JP2000010234A - Heat developable photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photographic material excellent in handleability and preservability before and after image formation and giving an image having high image quality and a cold black tone. SOLUTION: This heat developable photographic material has an org. silver salt, a reducing agent, at least one compd. represented by formula I and at least one compd. represented by formula II on a substrate. In the formula I, R1-R4 are each H or a monovalent substituent but all of R1-R4 are not H, L1 and L2 are each a combining group and n1 and n2 are each an integer of 0-3 but the both of n1 and n2 are not 0. In the formula II, Q is a group of atoms required to form a phthalazine ring, V is a monovalent substituent and n3 is an integer of 0-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable photographic material, and more particularly to a heat-developable photographic light-sensitive material (hereinafter sometimes referred to as a heat-developable light-sensitive material).

[0002]

2. Description of the Related Art A heat-developable photographic material for forming a photographic image by using a heat-development processing method is disclosed, for example, in US Pat.
No. 4,345,075, and "A Thermally Treated Silver System (Thermally Pr.)" By D. Morgan and B. Shely.
ocessed Silver Systems) "(Imaging Processes and
Materials, Neblette 8th edition, Sturge, V. Walworth, A.
Shepp, ed., Page 2, 1969).

[0003] Such heat-developable photographic materials are prepared by dispersing a reducible silver salt (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a reducing agent in a (organic) binder matrix. It is contained in a state. Although the photothermographic material is stable at room temperature, it can be reduced when heated to a high temperature (for example, 80 ° C. or higher) after exposure through a redox reaction between a silver salt (which functions as an oxidizing agent) and a reducing agent. Produces silver. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. Silver produced by the reaction of the organic silver salt in the exposed areas provides a black image,
This is in contrast to the unexposed areas, where the image is formed.

In the above-mentioned heat-developable photographic materials, a material called a "toning agent" is used as necessary in the light-sensitive material for the purpose of improving the image density (image density) of a silver image, the color tone of silver and the heat developability. .

In a heat-developable photographic material utilizing an organic silver salt, a wide range of toning agents are disclosed in JP-A-46-6077 and JP-A-47-10282.
Nos. 49-5019, 49-5020, 49-91215, 49
-91215, 50-5024, 50-32927, 50-67132
No. 50-67641, No. 50-114217, No. 51-3223, No. 5
1-27923, 52-14788, 52-99813, 53-1020
No. 53-76020, No. 54-156524, No. 54-156525,
No. 61-183642, JP-A-4-56848, JP-B-49-10727
No. 54-20333, U.S. Pat.Nos. 3,080,254, 3,44
No. 6,648, No. 3,782,941, No. 4,123,282, No.
4,510,236, UK Patent 1380795, Belgian Patent
No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as: naphthalimides (eg, N-hydroxy-
1,8-naphthalimide); cobalt complex (eg, 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) aryldicarboximides (for example, (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-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or a metal salt, or 4- (1-
Naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-
Derivatives such as dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; Phthalazine; phthalic acid and phthalic acid derivatives such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; quinazolinedione, benzoxazine or naphthoxazine derivatives; Rhodium complexes that function not only as regulators but also as sources of halide ions for silver halide formation in situ, such as hexachlororhodium (III)
Ammonium peroxide, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4 -Benzoxazine-2,4-diones such as dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine and Asymmetric-triazines (e.g., 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (e.g.,
3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-
Tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).

[0006] JP-B 1-225050 describes benzoic acids (eg, homophthalic acid, methyl homophthalate) in which a carboxyl group which may be esterified is substituted at the o-position via a linking group. It describes an effect that, in combination with phthalazinones or phthalazinediones, a heat-developable photographic material coated with an organic solvent has good temporal stability under high temperature and high heat.

These toning agents balance the performance required for the toning agent (improvement of image density, silver tone, heat developability) and the harmful effects (such as volatilization out of the light-sensitive material), and additives used in combination (such as antifoggants). There is a history of exploring and developing suitable and higher-performance materials from the viewpoint of combinations (with no side effects and no adverse effects) with phthalazine, and it is known that the combination of phthalazine and phthalic acid derivatives is excellent among them ing.

Conventionally, most of heat-developable photographic materials are toluene,
The photosensitive layer has been formed by applying a coating solution using an organic solvent such as methyl ethyl ketone or methanol as a solvent. The use of an organic solvent as a solvent may not only adversely affect the human body in the manufacturing process but also be disadvantageous in terms of cost due to recovery of the solvent and the like. Therefore, a method of forming a photosensitive layer (hereinafter, also referred to as “aqueous photosensitive layer”) using a coating solution of a water solvent which does not have such a concern has been considered. For example, Japanese Patent Application No. 9-185724 discloses an example in which a polymer latex soluble or dispersible in an aqueous solvent is used as a binder.
JP-A-116144 discloses an example using gelatin as a binder, and JP-A-50-151138 discloses an example using polyvinyl alcohol as a binder.
No. 747 describes an example in which gelatin and polyvinyl alcohol are used in combination. Another example is disclosed in
No. 28737 describes an example of a photosensitive layer using a water-soluble polyvinyl acetal as a binder.

Certainly, if a photosensitive layer is formed using such a coating solution of a water solvent, the environmental and cost advantages are great. However, when the photosensitive layer is formed with a coating solution using an organic solvent as a solvent, a combination of the above-mentioned color tone agents that gave a preferable silver tone (particularly, a combination of phthalazine and a phthalic acid derivative, a combination of homophthalic acid and phthalazinone) ), The following problems may occur when the photosensitive layer is formed using a coating solution of an aqueous solvent,
The improvement was an issue.

1) When the light-sensitive material after exposure is stored under high-temperature, high-humidity conditions or light irradiation, remarkable fog may occur in a non-image forming portion. 2) When the heat development is performed, the silver color tone becomes brown or reddish, and particularly in the case of heat-developable photographic materials for medical diagnostics and the like that require a clear black-blue silver color tone, there is a case where it cannot withstand being offered as a commercial product. is there.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable photographic material, particularly a heat-developable photographic light-sensitive material, which is excellent in storability before and after image formation and handleability, and gives a high-quality, cool black image. It is to be.

[0012]

This object has been achieved by the following means. (1) A heat characterized by having an organic silver salt, a reducing agent, at least one compound represented by the following general formula (I) and at least one compound represented by the general formula (II) on a support. Developed photographic materials.

[0013]

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[In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent substituent. However, all of R ₁ , R ₂ , R ₃ and R ₄ are not hydrogen atoms. L ₁ and L ₂ each represents a linking group. n ₁ and n ₂ each represent an integer of 0 or more and 30 or less. However,
n ₁ and n ₂ are never both 0. ]

[0015]

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[In the general formula (II), Q represents an atom group necessary for forming a phthalazine ring. V represents a monovalent substituent. n ₃ represents an integer of 0 or more and 6 or less. (2) The photothermographic material according to the above (1), having a photosensitive silver halide. (3) In the compound represented by the general formula (II), n ₃
Is from 1 to 6. The heat-developable photographic material according to the above (1) or (2).

[0017]

Embodiments of the present invention will be described below in detail. The photothermographic material of the present invention is a photothermographic material containing an organic silver salt and a reducing agent, and more preferably a photosensitive silver halide. In such a heat-developable photographic material, by containing the compound represented by the general formula (I) and the compound represented by the general formula (II), excellent photographic performance, good color tone, and before and after image formation are obtained. A heat-developable photographic material having excellent storage stability can be obtained. On the other hand, unless the compound represented by the general formula (I) is contained,
The sensitivity decreases, the color tone deteriorates, and the storage stability after image formation deteriorates. Also, the storage stability before image formation tends to be poor. When a compound such as phthalic acid or homophthalic acid different from the general formula (I) is used instead of the compound represented by the general formula (I), the storage stability before image formation deteriorates.

If a compound such as phthalazinone, which is a known color tone agent, is used instead of the compound represented by the general formula (II), the sensitivity is remarkably lowered.

The compound represented by formula (I) will be described in detail. R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent substituent. Where R ₁ , R ₂ , R ₃
And not all of R ₄ are hydrogen atoms. R ₁ , R ₂ ,
As the monovalent substituent represented by R ₃ and R ₄ , for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms,
For example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms)
2, particularly preferably 2 to 8, for example, propargyl, 3-pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 carbon atoms)
-20, particularly preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 0 carbon atoms).
6, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 1 carbon atoms).
To 8, for example, methoxy, ethoxy, butoxy, benzyloxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 carbon atoms)
To 16, particularly preferably 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 1 carbon atoms).
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 carbon atoms)
-16, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tetradecyloxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms).
0, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetylamino, propionylamino, benzoylamino, etc.), alkoxy A carbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 carbon atoms)
To 12, for example, phenyloxycarbonylamino and the like. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, octanesulfonylamino, benzenesulfonylamino, etc. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl) Moyl, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably having carbon thiol). Number 6 to 20, more preferably carbon number 6 to 16,
Particularly preferably, it has 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as mesyl and tosyl), and a sulfinyl group (preferably It has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like, and a ureido group (preferably 1 to 20 carbon atoms). More preferably, it has 1 to 16 carbon atoms, and particularly preferably, it has 1 to 1 carbon atoms.
12, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, carboxyl, sulfo,
Sulfino group (sulfinic acid group), mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxamic acid group,
And a hydrazino group and a heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino and the like). Further, the substituent capable of forming a salt with an alkali metal or the like may form a salt. These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent represented by R ₁ , R ₂ , R ₃ and R ₄ is preferably an alkyl group, an alkenyl group, an aryl group,
Alkoxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group,
Carbamoyl group, ureido group, phosphoric acid amide group, hydroxy group, carboxyl group, sulfo group, sulfino group, sulfonyl group, halogen atom, cyano group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, Alkoxy group, aryloxy group, acyl group, acylamino group, sulfonylamino group, sulfamoyl group,
A carbamoyl group, a hydroxy group, a sulfonyl group, a halogen atom, and a cyano group, and particularly preferably an alkyl group, an aryl group, an alkoxy group, and a halogen atom.

Particularly preferably, R _{1 to} R ₄ include a hydrogen atom and those described above as particularly preferred substituents.

L ₁ and L ₂ represent a linking group. The linking group represented by L ₁ and L ₂ is preferably a divalent linking group having a length of 1 to 4 atoms, and may further have a substituent. Preferred examples _{-CH 2 -, - CH 2 CH} 2 -, - C = O -, - CON
_{H -, - SO 2 NH -} , - can be exemplified O- a.

N ₁ and n ₂ each represent an integer of 0 or more and 30 or less. However, neither n ₁ nor n ₂ is 0. A preferred combination of L ₁ , L ₂ and n ₁ , n ₂ is that when L ₁ and L ₂ represent a linking group having a length of 1 to 2 atoms, n ₁ and n ₂ may be 0 to 10. Preferably, when L ₁ and L ₂ represent a linking group having a length of 3 to 4 atoms, n ₁ and n ₂ are preferably 0 to 6. . As a combination of L ₁ , L ₂ and n ₁ , n ₂ , L ₁ and L ₂ represent a linking group having a length of 1 to 2 atoms, and n ₁ and n _{2 each} preferably represent 0 to 6. preferable. As a combination of L ₁ , L ₂ and n ₁ , n ₂ , L ₁ and L ₂ are -CH _2- , -CH ₂ CH _2- , -C = O-, -CONH-, -S
It is particularly preferred that n represents O ₂ NH— and n ₁ and n ₂ represent 0 to 3.

The compound represented by the formula (I) may form a salt with an appropriate counter ion. Examples of counterions include inorganic or organic ammonium ions (eg,
Ammonium ion, triethylammonium ion,
Pyridinium ion), alkali metal ion (for example,
Examples include sodium ions, potassium ions), alkaline earth metal ions (eg, calcium ion, barium ion, magnesium ion), and other metal ions (eg, aluminum ion, zinc ion).
As the counter ion, an ionic polymer, another organic compound having a reverse charge, or a metal complex ion (for example, hydroxopentaaquaaluminum (III) ion, tris (2,2′-bipyridine) iron (II) ion)
Is also possible. Further, it may form an inner salt with another substituent in the molecule. Preferred are sodium ion, potassium ion, triethylammonium ion,
Pyridinium ions are more preferred, with sodium ions and potassium ions being more preferred.

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

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The compounds represented by the general formula (I) of the present invention are described, for example, in Tetrahedron, Vol. 31, (20), pp. 2607-19 (197)
5 years), Angewante Chem. 86 (9), page 349 (1974), and the methods described in the references cited therein and the like. Alternatively, a commercially available compound may be used. The amount of the compound represented by the general formula (I) is 1 to 1 mol of Ag.
It is preferably from 0 ^-3 mol to 10 mol, more preferably from 10 ^-2 mol to 1 mol.
Molar is preferred. The compound represented by formula (I) may be used alone or in combination of two or more.

Next, the compound represented by formula (II) will be described in detail. Q represents an atom group necessary for forming a phthalazine ring. As the substituent represented by V, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl , Iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, n-decyl, n-
Hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 carbon atoms)
To 20, more preferably 2 to 12, particularly preferably 2 to
8, for example, propargyl, 3-pentynyl and the like. ), An aryl group (preferably having 6 to 3 carbon atoms)
It has 0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 1 carbon atoms)
0, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino,
Dibenzylamino and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
-12, particularly preferably 1-8 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, acetyl, benzoyl, formyl, pivaloyl and the like can be mentioned. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl).
Aryloxycarbonyl group (preferably having 7 to 2 carbon atoms)
It has 0, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), and an acylamino group (preferably 2-20 carbon atoms, more preferably 2 carbon atoms
-16, particularly preferably 2-10 carbon atoms, such as acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like), aryloxycarbonylamino Group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 12 carbon atoms.
And for example, phenyloxycarbonylamino and the like. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), and sulfamoyl. Group (preferably having 0 to 2 carbon atoms)
It has 0, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoylg. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
Carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Equations 6 to 20,
More preferably, it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 carbon atoms.
To 12, for example, mesyl, tosyl, and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoramide and phenylphosphoramide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, thienyl, piperidyl, morpholino, etc.) And the like.). These substituents may be further substituted, and the substituent capable of forming a salt may form a salt. When V is 2 or more, V may combine with each other to form a ring, and such a ring includes a dioxolene ring and a benzene ring.

