JP2000194090A - Production of heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a photosensitive material having low fog and excellent aging stability of the coating liquid for emulsion layers by incorporating a specified compd. as a water dispersion into the coating liquid in the production method of a material having a specified antifog agent or the like. SOLUTION: When a photosensitive material containing an antifog agent or the like expressed by formula I is formed on one surface of a supporting body, at least one kind of compd. selected from compds. expressed by formulae II, III, IV or the like is incorporated. The selected compd. is added as a water dispersion to the coating liquid. In formula I, M is a hydrogen atom or k-valent cation, R is a substituent, n is an integer 1 to 4 and when n>=2, plural Rs may be same or different, k is an integer >=1, and when M is a hydrogen atom, k is 1. In formula II, each of R1, R2 and R3 is independently a hydrogen atom or substituent, and Z is an electron withdrawing group. In formula III, R4 is a substituent. In formula IV, each of X and Y is independently a hydrogen atom or substituent, and each of A and B is an alkoxy group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photothermographic material, and more particularly, to fog (Dmi).
The present invention relates to a method for producing a heat-developable ultra-high contrast photosensitive material having a very small value of n) and suitable for printing plate making.

[0002]

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

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

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

Fog is a major problem in photothermographic materials. Many studies have been made to reduce fog of silver halide photosensitive materials for thermography. For example, US Pat.
No. 3 discloses a mercury salt. In addition, US415216
No. 0 includes carboxylic acids such as benzene acid and phthalic acid, US4
No. 784939 discloses a benzoylbenzene acid compound, US Pat.
No. indane or tetralin carboxylic acid, US482061
No. 7 discloses a dicarboxylic acid, and US Pat. No. 4,626,500 discloses a heteroaromatic carboxylic acid. US4546075, US4756999
Nos. 4,445,885, 3,874,946 and 3,955,982 disclose halogenated compounds. US5028523 discloses halogen atoms or halogen atoms combined with heteroatom rings. US4103312 and GB1502670 palladium compounds, US4128428 US iron metals, US4
123374, US4129557 and US4125430 include substituted triazoles, US4213784, US4245033 and JP
-26019 to sulfur compounds, US4002479 to thiouracils, JP-A-50-123331 to sulfinic acid, US4125403
No. 4,415,160, US Pat. No. 4,307,187, a metal salt of thiosulfonic acid, JP-A-53-20923 and JP-A-53-19825 describe a combination of a metal salt of thiosulfonic acid and sulfinic acid,
-50810, JP-A-7-209797 and JP-A-9-43760 disclose thiosulfonic acid esters. Also,
JP-A-51-42529 and JP-B-63-37368 disclose disulfide compounds.

However, these compounds do not have sufficient fog-preventing ability, or if they are added in large amounts, Dmax
However, there is a drawback that the (highest density) decreases and the image storage stability after processing deteriorates, and a new antifoggant has been desired.

Further, Japanese Patent Application Laid-Open Nos.
-207244, 60-207140, US29
10377, U.S. Pat. No. 3,074,809, JP-A-2-25
No. 1838 discloses salicylic acid or a derivative thereof, but does not disclose any effect in a super-hard dry silver system.

Conventionally, photothermographic materials of this type have been known, but most of these materials are exposed to light by applying a coating solution using an organic solvent such as toluene, methyl ethyl ketone (MEK) or methanol as a solvent. The active layer is formed.

There has also been proposed a method of forming a photosensitive layer (hereinafter also referred to as "aqueous photosensitive layer") using a coating solution of an aqueous solvent. For example, JP-A-49-52626, JP-A-53-1
No. 16144 describes an example using gelatin as a binder. JP-A-50-151138 discloses an example in which polyvinyl alcohol is used as a binder. Further, JP-A-60-61747 describes an example in which gelatin and polyvinyl alcohol are used in combination. As another example, JP-A-58-28737 describes an example of a photosensitive layer using water-soluble polyvinyl acetal as a binder.

[0010] European Patent 762,196, JP-A-9-90550 and the like disclose photosensitive silver halide grains used in heat-developable image recording materials with metal ions or metal complexes of Group VII or VIII (Groups 7 to 10). It discloses that ions can be contained and that a hydrazine derivative can be contained in a photosensitive material to obtain high-contrast photographic characteristics.

As described above, it is known that the use of a hydrazine derivative in a photothermographic material can provide high contrast and high Dmax performance suitable for photolithography. There has been a problem that fogging increases and softens as time passes.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming apparatus which has an extremely small fog (Dmin),
In particular, it is an object of the present invention to provide a method for producing a photothermographic material having excellent stability over time in an emulsion layer coating solution, especially a photothermographic material having a super-high contrast.

[0013]

The above object has been achieved by the following means. (1) On at least one surface of the support, (a) a photosensitive silver halide, (b) a reducible silver salt, (c) a reducing agent, (d) a binder, and (e) a formula (1) A method for producing a photothermographic material having an antifoggant represented by formula (A1), formula (A2), formula (A3), or a compound represented by formula (H) Wherein the compound is added as a water dispersion to the coating solution when the compound is contained.

[0014]

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[In the formula (1), M represents a hydrogen atom or a k-valent cation, and R represents a substituent. n is 1 to 4
When n ≧ 2, a plurality of Rs may be the same or different. k is an integer of 1 or more, and when M is a hydrogen atom, k = 1. ]

[0016]

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[0017]

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[0018]

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[In the formula (A1), R ¹ , R ² and R ³
Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A1), R ¹ and Z, R ²
And R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. In the formula (A2), R ⁴ represents a substituent. In the formula (A3), X and Y each independently represent a hydrogen atom or a substituent,
A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the formula (A3), X and Y and A and B may be bonded to each other to form a cyclic structure. ]

[0020]

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[In the formula (H), R ²⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a block group, and G ¹ represents —CO—, —COCO—,
-C (= S) -, - SO 2 -, - SO -, - PO (R 30)
- group (. R ³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10), or an iminomethylene group. A ¹ and A ² each represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, and at least one of A ¹ and A ² is a hydrogen atom. m ¹ is 0 or 1, and when m ¹ is 0,
R ¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group. (2) at least one compound selected from the compounds represented by the formulas (A1), (A2) and (A3);
And a method for producing a photothermographic material, wherein both of at least one compound represented by formula (H) are added to a coating solution as an aqueous dispersion. (3) At least one compound selected from the compounds represented by Formula (A1), Formula (A2), Formula (A3), and Formula (H) is contained in an aqueous dispersion in a solid fine particle dispersed state. The method for producing a photothermographic material according to the above (1) or (2). (4) at least one compound selected from compounds represented by formula (A1), formula (A2), and formula (A3);
In addition, the method for producing a photothermographic material according to any one of the above (1) to (3), wherein both the at least one compound represented by the formula (H) is contained in the aqueous dispersion in the form of solid fine particles dispersed therein. (5) An image forming layer containing a photosensitive silver halide, wherein a polymer latex is used as 50% by weight or more of a binder of the image forming layer, and 60% by weight of a solvent
The method for producing a photothermographic material according to any one of the above (1) to (4), wherein the image forming layer is formed by applying a coating solution comprising water as described above.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the photothermographic material contains the antifoggant represented by the formula (1), and comprises the formulas (A1), (A2),
(A3) A coating solution containing a compound represented by (H), but containing a compound represented by formula (A1), (A2), (A3) or (H) as an aqueous dispersion. Therefore, even if the coating solution that has been aged is used, heat fogging in the non-image area can be suppressed, and high contrast can be maintained. Therefore, the photothermographic material obtained by the present invention is a heat-developable ultra-high contrast photothermographic material having extremely small fog (Dmin) and suitable for printing plate making having a low Dmin.

