JP2000221633A - Heat developable sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable ultrahigh-contrast sensitive material having low fog (Dmin) and ultrahigh-contrast photographic characteristics independently of the shelf life of an aqueous dispersion of a contrasting agent by using a specified compound and a specified polymer. SOLUTION: The sensitive material has a photosensitive silver halide, a reducible silver salt, a reducing agent, a binder and at least one compound selected from compounds of formulae I-III on the substrate and has at least one compound selected from a compound of formula IV, a polymer having repeating units derived from a monomer of formula V and a compound of formula VI. In the formulae I-III, R1-R3, X and Y are each H or a substituent, Z is an electron withdrawing group, R4 is a substituent and A and B are each alkoxy, alkylthio or the like. In the formulae IV-VI, X1-X3 are each the residue of a photographic inhibitor having an N-containing heterocycle, J is a divalent bonding group, B1 is a ballast group, (n) is an integer of >=1, Q is an ethylenically unsaturated group or the like and A1 is a group having a water-soluble group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly, to a photothermographic material having extremely small fog (Dmin) and suitable for plate making.

[0002]

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

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

[0004] Methods of forming an image by thermal development are described in, for example, US Patent Nos. 3,152,904 and 3,457,075, and US Pat.
Morgan and B.A. "Thermal Proces Silver System (Thermally Proces)" by Shely
sed Silver Systems) A "(Imaging Processes and M
aterials) Neblette 8th edition, Sturge, V.E.
Walworth, A .; Shepp
Edited, page 2, 1969). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

Fog is a major problem in photothermographic materials. Many studies have been made to reduce fog of silver halide photosensitive materials for thermography. For example, US Pat.
No. 3 discloses a mercury salt. In addition, US4152160
No. include carboxylic acids such as benzene acid and phthalic acid, US47
No. 84939, benzoylbenzene compound, US Pat. No. 4,569,906, indane or tetralin carboxylic acid, US Pat.
Discloses dicarboxylic acids and US Pat. No. 4,626,500 discloses heteroaromatic carboxylic acids. US4546075, US4756999
Nos. 4,445,885, 3,874,946 and 3,955,982 disclose halogenated compounds. US5028523 discloses a halogen molecule or a halogen atom bonded to a heteroatom ring. US4103312 and GB1502670 palladium compounds, US4128428 US iron metals, US4
123374, US4129557 and US4125430 include substituted triazoles, US4213784, US4245033 and JP
-26019 to sulfur compounds, US4002479 to thiouracils, JP-A-50-123331 to sulfinic acid, US4125403
No. 4,415,160, US Pat. No. 4,307,187, a metal salt of thiosulfonic acid, JP-A-53-20923 and JP-A-53-19825 describe a combination of a metal salt of thiosulfonic acid and sulfinic acid,
-50810, JP-A-7-209797 and JP-A-9-43760 disclose thiosulfonic acid esters. Also,
JP-A-51-42529 and JP-B-63-37368 disclose disulfide compounds.

[0006] European Patent 762,196, JP-A-9-90550 and the like disclose photosensitive silver halide grains used in heat-developable image recording materials to groups VII or VIII of the periodic table (groups 7 to 1).
It is disclosed that a metal ion or a metal complex ion of Group 0) is contained, and that a hydrazine derivative is contained in the photosensitive material to obtain high-contrast photographic characteristics.

As described above, it is known that the use of a hydrazine derivative also in a photothermographic material can provide high contrast and high Dmax (highest density) performance suitable for photolithography, but on the other hand, hydrazine An aqueous dispersion of a high contrast agent represented by a derivative has a problem that fogging occurs with time until it is added to a coating solution. The stability over time of an aqueous dispersion of a high contrast agent is an important problem relating to the stable production of photosensitive materials.

[0008]

Accordingly, an object of the present invention is to provide a fog (D) regardless of the aging of an aqueous dispersion of a high contrast agent.
min.) is to provide a heat-developable ultra-high contrast photosensitive material having extremely small photographic characteristics.

[0009]

The above object has been achieved by the following means. (1) On at least one same surface of the support, (a)
From photosensitive silver halide, (b) a reducible silver salt, (c) a reducing agent, (d) a binder, and (e) compounds represented by formulas (A), (B) and (C) A photothermographic material having at least one compound selected from the group consisting of a compound represented by the formula (1), a polymer having a repeating unit derived from a monomer represented by the formula (2), and a compound represented by the formula: A photothermographic material comprising at least one compound selected from the compounds represented by (3).

[0010]

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[0011]

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[0012]

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[In the formula (A), R ¹ , R ² and R ³ are
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. In equation (B),
R ⁴ represents a substituent. In the formula (C), X and Y each independently represent a hydrogen atom or a substituent;
Is each independently an alkoxy group, an alkylthio group,
Alkylamino group, aryloxy group, arylthio group, anilino group, heterocyclic oxy group, heterocyclic thio group,
Or a heterocyclic amino group. In the formula (C), X and Y, and A and B may be bonded to each other to form a cyclic structure. ]

[0014]

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In the formula (1), X ¹ represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring, J represents a divalent linking group, B ¹ represents a ballast group, and n represents 1 Represents the above integer. ]

[0016]

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[In the formula (2), Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group;
² represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring. ]

[0018]

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[In the formula (3), A ¹ represents a group having a water-soluble group, and X ³ represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring. (2) The photothermographic material according to the above (1), wherein the film surface pH is 3 or more and 7 or less.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photothermographic material of the present invention has an image forming layer containing a reducible silver salt and a binder on at least one surface of a support, and further comprises a photosensitive material on the same surface as the image forming layer. It has a layer containing a silver halide and a layer containing a reducing agent. Preferably, the image forming layer is a photosensitive layer containing a photosensitive silver halide, and the reducing agent is preferably contained in the same layer. In such a light-sensitive material, a layer on the same surface as the image forming layer contains at least one compound selected from the compounds represented by formulas (A) to (C) as a contrast agent, and further comprises a compound represented by the formula (1) ), A polymer having a repeating unit derived from a monomer represented by Formula (2), and a compound represented by Formula (3) (these are collectively represented by Formulas (1) to ( At least one compound selected from 3)).
By containing the seed, excellent photographic performance can be obtained, and stable and good photographic performance can be obtained even when an aqueous dispersion of the toning agent is aged. On the other hand, when a contrasting agent such as a hydrazine derivative is used, the contrasting property is reduced, and particularly when a water dispersion of the contrasting agent after aging is used, the contrasting property is greatly reduced. Fog also tends to increase. On the other hand, when a compound other than the above compounds such as the compound represented by the formula (I) is used, the softening becomes remarkable when the aqueous dispersion of the high contrast agent is used after a lapse of time, and stable performance cannot be obtained.

In order to obtain particularly good photographic performance, it is preferable that the surface pH of the surface on the image forming layer side is in the range of 3 to 7.

The compound represented by the formula (1), the polymer having a repeating unit derived from the monomer represented by the formula (2), or the compound represented by the formula (3) will be described in detail. .

In each of the formulas (1), (2) and (3), the residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring represented by X ¹ , X ² or X ³ is, for example, a photographic engineering compound. Basic silver salt edition (edited by the Photographic Society of Japan, Corona Co., Ltd.), page 354, chemistry of photography (Akira Sasai, Photo Industry Publishing Co., Ltd.), pages 168-169, or The Theory of Photographic Process (TH.
And the residue of an organic compound known as an inhibitor (or an antifoggant) in a conventional silver halide photographic light-sensitive material as described in pages 396 to 399 of James Mill, Inc. Is the solubility product of the silver salt of the compound in water at 25 ° C. (pK
sp) is a residue of 10 or more organic compounds.

The formulas (1), (2), and (3) of the present invention will be described below.
X in each of (3)¹, X^Two, X ^ThreeNitrogen-containing represented by
Formula embodying the residue of a photographic inhibitor having a heterocycle
(4) to (15) and (17) to (21) are shown.

[0025]

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In the formulas (4) to (10), R ²¹ ,
R ²² and R ²³ each represent a hydrogen atom, an alkyl group or an aryl group, and M ¹ represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue. Equation (6),
In (8) and (9), Y ¹ represents —N (R ²⁴ ) —, —O
— Or —S—, and R ²⁴ represents a hydrogen atom or an alkyl group. In the formula (10), Y ^10- represents a counter anion.

[0027]

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[0028] In formula (11) ~ (14), R 25 represents a hydrogen atom, an alkyl group or an aryl group, R ^26, R
²⁷ represents a hydrogen atom, an alkyl group, an aryl group or a nitro group, and R ²⁶ and R ²⁷ may combine to form a 5- or 6-membered ring; Y ² is —N (R ²⁸ ) —, —CH (R
²⁸ )-, -O- or -S-, wherein R ²⁸ is a hydrogen atom,
It represents an alkyl group or an aryl group, M ² represents the M ¹ group having the same meaning as.

[0029]

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In the formula (15), R ²⁹ represents a hydrogen atom, an alkyl group, an aryl group or a group of the formula (16),
R ³⁰ and R ³¹ each represent a hydrogen atom, an alkyl group, an aryl group or a nitro group, and R ³⁰ and R ³¹ may combine to form a 5- or 6-membered ring.

[0031]

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In the formulas (17) to (19), R ³³ ,
R ^34, R ^35, R ³⁶ are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, a hydroxyl group, an alkoxy group, R ³⁷ -NH- (R ³⁷ is a hydrogen atom, an alkyl group, an aryl group) or - And SM ³ (M ³ represents a group having the same meaning as M ¹ ).

[0033]

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In the formula (20), R ³⁸ and R ³⁹ each represent a hydrogen atom, an alkyl group or an aryl group, and M ⁴ represents a group having the same meaning as M ¹ .

[0035]

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In the formula (21), R ⁴⁰ and R ⁴¹ each represent a hydrogen atom, an alkyl group or an aryl group, and R ⁴⁰ and R ⁴¹
May combine to form a 5- or 6-membered ring. Y ³
Represents ＝ C (R ⁴² )-or ＮN-, and R ⁴² represents a hydrogen atom, an alkyl group or an aryl group. M ⁵ is the above-mentioned M ¹
Represents the same group as

The above formulas (4) to (15) and (17) to
In (21), the residue of the photographic inhibitor having a nitrogen-containing heterocyclic ring represented by X ¹ , X ² or X ³ is a —SM group (M is a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine). A nitrogen-containing heterocyclic residue having a nitrogen-containing heterocyclic ring represented by the formula (5) or (11) is particularly preferable.

