JP2000352789A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior antistatic performance and superior scratch resistance after heat development by incorporating a specified compound into a photosensitive layer or at least one of nonphotosensitive layers. SOLUTION: The heat developable photosensitive material contains a compound of the formula in a photosensitive layer containing photosensitive silver halide grains or at least one of nonphotosensitive layers on at least one side of the substrate. In the formula, (8) is 0 or 1, in the case of q=1, A is -(X)a-(Y)b-(Z)c-, X and Z are each a <=100C oxygen-containing hydrocarbon having one terminal ether residue, Y is -O-(C=O)-R-(C=O)- (R is a 1-82C hydrocarbon) or -O-(C=O)-NH-R' NH(-C=O)- (R' is a 2-13C hydrocarbon), (a) to (c) are each 0 or 1, (p) is 10-1,000 and the sign ← shows a coordinate bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material (hereinafter, also simply referred to as a "photosensitive material"), and particularly to a laser imager or a laser imagesetter having a high antistatic property and excellent scratch resistance after thermal development. The present invention relates to a photothermographic material.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquid caused by wet processing of an image forming material has been a problem in terms of workability. It is strongly desired to reduce the amount of waste liquid. Therefore, there is a need for a technique relating to a photosensitive material that can be efficiently exposed by a laser imager or a laser imagesetter, can form a high-resolution, clear black image, and can perform processing without processing waste liquid.

As this technique, for example, US Pat.
No. 152,904, No. 3,457,075, and D.C. Morgan Dry Silver Photo
graphic Material and D.M. Morgan
B. Shelly Thermally Procedures
sed Silversystems, Storage,
V. Walworth A. Shepp Editing Nebl
As described in ette, 8th edition, page 2, 1969, etc., a photothermographic material containing an organic silver salt, photosensitive silver halide grains and a reducing agent on a support is known.

[0004] These photothermographic materials are usually 80 to 14
Since the image is formed by thermal development at 0 ° C., in a transport system for photographing and developing the photothermographic material, a large amount of charge is generated due to friction or peeling with a roller during transport, and poor transport due to sticking due to static electricity. The photosensitive material must have a sufficient antistatic function both before and after development. Specifically, it is preferable that the surface electric resistance (Log Ω · cm) measured at 20% RH on at least one surface is reduced to 12.5 or less, preferably 12.0 or less, and more preferably 11.5 or less.

As a countermeasure against these problems, Japanese Patent Laid-Open Publication No.
It is effective to use the conductive metal oxide disclosed in No. 22. Generally, it is known that a metal oxide is contained in, for example, an undercoat layer provided between a support and a photosensitive layer. However, in these methods, scratch resistance after development is accompanied by deterioration, so that a photothermographic material without deterioration in scratch resistance after development has been desired.

[0006]

The above objects of the present invention are as follows.
An object of the present invention is to provide a photothermographic material for a laser imager or a laser imagesetter, which has an excellent antistatic ability and an excellent scratch resistance after thermal development.

[0007]

Means for Solving the Problems In the course of research on photothermographic materials, the present inventors have worked particularly on reducing the surface electric resistance after heating (heat development), and the constitution of the present invention has shown that It has been found that the surface electric resistance is sufficiently lowered without deteriorating the surface resistance and the scratch resistance after development is improved, and it has been found that the above object can be achieved by the following constitutions.

[0008] 1. In a photothermographic material having a photosensitive layer containing photosensitive silver halide grains and a non-photosensitive layer on at least one side of the support, at least one layer selected from the photosensitive layer and the non-photosensitive layer is used. And a photothermographic material comprising a compound represented by the following general formula (1).

[0009]

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In the formula, q is 0 or 1, and when q = 1, A
Is a-(X) a- (Y) b- (Z) c- group (provided that X and Z have a total of 10 carbon atoms having one terminal ether residue).
0 or less oxygen-containing hydrocarbon group, Y is -O- (C = O) -R
A — (C ＝ O) — group (where R is a hydrocarbon group having 1 to 82 carbon atoms) or —O— (C ＝ O) —NH—R′NH (—C =
O) -group (where R 'is a hydrocarbon group having 2 to 13 carbon atoms)
Wherein a, b and c are each 0 or 1, and p is 10 to 1000. In the formula, ← indicates a coordination bond.

2. In a photothermographic material having a photosensitive layer containing photosensitive silver halide grains and a non-photosensitive layer on at least one side of the support, at least one layer selected from the photosensitive layer and the non-photosensitive layer is used. And a photothermographic material comprising a compound represented by the following general formula (2).

Formula (2) [N = P (XR) (X'R ')] n wherein X and X' are groups selected from -O-, -NH- and -NR "-, R, R ', R "are H, B, C, N,
It is composed of at least one atom selected from O, F, P, S, Cl, Br, I, Na, and K, and n represents an integer of 3 or more.

Hereinafter, the present invention will be described in detail.

The photothermographic material of the present invention, which forms a photographic image by a heat development process, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. Is a photothermographic material containing a color tone agent or the like for controlling the color tone in a state dispersed in an organic matrix.

The compound represented by formula (1) of the present invention will be described.

