JPH09297368A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-developable photosensitive material ultrahigh in contrast and good in image reproducibility and suitable for forming a printing plate by incorporating a reducing agent and a hydrazine derivative and a nucleation promoter in a silver halide photosensitive layer and/or a layer adjacent to it. SOLUTION: The heat-developable photosensitive material contains an organic silver salt and the reducing agent and the hydrazine derivative and at least one kind of nucleation promoter, preferably, one of onium compounds represented by the formula and the like in at least one of the silver halide photosensitive layers and/or its adjacent layer formed on a support. In the formula, each of R10 , R20 , and R30 is an alkyl, aryl, cycloalkyl, cycloalkenyl, alkynyl, or heterocyclic group; Q is an N or P atom; L is an m-valent organic group combining through a C atom with Q<+> ; (m) is an integer of 1-4; X<n-> is an n-valent counter anion; and (n) is 1, 2, or 3.

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 in particular, it is suitable for 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 super-high contrast photosensitive material for development.

[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, gamma gamma is disclosed in Japanese Patent Publication No. 43-4924, Japanese Patent Publication No. 46582, Japanese Patent Publication No. 46-6074, Japanese Patent Publication No. 48-97523, Japanese Patent Application Laid-Open No. 7-2781, US Pat. (Gradation) is soft and not suitable for printing plate making.

In the printing field, ultra-high contrast photographic characteristics are desired as described above, and it has been proposed, for example, in USP5496695 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.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photothermographic material suitable for printing plate making which has super-high contrast and good image reproducibility.

[0006]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is as follows.
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 this layer and / or in an adjacent layer, said silver halide light-sensitive layer and / or adjacent layer The layer is a reducing agent, a hydrazine derivative and preferably the following general formula (A-1), general formula (A-2), general formula (A-3) or general formula (A-4).
The photothermographic material is characterized by containing at least one nucleation accelerator of the onium salt compound represented by

General formula (A-1)

[0008]

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(In the formula, R ₁₀ , R ₂₀ and R ₃₀ each represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group, and Q represents nitrogen. Represents an atom or a phosphorus atom, L represents an m-valent organic group which is bonded to Q ⁺ by its carbon atom, and m represents an integer of 1 to 4. X ^n-
Represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when R ₁₀ , R ₂₀ , R ₃₀ or L has an anion group as its substituent and forms an inner salt with Q ⁺ ,
X ^n- does not exist. ) General formula (A-2)

[0010]

[Chemical 6]

General formula (A-3)

[0012]

[Chemical 7]

(General formula (A-2) and general formula (A-
In 3), A ₁ , A ₂ , A ₃ and A ₄ together with a quaternized nitrogen atom each represent an organic residue for completing a substituted or unsubstituted unsaturated heterocycle. . Each B and C, alkylene, arylene, alkenylene, alkynylene, -SO ₂ -, - SO
-, -O-, -S-, -N (RN)-, -C = O-,-
It represents a divalent linking group composed of P = O- alone or in combination. However, RN represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. R ₁ and R ₂ each represent an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when forming an intramolecular salt, ^Xn- does not exist. ) General formula (A-4)

[0014]

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(Wherein Z represents an organic residue for completing a substituted or unsubstituted unsaturated heterocycle together with a quaternized nitrogen atom. R ₃ represents an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion,
Here, n represents an integer of 1 to 3. However, when forming an intramolecular salt, ^Xn- does not exist. )

[0016]

Embodiments of the present invention will be described below in detail. General formula (A-1) used in the present invention,
The onium salt compounds represented by (A-2), (A-3) and (A-4) will be described in detail below.

First, the general formula (A-1) will be described in detail.

[0018]

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In the general formula (A-1), R ₁₀ , R ₂₀ and R _{30 each} represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group, These may further have a substituent.

L represents an m-valent organic group bonded to Q ⁺ at its carbon atom, and m represents an integer of 1 to 4. X
^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when R ₁₀ , R ₂₀ , R ₃₀ or L has an anion group as a substituent and forms an inner salt with Q ⁺ , X
^n- is not needed.

In the general formula (A-1), examples of the groups represented by R ₁₀ , R ₂₀ , and R ₃₀ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and s.
a linear or branched alkyl group such as an ec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group; aryl groups such as phenyl group, naphthyl group, phenanthryl group; allyl group, vinyl group, 5-
Alkenyl groups such as hexenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group; alkynyl groups such as phenylethynyl group; pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group And heterocyclic groups such as benzothiazolyl group, morpholyl group, pyrimidyl group and pyrrolidyl group.

Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁₀ , R ₂₀ , and R ₃₀ , halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and nitro. Group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group (Including carboxylate), sulfonic acid group (including sulfonate), cyano group, oxycarbonyl group, acyl group and the like.