In particular, it has an image forming layer (emulsion layer) containing a photosensitive silver halide, a polymer latex is used as 50% by weight or more of the binder of the image forming layer, and 60% by weight or more of the solvent is water. The effect is great when the image forming layer is formed by a certain aqueous coating. Particularly, such an image forming layer coating solution is applied to the formulas (A1) to (A3) and the formula (H).
This is effective when a compound represented by the following formula is added. First,
Formula (1) used in the present invention will be described in detail. Equation (1) is shown below.

[0024]

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In the formula (1), M is a hydrogen atom or k
It represents a valent cation (eg, a metal ion such as a sodium ion, a potassium ion, a calcium ion, a barium ion, and a zinc ion, and an ammonium ion such as a tetramethylammonium ion and a tetrabutylammonium ion). k is an integer of 1 or more as shown by the exemplified ion, and is usually 1 or 2. When M is a hydrogen atom, k = 1.

In the formula (1), R represents a substituent,
For example, a linear, branched or cyclic alkyl group (preferably having 1 to 20, more preferably 1 to 12, particularly preferably 1 to 8, for example, methyl, ethyl, iso-propyl, t-butyl, n -Octyl, 1,1,3,3-tetramethylbutyl, t-amyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 2 carbon atoms)
20, more preferably 2 to 12, particularly preferably 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 12 carbon atoms).
To 8, for example, propargyl, 3-pentynyl and the like. ), An aralkyl group (preferably having 7 carbon atoms)
~ 30, more preferably 7 ~ 20, particularly preferably 7 ~
16, for example, benzyl, α-methylbenzyl,
α-ethylbenzyl, diphenylmethyl, naphthylmethyl, naphthylphenylmethyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 carbon atoms)
-20, particularly preferably 6-12, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20, more preferably 0 to 10, and still more preferably 0 to 6, for example,
Amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like can be mentioned. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms)
2, particularly preferably 1 to 8, for example, methoxy,
Ethoxy, butoxy and the like can be mentioned. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 20 carbon atoms)
16, particularly preferably 6 to 12, for example, phenyloxy, 2-naphthyloxy and the like. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16,
Particularly preferred is 1 to 12, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ),
An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably carbon The number is 7 to 20, more preferably 7 to 16, particularly preferably 7 to 10, and examples thereof include phenoxycarbonyl and the like, and an acyloxy group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms). Particularly preferably, 2 to 10
And examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 1 carbon atom)
-20, more preferably 2-16, particularly preferably 2-10, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), and an aryloxycarbonylamino group (preferably Has 7 to 20 carbon atoms, more preferably 7 carbon atoms
To 16, particularly preferably 7 to 12, and examples include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably Has 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms.
And include, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 0 to 20, more preferably 0 to 16, particularly preferably 0 to 16 carbon atoms)
To 12, for example, carbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), A ureido group (preferably having 1 to 20 carbon atoms, more preferably 1
To 16, particularly preferably 1 to 12, and examples thereof include ureido, methylureide, and phenylurey. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio, etc.),
An arylthio group (preferably having 6 to 20, more preferably 6 to 16, particularly preferably 6 to 12, and examples thereof include phenylthio, etc.), a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably Is 1 to 16, particularly preferably 1 to 12, and examples thereof include mesyl and tosyl.) And a sulfinyl group (preferably having 1 to 1 carbon atoms)
20, more preferably 1 to 16, particularly preferably 1 to 12, for example, methanesulfinyl, benzenesulfinyl and the like. ), A phosphoramide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 16 carbon atoms).
To 12, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxam group, sulfino group, hydrazino group, sulfonylthio group Thiosulfonyl group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholinyl, etc.),
And a disulfide group.

These substituents may be further substituted and, if the group is capable of forming a salt, may form a salt. Further, n is an integer of 1 to 4, but when there are two or more substituents, that is, when n ≧ 2, they may be the same or different. n is preferably 1 to 3, and most preferably 2.

These substituents are bonded to each other to form 5
A non-aromatic or aromatic carbon ring (for example, a benzene ring) having a 7 to 7-membered ring may be formed. Further, this ring may be substituted with another substituent (eg, a halogen atom, a carboxy group).

The substituent represented by R is preferably
Alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, amino group, alkoxy group, acyl group,
Alkoxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, alkylthio group, sulfonyl group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxy Group, a nitro group, a heterocyclic group, more preferably an alkyl group, an alkenyl group, an aralkyl group, an amino group, an alkoxy group, an alkylthio group, a hydroxy group,
A mercapto group, a halogen atom, a sulfo group, and a carboxy group.

Further, in the formula (1), it is particularly preferred that an alkyl group (including an aralkyl group) is substituted at the ortho position and / or the para position of the hydroxyl group.

Further, a bisphenol structure in which the compound of the formula (1) is bonded via one carbon is more preferable.

Next, specific examples of the antifoggant of the present invention are shown, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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As the antifoggant of the formula (1) of the present invention, a commercially available one may be used.
And the acid-catalyzed condensation reaction of salicylic acid with a carbonyl compound described in J. Med. Chem., 34, 342 (1991).

The antifoggant of the formula (1) of the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl It can be used by dissolving it in sulfoxide, methylcellosolve and the like.

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

The antifoggant of the formula (1) of the present invention may be added to the 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 preferably added to the forming layer or a layer adjacent thereto.
The image forming layer is a layer containing a reducible silver salt (organic silver salt), and is preferably a photosensitive layer further containing a photosensitive silver halide.

The addition amount of the antifoggant of the formula (1) of the present invention is represented by mol / mol Ag per mol of Ag), preferably from 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol / mol Ag. Preferably, it is 5 × 10 ^-5 to 1 × 10 ^-1 mol / molAg, and more preferably, 1 × 10 ^{-4 to} 5 × 10 ^-2 mol / molAg. These may be used alone or in combination of two or more.

In the photothermographic material of the present invention, a substituted alkene derivative represented by the formula (A1) to formula (A3), a substituted isoxazole derivative and a specific acetal compound represented by the formula (H) A hydrazine derivative represented by the formula: Formulas (A1) to (A3) as the high contrast agent
The compound represented by is more preferably used. The formula (A
1), Formula (A2), and Formula (A3) will be described.

[0045]

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In the formula (A1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A1), R ¹ and Z, R ² and R ³ , R ¹
And R ² or R ³ and Z may combine with each other to form a cyclic structure. In the formula (A2), R ⁴ represents a substituent. In formula (A3), 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, or a heterocyclic group. Represents an oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the formula (A3), X and Y or A and B may be bonded to each other to form a cyclic structure.

The compound represented by the formula (A1) will be described in detail. In the formula (A1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , or R ³ and Z may be bonded to each other to form a cyclic structure.

When R ¹ , R ² and R ³ represent a substituent, examples of the substituent include, for example, a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group and 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 group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, A droxy 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 , A sulfonyloxy group, an amino group, an (alkyl, aryl, or heterocyclic) amino group, an acylamino group, a sulfonamide group, a ureido group, a thioureido group, an isothioureido group, an imide group, an (alkoxy or aryloxy) carbonylamino group, Famoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfur Amoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acyl A sulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphoryl group, a group containing a phosphate amide or a phosphate ester structure, a silyl group,
And a stannyl group. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the formula (A1) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with an N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom,
Perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group, sulfo group (or salt thereof), heterocyclic group, alkenyl group, alkynyl group, acyloxy group, acylthio group , A sulfonyloxy group, or an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is an aromatic or non-aromatic, saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group, a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group. Groups, hydantoin-1-yl group, urazol-1-yl group, succinimide group, phthalimide group and the like. The electron-withdrawing group represented by Z in the formula (A1) may further have a substituent. As the substituent, R ¹ , R ² , and R ^{3 in} the formula (A1) are the same. The same substituents as the substituents which may be present at the time of expression are exemplified.

In the formula (A1), R ¹ and Z, R ² and R ³ , R ¹
And R ² , or R ³ and Z may be bonded to each other to form a cyclic structure.
It is a non-aromatic carbon ring or a non-aromatic hetero ring.