In the general formula (1), q is 0 or 1, and when q = 1, A is-(X) a- (Y) b-
(Z) c-group, wherein X and Z are oxygen-containing hydrocarbon groups having one terminal ether residue and having 100 or less carbon atoms, and Y is-
An O (-C = O) -R (-C = O)-group, wherein R is a hydrocarbon group having 1 to 82 carbon atoms or -O (-C =) O-NH-
R'NH- (C = O)-group, provided that R 'has 2 to 1 carbon atoms
3, a, b and c are each 0 or 1, and p is 10 to 100. In addition, ← in the formula
Represents a coordination bond.

Specific examples of the compound represented by formula (1) of the present invention will be given below, but the present invention is not limited to these.

[0018]

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[0019]

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[0020]

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[0021]

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The compound represented by the general formula (1) of the present invention can be easily synthesized by the methods described in JP-A Nos. 1-259051, 1-259052, 1-266153 and 1-230653. be able to. Further, the compound is commercially available from Boron International, and can be easily obtained.

The compound represented by the general formula (1) can be added by dissolving it in water, alcohol such as methanol, ethanol and isopropanol.

The addition layer of the compound represented by the general formula (1) is added to at least one of the photosensitive emulsion layer and the non-photosensitive layer, but is preferably provided farthest from the support. Layer.

[0025] The amount of addition is 0.01 to 5 g / m
² , preferably 0.5 to 3 g / m ² . If the added amount is less than 0.01 g / m ² , the desired antistatic effect cannot be obtained, and if it exceeds 5 g / m ² , the development processability is affected.

The compound represented by formula (2) will be described.

The compound represented by the general formula (2) is a phosphazene derivative whose basic skeleton is composed of a P = N bond, and a part of the substituent is an ionic side chain group or π which exhibits conductivity. These are an electronic side chain group and a polyether type side chain group. These compound groups include a high molecular weight compound group having a P = N bond and a cyclic compound group. A linear high molecular weight compound is synthesized by ring-opening polymerization of a cyclic compound.

The compounds represented by formula (2) are shown below, but the invention is not limited thereto.

2-1 (NP (NHC ₆ H ₅ ) _1.6 (NH
C ₆ H ₄ SO ₃ H) _0.4 ) _n 2-2 (NP (NHC ₆ H ₅ ) _1.6 (NHC ₆ H ₄ SO ₃ N)
a) _0.4 ) _n n is 3-12.

The method for synthesizing the compound represented by the general formula (2) will be described in more detail. (PNF ₂ ) ₃ , (PNF ₂ ) ₄ ,
(PNF ₂ ) n (n <15) or other such side chain group as an F atom trimer, tetramer, n-mer compound, (PNCl ₂ ) ₃ , (PN
A compound in which a side chain group such as Cl ₂ ) ₄ or (PNCl ₂ ) n (n <15) is a trimer, tetramer, or n-mer of a Cl atom;
r ₂ ) ₃ , (PNBr ₂ ) ₄ , (PNBr ₂ ) n (n <1
5) A compound in which a side chain group such as a Br atom is a trimer, tetramer, or n-mer, (PNI ₂ ) ₃ , (PNI ₂ ) ₄ , (PNI ₂ ) n
(N <15) or the like, wherein the side chain group is a trimer, tetramer, n
The halogen atom of the monomeric compound to C ₆ H ₅ ONa, CH ₃ C ₆
Reaction with a metal salt of an aromatic compound such as H ₄ ONa, (C ₆ H ₅ O) ₂ Ca, CF ₃ CH ₂ ONa, an aromatic compound having a hydroxyl group such as C ₆ H ₅ OH or CH ₂ ( CH ₃ ) = C
Aliphatic alcohols, such as -COOCH ₂ CH ₂ OH, C
Aromatic compounds capable of nucleophilic substitution with a halogen atom on a P atom such as aromatic amines such as ₆ H ₅ NH ₂ , amines such as aniline, and halogen acceptors such as sodium hydroxide and sodium carbonate A method by mixing with a compound can be mentioned.

The compound represented by the general formula (2) can generally be easily synthesized in this manner.

The aromatic side chain group is generally a group derived from a compound having an aromatic ring.

[0033]

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There is a group derived from a compound having a hydroxyl group as a functional group in the aromatic ring.

Further, a group derived from a compound having an amino group as a functional group in an aromatic ring such as aniline or phenylenediamine, or a compound having a mercapto group as a functional group in an aromatic ring such as thiophenol or dimercaptobenzene And the like. Further, the combination of the side chain groups may not necessarily be constituted by a single group, and may be a combination selected from a plurality of these groups.

Further, tetracyanoquinodimethane (TCN)
Q), tetrathiofulvalene, polyacetylene (TT
F), conjugated polymers such as cortellylene, polyparaphenylene, polythiophene, polypyrrole, and polyaniline, or polymers doped with an appropriate doping agent, or polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, and quaternary salt polymers For example, a compound composed of an ionic conductive polymer such as the above can also be used.

Further, fine particles or the like obtained by dispersing a carbon material in an organic polymer and curing the material can also be used. The carbon material is a material produced by a carbonization process using an organic compound as a starting material, and examples thereof include coke, carbon fiber, glassy carbon, pyrolytic carbon, whiskers, and carbon black.

