JPH09304875A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable photosensitive material having ultrahigh contrast, ensuring an image with less magnification, giving a stable image and fit for a printing plate making by incorporating a reducing agent, a hydrazine deriv. and a specified compd. into a silver halide photosensitive layer and/or its adjacent layer. SOLUTION: This heat developable photosensitive material has at least one silver halide photosensitive layer on the substrate, contains an org. silver salt in the layer and/or its adjacent layer and contains a reducing agent, a hydrazine deriv. and at least one of compds. represented by formulae I, II in the photosensitive layer and/or its adjacent layer. In the formulae, Z is a group of atoms required to complete a 5- or 6-membered arom. hetero ring consisting of two or more N atoms and atoms selected from among C, O, S, etc., Z may have a substituent, R is H, alkyl, aralkyl, phosphoric acid amido, etc., and each of these groups may have a substituent.

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, it is suitable for a printing plate making which can provide an image having super-high contrast, small image enlargement and excellent stability under developing conditions. The present invention relates to a heat-development ultrahigh contrast photosensitive material.

[0002]

2. Description of the Related Art In the field of printing, an image forming system showing a photographic characteristic of ultra-high contrast (especially gamma of 10 or more) has been developed in order to improve reproduction of continuous tone images or halftone images by halftone dot images. Although it is provided, it is strongly desired to reduce the treatment waste liquid from the viewpoint of environmental protection and space saving, and it has been studied and the waste liquid has been considerably reduced in recent years. It is impossible not to issue it at all. Therefore, even in this field, there is a demand for a thermal development processing system which eliminates the use of solution processing chemicals and is simpler and does not damage the environment.

An image forming method using a photothermographic material in which a developing step is performed by heat treatment has been proposed. For example, as disclosed in JP-B-43-4924, JP-B-44-6582, JP-A-46-6074, JP-A-48-97523, JP-A-7-2781, U.S. Pat. (Gradation) is soft and cannot be used for printing plate making.

In the printing field, ultra-high contrast photographic characteristics are desired as described above, and it is proposed, for example, in US Pat. No. 5,496,695 to obtain ultra-high contrast performance by using a hydrazine derivative. However, when a hydrazine derivative is used, an image becomes thicker due to infectious development, that is, so-called image enlargement becomes large and image reproducibility is deteriorated, and thus improvement is desired.

The use of a heterocyclic mercapto compound as a supersensitizer in a heat-developable light-sensitive material is disclosed, for example, in the formula (I) and the formula (I) of JP-B-63-35008.
I), (I) and (II) of JP-A-5-341432
And so on.

Further, regarding the heat-developable photosensitive material having super-high contrast performance using a hydrazine derivative, for example, US Pat.
Although super-high contrast performance can be obtained by using the hydrazine derivative disclosed in P54969695, changes due to variations in sensitivity and development time of halftone image and development temperature are greater than those when no hydrazine derivative is used, resulting in variation in development conditions. As a result, performance fluctuations increase. Although it is shown in this issue that a heterocyclic mercapto compound represented by Ar-SM or Ar-SS-Ar is used as a supersensitizer,
These products have large performance fluctuations and are desired to be improved.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photothermographic material suitable for printing plate making which can obtain a stable image such as ultra-high contrast and small image enlargement.

[0008]

The above object was achieved by the present invention described below. (1) In a silver halide light-sensitive material having at least one silver halide light-sensitive layer on a support and containing an organic silver salt in the layer and / or an adjacent layer, the silver halide light-sensitive layer and / or Alternatively, a photothermographic material comprising an adjacent layer containing a reducing agent, a hydrazine derivative, and at least one compound represented by the general formula (1) and the general formula (2).

[0009]

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In the general formulas (1) and (2), Z represents an atomic group for completing a 5- or 6-membered heteroaromatic ring containing at least two nitrogen atoms. R represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkyl- or aryl-substituted amino group, an amide group, a sulfonamide group, a ureido group, a urethane group,
It represents an aryloxy group, a sulfamoyl group, a carbamoyl group, an aryl group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, a cyano group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, or a phosphoric acid amide group. (2) In a silver halide light-sensitive material having at least one silver halide light-sensitive layer on a support and containing an organic silver salt in the layer and / or an adjacent layer, the silver halide light-sensitive layer and / or Alternatively, a photothermographic material comprising an adjacent layer containing a reducing agent, a hydrazine derivative, and a compound represented by the general formula (3).

[0011]

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In the general formula (3), R ₁ , R ₂ , R ₃
And R ₄ are each a hydrogen atom, a hydroxy group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a hydroxycarbonyl group, a hydroxyamino group, an alkyl group,
Aralkyl group, alkoxy group, alkyl or aryl substituted amino group, amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, phosphoramide group Represent. R ₃ and R ₄ may be bonded to each other to form a ring.

[0013]

Embodiments of the present invention will be described below in detail.

First, the compounds represented by the general formulas (1) and (2) used in the present invention will be described in detail below.

[0015]

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In the general formulas (1) and (2), Z contains at least two nitrogen atoms, carbon,
It represents an atomic group for completing a 5-membered and 6-membered heteroaromatic ring consisting of atoms selected from oxygen, sulfur, selenium, and tellurium. Z may further have a substituent. R is a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkyl- or aryl-substituted amino group, an amide group, a sulfonamide group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an aryl group. Groups, alkylthio groups, arylthio groups, hydroxy groups, halogen atoms, cyano groups, carboxy groups or salts thereof, sulfo groups or salts thereof, phosphoric acid amide groups and the like. These groups may further have a substituent.

The compounds represented by formulas (1) and (2) will be described in more detail.

In the general formulas (1) and (2), the ring which Z completes together with the carbon atom contains at least two nitrogen atoms and is composed of atoms selected from carbon, oxygen, sulfur, selenium and tellurium. It is a 5- and 6-membered heteroaromatic ring. Specific examples of the heteroaromatic ring include imidazole, pyrazole, triazole, tetrazole,
Examples thereof include thiadiazole, thiadiazine, pyridazine, pyrimidine, pyrazine and triazine.

In the general formulas (1) and (2), R
Is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, cyclohexyl group, etc.), an aralkyl group (benzyl group, etc.), an alkoxy group (methoxy, ethoxy group, etc.), an alkyl- or aryl-substituted amino group (dimethylamino group, etc.), Amide group (such as pentylamide group),
Sulfonamide group (methyl sulfonamide group, etc.), ureido group, urethane group (methyl urethane group, ethyl urethane group, etc.), aryloxy group (phenoxy, naphthoxy group, etc.), sulfamoyl group (sulfamoyl group, etc.), carbamoyl group (ethyl) Carbamoyl group, phenylcarbamoyl group, etc.), aryl group (phenyl, naphthyl group, etc.), alkylthio group (methylthio, hexylthio group, etc.), arylthio group (phenylthio group, etc.), hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine) Etc.), cyano group, carboxy group (may be a salt thereof), sulfo group (may be a salt thereof), phosphoric acid amide group and the like. These groups may further have a substituent, and examples thereof include the groups mentioned as R above. The total carbon number of R is preferably 0 to 20.

Specific examples of the compounds represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0021]

[Table 1]

General formula (1) and general formula (2) of the present invention
The compound of (1) is dissolved in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. You can

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

General formula (1) and general formula (2) of the present invention
The compound may be added to any of the silver halide emulsion layer or other layers on the silver halide emulsion layer side with respect to the support, but it is added to the silver halide emulsion layer or a layer adjacent thereto. It is preferable.