Next, the preferred range of the compound represented by the formula (A1) will be described. As the electron-withdrawing group represented by Z in the formula (A1), preferably the following groups 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, Imino group, imino group substituted by N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group,
A formyl group, a phosphoryl group, an acyloxy group, an acylthio group, or a phenyl group substituted with any electron-withdrawing group, and more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbonyl group, an imino group, An imino group substituted with an N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group; Particularly preferred are a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted with an N atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, and a formyl group.

In the formula (A1), the substituent represented by R ¹ is preferably a group having a total carbon number of 0 to 30, specifically, an electron-withdrawing group represented by Z in the above formula (A1). And an alkyl group, an alkenyl group, an alkoxy group,
Aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, arylamino group, heterocyclic amino group,
Examples include a ureido group, an acylamino group, a silyl group, and a substituted or unsubstituted aryl group.

In the formula (A1), R ¹ is preferably a group having the same meaning as the electron-withdrawing group represented by Z in the above formula (A1), a hydrogen atom, a substituted or unsubstituted aryl group, an alkenyl group, It is an alkylthio group, an arylthio group, an alkoxy group, a silyl group, or an acylamino group.

In formula (A1), R ¹ is more preferably an electron-withdrawing group, an aryl group, an alkenyl group or an acylamino group.

When R ¹ represents an electron-withdrawing group, the following groups having preferably 0 to 30 carbon atoms in total, ie, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group,
Aryloxycarbonyl group, thiocarbonyl group, imino group, imino group substituted with an N atom, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, perfluoroalkyl group, phosphoryl group, carboxy group, acyloxy group, acylthio group Or a heterocyclic group, and further 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, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, An acylthio group or a heterocyclic group is preferred.
Particularly preferred are a cyano group, formyl group, acyl group, alkoxycarbonyl group, carbamoyl group, acyloxy group, acylthio group, and heterocyclic group.

In the formula (A1), the substituents represented by R ² and R ³ are preferably, specifically, groups having the same meaning as the electron-withdrawing group represented by Z in the above-mentioned formula (A1), and alkyl groups. , A hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, Examples include a heterocyclic amino group, an acylamino group, and a substituted or unsubstituted phenyl group.

In formula (A1), R ² and R ³ are more preferably one of which is a hydrogen atom and the other is a substituent. Preferably as the substituent, an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group Group, an alkylamino group, an anilino group, a heterocyclic amino group, an acylamino group (particularly a perfluoroalkaneamide group), a sulfonamide group, a substituted or unsubstituted phenyl group, or a heterocyclic group,
More preferably a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group. And particularly preferably a hydroxy group (or a salt thereof), an alkoxy group, or a heterocyclic group.

In the formula (A1), Z and R ¹ , or R ²
It is also preferred that and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbocyclic or non-aromatic heterocyclic ring, preferably a 5- to 7-membered cyclic structure having a total carbon number including a substituent of 1 to 7. 4
0, more preferably 3 to 35.

[0059] Among the compounds represented by formula (A1), more One of preferred, Z is a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group,, R ¹ is Represents an electron-withdrawing group, and one of R ^{2 and} R ³ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group , An alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group.

One of the more preferable compounds represented by the formula (A1) is a compound in which Z and R ¹ are linked to form a non-aromatic 5- to 7-membered cyclic structure. , R ² or R ³ is a hydrogen atom and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group , A heterocyclic thio group, an amino group, or a heterocyclic group.

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

Next, the compound represented by the formula (A2) will be described. In the formula (A2), R ⁴ represents a substituent. The formula (A
Examples of the substituent represented by R ⁴ in 2) include a compound represented by the formula (A)
The same substituents as those described for the substituents of R ^{1 to} R ^{3 in} 1) can be mentioned.

The substituent represented by R ⁴ in the formula (A2) 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, perfluoroalkyl group, phosphoryl Group, imino group, sulfonamide group, or heterocyclic group, further cyano group, acyl group, formyl group, alkoxycarbonyl group,
A carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonamide group, and a heterocyclic group are preferred.

When R ⁴ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group having a total of 0 to 30 carbon atoms, and the substituent is represented by R ¹ , R ² , R ³ of the formula (A1). When represents a substituent, the same as those described as the substituent can be mentioned, but an electron-withdrawing group is preferable.

Next, the compound represented by formula (A3) will be described in detail. In the formula (A3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group,
Represents a heterocyclic 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 formula (A3), the same substituents as described for the substituents R ^{1 to} R ^{3 in} the formula (A1) can be mentioned. Specifically, alkyl groups (including perfluoroalkyl groups, trichloromethyl groups, etc.), aryl groups, heterocyclic groups, halogen atoms, cyano groups, nitro groups, alkenyl groups, alkynyl groups, acyl groups, formyl groups, alkoxy groups Carbonyl 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), sulfo group (or its salt), hydroxy group (or its salt), mercapto group (or its salt), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero group Ring thio group, amino group, alkylami Group, anilino group, heterocyclic amino group, a silyl group, and the like.

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 substituent represented by X and Y in the formula (A3) is preferably a group having a total of 1 to 40 carbon atoms, more preferably a group having a total of 1 to 30 carbon atoms, and is a cyano group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group , An acylamino group, an acyloxy group, an acylthio group, a heterocyclic group, an alkylthio group, an alkoxy group, or an aryl group.

In the formula (A3), 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, an acylamino group, a thiocarbonyl group, a sulfamoyl group,
An alkylsulfonyl group, an arylsulfonyl group, an imino group, an imino group substituted with an N atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group or an alkoxycarbonyl group , A carbamoyl group, an alkylsulfonyl group,
An arylsulfonyl group, an acyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, or a phenyl group substituted with any electron-withdrawing group; is there.

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 ring is preferably a 5- to 7-membered ring, and specifically, a non-aromatic 5- to 7-membered ring which can be formed by bonding Z and R ¹ of the formula (A1) to each other. The same examples are given, and their preferred ranges are also the same. These rings may further have a substituent, and the total number of carbon atoms is preferably 1 to 40, more preferably 3 to 35.

In the formula (A3), 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.

In the formula (A3), the groups represented by A and B are
Further, it may have a substituent, and is preferably a group having 1 to 40 carbon atoms in total, more preferably a group having 1 to 30 carbon atoms in total.

In the formula (A3), 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.

The compounds represented by the formulas (A1) to (A3) of the present invention may have incorporated therein an adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include U.S. Pat. Nos. 4,385,108 and 4,459,347 such as alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups.
JP-A-59-195233 and JP-A-59-200231.
Nos. 59-201045 and 59-201046
Nos. 59-201047 and 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
The group described in 3-234246 is mentioned. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

The compounds represented by the formulas (A1) to (A3) of the present invention may be those having a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. Good. 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,
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Examples of the polymer include, for example,
No. 00530.

The compounds represented by the formulas (A1) to (A3) of the present invention contain a cationic group (specifically, a group containing a quaternary ammonium group, or a quaternized nitrogen). A nitrogen-containing heterocyclic group containing an atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (carboxy group, Sulfo group,
Acylsulfamoyl group, carbamoylsulfamoyl group, etc.). 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-7-2
No. 34471, JP-A-5-333466, JP-A-6-633
19032, JP-A-6-19031, JP-A-5-4
No. 5761, U.S. Pat. No. 4,994,365, U.S. Pat.
88604, JP-A-73-259240, JP-A-7-259240
No. 5610, JP-A-7-244348, German Patent 4
No. 006032 and the like.

Next, specific examples of the compounds represented by formulas (A1) to (A3) of the present invention are shown below. However, the present invention is not limited to the following compounds.

