JP2000112071A - Heat-developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the storage stability of a heat-developable photosensitive material containing a contrast enhancing agent, especially, to restrain the increase of fog with time by forming a layer containing an organic silver salt and a silver halide and a reducing agent and at least one kind of a specified hydrazine derivative and incorporating at least one kind of a compound having a group capable of releasing a halogen radical in the molecule. SOLUTION: The heat-developable photosensitive material is provided on a support with at least one photosensitive layer containing an organic silver salt and a silver halide and a reducing agent and a compound having a group capable or releasing a halogen radical in the molecule and at least one kind of hydrazine derivative represented by the formula in which A0 is an aliphatic or aromatic or heterocyclic or -G0-D0 group each optionally substituted; B0 is a blocking group; each of A1 and A2 is H atom or one is H atom and the other is an acyl or sulfonyl or oxalyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material having excellent storage stability after development, and more particularly to a black-and-white photothermographic material.

[0002]

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

A photothermographic material for forming a photographic image by using a heat development method as a technique for this purpose is disclosed in, for example, US Pat. Nos. 3,152,904 and 3,457,075 and D.C.
Morgan and B.A. Shelley
y) "Heat treated silver system (The
rally Processed Silver S
systems) "(Imaging Processes and Materials)
es and Materials) Neblett
e, 8th edition, Sturge, V.E. Walworth, A .; Shep
p) Edit, page 2, 1969).

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

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

As a method for solving these problems, Japanese Patent Application Laid-Open No.
No. 60164, No. 9-244178, No. 9-2583
No. 67, No. 9-265150, No. 9-281640
And JP-A-9-319022 disclose polyhalogen compounds in which the above-mentioned disadvantages are improved. However, in particular, when these compounds are applied to a photothermographic material for output of a printing imagesetter containing a high contrast agent and having an oscillation wavelength of 600 to 800 nm, the above disadvantages are considerably improved, It is not enough.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to reduce the preservability of a photothermographic material containing a high contrast agent, in particular, to increase fog over time. To keep it down.

[0008]

The object of the present invention is to provide a photothermographic material having at least one photosensitive layer on a support, comprising an organic silver salt, a silver halide, a reducing agent,
A photothermographic material having a layer containing at least one hydrazine derivative represented by the general formula [H] and having at least one compound having a group capable of releasing a halogen radical in the molecule; A compound having a group capable of releasing a halogen radical therein is represented by the general formulas 1 to 3.
Represented by any of the above.

Hereinafter, the present invention will be described in detail.

The details of the photothermographic material are disclosed in the above-mentioned documents. Among them, in the present invention, an image is formed by thermally developing a photosensitive material at 80 to 140 ° C.
The feature is that no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, the hydrazine derivative is a compound represented by the general formula [H].

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, in -G ₀ -D ₀ group represented by A _0, G ₀ is -CO
Group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. G ₁ is a mere bond, -O-
A group, —S— group or —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, They can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferable D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group, and the like.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group, and the aromatic group and the heterocyclic group of A ₀ may have a substituent.
Specific examples of the substituent having an acidic group of Ka 7 to 11 include a sulfonamide group, a hydroxyl group, and a mercapto group.

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

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — group, and preferred G ₀ is —CO—
Group, particularly preferably at -COCO- group -COCO- group and the like, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group, D ₁ is an aliphatic Group, aromatic group,
Represents a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, they may be the same or different.
D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, Examples include an amino group, and more preferably an alkyl group and an amino group substituted with fluorine. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (Such as an ethoxalyl group).

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

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[0020]

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[0021]

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[0022]

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[0023]

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Other hydrazine derivatives that can be preferably used include compounds H-1 to H-2 described in columns 11 to 20 of US Pat. No. 5,545,505.
Compound Nos. 1 to 12 described in Columns 9 to 11 of JP-A No. 5464738 and No. 5464738 are exemplified.

These hydrazine derivatives can be synthesized by a known method.

The hydrazine derivative-added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is preferably from 10 ^-6 mol per mol of silver halide.
The range is preferably about 10 ^-1 mol, particularly preferably 10 ^-5 mol to 10 ^-2 mol.

Next, the compound represented by Formula 1 will be described in detail.