In the general formula (A-1), examples of the group represented by L include the groups having the same meanings as R ₁₀ , R ₂₀ and R ₃₀ when m is 1, and m is not limited thereto. Represents an integer of 2 or more, a polymethylene group such as a trimethylene group, a tetramethylene group, a hexamethylene group, a pentamethylene group, an octamethylene group, a dodecamethylene group, an arylene group such as a phenylene group, a biphenylene group and a naphthylene group, Examples thereof include polyvalent alkylene groups such as methylenemethyl group and tetramethylenemethyl group, and polyvalent arylene groups such as phenylene-1,3,5-toluyl group and phenylene-1,2,4,5-tetrayl group.

Examples of the counter anion represented by X ⁿ -in formula (A-1) include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion and benzoate. Carboxylate ions such as ions, p-toluenesulfonate, methanesulfonate, butanesulfonate,
Examples thereof include sulfonate ion such as benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion, and nitrate ion.

In the general formula (A-1), R ₁₀ , R ₂₀ ,
R ₃₀ is preferably a group having 20 or less carbon atoms, and when Q represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferred. When Q represents a nitrogen atom, an alkyl group having 15 or less carbon atoms, aralkyl And aryl groups are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, an aralkyl group, or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group, an aralkylene group, or a combination of these groups with a —CO— group, a —O— group,
-N (NR ') - group (NR' represents a hydrogen atom or R _10, R
₂₀ represents a group having the same meaning as R ₃₀ and, when a plurality of NR's are present in the molecule, these may be the same or different, and may be bonded to each other), -S- Base,
₂ formed by combining —SO— group and —SO ₂ — group
It is a valence group. When m represents 2, L is preferably a divalent group having a total carbon number of 20 or less bonded to Q ⁺ at its carbon atom. When m represents an integer of 2 or more, R in the molecule
_10, R _20, R ₃₀ are present in plural, but a plurality of R _10, R _20, R ₃₀ may be different even in the same, respectively.

The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion or a sulfate ion, and n is preferably 1 or 2.

Many of the compounds represented by formula (A-1) of the present invention are known and are commercially available as reagents. As a general synthesis method, when Q is a phosphorus atom, a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. is there. When Q is a nitrogen atom, there is a method of reacting a primary, secondary or tertiary amino compound with an alkylating agent such as an alkyl halide or a sulfonic acid ester.

Specific examples of the compound represented by formula (A-1) are shown below. However, the present invention is not limited to the following compounds.

[0029]

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[0030]

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[0031]

[Chemical 12]

[0032]

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[0033]

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[0034]

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Next, the general formula (A-2) and the general formula (A-
3) will be described in more detail.

[0036]

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General formula (A-2) and general formula (A-3)
In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent an organic residue containing a quaternized nitrogen atom for completing a substituted or unsubstituted unsaturated heterocyclic ring, a carbon atom, a hydrogen atom, It may contain an oxygen atom, a nitrogen atom or a sulfur atom, and may further have a condensed benzene ring. A ₁ , A ₂ , A ₃ , A ₄
Examples of the unsaturated heterocycle formed by pyridine ring,
Examples thereof include a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring, a pyrimidine ring and a pyrazole ring. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.

The divalent group represented by B and C is alkylene, arylene, alkenylene, alkynylene or --SO.
_2- , -SO-, -O-, -S-, -N (RN)-,-
What is constituted by C = O- and -P = O- alone or in combination is preferable. Here, RN represents an alkyl group, an aralkyl group, an aryl group, and a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -C = O
-, -O-, -S-, and -N (RN)-may be used alone or in combination.

R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substituent or An unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.),
(Alkyl or aryl) oxycarbonyl group, sulfo group (including sulfonate), carboxy group (including carboxylate), mercapto group, hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, etc.),
Aryloxy group, carbonamido group, sulfonamide group, sulfamoyl group, carbamoyl group, ureido group,
Thioureido, (alkyl or aryl) amino, cyano, nitro, alkylthio, arylthio and the like.

Particularly preferably, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include a carbamoyl group, an oxycarbonyl group, an acyl group,
Examples include an aryl group, a sulfo group (including sulfonate), a carboxy group (including carboxylate), and a hydroxy group.

The unsaturated heterocycle formed by A ₁ , A ₂ , A ₃ and A ₄ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . The substituent preferably has 6 to 10 carbon atoms.
Aryl group, alkyl group, carbamoyl group, (alkyl or aryl) amino group, oxycarbonyl group,
Alkoxy, aryloxy, (alkyl or aryl) thio, hydroxy, carbonamido,
Sulfonamide group, sulfo group (including sulfonate),
And carboxy groups (including carboxylate).

For the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compound of the present invention can be easily synthesized by a generally well-known method.
ev., 16, 163 (1962). Will be helpful.

General formula (A-2) and general formula (A-3)
Specific compounds of are shown below, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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Next, the general formula (A-4) will be described in more detail.

[0050]

[Chemical 21]

In the general formula (A-4), the nitrogen-containing unsaturated heterocycle containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom or a sulfur atom in addition to the nitrogen atom, and the benzene ring is a condensed ring. Or may have a substituent.
Examples of the formed hetero ring are the same as the examples of the nitrogen-containing unsaturated hetero ring formed by A ₁ , A ₂ , A ₃ , and A ₄ of the general formula (A-2) and the general formula (A-3). There are things. The preferred range is also the same, and a pyridine ring, a quinoline ring and an isoquinoline ring are preferred.