[0078]

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[0079]

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[0080]

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[0081]

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The compounds represented by the formulas (A1) to (A3) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515 and US Pat.
No. 9, U.S. Pat. No. 5,654,130, International Patent WO-97
/ 34196, Japanese Patent Application No. 9-354107, Japanese Patent Application No. 9-309813, and the method described in Japanese Patent Application No. 9-272002.

Next, the hydrazine derivative represented by the following formula (H) used in the present invention will be described. In the present invention, the hydrazine derivative is used as a high contrast agent or a development accelerator.

[0084]

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In the formula (H), R ²⁰ is an aliphatic group, an aromatic group,
Or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a block group, and G ¹ represents —CO—, —COCO—, —C (=
_{S) -, - SO 2 -} , - SO -, - PO (R 30) - group (R
³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10. ) Or iminomethylene group. A ¹ and A ^{2 each} represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. m ¹
Is 0 or 1, and when m ¹ is 0, R ¹⁰ is an aliphatic group,
Represents an aromatic group or a heterocyclic group.

In the formula (H), the aliphatic group represented by R ²⁰ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms.

In the formula (H), the aromatic group represented by R ²⁰ is a monocyclic or condensed-ring aryl group, such as a phenyl group or a naphthyl group derived from a benzene ring or a naphthalene ring. The heterocyclic group represented by R ²⁰ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, and the heterocyclic ring in these groups is, for example, a pyridine ring , A pyrimidine ring,
Imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, thiophene ring, triazine ring, morpholine ring, piperidine ring, piperazine ring, benzo [1,3]
And a dioxole ring.

Preferred as R ²⁰ is an aryl group, an alkyl group, or an aromatic heterocyclic group.

R ²⁰ may be substituted. Representative substituents include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, an active methine group). Alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Group, carboxy group or salt thereof, sulfonylcarbamoyl group,
Acyl carbamoyl group, sulfamoyl carbamoyl group, carbazoyl group, oxalyl group, oxamoyl group,
Cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group Carbamoyloxy group, (alkoxy or aryl) sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido Group, isothioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (Alkyl or aryl) sulfonyluureido, acylureido, acylsulfamoylamino, nitro, mercapto, (alkyl, aryl, or heterocycle) thio, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl Group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric acid amide or a phosphoric ester structure, a silyl group, a stanyl group, and the like. These substituents may be further substituted with these substituents.

[0090] Preferred examples of the substituent which may be R ²⁰ optionally has, when R ²⁰ represents an aromatic group or a heterocyclic group, (including an active methylene group) alkyl group, an aralkyl group, a heterocyclic group, Substituted amino group, acylamino group, sulfonamide group, ureido group, sulfamoylamino group,
Imide group, thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl , Aryl, or heterocycle)
Examples thereof include a thio group, a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group, and a nitro group.

When R ²⁰ represents an aliphatic group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide group, a thioureido group, Phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group,
Acyloxy group, acyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocycle) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group, etc. Is preferred.

In the formula (H), R ¹⁰ represents a hydrogen atom or a block group, and the block group specifically refers to an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group. (Monocyclic or condensed-ring aryl group),
Represents a heterocyclic group, an alkoxy group, an aryloxy group, a substituted or unsubstituted amino group or a hydrazino group.

The alkyl group represented by R ¹⁰ is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, trifluoromethyl, difluoromethyl, 2-carboxytetra. Fluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluoro (methylthio) methyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, hydroxymethyl group, methanesulfonamidomethyl group, 3-methanesulfonamidopropyl group, benzenesulfone Amidomethyl group, trifluoroacetylmethyl group, trifluoromethanesulfonamide group, dimethylaminomethyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxymethyl group, 4-ethylphenyl Nokishimechiru group, phenylthiomethyl group, t- butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, a methoxycarbonyl diphenylmethyl group, a cyano diphenylmethyl group, and a methylthio diphenylmethyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, for example, a vinyl group, a 2-ethoxycarbonylvinyl group, a 2-trifluoro-2-methoxycarbonylvinyl group, a 2,2-dicyanovinyl group, a 2-cyano group -2-methoxycarbonylvinyl group, 2-cyano-2-ethoxycarbonylvinyl group and the like. The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, a phenyl group, a perfluorophenyl group,
3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2-carbamoylphenyl group, 4,5-
Examples include a dicyanophenyl group, a 2-hydroxymethylphenyl group, a 2,6-dichloro-4-cyanophenyl group, and a 2-chloro-5-octylsulfamoylphenyl group.

Preferably, the heterocyclic group is a 5- to 6-membered group containing at least one nitrogen, oxygen and sulfur atom.
Saturated or unsaturated, monocyclic or condensed-ring heterocyclic group such as morpholino group, piperidino group (N-substituted),
Imidazolyl group, indazolyl group (such as 4-nitroindazolyl group), pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group, pyridyl group, pyridinio group (such as N-methyl-3-pyridinio group), quinolinio group, and quinolyl group , A hydantoyl group and an imidazolidinyl group.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group,
Examples include a 2-hydroxyethoxy group, a benzyloxy group, and a t-butoxy group. As the aryloxy group, a substituted or unsubstituted phenoxy group is preferable, and as the amino group, an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group ( (Including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom). Examples of substituted or unsubstituted amino groups include 2,2,6,6
-Tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, 3-hydroxypropylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl -3-pyridinioamino group and the like. As the hydrazino group, a substituted or unsubstituted hydrazino group,
Or a substituted or unsubstituted phenylhydrazino group (4
-Benzenesulfonamidophenylhydrazino group, etc.)
Is particularly preferred.

The group represented by R ¹⁰ may be substituted, and examples of the substituent include those exemplified as the substituent of R ²⁰ .

In the formula (H), R ¹⁰ is such as to cause a cyclization reaction which cleaves the G ¹ -R ¹⁰ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ¹ -R ¹⁰ moiety. And examples thereof include, for example,
No. 29751 and the like.

The hydrazine derivative represented by the formula (H) is
An adsorptive group that adsorbs to silver halide may be incorporated. Examples of such adsorptive groups include U.S. Pat. Nos. 4,643,086, such as alkylthio, arylthio, thiourea, thioamide, mercaptoheterocyclic, and triazole groups.
385,108 and 4,459,347, JP-A-5
Nos. 9-195233, 59-200231 and 59
No.-201045, No.59-201046, No.59-
No. 201047, No. 59-201048, No. 59-2
01049, JP-A-61-170733, and 61-170733.
Nos. 270744, 62-948, 63-2342
No. 44, No. 63-234245, No. 63-23424
The groups described in No. 6 are exemplified. These adsorbing groups to silver halide may be precursors.
Such a precursor is disclosed in Japanese Patent Application Laid-Open No. 28534/1990.
The groups described in No. 4 are exemplified.

R ¹⁰ or R ^{20 in} the formula (H) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. 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, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. Examples of the polymer include those described in JP-A-1-100530.

R ¹⁰ or R ²⁰ in the formula (H) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the formula (H) represents a polymer with respect to the hydrazino group. Specifically, for example, JP-A-64-86134, JP-A-4-16938, JP-A-5-197091, WO95-32
No. 452, WO95-32453, JP-A-9-235264
No., JP-A-9-235265, JP-A-9-235266, JP-A-9-23
No. 5,267, and compounds described in JP-A-9-179229.

R ¹⁰ or R ^{20 in} the formula (H) represents a cationic group (specifically, a group containing a quaternary ammonium group, or a nitrogen-containing heterocyclic ring containing a quaternized nitrogen atom). Group), 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 group, sulfo group, acylsulfamoyl) dissociable by a base A carbamoylsulfamoyl group). Examples of these groups include, for example, JP-A-7-234471, JP-A-5-333466,
JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, US Pat. No. 4,994,365, US Pat. No. 4,988,604, JP-A-73-259240
JP-A-7-5610, JP-A-7-244348
And the compounds described in German Patent No. 4006032.