The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom. More preferred are a chlorine atom and a bromine atom, and particularly preferred is a bromine atom.

Y represents a divalent linking group, specifically, -S
O ₂ —, —SO—, —CO—, —N (R ₁₁ ) —SO ₂ —,
—N (R ₁₁ ) —CO—, —N (R ₁₁ ) —COO—, —C
OCO-, -COO-, -OCO-, -OCOO-,-
SCO -, - SCOO -, - C (Z 1) (Z 2) -, alkylene, arylene, a divalent heterocyclic and divalent groups formed by any combination thereof. R
₁₁ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, and are not hydrogen atoms at the same time. The electron withdrawing group is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, and more preferably 0.1 or more.
These are the above substituents. Regarding Hammett's substituent constant, see Journal of Medicinal Ch.
chemistry, 1973, Vol. 16, No. 1
1, 1207-1216 and the like can be referred to.

Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06) and a chlorine atom (σp value
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (eg, C ₃ H) ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.45)), carbamoyl group ( σp value:
0.36), a sulfamoyl group (σp value: 0.57) and the like.

Z ₁ and Z ₂ are preferably a halogen atom, a cyano group or a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred. Y is preferably -SO
_2- , -SO-, -CO-, and more preferably -S
O ₂ —. n is preferably 1.

The electron-withdrawing group represented by A is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably 0.1 or more.

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

The aliphatic group represented by Q is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 12; Ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, etc., and an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, furthermore Preferably it is 2-12, for example, vinyl, allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (preferably having 2-3 carbon atoms)
0, more preferably 2 to 20, even more preferably 2 to 12
And for example, propargyl, 3-pentenyl and the like. ), And may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and a ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group. The aryl group represented by Q preferably has 6 to 30 carbon atoms.
A monocyclic or bicyclic aryl group (e.g., phenyl, naphthyl, etc.), more preferably a phenyl group having 6 to 20 carbon atoms, and still more preferably a phenyl group having 6 to 12 carbon atoms.
The aryl group may have a substituent, and as the substituent,
For example, a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group,
An oxycarbonylamino group or a ureido group;

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

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole and the like can be mentioned. Preferably as a heterocycle, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, Tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, more preferably triazine,
They are quinoline, thiadiazole, benzothiazole and oxadiazole, particularly preferably pyridine, quinoline, thiadiazole and oxadiazole. Q is preferably an aromatic nitrogen-containing heterocyclic group. m represents an integer of 3 or more and 4 or less, and preferably m is 3. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10, but is preferably 6.

In the compound represented by the formula (2), X ₁ , X ₂ and A have the same meanings as those described in the formula (1). Q represents an aromatic hetero 5-membered ring having one oxygen atom and two to three nitrogen atoms, a furan ring, a thiophene ring, and a pyrrole ring, where one oxygen atom and two nitrogen atoms
Specific examples of the 5-membered aromatic hetero ring having 3 or more and 3 or less include oxadiazole and oxatriazole. Preferred is oxadiazole. Preferred among the rings represented by Q is oxadiazole.

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

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

Y is -SO-, -CO-, -N (R ₁₁ )-
SO _2- , -N (R ₁₁ ) -CO-, -N (R ₁₁ ) -CO
O-, -COCO-, -COO-, -OCO-, -OC
OO -, - SCO -, - SCOO -, - C (Z 1)
(Z ₂ ) —, an alkylene, an arylene, a divalent heterocyclic ring, and a divalent substituent formed by any combination thereof. R ₁₁ represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but they are not a hydrogen atom at the same time. The electron-withdrawing group is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably 0.1 or more.

Z ₁ and Z ₂ are preferably a halogen atom, a cyano group or a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred. Y is preferably -SO
-, - CO -, - N (R 11) -SO 2 -, - N (R 11)
_{-CO -, - C (Z 1} ) (Z 2) - ; more preferably, _{-SO -, - C (Z 1} ) (Z 2) - represents a. n is preferably 1. Q represents an aliphatic group, an aromatic group, or a heterocyclic group. However, when Y is -SO-, Q represents a 5-membered aromatic heterocyclic group having at least one heteroatom other than N and a pyridine ring. These rings may be further condensed with other rings. Specific examples of the aromatic 5-membered heterocyclic group having at least one hetero atom other than N include thiazole, oxazole, thiophene, furan, pyrrole, thiadiazole, oxadiazole, thiatriazole,
It represents oxatriazole, and Q is preferably a thiadiazole ring, a pyridine ring or a quinoline ring.

