JP2000206653A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solvent coating system heat developable photosensitive material which suppresses the variation of gradation in raw stock preservation, has high contrast when used for making a printing plate and hardly develops curl even in the case of a rolled product and to obtain an aqueous coating system heat developable photosensitive material which suppresses humidity sensitization and the variation of gradation in raw stock preservation, has high contrast when used for making a printing plate and hardly develops curl even in the case of a rolled product. SOLUTION: A heat developable photosensitive material having organic silver salt grains, photosensitive silver halide grains and a reducing agent on the substrate is packed with a packing material having <=50 ml/ atm.m2.25 deg.C.day oxygen permeability or a packing material having <=10 g/ atm.m225 deg.C.day water permeability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly, to a solvent-coated photothermographic material and a water-based photothermographic material using a polymer latex.
Eliminates problems of gradation fluctuation during raw preservation, softening in systems employing high contrast technology, and curling in roll products, and increasing the humidity of photothermographic materials in water-based coating systems using polymer latex. This is to prevent feeling.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, a waste liquid accompanying wet processing of an image forming material has become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic applications, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution and clear black image. This technique includes, for example, U.S. Patent Nos. 3,152,904 and 3,487,075 and D.C. "Dry Silver Photograph" by Morgan
phy Materials) "(Handbook
of Imaging Materials, Ma
rcelDekker, Inc. 48, 1991)
And the like, a photothermographic material containing an organic silver salt, photosensitive silver halide grains, a reducing agent and a binder on a support is known.

[0003] These photothermographic materials form a photographic image by a heat development process, and include a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, a silver salt. A color toning agent for suppressing color tone is usually contained in a dispersed state in an (organic) binder matrix. The photothermographic material is stable at room temperature, but is exposed to high temperature (for example, 8
(0 ° C. to 140 ° C.). 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.

In the production of such a photothermographic material, coating is often performed in a state where a coating composition is dissolved in an organic solvent such as methyl ethyl ketone or acetone. In a photosensitive material using these organic solvents, as described in JP-A-6-301140 or the like, by keeping the amount of the residual solvent after coating constant, the fluctuation of the developing temperature and the fluctuation of the density over time can be reduced. It is known.

[0005] However, it is a fact that gradation adjustment during raw preservation cannot be prevented only by adjusting the amount of solvent in the layer.

A photosensitive material capable of obtaining a high-contrast image is required for printing plate-making, and such a high-contrast technology is disclosed in US Pat. Nos. 5,545,505 and 5,464,738. It is known that a hydrazine derivative is used in the above method, but there is a problem that a softening is remarkably caused in a solvent-coated photosensitive material employing such a high contrast technology.

On the other hand, it is known that a photothermographic material is applied to a photosensitive layer using a polymer latex by aqueous coating. In such a case, coating is often performed in a state where a coating composition in which 30% by weight or more of a solvent is water is dispersed or dissolved. These photosensitive materials are disclosed in JP-A-10-62899 and JP-A-10-690.
23, 10-81067, etc., but 1) a large amount of water remains in the photosensitive material due to the water-based coating. 2) Even if water in the photosensitive material is removed, there is a problem that water permeates from the outside of the package and is retained in the photosensitive material which is easily adapted to water. As a result, the reaction is accelerated in the above-described reaction for forming a black image, or the reaction in the non-image area is advanced, resulting in a problem of humidity sensitization. In fact, it was not possible to prevent gradation fluctuation during raw storage.

Further, when these photothermographic materials are used as printing plate-making materials, since the product is in the form of a roll, the curl is likely to be formed.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and the first object of the present invention is to suppress gradation fluctuation during raw preservation and to use it for printing plate making. An object of the present invention is to provide a solvent-applied photothermographic material which is hard and hard to form a curl even as a roll product. Secondly, the present invention provides a water-based photothermographic material which has a high contrast and is hard to be curled even as a roll product when used for printing plate making, in which humidity sensitization and gradation fluctuation during raw preservation are suppressed. Is to do.

[0010]

The first object of the present invention is to provide a support having organic silver particles, photosensitive silver halide particles and a reducing agent, and having an oxygen permeability of 50 ml / atm · m ² ···.
Packaging material of 25 ° C / day or less, or moisture permeability 10g
/ Atm · m ² · 25 ° C. · day, heat-developable photosensitive material packaged with a packaging material having a hydrazine derivative, the smoother value of the outermost surface on the side having the photosensitive layer is 40 mmHg or less, The smoother value of the outermost surface on the side opposite to the side having the photosensitive layer on the support is 80 mmH
g or more, and at least one layer containing a hydrophobic binder.

A second object of the present invention is to provide a support having organic silver particles, photosensitive silver halide particles, a reducing agent and a polymer latex, and having an oxygen permeability of 50 ml / atm · m ² · 2.
Packaging material of 5 ° C./day or less, or moisture permeability 10 g /
a photothermographic material packed with a packaging material of atm · m ² · 25 ° C. · day or less, containing a hydrazine derivative, and having a smoother value of 4 on the outermost surface on the side having the photosensitive layer.
0 mmHg or less, and the smoother value of the outermost surface on the side opposite to the side having the photosensitive layer on the support is 80 mmHg.
That is achieved by the above.