There are various forms of the carbon material depending on the raw material. The main components occupying 90 wt% or more of the constituent elements are C, O, H, and N in the descending order. The present invention can be achieved if the component is 70 wt% or more.

These components of 70 wt% or more are H, B,
The particle diameter (hereinafter, also referred to as particle diameter) of fine particles composed of atoms selected from C, N, O, F, P, S, Cl, Br, I, Na, and K is averaged in terms of smoothness and the like. Particle size 10μm
Or less, more preferably 1 μm or less.
The method for measuring the average particle size (hereinafter also referred to as the average particle size) is not particularly limited, but a method of dispersing in an appropriate solvent and obtaining from the centrifugal sedimentation speed is generally adopted.

However, the main components are H, B, C, N, O,
It may be obtained by an electron microscope from a sample arbitrarily sampled from a powder containing fine particles composed of atoms selected from F, P, S, Cl, Br, I, Na, and K. Further, the average particle size may be measured by a method other than the method described here.

The main components are H, B, C, N, O, F, P,
For the measurement of the specific gravity of the fine particles composed of atoms selected from S, Cl, Br, I, Na, and K, a method which is as close as possible to the specific gravity of the material constituting the fine particles is selected. For example, a method is generally used in which the weight is measured with an analytical balance, and then the volume of the fine particles is measured using an appropriate gas, fluid, or the like, to determine the specific gravity. The method of measuring the specific gravity is not particularly limited, but the main components are H, B, C, N, O, F, P,
Regarding the value of the specific gravity of the fine particles composed of atoms selected from S, Cl, Br, I, Na, and K, based on water at 20 ° C. to avoid the problem of sedimentation of the particles in the coating solution. 0 or less is preferable.

The method for producing these conductive or semiconductive particles may be any method as long as the object of the present invention can be achieved. For example, after dissolving the compound in a suitable solvent, the fine particles are formed by spray drying or the like. , A method of dispersing in a solvent and then pulverizing with a ball mill, sand grinder, etc., a method of pulverizing with a dry pulverizer such as a jet mill or a method of separating a solvent phase and a product into two phases at the time of compound production or two or more phases in advance. Any method can be used as long as the object of the present invention is achieved, such as a method of producing fine particles during production using a method of producing a compound in a separated state.

The powder and the conductive compound are used by being dispersed or dissolved in a binder. Alternatively, the metal oxide particles are subjected to surface treatment or treatment such as microencapsulation with a conductive polymer compound, and after mixing the metal oxide particles into a dissolved or dispersed solution of the conductive polymer compound, The coating may be performed by dispersing a powder which has been subjected to a treatment such as a spray drying method or a freeze drying method in a binder.

The amount added in the case of a coating method using particles and an organic binder is as follows. The conductive polymer compound is added to such an extent that physical properties such as conductivity are not impaired, and the amount added is not limited. The object of the invention is sufficiently achieved when the volume fraction in the polymer after drying is 60% or less, preferably 50% or less, more preferably 40% or less. However, the amount of such powder is preferably 30% or less, more preferably 20% or less, more preferably 20% or less.
% Or less. However, it is necessary to add 0.1% or more, preferably 0.5% or more in volume fraction, and it may be necessary to add 1% or more depending on the compound. However, the addition amount is particularly limited. is not.

By these additions, good transparency and antistatic properties can be obtained, and pressure fog, scratches and the like during the handling of the photothermographic material as well as the conductive substance can be prevented. . When the amount of addition is such, the surface specific resistance of the photothermographic material obtained in the present invention is 1
0 ¹³ Ω · cm, and antistatic properties can be achieved.

The amount of the compound represented by formula (2) of the present invention is 0.5 to 300 per m ^{2 of the} photothermographic material.
0 mg, more preferably 10 mg
１０００1000 mg.

The photosensitive silver halide grains in the present invention will be described.

The photothermographic material of the present invention preferably has a small average particle size in order to suppress white turbidity after image formation and obtain good image quality, and has an average particle size of 0.2 μm or less, more preferably It is 0.01 to 0.17 μm, particularly preferably 0.02 to 0.14 μm.

The grain size referred to herein means that when the silver halide grains are cubic or octahedral so-called normal crystals,
The term refers to the length of a ridge of a silver halide grain, and in the case where the silver halide grain is a tabular grain, the diameter when converted to a circular image having the same area as the projected area of the main surface. The silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. It is 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 The shape of silver halide grains is cubic, octahedral, tabular, spherical, rod-like, potato-like. In the present invention, cubic particles and tabular particles are particularly preferable.

When tabular silver halide grains are used, the average aspect ratio is preferably from 2 to 100, and more preferably from 3 to 50.

These tabular silver halide grains are described in US Pat. Nos. 5,264,337 and 5,314,798;
No. 5,320,958 and the like, and intended tabular grains can be easily obtained.

Further, grains having rounded corners of silver halide grains can be preferably used. The outer surface of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, more preferably 70% or more, and especially 80% or more. Is preferred. The ratio of the [100] plane of the Miller index is determined by the T.V. method using the dependence of the adsorption of the sensitizing dye on the [111] and [100] planes. Tani, J .; Imag
ing Sci. , 29, 165 (1985).