In the formula (H), A ¹ and A ² represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a Hammett substituent having a sum of -0.5 or more. Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more, or a linear group. A branched or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. )). A ¹ and A ² are most preferably hydrogen atoms.

Next, the preferred range of the hydrazine derivative represented by the formula (H) of the present invention will be described. In the formula (H), R ²⁰ is preferably a phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an aromatic heterocyclic group.

When R ²⁰ represents a phenyl group or an aromatic heterocyclic group, preferred substituents are a nitro group, a cyano group, an alkoxy group, an alkyl group, an acylamino group,
Examples thereof include a ureido group, a sulfonamide group, a thioureido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), an alkoxycarbonyl group, and a chloro atom.

[0105] When R ²⁰ represents a substituted alkyl group having 1 to 3 carbon atoms, R ²⁰ is more preferably a substituted methyl group, more preferably a disubstituted methyl group or trisubstituted methyl group, as a substituent Are specifically a methyl group, a phenyl group, a cyano group, an (alkyl, aryl or heterocycle) thio group, an alkoxy group, an aryloxy group, a chloro atom, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl A group, a sulfamoyl group, an amino group, an acylamino group, or a sulfonamide group is preferred, and a substituted or unsubstituted phenyl group is particularly preferred.

When R ²⁰ represents a substituted methyl group, more preferred specific examples include a t-butyl group, a dicyanomethyl group,
Dicyanophenylmethyl, triphenylmethyl (trityl), diphenylmethyl, methoxycarbonyldiphenylmethyl, cyanodiphenylmethyl, methylthiodiphenylmethyl, cyclopropyldiphenylmethyl, etc. preferable.

When R ²⁰ represents an aromatic heterocyclic group, more preferably, R ²⁰ represents a pyridine ring, a quinoline ring, a pyrimidine ring, a triazine ring, a benzothiazole ring, a benzimidazole ring, a thiophene ring or the like. It is time. In the formula (H), R ²⁰ is most preferably a substituted or unsubstituted phenyl group.

In the formula (H), m ¹ represents 1 or 0. When m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group or a heterocyclic group. When m ¹ is 0, R ¹⁰ is particularly preferably a phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an alkenyl group. Of these, for the phenyl group and the substituted alkyl group having 1 to 3 carbon atoms, its preferred range is the same as the preferable ranges of R ²⁰ as described above.
When R ¹⁰ is an alkenyl group, preferably R ¹⁰ is a vinyl group, and is a substituent selected from the following substituents: a cyano group, an acyl group, an alkoxycarbonyl group, a nitro group, a trifluoromethyl group, a carbamoyl group and the like. Vinyl groups having one or two groups are particularly preferred. In particular,
Examples thereof include a 2,2-dicyanovinyl group, a 2-cyano-2-methoxycarbonylvinyl group, a 2-cyano-2-ethoxycarbonylvinyl group, and a 2-acetyl-2-ethoxycarbonylvinyl group. m ¹ is preferably 1.

Among the groups represented by R ¹⁰ , preferred are a hydrogen atom, an alkyl group and an alkenyl group when R ²⁰ represents a phenyl group or an aromatic heterocyclic group and G ¹ is a —CO— group. , An alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and most preferably a hydrogen atom or an alkyl group. When R ¹⁰ represents an alkyl group, the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, a sulfonamide group, an amino group, an acylamino group, or a carboxy group. .

R ²⁰ represents a substituted methyl group, and G ¹ represents-
In the case of a CO- group, R ¹⁰ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group (unsubstituted amino group, alkylamino group, arylamino group, heterocyclic amino group) And more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group.

When G ¹ is a —COCO— group, irrespective of R ²⁰ , R ¹⁰ is preferably an alkoxy group, an aryloxy group or an amino group, particularly a substituted amino group, more specifically an alkylamino group or an arylamino group. Or a saturated or unsaturated heterocyclic amino group.

When G ¹ is a —SO ₂ — group, R ²⁰
Regardless, R ¹⁰ is preferably an alkyl group, an aryl group or a substituted amino group.

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

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

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

[0118]

[Table 4]

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

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

(Formula 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. Formula (I) described in JP-B-6-93082
And specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. Compounds represented by formulas (4), (5) and (6) described in JP-A-6-230497, specifically, Compounds 4-1 to 4-1 described on pages 25 and 26 of the same publication 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 formulas (1) and (2) described in the above publication, specifically, compounds 1-
1) to 1-17) and 2-1). JP-A-6-3139
Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in No. 36, 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 formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same publication. JP 7
Compounds represented by formulas (H) and (Ha) described in JP-A-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. B), compounds represented by formula (C), formula (D), formula (E), and formula (F), specifically, compounds N-1 to N-30 described in the publication. Compounds represented by formula (1) described in EP-713131A, specifically, compounds D-1 to D-55 described in the publication.

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

Formulas (A1) to (A3) of the present invention, and
The compound represented by (H) is added to the coating solution as an aqueous dispersion. It is preferable not to contain an organic solvent, but it may contain 10% by volume or less of alcohols (methanol, ethanol, propanol, fluorinated alcohol, etc.).

In the dispersion operation of the present invention, the compounds represented by the formulas (A1) to (A3) and (H) are dispersed in the presence of an aqueous solvent-soluble dispersant (dispersion aid). Is preferred. 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 polymer such as carboxymethyl cellulose, alginic acid, anionic polymer such as pectic acid, the compound described in JP-A-7-350753,
Known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, or naturally occurring polymer compounds such as gelatin can be appropriately selected and used.

Any surfactant such as a nonionic, anionic, cationic, or fluorine-based dispersing agent may be appropriately used. Anionic, nonionic and amphoteric surfactants are preferred, and the use of anionic and / or nonionic surfactants is particularly preferred. Specifically, JP-A-62-170950, fluorinated polymer surfactants described in U.S. Patent No. 5,380,644, JP-A-60-244945, JP-A-63-170945
188135 No. fluorinated surfactants described in U.S. Pat.
Polysiloxane surfactants described in 885,965 and the like,
Examples thereof include polyalkylene oxides and anionic surfactants described in JP-A-6-301140.

Prior to dispersion, the dispersing aids may be prepared according to the formulas (A1) to (A)
It is a general method to mix these compounds in the form of a powder or a wet cake with the compound represented by formula (H) or 3) and feed the mixture as a slurry to a dispersing machine. Heat treatment or treatment with a solvent may be performed in a state in which the agents are mixed to form a powder or a wet cake. The pH may be controlled by a suitable pH adjuster before, during or after dispersion.

Formulas (A1) to (A3) of the present invention, and
The compound represented by (H) is preferably added to the photosensitive material as a solid dispersion of fine powder (fine crystal particles). A fine (crystalline) particle solid dispersion of these compounds may be used as a dispersant by using an appropriate solvent containing water as a main component as described above (water may be used as a main component and alcohol may be contained). Known micronizing means in the presence (eg, ball mill, vibrating ball mill, planetary ball mill,
It can be prepared mechanically using a sand mill, a colloid mill, a jet mill, a roller mill, a microfluidizer).

The fine (crystalline) particles of these compounds are dispersed in a suitable solvent using a dispersing surfactant and then added to a poor solvent for these compounds to form fine particles. It can be obtained by a method of precipitating crystals or a method of first dissolving these compounds by controlling the pH and then changing the pH to perform microcrystallization. At this time, an organic solvent of 10% by volume or less may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after completion of the fine particle formation.

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 to dissolve the compound. An emulsified dispersion can be prepared and used as an aqueous dispersion.

The fine particles of the compounds represented by the formulas (A1) to (A3) and (H) have an average particle diameter of 0.005 μm to 0.005 μm.
The thickness is 30 μm, preferably 0.01 μm to 10 μm, more preferably 0.02 μm to 2 μm.

The prepared dispersion may be stored with stirring for the purpose of suppressing sedimentation of fine particles during storage, or stored in a highly viscous state (for example, in a jelly state using gelatin) with 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.

