JPH11231460A - Heat-developable photosensitive material and image recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-developable photosensitive material and image recording material prevented from rise of fog with time in a material after development processing and good in the color tone of a silver image. SOLUTION: The heat-developable recording material contains, on a supporting body, an organic silver salt, photosensitive silver halide, a reducing agent for silver ions, a binder, and at least one of compounds having at least one tribromomethyl group in the molecule, and a leuco compound to be allowed to form a blue dye by reaction with the oxidation product of this reducing agent. An image is formed this image recording method by exposing this heat- developable photosensitive material to infrared laser beams and developing it, preferably, by heating it at a temperature of 80 deg.C-250 deg.C.

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 an image recording method, and more particularly to a technique for improving fog and sensitivity, improving image storability and silver tone.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have been a problem in terms of workability. There is a strong demand for weight loss. Therefore, there has been a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As a technique for this purpose, a photothermographic material for forming a photographic image by using a heat development processing method is disclosed in, for example, US Pat. No. 3,152,904, US Pat. Morgan and B.A. "Thermally Processed Silver System" by Shely
Silver Systems) (Imaging Processes
And Materials (Imaging Processes and Materi
als) Neblette 8th edition, Sturge, V.A. Walworth, A .; Shepp, page 2, 1969).

In such a photothermographic material, a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a reducing agent are usually dispersed in a (organic) binder matrix. It is contained in a state. The photothermographic material is stable at room temperature, but generates silver through an oxidation-reduction reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature after exposure. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which is symmetrical with the non-exposed areas and the image is formed. An antifoggant for controlling the fogging of this image is used as needed in the light-sensitive material.
The most effective method as a conventional antifogging technique has been a method using a mercury compound as an antifoggant.

The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat. No. 358.
No. 9903. However, mercury compounds are environmentally unfavorable, and the development of non-mercury antifoggants has been desired. Non-mercury antifoggants include various polyhalogen compounds (for example, US Pat. No. 3,874,874).
No. 946, No. 4756999, No. 5340712,
European Patent Nos. 605981A1 and 622666A1
No. 631176A1, JP-B No. 54-165, and JP-A-7-2781). However, these compounds have a problem that the effect of preventing fogging is low or the color tone of silver is deteriorated. In addition, those having a high antifogging effect have problems such as lowering the sensitivity, and thus need to be improved. After aging under the forced conditions of humidification and heating in the form of laminating the photosensitive materials,
There is a problem that fogging in an unexposed portion increases when developed, and development of an antifoggant free of these problems has been desired.

As a method for solving these problems, Japanese Patent Application Laid-Open No.
No. 60164, No. 9-244178, No. 9-2583
No. 67, No. 9-265150, No. 9-281640
And JP-A-9-319022 disclose polyhalogen compounds in which the above-mentioned disadvantages are improved. However, particularly, it contains a photothermographic material for a laser imager for medical use, or contains a high contrast agent and has a wavelength of 600 to 800 nm.
When these compounds are applied to the photothermographic material for output of a printing imagesetter having an oscillation wavelength, the above-mentioned disadvantages are considerably improved, but the image of the developed sample is fogged up with time. It had a drawback that storage stability with time was poor.

At the same time as the problem of fogging, the color tone of the silver image is a yellowish-warm black tone. Especially when used for medical images, improvement is desired, but no effective improvement technique has been found yet. .

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material and an image recording method in which a developed sample does not cause fog to rise over time and has a good silver image color tone. It is in.

[0009]

Means for Solving the Problems The invention according to claim 1 for solving the above-mentioned problems is characterized in that an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, a binder, and A photothermographic material comprising at least one compound having at least one tribromomethyl group and a leuco compound which reacts with an oxidized form of the reducing agent to form a blue dye. .

According to a second aspect of the present invention, the compound having a tribromomethyl group according to the first aspect is represented by the following general formula 1
A photothermographic material characterized by being at least one of the compounds represented by the formulas (1) to (3).

[0011]

Embedded image [Wherein X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. m represents an integer of 3 or more and 4 or less. Q represents a heterocyclic group, an aryl group or an aliphatic group.
n represents an integer of 0 or more and 3 or less. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10. ]

[0012]

Embedded image [Wherein X ₁ and X ₂ represent a halogen atom. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group.
Q represents an aromatic hetero 5-membered ring, a furan ring, a thiophene ring or a pyrrole ring having one oxygen atom and two or more and three or less nitrogen atoms. However, when Q is a thiophene ring, X ₁ represents a bromine atom. ]

[0013]

Embedded image [Wherein X ₁ and X ₂ represent a halogen atom. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group.

Y is -SO-, -CO-, -N (R ₁₁ ) -SO _2- , -N (R ₁₁ ) -CO-
, -N (R ₁₁ ) -COO-, -COCO-, -COO-, -OCO-, -OCOO-,-
SCO—, —SCOO—, —C (Z ₁ ) (Z ₂ ) —, alkylene, arylene, a divalent heterocyclic ring, or a divalent linking group formed of any combination thereof. R
₁₁ represents a hydrogen atom or an alkyl group. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group. Z ₁ and Z ₂ are not hydrogen atoms at the same time. Q represents an aliphatic group, an aromatic group or a heterocyclic group. However, when Y is -SO-, Q
Represents an aromatic 5-membered heterocyclic group having at least one heteroatom other than N and a pyridine ring group. The invention according to claim 3 is a photothermographic material, wherein the leuco compound according to claim 1 is at least one compound represented by formulas 4 to 7.

[0015]

Embedded image Wherein W represents —NR ₁ R ₂ , —OH or —OZ; R ₁ and R ₂ each represent an alkyl group or an aryl group;
Represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂
Each nitrogen atom or = C _{(R 3)} - represents a. X is 5 to 5 together with Z ₁ , Z ₂ and carbon atoms adjacent thereto.
It represents an atomic group necessary to form a 6-membered aromatic hetero ring. R ₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.
R represents an aliphatic group or an aromatic group. p represents an integer of 1 to 2. CP1 represents the following groups. ]

[0016]

Embedded image [Wherein, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent that can be substituted on a benzene ring. Also R ₅
And R ₆ and R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meanings as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ and m is 1
Represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀ represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and _{R 23} has the same meaning as _{R 19} and _{R 20.} R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent. R ₂₆ is R
Synonymous with ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ is R
Synonymous with ₂₆ . R ₃₄ , R ₃₅ and R ₃₆ are R
₂₅ , R ₂₇ and R ₂₈ . R ₃₃ is R
Synonymous with ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ are R
₂₅ , R ₂₇ and R ₂₈ . R ₃₇ is R
Synonymous with ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ are R
₂₅ , R ₂₇ and R ₂₈ . R ₄₄ is R
Synonymous with ₂₆ . * Represents a bonding point between CP1 and another partial structure in the general formula 4. ]

[0017]

Embedded image [Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1, n, R and p represent R ₁ , R ₂ , R ₃ , R ₄ , CP in the general formula 4]
It is synonymous with 1, n, R and p. ]

[0018]

Embedded image [Wherein, R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂ , and CP 1 represent R ₃ , n, R ₄ , W, X, Z in the general formula 4]
_1, the same meaning as _{Z 2,} and CP1. ]

[0019]

Embedded image _{Wherein, R 1, R 2, R} 3, R 4, CP1 and n have the same meanings as _{R 1, R 2, R 3} , R 4, CP1 and n in the general formula 4. The invention described in claim 4 that solves the above-mentioned problem is described in claim 1.
An image recording method, wherein the photothermographic material according to any one of the above (1) to (3) is exposed with an infrared laser.