The formulas (1), (2), and (3) of the present invention will be described below.
X in each of (3)¹, X^Two, X ^ThreeNitrogen-containing represented by
Specific examples of the residue of a photographic inhibitor having a heterocyclic ring are shown below.

[0039]

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[0040]

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[0041]

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In the formula, *-indicates the position where the photographic inhibitor residue is bonded to another group. In the formula (1), specific examples of the divalent linking group represented by J include, but are not limited to, the following.

[0043]

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In the formula, R represents a hydrogen atom, an alkyl group or an aryl group. Furthermore, examples of the divalent linking group represented by J include those represented by the following formula (22).

[0045]

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In the formula, J ² and J ³ each represent a divalent linking group. Examples of the divalent linking group include —NH
CO-, -CONH-, -CO-, -COO-, -OC
O-, -SCO-, -COS-, -O-, -S-, -S
O -, -, and the like - SO _2. X ⁴ and X ⁵ each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include:
Alkylene group (eg, methylene group, propylene group, etc.), arylene group (eg, phenylene group, etc.), aralkylene group (eg, phenylmethylene group, etc.), alkylene arylene group (eg, methylene phenylene group, etc.)
Alternatively, an arylenealkylene group (for example, a phenylenemethylene group or the like) can be given. p ¹ , q ¹ , p ² and q ² each represent 0 or l. Next, specific examples of the divalent linking group represented by J in the formula (1) of the present invention are shown.

[0047]

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In the formula, *-indicates a position bonding to a photographic inhibitor residue represented by X ¹ and **-indicates a position bonding to a ballast group represented by B ¹ .

The ballast group represented by B ¹ in the formula (1) of the present invention includes a compound represented by the formula (1) of the present invention and its diffusibility during thermal development. an organic ballast group which comprises a molecular size and shape that is reduced or nondiffusible the, common organic ballast groups directly photographic inhibitor residue represented by X ¹ or (J ) A long-chain alkyl group bonded via a divalent linking group represented by n, and a benzene- or naphthalene-based aromatic directly or indirectly fused to the carbon ring nucleus or the like of the inhibitor residue Groups are included.

Useful ballast groups are generally those having at least 8 carbon atoms, more preferably substituted or unsubstituted alkyl groups having 8 to 40 carbon atoms. Also, a group having a group substituted with a hydrophilic group such as a sulfo group or a carboxy group and a group having a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms is the most effective ballast group. It is. Preferred specific examples of the ballast group are shown below.

[0051]

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[0052]

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In the formula, **-indicates a position at which the compound binds to the photographic inhibitor residue represented by X ¹ directly or via a divalent binding group represented by (J) n. Next, specific examples of the compound represented by the formula (1) of the present invention will be described, but are not limited thereto.

[0054]

[Table 1]

Q in the formula (2) represents an ethylenically unsaturated group or a group containing an ethylenically unsaturated group, and is preferably represented by the following formula (23).

[0056]

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In the formula, R ⁴³ represents a hydrogen atom, a carboxy group or an alkyl group (for example, a methyl group, an ethyl group, etc.), and this alkyl group may have a substituent. Atom, carboxyl group and the like. The carboxyl group represented by R ⁴³ and the carboxyl group of the substituent may form a salt. J ² , J ³ , X ⁴ ,
X ⁵ , p ¹ , q ¹ , p ² , and q ² each represent a group having the same meaning as in formula (22). Hereinafter, specific examples of the group represented by Q in the formula (2) will be shown.

[0058]

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In the formula, *-indicates the position of the bond to the photographic inhibitor residue represented by X ² . The molecular weight of the polymer having the monomer unit of the formula (2) is from 2000 to 1000 in weight average molecular weight.
It is preferably 00. Next, specific examples of the polymer compound having a repeating unit derived from the monomer represented by the formula (2) of the present invention are shown, but are not limited thereto.

[0060]

[Table 2]

The water-soluble group represented by A ¹ in the formula (3) represents a group capable of being anionized in a developer, and specifically includes a sulfonamide group, a sulfamoyl group, a phenolic hydroxyl group, a carboxyl group, Sulfo groups, and salts thereof. Preferred are a carboxyl group and a sulfo group. Hereinafter, specific examples of the group represented by A ¹ in the formula (3) are shown.

[0062]

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In the formula, **-indicates the position of the bond to the photographic inhibitor residue represented by X ³ . Next, the formula (3) of the present invention is used.
Specific examples of the compound represented by are shown below, but are not limited thereto.

[0064]

[Table 3]

Two or more compounds of formulas (1) to (3) may be used in combination, and the amount of the compounds used is preferably in the range of 0.01 to 100 mmol per 1 m ² of the photographic material. .

The compounds represented by the formulas (1) to (3) of the present invention can be used in any of a binder layer on the image forming layer side with respect to the support, that is, the image forming layer or another binder layer on this layer side. It may be added to the layer, but is preferably added to the image forming layer or the binder layer adjacent thereto.

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

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

Formulas (A) and (B) used in the present invention
The substituted alkene derivative represented by the formula (C), the substituted isoxazole derivative, and the specific acetal compound will be described in detail. These compounds are used as contrast agents.

[0070]

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

When R ¹ , R ² and R ³ in the formula (A) represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom),
Alkyl groups (including aralkyl groups, cycloalkyl groups, active methine groups, etc.), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (including N-substituted nitrogen-containing heterocyclic groups), and quaternized nitrogen A heterocyclic group containing an atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfonylcarbamoyl group,
Acyl carbamoyl group, sulfamoyl carbamoyl group, carbazoyl group, oxalyl group, oxamoyl group,
A cyano group, a thiocarbamoyl group, a hydroxy group or a salt thereof, an alkoxy group (including a group having a repeating ethyleneoxy or propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, (alkoxy or aryloxy) Carbonyloxy group,
A carbamoyloxy group, a sulfonyloxy group, an amino group, an (alkyl, aryl, or heterocycle) amino group, an acylamino group, a sulfonamide group, a ureido group,
Thioureido group, isothioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl ) Sulfonylureido, acylureido, acylsulfamoylamino, nitro, mercapto,
(Alkyl, aryl, or heterocycle) thio, acylthio, (alkyl or aryl) sulfonyl,
(Alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoryl group, group having a phosphoric acid amide or phosphate ester structure, silyl group, And a stannyl group.

These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the formula (A) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with an N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom,
Perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group, sulfo group (or salt thereof), heterocyclic group, alkenyl group, alkynyl group, acyloxy group, acylthio group , A sulfonyloxy group, or an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is an aromatic or non-aromatic, saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group, a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group. Groups, hydantoin-1-yl group, urazol-1-yl group, succinimide group, phthalimide group and the like. In the formula (A), the electron-withdrawing group represented by Z is
Further, it may have an optional substituent.

In the formula (A), the electron-withdrawing group represented by Z is preferably a group having a total number of carbon atoms of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carbonyl group,
Imino group, imino group substituted with N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acyloxy group, acylthio group, or any electron withdrawing And a phenyl group substituted with a functional group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbonyl group, an imino group,
An imino group substituted with an N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group; Particularly preferably, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted by an N atom, an alkylsulfonyl group, an arylsulfonyl group,
An acyl group or a formyl group.

In the formula (A), the substituent represented by R ¹ is preferably a group having a total carbon number of 0 to 30, specifically, an electron-withdrawing group represented by Z in the above formula (A). As well as alkyl, alkenyl, alkoxy, aryloxy, heterocyclic oxy, alkylthio, arylthio, heterocyclic thio, amino, alkylamino, arylamino, heterocyclic amino , A ureido group, an acylamino group, a silyl group, or a substituted or unsubstituted aryl group, more preferably
A group having the same meaning as the electron-withdrawing group represented by Z in (A), a hydrogen atom, a substituted or unsubstituted aryl group, an alkenyl group,
An alkylthio group, an arylthio group, an alkoxy group, a silyl group, or an acylamino group, more preferably an electron-withdrawing group, an aryl group, an alkenyl group, or an acylamino group.

When R ¹ represents an electron-withdrawing group, its preferred range is the same as the preferred range of the electron-withdrawing group represented by Z.

In the formula (A), the substituent represented by R ² and R ³ is preferably a group having the same meaning as the electron-withdrawing group represented by Z in the above formula (A), an alkyl group, a hydroxy group ( Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group,
Examples include an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group. R ² and R ³ are more preferably when one of them is a hydrogen atom and the other represents a substituent. Preferably as the substituent, an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group Group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly a perfluoroalkaneamide group), a sulfonamide group, a substituted or unsubstituted phenyl group, or a heterocyclic group, and more preferably a hydroxy group
(Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group, and particularly preferably. It is a hydroxy group (or a salt thereof), an alkoxy group, or a heterocyclic group.

In the formula (A), Z and R ¹ , or R ²
It is also preferred that and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number including a substituent of 1 to 7. 4
0, more preferably 3 to 35.

[0080] Among the compounds represented by formula (A), more One of preferred, Z is a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group,, R ¹ is Represents an electron-withdrawing group, one of R ^{2 and} R ³ is a hydrogen atom and the other is a hydroxy group
(Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group.

Further, among the compounds represented by the formula (A),
One of the more preferred is that Z and R ¹And connected
Forming a 5- to 7-membered aromatic ring structure,^TwoAlso
Is R^ThreeIs a hydrogen atom and the other is hydroxy
Group (or its salt), mercapto group (or its salt),
Coxy group, aryloxy group, heterocyclic oxy group,
Kirthio, arylthio, heterocyclic thio, amino
Or a compound that represents a heterocyclic group.

Here, the non-aromatic 5 formed by Z and R ¹
The 7-membered to 7-membered cyclic structure is specifically indane-1,3-
Dione ring, pyrrolidine-2,4-dione ring, pyrazolidine-3,5-dione ring, oxazolidine-2,4-dione ring, 5-pyrazolone ring, imidazolidine-2,4-dione ring, thiazolidine-2,4 A dione ring, an oxolane-2,4-dione ring, a thiolane-2,4-dione ring,
1,3-dioxane-4,6-dione ring, cyclohexane-1,3-dione ring, 1,2,3,4-tetrahydroquinoline-2,4-dione ring, cyclopentane-1,3
A dione ring, an isoxazolidine-3,5-dione ring,
Barbituric acid ring, 2,3-dihydrobenzofuran-3
-One ring, pyrazolotriazole ring (for example, 7H-pyrazolo [1,5-b] [1,2,4] triazole, 7H
-Pyrazolo [5,1-c] [1,2,4] triazole, 7H-pyrazolo [1,5-a] benzimidazole and the like, pyrrolotriazole ring (for example, 5H-pyrrolo [1,2-b] [1 , 2,4] triazole, 5H-pyrrolo [2,1-c] [1,2,4] triazole and the like),
2-cyclopentene-1,4-dione ring, 2,3-dihydrobenzothiophen-3-one-1,1-dioxide ring, chroman-2,4-dione ring, 2-oxazoline-
5-one ring, 2-imidazolin-5-one ring, 2-thiazolin-5-one ring, 1-pyrrolin-4-one ring, 5-
Oxothiazolidine-2-thione ring, 4-oxothiazolidine-2-thione ring, pyrrolopyrimidinone ring, 1,3
-Dithiolane ring and the like, in particular indane-1,3
-A dione ring, a pyrrolidine-2,4-dione ring, a pyrazolidine-3,5-dione ring, a 5-pyrazolone ring, a barbituric acid ring, a 2-oxazolin-5-one ring and the like are preferable.

