JP2001201817A - Heat developable photosensitive material, image- recording method and image-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material, having low fog level, high sensitivity and improved preservability, an image recording method using the photosensitive material and an image-forming method. SOLUTION: In the heat developable photosensitive material, containing at least an organic silver salt, photosensitive silver halide, a reducing agent and a binder on the base, a compound of formula 1 is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic material, an image recording method and an image forming method.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical care,
The waste liquid caused by the wet processing of the image forming material has become a problem in terms of workability, and in recent years, it has been strongly desired to reduce the amount of the treated waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there is a need for a technique relating to a photothermographic material capable of performing efficient exposure with a laser imagesetter or a laser imager and forming a high-resolution and clear black image.

As a technique for this purpose, silver halide photosensitive materials which form a photographic image by heat treatment are known. Morgan and B.A. U.S. Pat. No. 3,152,90 to Shelly
No. 4, No. 3,457,075 or D.C. H Thermally Treated Silver System (Thermally Pro) by H Klosterboer
cessed Silver Systems ”, Imaging Processes and Materials (Imaging Processes and Materials)
terials) Neblette Eighth Edition, Sturge, V.A. Walworth
th), A. Editing Shepp, # 279
1989, and the like.

Such a photothermographic material usually contains a reducible silver source (for example, organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide) and a reducing agent dispersed in an organic binder matrix. It is contained in. The photothermographic material is stable at room temperature, but generates silver by an oxidation-reduction reaction between a reducible silver source (acting as an oxidizing agent) and a reducing agent when heated to a high temperature after exposure.

[0005] This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by 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 and results in the formation of an image. An antifoggant for controlling fogging of this image is used, and the most effective method as a conventional antifogging technique is a method using a mercury compound as an antifoggant.

The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 89,903. However, the use of highly toxic mercury compounds is not preferred, and the development of non-mercury antifoggants has been desired. Non-mercury antifoggants include various polyhalides, for example, U.S. Pat. Nos. 3,874,946 and 4,756.
No. 999, No. 5,340,712, European Patent No. 60
No. 5,981A1, No. 622,666A1, No. 6
No. 31,176A1, Japanese Patent Publication No. 54-165,
-2781 and the like.

However, these compounds have problems in that they have low fogging preventing effect and deteriorate silver tone. Further, when the photosensitive materials are stored in a laminated form under forced conditions of humidification and heating, and then exposed and developed, there is a problem that fog in unexposed portions increases.

As a method for solving these problems, Japanese Patent Application Laid-Open No.
No. 160164, No. 9-244178, No. 9-258
No. 367, No. 9-265150, No. 9-281640
And JP-A-9-319022 disclose polyhalogen compounds in which the above problems are improved.

However, in particular, the photothermographic material for a laser imager for medical use or a high-contrast agent,
When the above-mentioned polyhalogen compound is applied to the photothermographic material for output of a printing laser imagesetter having an oscillation wavelength of 00 to 800 nm, although the above problems are considerably improved, the developed sample is There has been a problem that the storage stability of an image over time is poor, such as an increase in fog over time.

Further, JP-A-6-208193 discloses a photothermographic material having improved fog stability during the storage period by containing an antifogging compound and a compound having an isocyanate group. However, the storage stability of the image over time is not sufficient, and the reaction of these antifogging compounds progresses with time at the stage of the coating solution during the manufacturing process, and the sensitivity of the photosensitive material is thereby greatly changed. There was a big problem.

Further, JP-A-64-72145, JP-A-9-281637 and the like disclose a benzoylcarboxylic acid-based antifoggant compound to improve the fog stability during storage. Although a developed photosensitive material is disclosed, there is a problem that deterioration performance such as sensitivity fluctuation due to storage over time is caused.

[0012] From the above, there has been a demand for solving the problems described above, and in particular, for developing a photothermographic material having excellent fog stability during the storage period.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material having low fog, high sensitivity and excellent storability, and an image recording method and an image forming method using the same. is there.