That is, the present inventor has proposed that when packaging is made of a material having a small oxygen permeability or moisture permeability, gradation change during raw preservation and softening in a system employing a high contrast technology and a roll product can be obtained. It has been found that the problems of curling and humidity sensitization of the aqueous coating system can be solved, and surprisingly, the image storability after processing is also improved.

Hereinafter, the present invention will be described in detail.

The photothermographic material of the present invention, after being manufactured, has an oxygen transmission rate of 50 ml / atm · m ² · 25 ° C. · day
One feature is that it is packaged with the following packaging materials. Preferably 0 to 20 ml / atm · m ² · 25 ° C.
day or less.

The packaging materials that can be employed in the present invention include polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, and nylon (stretched or unstretched). ), Polyvinylidene chloride, polystyrene, polycarbonate,
Vinylon, EVAL, polyethylene terephthalate (P
ET), other polyesters, hydrochloride rubber, acrylonitrile butadiene copolymer, epoxy-phosphate resin (polymer described in JP-A-63-63037, polymer described in JP-A-57-32952). Examples include a synthetic resin material and pulp.

These are preferably made of a single material, but when used as a film, the films are laminated and bonded, but may be used as a coating layer or a single layer.

Further, for example, an aluminum foil or an aluminum vapor-deposited synthetic resin is used between the above-mentioned synthetic resin films.
It is more preferable to use various gas barrier films.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
μm, more preferably 50 to 1000 μm.

Another feature of the present invention is that after the photothermographic material is manufactured, the water permeability is 10 g / atm · m ² · 25 ° C.
-It is to be packaged with a packaging material of day or less. Further, it is preferably 0 to 5 g / atm · m ² · 25 ° C. · day or less.

The moisture permeability of the packaging material referred to here is determined by JI
It is a water vapor permeability measured by the measurement method of SK7129-1992. The measurement conditions were as follows: test temperature 40 ° C, relative humidity 90%.
RH.

Packaging materials satisfying the moisture permeability of the present invention include polyethylene resin, nylon resin, polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate. Copolymer resins, acrylonitrile-butadiene copolymer resins, cellophane resins, vinylon resins, vinylidene chloride resins, and the like. A resin such as a polypropylene resin or a nylon resin may be stretched, and may be further coated with a vinylidene chloride resin. In addition, low-density or high-density polyethylene resins can be used.

Among the above polymer materials, polyethylene (PE), nylon (Ny), vinylidene chloride resin (P
VDC) coated nylon (KNy), unstretched polypropylene (CPP), stretched polypropylene (OP
P), PVDC coated polypropylene (KO
P), polyethylene terephthalate (PET), PVD
It is preferable to use C-coated cellophane (KPT) and polyethylene-vinyl alcohol copolymer (EVAL). By using these resins, a packaging material having appropriate mechanical strength and moisture permeability in the present invention can be easily obtained.

In the present invention, a polymer material on which an inorganic compound is vapor-deposited can also be used. As such a polymer material, a conventionally known material can be used. As the polymer material on which the inorganic compound is deposited, any of the above materials can be used. Aluminum and aluminum oxide (Al
₂ O ₃ ), silicon oxide (SiOx) and the like. The thickness of the deposited film is in the range of 50 to 1000 °. As a method for vapor deposition, a known method such as a chemical vapor deposition method, a physical vapor deposition method, a vapor deposition method, and a sputtering method can be used. When the packaging material of the present invention has a multilayer structure, the thickness of each layer is appropriately set according to the desired moisture permeability, mechanical strength, and the like.
0 μm or less. The method for producing the multilayer packaging material is not particularly limited, and examples thereof include a method of bonding a resin layer and a resin layer with an adhesive or the like, a method of bonding a resin layer and a resin layer with a molten resin, an extrusion method, a lamination method, and the like. No.

The polymer material that can be used in the present invention includes:
Specific examples include, but are not limited to, the following. In the following, (outermost) /
The layer structure of (intermediate part) / (contact part with the heat developing material) is shown. For example, SiOx PET, Al ₂ O ₃ PET
Indicates that SiOx and Al ₂ O ₃ are deposited on PET, respectively.

(1) OPP / SiOx PET / CPP (2) OPP / SiOx PET / PE (3) OPP / Al ₂ O ₃ PET / CPP (4) Al ₂ O ₃ PET / Ny / CPP (5) PET / Al ₂ O ₃ PET / PE (6) KOP / Ny / PE (7) PE / KNy / PE (8) KPT / PE / Ny / PE (9) OPP / CPP (10) PET / Eval / PE (11) OPP / Eval / PE In each of the above specific examples, the film thickness of each layer may be set so as to obtain a water permeability suitable for the range of the present invention.

In the present invention, the oxygen permeability is 50 ml /
It is preferable to use a packaging material that satisfies both the condition of atm · m ² · 25 ° C. · day or less and the condition of moisture permeability 10 g / atm · m ² · 25 ° C. · day or less.