General formula (1) and general formula (2) of the present invention
Is preferably 1 × per mol of silver halide.
10 ^{−4 to} 5 × 10 ⁻² mol, more preferably 5 × 10 ⁻⁴ to
It is 1 × 10 ^-2 mol.

Next, the tetrazaindene compound of the general formula (3) (please name) will be described.

[0027]

[Chemical 6]

In the general formula (3), R _{1 to} R ₄ are each a hydrogen atom, a hydroxy group, a mercapto group, a halogen atom (fluorine, chlorine, bromine, iodine, etc.), a cyano group,
Sulfo group, hydroxycarbonyl group, hydroxyamino group, alkyl group (methyl, ethyl, propyl, cyclohexyl group, etc.), aralkyl group (benzyl group, etc.), alkoxy group (methoxy, ethoxy group, etc.), aryloxy group (phenoxy, naphthoxy group) Groups), alkyl- or aryl-substituted amino groups (such as dimethylamino groups),
Amido group, sulfonamide group, ureido group, urethane group, sulfamoyl group, carbamoyl group, aryl group (phenyl, naphthyl group, etc.), alkylthio group (methylthio, hexylthio group, etc.), arylthio group (phenylthio group, etc.), phosphoric acid amide Represents a group. These groups may further have a substituent, and are the above R _{1 to} R _1.
Examples thereof include the groups mentioned as ₄ and alkyloxycarbonyl groups. When R ₃ and R ₄ are especially alkyl groups,
These can also be bonded to each other to form a ring.

Of these, _{1 to 3} mercapto groups, hydroxy groups, hydroxyamino groups, alkoxy groups, and alkylthio groups as R _{1 to} R ₄ in the molecule, especially 1
Alternatively, it is preferable that two of them be included. OH, SH and the like are preferably contained in R ₁ , R _{2 and} R ₃ , and it is particularly preferable that R is OH, SH and NHOH.

Specific examples of the compound represented by the general formula (3) are shown below, but the invention is not limited thereto.

[0031]

[Table 2]

[0032]

[Table 3]

The compound of the general formula (3) of the present invention is water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve, etc.

By a well-known emulsification and dispersion method, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are used to dissolve and mechanically dissolve them. An emulsified dispersion can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The compound of the general formula (3) of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other layer. It is preferably added to the silver emulsion layer or a layer adjacent thereto.

The addition amount of the general formula (3) of the present invention is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻² per mol of silver halide.
The molar amount is more preferably 5 × 10 ⁻⁴ to 1 × 10 ⁻² mol.

The hydrazine derivative used in the present invention is
A compound represented by the following general formula (H) is preferable. General formula (H)

[0038]

[Chemical 7]

In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or Represents a hydrazino group, G ₁ is -C
O- group, -SO ₂ - group, -SO- group,

[0040]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

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

In the general formula (H), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group among the aromatic groups represented by R ₁ is a monocyclic or bicyclic aromatic or non-aromatic heterocycle, which may be condensed with an aryl group to form a heteroaryl group. . Examples thereof include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring and a benzothiazole ring. R ₁
Preferred as is an aryl group, particularly a phenyl group.

R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group (including an active methine group), an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocycle and a quaternized group. A group containing a heterocycle containing a nitrogen atom (for example, a pyridinio group), a hydroxy group, an alkoxy group (including a group containing a repeating ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino Group containing a group, group containing a quaternary ammonio group, mel Group, (alkyl, aryl, or hetero group) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group Group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, nitro group,
Examples include a phosphoric acid amide group, a group having a phosphate ester structure, a group having an acylurea structure, a group having a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure.

Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 20 carbon atoms) and alkoxy groups (preferably carbon atoms). C1-20), substituted amino groups (preferably C1-20 substituted amino groups), acylamino groups (preferably C2-3)
0), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), carbamoyl group (preferably having 1 to 30 carbon atoms) , A phosphoric acid amide group (preferably having a carbon number of 1 to 30) and the like.

In formula (H), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, a benzene ring. Is included.

The heterocyclic group is a 5- or 6-membered ring compound containing at least one nitrogen, oxygen and sulfur atom, and examples thereof include imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, pyridinio group and quinolinio group. , Quinolinyl group, etc. Pyridyl or pyridinio groups are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the unsubstituted amino group is an amino group, and the alkylamino group having 1 to 10 carbon atoms. A group, an arylamino group and a heterocyclic amino group are preferable.

R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable.

Preferred among the groups represented by R ₂ are hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxy group) when G ₁ is --CO-- group. Tetrafluoroethyl group, pyridiniomethyl group, 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group) , O-carbamoylphenyl group, 4
-Cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom and an alkyl group.

When G ₁ is a --SO ₂ --group, R 1
₂ is preferably an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, dimethylamino group).

When G ₁ is a --COCO-- group, it is preferably an alkoxy group, an aryloxy group or an amino group, particularly a substituted amino group (eg 2,2,6,6-tetramethylpiperidin-4-ylamino group, Propylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group and the like) are preferable.

[0053] Also, R ₂ is be as occurring cyclization reaction to form a cyclic structure containing disrupts portion of G ₁ -R ₂ from the remainder molecule, -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are hydrogen atoms, alkyl or arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl groups, or substituted so that the sum of Hammett's substituent constants is -0.5 or more). A phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is −0.5 or more, or a linear or branched group, or Cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, sulfonic acid groups). A
Most preferably, hydrogen atoms are used as ₁ and A ₂ .

The substituents of R ₁ and R _{2 in} the general formula (H) may be further substituted, and preferable examples thereof include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (H) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (H) may have an adsorptive group adsorbing to silver halide incorporated therein. Examples of the adsorptive group include an alkylthio group, an arylthio group, a thiourea group, a thioamide group,
U.S. Pat. Nos. 4,385,108 and 4,459,347, such as mercapto heterocyclic groups and triazole groups, JP-A-59-
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
And groups described in JP-A-63-234245 and JP-A-63-234246. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

R ₁ or R _{2 in} the general formula (H) may contain a plurality of hydrazino groups as a substituent, and in this case, the compound represented by the general formula (I) is a multimeric compound with respect to the hydrazino group. And specifically, for example, JP-A-64-86
134, JP-A-4-16938, JP-A-5-197.
No. 091.

Among the hydrazine derivatives used in the present invention, more preferable ones are represented by the following general formulas (H1) to (H4).

[0060]

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In the general formula (H1), general formula (H2), general formula (H3) and general formula (H4), R ₁₀ , R ₁₁ ,
R ₁₂ and R _{13 each} represent an aromatic group, specifically, an aryl group or an unsaturated heterocyclic group, and include A ₁₀ , A ₂₀ , A ₁₁ , A ₂₁ , and A
₁₂ , A ₂₂ , A ₁₃ , and A ₂₃ are A ₁ and A in the general formula (H).
Represents a group having the same meaning as ₂ .

In the general formula (H2), R ₂₁ is an alkyl group substituted with at least one electron-withdrawing group, an aryl group substituted with at least one electron-withdrawing group, a heterocyclic group, an amino group or an alkylamino group. Group, arylamino group, heterocyclic amino group, hydrazino group, alkoxy group,
Or an aryloxy group.

In the general formula (H3), R ₂₂ is an amino group,
Alkylamino group, arylamino group, heterocyclic amino group, hydrazino group, alkoxy group, aryloxy group,
Represents an alkyl group or an aryl group.