Specific examples of the compounds represented by formulas 1 to 3 will be shown below, but the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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These compounds are described, for example, in JP-A-54-1
No. 65, JP-A-6-340611 and 7-2781
Nos. 7-5621, 7-199553, U.S. Pat. Nos. 5,369,000, 5,374,514 and 5,
No. 460938, No. 5464737, European Patent No. 60
It can be synthesized according to the method described in No. 5981, No. 631176 and the like.

The amount of the compounds represented by the general formulas 1 to 3 is not particularly limited, but is preferably from 10 ^-4 mol to 1 mol / Ag mol, particularly preferably from 10 ^-3 mol to 0.3 mol / Ag mol. Is preferred. Also, a photosensitive layer or a non-photosensitive layer can be added, and a photosensitive layer is preferable. It is preferable that these compounds are added after being dissolved in an organic solvent.

The silver halide grains in the present invention function as a light sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm or less.
m to 0.1 μm, particularly preferably 0.02 μm to 0.08 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. The particle size is more preferably 30 or less, and particularly preferably 0.1% or more and 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the silver halide particles have an average particle size of 0.1.
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is preferably high, and this proportion is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means that the square root of the projected area is defined as a particle size rμm, and the thickness in the vertical direction is defined as hμ.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. These are disclosed in U.S. Pat. Nos. 5,264,337 and 5,314.
No. 798, No. 5,320,958, etc., and desired tabular grains can be easily obtained. When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements for the purpose of improving illuminance failure and adjusting gradation. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, a hexacoordinate complex ion or complex represented by the following general formula is preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 11 of the periodic table, L is a bridging ligand, and m is 0,-, 2- or 3-.
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

Specific examples of the transition metal coordination complex ion are shown below.

[0063] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{2 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2-23 : [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^2- 27: [Ir (NS) Cl _5] ^2- also may with ions or complex ions one kind of these metals, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions or complex ions is generally 1 × 10 ⁻⁹ per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, the particles can be contained in the particles with a distribution. It is preferable to have a distribution inside the particles. These metal compounds can be prepared from water or a suitable organic solvent (eg, alcohols, ethers, glycols,
Ketones, esters, and amides). For example, an aqueous solution of a powder of a metal compound or an aqueous solution of a metal compound and NaCl or KCl dissolved together may be added to water-soluble silver during particle formation. A silver halide grain is prepared by a method in which the silver halide solution is added to a salt solution or a water-soluble halide solution, or as a third aqueous solution when a silver salt solution and a halide solution are simultaneously mixed, and a three-solution simultaneous mixing method. A method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or another silver halide grain doped with metal ions or complex ions in advance during silver halide preparation is added and dissolved. There is a method to make it. In particular, an aqueous solution of a metal compound powder or a metal compound and N
It is preferable to add an aqueous solution in which aCl and KCl are dissolved together to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

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

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Preferred chemical sensitization methods are sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization as well known in the art. Sensitization can be used. As compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds, for example, compounds described in JP-A-7-128768 can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and US Pat. No. 2,448,060.
And British Patent No. 618061 can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also,
Reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

Organic silver salts are reducible silver sources, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10-30, preferably 15-25 carbon atoms). Aliphatic carboxylic acids and nitrogen-containing heterocycles are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Discl
Osure 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Salts of oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) −3,
3-dimethylthiourea); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-
Thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole And silver salts of nitrogen acids and silver selected from benzotriazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, arachidic acid and / or stearic acid.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a control double jet to prepare crystals of an organic silver salt. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 2
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.05 μm to 1.5 μm, particularly 0.05 μm
~ 1.0 µm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
It is. In the present invention, the tabular grains of the organic silver salt preferably account for at least 60% of the total organic silver. In the present invention, the tabular grains refer to those having a so-called aspect ratio (abbreviated as AR) of 3 or more, which is expressed by the ratio of average particle diameter to thickness, average particle diameter (μm) / thickness (μm).