According to a fifth aspect of the present invention, there is provided an image forming method wherein the photothermographic material according to any one of the first to third aspects is developed by heating at 80 ° C. to 250 ° C. Is the way.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The photothermographic material of the present invention comprises an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, a binder and at least a tribromomethyl group in the molecule on a support. It is characterized by containing a leuco compound which contains at least one compound having one and which reacts with an oxidized form of the reducing agent to form a blue dye.

As the compound having a tribromomethyl group, at least one of the compounds represented by the above general formulas 1 to 3 can be used.
It is preferably a seed, and the compound represented by the general formula 1 will be described first in detail.

The halogen atom represented by X ₁ and X ₂ is
A fluorine atom, a chlorine atom, a bromine atom and an iodine atom which may be the same or different from each other, preferably a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom and a bromine atom, particularly preferably bromine Is an atom.

Y represents a divalent linking group, specifically, -SO _2- , -SO-, -CO-, -N (R ₁₁ ) -SO _2- , -N (R ₁₁ ) -CO -,
-N (R ₁₁ ) -COO-, -COCO-, -COO-, -OCO-, -OCOO-,
_{-SCO-, -SCOO-, -C (Z 1} ) (Z 2) -, it represents an alkylene, arylene, a divalent hetero ring or a divalent linking group formed of these in any combination.

Preferred as Y are -SO _2- , -SO- and -C
O- is more preferable, and -SO _2- is more preferable.

N is preferably 1.

R ₁₁ represents a hydrogen atom or an alkyl group,
Preferably it is a hydrogen atom.

Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but Z ₁ and Z ₂ are not hydrogen atoms at the same time.

Preferred as the electron-withdrawing group are those having a Hammett's substituent constant σp value of 0.01 or more;
More preferably, the substituent is 0.1 or more.

Regarding the Hammett's substituent constant, see Journa
l of Medicinal Chemistry, 1973, Vol.16, No.11,1207-12
16 mag can be referred to.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σ
p value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl ( σp value: 0.33), trifluoromethyl (σ
p value: 0.54)), cyano group (σp value: 0.66),
Nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (eg, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value) Value: 0.5
0), benzoyl (σp value: 0.43)), ethynyl group (σp value: 0.09), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxy) Carbonyl (σp
Value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57).

Preferred as Z ₁ and Z ₂ are a halogen atom, a cyano group or a nitro group, and among the halogen atoms, preferred are a chlorine atom, a bromine atom and an iodine atom, and more preferred are a chlorine atom, A bromine atom is particularly preferred.

A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. The electron-withdrawing group represented by A is preferably a compound having a Hammett's substituent constant σp value of 0.01.
The above substituents are more preferable, and the σp value is more preferably 0.1.
These are the above substituents.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp value
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.29) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), ethynyl group (σp value
Value: 0.09), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp
Value: 0.45), phenoxycarbonyl (σp value: 0.
45)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57) and the like.

A is preferably an electron-withdrawing group,
More preferred are a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group, and particularly preferred is a halogen atom. Among the halogen atoms, preferred are chlorine atoms,
A bromine atom and an iodine atom are preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is particularly preferable.

Q represents an aliphatic group, an aromatic group or a heterocyclic group, and the aliphatic group represented by Q is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms; Preferred is C1-20, more preferred is C1
12, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), Alkenyl group (preferably having 2 to 2 carbon atoms)
30, more preferably 2 to 20 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, vinyl, allyl,
-Butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and still more preferably having 2 to 12 carbon atoms).
And for example, propargyl, 3-pentenyl and the like. ), And may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and a ureido group. Preferred as the aliphatic group represented by Q is an alkyl group, and more preferred is a chain alkyl group.

The aromatic group represented by Q is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably 6 to 20 carbon atoms. Phenyl group, more preferably 6-1
2 is a phenyl group. The aryl group may have a substituent, and examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and a ureido group.

The heterocyclic group represented by Q is N, O or S
A 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one atom, which may be a single ring or may form a condensed ring with another ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom, and even more preferably a nitrogen-containing 1-membered aromatic heterocyclic group. 5 to 6-membered aromatic heterocyclic group containing 1 to 2 atoms.

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, more preferably triazine, quinoline, thiadiazole, benzthiazole, oxadiazole, particularly preferred Is pyridine,
Quinoline, thiadiazole and oxadiazole.
Preferred as Q is an aromatic nitrogen-containing heterocyclic group.

M represents an integer of 3 or more and 4 or less, and preferably m is 3.

When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10, but preferably 6 or less.
It is.

In the general formula 1, when Y is —SO—, Q represents a 5-membered aromatic heterocyclic group having at least one heteroatom other than N and a pyridine ring group.

Next, the compound represented by Formula 2 will be described in detail.

In the formula, X ₁ , X ₂ and A have the same meanings as those described in formula 1.

Q represents an aromatic hetero 5-membered ring having one oxygen atom and two or more and three or less nitrogen atoms, a furan ring, a thiophene ring and a pyrrole ring, wherein one oxygen atom and two nitrogen atoms Specific examples of the aromatic hetero 5-membered ring having one or more and three or less include oxadiazole and oxatriazole, and oxadiazole is preferable.

Preferred among the rings represented by Q is oxadiazole.

In the general formula 2, when Q is a thiophene ring, X ₁ is a bromine atom.

Next, the compound represented by Formula 3 will be described in detail.

In the formula, X ₁ , X ₂ and A have the same meanings as those described in formula 1.

Y is -SO-, -CO-, -N (R ₁₁ ) -SO _2- , -N
(R ₁₁ ) -CO-, -N (R ₁₁ ) -COO-, -COCO-, -COO-, -OCO-,
-OCOO-, -SCO -, - SCOO - , - C (Z 1) (Z 2) -, represents an alkylene, arylene, a divalent hetero ring or a divalent linking group formed of these in any combination . R
₁₁ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but Z ₁ and Z ₂ are not hydrogen atoms at the same time.