V is preferably an alkyl group, an aryl group, or a halogen atom, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group. It is also preferable that n ₃ = 0 is unsubstituted, which is a preferable compound.

N ₃ represents an integer of 0 or more and 6 or less. n ₃ is preferably 0 to 4, more preferably 0 to 2, and particularly preferably 1 to 2. V may be substituted at any position of the compound represented by the general formula (II).
Substitution at the 6, 7, or 8 position is preferred.

In the general formula (II), preferable combinations of Q, V and n ₃ include phthalazine, 6-methylphthalazine, 5-methylphthalazine, 6-isopropylphthalazine, 6-isobutylphthalazine, 6-t- Butylphthalazine, 5,7-dimethylphthalazine and the like can be mentioned.

Hereinafter, specific examples of the compound represented by the general formula (II), including the preferred combinations described above, will be described, but the present invention is not limited to these.

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The compounds represented by the general formula (II) of the present invention include, for example, RGElderField, "Hetrocyclic Compound
s ", John Wiley and Sons, Vol. 1-9, 1950-1967 and ARKa
tritzky, "Comprehensive Heterocyclic Chemistry", Per
It can be synthesized by a known method described in gamon Press, 1984 and the like.

Most of the known synthetic methods basically synthesize the corresponding phthalic acid derivatives (phthalaldehyde, phthalic anhydride, phthalic ester, etc.) and condense these with hydrazine to form a phthalazine skeleton. However, as described in Tetrahedron letter, 22,345 (1981), it can be synthesized from a cyclization reaction of an aryl aldazine derivative.

When V has a nitro group, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a ureido group, a phosphoric amide group, etc., first, a nitro-substituted phthalazine is synthesized. After reducing this compound to convert it to amino-substituted phthalazine, it is reacted with various reactants,
It is common to form the above substituents.

Regarding the nitration of the phthalazine derivative,
The method described in J. Chem. Soc, Perkin Trans. 1, 1993, 211-216 and the like can be used.

When V has a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or the like, first, an alkoxycarbonyl-substituted phthalazine is synthesized, and the ester group is hydrolyzed to be converted into a carboxyl group. Alternatively, the substituent is generally formed by reacting the ester group with various reactants.

The alkoxycarbonyl-substituted phthalazine derivative can be synthesized, for example, by the method described in Heterocycles, 20, 1279 (1983).

When V has a mercapto group, a sulfo group, a sulfino group, a sulfamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, or a sulfinyl group, first, a halogen-substituted phthalazine derivative is synthesized, and the halogen atom is replaced with sodium hydrosulfide or A mercapto group such as an alkyl mercaptan, or an aryl mercaptan,
Alternatively, after substitution with an alkylthio group or an arylthio group, the compound is generally reacted with various reactants to form the above substituent.

When V has a hydroxy group, an alkoxy group, an aryloxy group, or an acyloxy group, first, an alkoxy-substituted phthalazine derivative is synthesized, and the O-alkyl bond is cleaved. It is common to form groups.

The alkoxy-substituted phthalazine derivatives are described, for example, in J. Pharm. Sci., 69, 120 (1980) or J. Org.
31, 1912 (1966).

The compound represented by the general formula (II) of the present invention varies depending on the desired purpose, but is expressed in an amount of 10 ^-4 to 1 mol, preferably 10 ^{-3 to} 0.3 mol, per mol of Ag. , More preferably ^{10-3 to} 0.1 mol. The compounds of the general formula (II) may be used alone or in combination of two or more.

The compounds represented by the general formulas (I) and (II) of the present invention may be added by any method such as a solution, a powder and a dispersion of solid fine particles. Dispersion of solid fine particles can be performed by a known micronizing means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.)
Done in When dispersing the solid fine particles, a dispersing aid may be used.

The compounds represented by the general formulas (I) and (II) of the present invention may be added to a layer on the image forming layer side of a photographic material, for example, a photosensitive layer which can be an image forming layer, and a non-photosensitive layer on this layer side. Can be added.

The organic silver salt that can be used in the present invention is
Relatively stable to light, but forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, in particular silver salts of long-chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor is preferably present in about 5-70 of the imaging layer.
% By weight. 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 aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate,
Silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

The organic silver salt preferably used in the present invention is
Alkali metal salts of organic acids shown above (Na salt, K salt,
It is prepared by reacting silver nitrate with a solution or suspension. The alkali metal salt of an organic acid of the present invention is obtained by treating the above organic acid with an alkali. The silver salt of an organic acid of the present invention can be carried out batchwise or continuously in any suitable vessel. The stirring in the reaction vessel can be performed by any stirring method depending on the required characteristics of the particles. As a method for preparing an organic acid silver salt, a method in which a silver nitrate aqueous solution is gradually or rapidly added to a reaction vessel containing an organic acid alkali metal salt solution or suspension,
A method in which a previously prepared organic acid alkali metal salt solution or suspension is gradually or rapidly added to a reaction vessel containing an aqueous silver nitrate solution, and a previously prepared silver nitrate aqueous solution and an organic acid alkali metal salt solution or suspension are added to the reaction vessel. Any of the methods of simultaneous addition into the inside can be preferably used.

The silver nitrate aqueous solution and the organic acid alkali metal salt solution or suspension may be of any concentration for controlling the particle size of the prepared organic acid silver, and may be added at any addition rate. Can be. The silver nitrate aqueous solution and the organic acid alkali metal salt solution or suspension can be added by a method of adding at a constant addition rate, an accelerated addition method by an arbitrary time function, or a deceleration addition method. Further, it may be added to the surface of the reaction solution or may be added to the reaction solution. In the case of a method in which a previously prepared aqueous silver nitrate solution and an organic acid alkali metal salt solution or suspension are simultaneously added to the reaction vessel, either the silver nitrate aqueous solution or the organic acid alkali metal salt solution or suspension is preceded. Although it can be added, it is preferable to add the silver nitrate aqueous solution in advance. The degree of precedence is preferably 0 to 50 vol% of the total amount added, and 0 to 25 vol%.
vol% is particularly preferred. As described in JP-A-9-127643, a method of adding while controlling the pH or silver potential of the reaction solution during the reaction can also be preferably used.

The pH of the silver nitrate aqueous solution or organic acid alkali metal salt solution or suspension to be added can be adjusted according to the required characteristics of the particles. Any acid or alkali can be added for pH adjustment. Depending on the required characteristics of the particles, for example, the temperature in the reaction vessel can be set arbitrarily for controlling the particle size of the prepared organic acid silver salt. Alternatively, the suspension can also be adjusted to any temperature. The organic acid alkali metal salt solution or suspension is preferably heated and kept at 50 ° C. or higher in order to ensure fluidity of the solution.

The organic acid silver used in the present invention is preferably prepared in the presence of a tertiary alcohol. Preferably, the tertiary alcohol is one having a total carbon number of 15 or less,
Particularly preferred is 10 or less. Preferred examples of the tertiary alcohol include tert-butanol, but the present invention is not limited thereto.

The tertiary alcohol used in the present invention may be added at any timing during the preparation of the organic acid silver salt. However, the tertiary alcohol may be added during the preparation of the organic acid alkali metal salt to dissolve and use the organic acid alkali metal salt. Is preferred. The amount of the tertiary alcohol of the present invention can be arbitrarily used in a weight ratio of 0.01 to 10 with respect to H ₂ O as a solvent at the time of preparing the silver salt of an organic acid. Is preferred.

In the present invention, a silver salt of a compound containing a mercapto group or a thione group and derivatives thereof can also be used. Preferred examples of these compounds include 3-
Silver salt of mercapto-4-phenyl-1,2,4-triazole, 2-
Silver salt of mercaptobenzimidazole, 2-mercapto-5
Silver thioglycolic acid such as silver salt of -aminothiadiazole, silver salt of 2- (ethylglycolamido) benzothiazole, silver salt of S-alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms) Salt, silver salt of dithiocarboxylic acid such as silver salt of dithioacetic acid, silver salt of thioamide, 5-
Silver salt of carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt described in U.S. Pat.No. 4,123,274, for example, 3-amino-5- Silver salts of 1,2,4-mercaptothiazole derivatives such as benzylthio-1,2,4-thiazole silver salt, 3- (3-carboxyethyl) -4-methyl-4- described in U.S. Pat.No. 3,301,678 It includes silver salts of thione compounds such as silver salts of thiazoline-2-thione. Furthermore, compounds containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, and US Pat. No. 4,220,709, such as silver salts of 1,2,4-triazole or 1-H-tetrazole, and silver salts of imidazole and imidazole derivatives. For example, various silver acetylide compounds as described in U.S. Pat. Nos. 4,761,361 and 4,775,613 can also be used.

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

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

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

After passing through such a step, it is preferable to mix with an aqueous solution of a photosensitive silver salt to produce a coating solution for a photosensitive image forming medium. When a heat-developable photographic light-sensitive material is prepared using such a coating solution, a heat-developable photographic light-sensitive material having low haze, low fog and high sensitivity can be obtained. In contrast,
When the photosensitive silver salt is coexistent when the dispersion is performed after converting into a high-pressure, high-speed flow, fog increases, and the sensitivity is liable to decrease remarkably. When an organic solvent is used instead of water as a dispersion medium, haze increases, fog increases, and sensitivity tends to decrease. On the other hand, when a conversion method for converting a part of the organic silver salt in the dispersion liquid to the photosensitive silver salt is used instead of the method of mixing the aqueous solution of the photosensitive silver salt, the sensitivity tends to be lowered.

In the above, the aqueous dispersion which is converted and dispersed under high pressure and high speed does not substantially contain a photosensitive silver salt, and its content is based on the non-photosensitive organic silver salt. 0.
The content is 1 mol% or less, and the photosensitive silver salt is not positively added.

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

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

As a dispersion device suitable for the present invention, a microfluidizer M-110S-EH manufactured by Microfluidics International Corporation is used.
(With G10Z interaction chamber), M-
110Y (with H10Z interaction chamber), M-140K (with G10Z interaction chamber), HC-5000 (L30Z or H23
With 0Z interaction chamber), HC-80
00 (with an E230Z or L30Z interaction chamber) and the like.

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

It is preferable that the raw material liquid is preliminarily dispersed before the dispersion operation. As means for preliminary dispersion, known dispersion means (for example, high-speed mixer, homogenizer, high-speed impact mill, Banbury mixer, homomixer, kneader, ball mill, vibration ball mill, planetary ball mill, attritor, sand mill, bead mill, colloid mill,
Jet mill, roller mill, tron mill, high-speed stone mill) can be used. Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing agent. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation.

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

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

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

Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then changing the pH in the presence of a dispersing agent. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the completion of the fine particle formation.

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

The particle size (volume-weighted average diameter) of the organic silver salt solid fine particle dispersion of the present invention is determined, for example, by irradiating a solid fine particle dispersion dispersed in a liquid with a laser beam and changing the scattered light fluctuation with time. It can be obtained from the particle size (volume weighted average diameter) obtained by obtaining the autocorrelation function. A solid fine particle dispersion having an average particle size of 0.05 μm or more and 10.0 μm or less is preferable. The average particle size is more preferably 0.1 μm or more and 5.0 μm or less, and still more preferably the average particle size is 0.1 μm or more and 2.0 μm or less.

The particle size distribution of the organic silver salt is preferably monodispersed. Specifically, the percentage of the standard deviation of the volume-weighted average diameter divided by the volume-weighted average diameter (coefficient of variation)
Is 80% or less, more preferably 50% or less, even more preferably 30%
% Or less.

The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion.

The organic silver salt solid fine particle dispersion used in the present invention preferably comprises at least an organic silver salt and water. The ratio between the organic silver salt and water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably from 5 to 50% by weight, particularly preferably from 10 to 30% by weight. Although it is preferable to use the aforementioned dispersing aid,
It is preferable to use a minimum amount in a range suitable for minimizing the particle size ゛, and it is preferably in a range of 1 to 30% by weight, especially 3 to 15% by weight based on the organic silver salt.

In the present invention, a photographic light-sensitive material can be produced by mixing an aqueous dispersion of an organic silver salt and an aqueous dispersion of a photosensitive silver salt, but the mixing ratio of the organic silver salt and the photosensitive silver salt may be varied depending on the purpose. The ratio of photosensitive silver salt to organic silver salt is 1
~ 30 mol% is preferred, more preferably 3-20 mol%, especially 5-15
A mole% range is preferred. Mixing two or more aqueous dispersions of organic silver salts with two or more aqueous dispersions of photosensitive silver salts during mixing is a method preferably used for adjusting photographic characteristics.

Although the organic silver salt of the present invention can be used in a desired amount, it is expressed in an amount per 1 m ^{2 of} the photographic material, and the silver amount is 0.1%.
55 g / m ² is preferred, and more preferably 1-3 g / m ² .