Examples of the substituent represented by R ⁴ in the formula (B) are the same as those described for the substituents R ^{1 to} R ^{3 in} the formula (A).

In the formula (B), the substituent represented by R ⁴ is
Preferably, it is an electron-withdrawing group or an aryl group. R ⁴
When represents an electron-withdrawing group, the total carbon number is preferably 0 to 3
The following groups of 0: a cyano group, a nitro group, an acyl group,
A formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a perfluoroalkyl group, a phosphoryl group, an imino group, a sulfonamide group, or a heterocyclic group; Group, acyl group, formyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group,
An arylsulfonyl group, a sulfonamide group and a heterocyclic group are preferred.

When R ⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and the substituent is represented by R ¹ , R ² , R ³ of the formula (A). When represents a substituent, the same as those described as the substituent can be mentioned, but an electron-withdrawing group is preferable.

The substituents represented by X and Y in the formula (C) are the same as those described for the substituents R ^{1 to} R ^{3 in} the formula (A). The substituent represented by X or Y is preferably a group having 1 to 50 total carbon atoms, more preferably a group having 1 to 35 total carbon atoms, and is a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acylamino group, acyloxy group, acylthio Preferred are a group, a heterocyclic group, an alkylthio group, an alkoxy group, an aryl group, and the like. More preferably substituted with a cyano group, nitro group, alkoxycarbonyl group, carbamoyl group, acyl group, formyl group, acylthio group, acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, imino group, N atom Imino group, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, Examples include an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, and a phenyl group substituted with any electron-withdrawing group.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the ring formed is preferably a 5- to 7-membered ring, and specifically, a non-aromatic 5- to 7-membered ring which can be formed by bonding Z and R ¹ of the formula (A) to each other. The same examples are given, and their preferred ranges are also the same. These rings may further have a substituent, and the total carbon number is preferably 1 to 40, more preferably 1 to 35.

The groups represented by A and B in the formula (C) may further have a substituent, and preferably have a total carbon number of 1
To 40, more preferably a group having 1 to 30 carbon atoms in total.

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

The compounds represented by the formulas (A), (B) and (C) of the present invention may have incorporated therein an adsorptive group that adsorbs to silver halide. A ballast group or a polymer commonly used in immobile photographic additives such as couplers may be incorporated, and a cationic group (specifically, a group containing a quaternary ammonium group, or
A nitrogen-containing heterocyclic group containing a graded nitrogen atom, etc.), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl, or heterocycle)
It may contain a thio group or a dissociable group that can be dissociated by a base (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.). Examples of these groups include, for example, JP-A-63-29751.
Nos. 4,385,108 and 4,459,
347, JP-A-59-195233, and JP-A-59-20
Nos. 0231, 59-201045, 59-201
Nos. 046, 59-201047, 59-2010
No. 48, 59-201049, JP-A-61-170
No. 733, No. 61-270744, No. 62-948
Nos. 63-234244 and 63-234245
No. 63-234246, JP-A-2-285344
JP-A-1-100530, JP-A-7-23447
No. 1, JP-A-5-333466, JP-A-6-1903
No. 2, JP-A-6-19031, JP-A-5-45761
No. 4,994,365, U.S. Pat.
4, JP-A-3-259240, JP-A-7-5610
, JP-A-7-244348, German Patent 400603
Compounds described in No. 2 and the like can be mentioned.

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

[0092]

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[0093]

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[0094]

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[0095]

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In the present invention, the compound represented by the formula (D) or (E) is most preferably used as a high contrast agent.

[0097]

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In the formula (D) or (E), Z ¹¹ and Z
^{1 2} each represents a nonmetallic atomic group capable to form a ring structure of 5-membered to 7-membered containing these, Y ¹¹ and Y ¹² each -C
(＝ O) — or —SO ₂ —, X ¹¹ and X ¹²
Is a hydroxy group (or a salt thereof), an alkoxy group,
Aryloxy group, heterocyclic oxy group, mercapto group
(Or a salt thereof), an alkylthio group, an arylthio group,
Represents a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an acylamino group, a sulfonamide group, or a heterocyclic group. Y ¹³ represents a hydrogen atom or a substituent.

The compounds represented by formulas (D) and (E) will be described in more detail. In the formula (D), Z
^{11, -Y 11 -C (= CH-} X 11) -C (= O) - with 5
Represents a non-metallic atomic group capable of forming a 7- to 7-membered ring structure. Z
¹¹ is preferably an atomic group selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hydrogen atom, and several atoms selected from these are connected to each other by a single bond or a double bond; Y ¹¹ -C (= CH-X ¹¹ ) -C
(= O)-forms a 5- to 7-membered ring structure. Z ¹¹ may have an optional substituent, and Z ¹¹ itself may be an aromatic or non-aromatic carbon ring, or a part of an aromatic or non-aromatic hetero ring. Case Z
^{11 -Y 1 1 -C (= CH-} X 11) -C (= O) - ring a 5- to 7-membered forming together will form a condensed ring structure.

In the formula (E), Z ¹² is -Y ¹² -C (=
Represents a ^{CH-X 12) -C (Y} 13) = non-metallic atomic group capable to form a 5-membered to 7-membered ring structure with N-. Z ¹² is preferably an atomic group selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hydrogen atom, and several atoms selected from these are connected to each other by a single bond or a double bond. ^{-Y 12 -C (= CH-X} 12) -C (Y 13) = N-
Together form a 5- to 7-membered ring structure. Z ¹² may have an optional substituent, and Z ¹² itself may be an aromatic or non-aromatic carbon ring, or a part of an aromatic or non-aromatic hetero ring. If Z ¹² is -Y
Ring structures ^{12 -C (= CH-X 12} ) -C (Y 13) = 5 -membered to 7-membered formed together with N- will form a condensed ring structure.

In the formula (D), Z ¹¹ is preferably an atomic group capable of forming a 5- or 6-membered cyclic structure, and specific examples thereof include a nitrogen atom, a carbon atom, a sulfur atom and an oxygen atom. Atomic group, for example, -N-N
-, -ON-, -NC, -OC-, -CC-,
-C = C-, -S-C-, -C = C-N-, -C = C-
O-, -N-C-N-, -N = C-N-, -C-C-C
-, -C = CC-, -OCO- and the like further have a hydrogen atom or a substituent. Z
¹¹ is more preferably -NN-, -NC-, -OC.
-, -CC-, -C = C-, -S-C-, -NC-
This is the case where the atomic group such as N-, -C = C-N- further has a hydrogen atom or a substituent, and particularly preferably -N-N-, -NC-, -C = C -, Etc., further have a hydrogen atom or a substituent.

Z ¹¹ itself becomes a part of an aromatic or non-aromatic carbon ring or an aromatic or non-aromatic hetero ring, and Z ¹¹ is represented by —Y ¹¹ —C (＝ CH—X ¹¹ ) -C
It is also preferable to form a condensed ring structure with a 5- to 7-membered ring structure formed together with (= O)-. Examples of the aromatic or non-aromatic carbon ring in this case, or an aromatic or non-aromatic hetero ring, for example, a benzene ring,
Examples include a naphthalene ring, a pyridine ring, a cyclohexane ring, a piperidine ring, a pyrazolidine ring, a pyrrolidine ring, a 1,2-piperazine ring, a 1,4-piperazine ring, an oxane ring, an oxolane ring, a thiane ring, and a thiolane ring. Among them, a benzene ring, a piperidine ring and a 1,2-piperazine ring are preferred, and a benzene ring is most preferred.

In the formula (E), Z ¹² is preferably an atomic group capable of forming a 5- or 6-membered cyclic structure, and specific examples thereof include a nitrogen atom, a carbon atom, a sulfur atom and an oxygen atom. The selected atomic group, for example, -N-,-
O-, -S-, -C-, -C = C-, -CC-, -N
The atomic groups such as -C-, -N = C-, -OC-, -S-C- and the like have a hydrogen atom or a substituent when possible.

Z ¹² itself forms part of an aromatic or non-aromatic carbocyclic ring or an aromatic or non-aromatic heterocyclic ring, and forms —Y ¹² —C (＝ CH—X ¹² ) —C (Y ¹³ )
It is also preferable to form a condensed ring structure with respect to a 5- to 7-membered ring structure formed together with = N-. Examples of the aromatic or non-aromatic carbon ring in this case, or an aromatic or non-aromatic hetero ring, for example, benzene ring, naphthalene ring, pyrrole ring, pyridine ring, cyclohexane ring, piperidine ring, pyrazolidine ring, A pyrrolidine ring,
Examples thereof include a 1,2-piperazine ring, a 1,4-piperazine ring, an oxane ring, an oxolane ring, a thiane ring, and a thiolane ring, and a benzene ring is more preferable.

In the formula (E), Z ¹² is more preferably-
An atomic group such as N-, -O-, -S-, -C-, -C = C- has a hydrogen atom or a substituent when possible, and particularly preferably -N. When possible, the atomic group such as-, -O- has a hydrogen atom or a substituent.

Examples of the substituent represented by Y ¹³ in the formula (E) include an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and an amino group. Group, (alkyl, aryl or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, alkoxy group, aryloxy group,
(Alkyl, aryl, or heterocycle) thio group and the like, and these substituents may be substituted with any substituent.

In the formula (E), Y ¹³ is preferably a hydrogen atom, an alkyl group, an aryl group (particularly a phenyl group or a naphthyl group), a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an (alkyl, (Aryl or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, imide group, alkoxy group, aryloxy group, or (alkyl, aryl,
Or heterocycle) thio group, and more preferably an alkyl group, a phenyl group, an amino group, an anilino group, an acylamino group, an alkoxy group, an aryloxy group, or a carbamoyl group. 30 is preferable, and 1 to 21 is more preferable.