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. In the present invention, silver bromide or silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodobromide content is 0.1 to 4
0 mol% is preferable, and 0.1 to 20 mol% or less is more preferable.

The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously.
A preferred example is silver iodobromide having a high silver iodide content inside the grains. Further, it is preferable to use silver halide grains having a core / shell structure.

The photographic emulsion used in the present invention is described in US Pat. Gl
Chimie et Physique by Afkids
e Photographique (Paul Mon
tel, 1967); F. By Duffin
Photographic Emulsion Chem
istry (published by The Focal Press, 19
66); L. M by Zelikman et al
aking andCoating Photogra
phi Emulsion (The Focal P
Ress, published in 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-side mixing method, a double-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,
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

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

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
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 transition metal complex ions are shown below, but the present invention is not limited to these.

[0064] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) 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- These metal ions, metal complexes or metal complex ions may be of one kind or a combination of two or more of the same and different metals. You may. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

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

In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added uniformly to the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in the above publication, the particles can be contained with a distribution inside the particles. Preferably, they are contained with a distribution inside the particles.

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

When adding to the surface of the particles, 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 during the physical ripening, or at the end of the chemical ripening.

The photosensitive silver halide grains can be desalted by a known desalting method such as a noodle method, flocculation method, ultrafiltration method, and electrodialysis method.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Examples of the sensitization method include known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization and reduction sensitization. A sensitization method can be used. These sensitization methods can be used in combination of two or more. For sulfur sensitization, thiosulfates, thiourea compounds, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization are described in JP-A-9-2.
The compounds described in No. 30527 can be mentioned.

Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide or US Pat. No. 2,448,060, British Patent 618, No. 061 and the like. As the shell-like compound in the reduction sensitization method, ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. Further, when the pH of the emulsion is 7
Reduction sensitization can be achieved by ripening while maintaining the above or pAg at 8.3 or less.

In the photothermographic material of the present invention, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
A holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye, and the like can be used. For example, Japanese Unexamined Patent Application Publication No.
No., 60-140335, 63-231437
No., 63-259,651 and 63-304242
No. 63-15245, U.S. Pat. No. 4,639,4
No. 14, No. 4,740,455, No. 4,741,
No. 966, No. 4,751,175, No. 4,83
The spectral sensitizing dyes described in 5,096 can be used.

Useful spectral sensitizing dyes for use in the photothermographic material of the present invention include, for example, Research Disclosure (RD)
Item 17643 IV-A (December 1978, p.
23), Item 1831X (p. Aug. 1978, p.
437) or in the literature cited. In particular, a spectral sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers and scanners can be advantageously selected. For example, JP-A-9-3407
Compounds described in Nos. 8, 9-54409 and 9-80679 are preferably used.

Useful cyanine dyes are, for example, cyanine dyes having a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred useful merocyanine dyes include:
In addition to the above basic nuclei, acidic nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus are also included.

These spectral sensitizing dyes may be used alone or in combination, and the combination of spectral sensitizing dyes is often used particularly for supersensitization.

Along with the spectral sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Useful spectral sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in the above-mentioned RD176.
Vol. 17643 (published December 1978), page 23, IV, paragraph J or JP-B-43-4933, JP-A-59-1.
Nos. 9032 and 59-192242.

The organic silver salt preferably used in the heat-developable light-sensitive material of the present invention is a reducible silver source, and a silver salt of an organic acid or a hetero organic acid containing a reducible silver ion source, especially a long chain ( A silver salt of an aliphatic carboxylic acid having 10 to 30, preferably 15 to 28, carbon atoms is preferred. Also useful are organic or inorganic silver complexes whose ligands have a complex stability constant for silver ions of 4.0 to 10.0, including, for example: silver salts of organic acids (eg, Silver salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, oleic acid, caproic acid, myristic acid, palmitic acid, maleic acid, linoleic acid, etc .; silver carboxyalkylthiourea salts (for example, 1
-(3-carboxypropyl) thiourea, silver salt such as 1- (3-carboxypropyl) -3,3-dimethylthiourea); silver complex of a polymer reaction product of aldehyde and hydroxy-substituted aromatic carboxylic acid (for example, Aldehydes (silver complexes such as formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (for example, 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, etc.), imidazole, pyrazole, urazole, 1,
Complexes or salts of silver with a nitrogen acid selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides.

Examples of suitable silver salts are described in RD Nos. 17029 and 29963, and a particularly preferred silver source is silver behenate.

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, or a method described in JP-A-9-1276.
The controlled double jet method described in No. 43 is preferably used.

The shape of the organic silver salt is not particularly limited, but a needle-like crystal having a short axis and a long axis is preferred. As is well known in photosensitive silver halide photosensitive materials, the inverse relationship between the particle size of silver salt crystal grains and their covering power also holds in the photothermographic material of the present invention, that is, the photothermographic material It is necessary to reduce the particle size of the organic silver salt because the larger the organic silver salt particle, which is the image forming portion, the smaller the covering power and the lower the image density.