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

Methods for forming light-sensitive silver halide are well known in the art, for example, Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458.
Can be used.Specifically, a photosensitive silver halide is prepared by adding a silver-supplying compound and a halogen-supplying compound to a gelatin or other polymer solution, and then the organic silver halide is added. A method of mixing with a silver salt is used. The grain size of the photosensitive silver halide is
For the purpose of suppressing white turbidity after image formation, it is preferably small, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.02 μm or more and 0.1 μm or more.
It is preferably 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. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high.
The proportion occupied by the {100} plane is preferably high. The ratio is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. The Miller index {100} plane ratio was determined by T. Tani; J. Imaging Sci., 29, 165 (1985), which utilizes the adsorption dependence of {111} and {100} planes on sensitizing dye adsorption. It can be determined by the method described.

The light-sensitive silver halide grains of the present invention may be formed of a Group VII or VIII (Groups 7 to 10) of the periodic table.
Of a metal or metal complex. Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is 1 × 10
The range is preferably from ^-9 mol to 1 × 10 ^-3 mol.
More preferably, the range is from ^-8 mol to 1 x 10 ^-4 mol. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III)
Complex salts, pentachloroacolodium (III) complex salts, tetrachlorodiachodium (III) complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts are exemplified.
These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used to stabilize a solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl, KBr, NaBr
Etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 5 × 10 ^-6 mol, particularly preferably 5 × 10 ^-8 mol to 1 × 10 mol per mol of silver halide.
10 ^-6 mol.

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

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-1-285941.
It is preferably added in the form of a water-soluble complex salt described in JP-A Nos. 2-20852 and 2-20855. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ⁿ -where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4.

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

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

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

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

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

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

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

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

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

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

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

The gold sensitizer used for sensitizing the silver halide emulsion of the present invention with gold may have a gold oxidation number of +1 or +3, and is usually used as a gold sensitizer. Gold compounds can be used. Representative examples include chloroauric acid, potassium chloroaurate, gold (III) chloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridinium trichloroaurate and the like.

[0108] The addition amount of the gold sensitizer may vary depending on various conditions, 10 ^-3 mol per mol of the silver halide 10 ^-7 mol or more as a guide, and more preferably 10 ^-6 mol to 5 × 10 ^- Not more than ⁴ moles.

The silver halide emulsion of the present invention is preferably used in combination with gold sensitization and another chemical sensitization. As other chemical sensitization methods, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used. When used in combination with the gold sensitization method,
For example, sulfur sensitization and gold sensitization, selenium sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization Preferred methods include sulfur sensitization, selenium sensitization, tellurium sensitization, and gold sensitization.

The sulfur sensitization preferably used in the present invention is
Usually, a sulfur sensitizer is added, and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

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

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in JP-A-5-3132.
It can be tested by the method described in No. 84. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals,
Tellurosulfonates, compounds having a P-Te bond, containing T
e Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, U.S. Patent Nos. 1,623,499 and 3,320,069,
No. 3,772,031, UK Patent No. 235,211 and No. 1,121,49
No. 6, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, Japanese Patent Application No. 3-53693,
3-131598, 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (19)
79), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. S.)
oc.Perkin.Trans.) 1,2191 (1980), S. Patai
Hen, The Chemistr of Organic Selenium and Tellurium Campounds
y of Organic Serenium and Tellunium Compounds), Vo
Compounds described in l.1 (1986) and Vol.2 (1987) can be used. In particular, the general formulas (II) and (I
Compounds represented by II) and (IV) are preferred.

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

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

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

The silver halide emulsion of the present invention is described in European Patent No.
A thiosulfonic acid compound may be added by the method described in Japanese Patent No. 293,917.

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

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

The preferred time for adding the silver halide of the present invention to the coating solution for the image forming layer is from 180 minutes to immediately before the coating, preferably from 60 minutes to 10 seconds before the coating. Is not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid sent to the coater is set to a desired time, by N. Harnby, MFE Edwards, AW Nienow, translated by Koji Takahashi There is a method using a static mixer or the like described in Chapter 8 of "Liquid Mixing Technology" (published by Nikkan Kogyo Shimbun, 1989).

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

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

For a semiconductor laser light source in the wavelength range of 750 to 1400 nm, various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes are spectrally advantageously sensitized. Can be done. 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 include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Patent 3,761,279,
3,719,495 and 3,877,943, British Patent 1,466,201
No. 1,469,117, No. 1,422,057, Tokuhei 3-10391
No. 6-52387, JP-A-5-341432, 6-94781,
It may be appropriately selected from known dyes as described in JP-A-6-301141.

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
72661, 6-222491, 2-230506, 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-301
No. 141, dyes described in U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524, JP-A-51-127719,
No. 52-80829, No. 54-61517, No. 59-214846, No. 60-67
No. 50, 63-159841, JP-A-6-35109, 6-59381
No., 77-146537, 77-146537, Tokuyohei 55-50111,
Dyes described in British Patent 1,467,638 and US Patent 5,281,515).

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

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. 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
Research Disclosure Volume 176, 17643 (December 1978) No. 23
Section IV of Page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

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

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

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

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

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

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

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

When an additive known as a "toning agent" for improving an image is contained, the optical density may be increased. Toning agents may also be advantageous in forming black silver images. The toning agent is preferably contained in an amount of 0.1 to 50 mol% per mol of silver on the surface having the image forming layer, and 0.1 to 50 mol%.
More preferably, the content is 5 to 20 mol%. Further, the toning agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable photographic material utilizing an organic silver salt, in addition to the compounds represented by formulas (I) and (II) of the present invention, a wide range of color toning agents are disclosed in JP-A-46-6077. ,
47-10282, 49-5019, 49-5020, 49-91215
Nos. 49-91215, 50-2524, 50-32927, 50-
67132, 50-67641, 50-114217, 51-3223
Nos. 51-27923, 52-14788, 52-99813, 53
-1020, 53-76020, 54-156524, 54-156525
No. 61-183642, JP-A-4-56848, JP-B-49-10727
No. 54-20333, U.S. Pat.No. 3,080,254, No. 3,446,648
No. 3,782,941, No. 4,123,282, No. 4,510,236,
It is disclosed in British Patent 1380795, Belgian Patent 841910 and the like. Examples of the toning agent include phthalimide and N-hydroxyphthalimide, succinimide, pyrazolin-5-one, quinazolinone, and 3-phenyl, in addition to the compounds represented by formulas (I) and (II) of the present invention. -
Cyclic imides such as 2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, Cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-
Mercaptans exemplified by 4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximide;
(E.g., (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents ( For example, 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-benzothiazolinylidene)
1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone And derivatives such as 2,3-dihydro-1,4-phthalazinedione; combinations of phthalazinone with phthalic acid derivatives such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; Quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes that function not only as color tone regulators but also in-situ as sources of halide ions for silver halide formation, such as ammonium hexachlororhodate (III), rhodium bromide , Rhodium nitrate and potassium hexachlororhodate (III); inorganic peroxides and persulfates; For example,
Ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine Benzoxazine-2,4-dione such as -2,4-dione; pyrimidine and asymmetric triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentane Ren derivatives (e.g., 3,6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene) is there. To the photothermographic material of the present invention, in addition to the compounds represented by formulas (I) and (II), these known color toning agents may be further added.

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

In the present invention, the organic silver salt-containing layer, which is the image forming layer, is preferably formed by applying and drying a coating solution in which 30% by weight or more of the solvent is water. As the binder of the above, those which are soluble or dispersible in an aqueous solvent (aqueous solvent) are preferable, and it is particularly preferable to use polymer latex. The most preferred form is one prepared so that the ionic conductivity is 2.5 mS / cm or less. As such a preparation method, a method of purifying using a separation functional membrane after synthesizing a polymer can be mentioned.

The aqueous solvent in which the polymer is soluble or dispersible is water or a mixture of water and 70% by weight or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include, for example, alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol; cell solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; ethyl acetate; and dimethylformamide. be able to.

Note that the term “aqueous solvent” is used herein even in a system in which the polymer is not thermodynamically dissolved but exists in a so-called dispersed state.

The polymers 25 that can be used in the present invention
The equilibrium water content at 60 ° C. and 60% RH is preferably 2% by weight or less, more preferably 0.01% by weight or more and 1.5% by weight or less, further preferably 0.02% by weight or more and 1% by weight or less.

The polymer is not particularly limited as long as it is soluble or dispersible in the above-mentioned aqueous solvent and has an equilibrium water content at 25 ° C. and 60% RH of 2% by weight or less. Among these polymers, polymers that can be dispersed in an aqueous solvent are particularly preferred.

Examples of the dispersion state include a latex in which fine particles of a solid polymer are dispersed, and a dispersion in which polymer molecules are dispersed in a molecular state or in the form of micelles.

In a preferred embodiment of the present invention, acrylic resin, polyester resin, rubber resin (for example, SBR
Resin), a polyurethane resin, a vinyl chloride resin, a vinyl acetate resin, a vinylidene chloride resin, a hydrophobic polymer such as a polyolefin resin. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The polymer has a number average molecular weight of 5000 to 100000, preferably 10,000 to 200,000. If the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

As the polymer which can be used in the present invention, it is preferable that these polymers are dispersed in an aqueous dispersion medium. Here, the aqueous system refers to a dispersion medium in which 30% by weight or more of the composition is water. The dispersion state may be any state such as emulsified and dispersed, micelle dispersed, and further dispersed in a molecular state of a polymer having a hydrophilic site in a molecule, and of these, latex is particularly preferred. .

Specific examples of preferred polymers include the following. In the following, the raw material monomers are used, the numerical value in parentheses is wt%, and the molecular weight is the number average molecular weight.

Latex of P-1; -MMA (70) -EA (27) -MAA (3)-(molecular weight 37000) P-2; -MMA (70) -2EHA (20) -St (5) -AA (5) -Latex (molecular weight 40000) P-3; -St (50) -Bu (47) -MAA (3) -Latex (molecular weight 45000) P-4; -St (68) -Bu (29) -AA (3)-latex (molecular weight 60000) P-5; -St (70) -Bu (27) -IA (3)-latex (molecular weight 120000) P-6; -St (75) -Bu ( 24) -AA (1) -Latex (Molecular weight 108000) P-7; -St (60) -Bu (35) -DVB (3) -MAA (2) -Latex (Molecular weight 150,000) P-8;- Latex of St (70) -Bu (25) -DVB (2) -AA (3)-(molecular weight 280000) P-9; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-latex (MW 80000) P-10; -VDC (85) -MMA (5) -EA (5) -MAA (5)-latex (MW 67000) P-11; -Et ( 90) -MAA (10)-latex (molecular weight 12000)

The abbreviations of the above structures represent the following monomers.
MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2-ethylhexyl acrylate, St; styrene, Bu; butadiene, AA; acrylic acid, DVB; divinylbenzene, VC; vinyl chloride, AN;
Acrylonitrile, VDC; vinylidene chloride, Et; ethylene, IA; itaconic acid.

The polymers described above are commercially available, and the following polymers can be used. Examples of acrylic resin include Sebian A-4635, 46683, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820, 85
Examples of polyester resins such as 7 (all manufactured by Zeon Corporation) include FINETEX ES650, 611, 675, 850 (all manufactured by Dainippon Ink and Chemicals), WD-size, WMS (all manufactured by Eastman Chemical Co., Ltd.) HYDRA is an example of a polyurethane resin.
Examples of rubber resins such as NAP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR 7310K, 3307B,
4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol Lx
Examples of vinyl chloride resins such as 416, 410, 438C, and 2507 (all manufactured by Nippon Zeon Co., Ltd.)
Examples of vinylidene chloride resin, such as L502,
Examples of olefin resins such as L513 (manufactured by Asahi Chemical Industry Co., Ltd.) include Chemipearl S120 and SA100 (Mitsui Petrochemical
And the like).

These polymers may be used alone as a polymer latex, or two or more of them may be blended if necessary.

The polymer latex that can be used in the present invention is particularly preferably a styrene-butadiene copolymer latex. The weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably from 40:60 to 95: 5. The ratio of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by weight. The preferred molecular weight range is the same as described above.

Styrene which is preferably used in the present invention
As the butadiene copolymer latex, the above-mentioned P-3
~ P-8, commercial products LACSTAR-3307B, 7132C, Nipol Lx4
16, and the like.

The organic silver salt-containing layer of the heat-developable photographic material of the present invention may optionally contain a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose and hydroxypropylcellulose. The amount of these hydrophilic polymers added is 30 wt% of the total binder in the organic silver salt-containing layer.
Or less, more preferably 20 wt% or less.

The organic silver salt-containing layer of the present invention is formed using a polymer latex. The amount of the binder in the organic silver salt-containing layer is such that the total binder / organic silver salt weight ratio is 1/10. 1010/1, more preferably 1/5 to 4/1.

[0153] Such an organic silver salt-containing layer is usually formed of a photosensitive layer (emulsion layer) containing photosensitive silver halide.
In such a case, the weight ratio of the total binder / silver halide is preferably in the range of 400 to 5, more preferably in the range of 200 to 10.

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

In the present invention, the solvent of the coating solution for the organic silver salt-containing layer of the light-sensitive material (the solvent and the dispersion medium are collectively referred to as a solvent for simplicity) is an aqueous solvent containing 30% by weight or more of water. As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate may be used. The water content of the solvent in the coating solution is preferably at least 50 wt%, more preferably at least 70 wt%. Examples of preferred solvent composition include water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / Ethyl cell solve = 8
5/10/5, water / methyl alcohol / isopropyl alcohol = 85/10/5, etc. (numerical value is wt%).