In the general formula (H4), G ₁₃ is —SO ₂
-Group, -SO- group, the following groups

[0065]

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(R ₃₀ is a group having the same meaning as R _{3 in} (Formula 4)), a thiocarbonyl group, or an iminomethylene group, and R ₂₃
Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, or a hydrazino group.

Among the compounds of the present invention represented by the general formula (H1), more preferred ones are those represented by the following general formula (H-1).
It is represented by

[0068]

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In the formula, X ₁₀ is a sulfonamide group, a ureido group, a thioureido group, an oxycarbonyl group, a sulfonamide group, a phosphonamido group, an alkylamino group, a halogen atom, a cyano group, an alkoxy group having a total carbon number of 2 or more, Represents an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an acylamino group having a total carbon number of 3 or more, a carbamoyl group, a sulfamoyl group, or an (alkyl or aryl) sulfonyl group, and m ₁₀ represents an integer of 0 to 5. Represent Y ₁₀ represents a group represented by X ₁₀ , a nitro group, a methoxy group, an alkyl group, or an acetamido group, and n ₁₀ represents an integer of 0 to 4. However m ₁₀ and n ₁₀
When the sum is not possible to exceed 5, also m ₁₀ is 0 and, A
Neither ₁₀₀ nor A ₂₀₀ is a hydrogen atom.

A ₁₀₀ and A ₂₀₀ are A in the general formula (H).
₁ represents a group having the same meaning as A ₂ m ₁₀ is preferably 1 or 2, n ₁₀ is preferably 0 or 1, and most preferably m ₁₀ is 1 and n ₁₀ is 0.

In the general formula (H2), R ₂₁ is preferably an alkyl group substituted with at least one electron withdrawing group or an aryl group substituted with at least one electron withdrawing group. Here, the electron-withdrawing group is a substituent having a positive Hammett's substituent constant σ _m , specifically, a halogen atom, a nitro atom, a cyano group, an acyl group, an oxycarbonyl group, and a sulfone group. It represents an amide group, a sulfamoyl group, a carbamoyl group, an acyloxy group, an (alkyl or aryl) sulfonyl group, an alkoxy group, an aryloxy group, a (alkyl or aryl) thio group or an imide group. R ₂₁ is more preferably an alkyl group substituted with at least one electron withdrawing group, and the electron withdrawing group is a fluorine atom,
Alkoxy groups and aryloxy groups are preferred.

In the general formula (H3), R ₂₂ is preferably an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group or an alkoxy group.

In the general formula (H4), G ₁₃ is preferably —SO ₂ — group, thiocarbonyl group,

[0074]

[Chemical 12]

(R ₃₀ is a group having the same meaning as R _{3 in} Chemical formula 8). R ₂₃ is preferably an alkyl group or an aryl group when G ₁₃ is —SO ₂ —, and is an alkoxy group, an aryloxy group or an (alkyl or aryl) amino group when G ₁₃ is (formula 8). In the case of a thiocarbonyl group, an (alkyl or aryl) amino group and a hydrazino group are preferable.

Specific examples of the compounds represented by formulas (H1) to (H4) are shown below. However, the present invention is not limited to these.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

[Chemical 21]

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

[Chemical formula 26]

[0091]

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[0092]

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[0093]

[Chemical 29]

In the formula (F3), m is an integer of 2 to 5. m is preferably 2, 3 or 4.

In the formula (F3), n is an integer of 1 to 5 required for charge balance. n is generally 1, 2 or 3.

The lake cyanine dye may be in the form of a double salt.

Examples of preferred lake cyanine dyes are shown below.

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4269929, No. 4276364, No. 42
No. 78748, No. 4385108, No. 4459347.
No. 4,478,928, 4560638, 46.
86167, 4912016, 4988604
No. 4,994,365, 5041355, 51
04769, British Patent No. 2011391B, European Patent Nos. 217310, No. 301799, and No. 35689.
No. 8, JP-A-60-179734 and JP-A-61-1707.
No. 33, No. 61-270744, No. 62-17824.
No. 6, No. 62-270948, No. 63-29751.
No. 63-32538, No. 63-104047,
63-121838, 63-129337, 63-223744, 63-234244, 6
3-234245, 63-234246, 63
-294552, 63-306438, 64-
10233, JP-A-1-90439, 1-100
No. 530, No. 1-105941, No. 1-105943
No. 1, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-283549, No. 1-2.
No. 85940, No. 2-2541, No. 2-77057.
No. 2, No. 2-139538, No. 2-196234, No. 2-196235, No. 2-198440, No. 2-1.
No. 98441, No. 2-198442, No. 2-2200.
42, 2-221953, 2-221954.
No. 2-285342, 2-285343, 2-289843, 2-302750, 2-3.
04550, 3-37642, 3-54549.
No. 3, No. 3-125134, No. 3-184039, No. 3-240036, No. 3-240037, No. 3-2.
59240, 3-280038, 3-2825.
No. 36, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230233, No. 4-96.
053, 4-216544, 5-45761.
No. 5, No. 5-45762, No. 5-45763, No. 5-
455764, 5-45765, and Japanese Patent Application No. 5-949.
Those described in No. 25 can be used.

In addition to these, the compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically the compounds described on pages 3 and 4 of the publication. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by the general formula (6), specifically, Compounds 4-1 to 4- described on pages 25 and 26 of the publication.
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same publication
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
A compound represented by (Chemical Formula 1) described in No. 13951, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I described in JP-A-7-77783)
The compound represented by I), specifically, pages 10 to 2 of the same publication.
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
compounds represented by a), specifically, pages 8 to 15 of the same publication.
Compounds H-1 to H-44 described on page. It is possible to use those described in.

The addition amount of the hydrazine derivative in the present invention is 1 × 10 ^{−6 to} 1 × 10 ⁶ mol per mol of silver.
^-1 mol is preferable, and a range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.

The hydrazine derivative of the present invention is a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

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

In the present invention, in combination with a hydrazine derivative,
It is preferable to use indazoles (for example, nitroindazole) as an antifoggant.

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 used in one of the image forming layers.
It should be present as .about.10% by weight. When a reducing agent is added to a layer other than the emulsion layer in a multilayer structure,
A slightly higher percentage, about 2-15% by weight, tends to be more desirable.

A wide range of reducing agents have been disclosed in the photothermographic material using an organic silver salt. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehydeazine; 2,2'-bis (hydroxymethyl A) a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid, such as a combination of propionyl-β-phenylhydrazine and ascorbic acid; polyhydroxybenzene, hydroxylamine,
A combination of reductone and / or hydrazine, such as a combination of hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine;
Hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azine and sulfonamidophenol (e.g., phenothiazine and 2,6-dichloro-
Α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-
Bis-β as exemplified by binaphthyl, 6,6′-bibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane
-Naphthol; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (eg, 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl-
5-pyrazolone, such as 5-pyrazolone; reductone as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4 Sulfonamidophenol reducing agents such as -benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7
Chromans such as -t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-
1,4-dihydropyridines such as 1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-tert-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)
Ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones. and so on.

Particularly preferred reducing agents in the present invention are the following general formula (R-I), general formula (R-II) and general formula (R-II).
I) and compounds represented by the general formula (R-IV).

[0107]

Embedded image

The ring structure formed by Z in the general formula (R-III) is as follows.

[0109]

[Chemical 31]

The ring structure formed by Z in the general formula (R-IV) is as follows.