Preferred as the electron-withdrawing group are those having a Hammett's substituent constant σp value of 0.01 or more;
More preferred are substituents of 0.1 or more. For the Hammett's substituent constant, see Journal of Medicinal Chemi.
stry, 1973, Vol. 16, No. 11, 1207-1216, etc. can be referred to.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp value
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.29) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), ethynyl group (σp value
Value: 0.09), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp
Value: 0.45), phenoxycarbonyl (σp value: 0.
45)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57) and the like.

Preferred as Z ₁ and Z ₂ are a halogen atom, a cyano group and a nitro group. Among the halogen atoms, preferred are a chlorine atom, a bromine atom and an iodine atom, more preferred are a chlorine atom and a bromine atom, and particularly preferred is a bromine atom.

Preferred as Y is -SO-, -CO-, -N
(R ₁₁ ) -SO _2- , -N (R ₁₁ ) -CO-, -C (Z ₁ ) (Z ₂ )-, and more preferably -SO-, -C (Z ₁ ) (Z ₂ )-.

N is preferably 1.

Q represents an aliphatic group, an aromatic group, or a heterocyclic group. However, when Y is -SO-, Q represents a 5-membered aromatic heterocyclic group having at least one heteroatom other than N and a pyridine ring. These rings may be further condensed with other rings.

Specific examples of the aromatic 5-membered heterocyclic group having at least one hetero atom other than N include thiazole, oxazole, thiophene, furan, pyrrole, thiadiazole, oxadiazole, thiatriazole,
Oxatriazole is mentioned, and Q is preferably a thiadiazole ring, a pyridine ring or a quinoline ring.

Specific examples of the compounds represented by the general formulas 1, 2 and 3 are shown below, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The compounds represented by formulas 1 to 3 are described, for example, in JP-A-54-165, JP-A-6-340611, JP-A-7-27881, JP-A-7-5621, and JP-B-7-119.
No. 953, U.S. Pat.
No. 14, 5460938, 5464737, and European Patent Nos. 605981 and 631176.

Hereinafter, specific examples of the synthesis of the compounds represented by formulas 1 to 3 will be described. (Synthesis Example 1) Synthesis of Exemplified Compound 1-1 2,4,6-tris-carboxymethylthio-1,3,2
Synthesis of 4-triazine 2,4,6-trimercapto-
23.0 g (0.13 mol) of 1,3,4-triazine,
While stirring 54.0 g (0.44 mol) of chloroacetic acid and 300 ml of ethanol at room temperature, an aqueous solution of 17.66 g (0.44 mol) of sodium hydroxide / 30 ml of water was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and further 17.6 g (0.44 mol) of sodium hydroxide / water 3
0 ml of the aqueous solution was slowly added dropwise. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture. The obtained crystals were collected by filtration and recrystallized with methanol to give 2,4,6-
35.4 g (0.10 mol) of tris-carboxymethylthio-1,3,4-triazine was obtained. 76% yield

Synthesis of 2,4,6-tris-tribromosulfonyl-triazine (Exemplified Compound 1-1) 49.1 g (1.23 mol) of sodium hydroxide / 1 liter of water was stirred at 0 to 5 ° C. Where bromine 31.
One milliliter was slowly dropped. Further, the 2,4,6-tris-carboxymethylthio-
8.2 g (0.023 mol) of 1,3,4-triazine,
An aqueous solution of 7.2 g (0.0857 mol) of sodium hydrogen carbonate and 150 ml of water was slowly added dropwise so that the internal temperature did not exceed 10 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized from ethanol to give Exemplified Compound 1 as a white solid.
-1 (11.3 g, 0.011 mol) was obtained. 48% yield

(Synthesis Example 2) Synthesis of Exemplified Compound 2-7 Synthesis of 2-carboxymethylthiofuran 20.0 g (0.20 mol) of 2-mercaptofuran, 27.0 g (0.22 mol) of chloroacetic acid and ethanol 3
While stirring 00 ml at room temperature, an aqueous solution of 8.8 g (0.22 mol) of sodium hydroxide / 15 ml of water was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and an aqueous solution of 8.8 g (0.22 mol) of sodium hydroxide / 15 ml of water was slowly added dropwise. After stirring at 50 ° C. for 3 hours,
After cooling to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize it.

The obtained crystals were collected by filtration and recrystallized from methanol to obtain 23.5 g (0.148 mol) of 2-carboxymethylthiofuran. 74% yield

Synthesis of 2-tribromomethylsulfonylfuran (Exemplified Compound 2-7) 49.1 g (1.23 mol) of sodium hydroxide / 1 liter of water was stirred at 0-5 ° C. .
One milliliter was slowly dropped. Further, 11.2 g of 2-carboxymethylthiofuran obtained by the above reaction was obtained.
(0.0706 mol), 7.2 g of sodium hydrogen carbonate
(0.0857 mol) and 150 ml of water were slowly added dropwise so that the internal temperature did not exceed 10 ° C.
After completion of the dropwise addition, the temperature was raised to room temperature and left overnight.

The precipitated solid was collected by filtration, washed with water, and then recrystallized from ethanol to give Exemplified Compound 2 as a white solid.
As a result, 11.5 g (0.0312 mol) of -7 was obtained. Yield 44
%

(Synthesis Example 3) Synthesis of Exemplified Compound 3-1 2-carboxymethylthio-5-methyl-1,3,4-
Synthesis of thiadiazole 2-mercapto-5-methyl-
While stirring 26.4 g (0.20 mol) of 1,3,4-thiadiazole, 27.0 g (0.22 mol) of chloroacetic acid and 300 ml of ethanol at room temperature, 8.8 g of sodium hydroxide (0. (22 mol) / water (15 ml) was added dropwise. After stirring for 20 minutes, the mixture was heated to 50 ° C., and further 8.8 g (0.22 mol) of sodium hydroxide / water 15
ml of the aqueous solution was slowly added dropwise. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, water was added until the reaction solution became homogeneous, and hydrochloric acid was further added to neutralize the mixture.

The obtained crystals were collected by filtration and recrystallized from methanol to give 28.7 g of 2-carboxymethylthio-5-methyl-1,3,4-thiadiazole (0.2 g).
150 mol). 75% yield

Synthesis of 2-tribromomethylsulfo-5-methyl-1,3,4-thiadiazole (Exemplified Compound 3-1) 49.1 g (1.23 mol) of sodium hydroxide in 1 liter of water While stirring at 30 ° C .;
One milliliter was slowly dropped. Furthermore, 2-carboxymethylthio-5-methyl-1, obtained by the above reaction,
An aqueous solution of 13.5 g (0.0706 mol) of 3,4-thiadiazole, 7.2 g (0.0857 mol) of sodium bicarbonate and 150 ml of water was slowly added dropwise so that the internal temperature did not exceed 5 ° C. After completion of the dropwise addition, the temperature was raised to room temperature and left overnight.