In the present invention, when the photothermographic material contains a hydrazine derivative as a high contrast agent, the effect can be fully exhibited.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0029]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group, each of which may have a substituent;
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, 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 represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, 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, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen 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. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent.

Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or 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.

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

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 ) — represents a group. Preferred G ₀ is -CO-
Group, -COCO- group, G ₁ is a mere bond,
—O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D ₁ are present in the molecule If so, 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, And an amino group. 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.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in columns 11 to 20 of US Pat. No. 5,545,505.
U.S. Pat. No. 5,464,738 column 9 to column 11
And compounds 1 to 12.

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.

The photothermographic material of the present invention includes hydroxylamine compounds, alkanolamine compounds and ammonium phthalate compounds described in US Pat. No. 5,545,505, and US Pat. No. 5,545,507. Hydroxamic acid compounds of US Pat. No. 5,558,983
N-acyl-hydrazine compounds described in U.S. Pat. No. 5,545,515, acrylonitrile compounds described in U.S. Pat. No. 5,937,449, and benzhydrol, diphenylphosphine, dialkylpiperidine and alkyl described in U.S. Pat. No. 5,937,449. It is preferable to add a hardening accelerator such as a hydrogen atom donor compound such as -β-ketoester. Among them, a quaternary onium compound represented by the following general formula (P) and an amino compound represented by the general formula (Na) are preferably used.

[0048]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Incidentally, R _{1 to} R ₄ may be connected to each other to form a ring.

[0050]

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In the general formula [Na], R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group, Represents an unsaturated heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ may form a ring. Particularly preferred are aliphatic tertiary amine compounds.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable, and examples thereof include those having the same meaning as the diffusion-resistant group in A in the general formula [H]. Preferred examples of the adsorptive group include a heterocycle, a mercapto group, a thioether group, a thione group, and a thiourea group.

More preferred nucleation accelerators than the nucleation accelerator represented by the general formula [Na] include compounds represented by the following general formula [Na2].

[0053]

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In the general formula [Na2], R ¹ , R ² , R
³ and R ⁴ are each a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
Represents a substituted alkynyl group, an aryl group, a substituted aryl group, or a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Also, R ¹ and R ² , R ³
And R ⁴ are not simultaneously hydrogen atoms. X is S, S
represents an e or Te atom. L ¹ and L ² each represent a divalent linking group. Specific examples include the following groups or combinations thereof, and groups having an appropriate substituent (eg, an alkylene group, an alkenylene group, an arylene group, an acylamino group, a sulfonamide group, and the like).

-CH _2- , -CH = CH-, -C ₂ H
₄ -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, - S
-, - (CO) -, - (SO 2) -, - CH 2 N-.

The linking group represented by L ¹ or L ² preferably contains at least one or more of the following structures in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ )
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
_{[OCH 2 C (OH) HCH} 2] -.

The following are specific examples of the nucleation accelerator represented by the general formula [Na] or [Na2].

[0059]

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[0060]

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[0061]

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[0062]

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In the general formula (P), the substituent represented by R _{1 to} R ₄ is an alkyl group (methyl group, ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

The ring which may be formed by linking R _{1 to} R ₄ includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

[0067] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0069]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0074] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0075]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value at the phenyl group is described in many literatures, for example, Journal of Medical C
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group ([sigma] P = -0.17 or less, and any group having a negative sigma value) can be seen in reports by C. Hansch et al.
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

The following are specific examples of the quaternary onium compound, but the invention is not limited thereto.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews 55 p. 3
35-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

A quaternary onium compound and an amino compound are
They may be used alone or in combination of two or more.
The compound may be added to any of the constituent layers of the photosensitive material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, further to the photosensitive layer and / or an adjacent layer thereof.

In the photothermographic material of the present invention, the smoother value of the outermost surface on the side having the photosensitive layer is 40 mmHg or less,
The smoother value of the outermost surface on the side opposite to the side having the photosensitive layer is preferably 80 mmHg or more.

Here, the smoother value is defined by the value of the suction pressure (mmHg) measured under the following conditions. The measurement is performed using a smoother SM-6B manufactured by Toei Electric Industry Co., Ltd.
High mmHg values correspond to large surface irregularities and / or large numbers of irregularities. Before the measurement, the humidity is adjusted at 23 ° C. and a relative humidity of 48% for 2 hours, and the measurement is performed by the above-mentioned device under the same environment.

In the present invention, the smoother value of the outermost surface on the side having the photosensitive layer is preferably from 0.1 mmHg to 3 mmHg.
The range is 5 mmHg, and more preferably, the range is 1 mmHg to 32 mmHg.

The smoother value of the outermost surface opposite to the side having the photosensitive layer is preferably from 85 mmHg to 400 mmHg.
g, more preferably from 90 mmHg to 25 mmHg.
The range is 0 mmHg.