When X ¹¹ and X ¹² in formula (D) or (E) represent a heterocyclic group, they are nitrogen-containing heterocyclic groups linked by a nitrogen atom, and are aromatic or non-aromatic, saturated or unsaturated. A monocyclic or condensed, substituted or unsubstituted nitrogen-containing heterocyclic group such as N-methylhydantoyl, succinimide, phthalimido, N, N′-
Examples include a dimethylurazolyl group, an imidazolyl group, a benzotriazolyl group, an indazolyl group, a morpholino group, and a 4,4-dimethyl-2,5-dioxo-oxazolyl group.

When X ¹¹ and X ¹² represent a hydroxy group (or a salt thereof) or a mercapto group (or a salt thereof), the salt means an alkali metal (sodium, potassium, lithium) or an alkaline earth metal (magnesium, And quaternary ammonium salts (tetraethylammonium salt, dimethylcetylbenzylammonium salt, etc.) and quaternary phosphonium salts.

In the formula (D) or the formula (E), X ¹¹ and X ¹² are preferably a hydroxy group (or a salt thereof),
An alkoxy group, a heterocyclic oxy group, an acylamino group, a mercapto group (or a salt thereof), an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, a sulfonamide group, or a heterocyclic group, more preferably Is a hydroxy group (or a salt thereof), an alkoxy group, a mercapto group (or a salt thereof), an alkylthio group, or a heterocyclic group, particularly preferably a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), and an alkoxy group. Or a heterocyclic group, most preferably a hydroxy group (or a salt thereof), or an alkoxy group. When X ¹¹ and X ¹² represent an alkoxy group, the total carbon number is preferably 1 to 20, more preferably 1 to 1
2 is preferable, and particularly preferably 1 to 5. When X ¹¹ and X ¹² represent a heterocyclic group, the total number of carbon atoms is 2 to 20.
Is preferable, and 2-16 are more preferable.

In the formulas (D) and (E), Y ¹¹ and Y ¹² represent a —C (＝ O) — group or a —SO ₂ — group, preferably a —C (＝ O) — group. is there.

The compound represented by the formula (D) preferably has a total carbon number of 6 or more, and the compound represented by the formula (E) preferably has a total carbon number of 12 or more. The upper limit of the total carbon number is not particularly limited, but the compound represented by the formula (D) is preferably 40 or less, more preferably 32 or less. The compound represented by the formula (E) is preferably at most 40, more preferably at most 32.

In the formula (D), Z ¹¹ , including its substituents, preferably has at least 2 carbon atoms, and more preferably at least 3 carbon atoms. In the formula (E), Z
^{In the case of 12} , it is preferable that the sum of the total number of carbon atoms of this and Y ¹³ including its substituents is 7 or more. In the formula (D), Z
¹¹ has a total carbon number of 3 or more and 40 or less including its substituents, and particularly preferably 6 or more and 30 or less. In formula (E), Z ¹² , including its substituents, preferably has a sum of the total number of carbon atoms of Y ¹³ with Y ¹³ of 7 or more and 40 or less, and more preferably 7 or more and 30 or less. Is particularly preferred.

The compounds represented by the formulas (D) and (E) may have incorporated therein an adsorptive group that adsorbs to silver halide. Ballast groups or polymers commonly used in immobile photographic additives such as couplers may be incorporated, and cationic groups (specifically, groups containing a quaternary ammonium group, or A nitrogen-containing heterocyclic group containing a graded nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group,
Alternatively, it may contain a dissociable group (such as a carboxy group, a sulfo group, an acylsulfamoyl group, or a carbamoylsulfamoyl group) that can be dissociated by a base. Particularly, a group containing an adsorptive group, a ballast group, a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, or a group containing an (alkyl, aryl, or heterocyclic) thio group is one of preferred examples of the present invention. One. Examples of these groups include, for example, JP-A-63-29751, U.S. Pat. Nos. 4,385,108 and 4,459,347.
And JP-A-59-195233 and JP-A-59-20023.
No. 1, No. 59-201045, No. 59-201046
Nos. 59-201047 and 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
JP-A-3-234246, JP-A-2-285344, JP-A-1-100530, JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, JP-A-5 No. 4,576,361, U.S. Pat. No. 4,994,365, U.S. Pat. No. 4,988,604, JP-A-3-259240, JP-A-7-5610, JP-A-7-244348, and German Patent 4006032.

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

[0116]

[Table 4]

[0117]

[Table 5]

The compounds represented by the formulas (A) to (E) of the present invention can be easily synthesized by known methods. For example, US Pat. No. 5,545,515, US Pat.
No. 35339, US Pat. No. 5,654,130, International Patent W
O-97 / 34196 or Japanese Patent Application No. 9-3541
07, Japanese Patent Application No. 9-309813, Japanese Patent Application No. 9-272
The compound can be synthesized with reference to the method described in No. 002.

The compounds represented by the formulas (A) to (E) of the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol) and ketones (acetone, methyl ethyl ketone). ), Dimethylformamide, dimethylsulfoxide,
It can be used by dissolving it in methylcellosolve or the like.

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

The compounds represented by the formulas (A) to (E) of the present invention may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer. Is preferably added to the image forming layer or a layer adjacent thereto.

The addition amount of the compounds represented by the formulas (A) to (E) of the present invention is preferably 1 × 10 ⁻⁶ to 1 mol per 1 mol of silver, and 1 × 10 ^{−5 to} 5 × 10 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is most preferred. The compounds represented by the formulas (A) to (E) of the present invention may be used alone or in combination of two or more.

In the present invention, a hydrazine derivative represented by the following formula (H) is preferably used as a high contrast promoting agent.

[0124]

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

Next, the hydrazine derivative represented by the following formula (H) will be described. The aliphatic group represented by R ¹² in the formula (H) is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 30 carbon atoms.

The aromatic group represented by R ¹² is a monocyclic or condensed-ring aryl group such as a phenyl group or a naphthyl group derived from a benzene ring or a naphthalene ring. The heterocyclic group represented by R ¹² is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, Examples include a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a triazine ring, a morpholine ring, a piperidine ring, a piperazine ring, and a benzo [1,3] dioxole ring. R ¹² may be substituted with any substituent.

R ¹² is preferably an aryl group, an alkyl group or an aromatic heterocyclic group, more preferably a substituted or unsubstituted phenyl group, having 1 to 1 carbon atoms.
3 substituted alkyl groups or aromatic heterocyclic groups.

R¹²Represents a substituted alkyl group having 1 to 3 carbon atoms.
Then R¹²Is more preferably a substituted methyl group,
Is preferably a disubstituted or trisubstituted methyl group
No. R ¹²Is a preferred specific example when represents a substituted methyl group.
T-butyl group, dicyanomethyl group, dicyanofe
Nylmethyl group, triphenylmethyl group (trityl group),
Phenylmethyl group, methoxycarbonyldiphenylmethyl
Group, cyanodiphenylmethyl group, methylthiodiphenyl
Methyl group, cyclopropyldiphenylmethyl group, etc.
Among them, a trityl group is most preferable.

When R ¹² represents an aromatic heterocyclic group, preferred hetero rings include a pyridine ring, a quinoline ring, a pyrimidine ring, a triazine ring, a benzothiazole ring, a benzimidazole ring, a thiophene ring and the like.

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

In the formula (H), R ¹¹ represents a hydrogen atom or a block group, and the block group is specifically an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group (a single group). Ring or fused ring aryl group),
Represents a heterocyclic group, an alkoxy group, an aryloxy group, a substituted or unsubstituted amino group or a hydrazino group.

R ¹¹ is preferably an alkyl group (a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group). , Pyridiniomethyl, difluoromethoxymethyl, difluorocarboxymethyl, hydroxymethyl, methanesulfonamidomethyl, benzenesulfonamidomethyl, trifluorosulfonamidomethyl, trifluoroacetylmethyl, dimethylaminomethyl, phenylsulfonyl Methyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxymethyl group,
4-ethylphenoxymethyl group, phenylthiomethyl group, t-butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, methoxycarbonyldiphenylmethyl group, cyanodiphenylmethyl group, methylthiodiphenylmethyl group, etc.), alkenyl group (C 1-
10 alkenyl groups such as vinyl, 2-ethoxycarbonylvinyl, 2-trifluoro-2-methoxycarbonylvinyl, 2,2-dicyanovinyl, 2-
Cyano-2-methoxycarbonylvinyl group, 2-cyano-2-ethoxycarbonylvinyl group, 2-acetyl-2
-Ethoxycarbonylvinyl group, etc.) and aryl groups (monocyclic or condensed-ring aryl groups containing a benzene ring are particularly preferred; for example, phenyl, perfluorophenyl, 3,5-dichlorophenyl, 2-methane) Sulfonamidophenyl group, 2-carbamoylphenyl group,
4,5-dicyanophenyl group, 2-hydroxymethylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2-chloro-5-octylsulfamoylphenyl group), heterocyclic group (5-6 membered saturated or unsaturated, containing at least one nitrogen, oxygen and sulfur atom)
Monocyclic or condensed ring heterocyclic groups such as morpholino, piperidino (N-substituted), imidazolyl, indazolyl (4-nitroindazolyl), pyrazolyl, triazolyl, benzimidazolyl, tetrazolyl, Pyridyl group, pyridinio group, quinolinio group, quinolyl group, hydantoyl group, imidazolidinyl group, etc.),
An alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, a 2-hydroxyethoxy group, a benzyloxy group, a t-butoxy group, etc.), an amino group (an unsubstituted amino group, and a 1 to 10 carbon atoms) Preferred are an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group (including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom), for example, 2,2,2.
6,6-tetramethylpiperidin-4-ylamino group,
Propylamino group, 2-hydroxyethylamino group, 3
-Hydroxypropylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group,
N-benzyl-3-pyridinioamino group and the like). R
^The group represented by ¹¹ may be substituted with any substituent.

Among the groups represented by R ¹¹ , preferred are a hydrogen atom, an alkyl group and an alkenyl group when R ¹² represents a phenyl group or an aromatic heterocyclic group and G ¹ is a —CO— group. , An alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and most preferably a hydrogen atom or an alkyl group. Here, when R ¹¹ represents an alkyl group, the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, a sulfonamide group, an amino group, an acylamino group, or a carboxy group. .

R¹²Represents a substituted methyl group, and G¹But-
In the case of a CO- group, R¹¹Is preferably a hydrogen atom,
Kill group, aryl group, heterocyclic group, alkoxy group,
Group (unsubstituted amino group, alkylamino group, aryl group
Amino group, heterocyclic amino group), more preferably
Hydrogen atom, alkyl group, aryl group, heterocyclic group, al
Coxy group, alkylamino group, arylamino group, hete
It is a ro-ring amino group. G ¹Is a -COCO- group
Is R¹²Regardless of R¹¹Is an alkoxy group, arylo
Xyl groups and amino groups are preferred, particularly substituted amino groups.
Or alkylamino, arylamino, or saturated
Alternatively, an unsaturated heterocyclic amino group is preferable.