The precipitated solid was collected by filtration, washed with water, and then recrystallized from ethanol to give Exemplified Compound 3 as a white solid.
-1 (13.2 g, 0.0332 mol) was obtained. Yield 47
%

The compounds of the present invention represented by the general formulas 1 to 3
The amount of addition is not particularly limited,^-Four Mol to 1 mol / A
g mole is preferred, especially 10^-3Mol to 0.3 mol / Ag
Molar is preferred. The compounds represented by the general formulas 1 to 3
Both the light-sensitive layer and the non-photosensitive layer can be added. Preferred
Is a photosensitive layer. The compounds represented by the general formulas 1 to 3 are
It is preferable to add it after dissolving it in an organic solvent.

The compound having at least one tribromomethyl group used in the present invention is represented by the general formula 1
In addition to the compounds shown in

[0077]

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Next, the leuco compounds represented by the general formulas 4 to 7 will be described.

In the general formulas 4 to 7, the alkyl group represented by R ₁ and R ₂ preferably includes a methyl group, an ethyl group, a propyl group, a butyl group and the like. These may be further substituted, and preferred substituents include a hydroxy group and a sulfonamide group.

The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.

As the monovalent substituent represented by R ₃ , an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group,
Hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group ( For example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc., alkoxyl group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), Cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonyl) Amino group,
Benzenesulfonylamino group, etc.), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group,
1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfa Moyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, Phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, imide group (eg, phthalimiyl group) Group), a Hajime Tamaki (e.g.,
Pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.).

The acyl group represented by R ₄ preferably includes an acetyl group, a trifluoroacetyl group, a benzoyl group and the like. Preferred examples of the sulfonyl group include a methanesulfonyl group and a benzenesulfonyl group. Preferred examples of the carbamoyl group include a diethylcarbamoyl group and a phenylcarbamoyl group. Preferred examples of the sulfamoyl group include a diethylsulfamoyl group. The alkoxycarbonyl group preferably includes a methoxycarbonyloxy group and an ethoxycarbonyloxy group. The aryloxycarbonyl group preferably includes a phenoxycarbonyloxy group and the like.

Examples of the alkali metal represented by Z include sodium, potassium and the like. Examples of the quaternary ammonium include ammonium having a total carbon number of 8 or more, such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium.

Examples of the 5- or 6-membered aromatic hetero ring composed of X, Z ₁ , Z ₂ and carbon atoms adjacent thereto include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring,
Triazine ring, tetrazine ring, pyrrole ring, furan ring,
Examples thereof include a thiophene ring, a thiazole ring, an oxazole ring, an imidazole ring, a thiadiazole ring, and an oxadiazole ring, and a pyridine ring is preferable.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include the same groups as the monovalent substituent described above for R ₃ , preferably an alkyl group, It is an acylamino group.

Examples of the 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ with each other include an aromatic carbon ring and a heterocyclic ring, preferably a benzene ring. it can.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include methyl, ethyl, propyl, and butyl groups, examples of the aryl group include phenyl and naphthyl groups, and examples of the heterocyclic group include O, 5- to 6-membered aromatic heterocyclic ring having at least one of S and N atoms in the ring (for example, a 6-membered ring azine such as a pyridine, pyrazine, pyrimidine ring and the like, and its benzerog: pyrrole, thiophene, furan and its benzerog) : 5-membered ring azoles such as imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole, oxadiazole and the like, and benzerogue, etc.). R
Preferable examples of ₁₀ and R ₁₁ include a phenyl group, a pyrazolyl group, and a pyridyl group.

[0088] As the alkyl group represented by _{R 16} include a methyl group, an isopropyl group, a pentyl group, t- butyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the sulfonyl group include a methine sulfonyl group and a benzenesulfonyl group.
Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group. Examples of the carbamoyl group include a diethylaminocarbamoyl group.

As the nitrogen-containing heterocyclic ring represented by Y1,
Each ring such as imidazole, triazole, tetrazole and the like and a benzo-fused ring thereof can be exemplified.

The alkyl group represented by R ₁₉ and R ₂₀ includes a methyl group, a pentyl group, a t-butyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group.

The substituents represented by R ₂₅ , R ₂₇ and R ₂₈ include a phenyl group, a methyl group, a benzoyl group,
Phenoxy group, ethoxy group and the like.

Examples of the aliphatic group represented by R include a hexyl group and a dodecyl group. As the aromatic group, p
-Toluene, dodecylbenzene and the like.

The compounds represented by formulas 4 to 7 will be specifically described below, but are not limited thereto.

[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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Synthesis Example 1 (Synthesis of Exemplified Compound 8) Reaction Route

[0107]

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(1) 3.9 g was dissolved in 50 ml of ethyl acetate, and 0.5 g of 5% Pd / C was added, followed by hydrogenation at normal pressure. The blue color of the reaction solution disappeared, and (2) was formed.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 1.5 g of acetyl chloride were added, and the mixture was stirred at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 3.8 g of the desired Exemplified Compound 8 (yield: 89).
%)Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 9) Reaction Route

[0112]

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3.9 g of Synthesis Example 1 (1) was added to ethyl acetate 5
The mixture was dissolved in 0 ml, and 0.5 g of 5% Pd / C was added thereto to carry out normal-pressure catalytic hydrogenation. The blue color of the reaction solution disappeared and (2)
Generated.

Next, 1.2 g of triethylamine was added to the reaction solution.
And 4.0 g of trifluoroacetic anhydride were added, followed by stirring at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 4.0 g of the desired Exemplified Compound 9 (yield 8
5%).

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 3 (Synthesis of Exemplified Compound 58) Reaction Route

[0117]

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Exemplified Compound 8 was added to 30 ml of methanol.
5 g was dissolved, and p-toluenesulfonic acid monohydrate 2.6
g and stirred.

Next, the reaction solution was poured into 300 ml of water, and collected by filtration to obtain 4.1 g (yield: 87%) of the desired Exemplified Compound 58.
Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Other compounds could be easily synthesized in the same manner as in the above synthesis examples.

The amount of the compound represented by formulas (4) to (7) in the present invention may be 1 mol of silver in a medical light-sensitive material.
It is preferable to contain 1 × 10 ⁻⁶ mol or more and less than 5 × 10 ⁻¹ mol for the effect of the present invention. Below this, the effect of improving the silver tone is small, and above this, the entire image is felt dark, which is preferable. Absent. More preferably, silver 1
In the case where it is contained in an amount of 5 × 10 ⁻⁵ mol or more and less than 5 × 10 ⁻² mol per mol, in particular, the case where it is contained in an amount of 5 × 10 ⁻⁴ mol or more and less than 1 × 10 ⁻² mol per mol of silver is preferable in terms of achieving the effect.