When the nitrogen-containing unsaturated heterocycle containing Z has a substituent, examples of the substituent are A ₁ , A ₂ , A ₃ in the general formula (A-2) and the general formula (A-3), The same examples as the substituents that the nitrogen-containing unsaturated heterocycle formed by A ₄ may have are mentioned, and the preferable ranges are also the same.

R ₃ represents an alkyl group or an aralkyl group, which may have 1 to 20 carbon atoms, may be substituted or unsubstituted, and may be linear or branched, or cyclic. As the substituent, R ₁ in the general formula (A-2),
The same examples as the examples of the substituent which the alkyl group represented by R ₂ may have are mentioned, and the preferable range is also the same.

For the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compound represented by the general formula (A-4) of the present invention can be easily synthesized by a generally well-known method, and is described in the literature Quart. Rev., 16, 163 (1962). Will be helpful.

Specific examples of the compound represented by formula (A-4) of the present invention are shown below, but the present invention is not limited thereto.

[0057]

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[0058]

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The compounds of the general formulas (A-1) to (A-4) of the present invention can be added to a light-sensitive material by a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), It can be used by dissolving it in ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

The compounds of the general formulas (A-1) to (A-4) of the present invention can be used in any of the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or another hydrophilic colloid layer. Although it may be added to the layer, it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto.

The addition amount of the compounds represented by formulas (A-1) to (A-4) of the present invention is 1 × 10 ^{-6 with} respect to 1 mol of silver halide.
２2 × 10 ^-2 mol is preferred, and 1 × 10 ^-5 to 2 × 10 ^-2.
Mole is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mole is most preferable.

In the present invention, an amine derivative, a disulfide derivative, a hydroxymethyl derivative or the like may be used as a nucleation accelerator, if necessary, in addition to the above general formulas (A-1) to (A-4). You can

As the amine derivative, JP-A-7-843 can be used.
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. A compound represented by the general formula [Na] described in JP-A-7-104426, specifically, the same publication 1
Compounds of Na-1 to Na-22 described on pages 6 to 20.
General formula (1), general formula (2), general formula (3), general formula (4), general formula (5), and general formula (7) described in Japanese Patent Application No. 7-37817.
A compound represented by the general formula (6) and the general formula (7),
Specifically, the compounds of 1-1 to 1-19, the compounds of 2-1 to 2-22, the compounds of 3-1 to 3-36, the compounds of 4-1 to 4-5 described in the same specification, Compounds of 5-1 to 5-41, compounds of 6-1 to 6-58 and 7-1 to 7-3
Compound of 8.

Examples of the disulfide derivative include compounds described in JP-A-61-198147.

Examples of the hydroxymethyl derivative include compounds described in USP4693956, US4777118 and EP231850, and more preferably a diarylmethanol derivative.

The hydrazine derivative used in the present invention will be described. The compound of the general formula (I) described in Japanese Patent Application No. 6-47961 is used in the present invention. Specifically, compounds represented by I-1 to I-53 described in the same specification are used.

The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically,
38 compounds. Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in JP-A-6-230497, specifically, the compounds 4-described on pages 25 and 26 of the same; 1 to Compound 4-10, Compounds 5-1 to 5-42 described on pages 28 to 36, and Compound 6-1 to Compound 6-7 described on pages 39 and 40. Compounds represented by the general formula (1) and the general formula (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). (Chem. 2) described in JP-A-6-313936
And compounds represented by (Chemical Formula 3).
Compounds described on pages 6-19. A compound represented by (Chemical Formula 1) described in JP-A-6-313951, specifically from page 3 to
Compounds described on page 5. Compounds represented by the general formula (I) described in JP-A-7-5610, specifically, pages 5 to 1 of the publication.
Compounds I-1 to I-38 described on page 0. JP-A-7-77783
Compound represented by the general formula (II) described in JP-A No. 10-27, specifically, the compounds II-1 to II-10 described on pages 10 to 27 of the publication.
2. Compounds represented by the general formula (H) and the general formula (Ha) described in JP-A-7-104426, specifically, pages 8 to 1 of the publication.
Compounds H-1 to H-44 described on page 5. Japanese Patent Application No. 7-191007
The compound characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group described in No.
(A), general formula (B), general formula (C), general formula (D), general formula
(E), compounds represented by the general formula (F), specifically compounds N-1 to N-30 described in the same publication. Compounds represented by the general formula (1) described in Japanese Patent Application No. 7-191007, specifically Compounds D-1 to D-55 described in the publication. USP5496695
Co-developer described in No., specifically column 6 of the same issue
Lines 3 to 38, and specific compound examples H-
1-H-28.

Specific examples of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

[Chemical formula 26]

[0072]

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[0073]

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[0074]

[Chemical 29]

[0075]

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[0076]

[Chemical 31]

[0077]

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[0078]

[Chemical 33]

[0079]

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[0080]

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[0081]

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

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, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention 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. It is preferably added to the adjacent layer.