Formulas (A1) to (A3) of the present invention, and
The compound represented by (H) may be added to the layer on the image forming layer side with respect to the support, that is, any layer of the image forming layer or another binder layer on the layer side. It is preferable to add it to the binder layer adjacent thereto.

Formulas (A1) to (A3) of the present invention, and
The amount of the compound represented by (H) was 1 × with respect to 1 mol of silver.
It is preferably from 10 ^-6 to 1 mol, more preferably from 1 x 10 ^{-5 to} 5 x 10 ^-1 mol, most preferably from 2 x 10 ^-5 to 2 x 10 ^-1 mol.

In the present invention, the compounds represented by the formulas (1) to (3) are preferably used as a contrast agent, and the compound represented by the formula (H) is preferably used as a contrast agent or a development accelerator. . When both are used in combination, the addition amount of the high contrast agent can be greatly reduced, so that the cost of the light-sensitive material can be reduced, which is preferable.

The molar ratio of the toning agent represented by the formulas (1), (2) and (3) to the compound represented by the formula (H) is 100: 1 to 1:10. Is preferably in the range of 10: 1
The range of １ ： 1: 5 is more preferable.

Formulas (A1) to (A) used in the present invention
3) and the compound represented by the formula (H) may be used alone or in combination of two or more. In addition to the above, US Pat. No. 5,545,515 and US Pat.
No. 9, U.S. Pat. No. 5,654,130, International Patent WO-97
No./34196, U.S. Pat. No. 5,686,228, or compounds disclosed in Japanese Patent Application Nos. 8-279962, 9-228888, 9-273935, 9-354107, and 9-354107. 9-309813, Japanese Patent Application No. 9-296174, Japanese Patent Application No. 9-282564,
Japanese Patent Application Nos. 9-272002 and 9-272003
And the compounds described in Japanese Patent Application No. 9-332388 may be used in combination.

Further, the present invention provides a method for forming a super-high contrast image.
A high contrast accelerator can be used in combination with the above-mentioned high contrast agent. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically, AM-1 to AM-5, and hydroxamic acids described in 5,545,507, specifically, HA-1 to HA-1
1, hydrazine compounds described in 5,558,983, specifically CA-1 to CA-6, onium salts described in Japanese Patent Application No. 8-132836, specifically A-1 to A- 42, B-1 to B-2
7, C-1 to C-14 and the like can be used.

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

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

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

The reducing agent of the present invention may be added by any method such as a solution, a powder, and a 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The above metal is 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 and a flocculation method, but in the present invention, it may or may not be desalted. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, and sulfur sensitization and selenium sensitization Method, tellurium sensitization method, gold sensitization method and the like are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As the sulfur sensitizer, known compounds can be used.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 the pH during chemical ripening, the temperature, and the size of silver halide grains.
It is 10 ^-7 to 10 ^-2 mol per mol, 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,
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, 3,320,069, 3,772,031, UK Patent 235,211 and 1,121,496,
No. 1,295,462, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-204640, JP-A-3-53693, JP-A-3-31598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibid 64
5 (1979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.
Trans.) 1,2191 (1980), edited by S. Patai, The Chemistry of Organ, Selenium and Tellurium Campounds
ic Serenium and Tellunium Compounds), Vol. 1 (198
6), Vol. 2 (1987). In particular, formulas (II), (III) and (IV) in JP-A-5-313284
Are preferred.

[0165] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

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

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

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

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

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

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 mol to 0.5 mol, more preferably 0.02 mol to 0.3 mol, and more preferably 0.03 mol to 1 mol of the organic silver salt. It is particularly preferably at least 0.25 mol. 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 organic silver salt which can be used as the reducible silver salt in the present invention is relatively stable to light,
A silver salt that forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of a photosensitive silver halide) and a reducing agent. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially (C 10-30, preferably 1
Silver salts of long chain fatty carboxylic acids (5-28) are preferred. Complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor material can preferably make up about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of the aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphorate,
And mixtures thereof.

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

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

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

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

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

In the above, the aqueous dispersion converted and converted to high pressure and high speed is substantially free of a photosensitive silver salt, and its content is relative to that of a 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, the solid dispersion apparatus and the technique used for carrying out the dispersion method as described above are described in, for example, “Dispersion Rheology and Dispersion Technique” (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 high pressure and high speed; It is considered that the particles are dispersed into fine particles by a dispersing force such as “cavitation force” generated when the particles are released. As an example of this type of dispersing apparatus, a Gaulin homogenizer is mentioned in the past.In this apparatus, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on a cylindrical surface, and the force is applied to the surrounding wall by the force. The particles collide and are emulsified and dispersed by the impact force. Working pressure is generally 10
0~600kg / cm ^2, the flow rate is in the range of a few M～30m / sec, be devised that the high flow rate portion was devised such increasing the number collisions in the saw-toothed in order to increase the dispersion efficiency I have. On the other hand, in recent years, apparatuses capable of dispersing at higher pressure and higher flow rate have been developed, and typical examples thereof include a microfluidizer (Microfluidex International Corporation) and a nanomizer (specialized machine). Industrial Co., Ltd.).

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

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

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

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

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

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

The prepared dispersion 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) with a hydrophilic colloid. You can also.
Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

[0188] While the organic silver salt according to the invention can be used in a desired amount, show a coating amount per the photosensitive material 1 m ^2, as silver
Preferably 0.1-5 g / m ^2, more preferably from 1 to 3 g / m ^2.

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

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

The color tone agent of the present invention 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.

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

At least one of the image forming layers of the present invention comprises the polymer latex described below in 50% of the total binder.
It is preferable that the image forming layer contains at least wt%. (Hereinafter, this image forming layer is referred to as “the image forming layer of the present invention” and the polymer latex used for the binder is referred to as the “polymer latex of the present invention.” May be used for layers,
In particular, when the photothermographic material of the present invention is used for printing in which dimensional change is a problem, it is necessary to use a polymer latex for the protective layer and the back layer. However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. For the polymer latex of the present invention, `` Synthetic resin emulsion (Hiroshi Okuda, edited by Hiroshi Inagaki, published by the Society of Polymer Publishing (1978)) '', `` Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, edited by Keiji Kasahara, Published by Polymer Publishing Association (1
993)) "," Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and those having a wide particle size distribution or those having a monodispersed particle size distribution may be used.

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

The glass transition temperature (Tg) of the polymer of the polymer latex used for the binder of the present invention is as follows:
The preferred range differs between the back layer and the image forming layer. In the image forming layer, the temperature is preferably 40 ° C. or lower, more preferably -30 to 40 ° C., in order to promote diffusion of the photographically useful material during thermal development. When used for the protective layer or the back layer, a glass transition temperature of 25 to 70 ° C. is preferable for contacting various devices.

The minimum film forming temperature (MFT) of the polymer latex of the present invention is preferably from -30 ° C to 90 ° C, more preferably from about 0 ° C to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the polymer latex, also called a plasticizer, and is described in, for example, `` Synthesis of Synthetic Latex (Souichi Muroi, published by Polymer Publishing Association (1970) )"It is described in.

Examples of the polymer used in the polymer latex of the present invention include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. There is. 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 molecular weight of the polymer is preferably from 5000 to 100000, more preferably from about 10,000 to 100,000 in number average molecular weight. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming property is poor, which is not preferable.