The silver halide emulsion according to the present invention or /
And the organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and can be stabilized against reduced sensitivity during storage in inventory. 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.
8,663 mercury salt, U.S. Pat.No. 3,287,135 urazole, U.S. Pat.No. 3,235,652 sulfocatechol, British Patent 623,448 Oxime,
Nitrone, nitroindazole, U.S. Patent No. 2,839,405
No. 3,220,839, thiuronium salts, and U.S. Pat.Nos. 2,566,263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.Nos. 4,108,665 and 4,442,202 No. 4,128,557
Nos. 4,137,079 and 4,138,365 and 4,
No. 4,59,350 and U.S. Pat.
And the phosphorus compounds described in No. 1,985.

The antifoggant preferably used in the present invention is an organic halide, for example, as described in JP-A-50-119624.
No. 50-120328, No. 51-121332, No. 54-58022, No.
56-70543, 56-99335, 59-90842, 61-12964
No. 2, 62-129845, JP-A-6-208191, 7-5621,
Nos. 7-2781, 8-15809, U.S. Pat.
Compounds such as those disclosed in US Pat.

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

Although not required to practice the present invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the emulsion layer. Preferred mercury (II) salts for this purpose are
Mercury acetate and mercury bromide. The amount of mercury used in the present invention is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻³ mol, per mol of the coated silver.
The range is from ^-9 mol to 1 × 10 ^-4 mol.

The photothermographic material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fogging. The benzoic acids of the present invention may be any benzoic acid derivative, but examples of preferred structures include those described in U.S. Pat.
No. 9, No. 4, 152, 160, Japanese Patent Application No. 8-151242, No. 8-151241
And the compounds described in JP-A-8-98051 and the like. The benzoic acid of the present invention may be added to any part of the photographic material, but it is preferable to add the benzoic acid to the layer having the photosensitive layer (image forming layer), and to add it to the organic silver salt-containing layer. More preferably, The benzoic acid of the present invention may be added at any time during the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be added at any time from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable after salt preparation and immediately before application. The benzoic acid of the present invention may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent.
The benzoic acid of the present invention may be added in any amount, but is preferably from 1 × 10 ⁻⁶ mol to 2 mol, more preferably from 1 × 10 ⁻³ mol to 0.5 mol, per mol of silver.

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

When a mercapto compound is used in the present invention, it may have any structure, but it may be Ar-SM, Ar-SSA
Those represented by r are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogens (e.g., Br and Cl), hydroxy, amino, carboxy,
Alkyl (e.g. one or more carbon atoms, preferably 1-4
Having one carbon atom) and alkoxy (e.g.,
One having at least one carbon atom, preferably having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
Mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5
-Diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-
4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4 -
Thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxysil-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methyl Pyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole,
Examples include 2-mercapto-4-phenyloxazole, but the present 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, more preferably 0.01 to 0.3 mol per mol of silver.
It is a molar amount.

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

In the heat-developable photographic material of the present invention, when a high contrast image is obtained, a substituted alkene represented by the following general formula (III), general formula (IV) or general formula (V) is used as a high contrast agent. It preferably contains a derivative, a substituted isoxazole derivative, and a specific acetal compound. General formula (III),
The general formula (IV) and the general formula (V) will be described.

[0166]

Embedded image

In the general formula (III), R ₃₁ , R ₃₂ , R
₃₃ independently represent a hydrogen atom or a substituent;
Represents an electron-withdrawing group or a silyl group. In the general formula (III) R _{3 1} and Z, R ₃₂ and R _33, R ₃₁ and R _32, or R ₃₃
And Z may combine with each other to form a cyclic structure. In the general formula (IV), R41 represents a substituent. General formula
In (V), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group,
Alkylthio group, alkylamino group, aryloxy group, arylthio group, anilino group, heterocyclic oxy group,
Represents a heterocyclic thio group or a heterocyclic amino group. In the general formula (V), X and Y or A and B may combine with each other to form a cyclic structure.

The compound represented by formula (III) will be described in detail. In the general formula (III), R ₃₁ , R ₃₂ , R ₃₃
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (III), R ₃₁ and Z, R ₃₂ and R ₃₃ , R ₃₁ and R ₃₂ , or R ₃₃ and Z may be bonded to each other to form a cyclic structure.

When R ₃₁ , R ₃₂ and R ₃₃ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) and an alkyl group (an aralkyl group, a cycloalkyl group). An alkyl group, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including an N-substituted nitrogen-containing heterocyclic group), and a heterocyclic group containing a quaternized nitrogen atom ( For example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfonylcarbamoyl group, an acylcarbamoyl group, Famoylcarbamoyl, carbazoyl, oxalyl, oxamoyl, cyano, thiocarbamoyl A hydroxy group or a salt thereof, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, and a carbamoyloxy group , Sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium, oxamoylamino, (alkyl or aryl) sulfonyluureido, acylureido, acylsulfamoylamino, nitro, mercapto, (alkyl, aryl, or heterocycle)
Thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoryl group, phosphorus Examples include groups having an acid amide or phosphate structure, silyl groups, stannyl groups, and the like. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the general formula (III) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxy group, A carbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom,
Thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom, perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group (or Salt), a sulfo group (or a salt thereof), a heterocyclic group, an alkenyl group, an alkynyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, or an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is a saturated or unsaturated heterocyclic group such as a pyridyl group, a quinolyl group, a quinoxanyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, and a hydantoin-1-yl group. , A succinimide group, a phthalimide group and the like.

The electron-withdrawing group represented by Z in the general formula (III) may further have a substituent, and the substituent may be any one of R ₃₁ , R ₃₂ and R in the general formula (III). _The same substituents as those which may be possessed when ₃₃ represents a substituent are exemplified.

In the general formula (III), R ₃₁ and Z, R ₃₂ and R
₃₃ , R ₃₁ and R ₃₂ , or R ₃₃ and Z may be bonded to each other to form a cyclic structure. The cyclic structure formed at this time is a non-aromatic carbon ring or non-aromatic Is a heterocycle.

Next, the preferred range of the compound represented by formula (III) will be described. Preferable examples of the silyl group represented by Z in the general formula (III) specifically include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl, triethylsilyl, triisopropylsilyl, and trimethylsilyldimethylsilyl groups. is there.

The electron-withdrawing group represented by Z in the general formula (III) is preferably a group having a total carbon number of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, A thiocarbonyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a perfluoroalkyl group, an acyl group, a formyl group, a phosphoryl group, an acyloxy group, an acylthio group, or A phenyl group or the like substituted with any electron-withdrawing group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
An acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group, and particularly preferably a cyano group, a formyl group,
An acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group.

In the general formula (III), the group represented by Z is
Electron withdrawing groups are more preferred. In general formula (III), R
_31, R _32, and examples of preferable substituents represented by R _33, a total group of a carbon number of 0 to 30, in particular above general formula
(III) a group having the same meaning as the electron-withdrawing group represented by Z, and an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
Examples include a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, an acylamino group, a sulfonamide group, and a substituted or unsubstituted aryl group.

In the general formula (III), R ₃₁ is preferably an electron-withdrawing group, an aryl group, an alkylthio group, an alkoxy group, an acylamino group, a hydrogen atom, or a silyl group.

When R ₃₁ represents an electron-withdrawing group, preferably the following groups having a total of 0 to 30 carbon atoms, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
An aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), Or a saturated or unsaturated heterocyclic group, and a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a sulfamoyl group, a carboxy group (or a salt thereof) Or a saturated or unsaturated heterocyclic group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a saturated or unsaturated heterocyclic group.

When R ₃₁ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms in total, and the substituent may be any substituent.
Among them, an electron-withdrawing substituent is preferable.

In formula (III), R ₃₁ is more preferably an electron-withdrawing group or an aryl group.

In the general formula (III), the substituents represented by R ₃₂ and R ₃₃ are preferably, specifically, groups having the same meaning as the electron-withdrawing group represented by Z in the general formula (III), Alkyl group, hydroxy group (or salt thereof), mercapto group
(Or salt thereof), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, anilino group, heterocyclic amino group, acylamino group, substituted or unsubstituted And a substituted phenyl group.

In the general formula (III), R ₃₂ and R ₃₃ are
More preferably, one of them is a hydrogen atom and the other represents a substituent. Preferably as the substituent,
Alkyl group, hydroxy group (or a salt thereof), mercapto group (or a salt thereof), alkoxy group, aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
A heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly a perfluoroalkaneamide group), a sulfonamide group, a substituted or unsubstituted phenyl group, or a heterocyclic group; More preferably, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group, Particularly preferred are a hydroxy group (or a salt thereof), an alkoxy group, and a heterocyclic group.

In the general formula (III), it is also preferable that Z and R ₃₁ , or R ₃₂ and R ₃₃ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number of 1 including a substituent.
To 40, more preferably 3 to 30.

Among the compounds represented by the general formula (III), one of the more preferable ones is that Z is a cyano group, a formyl group,
Represents an acyl group, an alkoxycarbonyl group, an imino group, or a carbamoyl group, R ₃₁ represents an electron-withdrawing group or an aryl group, one of R _{32 and} R ₃₃ is a hydrogen atom, and the other is a hydroxy group (or Salt), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
A compound representing a heterocyclic thio group or a heterocyclic group.

Further, among the compounds represented by formula (III), one of the particularly preferred compounds is that Z and R _{31 form a} non-aromatic 5- to 7-membered cyclic structure, _{One of 32} or R ₃₃ is a hydrogen atom and the other is a hydroxy group
(Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a heterocyclic group. At this time, Z forming a non-aromatic cyclic structure together with R ₃₁ includes an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group,
A sulfonyl group and the like are preferable, and R ₃₁ is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group, and the like.

Next, the compound represented by formula (IV) will be described. In the general formula (IV), R ₄₁ represents a substituent. Examples of the substituent in the general formula (IV) represented by R _41, may be the same as those described for R ₃₁ to R _{3 3} substituents of the general formula (III).

In formula (IV), the substituent represented by R ₄₁ is preferably an electron-withdrawing group or an aryl group.
When R ₄ represents an electron-withdrawing group, it preferably has a total carbon number of 0.
To 30 or less of the following groups: cyano group, nitro group, acyl group, formyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, trifluoromethyl group, phosphoryl Group, imino group, or a saturated or unsaturated heterocyclic group, and further a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group,
A carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic group are preferred.
Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a heterocyclic group.

When R ₄₁ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and examples of the substituent include R ₃₁ , R ₃₂ , and R of the general formula (III).
_{When 33} represents a substituent, the same as those described as the substituent can be mentioned.

In the formula (IV), R ₄₁ is particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group or a substituted or unsubstituted phenyl group, and most preferably a cyano group, a heterocyclic group. Or an alkoxycarbonyl group.

Next, the compound represented by formula (V) will be described in detail. In the general formula (V), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a hetero group. Represents a ring thio group, a heterocyclic oxy group, or a heterocyclic amino group. X and Y or A and B may be bonded to each other to form a cyclic structure.

As the substituents represented by X and Y in the general formula (V), the same as those described for the substituents of R _{31 to} R _{33 in} the general formula (III) can be mentioned. In particular,
Alkyl group (including perfluoroalkyl group, trichloromethyl group, etc.), aryl group, heterocyclic group, halogen atom, cyano group, nitro group, alkenyl group, alkynyl group, acyl group, formyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, imino group, imino group substituted with an N atom, carbamoyl group, thiocarbonyl group, acyloxy group, acylthio group, acylamino group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphoryl group, carboxy group (or Its salt),
A sulfo group (or a salt thereof), a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group,
Examples include an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, a heterocyclic amino group, and a silyl group.

These groups may further have a substituent. X and Y may be bonded to each other to form a cyclic structure, and the cyclic structure formed in this case may be a non-aromatic carbon ring or a non-aromatic hetero ring. .

The substituents represented by X and Y in the formula (V) are preferably groups having 1 to 40 carbon atoms in total, more preferably 1 to 30 carbon atoms in total, and include a cyano group and an alkoxycarbonyl group. An aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, a thiocarbonyl group, a sulfamoyl group, an alkylsulfonyl group,
Arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acylamino group, acyloxy group, acylthio group, heterocyclic group,
Examples thereof include an alkylthio group, an alkoxy group, and an aryl group.

In the general formula (V), X and Y are more preferably a cyano group, a nitro group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a formyl group, an acylthio group,
Acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, imino group, imino group substituted with N atom, phosphoryl group, trifluoromethyl group, heterocyclic group, substituted phenyl group, etc. Particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylthio group,
Examples include an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, and a phenyl group substituted with any electron-withdrawing group.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the formed cyclic structure is preferably a 5- to 7-membered ring, and has a total carbon number of 1 to 40, and more preferably 3 to 7 members.
30 is preferred. X and Y forming a cyclic structure include an acyl group, a carbamoyl group, an oxycarbonyl group,
Preferred are a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like.

In the general formula (V), A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group, which may be bonded to each other to form a cyclic structure.

The groups represented by A and B in the general formula (V) are preferably groups having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and further have a substituent. You may.

In the general formula (V), A and B more preferably combine with each other to form a cyclic structure. The cyclic structure formed at this time is preferably a 5- to 7-membered non-aromatic hetero ring, and preferably has a total carbon number of 1 to 40, and more preferably 3 to 30. In this case, an example in which A and B are linked (-AB-) is, for example, -O- (C
_{H 2) 2 -O -, -} O- (CH 2) 3 -O -, - S- (CH
_{2) 2 -S -, - S-} (CH 2) 3 -S -, - S-ph-S
_{-, - N (CH 3)} - (CH 2) 2 -O -, - N (CH 3)
_{- (CH 2) 2 -S -} , - O- (CH 2) 2 -S -, - O-
_{(CH 2) 3 -S -,} - N (CH 3) -ph-O -, - N
(CH ₃ ) -ph-S-, -N (ph)-(CH ₂ ) _2-
S- and so on.