[0014]

The above objects of the present invention have been attained by the following items 1 to 12.

1. A photothermographic material containing at least an organic silver salt, a photosensitive silver halide, a reducing agent and a binder on a support, wherein the compound represented by the formula (1) is contained. Photosensitive material.

2. 2. The photothermographic material according to the above item 1, wherein L ₁ is an alkylene group or an arylene group.

3. 2. The photothermographic material according to the above item 1, wherein L ₁ is a phenylene group.

4. 2. The photothermographic material according to item 1, wherein L ₁ is an orthophenylene group.

5. 5. The photothermographic material as described in 1, 2, 3, or 4, further comprising a compound represented by the general formula (2).

6. 4. The photothermographic material as described in 1, 2, or 3, further comprising a compound represented by the general formula (3).

7. 7. The photothermographic material according to the above item 6, wherein L ₂ is an alkylene group or an arylene group.

8. 7. The photothermographic material according to the above item 6, wherein L ₂ is a phenylene group.

9. 7. The photothermographic material according to the above item 6, wherein L ₂ is an orthophenylene group.

10. Exposure of the photothermographic material according to any one of 1 to 9 above using a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam is not substantially perpendicular. Characteristic image recording method.

[11] Using a laser scanning exposure machine wherein the scanning laser light when recording on a photosensitive material is a vertical multi,
10. An image recording method, comprising exposing the photothermographic material according to any one of items 9 to 9.

12. 10. An image forming method, wherein the photothermographic material according to any one of the above items 1 to 9 is heat-developed in a state where the photothermographic material contains a solvent in an amount of 1 to 1000 mg / cm < ² >.

Hereinafter, the present invention will be described in detail. In the photothermographic material of the present invention, a conventional photothermographic material is prepared by using a compound represented by the formula (1) having a sulfonyloxy group and a carboxyl group and / or a salt of a carboxyl group in the same molecule. It has been found that the benzoylcarboxylic acid-based antifoggant compound used in the above-mentioned method significantly improves the fog stability during the storage period, which has not been sufficiently improved.

Further, the fog stability during the storage period described above can be determined by using the compound represented by the general formula (2) or (3) together with the compound represented by the general formula (1). And further improved.

Further, the general formula (1) according to the present invention,
It was found that the use of the compounds represented by (2) and (3) improved the light fastness of the image after the development processing.

The compounds represented by formulas (1), (2) and (3) according to the present invention will be described.

In the general formulas (1), (2) and (3), R ₁ , R ₂ and R ₃ are respectively a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a nitro group and a sulfino group , A hydrazino group, a heterocyclic group, a hydrocarbon group, or a group that can be formed from a combination thereof.

The halogen atom represented by R ₁ , R ₂ and R ₃ includes a fluorine atom, a chlorine atom, a bromine atom and the like.

The hydrazino groups represented by R ₁ , R ₂ and R ₃ represent an alkylhydrazino group and an arylhydrazino group, and the alkyl group of the alkylhydrazino group includes a methyl group, an ethyl group, a propyl group, Butyl group, octyl group,
Decyl group and the like. Examples of the aryl group of the arylhydrazino group include a phenyl group and a naphthyl group. Each of the above-mentioned substituents may further have a substituent.

The heterocyclic group represented by R ₁ , R ₂ and R ₃ is preferably a 5- to 7-membered ring, and may be condensed. For example, an imidazolyl group, a pyridyl group, a furyl group, Examples include a piperidyl group and a morpholino group.