The particle size of the organic acid salt is 0.01 to 0.2 in the short axis.
0 μm and a major axis of 0.10 to 5.0 μm are preferred, and a minor axis of 0.01 to 0.15 μm and a major axis of 0.10 to 4.0 μm are more preferred.

The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion means the percentage of the value obtained by dividing the standard deviation of the lengths of the minor axis and major axis by the minor axis and major axis, respectively, is preferably 100% or less, more preferably 80% or less, and even more preferably 50% or less. Is good. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion.

As another method for measuring the monodispersity, there is a method of calculating the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) of the value divided by the volume-weighted average diameter is known.
Is preferably 100% or less, more preferably 80% or less, and further preferably 50% or less. As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with a laser beam, and an autocorrelation coefficient with respect to a time change of fluctuation of the scattered light is obtained from a particle size (volume weight average diameter) obtained. be able to.

In the photothermographic material of the present invention, the coating amount of an organic silver salt, particularly, an organic silver salt is 0.1 to 1 m ² per photographic material.
It is preferably from 5 to 5.0 g, and more preferably from 1.0 to 3.0 g.

Examples of reducing agents suitable for the photothermographic material of the present invention are described in US Pat. Nos. 3,770,448 and 3,77.
3,512, 3,593,863 and the RD
Nos. 17029 and 29996, and include the following.

Aminohydroxycycloalkenone 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 ,
Chromanes; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine); hindered phenols, 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).

[0088]

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In the general formula (A), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, -C
₄ H ₉ , 2,4,4-trimethylpentyl);
And R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, t-butyl).

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

[0091]

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[0092]

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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, and polyvinyl. Alcohol, hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copolystyrene-maleic anhydride copolymer, styrene-acrylonitrile Copolymer, styrene-butadiene copolymer, polyvinyl acetal (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resin, polyvinyl chloride Emissions, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, polyamides and the like, which may be non-hydrophilic or hydrophobic.

In the photothermographic material of the present invention, the amount of the binder in the photosensitive layer is preferably 1.5 to 10 g / m ² in order to prevent dimensional fluctuation after the heat development. More preferably, it is 1.7 to 8 g / m ² . When the amount of the binder in the photosensitive layer is less than 1.5 g / m ² , the density of the unexposed portion is significantly increased, and may not be usable.

The photothermographic material of the present invention preferably contains a matting agent on the side of the photosensitive layer, and a matting agent is provided on the surface of the photothermographic material to prevent damage to the image after heat development. Preferably, the matting agent is contained in a weight ratio of 0.5 to 10% based on all binders on the emulsion layer side.

The material of the matting agent preferably used in the photothermographic material of the present invention may be either an organic substance or an inorganic substance. For example, as the inorganic substance, Swiss Patent No. 330,
No. 158, French Patent No. 1,296,9
No. 95, British Patent No. 1,173,1
No. 81 or other alkaline earth metals or carbonates such as cadmium and zinc can be used as matting agents.
Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol as described,
Polystyrene or polymethacrylate described in Swiss Patent No. 330,158 and the like, US Pat. No. 3,079,
Organic matting agents such as polyacrylonitrile described in US Pat. No. 257 and the like and polycarbonate described in US Pat. No. 3,022,169 and the like can be used.

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

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

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

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

The method of adding 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, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a catalytically active amount of silver halide, a hydrazine derivative,
A reducing agent and, if necessary, a color tone agent for suppressing the color tone of silver,
Usually, it is preferable that the photothermographic material is contained in a dispersed state in an organic binder matrix.

The photothermographic material of the present invention is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. 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.

To control the amount or wavelength distribution of light passing through the photosensitive layer, a so-called backing layer is formed on at least one layer selected from a filter dye on the same side as the photosensitive layer and an antihalation dye layer on the opposite side. The photosensitive layer may contain a dye or a pigment. As the dyes and pigments to be used, any compounds may be used as long as they have a desired absorption in a desired wavelength range. Examples thereof include JP-A-59-6481 and JP-A-59-182436, and U.S. Pat. No. 4,271,263. No. 4,594,31
No. 2, European Patent Publication No. 533008, No. 652473
No. JP-A-2-216140, 4-348339
And compounds described in JP-A Nos. 7-191432 and 7-301890 are preferably used.

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

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. Various additives are photosensitive layer, non-photosensitive layer,
Alternatively, it may be added to any of the other forming layers.

In the photothermographic material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used.

The photothermographic material of the present invention preferably contains a toning agent. Toning agents are disclosed in US Pat.
0,254, 3,847,612 and 4,
As shown in 123,282, it is a material well known in the photographic art. Examples of suitable toning agents include the RD No. 1
No. 7029, which includes:

Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,2) Naphthalimides (e.g., N-hydroxy-1,8-naphthalimide); cobalt complexes (e.g., hexamine trifluoroacetate of cobalt), mercaptans (e.g., 4-thiazolidinedione).
3-mercapto-1,2,4-triazole); N-
(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaches (eg, N, N′-
Hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane)
A combination of bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothiazolinylidene (benzo) Thiazolinylidene))-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 and benzenesulfinic acid) Sodium or 8-methylphthalazinone and p
A combination of phthalazine and phthalic acid; phthalazine (including an adduct of phthalazine) with maleic anhydride and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride ( For example, phthalic acid, 4-methylphthalic acid, 4-
A combination with at least one compound selected from nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine, naphthoxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine Pyrimidines and asymmetric triazines (for example, 2,4-dione)
Dihydroxypyrimidine) and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, it is preferable to contain a mercapto compound, a disulfide compound or a thione compound in order to control development such as suppression or acceleration of development, to improve spectral sensitization efficiency or to improve storage stability before and after development.