Formula (III) which can be used in the present invention
The compound represented by formula (V) may have a built-in adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic,
U.S. Pat. No. 4,385,108 including triazole groups
No. 4,459,347, JP-A-59-19523.
No. 3, No. 59-200231, No. 59-201045
Nos. 59-201046 and 59-201047
Nos. 59-201048 and 59-201049
And JP-A-61-170733 and 61-27074.
No. 4, 62-948, 63-234244, 63-234245, and 63-234246. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

Formula (III) which can be used in the present invention
The compound represented by the general formula (V) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. Particularly, those incorporating a ballast group are one of preferred examples of the present invention. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group,
It can be selected from an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

Formula (III) which can be used in the present invention
The compound represented by the general formula (V) contains a cationic group (specifically, a group containing a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, etc.) ), A group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy, sulfo, acylsulfamoyl,
A carbamoylsulfamoyl group). Particularly, a group containing a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group or a group containing an (alkyl, aryl, or heterocyclic) thio group is one of preferred examples of the present invention. Specific examples of these groups include, for example, JP-A-7-234471 and JP-A-5-
333466, JP-A-6-19032, JP-A-6-19032
19031, JP-A-5-45761, U.S. Pat.
No. 94365, U.S. Pat. No. 4,988,604,
259240, JP-A-7-5610, JP-A-7-2
No. 44348, German Patent No. 4006032 and the like.

Next, the general formula (I) which can be used in the present invention
Specific examples of the compounds represented by II) to general formula (V) are shown below. However, the present invention is not limited to the following compounds.

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Formula (III) which can be used in the present invention
The compound represented by the general formula (V) may be water or a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsified dispersion can be prepared and used. Alternatively, by a method known as a solid dispersion method, a powder of a compound represented by the general formula (III) to the general formula (V) that can be used in the present invention is ball-milled or colloid-milled in a suitable solvent such as water. Alternatively, they can be dispersed and used by ultrasonic waves.

Formula (III) which can be used in the present invention
The compound represented by the general formula (V) may be added to a layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. It is preferable to add it to the layer adjacent thereto.

Formula (III) which can be used in the present invention
The amount of the compound represented by the general formula (V) is preferably 1 × 10 ⁻⁶ to 1 mol per 1 mol of silver, more preferably 1 × 10 ^{−5 to} 5 ×.
10 ^-1 mol is more preferable, and 2 x 10 ^-5 to 2 x 10 ^-1 mol is most preferable.

Formula (III) which can be used in the present invention
The compound represented by formula (V) can be easily synthesized by a known method. For example, US Pat.
No. 515, US Pat. No. 5,635,339, US Pat.
No. 4130, International Patent WO-97 / 34196, Japanese Patent Application No. 9-354107, and Japanese Patent Application No. 9-309813.
And the method described in Japanese Patent Application No. 9-272002.

Formula (III) which can be used in the present invention
~ Even if only one compound represented by the general formula (V) is used,
Two or more kinds may be used in combination. In addition to the above, US Pat. No. 5,545,515, US Pat. No. 5,635,339,
U.S. Pat. No. 5,654,130, International Patent WO-97 / 34
196, the compound described in US Pat. No. 5,686,228,
Alternatively, Japanese Patent Application Nos. 8-279962 and 9-22.
No. 8881, Japanese Patent Application No. 9-273935, Japanese Patent Application No. 9-3
No. 54107, Japanese Patent Application No. 9-309813, Japanese Patent Application No. 9-309
296174, Japanese Patent Application No. 9-282564, Japanese Patent Application No. 9
Compounds described in JP-A-272002, Japanese Patent Application Nos. 9-272003 and 9-332388 may be used in combination.

Further, in the present invention, Japanese Patent Application No. 9-16 / 1997
No. 6628, Japanese Patent Application No. 8-279957, Japanese Patent Application No. 9-2
The hydrazine derivatives described in No. 40511 can also be used in combination. Further, the following hydrazine derivatives can be used in combination. That is,
A compound represented by (Chemical Formula 1) described in No. 77138, specifically, a compound described on pages 3 and 4 of the same publication. Tokuhei 6-
Compounds represented by the general formula (I) described in No. 93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication. Compounds represented by formulas (4), (5) and (6) described in JP-A-6-230497, specifically, compound 4- described on pages 25 and 26 of the same publication. 1 to 4-10, compounds 5-1 to 5-42 described on pages 28 to 36, and compounds 6-1 to 6-7 described on pages 39 and 40. JP-A-6-289520
Compounds represented by the general formulas (1) and (2) described in the above publications, specifically, the compounds 1-1) to 1-17) and 2-1 described on pages 5 to 7 of the same publication. ). JP-A-6-31
Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in No. 3936, specifically, compounds described on pages 6 to 19 of the same publication. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-10 described on pages 10 to 27 of the same publication
2. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. A compound described in EP 713131A, which has an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. Particularly, a compound represented by the general formula (A): A compound represented by the formula (B), the general formula (C), the general formula (D), the general formula (E), or the general formula (F).
-1 to N-30. Compounds represented by the general formula (1) described in European Patent 713131A, and specifically, compounds D-1 to D-55 described in the publication.

Further, “Known Techniques (1 to
207) ”(published by Aztec) on pages 25 to 34. Compounds D-2 and D-39 of JP-A-62-86354 (pages 6 to 7).

These hydrazine derivatives are dissolved in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve, etc. Can be used.

Further, by a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve. 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.

These hydrazine derivatives may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side, but may be added to the image forming layer or a layer adjacent thereto. It is preferred to add.

The addition amount of these hydrazine derivatives is preferably 1 × 10 -6 ^{to 1} mol per mol of silver, and more preferably 1 × 10 ^{-5 to} 5 mol.
× 10 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1
Molar is most preferred.

In the present invention, a high-contrast accelerator can be used in combination with the above-mentioned high-contrast agent for forming a high-contrast image. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5, hydroxamic acids described in 5,545,507, specifically HA-1 to HA-1
1, acrylonitriles described in 5,545,507, specifically CN-1 to CN-13, hydrazine compounds described in 5,558,983, specifically CA-1 to CA-6, Japanese Patent Application No.
Onium salts described in No. 8-132836, specifically A-1 to
A-42, B-1 to B-27, C-1 to C-14 and the like can be used.

The synthesis method, addition method, addition amount and the like of these high contrast enhancement agents can be carried out as described in each of the cited patents.

The heat-developable photographic material of the present invention can be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.

The binder for the surface protective layer of the present invention may be any polymer, but preferably contains a polymer having a carboxylic acid residue in an amount of 100 mg / m ^{2 to} 5 g / m ² . Examples of the polymer having a carboxyl residue include natural polymers (gelatin, alginic acid, etc.), modified natural polymers (carboxymethylcellulose, phthalated gelatin, etc.), synthetic polymers (polymethacrylate, polyacrylate, polyalkyl methacrylate / acrylate). Copolymer, polystyrene / polymethacrylate copolymer, etc.). The content of carboxy residues in such a polymer is preferably from 1 × 10 ^-2 mol to 1.4 mol per 100 g of the polymer. Further, the carboxylic acid residue may form a salt with an alkali metal ion, an alkaline earth metal ion, an organic cation, or the like.

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

In the image forming layer or the protective layer of the image forming layer in the invention, US Pat. Nos. 3,253,921 and 2,27
Light absorbing substances and filter dyes as described in 4,782, 2,527,583 and 2,956,879 can be used. Also, for example, U.S. Pat.
The dye can be mordanted as described in US Pat. As the amount of filter dye used, the absorbance at the exposure wavelength is 0.
It is preferably from 1 to 3.0, and particularly preferably from 0.2 to 1.5.

The image-forming layer or the protective layer of the image-forming layer according to the present invention may comprise a matting agent such as starch, titanium dioxide, zinc oxide, silica, of the type described in US Pat. Nos. 2,992,101 and 2,701,245. Polymer beads, including beads, can be included. The matte degree of the emulsion surface may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably from 200 seconds to 10,000 seconds, particularly preferably from 300 seconds to 10,000 seconds.

The preparation temperature of the image forming layer coating solution of the present invention is 30.
It is preferable that the temperature is not less than 65 ° C and not more than 35 ° C.
It is not less than 60 ° C (preferably 55 ° C or less). In addition, the temperature of the image forming layer coating solution immediately after the addition of the polymer latex
It is preferable that the temperature is maintained at 30 ° C or higher and 65 ° C or lower. Also,
It is preferable that the reducing agent and the organic silver salt are mixed before the addition of the polymer latex.

The fluid containing an organic silver salt or the coating solution for the image forming layer in the present invention is preferably a so-called thixotropic fluid. The thixotropic property refers to a property in which the viscosity decreases as the shear rate increases. Although any apparatus may be used for the viscosity measurement of the present invention, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used and is measured at 25 ° C. Here, the viscosity of the organic silver salt-containing fluid or the image forming layer coating solution in the present invention at a shear rate of 0.1 S ^-1 is preferably 400 mPas or more and 100,000 mPas or less, more preferably 50 mPas or less.
0 mPa · s or more and 20,000 mPa · s or less. Also, the shear rate 1
In 000S- ¹ , the pressure is preferably from 1 mPa · s to 200 mPa · s, more preferably from 5 mPa · s to 80 mPa · s.

Various systems expressing thixotropy are known, and are described in “Lecture / Rheology”, edited by Polymer Publishing Association, Muroi,
It is described in Morino co-authored "Polymer Latex" (published by the Society of Polymer Publishing). In order for a fluid to exhibit thixotropic properties, it is necessary to contain a large amount of solid fine particles.
In order to enhance the thixotropic property, it is effective to include a thickened linear polymer, to increase the aspect ratio of the contained solid fine particles in an anisotropic shape, to use an alkali thickener, and to use a surfactant.

The heat-developable photographic emulsion of the present invention comprises one or more layers on a support. One layer construction must include optional additional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is the first
It must contain the organic silver salt and silver halide in the emulsion layer (usually the layer adjacent to the support) and some other components in the second or both layers. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, and may include all components in a single layer as described in U.S. Pat.No. 4,708,928. Is also good. In the case of a multi-dye, multi-color photothermographic material, each emulsion layer is generally, as described in U.S. Pat.No. 4,460,681,
By using a functional or non-functional barrier layer between each emulsion layer (photosensitive layer), it is kept distinct from each other.

In the photosensitive layer of the present invention, various dyes and pigments can be used from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer of the present invention may be any, for example, pigments and dyes described in the color index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye,
Organic dyes such as oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes and indophenol dyes, azo pigments, polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, etc.), dyeing lake pigments, Organic pigments including azine pigments, inorganic pigments and the like can be mentioned. Preferred dyes used in the present invention include anthraquinone dyes (e.g., compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), azomethine Dyes (e.g., compounds 17 to 47 described in JP-A-5-341441), indoaniline dyes (e.g., compound 1 described in JP-A-5-289227)
1 to 19, compound 47 described in JP-A-5-341441, JP-A-5-165
No. 147 described compounds 2-10 to 11) and azo dyes (compounds 10 to 16 described in JP-A-5-341441) are preferred as anthraquinone-based indanthrone pigments (CI Pi
gment Blue 60), phthalocyanine pigments (CIPigment
Copper phthalocyanine such as Blue 15, CI Pigment Blue 16
Metal-free phthalocyanine, etc.), dyed lake pigment based triarylcarbonyl pigments, indigo, inorganic pigments
(Ultra blue, cobalt blue, etc.). As a method for adding these dyes and pigments, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye or pigment is mordanted with a polymer mordant may be used. The amount of these compounds to be used is determined depending on the desired absorption, but generally 1 to ² per m2 of the photographic material.
It is preferable to use in the range of μg or more and 1 g or less. Also,
A dioxane-based pigment, a quinacridone-based pigment, a diketopyrrolopyrrole-based pigment, or the like may be used in combination for adjusting redness.

In the present invention, the antihalation layer can be provided on the side farther from the light source than the photosensitive layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably an absorption of an exposure wavelength of 0.5 or more and 2 or less, and an absorption in a visible region after processing of 0.001 or more. It is preferably less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3.

When antihalation dyes are used in the present invention, these dyes have the desired absorption in the wavelength range, have a sufficiently low absorption in the visible region after treatment, and have the desired absorbance spectrum shape of the antihalation layer. Any compound can be used as long as it is possible. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458, JP-A-Hei 2-
216140, 7-13295, 711432, U.S. Patent 5,380,
No. 635, JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9, and JP-A-3-24539, page 14, lower left column, page 16, lower right column The dyes that can be decolorized by the treatment include JP-A-52-139136, JP-A-53-132334, and
56-501480, 57-16060, 57-68831, 57-1018
No. 35, 59-182436, JP-A-7-36145, 7-199409
No., JP-B-48-33692, JP-B-50-16648, JP-B2-41734
Nos., U.S. Pat.Nos. 4,088,497, 4,283,487, 4,548,89
No. 6 and 5,187,049.

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

In the present invention, a matting agent may be added to the single-sided photographic material in order to improve transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Patent Nos. 1,939,213, 2,701,245, and 2,322,037.
No. 3,262,782, No. 3,539,344, No. 3,767,448, etc.
2,192,241, 3,257,206, 3,370,951, 3,52
Inorganic matting agents well-known in the art, such as inorganic matting agents described in the respective specifications such as 3,022 and 3,769,020, 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,
Examples of starch derivatives such as cellulose acetate, cellulose acetate propionate, carboxy starch, carboxynitrophenyl starch, urea-formaldehyde-
Gelatin hardened with a known hardener such as a starch reactant and hardened gelatin obtained by coacervate hardening to form fine capsule hollow particles can be preferably used. As examples of the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth can be preferably used. The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the coating film and the surface gloss, the particle size, shape, and particle size distribution can be adjusted as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, the matte degree of the back layer is preferably a Beck smoothness of 1200 seconds or less and 10 seconds or more, more preferably 700 seconds or less and 50 seconds or more.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the photographic material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferable to be contained.