The smoother value is determined by the combination of the amount of a binder such as polyvinyl butyral, cellulose acetate butyrate, polyester, or polymer latex in the constituent layers of the light-sensitive material, the particle size, shape, and addition amount of a matting agent, and the hardness. It is determined by the type and amount of the compound that changes the physical properties of the binder such as an agent and a plasticizer, the coating and drying conditions, and the like. In the present invention, the smoother value is adjusted to an optimum range by combining these techniques. By setting the content within this range, it is possible to further reduce the curl in the roll form.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a hetero organic acid containing a reducible silver ion source, especially a long chain (10 to 30, preferably 15 to 25, And the nitrogen-containing heterocycle is 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. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
And salts thereof: organic acid salts (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (Eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); 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)) and a silver salt or complex of a thione (e.g., 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thione, 3-carboxymethyl-4-thiazoline-2-thione))), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,2.
Complexes or salts of silver and a nitrogen acid selected from 4-triazole 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.)
Sodium behenate, sodium arachidate, etc.)
The soap and silver nitrate are added to produce organic silver salt crystals. At that time, silver halide grains may be mixed.

In the present invention, the silver halide grains 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 formula is 40% or less. More preferably 30%
Or less, 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, more preferably 7% or more.
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 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;
No. 314,798, No. 5,320,958, and the like, and the desired tabular grains can be easily obtained. When these tabular grains are used in the present invention,
Further, the sharpness of the image is 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.

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 the improvement. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

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 include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used.

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 from 0.5 g to 2.2 g 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 contains a reducing agent. Examples of suitable reducing agents are described in US Pat.
448, 3,773,512, 3,593,8
No. 63 and Research Disclosure
Nos. 17029 and 29996, and include the following. Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (eg, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0110]

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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.

[0113]

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[0114]

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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 polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, (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 (eg, poly (vinylformal) and poly (vinylbutyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or hydrophobic, but 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.

When a polymer latex is used, a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be dissolved and used.

Further, by a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexane is used to dissolve and dissolve mechanically. And emulsified and dispersed. Alternatively, ball mill, colloid mill,
Zirconia beads can be dispersed or used by ultrasonic waves.

As the binder when the polymer latex is used, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate Any one can be selected from such as. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral, butyl ethyl cellulose, methacrylate copolymer, maleic anhydride copolymer, polystyrene and butadiene-styrene copolymer. If necessary, two or more of these polymers can be used in combination.

The "polymer latex" referred to here is a polymer in which a water-insoluble hydrophobic polymer is 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. "Synthetic resin emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kankokai (197
8))), “Applications of Synthetic Latex (Edited by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Polymer Publishing Association (19)
93)) "and" Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970)) "and the like. The average particle size of the dispersed particles is 1 to 50000 nm, more preferably 5 to 50000 nm.
A range of about 1000 nm is preferable. 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, and so-called core / shell type latex may be used.

Examples of the polymer used for the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. 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.

Specific examples of the polymer latex include methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex and methyl methacrylate / 2
Latex of ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, styrene / butadiene /
Latex of 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 can be mentioned. Such polymers are also commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4
635, 46583, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 82
1, 820, 857 (Nippon Zeon Co., Ltd.), etc.
As a polyester resin, FINETEX ES65
0, 611, 675, and 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, WMS (all manufactured by Eastman Chemical), and the like.
LAST is a rubber-based resin such as RAN AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.).
AR 7310K, 3307B, 4700H, 7132
C (manufactured by Dainippon Ink and Chemicals, Inc.), Nipol L
x416, 410, 438C, 2507 (all manufactured by Nippon Zeon Co., Ltd.) and the like.
G576 (all manufactured by Zeon Corporation); vinylidene chloride resins such as L502 and L513 (all manufactured by Asahi Kasei Corporation); olefin resins such as Chemipearl S
120, SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone or as a mixture of two or more as necessary.

The molecular weight of the above polymer is 5 in number average molecular weight.
000 to 1,000,000, more preferably 1
It is about 0000 to 100,000.

It is preferable that the above-mentioned polymer latex is used as 50% by weight or more of the total binder, and it is more preferable that the above-mentioned polymer latex is used as 70% by weight or more.

The minimum film forming temperature of polymer latex (MF
T) is −30 ° C. to 90 ° C., more preferably 0 ° C. to 70 ° C.
It is about. 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) which is also called a plasticizer and lowers the minimum film-forming temperature of the polymer latex. For example, the above-mentioned "Synthetic Latex Chemistry (Souichi Muroi, published by Polymer Publishing Association, 197
0)) ".

The polymer of the polymer latex used in the present invention has an equilibrium water content at 25 ° C. and 60% RH of 2 wt.
%, More preferably 1% by weight or less.

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, in the solvent coating system, the amount of the binder in the photosensitive layer is preferably from 1.5 to 1.5 in order to increase the speed of thermal development.
It is preferably 10 g / m ² . More preferably, it is 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.

The total amount of the binder in the photosensitive layer of the aqueous coating was 0.1.
The range is preferably ^{2 to} 30 g / m ² , more preferably 1 to 15 g / m ² . Further, a cross-linking agent for cross-linking, a surfactant for improving coating properties, and the like may be added.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and in order to prevent damage to the image after thermal development, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferable that the matting agent is contained in a weight ratio of 0.5 to 30% 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 shape of the matting agent may be either regular or irregular, but is preferably regular and spherical.