The addition amount of the hydrazine derivative of the present invention is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁵ per mol of silver halide.
^-2 mol, more preferably 1 x 10 ^{-4 to} 5 x 10 ^-3 mol.

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.
Should be present as ~ 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%, tends to be more desirable.

A wide range of reducing agents have been disclosed in the photothermographic materials using organic silver salts. For example, amidoximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; for example, azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2'-bis (hydroxymethyl) propionyl. a combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid such as a combination of β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg hydroquinone and bis (ethoxy) Ethyl) hydroxylamine,
A combination of piperidinohexose reductone or formyl-4-methylphenylhydrazine); hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alininehydroxamic acid;
Combination of azine and sulfonamide phenol (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamide phenol); α such as ethyl-α-cyano-2-methylphenylacetate, ethyl-α-cyanophenylacetate -Cyanophenylacetic acid derivative; 2,2
'-Dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl and bis (2-hydroxy-1-naphthyl) methane -β-naphthol; bis-β-naphthol and 1,
A combination of 3-dihydroxybenzene derivatives (such as 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl-5-
5-pyrazolones, such as pyrazolones; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone;
Sulfonamide phenol reducing agents such as 6-dichloro-4-benzenesulfonamidephenol and p-benzenesulfonamidephenol; 2-phenylindane-1,3-dione etc .; 2,2-dimethyl-7-t-butyl-6 -Chromans such as hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; bisphenols (eg bis (2-hydroxy-3-t-butyl- 5-methylphenyl) methane, 2,2-bis
(4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol),
1,1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,
5,5-trimethylhexane and 2,2-bis (3,5-dimethyl
-4-hydroxyphenyl) propane); ascorbic acid derivatives (eg 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indane-1,3 -There are Zeon and others.

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

[0089]

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

[0091]

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

[0093]

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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
~R 10, R 1 '~R 5} ', R 11 ~R 13, R 11 '~
R ₁₃ ′, R _{21 to} R ₂₆ , and R ₂₁ ′ to R ₂₄ ′ are 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 —OA. It is a substituent represented. Provided that at least one and R7～R ₁₀ of R ₁ at least one and R ₁ of ~R ₅ '~R _5'
At least one of the groups is a group represented by -OA. Also, R
A ring may be formed together. A and A ′ represent a hydrogen atom, an alkyl group (C 1 to C 30), an acyl group (C 1 to C 3)
0), an aryl group, a phosphate group, and a sulfonyl group.
R, A and A ′ may be substituted, and typical examples of the substituent include, for example, an alkyl group (including an active methine group), a nitro group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group. A group containing a heterocycle containing a quaternized 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,
Acyloxy group, acyl 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, hydrazino group Group containing, group containing quaternary ammonio group, mercapto group, (alkyl, aryl, or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acyl Sulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, phosphoric acid amide group, group containing phosphate ester structure, group having acylurea structure, selenium Group containing a child or tellurium atom, 3
And a group having a quaternary sulfonium structure or a quaternary sulfonium structure. The substituents of R, A and A ′ may be further substituted, and preferable examples thereof include those exemplified as the substituent of R. Further, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent,..., Etc., may be substituted multiple times. Preferred examples are also the substituents of R, A, A ′. The illustrations apply.

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.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

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

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 for forming the photosensitive silver halide in the present invention is well known in the art, and for example, the method described in Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458 is used. be able to. 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 white turbidity after image formation, specifically 0.20.
μm or less, more preferably 0.01 μm or more and 0.15 μm or less,
More preferably, the thickness is 0.02 μm or more and 0.12 μm or less. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to 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 plane index (mirror index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high, and the proportion of {100} planes is high. preferable. The ratio is preferably at least 50%, more preferably at least 65%, even more preferably at least 80%. The ratio of Miller index {100} plane is {11} in the adsorption of sensitizing dye.
T. Tan using the adsorption dependence of the 1} and {100} planes
i; J.Imaging Sci., 29, 165 (1985). The halogen composition of the photosensitive silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide. In the present invention, silver bromide or silver iodobromide can be preferably used. Silver iodobromide is particularly preferable, and the silver iodide content is preferably 0.1 mol% or more and 40 mol% or less, and 0.1 mol% or more and 20 mol% or less.
% Or less is more preferable. 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 preferred 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 2
Core / shell particles having a ５5-fold structure, more preferably a 2- to 4-fold structure, 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. 1 of these metal complexes
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 structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used. As the compound of cobalt and iron, a hexacyano metal complex can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion, and the like, but are not limited thereto. The phase containing the metal complex in the silver halide may be uniform, may be contained in the core at a high concentration, or may be contained in the shell at a high concentration, and there is no particular limitation.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method, but in the present invention, they 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, diacyltellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, compounds having a P—Te bond, tellurocarboxylates, Te-organyl tellurocarboxylates, di Use of (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, etc. You can Examples of compounds preferably used in the noble metal sensitization method include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and U.S. Pat.
Compounds described in, for example, 48060 and British Patent 618061 can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also,
Reduction sensitization can be carried out by ripening while maintaining the pH of the emulsion at 7 or more or 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 amount of the photosensitive silver halide of the present invention to be used is preferably 0.01 mol 0.5 mol or less, more preferably 0.02 mol or more and 0.3 mol or less, and more preferably 0.03 mol or more with respect to 1 mol of the organic silver salt. It is particularly preferably 0.25 mol or less. Regarding the mixing method and 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 mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer, etc. Or a method of preparing an organic silver salt by mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, but the effect of the present invention is sufficient. There is no particular limitation as long as it appears.