In the present invention, suitable binders for the back layer 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, and poly (vinyl). (Alcohol), hydroxyethylcellulose, 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 (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal))
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the present invention, the back layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range.
More preferably absorption is 0.5 or more and 2 or less, and the absorption in the visible region after the treatment is preferably 0.001 or more and less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3. . Examples of the antihalation dye used in the back layer are the same as those of the antihalation layer described above.

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

A hardener may be used in each of the layers such as the image forming layer, the protective layer and the back layer according to the invention. Examples of hardeners include
"THE THEORY OF THE PHOTOGRAPHIC PROCES" by THJames
S FOURTH EDITION "(Macmillan Publishing Co., Inc.
Published in 1977) There are various methods described on pages 77 to 87, polyvalent metal ions described on page 78 of the same book, U.S. Patent 4,281,060
Polyisocyanates such as JP-A-6-208193, epoxy compounds such as U.S. Pat.
Vinyl sulfone compounds such as 89048 are preferably used.

The hardener is added as a solution. The time of adding this solution to the coating solution for the protective layer is from 180 minutes to immediately before coating, preferably from 60 minutes to 10 seconds before coating. The mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. As a specific mixing method, a method of mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid sent to the coater is set to a desired time, by N. Harnby, MFE Edwards, AW Nienow, translated by Koji Takahashi There is a method using a static mixer or the like described in Chapter 8 of "Liquid Mixing Technology" (published by Nikkan Kogyo Shimbun, 1989).

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

Examples of the solvent used in the present invention include New Solvent Pocket Book (Ohm Co., 1994), but the present invention is not limited thereto. The solvent used in the present invention has a boiling point of 40 ° C or more and 180 ° C or more.
C. or lower is preferred.

Examples of the solvent of the present invention include hexane, cyclohexane, toluene, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, 1,1,1-trichloroethane, tetrahydrofuran,
Triethylamine, thiophene, trifluoroethanol, perfluoropentane, xylene, n-butanol,
Phenol, methyl isobutyl ketone, cyclohexanone, butyl acetate, diethyl carbonate, chlorobenzene, dibutyl ether, anisole, ethylene glycol diethyl ether, N, N-dimethylformamide, morpholine,
Examples include propane sultone, perfluorotributylamine, and water.

The heat-developable photographic emulsion of the present invention can be coated on various supports. Typical supports are polyester film, primed polyester film, poly (ethylene terephthalate) film (PET)
Film), polyethylene naphthalate film, cellulose nitrate film, cellulose ester film, poly (vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper, metal and the like. Flexible substrates, especially α-olefins having 2-10 carbon atoms, such as partially baryta and / or acetylated α-olefin polymers, especially polyethylene, polypropylene, ethylene-butene copolymers.
A paper support coated with an olefin polymer,
Typically used. Such a support may be transparent or opaque, but is preferably transparent.

The photographic material of the present invention comprises an antistatic or conductive layer such as a soluble salt (eg, chloride, nitrate, etc.), a vapor-deposited metal layer, US Pat. Nos. 2,861,056 and
It may have a layer containing an ionic polymer as described in US Pat. No. 3,206,312 or an insoluble inorganic salt as described in US Pat. No. 3,428,451.

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

The photothermographic material of the present invention may be applied by any method. Specifically, extrusion coating, slide coating, curtain coating, dip coating, knife coating,
Various coating operations are used, including flow coating or extrusion coating using a hopper of the type described in U.S. Pat. No. 2,681,294, and are described by Stephen F. Kistl.
er, "LIQUID FILM COATING" by Peter M. Schweizer (C
Extrusion coating or slide coating described on pages 399 to 536, published by HAPMAN & HALL (1997) is preferably used, and particularly preferably slide coating is used. An example of the shape of the slide coater used for slide coating is shown in Figure 11 on page 427 of the same book.
in b.1. Also, if desired, the method described on page 399 to 536 of the same book, U.S. Pat.No. 2,761,791 and British Patent 837,0
Two or more layers can be coated simultaneously by the method described in No. 95.

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

The heat-developable photographic light-sensitive material of the present invention may be developed by any method, but is usually developed by raising the temperature of the photographic light-sensitive material exposed imagewise. A preferred development temperature is 80 to 250 ° C, more preferably 100 to 14 ° C.
0 ° C. The development time is preferably 1 to 180 seconds, and 10 to 180 seconds.
~ 90 seconds is more preferred.

The heat-developable photographic light-sensitive material of the present invention may be exposed by any method, but a laser beam is preferred as an exposure light source. As the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a semiconductor laser and a second harmonic generation element can be used.

The heat-developable photographic light-sensitive material of the present invention has a low haze upon exposure and tends to cause interference fringes. Examples of this interference fringe prevention technology include a technology for obliquely entering a laser beam into a photographic material as disclosed in JP-A-5-113548 and a multi-mode disclosed in WO95 / 31754 and the like. A method using a laser is known,
It is preferable to use these techniques.

Exposure of the heat-developable photographic material of the present invention can be performed using a laser as disclosed in SPIE vol.169 Laser Printing, pp. 116-128 (1979), JP-A-4-51043, WO95 / 31754, and the like. It is preferable that the exposure is performed so that the light overlaps so that the scanning lines are not visible.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of the heat-developable photographic material of the present invention. FIG. 1 is a side view of the heat developing machine. An endless belt 4 for conveyance suspended by a plurality of feed rollers 3 is pressed against a peripheral surface of a cylindrical heat drum 2 containing a halogen lamp 1 as a heat source of a heating means therein, and the endless belt 4 and the heat drum The heat-developable photographic material 5 is conveyed with the heat-developable photographic material 5 interposed therebetween. Photothermographic material 5 during transport
Is heated to the development temperature, and thermal development is performed. In this case, the light distribution of the lamp is optimized, and the temperature control in the width direction is performed accurately.

Near the outlet 6 from which the heat-developable photographic material 5 is sent out between the heat drum 2 and the endless belt 4, the heat-development photographic material 5 released from the curvature of the peripheral surface of the heat drum 2 is straightened. A guide plate 7 is provided. In the vicinity of the correction guide plate 7, the ambient temperature is adjusted so that the temperature of the photothermographic material 5 does not fall below a predetermined temperature.

A pair of feed rollers 8 for feeding the heat-developable photographic material 5 is provided downstream of the outlet 6, and the heat-developable photographic material 5 is maintained in a flat state adjacent to the roller pair 8 downstream thereof. A pair of flat guide plates 9 for guiding the guide rollers 9 are provided, and further downstream thereof, another pair of feed rollers 10 are provided adjacent to the flat guide plates 9. The flat guide plate 9 is long enough to cool the photothermographic material 5 while the photothermographic material 5 is being conveyed therebetween. That is, during this time, the photothermographic material 5 is cooled until the temperature thereof becomes 30 ° C. or lower. As the cooling means, a cooling fan 1
1 is installed.

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

[0262]

EXAMPLES Example 1 Hereinafter, the present invention will be described specifically with reference to Examples. Example 1 << Preparation of PET support >> Terephthalic acid and ethylene glycol
And PET having an intrinsic viscosity IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) using a conventional method. After pelletizing and drying at 130 ° C for 4 hours, 30
After being melted at 0 ° C., it was extruded from a T-die and quenched to prepare an unstretched film having a thickness of 175 μm after heat setting.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively.
After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

<< Surface Corona Treatment >> Using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, it was found that the support was treated at 0.375 kV · A · min / m ² . At this time, the processing frequency was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

<< Preparation of Undercoating Support >> (Preparation of Undercoating Coating Solution A) Polystyrene fine particles (average particle size: 0.2 μm) were added to 200 ml of a polyester copolymer water dispersion Pesresin A-515GB (30 wt%, manufactured by Takamatsu Oil & Fats Co., Ltd.). ) 1g, surfactant
20 ml of 1 (1 wt%) was added, and distilled water was added thereto to make 1000 ml, thereby obtaining an undercoat coating liquid A.

(Preparation of Undercoating Coating Solution B) Styrene-butadiene copolymer aqueous dispersion (styrene / butadiene / itaconic acid = 47/50/3 (weight ratio), concentration 30 wt%) in 680 ml of distilled water, 200 ml,
Add 0.1 g of polystyrene fine particles (average particle size 2.5 μm),
Further, distilled water was added to make 1000 ml, thereby obtaining an undercoating coating solution B.

(Preparation of Undercoating Coating Solution C) Inert Gelatin 1
0 g was dissolved in 500 ml of distilled water, and 40 g of an aqueous dispersion (40 wt%) of tin oxide-antimony oxide composite fine particles described in JP-A-61-20033 was added thereto, and distilled water was added thereto. Ten
Undercoating solution C was made up to 00 ml.

(Preparation of Undercoating Support) After the above-mentioned corona discharge treatment, the undercoating coating solution A was applied using a bar coater so that the wet coating amount was 5 ml / m ² , and dried at 180 ° C. for 5 minutes. The dry film thickness was about 0.3 μm. Then this back
After applying the corona discharge treatment to the (back side), the undercoat coating liquid
B is applied with a bar coater so that the wet coating amount is 5 ml / m ² , and the dried film thickness is about 0.3 μm, dried at 180 ° C. for 5 minutes, and further, the undercoat coating solution C is wet-coated with the bar coater. An undercoating support was prepared by applying the solution in an amount of 3 ml / m ² and a dry film thickness of about 0.03 μm and drying at 180 ° C. for 5 minutes.

<< Preparation of Organic Acid Silver Dispersion >> 43.8 g of behenic acid (product name: Edenor C22-85R) manufactured by Henkel, 730 ml of distilled water,
While stirring tert-butanol (60 ml) at 79 ° C., 1N-NaOH aqueous solution (117 ml) was added over 55 minutes and reacted for 240 minutes. Then
112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and cooled to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content of the filtrate had a conductivity of 30 μS / cm.
And washed with water. The solid content thus obtained is handled as a wet cake without drying, and
To 100 g of the wet cake, 7.4 g of polyvinyl alcohol (trade name: PVA-205) and water were added to make the total amount 385 g, and the mixture was predispersed with a homomixer.

Next, the predispersed undiluted solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² and the mixture was treated three times to obtain a silver behenate dispersion B. The silver behenate particles contained in the silver behenate dispersion thus obtained were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%. For particle size measurement, use MasterSizerX manufactured by Malvern Instruments Ltd.
I went in. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature.

<< Preparation of 25 wt% Dispersion of Reducing Agent >> 1,1-bis
(2-Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 80 g and Kuraray Co., Ltd. did. 800 g of zirconia beads having an average diameter of 0.5 mm were prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 5 hours to obtain a reducing agent dispersion.
The reducing agent particles contained in the reducing agent dispersion thus obtained had an average particle size of 0.72 μm.

<< Preparation of 20 wt% Dispersion of Mercapto Compound >> 32 g of a 20 wt% aqueous solution of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole 64 g and modified polyvinyl alcohol poval MP203 manufactured by Kuraray Co., Ltd. 224 g of water was added thereto and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm were prepared, placed in a vessel together with the slurry, and dispersed with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 10 hours to obtain a dispersion. The mercapto compound particles contained in the thus obtained dispersion of the mercapto compound had an average particle size of 0.67 μm.

<< Preparation of 30 wt% dispersion of organic polyhalogen compound >> 48 g of tribromomethylphenylsulfone and 3-tribromomethylsulfonyl-4-phenyl-5-tridecyl-
224 g of water was added to 48 g of 1,2,4-triazole and 48 g of a 20 wt% aqueous solution of modified polyvinyl alcohol poval MP203 manufactured by Kuraray Co., Ltd., and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm are prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 5 hours to obtain an organic polyhalogen compound dispersion. Was. The polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had an average particle size of 0.74 μm.

<< Preparation of Methanol Solution of Compound of the Present Invention Represented by Formula (II) or Comparative Compound >> Compound of the Present Invention Represented by Formula (II) or Comparative Compound 15
0 mmol was dissolved in 100 ml of methanol and used.

<< Preparation of 20 wt% dispersion of pigment >> CI Pigmen
t 64 g of Blue 60 and 6.4 g of Demol N manufactured by Kao Corporation, 250 g of water
Was added and mixed well to obtain a slurry. Average diameter 0.5mm
Of zirconia beads was placed in a vessel together with the slurry, and dispersed by a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 25 hours to obtain a pigment dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

<< Preparation of Silver Halide Grain 1 >> Distilled water 1421c
Add 1wt% potassium bromide solution 6.7cc to c and add 1N nitric acid
While stirring the liquid containing 8.2 cc and 21.8 g of phthalated gelatin in a titanium-coated stainless steel reaction vessel, the liquid temperature was maintained at 35 ° C, and a solution obtained by adding distilled water to 37.04 g of silver nitrate to 159 cc and diluting the solution a1 with odor was added. A solution b1 prepared by diluting 32.6 g of potassium iodide to a volume of 200 cc with distilled water was prepared, and the entire amount of the solution a1 was added over 1 minute at a constant flow rate while maintaining the pAg at 8.1 by the control double jet method. (Solution b1 was added by the controlled double jet method.) Then, 30 cc of a 3.5 wt% aqueous hydrogen peroxide solution was added, and 3 wt% of benzimidazole was further added.
36 cc of a 30% aqueous solution was added. Then, the solution a1 was again diluted with distilled water to 317.5 cc, and the solution b1 was dissolved with dipotassium hexachloride iridium acid so that the final concentration was 1 × 10 ^-4 mol per mol of silver with respect to the solution b1. Using a solution b2 diluted with distilled water to 400 cc twice the amount of the solution b1, again by the controlled double jet method, while maintaining the pAg at 8.1, the entire amount of the solution a2 was added at a constant flow rate over 10 minutes. . (Solution b2
Is added by the controlled double jet method)
50cc of a 0.5 wt% methanol solution of mercapto-5-methylbenzimidazole was added, the pAg was further increased to 7.5 with silver nitrate, the pH was adjusted to 3.8 with 1N sulfuric acid, and stirring was stopped.
A precipitation / desalting / washing step was performed, 3.5 g of deionized gelatin was added, and 1N sodium hydroxide was added to adjust to pH 6.0 and pAg 8.2 to prepare a silver halide dispersion.