Specific examples of the polymer latex used as a binder in the image forming layer of the photothermographic material of the present invention include the following. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2 ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer and the like.
Such polymers are also commercially available, and the following polymers can be used. For example, as examples of acrylic resin, Sebian A-4635,46583,4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811,814,821,820,857
(Nippon Zeon Co., Ltd.) and other polyester resins, such as FINETEX ES650, 611, 675, 850 (Dai Nippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical Co., Ltd.), etc. HYDRAN AP10 as polyurethane resin,
LACSTAR 7310K, 3307B, 4700H, 7132C as rubber resins such as 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.)
(Dai Nippon Ink Chemical Co., Ltd.), Nipol Lx416, 410,
438C, 2507 (Nippon Zeon Co., Ltd.), etc., vinyl chloride resins such as G351 and G576 (Nippon Zeon Co., Ltd.), etc., and vinylidene chloride resins L502, L513 (Nippon Zeon Co., Ltd.) , Alon D7020, D504, D5071 (Mitsui Toatsu Co., Ltd.) and other olefin resins such as Chemipearl S
120 and SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.). These polymers may be used alone or as a blend of two or more as necessary.

In the image forming layer of the present invention, it is preferable to use the polymer latex as 50% by weight or more of the total binder, and it is more preferable to use the polymer latex as 70% by weight or more.

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

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

The total amount of 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.

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

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

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

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
No. 72661, No. 6-222491, No. 2-230506, No. 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.
No. 141, dyes described in U.S. Patent No.
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. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are
Research Disclosure Volume 176, 17643 (Issued December 1978) No. 23
Section IV on page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

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

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

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

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

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

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

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

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

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

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

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

In the present invention, the image forming layer or the protective layer of the image forming layer is described in US Pat. No. 3,253,921 and US Pat.
Light absorbing substances and filter dyes as described in 4,782, 2,527,583 and 2,956,879 can be used. Also, for example, U.S. Pat.
The dye can be mordanted as described in US Pat. As the amount of filter dye used, the absorbance at the exposure wavelength is 0.
1-3 are preferable, and 0.2-1.5 are particularly preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Additional layers in the photothermographic material of the present invention, such as a dye-receiving layer for receiving a moving dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques A known primer layer or the like can be included. The light-sensitive material of the present invention is preferably capable of forming an image with only one light-sensitive material, and it is preferable that a functional layer required for image formation such as an image receiving layer does not become another light-sensitive material.

The photothermographic material of the present invention may be developed by any method. Generally, the photosensitive material exposed imagewise is heated and developed. As a preferred embodiment of the heat developing machine to be used, a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum is disclosed in Japanese Patent Publication No. 5-56499, Japanese Patent No. 684453, and Japanese Patent Application Laid-Open No. 9-292695.
No. 9-297385 and the thermal developing machine described in International Patent Publication No. WO95 / 30934.
4, International Patents WO97 / 28489, 97/28488 and 9
There is a heat developing machine described in 7/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C, more preferably 100 to 140 ° C.
° C. The development time is preferably from 1 to 180 seconds, from 10 to 180 seconds.
90 seconds is more preferred.

As a method for preventing processing unevenness due to the dimensional change during the heat development of the photothermographic material of the present invention, a temperature of 80 ° C.
A method of forming an image by heating at a temperature of at least 115 ° C. (preferably 113 ° C. or less) for 5 seconds or more so as not to form an image, and then thermally developing at 110 ° C. or more (preferably 130 ° C. or less) (so-called multi Step heating method) is effective.

The 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, gas laser, YAG
Laser, dye laser, semiconductor laser and the like are preferable. Further, a semiconductor laser and a second harmonic generation element can be used.

The 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 photosensitive material as disclosed in JP-A-5-113548 and a multi-mode laser disclosed in WO95 / 31754 and the like. Are known, and it is preferable to use these techniques.

For exposing the light-sensitive material of the present invention, SPIE vo
l.169 Laser Printing 116-128 (1979), JP-A-4-5104
No. 3, WO95 / 31754, etc., it is preferable to expose the laser beams so that they overlap each other so that the scanning lines are not visible.

FIG. 1 shows an example of the construction of a heat developing machine used for the heat development of the photothermographic material of the present invention. FIG. 1 is a side view of the heat developing machine. As a heat source of the heating means, an endless belt 4 for conveyance suspended by a plurality of feed rollers 3 is pressed against the peripheral surface of a cylindrical heat drum 2 containing a halogen lamp 1, and the endless belt 4 and the heat drum 2, the photothermographic material 5 is conveyed. Photothermographic material 5 while transported
Is heated to a development temperature and thermal development is performed. In this case, the orientation of the lamp is optimized, and the temperature control in the width direction is performed accurately.

In the vicinity of the outlet 6 from which the photothermographic material 5 is sent out between the heat drum 2 and the endless belt 4, the heat development forming material 5 released from the curvature of the peripheral surface of the heat drum 2 is flattened. 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 photothermographic material 5 is provided downstream of the outlet 6, and the downstream side thereof is adjacent to the roller pair 8 and the photothermographic material 5 is maintained in a planar state. And a pair of feed rollers 10 is provided downstream thereof adjacent to the flat guide plate 9. The flat guide plate 9 has a length sufficient 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 of the photothermographic material 5 becomes 30 ° C. or less. As this cooling means, a cooling fan 11 is provided.

Although the above has been described with reference to the illustrated example, 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.

[0248]

EXAMPLES The effects of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 << Preparation of Silver Halide Emulsion >> (Emulsion A) After dissolving 11 g of phthalated gelatin, 30 mg of potassium bromide and 10 mg of sodium benzenethiosulfonate in 700 ml of water and adjusting the pH to 5.0 at a temperature of 55 ° C. , Silver nitrate 18.
An aqueous solution containing 159 ml of an aqueous solution containing 6 g and an aqueous solution containing potassium bromide at 1 mol / liter were added by a control double jet method over 6 minutes and 30 seconds while keeping the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate and a halogen salt aqueous solution containing 1 mol / l of potassium bromide were added by a control double jet method over 28 minutes and 30 seconds while keeping the pAg at 7.7. Thereafter, the pH was lowered to cause coagulation and sedimentation, followed by desalting treatment, and 0.17 g of compound A and 23.7 g of deionized gelatin (calculated as 20 ppm or less) were added to adjust the pH to 5.9 and pAg 8.0. The obtained particles were cubic particles having an average particle size of 0.11 μm, a projection area variation coefficient of 8%, and a (100) plane ratio of 93%.

The silver halide grains thus obtained were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver.
Mole was added and aged for 100 minutes.

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

[0251]

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

[0253] Next, the pre-dispersed stock solution of a dispersing machine (trade name: Microfluidizer M-110S-EH, Microfluidex International Corporation, G ¹ 0Z interaction chamber) the pressure of the 1750kg / cm ² The mixture was adjusted and treated three times to obtain an organic acid silver dispersion A. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.04 μm and an average major axis of 0.8 μm.
m, needle-like particles having a variation coefficient of 30%. The measurement of the particle size was performed by MasterSizerX manufactured by Malvern Instruments Ltd. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. Thus, organic acid silver A having a silver behenate content of 85 mol% was prepared.

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

<< Preparation of Solid Fine Particle Dispersion of Tribromomethylphenyl Sulfone >> 30 g of tribromomethylphenylsulfone was added to hydroxypropylmethylcellulose.
0.5 g, 0.5 g of compound C and 88.5 g of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of tribromomethylphenylsulfone was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. The particle size is
80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

<< Preparation of dispersion of solid fine particles of antifoggant of the present invention >> To 2.5 g of the antifoggant of the present invention, 1 g of MP-203 of MP polymer manufactured by Kuraray Co., Ltd. and 30 ml of water were added. The mixture was well stirred and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the antifoggant of the present invention was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80 wt% of the particles were 0.3 μm or more and 1.0 μm or less.

<< Preparation of Aqueous Dispersion of Solid Fine Particles of Organic Hardener of the Present Invention and Organic Solvent Solution >><Addition Method A / Methanol Solution> 5 g of the hardener was dissolved in 10 cc of methanol. <Addition method B / aqueous dispersion of solid fine particles> 2.5 g of polyvinyl alcohol (trade name: PVA-217), 0.5 g of compound C, and 92 g of water are added to 5 g of a contrast agent, and the mixture is stirred well and converted into a slurry for 3 hours. I left it. Thereafter, a solid fine particle dispersion of a high contrast agent was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80% by weight of the particles was 0.3 μm or more and 1.0 μm or less (average particle diameter 0.5 μm).