Organic silver salts that can be used in the present invention are
Relatively stable to light, but in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent,
A silver salt that forms a silver image when heated to 80 ° C. or higher. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, particularly silver salts of long-chain fatty carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferable. Ligand is 4.0
Complexes of organic or inorganic silver salts having complex stability constants in the range of 10.0 are also preferred. 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, silver palmitate, silver maleate, silver fumarate, and tartaric acid. It includes silver, 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 derivatives thereof. Preferred examples of these compounds include 3-mercapto-4-
Phenyl-1,2,4-triazole silver salt, 2-mercaptobenzimidazole silver salt, 2-mercapto-5-aminothiadiazole silver salt, 2- (ethylglycolamido) benzothiazole silver salt, S-alkylthio Silver salt of thioglycolic acid such as silver salt of glycolic acid (wherein the alkyl group has 12 to 22 carbon atoms), silver salt of dithiocarboxylic acid such as silver salt of dithioacetic 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, for example 3-amino-5- Silver salt of 1,2,4-mercaptothiazole derivative such as benzylthio-1,2,4-thiazole silver salt, 3- (3-carboxyethyl) -described in U.S. Pat. No. 3,301,678.
Includes silver salts of thione compounds such as 4-methyl-4-thiazoline-2-thione silver salts. 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 benzotriazoles such as silver 5-chlorobenzotriazole, U.S. Pat. First
1,2,4-triazole as described in 4220709 or 1-
It includes silver salts of H-tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, U.S. Pat.
It is also possible to use various silver acetylide compounds as described in U.S. Pat.

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. Since the inversely proportional relationship between the size of silver salt crystal grains and the covering power is well established in the photothermographic material of the present invention as well known in the light-sensitive silver halide photographic material, that is, the photothermographic material It is necessary to reduce the size of the organic silver salt, because if the organic silver salt particles that are the image forming part of the material are large, it means that the covering power is low and the image density is low. 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. Monodisperse is the percentage of the value obtained by dividing the standard deviation of the length of each of the short axis and the long axis by each of the short axis and the long axis, preferably 100% or less, more preferably 80% or less, further preferably 50% or less. is there. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. Another way to measure monodispersity is:
There is a method for 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 80% or less,
It is more preferably 50% or less. As a measuring method, for example, the particle size (volume-weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with a laser beam and obtaining an autocorrelation function for the time change of the scattered light fluctuation You can

The coating amount of silver in the present invention is the same as that of the light-sensitive material 1.
m ² per 0.1~10g is preferable, and 0.5
5 g is preferred.

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 dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholer cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643IV-A (December 1978).
p.23), and Item 1831X (P.437, August 1979) of the same item, or in the literature cited.

Especially, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate-making cameras can be advantageously selected.

As an example of spectral sensitization to red light, He-
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 a combination thereof may be used, and the combination of sensitizing dyes is often used particularly 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 Disclosure 176, 17643 (December 1978).
Monthly) Page 23, IV, Section J, or the aforementioned Tokubo Sho 49-2
5500, 43-4933, JP-A-59-19032
And No. 59-192242.

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 or a thione compound is contained for the purpose of suppressing or accelerating the development and controlling the development, improving the spectral sensitization efficiency, and improving the preservability before and after the development. be able to.

When the 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-bearing component. Toning agents include U.S. Pat. No. 3,080,254,
It is a material well known in the photographic art, as shown in U.S. Pat. Nos. 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 hexachlorodium (III) Ammonium acid, rhodium bromide, rhodium nitrate and potassium hexachlorodium (III); inorganic peroxides and persulfates such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4- Dione, 8-methyl-1,3
-Benzoxazine-2,4-diones such as benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidines and asymmetric-triazines (e.g. 2,4- Dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.),
Azauracil and tetraazapentalene derivatives (eg 3,6-dimercapto-1,4-diphenyl-1)
H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6
-Dimercapto-1H, 4H-2,3a, 5,6a-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 guideline for at least retaining the organic silver salt, the ratio of the binder to the organic silver salt is 15:
The range of 1 to 1: 2, particularly 8: 1 to 1: 1 is preferable. 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 waxes, silica particles, styrene-containing elastomeric block copolymers (eg styrene-butadiene-styrene, styrene-isoprene-
Styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and mixtures thereof.