In the present invention, any of the compounds represented by the general formulas 4 to 7 may be added according to the properties of the respective compounds. For example, a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and adding after dispersing, and a water miscible organic solvent (for example, methanol,
(Ethanol, acetone, etc.). As a preferable method, a method of adding as a solid fine particle dispersion or a method of dissolving in a water-miscible organic solvent (for example, methanol, ethanol, acetone or the like) and adding the same is used. When added as a solid fine particle dispersion, a known dispersion method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied. Although it can be taken, it is preferably 0.01 to 20 μm, more preferably 0.03 to 2 μm.

The molar ratio of the compound represented by the general formulas 6 and 7 to RSO ₃ H is 1 to ₃ mol of RSO ₃ H per 1 mol of the compound represented by the general formulas (6) and (7). Is preferred.

The compounds represented by formulas (4) to (7) of the present invention can be contained in any of the layers constituting the photographic element, but are preferably contained in the photosensitive layer or a layer adjacent to the photosensitive layer. It is particularly preferable that the compound is contained in the photosensitive layer.

In the present invention, the silver halide grains of the photosensitive silver halide function as an optical sensor.
In order to suppress white turbidity after image formation and obtain good image quality, it is preferable that the average particle size is small, and the preferable average particle size is 0.20 μm or less, more preferably 0.03 μm to 0.15 μm. , Especially 0.03
μm to 0.11 μm is preferred. Here, the average grain size refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is based on the adsorption dependence of the [111] plane and the [100] plane in the adsorption of the sensitizing dye.
It can be determined by T. Tani, J. Imaging Sci., 29, 165 (1985).

The average particle diameter of the monodisperse particles is 0.1 μm.
The following is preferable, and more preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm.

Another preferred form of silver halide grains is tabular grains. Here, the tabular grains are:
The aspect ratio (= r / h) is 3 or more when the square root of the projected area of the particle is r μm and the thickness in the vertical direction is h μm. Among them, those having an aspect ratio of 3 or more and 50 or less are preferable.

The average particle diameter of the tabular grains is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm.
μm is more preferred. These are disclosed in U.S. Pat.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained. In the present invention, when these tabular grains are used, the sharpness of an image is further improved.

The composition of silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is Chimie et Physique Photographiq by P. Glafkides.
ue (Paul Montel, 1967), Photograph by GFDuffin
ic Emulsion Chemistry (The Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be prepared by the method described in Emulsion (The Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used. In order to form a solution by reacting a soluble silver salt and a soluble halide, a one-side mixing method, a simultaneous mixing method, a combination thereof and the like are used. Either may be used.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source.

The silver halide may be prepared by converting part or all of the silver in the organic silver salt to silver halide by the reaction of the organic silver salt with a halogen ion.
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

In general, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains ions or complex ions of metals belonging to VIB, VIIB, VIII and IB belonging to transition metals of the periodic table. Examples of the above-mentioned metals include Cr, W (the above-mentioned VIB group): R
e (Group VIIB): Fe, Co, Ni, Ru, Rh, Pd, O
s, Ir, Pt (more than VIII group): Cu, Au (more than IB group) are preferable, and when used for a photosensitive material for printing plate making, it is preferably selected from Rh, Re, Ru, Ir, and Os.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from Group VIB, VIIB, VIII and IB of the Periodic Table of the Elements, L is a bridging ligand, m is 0,-
Represents 1, -2 or -3.

Specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and alcohols. Each ligand of
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), and osmium (Os).

The following are specific examples of the transition metal coordination complex.

[0142] ^{_{1: [RhCl 6] 3- 2}} : [RuCl 6] 3- 3: [ReCl 6] 3- 4: [RuBr 6] 3- 5: [OsCl 6] 3- 6: [CrCl 6] 4 ^{- 7: [Ru (NO)} Cl 5] 2- 8: [RuBr 4 (H 2 O)] 2- 9: [Ru (NO) (H 2 O) Cl 4] - 10: [RhCl 5 (H 2 ^{O)] 2- 11: [Re} (NO) Cl 5] 2- 12: [Re (NO) CN 5] 2- 13: [Re (NO) ClCN 4] 2- 14: [Rh (NO) 2 Cl ^{_{4] - 15: [Rh (}} NO) (H 2 O) Cl 4] - 16: [Ru (NO) CN 5] 2- 17: [Fe (CN) 6] 3- 18: [Rh (NS) Cl ^{_{5] 2- 19: [Os (}} NO) Cl 5] 2- 20: [Cr (NO) Cl 5] 2- 21: [Re (NO) Cl 5] - 22: [Os (NS) Cl 4 (TeCN ^{)] 2- 23: [Ru (} NS) Cl 5] 2- 24: [Re (NS) Cl 4 (SeCN)] 2- 25: [Os (NS) Cl (SCN) 4] 2- 26: [Ir (NO) Cl ₅ ] ^2-

One of these metal ions or complex ions may be used, or two or more of the same metal and different metals may be used in combination.

The content of these metal ions or complex ions is generally 1 mol per mol of silver halide.
^X10-9 to ^1x10-2 mol is appropriate, and preferably ^1x10-8 to ^1x10-4 mol.

The compounds providing these metal ions or complex ions are preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening,
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation and placed, or a silver salt solution and a halide solution are used. When mixed simultaneously, a third aqueous solution is added to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The organic silver salt used in the present invention is a reducible silver source, and a silver salt of an organic acid and a hetero organic acid containing a reducible silver ion source, particularly a long chain (having preferably 10 to 30 carbon atoms). , An aliphatic carboxylic acid having 15 to 25 carbon atoms, and a nitrogen-containing heterocyclic ring are more preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Discl
Osure 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Salts of oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (eg, 1- (3-carboxypropyl) thiourea,
1- (3-carboxypropyl) -3,3-dimethylthiourea); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.); Hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,
5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene, and 3
-Carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,
Complexes or salts of silver and nitrogen acids selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides. The preferred silver source is silver behenate.

The addition amount of the organic silver salt was 4 g / m
^The content is preferably ² or less, more preferably 2 g / m ² or less.

The organic silver salt can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver. The organic silver salt is described in Japanese Patent Application Laid-Open No. 9-127643, forward mixing method, reverse mixing method, simultaneous mixing method. The controlled double jet method is preferably used.