[0111]

Embedded image

In the formula, L ₁ and L ₂ are a group represented by CH-R ₆ or a sulfur atom. n represents a natural number.

R (R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R ₁₁ to
Including _{R 13, R 11 '~R 13} ', R 21 ~R 26, R 21 '~R 24') is a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms),
An aryl group, an aralkyl group, a halogen atom, an amino group, or a substituent represented by -OA. However, R ₁
To R ₅ and at least one of R ₁ ′ to R ₅ ′ and at least one of R _{7 to} R ₁₀ are —OA
Is a group represented by Further, R may form a ring with each other. A and A'are hydrogen atoms and alkyl groups (having 1 to 3 carbon atoms).
0), an acyl group (1 to 30 carbon atoms), an aryl group, a phosphate group, and a sulfonyl group. R, A, and A 'may be substituted, and typical substituents include, for example, an alkyl group (including an active methine group), a nitro group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring, A group containing a quaternary heterocycle containing a nitrogen atom (for example, a pyridinio group), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group Group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group A hydrazino group, a quaternary ammonium group, a mercapto group, an (alkyl, aryl, or heterocycle) thio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group, Sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, phosphoric amide group, group containing a phosphoric ester structure, acyl Group having a rare structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. R,
The substituents of A and A 'may be further substituted, and preferred examples include those exemplified as the substituent of R. Further, the substituent may be substituted multiple times such as the substituent, the substituent of the substituent, the substituent of the substituent of the substituent,... The illustrations apply.

In the following, the general formula (R-I) and the general formula (R-
Illustrative examples of compounds represented by II), general formula (R-III) and general formula (R-IV) are shown below. However, the present invention is not limited to the following compounds.

[0115]

[Table 4]

[0116]

[Table 5]

[0117]

[Table 6]

[0118]

[Table 7]

[0119]

[Table 8]

[0120]

[Table 9]

[0121]

[Table 10]

[0122]

[Table 11]

The amount of the reducing agent used in the present invention is preferably 1 × 10 ⁻³ to 10 mol per mol of silver,
More preferably, it is 1 × 10 ^{-2 to} 1.5 mol.

Further, in the present invention, it is preferable to set the molar ratio of the reducing agent to the hydrazine derivative in the range of 1:10 ^-3 to 1:10 ^-1 .

The method of forming the photosensitive silver halide in the present invention is well known in the art, for example, Research Disclosure, June 1978, No. 17029,
And the method described in US Pat. No. 3,700,458 can be used. As a specific method that can be used in the present invention, a method of converting a part of silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin, Alternatively, a method in which a photosensitive silver halide grain is prepared by adding a silver-supplying compound and a halogen-supplying compound to another polymer solution and mixed with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation to be low, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.01 μm or less
The thickness is preferably 2 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 a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1.
Is good. 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. However, the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high. preferable. The ratio is preferably 50% or more, and 65%
The above is more preferable, and 80% or more is further preferable. The ratio of Miller index {100} planes is based on the adsorption dependence of {111} planes and {100} planes in the adsorption of sensitizing dyes.
T. Tani; J. Imaging Sci., 29, 165 (1985)
Year). The halogen composition of the photosensitive silver halide is not particularly limited, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide,
Although any of silver iodide may be used, in the present invention, silver bromide or silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodide content is preferably 0.1 mol% or more and 40 mol% or less.
More preferably, it is 1 mol% or more and 20 mol% or less. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously, but as a preferable example, the silver iodide content inside the grains is High silver iodobromide grains can be used. Preferably, silver halide grains having a core / shell structure can be used. The structure is preferably a two- to five-fold structure, more preferably a two to four-fold structure.
Heavy core / shell particles can be used.

The photosensitive silver halide grain of the present invention preferably contains at least one metal complex selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt or iron. These metal complexes are 1
One kind may be used, or two or more kinds of same metal and different metal complexes may be used in combination. The preferred content is 1 per mol of silver
The range is preferably from nmol to 10 mmol, more preferably from 10 nmol to 100 μmol. As a specific metal complex structure, a metal complex having a structure described in Japanese Patent Application No. 7-225449 can be used. cobalt,
For the iron compound, a hexacyano metal complex can be preferably used. Specific examples thereof include, but are not limited to, ferricyanate ion, ferrocyanate ion, and hexacyanocobaltate ion. The layer containing the metal skeleton in the silver halide may be uniform, may be contained at a high concentration in the core portion, or may be contained at a high concentration in the shell portion, and there is no particular limitation.

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

The photosensitive silver halide grain in the invention is preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. 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-organyl tellurocarboxylic acid esters, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, and Te
Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, etc. can be used. As the compound preferably used in the noble metal sensitization method, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, or compounds described in US Pat. No. 2,448,060 and British Patent No. 618061 are preferable. 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. . Reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation.

The photosensitive silver halide of the present invention is used in an amount of 0.0 mol of photosensitive silver halide per mol of organic silver salt.
The amount is preferably 1 mol or more and 0.5 mol or less, more preferably 0.02 mol or more and 0.3 mol or less, and particularly preferably 0.03 mol or more and 0.25 mol or less. It is preferable that the silver halide emulsion layer contains an organic silver salt. When the organic silver salt is contained in the silver halide emulsion layer, regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and the organic silver salt, the prepared silver halide grains and the organic silver salt are respectively prepared. A method of mixing with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer, or the like, or mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt to form an organic silver salt. Although there is a method of preparation, there is no particular limitation as long as the effects of the present invention are sufficiently exhibited.

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

It is also possible to use silver salts of compounds containing a mercapto group or a thione group and their derivatives.
Preferred examples of these compounds include silver salts of 3-mercapto-4-phenyl-1,2,4-triazole,
-Silver salt of mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamido) benzothiazole, S-alkylthioglycolic acid (wherein the alkyl group has 12 to 12 carbon atoms).
22) silver salt of thioglycolic acid, silver salt of dithioacetic acid such as dithiocarboxylic acid, silver salt of thioamide, 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine. Silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, the silver salt described in U.S. Pat. No. 4,123,274, such as 3-amino-5-benzylthio-1,2,4-thiazole silver salt. 1,2,4-mercaptothiazole derivative silver salt, 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-described in U.S. Pat. No. 3,301,678.
Includes silver salts of thione compounds such as silver salts of thione. Furthermore, compounds containing an imino group can be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, and US Pat. No. 4,220,709, and silver salts of 1,2,4-triazole or 1-H-tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, US Pat. No. 476136.
Various silver acetylide compounds as described in No. 1 and No. 4775613 can also be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but needle crystals having a short axis and a long axis are preferable. As is well known in the light-sensitive silver halide light-sensitive material, the inversely proportional relationship between the size of silver salt crystal grains and the covering power is also established in the heat-developable light-sensitive material of the present invention. It is necessary to reduce the size of the organic silver salt, because a large organic silver salt particle in the image forming portion means a small covering power and a low image density. In the present invention, the minor axis 0.
It is preferably from 01 μm to 0.20 μm, the major axis is from 0.10 μm to 5.0 μm, and the minor axis is from 0.01 μm to 0.1 μm.
15 μm or less, more preferably 0.10 μm or more and 4.0 μm or less on the major axis. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion means the percentage of the value obtained by dividing the standard deviation of the lengths of the minor axis and major axis by the minor axis and major axis, respectively, is preferably 100% or less, more preferably 80% or less, and even more preferably 50% or less. It is. 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 for measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage variation coefficient of the value divided by the volume-weighted average diameter is preferably 100% or less, more preferably It is 80% or less, more preferably 50% or less. As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with a laser beam, and the autocorrelation coefficient with respect to the time change of the fluctuation of the scattered light is obtained from the particle size (volume weight average diameter) obtained. be able to.