When a mercapto compound is used in the present invention, it may be of any structure, but may be ArSM, Ar-
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, naphthoimidazole,
Complexes such as benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzoterzole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone It is an aromatic ring.

The heteroaromatic ring includes, for example, a halogen atom (for example, each atom such as Br and Cl), a hydroxy group, an amino group, a carboxy group, and an alkyl group (for example, one or more carbon atoms, Those having 4 carbon atoms) and alkoxy groups (eg one or more carbon atoms,
The heteroaromatic compound substituted with a mercapto group which may have a substituent selected from the group consisting of those having preferably 1 to 4 carbon atoms) includes 2-mercaptobenzimidazole, -Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobisbenzothiazole, 3-mercapto-1,2,4 −
Triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-
2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4-
(3H) quinazolinone, 7-trifluoromethyl-4-
Quinolinethiol, 2,3,5,6-tetrachloro-4
-Pyridinethiol, 4-amino-6-hydroxy-2
-Mercaptopyrimidine monohydrate, 2-amino-
5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole,
-Hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4
Examples thereof include a heteroaromatic compound substituted with a mercapto group such as -triazole and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, more preferably 0.01 to 0.3 mol per mol of silver. Is the amount of

What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a photothermographic material is disclosed, for example, in US Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Non-mercury antifoggants include, for example, US Pat.
No. 075 and 4,452,885 and JP-A-59
Preferred are antifoggants such as those disclosed in US Pat.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,99.
Compound-C (X1) (X
2) (X3) (where X1 and X2 are halogen atoms and X
3 is a heterocyclic compound having one or more substituents represented by a hydrogen atom or a halogen atom). As preferred examples of the antifoggant, compounds described in paragraph numbers [0062] to [0063] of JP-A-9-90550 are preferably used.

Further, more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and British Patent Application 9,22.
Nos. 2,138.4, 9,300,147.7 and 9,311,790.1.

In the photosensitive layer according to the present invention, a polyhydric alcohol (for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. Nos. 60,404), U.S. Pat.
Fatty acids or esters described in U.S. Pat. No. 121,060 and silicone resins described in British Patent No. 955,061 can be used.

A hardening agent may be used for each layer such as a photosensitive layer, a protective layer and a back layer of the photothermographic material of the present invention. Examples of the hardening agent include isocyanate compounds and US Pat. No. 4,791. No. 4,042, etc., and the photothermographic materials of the present invention using the vinylsulfone-based compounds described in JP-A-62-89048 and the like are used to improve the coating properties and the chargeability. A surfactant may be used for the purpose. Examples of surfactants include:
Any material such as anionic, cationic, betaine, nonionic, and fluorine can be used as appropriate. Specifically, Japanese Patent Application Laid-Open No. Sho 62-170950, U.S. Pat.
2,504 or the like, a fluoropolymer surfactant,
JP-A-60-244945, JP-A-63-18813
No. 5, fluorinated surfactants described in US Pat.
Examples thereof include polysiloxane-based surfactants described in 885,965 and the like, polyalkylene oxides and anionic surfactants described in JP-A-6-301140 and the like.

The photothermographic material of the present invention can be prepared by various coating methods including a dip coating method, an air knife coating method, a flow coating method and an extrusion coating method using a hopper of the type described in US Pat. No. 2,681,294. Can be used. Also, if necessary, US Pat. No. 2,761,791
Two or more layers can be applied simultaneously by the method described in U.S. Pat.

The support used in the photothermographic material of the present invention may be a plastic film, for example, polyethylene terephthalate, polycarbonate, polyimide, in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. Nylon, cellulose triacetate, polyethylene naphthalate and the like are preferred. Particularly preferred are supports of polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate (hereinafter abbreviated as PEN), and plastic (hereinafter abbreviated as SPS) containing a styrene-based polymer having a syndiotactic structure. Can be

The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

A plastic support which has been heat-treated 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 photosensitive 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.

Next, the plastics preferably used for the support of the photothermographic material of the present invention will be described.

The PET preferably used for the support of the photothermographic material of the present invention is one in which the polyester component is all polyethylene terephthalate. In addition to polyethylene terephthalate, terephthalic acid and naphthalene-2,6 are acid components. -Modified polyester component of dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, etc. and glycol component such as ethylene glycol, propylene glycol, butanediol, cyclohexane dimethanol, etc. is 10 mol% of all polyester The polyester included below may be used.

As PEN, polyethylene-2,6-
Copolyesters comprising naphthalate and terephthalic acid, 2, -6 naphthalenedicarboxylic acid and ethylene glycol, and polyesters comprising as a main component a mixture of two or more of these polyesters are preferred. Also,
Further, another copolymer component may be copolymerized, or another polyester may be mixed.