<< Preparation of Emulsion Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Thus, an emulsion layer coating solution was obtained. Binder; Luck Star 3307B 470 g as solids (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 , 5-Trimethylhexane 110g as solid content Tribromomethylphenylsulfone 25g as solid content Sodium benzenethiosulfonate 0.1g Polyvinyl alcohol (MP-203 manufactured by Kuraray Co., Ltd.) 46g 6-iso-butylphthalazine 0.12mol Dye A 0.62 g Silver halide emulsion A 0.05 mol as Ag content Hardener of the present invention Table 5 shows addition method, type and amount (as compound) Antifoggant of the present invention Table 5 shows type and amount (as compound)

[0259]

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<< Preparation of Coating Solution for Emulsion Surface Protective Layer >> Solid Content 27.5
wt% polymer latex (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1
3.75 g of H ₂ O was added to 109 g of a copolymer of the following, and 4.5 g of benzyl alcohol, 0.45 g of compound D, 0.125 g of compound E, 0.0125 mol of compound F, and 0.0125 mol of polyvinyl alcohol (49 g) were added as film forming aids. PVA-, manufactured by Kuraray Co., Ltd.
217) 0.225 g was added, and further H ₂ O was added to make 150 g, thereby obtaining a coating solution.

[0261]

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

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

[0264] (2) Undercoat layer (a) Polymer latex - styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene = 67/30 / 2.5 / 0.5 (wt%) 160 mg / m ² 2,4-dichloro-6-hydroxy - s-Triazine 4mg / m ² Matting agent (polystyrene, average particle size 2.4μm) 3mg / m ²

(3) 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 1.0

(4) Conductive layer Julimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² Gelatin 50 mg / m ² Compound A 0.2 mg / m ² Polyoxyethylene phenyl ether 10 mg / m ² Sumitex Resin M -3 18mg / m ² (Water-soluble melamine compound manufactured by Sumitomo Chemical Co., Ltd.) Dye A Coating amount at which optical density of 780 nm becomes 1.0 SnO ₂ / Sb (9/1 weight ratio, needle-like fine particles, long axis / short axis) Axis = 20-30; manufactured by Ishihara Sangyo Co., Ltd.) 120 mg / m ² Matting agent (polymethyl methacrylate, average particle size 5 μm) 7 mg / m ²

(5) Protective layer Polymer latex-methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer) 1000 mg / m ² Polystyrene sulfonate (Molecular weight 1000-5000) 2.6 mg / m ² Cellosol 524 (manufactured by Chuo Yushi Co., Ltd.) 30 mg / m ² Sumitex Resin M-3 218 mg / m ² (Water-soluble melamine compound, Sumitomo Chemical ( Co., Ltd.)

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

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

<< Preparation of Photothermographic Material >> The above-mentioned emulsion layer coating solution was coated on the undercoat layer of the PET support having the back / undercoat layer so that the coating amount of silver was 1.6 g / m ² . Further, the coating liquid for the emulsion surface protective layer was applied thereon so that the coating amount of the solid content of the polymer latex was 2.0 g / m ² .

<< Evaluation of Photographic Performance >> (Exposure Processing) The obtained coated sample was passed through an interference filter having a peak at 780 nm and a step wedge.
Exposure was performed with xenon flash light having an emission time of ^10-6 seconds.

(Heat Developing Process) The heat developing machine shown in FIG.
No.-13294 having a structure similar to that of the heat developing machine shown in FIG. 3 in which two types of heat sources are arranged, so that two-stage heating can be performed continuously. The exposed sample was subjected to the following thermal development processing using this thermal developing machine. After treatment at 105 ° C. for 10 seconds (condition under which no image appears), 12
Treatment at 0 ° C for 22 seconds.

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

(Evaluation of Stability of Emulsion Layer Coating Solution with Time) After the completion of the emulsion layer coating solution, the mixture was aged at 30 ° C. for 10 hours, and a photographic material was similarly prepared. This sample was similarly evaluated for heat development and photographic performance (fog, gradation). Practically, the fog value must be 0.15 or less and the gradation must be 15 or more, regardless of the aging of the emulsion layer coating solution.
Table 5 shows the results. Those without aging are expressed as fresh.

[0275]

[Table 5]

(Results) By using the compounds of the present invention in combination, a photothermographic material having high emulsion layer coating solution stability while satisfying super-high contrast property was obtained. It was also found that the combined use of the compounds of the formulas (A1) to (A3) and the compound of the formula (H) can reduce the amount of these compounds used.

[0277]

According to the present invention, a photothermographic material having high stability in the coating solution of the emulsion layer, low fog and high contrast can be 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 exit 7 guide plate 8 feed roller pair 9 flat guide plate 10 feed roller pair 11 cooling fan

Claims (5)

[Claims] 1. The method according to claim 1, wherein on at least one surface of the support,
(A) a photosensitive silver halide, (b) a reducible silver salt,
A method for producing a photothermographic material comprising (c) a reducing agent, (d) a binder, and (e) an antifoggant represented by the formula (1), wherein the formula (A1), the formula (A2), the formula (A) A3) and the formula (H)
Wherein at least one compound selected from the compounds represented by formula (1) is contained, the compound is added as an aqueous dispersion to a coating solution. Embedded image [In the formula (1), M represents a hydrogen atom or a k-valent cation, and R represents a substituent. n is an integer of 1 to 4;
When ≧ 2, a plurality of Rs may be the same or different. k is an integer of 1 or more, and when M is a hydrogen atom, k = 1
It is. ] Embedded image Embedded image [In the formula (A1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and Z represents an electron-withdrawing group. In the formula (A1), R ¹ and Z, R ² and R ³ , R ¹ and R ² , and R ³ and Z may be mutually bonded to form a cyclic structure. In the formula (A2), R ⁴ is
Represents a substituent. In the formula (A3), X and Y each independently represent a hydrogen atom or a substituent;
Are each independently an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group,
Represents an anilino group, a heterocyclic oxy group, a heterocyclic thio group, or a heterocyclic amino group. In the formula (A3), X and Y
And A and B may be bonded to each other to form a cyclic structure. ] [In the formula (H), R ²⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a block group, and G ¹ represents -CO-, -COCO-, -C ( = S)
_{-, - SO 2 -, -} SO -, - PO (R 30) - group (. R ³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10), or imino Represents a methylene group.
A ¹ and A ² each represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group;
At least one of among ¹ and A ² are hydrogen atoms.
m ¹ is 0 or 1, and when m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group. ] 2. The formula (A1), the formula (A2), and the formula (A)
A method for producing a photothermographic material, wherein both of at least one compound selected from the compounds represented by the formula (3) and at least one compound represented by the formula (H) are added to a coating solution as an aqueous dispersion. 3. The formula (A1), the formula (A2), the formula (A3),
3. The method for producing a photothermographic material according to claim 1, wherein at least one compound selected from the group consisting of and a compound represented by the formula (H) is contained in the aqueous dispersion in the form of solid fine particles dispersed therein. 4. The formula (A1), the formula (A2), and the formula (A)
At least one compound selected from the compounds represented by the formula (3) and at least one compound represented by the formula (H) are both contained in an aqueous dispersion in a solid fine particle dispersed state. 3. The method for producing a photothermographic material according to any one of 3. 5. An image forming layer containing a photosensitive silver halide, wherein a polymer latex is used as 50% by weight or more of a binder of the image forming layer, and 60% of a solvent is used.
The method for producing a photothermographic material according to any one of claims 1 to 4, wherein the image forming layer is formed by applying a coating liquid containing water in an amount of not less than water by weight.