The sensitizing dye in the present invention may be any one 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 holo-holerocyanine 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 1
7643IV-A (December 1978 p.23) Item 1831X (1979)
, P.437), or in the literature cited. Especially various laser imagers, scanners,
A sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of a light source of an image setter or a plate making camera can be advantageously selected.

As an example of spectral sensitization to red light, He-
Japanese Patent Laid-Open No. 54-18726 discloses a Ne laser light source.
Compounds I-1 to I-38 described in JP-A-6-7
Compounds I-1 to I-35 described in JP-A-5322 and I-1 to I-34 described in JP-A-7-287338.
JP-B-55-3981 for the compound and LED light source
Dyes 1 to 20 described in JP-A-62-28434
Compounds I-1 to I-37 described in No. 3 and compounds I-1 to I-34 described in JP-A-7-287338 are advantageously selected.

The silver halide grains are spectrally sensitized in any wavelength range from 750 to 1400 nm. Specifically, a photosensitive silver halide is replaced with cyanine, merocyanine,
A variety of known dyes, including styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes, can be spectrally advantageously sensitized. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes are, in addition to the basic nucleus described above, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus,
It also includes acidic nuclei such as thiazolinone nuclei, malononitrile nuclei and pyrazolone nuclei. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, US Pat. No. 3,761,
No. 279, No. 3719495, No. 3877943
No., British Patent Nos. 1466201 and 1469117
No. 14222057, Japanese Examined Patent Publication No. 3-10391,
JP-B-6-52387, JP-A-5-341432,
It may be appropriately selected from known dyes described in JP-A-6-194781 and JP-A-6-301141. A particularly preferable dye structure is a cyanine dye having a thioether bond.
2-58239, 3-138638, 3-13
No. 8642, No. 4-255840, No. 5-72659
No. 5, No. 5-72661, No. 6-222491, No. 2
-230506, 6-258757, 6-31
No. 7868, No. 6-324425, Tokuyohei 7-500
The cyanine dyes described in No. 926 are mentioned.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclos
ure) Volume 176 17643 (issued in December 1978) Page 23, IV, J
Or the aforementioned Japanese Examined Patent Publication Nos. 49-25500 and 43.
-4933, JP-A-59-19032 and 59-1.
92242 and the like.

The sensitizing dyes used in the present invention may be used in combination of two or more kinds. To add sensitizing dyes to a silver halide emulsion, they may be directly dispersed in the emulsion,
Or water, methanol, ethanol, propanol,
Acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol , N, N-dimethylformamide, etc. may be added to the emulsion by dissolving them in a single solvent or in a mixed solvent.

Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, this solution is dispersed in water or a hydrophilic colloid, and this dispersion is used as an emulsion. Method of adding to the inside, Japanese Patent Publication No.44-
23389, 44-25555, 57-220.
As disclosed in No. 91, etc., the dye is dissolved in an acid,
A method in which this solution is added to an emulsion or an aqueous solution is added to the emulsion in the presence of an acid or a base, US Pat.
A method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to the emulsion as disclosed in, for example, No. 822135 and No. 4006025.
As disclosed in JP-A-53-102733 and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion is disclosed in JP-A-51-74624. As disclosed, it is also possible to use a method in which a dye is dissolved using a red-shifting compound and this solution is added to the emulsion. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any step in the preparation of emulsions which has heretofore been found to be useful. For example, US Pat. Nos. 2,735,766 and 3635.
No. 28960, No. 4183756, No. 42256
66, JP-A-58-184142 and 60-196.
No. 749, etc., the period before the grain formation step and / or desalting of the silver halide, the period during the desilvering step and / or after the desalination to the start of chemical ripening, As disclosed in the specification of JP-A-58-113920 and the like, immediately before or during the chemical ripening, at any time and after the chemical ripening and before the coating until the emulsion is coated. May be added at.
Also, U.S. Pat. No. 4,225,666 and JP-A-58-76.
29, etc., the same compound alone or in combination with a compound having a different structure, for example, divided into a grain formation step and a chemical ripening step or after chemical ripening, The compound may be added in divided portions, such as before aging or during the process and after completion, or the compound and the combination of compounds may be added in different types.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to suppress or accelerate development and control development, to improve spectral sensitization efficiency, to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may have any structure, but Ar-SM, Ar
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzoterzole, imidazole, oxazole,
Pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is, for example, a halogen (for example,
Br and Cl), hydroxy, amino, carboxy,
Alkyl (eg one or more carbon atoms, preferably 1
May also have a substituent selected from the group consisting of those having from 1 to 4 carbon atoms) and alkoxy (e.g., having at least one carbon atom, preferably having from 1 to 4 carbon atoms). Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline , 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-
Trifluoromethyl-4-quinolinethiol, 2,3
5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4
-Thiadiazole, 3-amino-5-mercapto-1,
2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-
Examples include 4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole, and the like, but the invention is not limited thereto.

The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, and more preferably 0.01 to 0.3 mol per mol of silver. Is the amount of.

It may be advantageous to include additives known as "toning agents" to improve the image. For example, the toning material may be present in an amount of 0.1 to 10% by weight of the total silver carrying component. Toning agents are materials well known in the photographic art, as shown in U.S. Pat. Nos. 3,080,254, 3,847,612 and 4,123,282.

Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazoline-
5-one, and quinazolinone, 3-phenyl-2-
Cyclic imides such as pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (e.g. N-hydroxy-
1,8-naphthalimide); cobalt complex (for example, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl- Mercaptans exemplified by 1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximide [eg, (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-benzo Thiazolinylidene) -1-methylethylidene] -2-thio-2,
4-oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl)
Phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-
Derivatives such as phthalazinedione; phthalazinone and phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid, 4
-Nitrophthalic acid and tetrachlorophthalic anhydride, etc.); phthalazine, phthalazine derivatives or metal salts, or 4- (1-naphthyl) phthalazine, 6
-Derivatives such as chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Etc.); quinazolinediones, benzoxazine or naphthoxazine derivatives; rhodium complexes that function not only as toning agents but also as a source of halide ions for silver halide formation in situ, eg hexachlororhodium (III) Ammonium acid, rhodium bromide, rhodium nitrate and hexachlororhodium (II
I) Potassium acid and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide;
Benzoxazines such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione -2,4-dione; pyrimidine and asymmetric-triazine (for example, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivative (for example, 3,6-dimercapto) -1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl)
-3,6-dimercapto-1H, 4H-2,3a, 5
6a-tetraazapentalene) and the like.

As the binder for the emulsion layer in the present invention, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride,
Any one can be selected from polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral, butyl ethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene and butadiene-styrene copolymers. 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 1
The range of 5: 1 to 1: 2, particularly 8: 1 to 1: 1 is preferred.

The light-sensitive material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.
Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials are wax, silica particles, styrene-containing elastomeric block copolymers.
(For example, styrene-butadiene-styrene, styrene
-Isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and mixtures thereof.

The emulsion layer or the protective layer for the emulsion layer in the present invention is described in US Pat. Nos. 3,253,921 and 22,747.
No. 82, No. 2527583 and No. 295687.
Can be used in photographic elements containing light absorbing materials and filter dyes as described in No. 9,
Further, for example, a dye can be mordanted as described in US Pat. No. 3,282,699.