In the present invention, the emulsion layer or the protective layer for the emulsion layer includes US Pat. Nos. 3,253,921 and 2,274,782.
No. 2,527,583 and 2,956,879 and can be used in photographic elements containing light absorbing materials and filter dyes. Alternatively, dyes can be mordant as described in, for example, US Pat. No. 3,282,699.

In the emulsion layer or the protective layer of the emulsion layer in the present invention, matting agents such as starch, titanium dioxide, zinc oxide, silica, US Pat. Nos. 2,992,101 and 2,
Polymer beads, including beads of the type described in 701,245, can be included. 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 1000 seconds to 10,000 seconds, particularly preferably from 2,000 seconds to 10,000 seconds.

Silver halide emulsion and // in the present invention
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 the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716, U.S. Pat.Nos. 2,886,437 and 2,444,605. Azaindene, U.S. Pat.
No. 728,663, mercury salts described in U.S. Pat.No. 3,287,135, sulphocatechol described in U.S. Pat.No. 3,235,652, oximes described in British Patent No.
No. 405, polyvalent metal salts, U.S. Pat.No. 3,220,839, thyuronium salts, and U.S. Pat.
, Platinum and gold salts described in U.S. Pat. No. 4,597,915 and U.S. Pat. Nos. 4,108,665 and 4,442,20.
Halogen-substituted organic compounds described in US Pat. No. 4,12
Examples thereof include triazines described in US Pat. Nos. 8,557 and 4,137,079, 4,138,365 and 4,459,350, and phosphorus compounds described in US Pat. No. 4,411,985.

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 960,404), fatty acids or esters described in US Pat. Nos. 2,588,765 and 3,121,060, silicone resins described in British Patent 955,061 and the like can be used.

A hardener may be used in each layer such as the photosensitive layer, the protective layer and the back layer of the present invention. Examples of hardeners include:
Polyisocyanates described in US Pat. No. 4,281,060 and JP-A-6-208193, epoxy compounds described in US Pat. No. 4,791,042, JP-A-62-890
Vinyl sulfone compounds described in No. 48 and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coatability and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically,
62-170950, U.S. Pat. No. 5,382,504, and other fluorine-containing polymer surfactants, JP-A-60-244945, and JP-A-63
-Fluorinated surfactants described in 188135, etc., U.S. Patent
No. 3,885,965, etc.
Examples thereof include polyalkylene oxides and anionic surfactants described in JP-A-6-301140.

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.

In the emulsion layer or the protective layer of the emulsion layer in the present invention, US Pat. Nos. 3,253,921 and 2,274,782
No. 2,527,583 and 2,956,879 and can be used in photographic elements containing light absorbing materials and filter dyes. Alternatively, dyes can be mordant as described in, for example, US Pat. No. 3,282,699.

In the emulsion layer or the protective layer of the emulsion layer in the present invention, a matting agent such as starch, titanium dioxide, zinc oxide, silica, US Pat. Nos. 2,992,101 and 2,
Polymer beads, including beads of the type described in 701,245, can be included. 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 1000 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
-A paper support coated with a polymer of an alpha-olefin having 2 to 10 carbon atoms, such as a butene copolymer, is 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, for example, a soluble salt (eg chloride, nitrate, etc.), a vapor-deposited metal layer, an ion as described in US Pat. Nos. 2,861,056 and 3,206,312. It may have a layer containing an organic polymer or an insoluble inorganic salt as described in US Pat. No. 3,428,451.

As a method for obtaining a color image using the photothermographic material of the present invention, there is a method described in JP-A-7-13295, page 10, left column, line 43 to 11 left column, line 40. Examples of color dye image stabilizers include British Patent No. 1,326,889, U.S. Patent Nos. 3,432,300, 3,698,909, and 3,574,
Nos. 627, 3,573,050, 3,764,337 and 4,042,394.

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 hoppers of the type described in US Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761,791 and GB 837,095.

In the heat-developable photographic materials of the present invention, additional layers such as dye-receiving layers for receiving transfer dye images, opacifying layers when reflective printing is desired, protective topcoat layers and photothermographic techniques. Known primer layers and the like can be included. 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 used in the present invention is 50 to 99.9% by weight, preferably 70 to 99.
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. 38523
No. 78 vinylidene chloride / alkyl acrylate /
A copolymer of acrylic acid, US Pat. No. 269823
Examples thereof include a vinylidene chloride / acrylonitrile / itaconic acid copolymer described in No. 5, a vinylidene chloride / alkyl acrylate / itaconic acid copolymer described in U.S. Pat. No. 3,788,856. Specific examples of the compounds are shown below, but the present invention is not limited thereto. All numbers in parentheses represent 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: 6: 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 obtained by dissolving these polymers in a suitable organic solvent or a solution obtained by dispersing them in water is generally well known, and the dip coating method and the air knife method are well known. 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.

As described above, the photothermographic material of the present invention has a photosensitive layer containing at least one silver halide emulsion on one side of the support and a back layer on the other side. It is preferably a single-sided photosensitive material.