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.

These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a sliding agent such as a polysiloxane compound, wax or liquid paraffin.

In the photothermographic material of the present invention, various surfactants are used as a coating aid. Among them, a fluorine-based surfactant is preferably used for improving charging characteristics and preventing spot-like coating failure.

The light-sensitive 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.

Examples of suitable toning agents used in the present invention are R.
essearch Disclosure No. 17029.

In the heat-developable material of the present invention, a mercapto compound, a disulfide compound, a thione compound and a thione compound are used to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. Compounds can be included.

The photothermographic material of the present invention may contain an antifoggant.

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 may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. These additives and the other additives mentioned above are Re
search Disclosure Item170
29 (p. 9-15, June 1978) can be preferably used.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. , Polyethylene naphthalate).

Among them, a preferred support is a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene polymer having a syndiotactic structure. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm, and more preferably 110 to 17 μm.
0 μm.

A plastic support which has been heat-treated to improve dimensional stability and distortion due to heat development can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the image forming layer is applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

As the method of forming a film and the method of producing an undercoat according to the present invention, known methods can be used, but preferably, paragraphs [0030] to [0] of JP-A-9-50994 are used.
070].

When the packaging material according to the present invention is applied to the photothermographic material using the above-described support and packaged, the distortion during thermal development is further improved, or the photothermographic material may be stored over time or under high temperature and high humidity conditions. It has the advantage of excellent dimensional stability.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be included in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.

[0146]

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 PET Support) A commercially available biaxially stretched heat-fixed PET film having a thickness of 100 μm was coated on both surfaces with 8 w /
m ² · m of corona discharge treatment, the following undercoating coating liquid a-1 is applied to one side to a dry film thickness of 0.8 μm, and dried to form an undercoating layer A-1, and vice versa. On the side surface, the following antistatic coating solution b-1 was applied with a dry film thickness of 0.8 μm
And dried to form an antistatic subbing layer B-
It was set to 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 polystyrene fine particles (average particle diameter 3 μm) 0.05 g colloidal silica (average particle diameter 90 μm) 0 .1 g with water 1 l << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) Styrene ( 20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g hexa Styrene-1,6-bis subsequently finish 1l in (ethyleneurea) 0.8 g Water, to the undercoat layer A-1 and the upper surface 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 undercoating layer A-2, the undercoating layer B-1 is coated with the following undercoating upper 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 Undercoating >> 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

[0150]

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[0151]

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(Heat Treatment of Support) The above-mentioned subbed support was placed in a heat treatment zone having a total length of 150 m set at 200 ° C., and was conveyed at a tension of 4 kg / cm ² and a conveyance speed of 10 m / min. After that, pass through the zone of 40 ° C. for 20 seconds, 9k
The film was wound at a winding tension of g / cm ² .

(Preparation of Emulsion A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the temperature was adjusted to 35 ° C. and the pH to 3.0.
g of an aqueous solution containing sodium chloride, potassium bromide and potassium iodide in a molar ratio of (60/38/2) and [Ir (NO) Cl ₅ ] salt in an amount of 1 × 10 ⁻⁶ per mole of silver. The mol and rhodium chloride salt were added by the controlled double jet method at 1 × 10 ⁻⁶ mol per mol of silver while keeping the pAg at 7.7. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 8 with NaOH, and the pAg was adjusted to 6.5 to perform reduction sensitization to obtain an average particle size of 0.06 μm.
The coefficient of variation of the projected diameter area with a monodispersity of 10% is 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and desalting treatment was performed.

(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 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. 147m of 1M silver nitrate solution
was added over 7 minutes, and the mixture was further stirred for 20 minutes, and the 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 was formed, the water was removed, washed six times with water and removed, and then dried.

(Preparation of Photosensitive Emulsion) The preform emulsion thus obtained was divided, and a solution of polyvinyl butyral (average molecular weight: 3000) in methyl ethyl ketone (17w) was prepared.
t%) 544 g and toluene 107 g were gradually added and mixed, and then a medium disperser using a 0.5 mm size ZrO ₂ bead mill at 4000 psi at 30 ° C. and 10 ° C.
Minutes of dispersion.

The following layers were simultaneously coated on both sides of the support to prepare a sample. The drying was performed at 60 ° C. for 15 minutes.

(Coating on Back Side) A liquid having the following composition was coated on the B-1 layer of the support.

Cellulose acetate butyrate 15 ml / m ² (10% methyl ethyl ketone solution) Dye-A 7 mg / m ² Dye-B 7 mg / m ² Matting agent: monodispersity 15% Average particle size 8 μm monodisperse silica 90 mg / m ² _{C 8 F 17 (CH 2 CH} 2 O) 12 C 8 F 17 50mg / m 2 C 9 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2

[0160]

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(Coating on Photosensitive Layer Side) Photosensitive Layer 1: A solution having the following composition was coated on layer A-1 of the support so that the coated silver amount was 2.4 g / m ² .