The emulsion layer or the protective layer of the emulsion layer in the present invention contains a matting agent such as starch, titanium dioxide, zinc oxide, silica, beads of the type described in US Pat. Nos. 2,992,101 and 2,701,245. It may contain polymer beads and the like. The matteness of the emulsion surface may be anything as long as stardust failure does not occur, but the Beck's smoothness is preferably 1000 seconds or more and 10,000 seconds or less, and particularly preferably 2000 seconds or more and 10,000 seconds or less.

In the present invention, the silver halide emulsion and / or
Alternatively, the organic silver salt can be further protected against the formation of additional fog and stabilized against loss of sensitivity during inventory storage by antifoggants, stabilizers and stabilizer precursors. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are described in US Pat.
Thiazonium salt described in No. 16, US Patent No. 28864
Azaindene described in Nos. 37 and 2444605, mercury salts described in U.S. Pat. No. 2,728,663, urazoles described in U.S. Pat. No. 3,287,135, sulfocatechol described in U.S. Pat. No. 3,235,652, and British Patent No. 623448. Oxime, nitrone, nitroindazole, polyvalent metal salt described in U.S. Pat. No. 2,839,405, thyuronium salt described in U.S. Pat. No. 3,208,839, and palladium, platinum described in U.S. Pat. Nos. 2,566,263 and 2,597,915. And gold salts, U.S. Pat. Nos. 4,108,665 and 4,444.
No. 2202, halogen-substituted organic compounds described in U.S. Pat. Nos. 4,128,557 and 4,137,079;
And triazines described in US Pat. No. 4,441,1985 and the like.

The photosensitive layer in the present invention contains a polyhydric alcohol as a plasticizer and a lubricant (see, for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. No. 960404), U.S. Pat.
The fatty acid or ester described in No. 21060, the silicone resin described in British Patent No. 955061 and the like can be used.

A hardener may be used in each of the layers such as the photosensitive layer, the protective layer and the back layer of the present invention. Examples of hardeners include:
Polyisocyanates described in U.S. Pat. No. 4,281,060 and JP-A-6-208193, epoxy compounds described in U.S. Pat. No. 4,791,042, vinyl sulfone described in JP-A-62-89048 and the like. Compounds and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coatability and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically, the fluoropolymer surfactants described in JP-A-62-170950, US Pat. No. 5,382,504 and the like, JP-A-60-24.
No. 4945, Japanese Patent Application Laid-Open No. 63-188135, and the like, Fluorine-based surfactants, polysiloxy acid-based surfactants, such as those described in US Pat. No. 3,885,965, and Japanese Patent Application Laid-Open No. 6-3011.
Examples thereof include polyalkylene oxides described in No. 40 and anionic surfactants.

The light-sensitive material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.
Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials are wax, silica particles, styrene-containing elastomeric block copolymers.
(For example, styrene-butadiene-styrene, styrene
-Isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and mixtures thereof.

The emulsion layer or the protective layer for the emulsion layer in the present invention is described in US Pat. Nos. 3,253,921 and 2274.
No. 782, No. 2527583 and No. 29568.
Light absorbing materials and filter dyes such as those described in No. 79 may be included. Further, a dye can be mordanted as described in US Pat. No. 3,282,699.

Matting agents such as starch, titanium dioxide, zinc oxide, silica, beads of the type described in US Pat. Nos. 2,992,101 and 2,701,245 are used in the emulsion layer or protective layer of the emulsion layer in the present invention. It may contain polymer beads, etc. The matt degree of the emulsion surface may be any value as long as no stardust failure occurs, but the Beck smoothness is preferably from 1,000 seconds to 10,000 seconds, particularly preferably from 2,000 seconds to 10,000 seconds.

The photographic emulsion for heat development in the present invention can be coated on various supports. Typical supports include polyester films, subbed 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. Including materials, as well as glass, paper, metal and the like. Flexible substrates, especially partially acetylated, or baryta and / or α-olefin polymers, especially polyethylene, polypropylene, ethylene
-Paper supports coated with polymers of C2-C10 alpha-olefins such as butene copolymers are typically used. The support may be transparent or opaque, but is preferably transparent.

The light-sensitive material of the present invention comprises an antistatic or conductive layer such as a soluble salt (eg chloride, nitrate, etc.), a vapor-deposited metal layer, an ion as described in US Pat. Nos. 2861056 and 3206312. It may have a layer containing an organic polymer or an insoluble inorganic salt as described in US Pat. No. 3,428,451.

A method for obtaining a color image using the photothermographic material of the present invention is described in JP-A-7-132951.
There is a method described on page 0, left column, line 43 to 11 left column, line 40. Further, examples of stabilizers for color dye images include British Patent No. 1326889, U.S. Pat. No. 3,432,300, No. 3698909, No. 3574627, and No. 35.
73050, 3764337 and 404.
2394.

The photothermographic emulsions of this invention can be coated by a variety of 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, US Pat. No. 2,761,791 and British Patent No. 83
Two or more layers can be coated simultaneously by the method described in US Pat.

Additional layers in the photothermographic material of the present invention, such as a dye-receiving layer for receiving a moving dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques 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 serve as another light-sensitive material.

The vinylidene chloride copolymer in the present invention is 50 to 99.9% by weight, preferably 70 to 99% by weight.
A copolymer containing vinylidene chloride in a weight percentage, for example, a copolymer of vinylidene chloride / acrylic acid ester / a vinylidene monomer having an alcohol in a side chain described in JP-A-51-135526, U.S. Pat. 28523
No. 78 vinylidene chloride / alkyl acrylate /
A copolymer of acrylic acid, US Pat. No. 269823
Examples thereof include a copolymer of vinylidene chloride / acrylonitrile / itaconic acid described in No. 5, a copolymer of vinylidene chloride / alkyl acrylate / itaconic acid described in US Pat. No. 3,788,856, and the like. Specific examples of the compounds are shown below, but the present invention is not limited thereto. All numbers in parentheses are weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83: 12: 5) Copolymer of vinylidene chloride: hydroxyethyl methacrylate: hydroxypropyl acrylate (82: 10: 8) Vinylidene chloride: hydroxydiethyl methacrylate (92: 8) copolymer vinylidene chloride: butyl acrylate: acrylic acid (9
2: 4: 2) copolymer vinylidene chloride: butyl acrylate: itaconic acid (7
5: 20: 5) copolymer vinylidene chloride: methyl acrylate: itaconic acid (9
0: 8: 2) copolymer vinylidene chloride: itaconic acid monoethyl ester (9
6: 4) copolymer vinylidene chloride: acrylonitrile: acrylic acid (9
6: 3.5: 1.5) copolymer vinylidene chloride: methyl acrylate: acrylic acid (9
2: 5: 3) copolymer vinylidene chloride: methyl acrylate: 3-chloro-2
-Copolymer of hydroxypropyl acrylate (84: 9: 7) Copolymer of vinylidene chloride: methyl acrylate: N-ethanol acrylamide (85: 10: 5)

As the method for coating the vinylidene chloride copolymer in the present invention, a solution prepared by dissolving these polymers in a suitable organic solvent or a solution prepared by dispersing these polymers in water is well known, and is generally known as a dip coating method or an air knife method. Coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat.
It can be applied by an extrusion-coating method using a hopper described in No. 294. Further, it is possible to use a so-called extrusion coating method in which a melted polymer is made to flow down to a moving object to be coated and is bonded by pressure at the same time as cooling, or a laminating method in which a polymer in a film form is bonded by a paste and heat. Good.