In the present invention, the single-sided light-sensitive material may contain a matting agent 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 Bekk 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, the layer functioning as the outermost surface layer, or the layer close to the outer surface, and also the layer acting as a so-called protective layer. It is preferably 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 a 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 the desired absorption in the desired wavelength range, the absorption outside the desired wavelength range is sufficiently low, and the shape of the preferable absorbance spectrum of the back layer is Any compound may be used as long as it can be obtained. For example, compounds described in JP-A-7-13295 and US Pat. No. 5,380,635, JP-A-2-68
The compounds described in JP-A-539, page 13, lower left column, line 1 to page 14, left lower column, line 9 and JP-A 3-24539, page 14, lower left column to page 16, lower right column, can be mentioned. The invention is not limited to this.

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.

[0158]

The present invention will be described in more detail with reference to the following 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 a temperature of 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
X10 ^-5 mol / l), 6 potassium iron cyanide (amount of 1 × 10 ^-5 per mol of finished silver halide) and potassium bromide at 1 mol / l kept in pAg 7.7. While being added by the control double jet method over 30 minutes. After that, the pH is lowered and the precipitate is coagulated and sedimented for desalting, 0.1 g of phenoxyethanol is added, and the pH is 5.9, pAg
8.2 silver iodobromide grains (iodine content core 8 mol%,
Preparation of an average of 2 mol%, an average size of 0.05 μm, a projected area variation coefficient of 8%, and a cubic grain of (100) plane ratio of 88% was completed.

The halogenated particles thus obtained were heated to 60 ° C., and 85 μmol of sodium thiosulfate and 11 μmol and 15 μmol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide were added per mol of silver. 3 moles of tellurium compound 1, 4.0 × 10 ⁻⁶ moles of gold acid, and 3.0 × 10 ⁻⁴ moles of thiocyanic acid were added, and after aging for 120 minutes, 3
It was rapidly cooled to 0 ° C. to obtain a silver halide emulsion.

<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 silver halide grains prepared beforehand (amount of silver halide of 2.5 m
Mol) was added. Furthermore, 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, 2.5 wt% of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo KK) was added to this oil layer.
% 2-butanone solution (20 g) was added and stirred. further,
Pyridinium perbromide (0.1 mmol) and calcium bromide dihydrate (1.8 × 10 ^-4 mol) were added together with 0.7 g of methanol, and then 2-butanone (40 g) and polyvinyl butyral (PVB B-76 manufactured by Monsanto) were added. No. 7.8 g was added and dispersed by a homogenizer to obtain an organic acid silver salt emulsion (acicular particles having an average particle size of 0.04 μm, an average major axis of 1 μm and a coefficient of variation of 30%).

<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 set to 35 ° C., 1.5 liters of a 2% aqueous solution of potassium bromide was added over 2 minutes with stirring, and then the mixture was stirred for 30 minutes to prepare 1% of N-bromosuccinimide.
2.4 liter of aqueous solution was added. While stirring, 3300 g of 1.2% by weight polyvinyl acetate in butyl acetate was added to this aqueous mixture, 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 dispersed in 1800 g of a 2.6% isopropyl alcohol solution of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo KK), Furthermore, polyvinyl butyral (Denki Kagaku Kogyo Co., Ltd.)
Denka Butyral # 4000-2) (600 g) and isopropyl alcohol (300 g) were dispersed to obtain an organic acid silver salt emulsion (acicular particles having an average minor axis of 0.05 μm, an average major axis of 1.2 μm and a coefficient of variation of 25%). The average size of the silver bromide formed by the addition of potassium bromide was 0.06 μm.

Example 1 <Preparation of Coating Solution for Emulsion Layer> Each chemical was added to the organic acid silver emulsion-A or the organic acid silver emulsion-B obtained above in the following amounts per mol of silver. At 25 ° C sodium phenylthiosulfonate 10 mg, 70 mg of dye a, 30 mg of 2,
2-mercapto-5-methylbenzimidazole 2 g,
4-chlorobenzophenone-2-carboxylic acid 21.5 g
And 2-butanone 580 g, dimethylformamide 220
g was added with stirring and left for 3 hours. Then, 5-
Tribromomethylsulfonyl-2-methylthiadiazole 8g, 2-tribromomethylsulfonylbenzothiazole 6g, 4,6-ditrichloromethyl-2-phenyltriazine 5g, disulfide compound a 2g, developer (shown in Table 1) 0 0.5 g, tetrachlorophthalic acid 5 g, Megafax F-176P (Dainippon Ink and Chemicals, Inc. fluorinated surfactant) 1.1 g, 2-butanone 590 g, and methyl isobutyl ketone 10 g were added with stirring. .

<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 side> A polyethylene terephthalate film (100 μm) having a moisture-proof undercoat layer of vinylidene chloride copolymer on both sides was applied to a support having the following formulation solution to give a dry film thickness of 15 μm. And then dried. (Dry; 50 ° C for 10 minutes)

<Preparation of coating solution for back surface> 60 g of a 10% isopropyl alcohol solution of polyvinyl butyral # 4000-2 (manufactured by Denki Kagaku Kogyo KK), 10 g of isopropyl alcohol, 3-isocyan-trimethyl 3,3.
Absorption of exposure wavelength of 8 g of an 8% ethyl acetate solution of 5,5-trimethylcyclohexyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) and dye D-1 (0.2 g dissolved in 10 g of methanol and 20 g of acetone) To 0.8.