In the present invention, the organic silver salt preferably has an average particle size of 1 μm or less and is monodispersed. The average particle size of the organic silver salt means that the particles of the organic silver salt are, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of the organic silver salt grains. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm.
m to 0.5 μm is preferred. The term “monodisperse” has the same meaning as in the case of silver halide grains, and the preferred monodispersity is 1%.
３０30%. In the present invention, the organic silver salt is more preferably monodisperse particles having an average particle size of 1 μm or less,
By setting it in this range, an image with high density can be obtained.

In the present invention, in order to obtain a predetermined optical transmission density, the total amount of silver halide and organic silver salt is preferably from 0.3 g to 1.5 g per m ² in terms of silver. preferable. By setting it in this range, a high-contrast image can be obtained.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research Disclosure
Nos. 17029 and 29996, and include the following.

Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (eg, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

The hindered phenols include compounds represented by the following general formula (A).

[0156]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group _(e.g., -C ₄ H _9, 2,4,4-
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, t-
Butyl).

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

[0159]

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[0160]

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The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mole of silver.
10 ⁻² to 10 mol, particularly preferably 1 × 10 ⁻² to
1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer 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 (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly ( Ester), poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). These may be hydrophilic or non-hydrophilic.

[0163] In the present invention, the binder of the photosensitive layer is preferably 1.5~6g / ^{m 2,} more preferably from 1.7~5g / ^{m 2.} 1.5g / m
^If it is less than ² , the density of the unexposed portion is significantly increased, and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to improve the dimensional repetition accuracy of the present invention, a polymer matting agent or an inorganic matting agent is added to all binders on the emulsion layer side. , 0.5 to 10 by weight
%. The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, Swiss Patent No. 330,1
No. 58, etc., French Patent No. 1,296,99
Glass powder described in No. 5, etc., British Patent No. 1,173,18
Alkaline earth metals or carbonates such as cadmium and zinc described in No. 1 and the like can be used as a matting agent.
Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol as described,
Polystyrene or polymethacrylate described in Swiss Patent No. 330,158 and the like, US Pat. No. 3,079,
Organic matting agents such as polyacrylonitrile described in US Pat. No. 257 and the like and polycarbonate described in US Pat. No. 3,022,169 and the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably used in order to achieve the object of the present invention. Is a constituent layer other than the photosensitive layer, and is more preferably the outermost layer as viewed from the support.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

In the present invention, when the photothermographic material is a photothermographic material for output of a printing imagesetter having an oscillation wavelength of 600 to 800 nm, the hydrazine compound may be contained in the photothermographic material. .

The preferred hydrazine compound is a compound represented by the following general formula [H].

[0172]

Embedded image Wherein A ₀ is an aliphatic group which may have a substituent,
Aromatic group, a -G ₀ -D ₀ group or heterocyclic group, B ₀ represents a blocking group, A _1, A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl Represents a group. G ₀ is a -CO- group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )-
Group, -SO- group, -SO ₂ - group or _{-P (O) (G 1 D} 1) - represents a group, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁ )-represents a group, D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, D ₀
Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly 1 to 2 carbon atoms.
A linear, branched or cyclic alkyl group of 0 is preferable, and examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group, and these are further suitable substituents (for example, an aryl group, Alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamido, sulfamoyl, acylamino, ureido, etc.).

In the formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atoms in a single ring or a condensed ring, such as a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, A quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring;
Particularly preferred as ₀ are an aryl group and a heterocyclic group, and the aromatic group and the heterocyclic group represented by A ₀ may have a substituent.
And specific examples thereof include a sulfonamide group, a hydroxyl group and a mercapto group.

In the general formula [H], -G _0- represented by A ₀
The D ₀ group will be described.

G ₀ represents -CO-, -COCO-, -CS-, -C (= NG
₁ D ₁ ) -group, -SO- group, -SO ₂ -group or -P (O) (G ₁ D ₁ ) -group, and preferable G ₀ is -CO- group, -COCO- group, Particularly preferably-
COCO- groups. G ₁ represents a mere bond, -O- group, -S- group or -N (D ₁ )-group, D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and When a plurality of D ₁ are present, they may be the same or different.

D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Preferred D ₀ is a hydrogen atom, an alkyl group, Alkoxy group, amino group,
And an aryl group.

In the general formula [H], A ₀ preferably contains at least one of a diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, a photographically inactive alkyl group having 8 or more carbon atoms, alkenyl group, alkynyl group, alkoxy group Group, phenyl group, phenoxy group, alkylphenoxy group and the like.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

[0179] In formula (H), B ₀ represents a blocking group, preferably a -G ₀ -D _0, -G in A _{0 0} -D ₀
Has the same meaning as the group, and A ₀ and B ₀ may be the same or different.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg, acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, toluenesulfonyl group, etc.) ) Or an oxalyl group (such as an ethoxalyl group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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As the hydrazine compound used in the present invention, the following compounds can be used in addition to the above.

RESEARCHDISCLOSURE Item 23516 (11/1983
, P. 346) and the references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,269,929,
4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4,560,638, and 4 No. 4,686,167, 4,912,016, 4,988,604, 4,994,365, 5,041,355, 5,104,769, British Patent No. 2 , 011,391B, EP 217,3
No. 10, No. 301,799, No. 356,898, JP-A-60-179834, JP-A-61-170733,
Nos. 61-270744, 62-178246, 62-270948, 63-29751, 63
No. 32538, No. 63-104047, No. 63-1
Nos. 21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
No. 245, No. 63-234246, No. 63-2945
No. 52, No. 63-306438, No. 64-10233
No., JP-A-1-90439, JP-A-1-100530,
No. 1-1055941, No. 1-105943, No. 1-
No. 276128, No. 1-280747, No. 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962
No. 35, No. 2-198440, No. 2-198441
No. 2-198442, No. 2-220042, No. 2-221953, No. 2-221954, No. 2-2
No. 85342, No. 2-285343, No. 2-2898
No. 43, No. 2-302750, No. 2-304550
No. 3-37642, 3-54549, 3-
No. 125134, No. 3-184039, No. 3-240
No. 036, No. 3-240037, No. 3-259240
No. 3-2820038, No. 3-282536, No. 4-51143, No. 4-56842, No. 4-841
No. 34, No. 2-230233, No. 4-96053,
4-216544, 5-45761, 5-4
No. 5762, No. 5-45763, No. 5-45764
No. 5-45765, No. 6-289524, No. 9
-160164 and the like.

Other than these, 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 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 formula (6), specifically, compounds 4-1 to 4-
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.
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
Compounds represented by Chemical Formula 1 described in No. 13951, specifically, compounds described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in No. 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.
Compounds represented by I), specifically, pages 10 to 2 of the publication
Compounds II-1 to II-102 described on page 7. JP 7
Compounds represented by general formula (H) and general formula (Ha) described in JP-A-104426, specifically, from page 8 to
Compounds described in Compounds H-1 to H-44 on page 15 can be used.