The photothermographic material of the present invention has a photosensitive layer containing at least one silver halide emulsion on one side of a support and a back layer (backing layer) on the other side.
A so-called single-sided photosensitive material having

In the present invention, a matting agent may be added to the one-sided photosensitive material in order to improve transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. As the matting agent, any matting agent can be used. For example, U.S. Pat. Nos. 1,939,213, 2,701,245, 2,322,037, 3,226,672, and 3
Organic matting agents described in the respective specifications, such as 593344 and 376,448, 1260772, 21st
No. 92241, No. 3257206, No. 33709
Inorganic matting agents well-known in the art such as inorganic matting agents described in the respective specifications such as No. 51, No. 3523022, and No. 3769020 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 Starch, urea-formaldehyde-starch reactants, etc.
Gelatin hardened with a known hardener, hardened gelatin obtained by coacervate hardening to form hollow microcapsules, and the like can be preferably used. Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide,
Aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth and the like 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. The particle size distribution of the matting agent may be narrow or wide. On the other hand, the matting agent is the haze of the photosensitive material,
Since it greatly affects the surface gloss, it is preferable that the particle size, the shape, and the particle size distribution are brought into a required state at the time of preparing the matting agent or by mixing a plurality of matting agents.

In the present invention, the Beck's smoothness of the back layer is preferably 250 seconds or less and 10 seconds or more,
More preferably, it is 180 seconds or less and 50 seconds or more.

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. It is preferable to be contained.

Suitable binders for the back layer in the present invention are transparent or translucent, generally colorless, and include natural polymers such as synthetic resins, polymers and copolymers, and other film forming media such as: gelatin, gum arabic, poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s [eg poly (vinyl formal) and poly (vinyl butyral)],
Poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

In the present invention, the back layer preferably has a maximum absorption in the desired wavelength range of 0.3 or more and 2 or less, and more preferably an antihalation layer having an optical density of 0.5 or more and 2 or less. It is preferable.

When the antihalation dye is used in the present invention, the dye has a desired absorption in a desired wavelength range, has a sufficiently small absorption in the visible region, and has a preferable absorbance spectrum shape of the back layer. Any compound may be used. For example, compounds described in JP-A-7-13295 and US Pat. No. 5,380,635, JP-A-2-68539.
No. 1, page 13, lower left column, line 1 to page 14, lower left column, line 9 of the same, gazette 3-24539, page 14, lower left column to the same
The compounds described in the lower right column of page 6 are exemplified, but the present invention is not limited thereto.

US Pat. Nos. 4,460,681 and 4,
Backside resistive heating layer (bac
kside resistive heatinng layer) can also be used in the photothermographic image system.

[0173]

The present invention will be described below in more detail with reference to examples.

<Preparation of silver halide grains> 22 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water and the pH was adjusted to 5.0 at 35 ° C., and then 159 ml of an aqueous solution containing 18.6 g of silver nitrate. And an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 92: 8, pAg 7.7.
While maintaining the above value, the control double jet method was added over 10 minutes. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and dipotassium hexachloroiridate (1.2 x
10 ^-5 mol / l) pAg and an aqueous solution containing 6 cyano iron 4 Potassium (finished silver halide a molar per 1 × 10 ^-5 amount) and potassium bromide (1 mol / liter)
Controlled by the control double jet method while keeping at 7.7
Added over 0 minutes. After that, the pH is lowered to cause coagulation sedimentation, desalting treatment, 0.1 g of phenoxyethanol is added to adjust the pH to 5.9 and pAg to 8.2, and silver iodobromide grains (iodine content core: 8 mol%, average: 2 mol%) are added. , Average size 0.05
μm, projected area variation coefficient 8%, (100) plane ratio 88%
Of cubic particles) was completed.

The silver halide grains thus obtained were heated to 60 ° C. and 85 μmol of sodium thiosulfate and 11 μmol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide were added per mol of silver. 15 μmol of tellurium compound 1, 4.0 × 10 ⁻⁶ mol of chloroauric acid and 3.0 × 10 ⁻⁴ mol of thiocyanic acid were added, ripened for 120 minutes and then rapidly cooled to 30 ° C. to obtain a silver halide emulsion. It was

<Preparation of Organic Acid Silver Emulsion-A> 1.3 g of stearic acid, 0.5 g of arachidic acid, 8.5 g of behenic acid,
300 ml of distilled water was mixed at 90 ° C for 15 minutes, 31.1 ml of 1N-NaOH aqueous solution was added over 15 minutes with vigorous stirring, and then the temperature was lowered to 30 ° C. Next, 7 ml of 1N-phosphoric acid aqueous solution was added, and 0.012 g of N-bromosuccinimide was added with vigorous stirring, and then the above-prepared silver halide grains (silver halide amount 2.5 mmol) were added. Was added. Further, 25 ml of 1N-silver nitrate aqueous solution was added over 2 minutes, and stirring was continued for 90 minutes. Then, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS · cm. 37 g of a 1.2% by weight solution of polyvinyl acetate in butyl acetate was added to the solid content thus obtained, and the mixture was stirred. The stirring was stopped and the mixture was allowed to stand to separate into an oil layer and an aqueous layer. Was. Next, 20 g of a 2.5 wt% 2-butanone solution of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo KK) was added to this oil layer and stirred.
Further, 0.1 mmol of pyridinium perbromide and 1.8 × 10 ⁻⁴ mol of calcium bromide dihydrate were added together with 0.7 g of methanol, and then 40 g of 2-butanone and polyvinyl butyral (PVB B- manufactured by Monsanto Co.) were added. 76) 7.
Add 8 g and disperse with a homogenizer to obtain an organic acid silver salt emulsion (average particle size 0.04 μm, average major axis 1 μm, coefficient of variation 3).
0% needle-shaped particles).

<Preparation of Organic Acid Silver Emulsion-B> Behenic Acid 84
While 0 g and 95 g of stearic acid were added to 12 liters of water and kept at 90 ° C, a solution of 48 g of sodium hydroxide and 63 g of sodium carbonate dissolved in 1.5 liter of water was added. After stirring for 30 minutes, the temperature was raised to 50 ° C., 1.1 liter of a 1% aqueous solution of N-bromosuccinimide was added, and then 2.3 liter of a 17% aqueous silver nitrate solution was gradually added with stirring. Further, the liquid temperature was adjusted to 35 ° C., 1.5 liter of potassium bromide 2% aqueous solution was added over 2 minutes while stirring, and then stirred for 30 minutes, and 2.4 liter of N-bromosuccinimide 1% aqueous solution was added. To this aqueous mixture was added 3300 g of a 1.2% by weight solution of polyvinyl acetate in butyl acetate while stirring, and the mixture was allowed to stand for 10 minutes to separate into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. did. The gel-like mixture of behenic acid / silver stearate and silver bromide thus obtained was used as polyvinyl butyral (Denka Butyral # 3000- manufactured by Denki Kagaku Kogyo KK).
1800 g of 2.6% isopropyl alcohol solution of K)
600 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.),
An organic acid silver salt emulsion dispersed with 300 g of isopropyl alcohol (average minor axis 0.05 μm, average major axis 1.2 μm,
Needle-like particles having a coefficient of variation of 25% were obtained.