The SPS is a polystyrene having steric regularity unlike ordinary polystyrene (atactic polystyrene). The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that there are more regular parts such as two, three, five or more. In the present invention, the racemo chain is 2 It is preferably 85% or more in the chain, 75% or more in the three chains, 50% or more in the five chains, and 30% or more in the further chains. The polymerization of SPS can be carried out according to the method described in JP-A-3-131843.

As the method for forming a support and the method for producing an undercoat used in the present invention, known methods can be used. Preferably, paragraph No. [003] of JP-A-9-50094 is used.
0] to [0070].

[0130]

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

Example 1 (Powder P1) (NP (NHC ₆ H ₅ ) _1.6 (NHC ₆ H ₄ S
A 10% solution of O ₃ H) _0.4 ) _n (n is 3 to 12) is spray-dried by a spray-drying method and then collected as a powder. The obtained powder had an average particle size of 0.15 μm and a ratio of 1.2.
5. The volume resistivity was 2.3 × 10 ⁻⁴ Ωcm.

(Powder P2) (NP (NHC ₆ H ₅ )
_1.6 after spray drying by _{(NHC 6 H 4 SO 3 Na} ) 0.4) n (n is 3-12) spray drying of a 10% solution of recovered as a powder. The obtained powder had an average particle size of 0.11.
μm, ratio 1.35, volume resistivity 8.5 × 10 ⁻⁴ Ω ·
cm.

(Preparation of Subbed Photosensitive Material Support) A commercially available biaxially stretched and heat-fixed PET film having a thickness of 100 μm was subjected to a corona discharge treatment of 8 W / m ² .min. The following undercoating coating solution a-1 was dried at a thickness of 0.8 μm.
m and dried to obtain an undercoat layer (A-1).

Next, the undercoating coating solution b-
1 was applied so as to have a dry film thickness of 0.8 μm, and dried to obtain an undercoat layer (B-1).

<Undercoat Coating Solution a-1> Co-weight of butyl acrylate (30% by weight), t-butyl acrylate (20% by weight), styrene (25% by weight), and 2-hydroxyethyl acrylate (25% by weight) Combined latex liquid (solid content 30%) 270 g Compound (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

<Undercoating coating solution b-1> Copolymer latex of butyl acrylate (40% by weight), styrene (20% by weight), and glycidyl acrylate (40% by weight) (solid content: 30%) 270 g Compound (C- 1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Make up to 1 liter with water.

Next, the coated undercoat layers (A-1) and (B-
A corona discharge of 8 W / m ² · min. Is applied to the surface of 1), and the following undercoating upper layer coating solution a-2 is coated on the undercoating layer (A-1) so as to have a dry film thickness of 0.1 μm. The undercoating layer (A-2) is applied, and the undercoating layer (B-1) is coated with the undercoating upper layer coating solution b-2 described below so as to have a dry film thickness of 0.8 μm. B
-2) An undercoating upper layer was applied.

Further, a solution obtained by removing the compounds (C-4) and (C-5) from the following undercoating upper layer coating solution b-2 was used as an undercoating upper layer coating solution (b-3). An undercoating layer (B-3) coated on the undercoating upper layer so as to have a thickness of 0.8 μm was also prepared.

<Coating solution a-2 for lower undercoat> Gelatin 0.4 g / m ² amount Compound (C-1) 0.2 g Compound (C-2) 0.2 g Compound (C-3) 0.1 g Silker particles (average particle size: 3 μm) 0.1 g Make up to 1 liter with water.

<Undercoat upper layer coating solution b-2> Compound (C-4) 60 g Latex containing compound (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g Compound (C-6) 12 g Polyethylene Glycol (average molecular weight 600) 6 g Make up to 1 liter with water.

[0141]

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[0142]

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(Preparation of silver halide emulsion A) 900 m of water
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and then 370 ml of an aqueous solution containing 74 g of silver nitrate (98/98).
Aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 2) and [Ir (NO) Cl _5] ^3- salt per mole of silver 1
× 10 ^-4 mol was added over 10 minutes by a controlled double jet method while keeping the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was adjusted to 5 with NaOH.
Thus, cubic silver iodobromide grains having an average grain size of 0.06 μm, a grain size variation coefficient of 11%, and a [100] face ratio of 87% were obtained.

This emulsion was subjected to coagulation sedimentation using a gelatin coagulant to perform desalting treatment. Thereafter, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion A.

(Preparation of Na Behenate Solution) 34 g of behenic acid was dissolved in 340 ml of isopropanol at 65 ° C. Next, a 0.25N aqueous sodium hydroxide solution was added thereto with stirring so as to have a pH of 8.7. At this time, 400 ml of an aqueous sodium hydroxide solution was required. The obtained aqueous sodium behenate solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

(Preparation of silver behenate) 2.9 ml of a solution prepared by dissolving 30 g of ossein gelatin in 750 ml of distilled water.
A 4 mol silver nitrate solution was added to bring the silver potential to 400 mV. The sodium behenate aqueous solution 37 was added thereto at a temperature of 78 ° C. using a controlled double jet method.
Add 4 ml at a rate of 44.6 ml / min, and at the same time 2.
A 94 mol aqueous silver nitrate solution was added so that the silver potential became 400 mV. The amounts of sodium silver behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.