Preform emulsion 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Oxidizing agent ( 10 ml methanol solution) 1.2 ml 2-4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml hydrazine Derivative H-26 0.4 g Hardening accelerator P-51 0.3 g Phthalazine 0.6 g 4-Methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate having an average particle size of 3 μm 0.1 g A-4 (20 % Methanol solution) 20.5ml Isocyanate Compound 0.5g (Mobay Corp., Desmodur N3300)

[0163]

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Surface protective layer: A solution having the following composition was coated simultaneously on the photosensitive layer.

[0165] 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 developer (20% methanol solution) 10 ml / m ² Matting agent: Monodisperse Degree 10% average particle size 4 μm monodisperse silica 5 mg / m ² CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ＝ CH ₂ 35 mg / m ² fluorinated surfactant C ₁₂ F ₂₅ (CH ₂ CH ₂ O) ₁₀ C1 smooster value of ^{_{2 F 25 10mg / m 2 C}} 8 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2 photosensitive layer side of the surface is 25 mmHg, smooster backing side of the surface The value is 200mm
Hg. The smoother value was measured by keeping the sample unexposed and humidifying at 23 ° C. and 48% RH for 2 hours, and measuring the smoother value of the surface on the photosensitive layer side in the same environment by using a SM-produced by Toyo Denshi Kogyo KK. 6B.

Using the sample after forming the coating film, removing the binder, and observing with an electron microscope by a replica method, the organic silver particles were found to have a major axis diameter of 0.5 ± 0.05 μm.
m, tabular grains having a minor axis diameter of 0.4 ± 0.05 μm and a thickness of 0.01 μm are monodispersity of 5%, which is 90% of all organic silver grains.
Particles.

The photothermographic material prepared above was cut into a 30 cm width and 50 m length in a dark room, and wound around a core made of cardboard having an inner diameter of 10 cm to prepare a roll-shaped sample. Further, the sample produced in the dark room was wound with a packaging material of 60 cm × 2 m made of the material shown in Table 1.

<< Forced Deterioration Test >> The packaged photothermographic material sample prepared above was subjected to a forced deterioration condition of 40 ° C.
Heated at 80% RH for 5 days.

<< Exposure and development treatment >> Thereafter, 780 nm
300 using a Dolev 2dry manufactured by Scitex, an image setter equipped with a semiconductor laser
Exposure the halftone dots to change the exposure amount in 5% steps with a line,
Thermal development was performed at 120 ° C. for 25 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

<< Test of winding habit >> A sample subjected to the above-mentioned forced deterioration was cut into a piece having a width of 20 cm and a length of 60 cm.
In a room conditioned to RH, it was measured how much the edge curled and jumped off the floor when the sample was placed on a flat floor. It can be seen that the larger the bounce, the stronger the winding habit.

<< Transportability Test >> The exposure of the sample subjected to the forced deterioration described above and the heat development were repeated 100 times. At that time, the number of sheets having a conveyance failure was counted. A sample having a strong curl tends to cause transport failure.

<Evaluation of Softening> The sample subjected to the forced deterioration described above was heat-exposed to light and 5% of the halftone dot was visually observed with a 100-fold loupe. We scored 5 without any fringes and dropped ranks as the fringes came out. Less than three ranks are not practical.

<< Evaluation of Change in Density after Thermal Development >> The sample subjected to the forced deterioration described above was subjected to exposure and heat development, and the two were divided into two. It was put into the machine for 5 days. The density was measured using a densitometer to determine how much the density changed from 2.5 before the thermometer was injected to the thermometer.

The results are shown in Table 2.

[0175]

[Table 1]

[0176]

[Table 2]

Example 2 A photothermographic material was prepared in the same manner as in Example 1, except that the silver halide emulsion was changed to B below, the hydrazine derivative of the photosensitive layer was changed to H-14, and the high contrast accelerator was changed to P-42. Produced. The produced photothermographic material was cut into a 30 cm width and 50 m length in a dark room, and wound around a core made of cardboard having an inner diameter of 10 cm to prepare a roll-shaped sample. Further, a sample prepared in a dark room was made of the material shown in Table 3 and was 60 cm × 2 m.
Wrapped tightly in the packaging material. Table 4 shows the results of the evaluation performed in the same manner as in Example 1.

(Preparation of Silver Halide Emulsion B) A silver chlorobromide core particle having an average thickness of 0.01 μm and an average diameter of 0.05 μm composed of silver chloride of 70 mol% and the remainder of silver bromide was prepared by a double jet method. Prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ I
rCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion had an average thickness of 0.02 μm and an average diameter of 0.09
μm core / shell monodispersion (coefficient of variation 10%) (1
(00) plane as a main plane.
Mol%, 0.2 mol% of silver iodobromide, and the remainder being silver bromide). Then, JP-A-2-280
No. 139, page 287 (3).
(The amino group in gelatin was substituted with phenylcarbamyl) for desalting.