The grains in the completed silver halide emulsion are pure silver bromide grains having an average sphere equivalent diameter of 0.031 μm and a variation coefficient of the equivalent sphere diameter of 11%. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The {100} plane ratio of these particles was determined to be 85% using the Kubelka-Munk method.

The above emulsion was heated to 50 ° C. while stirring, and N,
5 ml of a 0.5 wt% methanol solution of N'-dihydroxy-N '', N ''-diethylmelamine and 5 cc of a 3.5 wt% methanol solution of phenoxyethanol were added, and after 1 minute, sodium benzenethiosulfonate was added to 1 mol of silver. 3 × 10 ^-5 mol was added. After 2 minutes, a solid dispersion of the spectral sensitizing dye 1 (aqueous gelatin solution) was added at 5 × 10 ⁻³ mol per mol of silver, and after 2 minutes, the tellurium compound was added at 5 × 10 ⁻⁵ mol per mol of silver. Aged for 50 minutes. Immediately before the completion of the ripening, the temperature was lowered by adding 1 × 10 ⁻³ mol of 2-mercapto-5-methylbenzimidazole per 1 mol of silver, and the chemical sensitization was terminated to prepare silver halide grains 1.

<< Preparation of silver halide grains 2 >> After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water, adjusting the pH to 5.0 at a temperature of 35 ° C., containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate An aqueous solution containing 159 ml of an aqueous solution and a 92: 8 molar ratio of potassium bromide and potassium iodide was pA
While maintaining the g at 7.7, it was added over 10 minutes by the control double jet method. Then, 1 ml in 476 ml and 1 liter of an aqueous solution containing 55.4 g of silver nitrate and 2 g of ammonium nitrate
An aqueous solution containing × 10 ⁻⁵ mol of dipotassium hexachloride iridate and 1 mol of potassium bromide was added over 30 minutes by a control double jet method while maintaining the pAg at 7.7.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (1 g) was added, and the pH was further lowered to cause coagulation and sedimentation for desalination. After that, 0.1 g of phenoxyethanol was added, and pH 5.
9, adjusted to pAg8.2 silver iodobromide grains (iodine content core 8 mol%,
Average 2 mol%, average size 0.05 μm, projection area variation coefficient 8
%, Cubic particles having a {100} face ratio of 88%).

The silver halide grains thus obtained were heated to 60 ° C., and 85 μmol of sodium thiosulfate and 2,2
1.1 × 10 ⁻⁵ mol of 3,4,5,6-pentafluorophenyldiphenylphosphine selenide, 1.5 × 10 ⁻⁵ mol of tellurium compound, 3.5 × 10 ⁻⁸ mol of chloroauric acid, 2.7 × 10 ^{− Four}
After aging for 120 minutes, the mixture was rapidly cooled to 40 ° C., and 1 × 10 ^-4 mol of spectral sensitizing dye 1 and 5 × 10 ^-4 mol of 2-mercapto-5-methylbenzimidazole were added. The mixture was rapidly cooled to ° C. to obtain a silver halide emulsion 2.

<< Preparation of Emulsion Layer Coating Solution >> (Emulsion Layer Coating Solution) 103 g of the organic acid silver dispersion obtained above and 5 g of a 20 wt% aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.)
Into a mixture maintained at 40 ° C., and the above 25 wt% reducing agent dispersion 23.
2 g, 20 wt% aqueous dispersion of pigment CI Pigment Blue 60
g, an organic polyhalogen compound 30 wt% dispersion 10.7 g, and a mercapto compound 20 wt% dispersion 3.1 g were added. Then 40 ° C
Ultrafiltration (UF) purified SBR latex 40 wt%
After adding 106 g and stirring sufficiently, the compound of the general formula (I
6 ml of a methanol solution of the compound represented by I) or the compound for comparison was added to obtain a liquid containing silver organic acid. Also, 5 g of silver halide grains 1 and 5 g of silver halide grains 2 are mixed well in advance and mixed with a solution containing an organic acid silver with a static mixer immediately before coating to prepare an emulsion layer coating solution, and the silver coating is directly applied to a coating die. The solution was fed so that the amount became 1.4 g / m ² .

The viscosity of the above emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki Co., Ltd., and was 85 mPa · s at 40 ° C. (No. 1 rotor).
s]. The viscosity of the coating solution at 25 ° C. using an RFS Fluid Spectrometer manufactured by Rheometrics Far East Co., Ltd. was determined at a shear rate of 0.1, 1, 10, 100, 1000 [1 /
Sec] were 1500, 220, 70, 40, and 20 [mPa · s], respectively.

The UF-purified SBR latex was obtained as follows. The following SBR latex was diluted 10 times with distilled water to obtain a UF-purification module, FS03-FC-FUY03
The product was diluted and purified using A1 (Daisen Membrane System Co., Ltd.) until the ionic conductivity became 1.5 mS / cm. At this time, the latex concentration was 40% by weight.

(SBR latex: -St (68) -Bu (29) -AA (3)-
(Latex) Average particle size 0.1μm, equilibrium water content at 25 ° C and 60% RH 0.6wt%, concentration 45wt%, ionic conductivity 4.2mS / cm (Ion conductivity is measured by Toa Denpa Kogyo Co., Ltd. Latex stock solution (40wt%) measured at 25 ° C using CM-30S), pH 8.2

<< Preparation of Emulsion Surface Intermediate Layer Coating Solution >> (Intermediate Layer Coating Solution) Polyvinyl alcohol PVA-205 (Kuraray)
772 g of a 10 wt% aqueous solution of methyl methacrylate / styrene / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 59
/ 9/26/5/1) Aerosol OT in 27.5wt% latex liquid 226g
2 ml of a 5 wt% aqueous solution (manufactured by American Cyanamid Co., Ltd.), 4 g of benzyl alcohol, 1 g of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 10 mg of benzoisothiazolinone were added to the intermediate layer. The solution was fed to a coating die at 5 ml / m ² . The viscosity of the coating solution was 21 mPa · s at 40 ° C. (No. 1 rotor) using a B-type viscometer.

<< Preparation of Emulsion Surface Protective Layer First Layer Coating Solution >> (Protective Layer First Layer Coating Solution) 80 g of inert gelatin was dissolved in water, and the compound represented by formula (I) of the present invention or a compound for comparison was prepared. 138 ml of a 10 wt% methanol solution of the compound, 28 of 1N sulfuric acid
ml, 5w of Aerosol OT (American Cyanamid)
5% aqueous solution of t%, 1 g of phenoxyethanol were added, and the total amount was 1
000 g of water to make the protective layer first layer coating solution,
The solution was fed to the coating die so as to be 10 ml / m ² . The viscosity of the coating solution was 17 mPa with a B-type viscometer at 40 ° C (No. 1 rotor).
[S].

<< Preparation of Emulsion Surface Protective Layer Second Layer Coating Solution >> (Protective Layer Second Layer Coating Solution) Inert gelatin (100 g) was dissolved in water, and N-perfluorooctylsulfonyl-N-propylalanine potassium salt was 5 wt%. 20 ml of solution, aerosol
16 ml of a 5 wt% solution of OT (manufactured by American Cyanamid Co., Ltd.), polymethyl methacrylate fine particles (average particle size 4.0 μm) 25
g, 44 ml of 1N sulfuric acid, 10 mg of benzoisothiazolinone and water to a total amount of 1555 g, 4 wt% of chromium alum and 0.67 wt% of the compound represented by the general formula (I) of the present invention or A mixture of 445 ml of an aqueous solution containing a compound for use with a static mixer immediately before coating was applied to the protective layer 2
The solution was supplied to a coating die so as to be 10 ml / m ² . The viscosity of the coating solution was 9 [mPa · s] with a B-type viscometer at 40 ° C. (No. 1 rotor).

<< Preparation of Back Surface Coating Solution >> (Preparation of Solid Precursor Dispersion of Base Precursor) 64 g of a base precursor compound and 10 g of a surfactant Demol N manufactured by Kao Corporation were mixed with 246 ml of distilled water, and the mixed solution was mixed. Beads are dispersed using a sand mill (1/4 Gallon sand grinder mill, manufactured by AIMEX Co., Ltd.), and the average particle diameter is 0.2 μm.
The solid precursor dispersion liquid of the base precursor was obtained.

(Preparation of Dye Solid Fine Particle Dispersion) 9.6 g of a cyanine dye compound and 5.8 g of sodium p-alkylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixed solution was subjected to a sand mill (1/4 Gallon sand grinder mill, Amimex Co., Ltd.). )) To disperse the beads to obtain an average particle diameter of 0.
A dye solid fine particle dispersion of 2 μm was obtained.

(Preparation of anti-halation layer coating solution) Gelatin 17 g, polyacrylamide 9.6 g, solid fine particle dispersion of the above base precursor 70 g, solid fine particle dispersion of the above dye 56 g, polymethyl methacrylate fine particles (average particle size 6.5 μm) 1.5 g, 2.2 g of sodium polyethylene sulfonate, 0.2 g of a 1% by weight aqueous solution of a coloring dye compound, 844 H ₂ O
The mixture was mixed to prepare an antihalation layer coating solution.

(Preparation of Coating Solution for Protective Layer) The container was kept warm at 40 ° C., and 50 g of gelatin and sodium polystyrene sulfonate were prepared.
0.2 g, N, N'-ethylenebis (vinylsulfoneacetamide) 2.4 g, t-octylphenoxyethoxyethaneethanesulfonate 1 g, benzoisothiazolinone 30 mg,
32 mg of C ₈ F ₁₇ SO ₃ K, C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -S
64 mg of O ₃ Na and 950 ml of H ₂ O were mixed to prepare a coating solution for a protective layer.

[0292]

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<< Preparation of heat-developable photographic light-sensitive material >> On the undercoated support, the coating amount of the antihalation layer was 0.04 g / m ² , and the coating amount of the protective layer was gelatin. Is 1 g / m ² at the same time, and dried to form an antihalation back layer, and then the emulsion layer, intermediate layer, protective layer first layer, and protective layer Coating was performed simultaneously in two layers by slide bead coating to prepare a sample of heat-developable photographic light-sensitive material (sensitive material sample) (Table 1). The emulsion surface was applied without winding after coating the back surface.

The coating was performed at a speed of 160 m / min, the distance between the tip of the coating die and the support was set to 0.18 mm, and the pressure in the decompression chamber was set 392 Pa lower than the atmospheric pressure. In the subsequent chilling zone, the dry bulb temperature is 18 ° C and the wet bulb temperature is 12 ° C
After blowing the wind at an average wind speed of 7 m / sec for 30 seconds to cool the coating solution,
A dry air having a dry-bulb temperature of 30 ° C. and a wet-bulb temperature of 18 ° C. was blown out of the hole at an air velocity of 20 m / sec for 200 seconds to volatilize the solvent in the coating solution. Table 1 shows the results of the following evaluations performed on each photosensitive material sample.

(Evaluation of photographic performance) 647 nm Kr laser sensitometer
After exposing the photographic material at an inclination of 30 degrees to the normal line (maximum output 500 mW), process the photographic material at 120 ° C for 15 seconds
(Development), and the obtained image was evaluated using a densitometer.
The measurement results were evaluated in terms of Dmin (fog) and sensitivity (the reciprocal of the ratio of the amount of exposure that gives a density higher than Dmin by 1.0). The sensitivity of the photographic light-sensitive material 1-3 was set to 100.

(Evaluation of Color Tone) The image color tone of the area having the density of 1 was visually evaluated based on the following criteria.・ ・ ・: Cool black tone.・ ・ ・: Slightly warm, but not bothersome. Δ: Warm, but practically acceptable. ×: Not very warm and not possible.

(Evaluation of forced storage stability) Each photographic light-sensitive material was cut into a size of 30.5 cm × 25.4 cm, and a round corner having an inner diameter of 0.5 cm was left for 1 day at 25 ° C. and 50% RH. Ten pieces of each photosensitive material were sealed in a bag made of a moisture-proof material, placed in a 35.1 cm × 26.9 cm × 3.0 cm dressing box, and aged at 50 ° C. for 5 days (forced aging). The same processing as in the evaluation of photographic performance was performed on this sample and a sample prepared in the same manner as in forced aging except that the storage temperature was 4 ° C. for comparison, and the density of the fog portion was measured. The storage stability over time was evaluated as a fog increase rate.

(Fog increase rate) = [((fog of forced-aged sample) − (fog of comparative sample)) / {(highest concentration of comparative sample) − (concentration of support)} × 100 Low fog increase rate The longer the storage stability with time, the better. The fog values are shown in the table.