Each of the hydrocarbon groups represented by R ₁ , R ₂ and R ₃ is, for example, a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
To 30, more preferably 1 to 20, particularly preferably 1 to
16, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-ethylhexyl And the like. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 16 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 carbon atoms)
To 20, particularly preferably 2 to 16, and examples thereof include an ethynyl group, a 1-propynyl group, and a 3-pentynyl group. ), An aryl group (preferably having 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 16 carbon atoms, such as phenyl, naphthyl, antonyl, phenanthonyl, pyrenyl and the like), and an aralkyl group (preferably Has 7 to 30 carbon atoms, more preferably 7 to 2 carbon atoms.
0, particularly preferably 7-16, for example benzyl,
Phenethyl, diphenylmethyl, trityl and the like. ) And the like. The hydrocarbon group described above further includes a hydroxyl group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom),
It further has a substituent such as a cyano group, a sulfo group, a nitro group, a sulfino group, a hydrazino group, a heterocyclic group (for example, an imidazolyl group, a pyridyl group, a furyl group, a piperidyl group, a morpholino group, etc.). Is also good.

In the above description, hydrocarbon groups are preferably used as the substituents represented by R ₁ , R ₂ and R ₃ .
More preferably, an alkyl group, an aryl group, and an aralkyl group, particularly preferably, an alkyl group and an aryl group, and most preferably, each having a halogen atom.
An alkyl group and an aryl group.

As the divalent hydrocarbon group represented by L ₁ or L ₂ , for example, a linear, branched or cyclic alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms)
6, particularly preferably 1-3, for example, a methylene group,
Examples include an ethylene group, a trimethylene group, a propylene group, an ethylethylene group, a hexamethylene group, and a 1,2-cyclohexylene group. ), An alkenylene group (preferably having 2 to 10, more preferably 2 to 6, particularly preferably 2 to 4, and examples thereof include a vinylene group and a propenylene group.), An alkynylene group (preferably having 2 carbon atoms). -10, more preferably 2-6, particularly preferably 2-4, and examples thereof include an ethynylene group and a 3-pentynylene group, and an arylene group (preferably having 6 to 20 carbon atoms, more preferably 6 to 6 carbon atoms). 16, particularly preferably 6 to 12, for example, phenylene group, naphthylene group and the like.) And aralkylene group (preferably 7 to 20, more preferably 7 to 16, particularly preferably 7 to 12 carbon atoms). , For example, a xylylene group).

In the above description, the divalent hydrocarbon group represented by L ₁ or L ₂ is preferably an alkylene group or an arylene group, more preferably an alkylene group or a phenylene group. Specifically, a methylene group, an ethylene group, a propylene group, and a phenylene group are preferable, more preferably a phenylene group, and particularly preferably.
An orthophenylene group.