The EAg after desalting was 190 mV at 50 ° C. 4-hydroxy-6-methyl-1,3,3a, 7
Tetrazindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5.5.
6. Adjust the EAg to 123 mV and adjust chloroauric acid to 2 × 10
After the addition of ^-5 mol, 3 × 10 ^-6 mol of inorganic sulfur was added, and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After aging, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ per mole of silver.
Mole, 1-phenyl-5-mercaptotetrazole
× 10 ^-4 mol and gelatin were added.

[0180]

[Table 3]

[0181]

[Table 4]

Example 3 (Preparation of silver halide particles C) In 700 ml of water, 22 g of phthalated gelatin and 30 mg of potassium bromide were dissolved, and the pH was adjusted to 5.0 at a temperature of 40 ° C.
159 ml of an aqueous solution containing 8.6 g and an aqueous solution containing potassium bromide were added over 10 minutes by a control double jet method while maintaining the pAg at 7.7. K ₃ [IrC
l _6] ^3- was added 8 × 10 ^-6 mol / L of potassium bromide over 30 minutes by the controlled double jet method while maintaining the pAg7.7 an aqueous solution containing 1 mol / L. Thereafter, the pH and the pAg were adjusted to 5.9 and 8.0 (average particle size 0.07 μm, variation coefficient of projected area diameter 8%, (10
0) Cubic particles having an area ratio of 86%. ).

The above silver halide grains C were heated to a temperature of 60 ° C. to give 8.5 × 10 ^-5 mol of sodium thiosulfate and 1.1 × 10 ^-5 mol of 2,3,4 per mol of silver. , 5,6
-Pentafluorophenyldiphenylsulfin selenide, 3.3 × 10 ^-6 mol of chloroauric acid, 2.3 × 10 ^-4 mol of thiocyanic acid were added, and the mixture was aged for 120 minutes. Thereafter, the temperature was raised to 50 ° C., 8 × 10 ⁻⁴ mol of sensitizing dye was added with stirring, and 3.5 × 10 ⁻² mol of potassium iodide was added, followed by stirring for 30 minutes. And the preparation of silver halide grains was completed.

(Preparation of Organic Crystalline Silver Crystal Dispersion) 40 g of behenic acid, 7.3 g of stearic acid and 500 ml of distilled water were added to 9
Mix at 0 ° C. for 15 minutes, and add 1N-Na with vigorous stirring.
187 ml of an OH aqueous solution was added over 15 minutes, and 61 ml of a 1N-nitric acid aqueous solution was added, and the temperature was lowered to 50 ° C. next,
124 ml of a 1N silver nitrate aqueous solution is added and
Stirred for minutes. Thereafter, the solid content was filtered by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. The solid content thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol was added to a wet cake equivalent to 34.8 g of dry solid content.
And 150 ml of water were added and mixed well to form a slurry. 840 g of zirconia beads having an average diameter of 0.5 mm
And placed in a vessel together with the slurry, and dispersed for 5 hours with a dispersing machine (1 / 4G-sand grinder mill: manufactured by Imex Co., Ltd.) to obtain a volume-weighted average of 1.5 μm.
m of organic acid silver microcrystal dispersion was obtained.

(Preparation of Material Solid Fine Particle Dispersion) Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
Solid fine particle dispersions were prepared for 5-trimethylhexane, phthalazine, and tribromomethylsulfonylbenzene.

To tetrachlorophthalic acid, 0.81 g of hydroxypropylcellulose and 94.2 ml of water were added, stirred well, and left as a slurry for 10 hours. Thereafter, 100 ml of zirconia beads having an average diameter of 0.5 mm and a slurry were put together in a vessel, and dispersed in a dispersing machine of the same type as that used for preparing the silver salt of organic acid microcrystals for 5 hours. A solid microcrystalline dispersion of the acid was obtained. As for the particle size of the solid fine particles, 70 wt% was 1.0 μm or less.

With respect to other materials, the amount of the dispersant used and the dispersion time were appropriately changed in order to obtain a desired average particle size, and a solid fine particle dispersion was obtained.

(Preparation of Emulsion Layer Coating Solution) Each of the following compositions was added to the previously prepared organic acid silver microcrystal dispersion to prepare an emulsion coating solution.

Organic acid silver microcrystal dispersion 1 mol Silver halide particles C 0.05 mol Binder: latex of styrene-butadiene copolymer (LACSTAR 3307B, manufactured by Dainippon Ink and Chemicals, Inc .; 0.15 μm) 430 g Tetrachlorophthalic acid 5 g 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g Phthalazine 9.0 g Tribromomethylphenylsulfone 12 g 4-methylphthalate Acid 7 g N- (2-methoxyphenyl) -N'-formylhydrazine 15 g (Preparation of coating solution for emulsion protective layer) Polymer latex having a solid content of 27.5% (methyl methacrylate / styrene-2-
Ethylhexyl acrylate / 2-hydroxyethyl methacrylate methacrylic acid = 59/9/26/5/1
Glass transition temperature of 55 ° C.) 109 g of H ₂ O
3.75 g was added, and 4.5 g of benzyl alcohol, 0.45 g of compound D, and 0.125 of compound E were used as film-forming aids.
g, 0.0125 g mol of compound F, and 2.25 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-217)
Was further added, and H ₂ O was further added to make 150 g to obtain a coating solution.