The added layer of the hydrazine compound (derivative)
It is a photosensitive layer and / or a constituent layer adjacent to the photosensitive layer.
The addition amount is the particle size of the silver halide grains, the halogen composition,
The optimum amount is not uniform depending on the degree of chemical sensitization, the type of reducing agent, the type of inhibitor, etc.
0 ^-6 mol ^{to 10 -1} moles, especially ^{10 -5} mol to 1
0 ^-2 mols is preferred.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to high temperature after exposure. The heating temperature is preferably from 80 ° C to 250 ° C, more preferably from 100 ° C to 200 ° C. If the heating temperature is 80 ° C. or less, a sufficient image density cannot be obtained in a short time, and if the heating temperature is 250 ° C. or more, the binder is melted, which adversely affects the image itself and transferability such as transfer to a roller, which is not preferable. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support, and only the photosensitive layer may be formed on the support. It is preferable to form at least one non-photosensitive layer. A filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. . As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred.
The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

It is preferable to add a color tone agent to the photothermographic material of the present invention. An example of a suitable toning agent is Research D
Isclosure No. 17029, which includes:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2 , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaching combinations (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used. Useful sensitizing dyes for use in the present invention are, for example, RESEARCH DISCLOSURE Item 17643
Item IV-A (p.23 of December 1978), Item 1831X (August 1978
p.437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
162247, JP-A-2-48653, U.S. Pat. No. 2,161,331, West German Patent 936,071 and Japanese Patent Application No. 3-189532, B) Helium-neon laser light source Are described in JP-A-50-62425, JP-A-54-18726, and
Trinuclear cyanine dyes described in JP-A-9-102229, merocyanines described in Japanese Patent Application No. 6-103272,
C) For LED light source and red semiconductor laser, JP-B-48-42172, JP-B-51-9609, and JP-B-55-59
Japanese Patent Application Laid-Open No. 62-284343 and Japanese Patent Application Laid-Open No.
Thiacarbocyanines described in No.-105135,
D) Japanese Unexamined Patent Application Publication No.
No. 91032, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242,
General formula (IIIa) and general formula (IIIb) of JP-A-3-67242
The dicarbocyanines containing a 4-quinoline nucleus described in (1) are advantageously selected. Further, the wavelength of the infrared laser light source is 750 nm or more, more preferably 800 nm.
In order to cope with a laser in such a wavelength range in the above case, Japanese Patent Application Laid-Open Nos. 4-182639 and 5-341.
432, Tokiko 6-52387, 3-10931, U
S5, 441, 866 and sensitizing dyes described in JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Exposure of the photothermographic material of the present invention is performed by using an Ar laser (488 nm) and a He-Ne laser (633n).
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 820 nm) and the like are preferably used. In terms of high laser power and transparency of a photosensitive material, an infrared semiconductor laser is preferably used. Lasers are more preferably used.

[0198]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 [Preparation of Subbed Photographic Support] <Preparation of PET Subbed Photographic Support> A commercially available biaxially stretched and heat-fixed PET film having a thickness of 100 μm and 8 w / m on both sides. Apply a corona discharge treatment for ² minutes, apply the following undercoating coating solution a-1 on one surface so as to have a dry film thickness of 0.8 μm, and dry to form an undercoating layer A-1. Was coated with the following undercoating coating solution b-1 so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

<< Undercoat Coating Solution b-1 >> Copolymer latex liquid of butyl acrylate (40% by weight) styrene (20% by weight) glycidyl acrylate (40% by weight) (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Make up to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 w / m ² · min is applied to the upper surface of the lower layer, and the lower layer upper layer coating solution a-2 described below is coated on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. Sublayer B as Layer A-2
-1 is coated with the following undercoating layer coating solution b-2 having a dry film thickness of 0.
Coating was performed as a subbing upper layer B-2 having an antistatic function so as to have a thickness of 8 μm.

<< Undercoating upper layer coating solution a-2 >> Gelatin 0.4 g / m^Two (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles (average particle size 3 μm) 0.1 g Finished to 1 liter with water.

<< Lower Coating Upper Layer Coating Solution b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol ( (Weight average molecular weight: 600) 6 g Finished to 1 liter with water.

[0205]

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[0206]

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(Preparation of Emulsion A) In 900 ml of water, 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved and adjusted to a temperature of 35 ° C. and a pH of 3.0.
g of the aqueous solution containing potassium bromide and potassium iodide at a molar ratio of (98/2) and rhodium chloride in an amount of 1 × 10 −4 mol per mol of silver and pAg of 7.7.
, And added over 10 minutes by a controlled double jet method. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the average particle size was 0.0.
Cubic silver iodobromide grains having a size of 6 μm, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then 0.1 g of phenoxyethanol was added to the emulsion to give a pH of 5.9 and a pAg of 7.5.
To obtain a silver halide emulsion. JP-A-9-12
No. 7643 According to the method of Example 1, silver behenate was prepared in the following manner.

Preparation of Na Behenate Solution 34 g of behenic acid was added to 340 ml of isopropanol for 65 days.
Dissolved at ° C. Next, while stirring, a 0.25N aqueous sodium hydroxide solution was added so as to have a pH of 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required.
Next, the aqueous sodium behenate solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

Preparation of Silver Behenate A 2.94M silver nitrate solution was added to a solution of 30 g of ossein gelatin in 750 ml of distilled water, and the silver potential was adjusted to 4%.
00 mV. To this, 374 ml of the above sodium behenate solution was added at a speed of 44.6 ml / min at a temperature of 78 ° C. by using a controlled double jet method, and simultaneously a 2.94 M silver nitrate aqueous solution was supplied with a silver potential of 400 mV.
It was added so that it became. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.
Mole. After the addition was completed, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration.

Preparation of Photosensitive Emulsion To this silver behenate dispersion, 0.01 mol of each of the above silver halide emulsions was added, and 100 g of a solution of polyvinyl acetate in n-butyl acetate (1.2 wt%) was gradually added with stirring. To form a floc of the dispersion, remove the water,
After two further water washes and removal of water, polyvinyl butyral (average molecular weight 3000) was used as a binder.
5wt% butyl acetate and isopropyl alcohol 1:
(2) After adding 60 g of the mixed solution with stirring, polyvinyl butyral (average molecular weight of 40) was added as a binder to the gel-like mixture of behenic acid and silver halide thus obtained.
00) and isopropyl alcohol.

[0211] The following layers were sequentially formed on a support to prepare samples. In addition, each drying was performed at 75 ° C. for 5 minutes.

Coating on back side: A liquid having the following composition was applied to a wet thickness of 80 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0214]

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Photosensitive layer surface side coating Photosensitive layer: A solution having the following composition was applied.
m ² , polyvinyl butyral as a binder.
It was applied so as to be ² g / m ² .