The divalent hydrocarbon group represented by L ₁ or L ₂ may have a substituent, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms).
12, particularly preferably 1 to 8, for example, a methyl group,
Ethyl group, iso-propyl group, tert-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
Examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group. ), An alkynyl group (preferably having 2 to 20, more preferably 2 to 12, particularly preferably 2 to 8, and examples thereof include a 1-propynyl group and a 3-pentynyl group),
An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group and a naphthyl group), and an amino group (preferably having 0 to 20 carbon atoms). , More preferably 0 to 1
0, particularly preferably 0 to 6, for example, amino group, methylamino group, dimethylamino group, diethylamino group,
And a dibenzylamino group. ), An alkoxyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to
12, particularly preferably 1 to 8, for example, methoxy group, ethoxy group, butoxy group and the like. ), An aryloxy group (preferably having 6 to 20, more preferably 6 to 16, and particularly preferably 6 to 12 carbon atoms, such as a phenyloxy group and a 2-naphthyloxy group), and an acyl group ( It preferably has 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, and includes, for example, an acetyl group, a benzoyl group, a formyl group, a pivaloyl group and the like, an alkoxycarbonyl group (preferably a carbon atom). Numbers 2 to 20, more preferably 2
16, particularly preferably 2 to 12, for example, methoxycarbonyl group, ethoxycarbonyl group and the like. ), An aryloxycarbonyl group (preferably having 7 to 20, more preferably 7 to 16, and particularly preferably 7 to 10; examples thereof include a phenyloxycarbonyl group), and an acyloxy group (preferably having a carbon number of 7). 2-20, more preferably 2-16, particularly preferably 2-10, for example, acetoxy, benzoyloxy and the like.), Acylamino group (preferably 2-20 carbon atoms, more preferably 2-16, It is particularly preferably 2 to 10, for example, acetylamino group, benzoylamino group and the like.), Alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms). And, for example, a methoxycarbonylamino group and the like.), Aryloxycarbonyl Amino group (preferably 7 carbon atoms
20, more preferably 7 to 16, particularly preferably 7 to 1
2, such as a phenyloxycarbonylamino group. ), An alkylsulfonylamino group or an arylsulfonylamino group (preferably having 1 to carbon atoms)
20, more preferably 1 to 16, particularly preferably 1 to 1
And examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0
To 16, particularly preferably 0 to 12, and examples thereof include a sulfamoyl group and a methylsulfamoyl group. ), A carbamoyl group (preferably having 1 to 20 carbon atoms,
It is more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a carbamoyl group, a methylcarbamoyl group, and a phenylcarbamoyl group. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1
To 16, particularly preferably 1 to 12, and examples thereof include a methylthio group and an ethylthio group. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 carbon atoms)
To 16, particularly preferably 6 to 12, and examples thereof include a phenylthio group. ), A sulfonyl group (preferably having 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a mesyl group and a tosyl group), and a sulfinyl group (preferably having 1 carbon atom). -20, more preferably 1-16, particularly preferably 1-12, for example, methanesulfinyl group, benzenesulfinyl group, etc.), hydroxyl group, mercapto group, halogen atom (for example, fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, nitro group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino and the like). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

Examples of the substituent of the group represented by L ₁ or L ₂ include an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, An acyloxy group, an acylamino group, an alkoxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, a halogen atom, a cyano group, a heterocyclic group, and the like are preferable, and an alkyl group and a halogen atom are more preferable. Is an alkyl group. Further, the group represented by R ₁ , R ₂ or R ₃ and the group represented by L ₁ or L ₂ may be linked to form a ring.

The cation represented by M represents an organic or inorganic cation, such as an alkali metal ion (such as lithium ion, sodium ion, potassium ion, or cesium ion), or an alkaline earth metal ion (such as magnesium ion or calcium ion). , Ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc.), pyridinium, imidazolium, phosphonium and the like.

M is preferably a hydrogen atom or an alkali metal ion, and more preferably a hydrogen atom.

This compound is generally used in the photosensitive layer in an amount of at least 0.005 mol / mol of silver. Usually, it is in the range of from 0.005 to 0.3 mol per mol of silver, preferably from 0.01 to 0.3 mol per mol of silver.
It is in the range of 15 moles.

Hereinafter, specific examples of the compound represented by the formula (1) will be shown, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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Hereinafter, specific examples of the compound represented by the general formula (2) will be shown, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Hereinafter, specific examples of the compound represented by formula (3) will be shown, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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The general formulas (1) to (4) according to the present invention described above.
As the compound represented by (3), a commercially available compound can be used, respectively. Pharm. Bu
lletin, 31 (8), 2632 (1983),
J. Chem. Soc. , Section B Phys
local Organic Chemistry, P
art1. pp. 145-148 (1971); A
mer. Chem. Soc. 77, 1909 (195
5), Org. Prep. Proced. Int. 28
(5), 609 (1996), Chem. Ber. 4
4, 1236 (1911); Amer. Chem.
Soc. 60, 2502 (1938), Bull. So
c. Khim. Fr. 25 (3) 173 (1901),
Chem. Abstr. 9861 (1960), German Patent No. 2,970,18, JustusLiebigs
Ann. Chem. 300, 299 (1898) and the like.

The above general formula (1) according to the present invention,
As the mixing ratio (mass ratio) of the compound represented by (2),
The ratio is preferably from 100: 5 to 100: 100, more preferably from 100: 10 to 100: 50.