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

[0168]

Embedded image

(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 nm
Similarly exposed through an interference filter with a peak at and a Tep wedge and a 50% tint screen. Then 1
Heat development treatment was performed at 10 ° C. for 20 seconds, 30 seconds, and 40 seconds.

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

For the evaluation of photographic characteristics, gamma (G0313 and G0330) in 30 second development was evaluated.

G0313: Concentrations of 0.3 and 1.
Image enlargement (ΔD50) was evaluated for the slope of the straight line connecting the three points G0330; the slope of the straight line connecting the points of density 3.0 and 1.3 on the characteristic curve. ΔD50: Difference in halftone dot area ratio between 20 second development and 40 second development in the step where the halftone dot area ratio became 50% in 20 second development. Therefore, the larger the value, the larger the image enlargement.

[0173]

[Table 9]

From the results of Table 9, sample No. 10 of the comparative sample was obtained.
In Nos. 1 to 104 and 123, the gradation becomes harder according to the amount of the hydrazine derivative added, but the image enlargement becomes larger as the tonality increases. On the other hand, each of the samples of the present invention has a high contrast of gamma of 10 or more, and the image enlargement is suppressed to a very small level.

Example 2 Hydrazine derivative H- added to the emulsion layer of Example 1
58 to H-1, H-14, H-16, H-26, H-2
7, H-32, H-46, H-54, H-62 and H
In place of −65, the addition amount is adjusted, and general formula (A-1) to
As a result of preparing a sample combined with (A-4) and evaluating the performance in the same manner as in Example 1, in the aspect of the present invention, good performance was obtained as in Example 1.

Example 3 The sample of Example 1 was similarly exposed through an interference filter having a peak at 633 nm, a Tep wedge, and a tint net of 80% and 20%, respectively. Then, at 110 ℃ 2
Thermal development processing was performed for 0 seconds, 30 seconds, and 40 seconds. As a result of measuring the dot area ratios of these samples and evaluating ΔD20 and ΔD80, the sample of the present invention showed small image enlargement and good performance as in Example 1.

The sample of Example 1 was exposed with a 633 nm He-Ne laser sensitometer for 20 seconds to give a dot area ratio of 20%, 50% and 80%, and ΔD20 was applied in the same manner as in Example 1. As a result of evaluating ΔD50 and ΔD80, the performance was good as in the case of Example 1 and Example 3.

Example 4 Instead of the hydrazine derivative H-58 in Example 1, H-16, H-19, H-21, H-22, H-2.
6, H-27, H-34, H-48, H-57, H-6
4 was used. Good results were obtained in the same manner as in Example 1.

[0179]

From the above results, according to the present invention, it is suitable for a printing plate making plate which has a super-high contrast performance and can obtain a stable image with a small change in image enlargement due to a change in development processing time. It is possible to provide a completely dry photothermographic material.

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 this layer and / or in an adjacent layer, wherein the silver halide light-sensitive layer. And / or an adjacent layer contains a reducing agent, a hydrazine derivative and a nucleation accelerator, and a photothermographic material. 2. The nucleation accelerator is represented by the following general formula (A-1), general formula (A-2), general formula (A-3) or general formula (A-
The photothermographic material according to claim 1, which is represented by 4). General formula (A-1) (In the formula, R ₁₀ , R ₂₀ and R ₃₀ each represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group. Q is a nitrogen atom or a phosphorus atom. Represents an atom, L represents an m-valent organic group bonded to Q ⁺ at its carbon atom, m represents an integer of 1 to 4, X ^{n −} represents an n-valent counter anion, and n represents n. Represents an integer of 1 to 3.
However, when R ₁₀ , R ₂₀ , R ₃₀ or L has an anion group in its substituent and forms an intramolecular salt with Q ⁺ , X ^{n −} does not exist. ) General formula (A-2): General formula (A-3): (In the general formula (A-2) and the general formula (A-3),
A ₁ , A ₂ , A ₃ and A ₄ together with a quaternized nitrogen atom each represent an organic residue for completing a substituted or unsubstituted unsaturated heterocycle. Each B and C, alkylene, arylene, alkenylene, _{alkynylene, -SO 2 -, - SO -} , - O -, -
S-, -N (RN)-, -C = O-, and -P = O- represent a divalent linking group constituted alone or in combination. However, RN represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. R ₁ and R ₂ each represent an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when forming an intramolecular salt, ^Xn- does not exist. ) General formula (A-4): (In the formula, Z represents an organic residue for completing a substituted or unsubstituted unsaturated heterocycle together with a quaternized nitrogen atom. R ₃ represents an alkyl group or an aralkyl group. X ^n- represents an n-valent counter anion, where n is 1
Represents an integer of 3 to 3. However, when forming an inner salt, X
^n- does not exist. )