When G ¹ is a —SO ₂ — group, R ¹¹ is preferably an alkyl group, an aryl group or a substituted amino group, regardless of R ¹² .

In the formula (H), G ¹ is preferably -CO
Or a -COCO- group, particularly preferably -C
O-group.

In the formula (H), A ¹¹ and A ¹² represent a hydrogen atom,
An alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more), an acyl group having 20 or less carbon atoms (Preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more, or a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group) is there. A ¹¹ and A ¹² are most preferably hydrogen atoms.

In the formula (H), m ¹ represents 1 or 0. When m ¹ is 0, R ¹¹ represents an aliphatic group, an aromatic group or a heterocyclic group. When m ¹ is 0, R ¹¹ is particularly preferably a phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an alkenyl group. Of these, for the phenyl group and the substituted alkyl group having 1 to 3 carbon atoms, its preferred range is the same as the preferable ranges of R ¹² described above.
When R ¹¹ is an alkenyl group, preferably R ¹¹ is a vinyl group, and is a substituent selected from the following substituents: a cyano group, an acyl group, an alkoxycarbonyl group, a nitro group, a trifluoromethyl group, a carbamoyl group and the like. Vinyl groups having one or two groups are particularly preferred. In particular,
Examples thereof include a 2,2-dicyanovinyl group, a 2-cyano-2-methoxycarbonylvinyl group, a 2-cyano-2-ethoxycarbonylvinyl group, and a 2-acetyl-2-ethoxycarbonylvinyl group. m ¹ is preferably 1.

In the formula (H), R¹¹Is G¹-R¹¹Part of
From the residual molecule, and -G¹-R ¹¹Including partial atoms
That cause a cyclization reaction that produces a cyclic structure
And a hydrazine derivative represented by the formula (H).
The conductor has an adsorptive group that adsorbs to silver halide.
It may be incorporated. R of formula (H)¹¹Or R¹²To
Is used in immobile photographic additives such as couplers.
Incorporates commonly used ballast groups or polymers
And R in formula (H)¹¹Or R
¹²May have a plurality of hydrazino groups as substituents.
Often, the compound represented by the formula (H) is hydrazino
Represents a multimer for the group. Further, R of the formula (H)¹¹Also
Is R¹²Has a cationic group (specifically, a quaternary
A group containing an ammonium group or a quaternized nitrogen atom
Including nitrogen-containing heterocyclic group), ethyleneoxy group or
Groups containing repeating units of a propyleneoxy group, (alkyl
, Aryl, or heterocycle) thio group or base
Dissociable groups (carboxy group, sulfo group,
Acylsulfamoyl group, carbamoylsulfamoyl
And the like) may be contained. These examples include
For example, JP-A-63-29751, U.S. Pat.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948 and 63-234244
No. 63-234245, No. 63-234246
JP-A-2-285344, JP-A-1-005305
No. 0, JP-A-64-86134, JP-A-4-16938, JP-A-5
-199701, WO95-32452, WO95-32
No. 453, JP-A-9-235264, JP-A-9-235265, JP
Hei 9-235266, JP Hei 9-235267, JP Hei 9-179229,
JP-A-7-234471, JP-A-5-333466
JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat. No. 4,994,365.
No. 4,988,604, JP-A-3-25924.
No. 0, JP-A-7-5610, JP-A-7-244348
And compounds described in German Patent 4006032 and the like.
Can be

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

[0142]

[Table 6]

[0143]

[Table 7]

[0144]

[Table 8]

[0145]

[Table 9]

The hydrazine derivative used in the present invention is
One type may be used alone, or two or more types may be used in combination. In addition to the above, the following hydrazine derivatives are also preferably used. (In some cases, they can be used in combination.) The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following patents.

That is, JP-A-10-10672, JP-A-10-161270, JP-A-10-62898, JP-A-9-304870, JP-A-9-304872,
JP-A-9-304871, JP-A-10-31282
No. 5,496,695, European Patent 714320
All the hydrazine derivatives described in A.

The hydrazine derivative of the present invention may be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), It can be used by dissolving it in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like.

Further, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and co-solvents such as ethyl acetate and cyclohexanone are prepared by a well-known emulsification dispersion method. To dissolve and mechanically produce and use an emulsified dispersion. Alternatively, the hydrazine derivative powder can be dispersed in a suitable solvent such as water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side. Preferably, it is added to the layer.

The hydrazine derivative of the present invention is preferably from 1 × 10 ⁻⁶ to 1 mol, and more preferably from 1 × 10 ^{−5 to} 5 × 1 per mol of silver.
0 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is most preferred.

Further, the present invention provides a method for forming a super-high contrast image.
In addition to the hydrazine derivative, a contrast enhancement agent can be used in combination. For example, the amine compounds described in U.S. Patent No. 5,545,505, specifically AM-1 to AM-5,
No. 7 hydroxamic acids, specifically HA-1 to H
A-11, hydrazine compounds described in US Pat. No. 5,558,983, specifically CA-1 to CA-6, onium salts described in Japanese Patent Application No. 8-132836, specifically A-1 to A-42, B-1 ~
B-27, C-1 to C-14 and the like can be used.

The method for synthesizing, adding, and adding amounts of the above-mentioned high contrast agents and these high contrast accelerators can be carried out as described in each of the cited patents.

In the present invention, it is preferable to use an acid formed by hydration of diphosphorus pentoxide or a salt thereof in combination with a high contrast agent (nucleating agent). Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline Acids (salts); Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, Examples include sodium hexametaphosphate and ammonium hexametaphosphate.

The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto in that the desired effect is exhibited in a small amount. .

The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide used in the present invention (the coating amount per 1 m ^{2 of the} light-sensitive material) may be a desired amount in accordance with the performance such as sensitivity and fog. However, 0.1 to 500 mg / m ² is preferable, and 0.5 to 100
mg / m ² is more preferred.

The photothermographic material of the present invention contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In photothermographic materials utilizing organic silver salts, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
47-33621, 49-46427, 49-115540, 50-14
No. 334, No. 50-36110, No. 50-147711, No. 51-32632,
No. 51-1023721, No. 51-32324, No. 51-51933, No. 52-8
4727, 55-108654, 56-146133, 57-82828
No. 57-82829, JP-A-6-3793, U.S. Pat.
No. 86, No. 3,679,426, No. 3,751,252, No. 3,751,255
Nos. 3,761,270, 3,782,949, 3,839,048,
3,928,686, 5,464,738, German patent 2321328,
It is disclosed in European Patent No. 692732 and the like. For example, phenylamide oxime, 2-thienylamide oxime and
Amide oximes such as p-phenoxyphenylamide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; combinations of 2,2′-bis (hydroxymethyl) propionyl-β-phenylhydrazine with ascorbic acid A combination of such an aliphatic carboxylic acid aryl hydrazide and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone Or a combination of formyl-4-methylphenylhydrazine, etc.); phenylhydroxamic acid, p
Hydroxamic acids such as -hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano Α-cyanophenylacetic acid derivatives such as 2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy Bis-β-naphthol as exemplified by -1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4
-Dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl
5-pyrazolone, such as -5-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone;
Sulfonamidophenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-
A dione or the like; a chroman such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; a 1,4-dihydropyridine such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; Bisphenols (e.g., bis (2-hydroxy
-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene
-Bis (2-t-butyl-6-methylphenol), 1,1-bis (2-
Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (for example, 1-palmitic acid) And aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidones and certain indan-1,3-diones; chromanols (such as tocopherols).

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

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

The method of forming the photosensitive silver halide in the present invention is well known in the art, and uses, for example, the methods described in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. be able to. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method in which a silver supply compound and a halogen supply compound are added to another polymer solution to prepare photosensitive silver halide grains and mixed with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The particle size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation to be low.
20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less,
More preferably, the thickness is 0.02 μm or more and 0.12 μm or less. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

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

The light-sensitive silver halide grains used in the present invention are selected from the group VII or VIII (groups 7 to 7) of the periodic table.
It preferably contains a metal of Group 10) or a metal complex. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 10 ^-9 mol to 10 ^-2 mol, preferably 10 ^-8 mol to 10 ^-4 mol, per mol of silver. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

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

The addition amount of these rhodium compounds is
1 × 10 per mole of silver halide^-8Mol ~ 5 x 10^-6Mole of
The range is preferably, particularly preferably 5 × 10^-8Mol ~ 1x
10 ^-6Is a mole.

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

Rhenium, ruthenium and osmium preferably used in the present invention are described in JP-A-63-2042 and JP-A-1-2859.
It is added in the form of a water-soluble complex salt described in JP-A Nos. 41, 2-20852, 2-20855 and the like. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ⁿ -where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4.

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

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

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

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

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

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

In order to add the metal complex to the particle surface, a required amount of an aqueous solution of a metal complex may be charged into the reaction vessel immediately after the formation of the particle, during or at the end of physical ripening, or at the time of chemical ripening.

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

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

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

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

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization. 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 and selenium sensitization Method, tellurium sensitization method, gold sensitization method and the like are preferable.

The sulfur sensitization used in the present invention is usually carried out by
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ° C or more.
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, for example, in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds, such as
Thiosulfate, thioureas, thiazoles, rhodanine
Can be used. Preferred sulfur compounds are
Osulfates and thiourea compounds. Amount of sulfur sensitizer added
Indicates the pH, temperature, and size of silver halide grains during chemical ripening
Changes under various conditions, such as silver halide.
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748, JP-B-43-13489, JP-A-4-25832,
The compounds described in JP-A Nos. 4-109240 and 4-324855 can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in JP-A-4-324855.

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

[0183] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

The noble metal sensitizer used in the present invention includes gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used.

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

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

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

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

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

The organic silver salt which can be used as the reducible silver salt in the present invention is relatively stable to light,
A silver salt that forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially (C 10-30, preferably 1
Silver salts of long chain fatty carboxylic acids (5-28) are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor material can preferably make up about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of the aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphorate,
And mixtures thereof.

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

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

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

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

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

In the above, the aqueous dispersion which is dispersed after being converted to a high-pressure and high-speed liquid contains substantially no photosensitive silver salt, and its content is relative to that of the non-photosensitive organic silver salt. 0.
The content is 1 mol% or less, and the photosensitive silver salt is not positively added.