Emulsion A Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% DMF solution) 2 mg Compounds of general formulas 1-3, comparative compound (2% acetone solution) Table 1 General formula 4 Compounds 1 to 7 (1% methanol solution) Table 1 Phthalazone (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 13 ml Hardener H (1% methanol / DMF = 4: 1 solution) 2 ml

[0219]

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[0218]

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Surface protective layer: A liquid having the following composition was wetted to a thickness of 1
It was applied on each photosensitive layer so as to have a thickness of 00 μm.

Acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5 g monodisperse having an average particle size of 4 μm 1% (W / W) based on silica binder

[Evaluation of Sensitometry] The coated sample was cut into 3.5 cm × 15 cm and exposed with a laser sensitometer equipped with an 820 nm diode, and then the photographic material was processed at 120 ° C. for 15 seconds (development). The obtained image was evaluated using a densitometer. The result of the measurement is Dmi
n, and sensitivity (reciprocal of the ratio of the exposure amount giving a density higher than Dmin by 1.0). Table 2 shows relative sensitivities with the sensitivity of 1 being 100. Table 2 shows the results.

<Evaluation of Image Preservation> Two samples treated in the same manner as in the sensitometry evaluation were subjected to the test at 25 ° C. and 55 ° C.
% At 7% at 25 ° C and 55% for 7 days.
After exposure to natural light for one day, the density of both fog portions was measured. Table 2 shows the results. (Fog increase 2) = (Fog when exposed to natural light)
-(Fog when stored in shade)

<Evaluation of Silver Tone> Each of the coated samples was subjected to the same processing as in the sensitometry, and the obtained developed samples were visually evaluated in the following five stages. . Table 2 shows the results.

5: No yellowness at all, cool black tone 4: Slightly yellowish, but barely noticeable 3: Yellowish, but practically acceptable 2: Strong yellowishness, which is problematic for practical use 1: Extremely strong yellowishness, not suitable for practical use

[0225]

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[0226]

[Table 1]

[0227]

[Table 2]

From Table 2, it can be seen that the sample of the present invention has sufficient sensitivity, low fog, and good image storability and silver tone of the photographic material.

[0229]

According to the present invention, it is possible to provide a photothermographic material having a developed image in which the fog does not rise over time and the silver image has a good color tone.

Claims (5)

[Claims] 1. A support comprising at least one of an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, a binder and a compound having at least one tribromomethyl group in a molecule. And a photothermographic material comprising a leuco compound which reacts with an oxidized form of the reducing agent to form a blue dye. 2. The compound having a tribromomethyl group,
2. The photothermographic material according to claim 1, wherein the photothermographic material is at least one compound represented by the following general formulas 1 to 3. Embedded image [Wherein X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group. m represents an integer of 3 or more and 4 or less. Q represents a heterocyclic group, an aryl group or an aliphatic group.
n represents an integer of 0 or more and 3 or less. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10. ] [Wherein X ₁ and X ₂ represent a halogen atom. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group.
Q represents an aromatic hetero 5-membered ring, a furan ring, a thiophene ring or a pyrrole ring having one oxygen atom and two or more and three or less nitrogen atoms. However, when Q is a thiophene ring, X ₁ represents a bromine atom. ] [Wherein X ₁ and X ₂ represent a halogen atom. A represents a hydrogen atom, a halogen atom or another electron-withdrawing group.
Y is -SO -, - CO -, - N (R 11) -SO 2 -, - N (R 11) -CO -, - N (R 11) -COO
-, - COCO -, - COO -, - OCO -, - OCOO -, - SCO -, - SCOO -, - C (Z 1)
(Z ₂ ) — represents an alkylene, an arylene, a divalent heterocyclic ring, or a divalent linking group formed by any combination thereof. R
₁₁ represents a hydrogen atom or an alkyl group. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group. Z ₁ and Z ₂ are not hydrogen atoms at the same time. Q represents an aliphatic group, an aromatic group or a heterocyclic group. However, when Y is -SO-, Q
Represents an aromatic 5-membered heterocyclic group having at least one heteroatom other than N and a pyridine ring group. ] 3. The photothermographic material according to claim 1, wherein said leuco compound is at least one of the compounds represented by formulas 4 to 7. Embedded image [Wherein, W represents -NR ₁ R ₂ , -OH or -OZ, R ₁ and R ₂ each represent an alkyl group or an aryl group,
Represents an alkali metal ion or a quaternary ammonium ion. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. Z ₁ and Z ₂
Each nitrogen atom or = C _{(R 3)} - represents a. X is 5 to 5 together with Z ₁ , Z ₂ and carbon atoms adjacent thereto.
It represents an atomic group necessary to form a 6-membered aromatic hetero ring. R ₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.
R represents an aliphatic group or an aromatic group. p represents an integer of 1 to 2. CP1 represents the following groups. [Chemical formula 5] [Wherein, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent that can be substituted on a benzene ring. Also R ₅
And R ₆ and R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meanings as R ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ and m is 1
Represents an integer of 1 to 3. Y1 represents an atomic group necessary for constructing a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. R ₁₉ and R ₂₀ represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and _{R 23} has the same meaning as _{R 19} and _{R 20.} R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent. R ₂₆ is R
Synonymous with ₄ . R ₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ . R ₃₀ is R
Synonymous with ₂₆ . R ₃₄ , R ₃₅ and R ₃₆ are R
₂₅ , R ₂₇ and R ₂₈ . R ₃₃ is R
Synonymous with ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ are R
₂₅ , R ₂₇ and R ₂₈ . R ₃₇ is R
Synonymous with ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ are R
₂₅ , R ₂₇ and R ₂₈ . R ₄₄ is R
Synonymous with ₂₆ . * Represents a bonding point between CP1 and another partial structure in the general formula 4. ] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , CP 1, n, R and p represent R ₁ , R ₂ , R ₃ , R ₄ , CP in the general formula 4]
It is synonymous with 1, n, R and p. ] [Wherein, R ₃ , n, R ₄ , W, X, Z ₁ , Z ₂ , and CP 1 represent R ₃ , n, R ₄ , W, X, Z in the general formula 4]
_1, the same meaning as _{Z 2,} and CP1. Embedded image _{Wherein, R 1, R 2, R} 3, R 4, CP1 and n have the same meanings as _{R 1, R 2, R 3} , R 4, CP1 and n in the general formula 4. ] 4. An image recording method, wherein the photothermographic material according to claim 1 is exposed with an infrared laser. 5. An image forming method, wherein the photothermographic material according to claim 1 is developed by heating at a temperature of 80 ° C. or more and 250 ° C. or less.