The organic silver having such a shape can be obtained by dispersing and pulverizing the organic silver crystal with a binder, a surfactant and the like using a ball mill or the like. Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g or more and 2.2 g or less per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,737,512, and 35.
No. 93863, and Research Disclos
ure Nos. 17029 and 29996,
There are the following: Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (for example, Np-methylphenyl-
Hydrazones of aldehydes or ketones (e.g., anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone) And (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxamic acid); sulfonamidoanilines (e.g., 4- (N-methanesulfonamido) aniline); 2-tetra Zolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (for example, 1,2,3,4-tetrahydroquinoxaline); amido Synths; Azines (for example, a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid); Polyhydroxybenzene and hydroxylamine; reductone and / or hydrazine; Hydroxanoic acids; Azines and sulfonamidophenols Α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,
Chromanes; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0072]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, t- butyl ).

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

[0075]

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[0076]

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The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymers, synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic. , Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (vinyl chloride) Acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly ( Esters), Li (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

Further, in order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer can be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the speed of thermal development. More preferably, 1.7 to 8 g /
m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to prevent the image after thermal development from being damaged, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferred that the agent be contained in an amount of 0.5 to 30% by weight based on all binders on the photosensitive layer side.
When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent to prevent slippage of the photosensitive material and prevention of fingerprint adhesion. Also, it is preferable to provide a matting agent on the surface of the photosensitive material, and it is preferable that the matting agent is contained in a weight ratio of 0.5 to 40% with respect to all binders in the layer on the side opposite to the photosensitive layer side.

The material of the matting agent may be either an organic substance or an inorganic substance. For example, as the inorganic substance, silica described in Swiss Patent No. 330158 or the like, French Patent No. 1296
No. 995, glass powder described in British Patent No. 117318
Alkaline earth metals or carbonates such as cadmium and zinc described in No. 1 and the like. Organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625451, British Patent No. 981198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, and Swiss Patent No. 3301
Organic matting agents such as polystyrene or polymethacrylate described in No. 58, etc., polyacrylonitrile described in U.S. Pat. No. 3,079,257, and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

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

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The variation coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. The coefficient of variation is a value represented by (standard deviation of particle size) / (average value of particle size) × 100.

The matting agent can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer.
More preferably, it is the outermost layer as viewed from the support.

The method of applying the matting agent may be a method of dispersing in a coating solution in advance and applying the same, or a method of applying the coating solution and spraying the matting agent before drying is completed. Is also good. When a plurality of types of matting agents are added, both methods may be used in combination.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer on the opposite side, a so-called backing layer, may be formed. Dyes or pigments may be included. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range.
Nos. 9-6481, 59-182436, U.S. Pat. Nos. 4,271,263 and 4,594,312, European Patent Publication Nos. 533,008, 652473, and JP-A-2-21.
No. 6140, No. 4-348339, No. 7-19143
Compounds described in Nos. 2, 7-301890 and the like are preferably used.

The non-photosensitive layer preferably contains the binder or matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

The heat-developable photographic light-sensitive material of the present invention forms a photographic image by heat-development processing. It is preferable that the color tone agent which suppresses the color tone of silver is contained in a state usually dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but has a high temperature after exposure (for example, 80 ° C to 140 ° C).
Developed by heating. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

Examples of suitable toning agents used in the present invention are R
No. 17029, which includes the following:

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

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

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy (eg, For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole,
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
2-mercaptoquinoline, 8-mercaptopurine, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like,
The present invention is not limited to these.

The heat-developable photographic light-sensitive material of the present invention includes, for example, JP-A-63-159814 and JP-A-60-140335.
No. 63-231437, No. 63-296551
No. 63-304242, No. 63-15245,
U.S. Pat. Nos. 4,639,414 and 4,740,45
No. 5, 4,741,966, 4,751,175
And sensitizing dyes described in JP-A Nos. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item 1
7643IV-A (p.23, December 1978) and Item 1831X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-806
The compounds described in No. 79 are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the present invention includes, for example, a surfactant, an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers, coating aids, and the like may be used. These additives and the other additives mentioned above are Research Disclosure Item 1
Compounds described in No. 7029 (pp. 9-15, June 1978) can be preferably used.