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

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

As a dispersing apparatus suitable for the present invention, a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation is used.
(G ¹ 0Z with interaction chamber), M-
110Y (with H10Z interaction ^{chamber), M-140K (G 1} 0Z with interaction chamber), HC-5000 (L30Z or H23
With 0Z interaction chamber), HC-80
00 (with an E230Z or L30Z interaction chamber) and the like.

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

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

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

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

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

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

[0206] While the organic silver salt according to the invention can be used in a desired amount, show a coating amount per photographic material 1 m ^2, 0.1 as silver
55 g / m ² is preferred, and more preferably 1-3 g / m ² .

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

In a photothermographic material using an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077 and JP-A-47-10282.
Nos. 49-5019, 49-5020, 49-91215, 49-9
No. 1215, No. 50-2524, No. 50-32927, No. 50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-279
No. 23, No. 52-14788, No. 52-99813, No. 53-1020, No. 5
3-76020, 54-156524, 54-156525, 61-1836
No. 42, JP-A-4-56848, JP-B-49-10727, 54-2033
No. 3, U.S. Pat.Nos. 3,080,254, 3,446,648, 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent 138079
No. 5, Belgian Patent No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimides (eg, N
-Hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-
Mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole Illustrative mercaptans; N- (aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl)-
Naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N′-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1 , 8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl-5 [(3-ethyl-2-benzothia) Zolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7- Derivatives such as dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic acid) Combination of anhydride such as phthalic acid); phthalazine, phthalazine derivatives (e.g., 4- (1-naphthyl) phthalazine, 6
-Chlorophthalazine, 5,7-dimethoxyphthalazine, iso-
Propylphthalazine, 6-iso-butylphthalazine, 6-tert
-Butylphthalazine, 5,7-dimethylphthalazine, and
Derivatives such as 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives
(Eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; silver halide in situ as well as color tone modifier Rhodium complex that also functions as a source of halide ions for formation, such as hexachlororhodium
(III) ammonium, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine- 2,4-
Benzoxazine-2,4-diones such as dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and asymmetric -Triazines (e.g., 2,4-dihydroxypyrimidine,
2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (e.g., 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6
-Dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).

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

As the binder for the image forming layer (photosensitive layer, emulsion layer) in the present invention, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefin, Any material can be selected from polyester, polystyrene, polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral, butyl ethyl cellulose, methacrylate copolymer, maleic anhydride copolymer, polystyrene and butadiene-
It is a styrene copolymer. If necessary, two or more of these polymers can be used in combination. Such a polymer is used in an amount sufficient to hold the components therein. That is, it is used in a range effective to function as a binder. The effective range can be appropriately determined by those skilled in the art. As a guide when at least the organic silver salt is retained, the ratio of the binder to the organic silver salt is preferably 15: 1 to 1: 2, particularly preferably 8: 1 to 1: 1.

At least one of the image forming layers of the present invention comprises the polymer latex described below in 50% of the total binder.
The image forming layer is preferably used in an amount of not less than wt%. (Hereinafter, this image forming layer is referred to as "the image forming layer of the present invention",
The polymer latex used for the binder is referred to as “the polymer latex of the present invention”. In addition, the polymer latex may be used not only for the image forming layer, but also for the protective layer and the back layer. It is necessary to use a polymer latex also for the back layer. However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. Regarding the polymer latex of the present invention, `` synthetic resin emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (1978)) '', `` application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, edited by Keiji Kasahara, Published by Kobunshi Kankokai (1993)), `` Chemistry of Synthetic Latex (Souichi Muroi,
Published by Kobunshi Kankokai (1970)). The average particle size of the dispersed particles is 1 to 50,000 nm, more preferably 5 to 100.
A range of about 0 nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and those having a wide particle size distribution or those having a monodispersed particle size distribution may be used.

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

The glass transition temperature (Tg) of the polymer of the polymer latex used for the binder used in the present invention
The preferred ranges differ between the protective layer, the back layer and the image forming layer. In the image forming layer, the temperature is 40 ° C. or less to promote the diffusion of useful photographic materials during thermal development.
C is preferred. When used for the protective layer or the back layer, a glass transition temperature of 25 to 70 ° C. is preferable for contacting various devices.

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

The polymer type used in the polymer latex used in the present invention includes acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or a copolymer thereof. There are coalescence. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The polymer has a number average molecular weight of 5000 to 100000, preferably 10,000 to 100,000.
The degree is preferred. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder for the image forming layer of the photothermographic material of the present invention include the following. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2 ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer and the like.
Such polymers are also commercially available, and the following polymers can be used. For example, as examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,857
(Nippon Zeon Co., Ltd.) and other polyester resins, such as FINETEX ES650, 611, 675, 850 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical Co., Ltd.), etc. HYDRAN AP10 as polyurethane resin,
LACSTAR 7310K, 3307B, 4700H, 7132C as rubber resins such as 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
(Dai Nippon Ink Chemical Co., Ltd.), Nipol Lx416, 41
G351 and G576 (both manufactured by Zeon Corporation) as vinyl chloride resins, such as 0, 438C and 2507 (both manufactured by Nippon Zeon Co., Ltd.)
Examples of vinylidene chloride resins include L502 and L513 (all manufactured by Asahi Kasei Kogyo Co., Ltd.), Aron D7020, D504, and D5071 (all manufactured by Mitsui Toatsu Co., Ltd.). Chemical Co., Ltd.). These polymers may be used alone or as a blend of two or more as necessary.

In the image forming layer of the present invention, the polymer latex is preferably used in an amount of 50% by weight or more of the total binder, and more preferably 70% by weight or more.

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

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

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

The surface pH of the photothermographic material of the present invention before the heat development processing is preferably 3 or more and 7 or less. Membrane surface p
For the adjustment of H, known acids and alkali solutions can be used, but phthalic acid derivatives (e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and organic acids such as tetrachlorophthalic anhydride, and the like) It is preferable to adjust the addition amount of a non-volatile acid such as sulfuric acid or phosphoric acid, or to use a volatile base such as ammonia.

In particular, ammonia is easily volatilized and can be removed before the coating step or thermal development.
It is preferable in achieving.

In the measurement of the film surface pH of the present invention, the photothermographic material 2.5 cm × 2.5 cm before the heat development was folded into a boat shape, 300 μl of distilled water was dropped on the image forming layer side, and the solution was allowed to stand for 30 minutes. After dropping, add the dropping solution to pH BOY-P2 (Shindengen Kogyo Co., Ltd.)
And a semiconductor type pH meter) for 1 minute.

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

As an example of spectral sensitization to red light, He-Ne
For a so-called red light source such as a laser, a red semiconductor laser or an LED, a compound of I-1 to I-38 described in JP-A-54-18726, and a compound of I-1 described in JP-A-6-75322. I-3
5 and the compounds I-1 to I- described in JP-A-7-287338.
34 compounds, dyes 1 to 20 described in JP-B-55-39818,
The compounds I-1 to I-37 described in JP-A-62-284343 and the compounds I-1 to I-34 described in JP-A-7-287338 are advantageously selected.

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

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
No. 72661, No. 6-222491, No. 2-230506, No. 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, JP-A-6-30114)
No. 1, U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes
(JP 47-6329, JP 49-105524, JP 51-127719, JP
52-80829, 54-61517, 59-214846, 60-6750
No. 63-159841, JP-A-6-35109, JP-A-6-59381,
And the dyes described in JP-A-7-146537, JP-A-7-146537, JP-T-55-50111, British Patent 1,467,638, and US Patent 5,281,515.

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

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

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

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid. To Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, the dye is dissolved in an acid and this solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or base. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, as disclosed in U.S. Patent Nos. 3,822,135 and 4,006,025, JP-A-53-102733. JP-A-51-746, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion as disclosed in JP-A-58-105141.
As disclosed in Japanese Patent No. 24, a method in which a dye is dissolved using a compound that causes a red shift, and this solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

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

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

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are used for controlling development by suppressing or accelerating development, improving spectral sensitization efficiency, and improving storage stability before and after development. Can be used in combination with the above inhibitor.

When a mercapto compound is used in the present invention, it may have any structure, but may be any of Ar-SM ⁰ , Ar-SSA
Those represented by r are preferred. In the formula, M ⁰ is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogens (e.g., Br and Cl), hydroxy, amino, carboxy,
Alkyl (e.g. one or more carbon atoms, preferably 1-4
Having one carbon atom), alkoxy (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and aryl (optionally having substituents)
And a substituent selected from the group consisting of:
As mercapto-substituted heteroaromatic compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5
-Methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2- Mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto
-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate , 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole,
4-Hydrocyr-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2
-Mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1-phenyl
-5-mercaptotetrazole, 3- (5-mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N'-
Examples include [3- (5-mercaptotetrazolyl) phenyl] urea, 2-mercapto-4-phenyloxazole, and the like, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is 0.0001 to 1 per mol of silver in the emulsion layer (image forming layer).
A molar range is preferred, more preferably an amount of 0.001 to 0.3 mole per mole of silver.

In the image forming layer (photosensitive layer) in the present invention, a polyhydric alcohol (for example, glycerin and diol of the type described in US Pat. No. 2,960,404) as a plasticizer and a lubricant, and US Pat. No. 2,588,765 are used. And fatty acids or esters described in US Pat. No. 3,121,060, and silicone resins described in UK Patent No. 955,061 can be used.

The photothermographic material according to the invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.

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

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

In the image forming layer or the protective layer of the image forming layer in the invention, US Pat. Nos. 3,253,921 and 2,27
Light absorbing substances and filter dyes as described in 4,782, 2,527,583 and 2,956,879 can be used. Also, for example, U.S. Pat.
The dye can be mordanted as described in US Pat. As the amount of filter dye used, the absorbance at the exposure wavelength is 0.
1-3 are preferable, and 0.2-1.5 are particularly preferable.

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

The photothermographic material of the present invention has at least one light-sensitive layer (image forming layer) containing a silver halide emulsion on one side of a support, and has a back layer on the other side. It is preferably a so-called one-sided photosensitive material.