Example 1 <Preparation of Photosensitive Layer Coating Solution> Each chemical was added to the organic acid silver emulsion-A obtained above in the following amounts per mol of silver. 10m sodium phenylthiosulfonate at 25 ° C
g, 70 mg of dye a, 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-2-
21.5 g of carboxylic acid, compound of general formula (1) or general formula (2) or general formula (3) (shown in Table 12)
0.0064 mol, 580 g of 2-butanone and 220 g of dimethylformamide were added with stirring and the mixture was allowed to stand for 3 hours. Then, 5-tribromomethylsulfonyl-2-
Methyl thiadiazole 8 g, 2-tribromomethylsulfonylbenzothiazole 6 g, 4,6-ditrichloromethyl-2-phenyltriazine 5.2 g, disulfide compound a 2 g, reducing agent (shown in Table 12) 0.35 mol, tetra Chlorophthalic acid 5 g, hydrazine derivative (shown in Table 12) 0.008 mol, Megafax F-17
1.1 g of 6P (fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.), 590 g of 2-butanone, and 10 g of methyl isobutyl ketone were added with stirring.

[0179]

[Chemical 33]

<Emulsion side protective layer coating solution> CAB171-1
5S (Cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.) 75 g, 4-methylphthalic acid 5.7 g, tetrachlorophthalic anhydride 1.5 g, phthalazine 15 g, 0.3
g Megafax F-176P, Syldex H31
(Doikai Chemical Co., Ltd. spherical silica average size 3 μm) 2 g,
A solution prepared by dissolving 7.5 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) in 3070 g of 2-butanone and 30 g of ethyl acetate was prepared.

<Preparation of Support Having Back Surface> A support of polyethylene terephthalate film (100 μm) having a moisture-proof undercoat layer of vinylidene chloride copolymer on both surfaces was applied with a solution having the following formulation so that the dry film thickness would be 15 μm. And then dried. (Dry; 50 ° C for 10 minutes)

<Preparation of Back Surface Coating Liquid> Polyvinyl butyral # 4000-2 (manufactured by Denki Kagaku Kogyo KK) 60% isopropyl alcohol 10% solution, 10 g isopropyl alcohol, 3-isocyanatomethyl-3,5,5.
5-trimethylcyclohexyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) 8 g ethyl acetate 8% solution, and Dye D
A solution obtained by dissolving 0.2 g of -1 in 10 g of methanol and 20 g of acetone was added so that the absorption at the exposure wavelength was 0.8.

After coating the emulsion layer coating liquid on the side opposite to the back surface on the support prepared as described above so that the silver content was 1.8 g / m ² , the emulsion surface protective layer coating liquid was applied on the emulsion surface. Was applied to give a dry thickness of 2 μm.

(Exposure and Development Treatment) The sample thus prepared was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through an interference filter having a peak at 633 nm and a Tep wedge. Also, another sample is 633
Similarly exposed through an interference filter with a peak at nm and a Tep wedge and a 50% tint screen, respectively. Then, heat development treatment was performed at 110 ° C. for 20 seconds, 30 seconds, and 40 seconds.

(Evaluation of Photographic Properties) The density and halftone dot area ratio of the obtained image were measured.

Regarding the evaluation of photographic characteristics, gamma (G0330) in 30 second development and Dmin in 40 second development were evaluated. G0330: The image enlargement (ΔD50) was evaluated for the slope of the straight line connecting the points of density 0.3 and 3.0 in the characteristic curve.

ΔD50; halftone dot area ratio of 50 after development for 20 seconds
The difference in halftone dot area ratio between the development for 20 seconds and the development for 40 seconds in the step which became%. Therefore, the larger the value, the larger the image enlargement.

[0188]

[Table 12]

[0189]

Embedded image

From the results of Table 12, sample No. containing no compound of the present invention. 101, 110, 112, 114, 1
In 16, 118, 120, 126, Dmin is high,
Image enlargement is also large. Also, a sample N containing a comparative compound
o. In 105 to 109, the fog suppressing effect is small and the image enlargement is large. On the other hand, the samples of the present invention do not impair the high-contrast property, have a low Dmin, have a small image enlargement, and obtain good photographic performance.

Example 2 Organic acid silver emulsion-A in the emulsion layer of Example 1 was replaced with organic acid silver emulsion-
As a result of testing the embodiment of the present invention in place of B, the same result as in Example 1 was obtained. It should be noted that such effects can be obtained by using H-20, H-23, H-27,
H-32, H-33, H-37, H-44, H-53,
H-67, H-69, H-71, H-76, H-79,
R-I-3, R-I-11, R-I-3 as reducing agents
7, R-II-9, R-III-1, general formula (1),
1-10, 1-13, 3 as compounds of (2) and (3)
It was also realized by using -10, 3-26 and 3-46.

From the above results, according to the present invention, a printing plate having super-high contrast performance, a low fog density, a small change in image enlargement due to variations in development processing time, and a stable image can be obtained. A completely dry photothermographic material suitable for use can be provided.

[0193]

INDUSTRIAL APPLICABILITY According to the present invention, it is suitable for a printing plate making which can obtain an extremely stable image because it has an ultra-high contrast and has a very small image enlargement due to a change in developing conditions. A heat-developable photosensitive material is realized.

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[Procedure amendment]

[Submission date] February 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

In the general formulas (1) and (2), the ring which Z completes together with the carbon atom contains at least two nitrogen atoms and is composed of atoms selected from carbon, oxygen, sulfur, selenium and tellurium. It is a 5- and 6-membered heteroaromatic ring. Specific examples of the heteroaromatic ring include imidazole, pyrazole, triazole, tetrazole,
Examples thereof include thiadiazole, thiadiazine, pyridazine, pyrimidine, pyrazine and triazine. Examples of other heterocycles include oxadiazoline and thiadiazoline.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

Next, the tetrazaindene compound represented by the general formula (3) will be described.

Claims (2)

[Claims] 1. A silver halide light-sensitive material having at least one silver halide light-sensitive layer on a support and containing an organic silver salt in the layer and / or an adjacent layer, wherein the silver halide light-sensitive layer. And / or a layer adjacent to the photothermographic material, which contains a reducing agent, a hydrazine derivative, and at least one compound represented by the general formula (1) or (2). Embedded image In the general formulas (1) and (2), Z represents an atomic group for completing a 5- or 6-membered heteroaromatic ring containing at least two nitrogen atoms. R represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkyl- or aryl-substituted amino group, an amide group, a sulfonamide group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an aryl group,
It represents an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, a cyano group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, or a phosphoric acid amide group. 2. A silver halide light-sensitive material having at least one silver halide light-sensitive layer on a support and containing an organic silver salt in the layer and / or an adjacent layer, the silver halide light-sensitive layer. And / or a layer adjacent to the photothermographic material, which contains a reducing agent, a hydrazine derivative, and a compound represented by the general formula (3). Embedded image In the general formula (3), R ₁ , R ₂ , R ₃ and R ₄
Are a hydrogen atom, a hydroxy group, a mercapto group,
Halogen atom, cyano group, sulfo group, hydroxycarbonyl group, hydroxyamino group, alkyl group, aralkyl group, alkoxy group, alkyl- or aryl-substituted amino group, amide group, sulfonamide group, ureido group, urethane group, aryloxy group, It represents a sulfamoyl group, a carbamoyl group, an aryl group, an alkylthio group, an arylthio group or a phosphoric acid amide group. R ₃ and R ₄ may be bonded to each other to form a ring.