ₂ are each independently
Represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carbamoyl group, or a nitrile group. R ₂
And R ₄ and R ₁ and R ₃ may be linked to each other to form a ring structure. L ₁ and L ₂ each _{independently, -N (R 5) -,} -
Represents O- or a single bond. R ₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group. X represents a hydrogen atom or a group capable of leaving by an oxidative coupling reaction with a developing agent. 12. The heat-developable color image forming method according to claim 11, wherein the reducing agent is a compound represented by the following general formula (2). Embedded image In the general formula (2), Q ₁ represents — via a carbon atom.
Aromatic group binds to NHNH-Q _2, or represents a 5- to 7-membered unsaturated ring. Q ₂ is a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Represents a sulfonyl group or a sulfamoyl group.