The support used in the present invention is preferably a plastic film (eg, polyethylene terephthalate (PET), polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate) in order to prevent deformation of the image after development processing. . The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm. A heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming the support and before the photosensitive layer is applied, the support is heated from the glass transition point of the support by 30 degrees.
At a high temperature, preferably at least 35 ° C,
It is more preferable to heat at a temperature higher than 40 ° C. and not exceeding the melting point of the support.

The method of forming a film of a support and the method of producing an undercoat according to the present invention may be a known method. Preferably, paragraphs [0030] to [0] of JP-A-9-50094 are used.
070].

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.
In the present invention, US Patent No. 5,244,773 column 1
The conductive compounds described in 4 to 20 are preferably used.

[0100]

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

Example 1 (Preparation of Subbed Photographic Support) A commercially available biaxially stretched and heat-fixed blue-colored PET film having a thickness of 175 μm was subjected to a corona discharge treatment of 8 w / m ² · min. On one side, the undercoating coating solution a-1 shown below was applied to a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The coating solution b-1 was applied so as to have a dry film thickness of 0.8 μm and dried to obtain an antistatic-processed undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << Undercoat coating solution b-1 >> Butyl acrylate (40% by weight) ) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water Then, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Lower Substrate >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower upper layer coating solution b-2 >> (C-4) 60 g Latex solution containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0104]

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[0105]

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(Heat Treatment of Support) In the above-mentioned undercoat drying step of the undercoated support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of Emulsion A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0.
g of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) and [Ir (N
O) Cl ₅ ] salt was added in an amount of 1 × 10 ^-6 mole per silver mole and rhodium chloride salt in an amount of 1 × 10 ^-6 mole per silver mole, pA
After the addition by the controlled double jet method while maintaining the pH at 7.7, reduction sensitization was performed at pH 8.7 and pAg 6.5. Thereafter, 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetrazaindene and add NaOH to p.
By adjusting H to 5, cubic silver iodobromide grains having an average grain size of 0.06 μm, a monodispersity of 10%, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87% were obtained. After coagulating and sedimenting this emulsion using a gelatin coagulant and desalting, 0.1 g of phenoxyethanol was added, pH 5.9, pAg7.
Adjusted to 5 to obtain a silver halide emulsion.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later, 1M silver nitrate solution 14
7 ml was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion has formed, the water is removed and an additional 6
After washing with water and removing water several times, it was dried.

(Preparation of photosensitive emulsion) Polyvinyl butyral (average molecular weight: 300
544 g of 0) methyl ethyl ketone solution (17 wt%)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 psi.

(Back side coating) A back layer coating solution having the following composition was applied by an extrusion coater to a wet film thickness of 30 μm, and dried at 60 ° C. for 3 minutes.

Back layer coating liquid: cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² monodispersity 15%, monodisperse silica having an average particle size of 8 μm Matting agent 30 mg / m ² C ₉ F ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0113]

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(Coating of photosensitive layer side) A coating solution of a photosensitive layer having the following composition and a coating solution of a protective layer were coated thereon in an extrusion coater at a speed of 20 m / min. At this time, the silver was applied such that the amount of silver applied was 2.4 g / m ² . afterwards,
Drying was performed at 55 ° C. for 15 minutes.

Photosensitive layer coating solution: Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Antifoggant-described in Table 1 (10% methanol solution) 1.2 ml Hydrazine compound-described in Table 1 (5% methanol solution) 2 ml 2-4-Chlorobenzoylbenzoic acid (12% methanol solution) 9 0.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml Developer-1 (20% methanol solution) 29.5 ml phthalazine 0.6 g 4-methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Coating solution for surface protective layer: Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² monodispersity 10%, monodisperse silica having an average particle size 4μm matting agent 70 mg / m ² CH ₂ ＣＨCH—SO ₂ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —SO ₂ —CH ₂ —CH ₂ CH ₂ 35 mg / m ² Spot inhibitor 50 mg / m ² C ₉ H ₁₇ —C ₆ H ₄ — SO ₃ Na 10 mg / m ²

[0116]

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<< Exposure and Development >> The heat-developable photographic photosensitive material prepared above was exposed with an imager having a semiconductor laser of 810 nm. Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

<< Evaluation of Photographic Performance >> The obtained images were evaluated with a densitometer. Evaluation of sensitivity is fog density +3.0
The reciprocal of the exposure amount that gives the transmission density of
o. The relative sensitivity when the sensitivity of 1 was 100. The fog density here refers to the density of a portion where halftone dots are exposed to 0%, and the smaller the value, the better. Also, the gradient of a straight line connecting the points of density 0.3 and 3.0 on the characteristic curve is shown as gradation γ.