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

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

In the present invention, a suitable binder for the back layer is transparent or translucent, generally colorless, and includes natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, and poly (vinyl). (Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal))
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the present invention, the single-sided photosensitive material may be prepared by adding a matting agent to the surface protective layer of the photosensitive emulsion layer (image forming layer) and / or the back layer or the surface protective layer of the back layer in order to improve the transportability. good. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Pat.
No. 213, No. 2,701,245, No. 2,322,037, No. 3,262,782
Nos. 3,539,344, 3,767,448, etc., the organic matting agents described in each specification, 1,260,772, 2,192,241, 3,3
257,206, 3,370,951, 3,523,022, 3,769,0
Those well known in the art, such as an inorganic matting agent described in each specification such as No. 20, can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of water-dispersible vinyl polymers, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, etc., and starch derivatives such as carboxy starch, carboxynitrophenyl Gelatin hardened with a known hardener such as starch, urea-formaldehyde-starch reactant, and hardened gelatin formed into microcapsule hollow granules by coacervate hardening are preferably used. Can be. As examples of the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth can be preferably used. The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze and surface gloss of the light-sensitive material, the particle size, shape, and particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

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

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. Preferably, it is contained. The matte degree of the emulsion surface protective layer may be any value as long as no stardust failure occurs, but the Beck smoothness is 500 seconds or more.
It is preferably at most 000 seconds, particularly preferably at least 500 seconds and at most 2,000 seconds.

The heat-developable photographic emulsion of the present invention comprises one or more layers on a support. One layer must contain additional optional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is the first
It must contain the organic silver salt and silver halide in the emulsion layer (usually the layer adjacent to the support) and some other components in the second or both layers. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, and may include all components in a single layer as described in U.S. Pat.No. 4,708,928. Is also good. In the case of a multi-dye, multi-color photosensitive heat-developable photographic material, each emulsion layer is generally, as described in U.S. Pat.
By using a functional or non-functional barrier layer between each emulsion layer (photosensitive layer), it is kept distinct from each other.

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

A hardener may be used for each layer such as the image forming layer (photosensitive layer), the protective layer and the back layer of the present invention. Examples of hardeners include U.S. Pat.No. 4,281,060 and JP-A-6-20819.
For example, polyisocyanates described in No. 3, etc., epoxy compounds described in US Pat. No. 4,791,042, vinyl sulfone compounds described in JP-A-62-89048 and the like are used.

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

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

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

The photothermographic material of the present invention may be, for example, a soluble salt (for example, chloride or nitrate), a vapor-deposited metal layer, US Pat. No. 2,861,056 and US Pat.
No. 206,312 or a layer containing an insoluble inorganic salt as described in U.S. Pat. May be provided.

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

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

In the photothermographic material of the present invention, additional layers, such as a dye-receiving layer for receiving a moving dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques It may include a known primer layer and the like. The light-sensitive material of the present invention is preferably capable of forming an image with only one light-sensitive material, and it is preferable that a functional layer necessary for image formation such as an image receiving layer does not become another light-sensitive material.

In the present invention, the exposure apparatus used for imagewise exposure may be any apparatus capable of performing exposure with an exposure time of less than 10 ⁻⁷ seconds, but is generally a laser diode (LD), Light Emitting Diode Light Emi
An exposure apparatus using a tting diode (LED) as a light source is preferably used. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

The exposure of the present invention is performed by overlapping the light beams of the light source with each other. The term "overlap" means that the sub-scanning pitch is smaller than the beam diameter. The overlap means, for example, that the beam diameter is equal to the full width at half maximum of the beam intensity (FWHM).
Can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient). In the present invention, this overlap coefficient is 0.2 or more (preferably 1).
The following is preferred.

The scanning method of the light source of the exposure apparatus used in the present invention is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. Also,
The channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface type, a multi-channel is preferably used.

The photothermographic material of the present invention has a low haze at the time of exposure and tends to cause interference fringes. Examples of the interference fringe prevention technology include a technology disclosed in Japanese Patent Application Laid-Open No. HEI 5-113548 and the like, in which a laser beam is obliquely incident on a photosensitive material, and a technology disclosed in International Patent WO95 / 31754 and the like. Methods using a mode laser are known, and it is preferable to use these techniques.

In the heat development step of the image forming method of the present invention, development may be performed by any method. Usually, development is performed by raising the temperature of a photosensitive material exposed imagewise. As a preferred embodiment of the thermal developing machine to be used, as a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum, Japanese Patent Publication No. 5-56499, Patent Publication No. 684453, Japanese Patent Application Laid-Open No. 9-292695, Kaihei 9-297385 and International Patent WO
No. 95/30934, as a non-contact type, JP-A-7-13294, International Patent WO 97/28489, and 97/2848
Nos. 8 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C, more preferably 100 to 140 ° C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

As a method for preventing processing unevenness due to a dimensional change during thermal development of the photothermographic material of the present invention, a temperature of 80.degree.
A method of forming an image by heating at a temperature of less than 5 ° C. (preferably 113 ° C. or less) for 5 seconds or more so that an image is not formed, and then performing thermal development at 110 ° C. or more and 140 ° C. or less (a so-called multi-stage heating method) It is valid.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine shown in FIG. 1 carries a pair of carry-in rollers 11 (a lower roller is a heat roller) for carrying the heat-developable photosensitive material 10 into a heating section while correcting and pre-heating the heat-developable photosensitive material 10 in a planar shape, and a photothermographic material after thermal development after thermal development. It has an unloading roller pair 12 that unloads the material 10 from the heating unit while correcting it into a planar shape. The photothermographic material 10 is thermally developed while being transported from the carry-in roller pair 11 to the carry-out roller pair 12. The photothermographic material 10 during this thermal development
A plurality of rollers 13 are installed on the side where the surface having the image forming layer comes into contact, and a non-woven fabric (for example, made of aromatic polyamide or Teflon) or the like is provided on the side where the back surface contacts the opposite side. The bonded smooth surface 14 is provided. The back surface of the photothermographic material 10 is conveyed by sliding on the smooth surface 14 by driving a plurality of rollers 13 that come into contact with the surface having the image forming layer. A heating means is provided on the upper portion of the roller 13 and the lower portion of the smooth surface 14 so as to be heated from both sides of the photothermographic material 10.
Is installed. As a heating means in this case, a plate heater or the like can be used. Although the clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, it is appropriately adjusted to a clearance that can transport the photothermographic material 10. Preferably it is 0 to 1 mm.

Material of Roller 13 Surface and Smooth Surface 1
The member 4 is durable at high temperature and may be anything as long as it does not hinder the conveyance of the photothermographic material 10, but the material of the roller surface is made of silicone rubber, and the member of the smooth surface is made of aromatic polyamide or Teflon (PTFE). Non-woven fabrics are preferred. It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section is composed of a pre-heating section A having a carry-in roller pair 11 and a heat development section B having a heating heater 15. The pre-heating section A upstream of the heat development section B is provided. Is lower than the heat development temperature (for example, 10 to 30).
It is preferable that the temperature is set to be higher than the glass transition temperature (Tg) of the support of the photothermographic material 10 so that development unevenness does not occur.

Further, a guide plate 16 is provided downstream of the heat development processing section B, and a slow cooling section C having the carry-out roller pair 12 and the guide plate 16 is provided. The guide plate is preferably made of a material having low thermal conductivity, and is preferably cooled gradually.

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

[0271]

EXAMPLES The effects of the present invention will be described below with reference to examples.
However, the present invention is not limited to this. Example 1 << Preparation of silver halide emulsion >> (Emulsion A) 11 g of phthalated gelatin and
30 mg of lithium, 10 mg of sodium benzenethiosulfonate
After dissolving and adjusting the pH to 5.0 at a temperature of 55 ° C., silver nitrate 18.
1 mol / l of 159 ml of aqueous solution containing 6 g and potassium bromide
, (NH_Four)_TwoRhCl_Five(H_TwoO) 5 × 10 ^-6Mol / l, K_ThreeIrCl
₆2 × 10^-FiveAqueous solution containing mol / liter is maintained at pAg7.7
While taking control for 6 minutes 30 seconds by double jet method
Was added. Then, with 476 ml of an aqueous solution containing 55.5 g of silver nitrate
1 mol / l potassium bromide, K_ThreeIrCl₆2 × 10 ^-FiveMole
While maintaining the aqueous solution of the halogen salt in pAg7.7
28 minutes 30 seconds by control double jet method
Added. After that, the pH is lowered to cause coagulation and sedimentation,
And 0.17 g of compound A in deionized gelatin (calcium
23.7 g), pH 5.9, pAg 8.0
Was adjusted to The resulting particles have an average particle size of 0.08 μm,
Cubic particles with a projected area variation coefficient of 9% and a (100) face ratio of 90%
Was.

The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate per mol of silver were added.
Add mol, ripen for 100 minutes, and add 4-hydroxy-6-methyl
After adding 5 × 10 ^-4 mol of -1,3,3a, 7-tetrazaindene, 4
The temperature was lowered to 0 ° C.

Thereafter, the temperature was maintained at 40 ° C.
12.8 × 10 ^-4 mol of sensitizing dye A per mol, 6.4 × 10 ^-3
A mole of compound B was added with stirring, and after 20 minutes, the mixture was rapidly cooled to 30 ° C. to complete the preparation of silver halide emulsion A.

[0274]

Embedded image

<< Preparation of Organic Acid Silver Dispersion >><Organic acid silver A> 6.1 g of arachidic acid, 37.6 g of behenic acid, 700 ml of distilled water, 70 ml of tert-butanol, and 123 ml of a 1N aqueous solution of NaOH were mixed at 75 ° C. The mixture was stirred for an hour to react, and the temperature was lowered to 65 ° C. Then, 112.5 ml of an aqueous solution of 22 g of silver nitrate was added over 45 seconds, left as it was for 5 minutes, and cooled to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid content thus obtained is treated as a wet cake without drying,
To a wet cake having a dry solid content of 100 g, 5 g of polyvinyl alcohol (trade name: PVA-217) and water were added to make the total amount 500 g, and the mixture was predispersed with a homomixer.

Next, the pre-dispersed stock solution is dispersed in a disperser (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain an organic acid silver dispersion A. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.04 μm, an average major axis of 0.8 μm,
Needle-like particles having a coefficient of variation of 30%. The measurement of the particle size was performed by MasterSizerX manufactured by Malvern Instruments Ltd. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. Thus, organic acid silver A having a silver behenate content of 85 mol% was prepared.

<< Preparation of Solid Fine Particle Dispersion of 1,1-Bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (Reducing Agent) >> (Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 20g to Kuraray Co., Ltd.MP polymer MP-203 3.0g and water 77ml was added and stirred well, as a slurry Left for 3 hours. After that, 360 g of 0.5 mm zirconia beads are prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 3 hours to prepare a solid fine particle dispersion of a reducing agent. did. The particle size is
80 wt% was 0.3 μm or more and 1.0 μm or less.