The above general formula (1) according to the present invention,
The mixing ratio of the compound represented by (3) is 100: 5
To 100: 300, preferably 10: 300.
0:10 to 100: 150.

The mixing ratio of the compounds represented by the above general formulas (1), (2) and (3) according to the present invention is 100: (5-100) :( 5-300). Preferably, more preferably, 100: (10-50) :( 1
0 to 150).

The silver halide grains according to the present invention function as an optical sensor. In the present invention, the average particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, particularly preferably 0.01 μm to 0.1 μm, in order to suppress white turbidity after image formation and obtain good image quality. 0.
02 μm to 0.08 μm.

The term “grain size” as used herein refers to the length of the edge 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, the diameter of a sphere equivalent to the volume of silver halide grains is indicated. Further, the silver halide is preferably monodispersed.

The term “monodispersion” as used herein means a case where the degree of monodispersion obtained by the following equation is 40% or less. In the present invention, the monodispersity 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 In the present invention, the silver halide particles have an average particle size of 0.1.
It is more preferable that the particle size is not more than μm and that the particles are monodisperse particles.

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

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means that the thickness in the vertical direction is h.mu.
When m, the aspect ratio = r / h means 3 or more. Among them, the aspect ratio is more preferably 3 or more and 50 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. These are described in U.S. Patent Nos. 5,264,337, 5,314,798, and 5,320,958, and the like. Can be.

When these tabular grains are used in the present invention, the sharpness of an image is further improved. The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. The AgX particles according to the present invention are P.I. Glafide
Chimie et Physique Photo
ographique (published by Paul Montel,
1967); F. Photograph by Duffin
raphic Emulsion Chemistry
(Published by The Focal Press, 1966),
V. L. By Zelikman et al Makin
g and Coating Photographi
c Emulsion (The Focal Pres
s, 1964) and the like, and can be prepared using an Ag emulsion prepared by a method described in US Pat.

The silver halide according to the present invention is preferably contained in an amount of 0.75 to 30% by mass based on the organic silver salt.

The silver halide according to 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, Pt, A
u is 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 the 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. 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: [R (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 may be a metal complex or metal complex ions one type, the metal of the same kind of metal or different may be used alone or in combination. 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.

Compounds which provide these metal ions or complex ions are added during silver halide grain formation.
It is preferably incorporated into silver halide grains, and may be added at any stage before and after preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical sensitization. It is preferably added at the stage of physical ripening, more preferably at the stage of nucleation and growth, and most preferably 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 to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided 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 may be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

The silver halide grains according to the present invention may or may not be desalted after grain formation. When desalting is performed, methods known in the art such as noodle method and flocculation method are used. It can be desalted by washing with water.

The silver halide grains according to the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. Known compounds can be used as the compound preferably used for the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method,
Compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, and P = Te Compounds having a bond, tellurocarboxylates, tellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te heterocycles, Tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used for the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, British Patent No. 618,061 and the like. Can be preferably used.

As specific compounds for the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like are used. be able to. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

The organic silver salt according to the present invention is a reducible silver source and is an organic acid containing a reducible silver ion source.
Examples of the organic acid used in the present invention include an aliphatic carboxylic acid, a carbocyclic carboxylic acid, a heterocyclic carboxylic acid, a heterocyclic compound and the like, and particularly a long chain (10 to 30, preferably 15 to 25 (Carbon atoms) aliphatic carboxylic acids and heterocyclic carboxylic acids having a nitrogen-containing heterocyclic ring are preferably used. Further, an organic silver salt complex in which the ligand has a total stability constant for silver ions of 4.0 to 10.0 is also useful.

[0085] The content of the light-sensitive material of the organic silver salt according to the present invention is preferably from 3 g / m ² or less, more preferably 2 g / m ² or less, particularly preferably 0.2~2g
/ M ² .