(Evaluation of Light-Irradiated Image Storage Property) A photographic photosensitive material exposed and developed in the same manner as in the evaluation of photographic performance was stuck inside a glass window exposed to direct sunlight, and allowed to stand for one month. evaluated. A: There is almost no change.・ ・ ・: There is a slight change in color tone, but it does not matter. Δ: Discoloration in the image area is observed, but practically acceptable. ×: Dmin discolored and density could not be increased. (Evaluation of Storage Property of Dark Thermal Image) A photographic photosensitive material exposed and developed in the same manner as in the evaluation of photographic properties was allowed to stand at 40 ° C. for 1 month under light-shielded conditions, and the appearance of images was visually evaluated according to the following criteria. A: There is almost no change.・ ・ ・: There is a slight change in color tone, but it does not matter. Δ: Discoloration in the image area is observed, but practically acceptable. ×: Dmin discolored and density could not be increased.

[0300]

[Table 1]

Table 1 shows the following. The heat-developable photographic material of Sample No. 1-1 which does not contain the compound of the present invention has low sensitivity and remarkably poor light-irradiation image storage property and dark heat image storage property. Sample Nos. 1-2 and 1 containing compounds outside the scope of the present invention
The light-sensitive material of No. -4 has significantly larger fog, especially after forced storage over time, as compared with the samples of the present invention of 1-3 and 1-5, and is difficult to provide as a commercial product. The general formulas (I) and (I) of the present invention
Comparative compound C-2, instead of the compound represented by I),
The light-sensitive material of Sample No. 1-13 using C-3 is deteriorated in any respects. Further, the light-sensitive material of Sample No. 1-14 in which the compound represented by the general formula (II) of the present invention was not used,
The sensitivity is extremely low. On the other hand, all the samples within the scope of the present invention have high sensitivity, have less fog before and after image formation, and have greatly improved image storability as compared with the sample of the comparative example. Further, the samples of the present invention have good image color tone. From the above results, the effect of the present invention is clear.

Example 2 (Preparation of silver halide grains A) 11 g of phthalated gelatin, 30 mg of potassium bromide and 10 mg of sodium benzenethiosulfonate were dissolved in 650 ml of water, and the pH was adjusted to 5.0 at a temperature of 55 ° C. Then, while maintaining 159 ml of an aqueous solution containing 18.6 g of silver nitrate and an aqueous solution of potassium bromide at a pAg of 7.7, a controlled double jet method was carried out for 6 minutes and 30 minutes.
The addition was made over a second period. Then, while maintaining 476 ml of an aqueous solution containing 55.5 g of silver nitrate and an aqueous solution of potassium bromide at a pAg of 7.7, a controlled double jet method was used for 28 minutes 3
Added over 0 seconds. Thereafter, the pH was lowered to cause coagulation and sedimentation, followed by desalting treatment. 0.17 g of Compound A and 23.7 g of deionized gelatin (calculated from 20 ppm or less) were obtained.
Was adjusted to pH 5.9 and pAg 8.0.

The particles obtained had an average particle size of 0.11 μm.
m (projected area diameter), variation coefficient of projected area diameter 8%,
Cubic particles having a (100) face ratio of 93%.

To the particles thus obtained, the temperature was raised to 60 ° C., and 76 μmol of sodium benzenethiosulfonate per 1 mol of silver was added. After 3 minutes, 154 μmol of sodium thiosulfate was added. And aged for 100 minutes.

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

[0306]

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(Preparation of Organic Acid Silver Dispersion) 85 g of arachidic acid, 39.4 g of behenic acid, and 770 ml of distilled water were added to 85 parts of the mixture.
While stirring at a temperature of 103 ° C., 103 ml of a 1N aqueous NaOH solution
It was added over 0 minutes and reacted for 240 minutes, and the temperature was lowered to 75 ° C. Next, 112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, and the mixture was allowed to stand for 20 minutes.
The temperature dropped. Thereafter, the solid content was separated by absorption filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm.

The solid content thus obtained was handled as a wet cake without drying, and 100 g of dry solid content was obtained.
To a considerable amount of the wet cake, 10 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; PVA-205) and water were added to make the total amount 500 g, and the mixture was predispersed with a homomixer.

Next, the predispersed undiluted solution is dispersed in a dispersing machine (trade name: Microfluidizer M-11OS-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² , and the mixture was treated three times to complete the preparation of an organic acid silver microcrystal dispersion having a volume-weighted average diameter of 0.93 μm. For particle size measurement, use the Malvern Instrume
Performed with Master SizerX manufactured by nts Ltd. The cooling operation was performed by installing a coiled heat exchanger before and after the interaction chamber and adjusting the temperature of the refrigerant to a desired dispersion temperature.

(1,1-bis (2-hydroxy-3,5)
Preparation of solid fine particle dispersion of -dimethylphenyl) -3,5,5-trimethylhexane) 20 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 3.0 g of MP203 (manufactured by Kuraray Co., Ltd.) and 77 ml of water were added, and the mixture was stirred well and left as a slurry for 3 hours. Then 0.5
360 g of zirconia beads having a diameter of 0.3 mm were prepared, put into a vessel together with the slurry, and dispersed for 3 hours with a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) to prepare a dispersion of solid fine particles of a reducing agent. . As for the particle size, 80% by weight of the particles were in the range of 0.3 μm to 1.0 μm.

(Preparation of solid fine particle dispersion of tribromomethylphenylsulfone) To 30 g of tribromomethylphenylsulfone were added 0.5 g of hydroxypropylmethylcellulose, 0.5 g of compound C and 88.5 g of water, and the mixture was stirred well. The slurry was left for 3 hours. afterwards,
A solid fine particle dispersion of an antifoggant was prepared in the same manner as in the preparation of the reducing agent solid dispersion. Particle size is 80wt% 0.3
It was not less than μm and not more than 1.0 μm.

(Preparation of Emulsion Layer Coating Solution) The following binder, material and silver halide particles A were added to 1 mol of silver of the previously prepared organic acid silver microcrystal dispersion, and water was added. An emulsion layer coating solution was obtained. Binder; Luckstar 3307B 470 g as solid content (manufactured by Dainippon Ink and Chemicals, Inc .; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5 1,5-trimethylhexane 110 g as solid content Tribromomethylphenylsulfone 25 g as solid content Sodium benzenethiosulfonate 0.25 g polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) 46 g Compound of formula (II) or compound for comparison 12 mol 2- [2,4-bis- (1,1-dimethylpropyl) -phenoxy] -N- [4- (4-hydroxymethylene-3,5-dioxopyrazolidin-1-yl) phenyl] acetamide Sodium salt (Na salt of C-61) 1.85 g Dye A 0.62 g Silver halide grains A 0.05 mol as Ag amount

[0313]

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(Preparation of PET Support with Back / Undercoat Layer) (1) Support Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 (phenol / tetrachloride) according to a conventional method. PET (measured at 25 ° C. in ethane = 6/4 (weight ratio)). This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled.
An unstretched film having a thickness of 120 μm after heat setting was prepared.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. 3. After slitting the chuck portion of the tenter, knurling is performed on both ends.
The film was wound at 8 kg / cm ² . In this way, the width 2.4 m,
A roll having a length of 3500 m and a thickness of 120 μm was obtained.

(2) Undercoat Layer / Undercoat Layer (a) Polymer Latex-1 Styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (% by weight) 160 mg / m ² 2, 4-dichloro-6-hydroxy-s-triazine 4 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 3 mg / m ²・ Undercoat layer (b) Alkali-treated gelatin (Ca ²⁺ content 30 ppm, jelly strength 230 g) ) 50 mg / m ² Dye A Coating amount at which the optical density of 780 nm becomes 0.7

(3) Conductive layer Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 38 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle diameter 0.25 μm) 120 mg / m ² matting agent ( Polymethyl methacrylate, average particle size 5 μm) 7 mg / m ² melamine 13 mg / m ²

(4) Protective Layer Chemipearl S-120 (manufactured by Mitsui Petrochemical Co., Ltd.) 500 mg / m ² Snowtex-C (manufactured by Nissan Chemical Co., Ltd.) 40 mg / m ² Denacol EX-614B (Nagase Chemical Industries, Ltd.) 30mg / m ²

An undercoat layer (a) and an undercoat layer (b) were sequentially applied to both sides of the support, and each was dried at 180 ° C. for 4 minutes. Next, a conductive layer and a protective layer are sequentially applied to one surface on which the undercoat layer (a) and the undercoat layer (b) are applied, and dried at 180 ° C. for 4 minutes, respectively, and PET with a back layer / undercoat layer is provided. A support was made.

The PET support provided with the back / undercoat layer prepared as described above was set at 160 ° C. for a total length of 30 m.
, Heat treatment zone, tension 14g / cm ² , transfer speed 20m
/ Min. Afterwards, 15
The film was wound for 10 seconds at a winding tension of 10 kg / cm ² .

(Preparation of Coating Solution for Emulsion Surface Protective Layer) Solid Content 2
7.5 wt% polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-
Hydroxyethyl methacrylate / acrylic acid = 59 /
(9/26/5/1 copolymer with a glass transition temperature of 55 ° C)
To 109 g, 3.75 g of H ₂ O was added, and as a film-forming auxiliary, 4.5 g of benzyl alcohol, 0.45 g of compound D, 0.125 g of compound E, a compound of the general formula (I) of the present invention shown in Table 2 or a compound for comparison 0.0125 mol and polyvinyl alcohol (Kuraray Co., Ltd., PVA-
217) 0.225 g was added, and further H ₂ O was added to add 1
50 g, which was used as a coating solution.

[0322]

Embedded image

[0323] applied to a coated silver amount of the emulsion layer coating solution on the undercoat layer (photothermographic creation of the photosensitive material) the back / subbing layers marked with PET support is 1.6 g / m ² did. Further, the emulsion surface protective layer coating solution was applied thereon so that the coating amount of the solid content of the polymer latex was 2.0 g / m ² , thereby preparing Samples 2-1 to 2-12 of the photothermographic materials.

(Evaluation of photographic performance) The obtained photothermographic material was exposed to xenon flash light having a light emission time of 10 ^-6 seconds through an interference filter having a peak at 780 nm and a step wedge. 115 in developing machine
Developed at 15 ° C for 15 seconds.
Performed by TD904 (visible density).

In the drum type heat developing machine shown in FIG. 1, the light distribution of the lamp was optimized and the temperature accuracy in the width direction was set at ± 1 ° C. The ambient temperature was adjusted so that the temperature of the photothermographic material near the correction guide plate 7 did not fall below 90 ° C.

The measurement results were evaluated in the same manner as in Example-1. The sensitivity was expressed as a relative sensitivity, taking the sensitivity of the photothermographic material 2-3 as 100. Table 2 shows the obtained results.

[0327]

[Table 2]

[0328]

Embedded image

From Table 2, it is clear that the present invention is also effective for photothermographic materials containing a high contrast agent.

[0330]

According to the present invention, an excellent heat-developable photographic light-sensitive material which can form a high-quality image having a cool black tone, and has good storability and handleability before and after the image formation is obtained.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration example of a heat developing machine used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 halogen lamp 2 heat drum 3 feed roller 4 endless belt 5 photothermographic material 6 outlet 7 guide plate 8 feed roller pair 9 flat guide plate 10 feed roller pair 11 cooling fan

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 22, 1998 (1998.10.
22)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image [In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent substituent. However, all of R ₁ , R ₂ , R ₃ and R ₄ are not hydrogen atoms. L ₁ and L ₂ each represent a linking group. n ₁ and n ₂ each represent an integer of 0 or more and 30 or less. However, _{n 1} and _{n 2} are not both of them are 0. ]

Embedded image [In the general formula (II), Q represents an atomic group necessary for forming a phthalazine ring. V represents a monovalent substituent. n ₃ 0
It represents an integer of 6 or more and 6 or less. ]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

[0012]

This object has been achieved by the following means. (1) An organic silver salt, a reducing agent, at least one compound represented by the following general formula (I) or at least one salt thereof, and at least one compound represented by the following general formula (II) are provided on a support. Heat-developable photographic material.

[Procedure amendment 3]

[Document name to be amended] Abstract

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Abstract

【wrap up】

PROBLEM TO BE SOLVED: To provide a heat-developable photographic material which is excellent in storability before and after image formation and which gives a high-quality, dark-black image.

SOLUTION: An organic silver salt, a reducing agent, at least one compound represented by the following general formula (I) or at least one salt thereof, and at least one compound represented by the general formula (II) are provided on a support. A heat-developable photographic material.

Embedded image [In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent substituent. However, all of R ₁ , R ₂ , R ₃ and R ₄ are not hydrogen atoms. L ₁ and L ₂ each represent a linking group. n ₁ and n ₂ each represent an integer of 0 or more and 30 or less. However, _{n 1} and _{n 2} are not both of them are 0. In the general formula (II), Q represents an atom group necessary for forming a phthalazine ring. V represents a monovalent substituent. n ₃
Represents an integer of 0 or more and 6 or less. ]

[Selection diagram] None

Claims (3)

[Claims] An organic silver salt, a reducing agent, at least one compound represented by the following general formula (I), and at least one compound represented by the following general formula (II) are provided on a support. Heat-developable photographic material. Embedded image [In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent substituent. Where R ₁ ,
R ₂ , R ₃ and R ₄ are not all hydrogen atoms. L ₁
And L ₂ each represent a linking group. n ₁ and n ₂ each represent an integer of 0 or more and 30 or less. Where n ₁ and n
₂ is never 0. ] [In the general formula (II), Q represents an atomic group necessary for forming a phthalazine ring. V represents a monovalent substituent. n ₃ represents an integer of 0 or more and 6 or less. ] 2. The photothermographic material according to claim 1, further comprising a photosensitive silver halide. 3. The photothermographic material according to claim 1, wherein n ₃ is 1 or more and 6 or less in the compound represented by the general formula (II).