The results are shown in Table 1.

[0120]

[Table 1]

As is clear from the table, by using the antifoggant of the present invention, a heat-developable photographic light-sensitive material having high sensitivity, low fog and high contrast was obtained.

Example 2 The photothermographic material prepared as described above was charged into a thermo machine at 50 ° C. and 50% RH for 5 days, and then similarly exposed with an imager having a semiconductor laser of 810 nm, and an automatism having a heat drum was obtained. Heat development was performed at 110 ° C. for 15 seconds using a developing machine. At that time, exposure and development are 23 ° C, 50%
Performed in a room conditioned to RH.

<< Evaluation of Raw Storage Property of Photothermographic Material >> Evaluation of sensitivity, fog and γ was performed in the same manner as in Example 1.

Table 2 shows the results.

[0125]

[Table 2]

While the comparative sample showed a decrease in sensitivity, softening, and a remarkable increase in fog due to storage at high temperature, the sample of the present invention maintained high sensitivity and high contrast even after storage at high temperature, It can be seen that there is almost no increase in fog.

[0127]

According to the present invention, a heat-developable photographic light-sensitive material excellent in raw preservability and suitable for use in printing plate making can be obtained.

Claims (2)

[Claims] 1. A photothermographic material having at least one photosensitive layer on a support, comprising at least one hydrazine derivative represented by the general formula [H], an organic silver salt, silver halide, a reducing agent, A photothermographic material comprising at least one compound having a layer containing a species and having a group capable of releasing a halogen radical in a molecule. Embedded image [In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent, B ₀ represents a blocking group, and A ₁ and A ₂ Each represents a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. G ₀ is a -CO- group, -COCO-
Group, -CS- group, -C (= NG ₁ D ₁ )-group, -SO-
A —SO ₂ — group or —P (O) (G ₁ D ₁ ) — group, where G ₁ is a mere bond, a —O— group, a —S— group, or a —N
Represents a (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different. Is also good. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group,
Represents an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. ] 2. The photothermographic material according to claim 1, wherein the compound having a group capable of releasing a halogen radical in the molecule is represented by any of the following formulas (1) to (3). Embedded image [In the formula, X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom, or another electron-withdrawing group. m represents an integer of 3 or more and 4 or less. Q represents a heterocyclic group, an aryl group, or an aliphatic group. n
Represents an integer of 0 or more and 3 or less. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10. [Chemical formula 3] [Wherein, X ₁ , X ₂ and A have the same meanings as those described in formula 1. Q represents an aromatic hetero 5-membered ring having one oxygen atom and 2 to 3 nitrogen atoms, a furan ring, a thiophene ring, and a pyrrole ring. However, when Q is a thiophene ring, X ₁ represents a bromine atom. [Formula 4] [Wherein, X ₁ , X ₂ and A have the same meanings as those described in formula 1. Y is -SO -, - CO -, - N (R 11) -S
O _2- , -N (R ₁₁ ) -CO-, -N (R ₁₁ ) -COO
-, -COCO-, -COO-, -OCO-, -OCO
O -, - SCO -, - SCOO -, - C (Z 1) (Z 2)
-Represents an alkylene, an arylene, a divalent hetero ring, or a divalent substituent formed by any combination thereof. R ₁₁ represents a hydrogen atom or an alkyl group. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group. Z ₁ and Z ₂ are not hydrogen atoms at the same time. Q represents an aliphatic group, an aromatic group, or a heterocyclic group. However, when Y is -SO-, Q represents a 5-membered aromatic heterocyclic group or a pyridine ring group having at least one heteroatom other than N. ]