<< Preparation of solid fine particle dispersion of antifoggant X >> 0.5 g of hydroxypropylmethylcellulose, 0.5 g of compound C and 88.5 g of water were added to 30 g of antifoggant X, and the mixture was stirred well and left as a slurry for 3 hours. did. Thereafter, a solid fine particle dispersion of the antifoggant X was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

<Preparation of solid fine particle dispersion of antifoggant Z> To 2.5 g of antifoggant Z, 1 g of MP-203, an MP polymer manufactured by Kuraray Co., Ltd., and 30 ml of water were added, and the mixture was thoroughly stirred.
The slurry was left for 3 hours. Thereafter, a solid fine particle dispersion of the antifoggant Z was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. The particle size is 80 wt% of the particles 0.3
It was not less than μm and not more than 1.0 μm.

<< Preparation of Solid Fine Particle Dispersion of the Present Invention or Comparative Toning Agent >> 2.5 g of polyvinyl alcohol (trade name: PVA-217), compound C0.5 per 5 g of the toning agent shown in Table 10
g and 92 g of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of a high contrast agent was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

<< Comparison of the Present Invention or Preparation of Solid Fine Particle Dispersion of Inhibitor >> 2.5 g of polyvinyl alcohol (trade name: PVA-217) and 0.5 g of compound C per 5 g of the inhibitor shown in Table 10
And 92 g of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the inhibitor was prepared in the same manner as the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

The weight average molecular weight Mw of Exemplified Compound 2-2 was 5000, and Mw of Exemplified Compound 2-12 was 1500.
0, Mw of Exemplified Compound 2-20 is 30,000.

<< Preparation of Emulsion Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Thus, an emulsion layer coating solution was obtained.

Binder; Luckstar 3307B 406 g as solid content (manufactured by Dainippon Ink and Chemicals, Incorporated; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl)- 3,5,5-Trimethylhexane solid fine particle dispersion 119 g as solid content Solid antifoggant X solid fine particle dispersion 21.6 g sodium benzenethiosulfonate 0.44 g benzotriazole 1.25 g polyvinyl alcohol (manufactured by Kuraray Co., Ltd.) MP-203) 20g iso-propylphthalazine 0.10mol Sodium dihydrogen orthophosphate 0.13g Solid fine particle dispersion of antifoggant Z 9.38g as solid Content of Dye A 783nm Coating amount to give optical density of 0.3 Silver halide emulsion A 0.05 mol as Ag content Solid fine particle dispersion of contrast agent or comparative compound (H) of the present invention Kind and amount are described in Table 10 Inhibitor or comparative compound (a) of the present invention, ( Wherein the type, the amount solid fine particle dispersion Table 10)

[0285]

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<< Preparation of Coating Solution for Emulsion Surface Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59
3.75 / 9/26/5/1 (wt%) polymer latex (glass transition temperature of 54 ° C, solid content concentration of 44%, compound D as film-forming aid 15 wt%) of 102 g of 3.75 H ₂ O g, and add carbana wax (Cellosol 524, manufactured by Chukyo Yushi Co., Ltd.)
1.89 g of 0 wt% solution, 0.188 g of compound E, 2.55 g of compound F, 0.56 g of matting agent (polystyrene particles, average particle diameter 7 μm) and 0.4 of polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 0.4
g, and further H ₂ O was added to make 150 g, which was used as a coating solution.
The pH of the coating solution was 6.8.

[0287]

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

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

(2) Undercoat layer (a) Polymer latex-a core-shell type latex having a core of 90% by weight and a shell of 10% by weight. Core: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93 / 3/3 / 0.9 / 0.1 (% by weight) Shell: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3/3 (% by weight) Weight average molecular weight 38000 Solids 3.0g / m ² 2,4-dichloro-6-hydroxy-s-triazine 23 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ²

(3) Undercoat layer (b) Alkali-treated gelatin (Ca ²⁺ content 30 ppm, jelly strength 230 g) 50 mg / m ²

(4) Conductive Layer Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 42 mg / m ² deionized gelatin (Ca ^{2 +} content 0.6 ppm) 8 mg / m ² compound A 0.2 mg / m ² polyoxyethylene phenyl ether 10 mg / m ² Sumitex resin M-3 18mg / m ² (water-soluble melamine compound by Sumitomo chemical Co., Ltd.) dye A Coating amount SnO ₂ / Sb (9/1 weight ratio, needle-like fine particles, major axis / minor axis = 20 to 30; manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² matting agent (poly Methyl methacrylate, average particle size 5μm) 7mg / m ²

(5) Protective layer Polymer latex-methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer) 1000 mg / m ( ²⁾ Polystyrene sulfonate (molecular weight: 1,000 to 5,000) 2.6 mg / m ² Cellosol 524 (manufactured by Chuo Yushi Co., Ltd.) 25 mg / m ² Sumitex Resin M-3 218 mg / m ² (water-soluble melamine compound, Sumitomo Chemical ( Co., Ltd.)

The undercoat layer (a) and the undercoat layer (b) are formed on one side of the support.
Were sequentially applied and dried at 180 ° C. for 4 minutes. Then, a conductive layer and a protective layer are sequentially coated on the opposite side to which the undercoat layer (a) and the undercoat layer (b) have been applied, and dried at 180 ° C. for 30 seconds, respectively, for a PET support having a back / undercoat layer. It was created.

The PET support provided with the back / undercoat layer thus prepared was placed in a heat treatment zone having a total length of 30 m set at 150 ° C., and was transported under its own weight at a tension of 1.4 kg / cm ² and a transfer speed of 20 m / min. After that, pass through the 40 ° C zone for 15 seconds, 10kg / c
The film was wound with a winding tension of m ² .

[0296]

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<< Preparation of Photothermographic Material (Sample) >> The above-mentioned emulsion layer coating solution was coated on the undercoat layer of the PET support on which the undercoat layer (a) and the undercoat layer (b) had been coated. 1.7g / m
² , and further coated thereon the emulsion surface protective layer coating solution with a solid content of the polymer latex of 3.
Co-layer coating was carried out simultaneously with the emulsion coating solution so as to obtain 0 g / m ² . The film surface pH of the resulting photothermographic material was 5.1.

<< Evaluation of Photographic Performance >> (Exposure Processing) The obtained photothermographic material was subjected to a beam diameter (FWHM of 1/2 of beam intensity) of 12.56 μm and a laser output of 50 m.
W, using a single-channel cylindrical inner surface laser exposure device equipped with a semiconductor laser with an output wavelength of 783 nm, adjust the exposure time by changing the number of rotations of the mirror, adjust the exposure amount by changing the output value, 2 Exposure was performed in × 10 ⁻⁸ seconds. At this time, the overlap coefficient (FWHM / the pitch width of the sub-scan) is 0.5, and the pitch of the sub-scan is 28 μm.

(Thermal Development Processing) The exposed photothermographic material was heated using the thermal developing machine shown in FIG. 1 and the roller surface material of the thermal development processing section was made of silicone rubber, and the smooth surface was made of an aromatic polyamide nonwoven fabric. A heat development process was performed at 90 to 100 ° C. for 5 seconds and a heat development processing unit at 120 ° C. for 20 seconds. The temperature accuracy in the width direction was ± 1 ° C.

(Evaluation of photographic performance) The obtained images were evaluated using a Macbeth TD904 densitometer (visible density). The measurement results were evaluated by fog (Dmin) and gradation (contrast). Contrast is expressed as the logarithm of the exposure amount on the horizontal axis, and the density is 0.
Expressed by the slope of the line connecting points 3 and 3.0.

(Evaluation of temporal stability of solid fine particle dispersion of high contrast agent) After the solid fine particle dispersion of the high contrast agent was aged at 40 ° C. for 10 days, it was added to the emulsion layer coating solution to prepare a photothermographic material. did. Photographic performance was compared with that of a photothermographic material prepared using a solid fine particle dispersion of a contrast agent immediately after dispersion.

Practically, the fog value must be 0.15 or less and the gradation must be 10 or more.
It is preferable that the gradation is 13 or less and the gradation is 15 or more.

Table 10 shows the results. The one using the dispersion of the contrast agent immediately after the dispersion is indicated as fresh, and the one using the storage after 10 days are displayed as 10 days.

[0304]

[Table 10]

(Results) By using the compounds of the present invention in combination, a photothermographic material which is super-hard and hard to fog can be obtained even with the use of aged aqueous dispersions of the toning agents.

Example 2 In the photothermographic material described in Example 1, Table 11 shows the compound F added to the coating solution for the emulsion surface protective layer using an inhibitor and a high contrast agent as shown in Table 11. The surface pH was changed by adding NaOH to the emulsion surface protective layer coating solution in the amount shown in Table 11, or
Evaluation was performed in the same manner as in Example 1. Table 11 shows the results. In addition, Mw of the exemplary compound 2-1 of the inhibitor is 10,000.

[0307]

[Table 11]

(Results) In particular, preferred film surface pH of the present invention
By using the compound of the present invention in combination within the range described above, a photothermographic material which is super-high contrast and hard to fog even when an aqueous dispersion of a contrast agent aged over time can be obtained.

[0309]

According to the present invention, excellent performance as a high contrast sensitive material is obtained, and good performance can be obtained even when an aqueous dispersion of a high contrast agent aged is used.

[Brief description of the drawings]

FIG. 1 is a side view illustrating a configuration example of a heat developing machine.

[Explanation of symbols]

 DESCRIPTION OF REFERENCE NUMERALS 10 photothermographic material 11 carry-in roller pair 12 carry-out roller pair 13 roller 14 smooth surface 15 heating heater 16 guide plate A preheating section B heat development processing section C slow cooling section

Claims (2)

[Claims] 1. At least one surface of a support,
(A) a photosensitive silver halide, (b) a reducible silver salt,
A photothermographic material comprising (c) a reducing agent, (d) a binder, and (e) at least one compound selected from the compounds represented by formulas (A), (B) and (C). And at least one compound selected from a compound represented by the formula (1), a polymer having a repeating unit derived from a monomer represented by the formula (2), and a compound represented by the formula (3) A photothermographic material comprising a compound. Embedded image Embedded image Embedded image [In the formula (A), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A), R ¹ and Z, R ² and R ³ , R ¹ and R ² ,
And R ³ and Z may be bonded to each other to form a cyclic structure. In the formula (B), R ⁴ represents a substituent. In the formula (C), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the formula (C), X and Y, and A and B
May be bonded to each other to form a cyclic structure. ] [In the formula (1), X ¹ represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring, J represents a divalent linking group, and B ¹
Represents a ballast group, and n represents an integer of 1 or more. ] [In the formula (2), Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X ² represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring. ] [In the formula (3), A ¹ represents a group having a water-soluble group, and X ³ represents a residue of a photographic inhibitor having a nitrogen-containing heterocyclic ring. ] 2. The film surface pH is 3 or more and 7 or less.
Photothermographic material.