After completion of the addition, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration.

(Preparation of Photosensitive Emulsion) 15.1 g of the above-mentioned silver halide emulsion A was added to the above-mentioned behenic acid dispersion, and a solution of polyvinyl acetate in n-butyl acetate (1.2 g) was stirred.
100 g) was gradually added to form a floc of the dispersion, then water was removed. After two water washes and removal of water, 2.5 wt% of polyvinyl butyral (average molecular weight 3000) was used as a binder. 60 g of a 1: 2 mixed solution of n-butyl acetate and isopropyl alcohol was added with stirring, and then polyvinyl butyral (average molecular weight 4000) and isopropyl were added as binders to the resulting mixture of silver behenate and silver halide. Alcohol was added and dispersed.

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

<Back surface side coating> A liquid having the following composition was applied to a dry film thickness of 5 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml / m ² Dye-B 70 mg / m ² Dye-C 70 mg / m ²

[0152]

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(Coating on Photosensitive Layer Surface Side) <Photosensitive Layer> A solution having the following composition was applied using polyvinyl butyral as a binder so that the film thickness after drying was 25 μm.

Photosensitive Emulsion A Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% N, N-dimethylformamide solution) 2 ml Antifoggant-2 (1.5% methanol solution) 8 ml Developer-1 (2.4% N, N-dimethylformamide solution) 5 ml Phthalazone (4.5% N, N-dimethylformamide solution) 8 ml Compound of the present invention represented by formula (1) described in Table 1. Amount The compound represented by the general formula (2) of the present invention The amount described in Table 1 The compound represented by the general formula (A) Exemplified A-4 (10% methanol solution) 13 ml Hardening agent H (1% methanol / N) , N-dimethylformamide solution 4: 1 solution) 2 ml

[0155]

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[0156]

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

Acetone 175 ml / m ² 2-propane 40 ml / m ² Methanol 15 ml / m ² Cellulose acetate 8.0 g / m ² Phthalazine 1.0 g / m ² 4-methylphthalic acid 0.72 g / m ² Tetrachlorophthalic acid 0 0.22 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Matting agent (monodispersity 10% average particle size 4 μm monodisperse silica) 30 mg / m ² (performance evaluation of photothermographic material) <Exposure and development Processing> The photothermographic material prepared above was exposed with an imager having a semiconductor laser of 810 nm. Thereafter, heat development was performed at 110 to 130 ° 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.

<Measurement of surface resistivity> 13.5 × 10 cm
After heating the sample cut at 80 ° C. for 5 minutes, 23 ° C.
The humidity was adjusted for 2 hours under the condition of 20% RH, and the surface electric resistance of the photosensitive layer side was measured using a tera ohm meter VE-30 (manufactured by Kawaguchi Electric Co., Ltd.). .

<Evaluation of Scratch Resistance> A sapphire needle having a tip of a radius of 0.1 mm was pressed against the sample surface, and a load was continuously applied within a range of 0 to 200 g while moving in parallel on the film surface at a speed of 10 mm for 1 second. The load on the needle that caused damage to the film surface of the sample was determined by changing the value of

Table 1 shows the above results.

[0162]

[Table 1]

From Table 1, it can be seen that the photothermographic material containing the compound represented by formula (1) or (2) in the photosensitive layer of the present invention has a low surface specific resistance and a poor scratch resistance after thermal development. It can be seen that is also excellent.

[0164]

As demonstrated in the examples, the photothermographic material according to the present invention has excellent antistatic ability and excellent scratch resistance after thermal development.

Claims (2)

[Claims] 1. A photothermographic material having a photosensitive layer containing photosensitive silver halide grains and a non-photosensitive layer on at least one side of a support, selected from the photosensitive layer and the non-photosensitive layer. In at least one layer, the following general formula (1)
A photothermographic material comprising a compound represented by the formula: Embedded image In the formula, q is 0 or 1, and when q = 1, A is-(X) a
-(Y) b- (Z) c-group (where X and Z are oxygen-containing hydrocarbon groups having one terminal ether residue and having a total of 100 or less carbon atoms, and Y is -O- (C = O) -R- (C = O)
-Group (where R is a hydrocarbon group having 1 to 82 carbon atoms) or-
An O- (C = O) -NH-R'NH (-C = O)-group (where R 'is a hydrocarbon group having 2 to 13 carbon atoms);
b and c are each 0 or 1, and p is 10 to 100.
0. In the formula, ← indicates a coordination bond. 2. A photothermographic material having a photosensitive layer containing photosensitive silver halide grains and a non-photosensitive layer on at least one side of a support, wherein the photothermographic material is selected from the photosensitive layer and the non-photosensitive layer. In at least one layer, the following general formula (2)
A photothermographic material comprising a compound represented by the formula: General formula (2) [N = P (XR) (X′R ′)] n In the formula, X and X ′ are groups selected from —O—, —NH— and —NR ″ —, and R and R ', R "are H, B, C, N,
It is composed of at least one atom selected from O, F, P, S, Cl, Br, I, Na, and K, and n represents an integer of 3 or more.