(Preparation of Back Surface 3 Coating Solution) The following compositions were added to polyvinyl alcohol to prepare a back surface coating solution.

Polyvinyl alcohol 30 g Dye C 5 g Water 250 g Spherical silica 1.8 g (manufactured by Dokai Chemical Co., Ltd., Sildex H121, average size 12 μm)

[0192]

Embedded image

(Preparation of Back Surface 4 Coating Solution) A back surface 4 coating solution was prepared in the same manner as the back surface 3 coating solution except that the amount of the spherical silica material was changed to 2.5 g.

The emulsion layer coating solution prepared as described above was coated with 1.6 g / m ^{2 of} silver on a polyethylene terephthalate support.
The emulsion layer protective layer coating solution was simultaneously coated thereon so as to obtain a dry film thickness of 2 μm. After drying, a coating solution for the back surface was applied on the surface opposite to the emulsion layer so that the optical density at 780 nm became 0.7, thereby preparing a sample. The drying was performed at 60 ° C. for 30 minutes.

The smoother value of the surface on the photosensitive layer side is 20 m
mHg, and the smoother value of the surface on the backing side was 40 mmHg for the back surface 3 and 150 mmH for the back surface 4.
g.

The heat-developable photosensitive material prepared above was used as a roll-shaped sample similarly wound with a packaging material, and evaluated in the same manner as in Example 1. Humid sensitization was also evaluated as follows.

<< Evaluation of Humidity Sensitization Evaluation >> 1) Evaluation of Optical Transmission Density at 400 nm Over Time after Thermal Development Processing The prepared sample was divided into two, and one of them was evaluated at 25.degree. It was thrown into the RH thermostat for 3 days. The unexposed sample was thermally developed at 120 ° C. for 25 seconds, and the transmission density at 400 nm of the unexposed portion was measured using a spectrophotometer U-3000 manufactured by Hitachi, Ltd. From the transmission density before storage, the rate of change of the transmission density after storage was evaluated. The larger the fluctuation rate, the longer it takes to expose the PS plate in the next step, or the problem that fine dots and lines are not reproduced is likely to occur (the higher the fluctuation rate, the higher the sensitivity. ing).

2) Evaluation of Performance Fluctuation due to Changes in Thermal Development Processing Conditions The prepared sample was divided into two samples, and one of them was put into a thermostat at 25 ° C. and 80% RH for 3 days as an evaluation for the age. Halftone dots were exposed using the image setter at 300 lines so as to change the amount of exposure at 5% intervals, and subjected to heat development at 120 ° C. for 25 seconds. At that time, exposure and development are 23 ° C, 50%
Performed in a room conditioned to RH. The density of the developed sample was measured with an optical densitometer (manufactured by Konica Corporation: PDA-65) and the density was 3
The sensitivity before storage was set to 100, and from the sensitivity before storage, the rate of change of the sample after 3 days in a thermostat was evaluated as the sensitivity (a higher rate of change means higher sensitization).

Tables 5 and 6 show the relationship between the oxygen permeability of the packaging material and each evaluation result, and Tables 7 and 8 show the relationship between the moisture permeability and each evaluation result.

[0200]

[Table 5]

[0201]

[Table 6]

[0202]

[Table 7]

[0203]

[Table 8]

[0204]

According to the present invention, it is possible to soften a solvent-applied photothermographic material and a water-based photothermographic material in a system which employs gradation fluctuation during raw storage and high contrast technology. The problem of the curl in the roll product can be solved, the sensitization of humidity of the water-based photothermographic material can be suppressed, and the image storability after processing can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/498 502 G03C 1/498 502

Claims (9)

[Claims] An organic silver particle, a photosensitive silver halide particle and a reducing agent are provided on a support, and an oxygen transmission rate is 50 ml / at.
A photothermographic material, wherein the photothermographic material is packaged with a packaging material having a temperature of at most m · m ² · 25 ° C. · day. 2. The photothermographic material according to claim 1, further comprising a hydrazine derivative. 3. A support having organic silver particles, photosensitive silver halide particles and a reducing agent on a support, and having a water permeability of 10 g / atm.
A photothermographic material, wherein the photothermographic material is packaged with a packaging material having a temperature of m ² · 25 ° C. · day or less. 4. The photothermographic material according to claim 3, further comprising a hydrazine derivative. 5. The moisture permeability of the packaging material is 10 g / a.
3. The photothermographic material according to claim 1, wherein the temperature is not more than tm.m < ² > .25 DEG C..day. 6. The photothermographic material according to claim 1, wherein the smoother value of the outermost surface on the side having the photosensitive layer is 40 mmHg or less. 7. The smoother according to claim 1, wherein the outermost surface on the side opposite to the side having the photosensitive layer on the support has a smoother value of 80 mmHg or more. Photothermographic material. 8. The photothermographic material according to claim 1, wherein at least one layer contains a hydrophobic binder. 9. The photothermographic material according to claim 1, wherein at least one layer contains a polymer latex.