Examples of the organic acid silver salt according to the present invention include R
Escher Disclosure Nos. 17029 and 29996, and include: silver salts of fatty acids (eg, silver salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.). A carboxyalkylthiourea salt of silver (eg, 1- (3-carboxypropyl) thiourea, 1-
(3-carboxypropyl) -3,3-dimethylthiourea, etc.); a silver complex of a polymerization reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid (for example, an aldehyde (formaldehyde, acetaldehyde, butyraldehyde, etc.) and a hydroxy-substitution) Silver complexes or the like of polymerization reaction products with aromatic carboxylic acids (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, etc.), and silver salts or complexes of thiones (for example, ,
3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione, and 3-carboxymethyl-4-thiazoline-2-thione), imidazole,
Pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-
Complexes and salts of silver with a nitrogen acid selected from 1,2,4-triazole and benzotriazole; saccharin, 5
A silver salt such as chlorosalicylaldoxime; and a silver salt of a mercaptan derivative. Among the organic silver salts described above, silver salts of fatty acids are preferably used, and silver behenate, silver arachidate and silver stearate are more preferably used.

The aqueous organic silver salt dispersion according to the present invention can be obtained by mixing silver nitrate and an organic acid alkali metal salt. Simultaneous addition and mixing of silver nitrate and silver halide at the time of organic silver salt formation are carried out. It is preferably produced using a method.

For example, after adding an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid to prepare an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.) The aqueous organic silver salt dispersion according to the present invention can be prepared by simultaneously adding and mixing silver nitrate and silver halide using a controlled double jet method.

Further, the aqueous organic silver salt dispersion according to the present invention can be prepared by a so-called control triple jet method in which an alkali metal salt of an organic acid, silver nitrate and silver halide are simultaneously added and mixed, respectively.

In the present invention, from the viewpoint of simplicity in the production process, the above-mentioned method for producing an aqueous organic silver salt dispersion using the control double jet method is preferably used. From the viewpoint of producing a high-sensitivity photothermographic material, the method for producing an aqueous organic silver salt dispersion using the above-described control triple jet method is preferably used.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research D
No. 17029 and 29996, and include the following: Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (e.g., Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (e.g., anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (E.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone, and (2,5-dihydroxy-phenyl) methylsulfone); sulfohydroxamic acids (e.g., benzenesulfohydroxam) ); Sulfonamides anilines (e.g., 4-(N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amides (eg, phenylamidoxime, 2-thienyl-amidoxime, p-phenoxy-phenylamidoxime, etc.); azines (eg, a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid) Combinations of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxamic acids; combinations of azines and sulfonamide phenols; α-cyanophenylacetic acid derivatives; bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolone; sulfonamide phenol reducing agent; 2-phenylindane-1,3-dione; chroman; 1,4-dihydropyridines (for example, 2,6-
Dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2
-Hydroxy-3-t-butyl-5-methylphenyl)
Methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-
3-methylphenyl) propane, 4,5-ethylidene-
Bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0092]

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In the formula, R is a hydrogen atom or a group having 1 to carbon atoms.
Represents an alkyl group of 10 (eg, butyl group, 2,4,4-trimethylpentyl group, etc.), and R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, t- Butyl group).

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

[0095]

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[0096]

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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.

The photothermographic material of the present invention may contain an antifoggant. Known as an effective antifoggant is mercury ion, and the use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. However, mercury compounds are environmentally unfavorable and are, for example, disclosed in U.S. Patent Nos. 4,546,075 and 4,452.
Non-mercury antifoggants such as those disclosed in JP-A-885-85 and JP-A-59-57234 are preferably used in the present invention.

Particularly preferred non-mercury antifoggants include US Pat. Nos. 3,874,946 and 4,75.
No. 6,999, the compound -C (X
₁ ) Heterocyclic compounds having at least one substituent represented by (X ₂ ) (X ₃ ) (where X ₁ and X ₂ each represent a halogen atom, and X ₃ represents hydrogen or a halogen atom). Can be

Other suitable antifoggants include paragraph [0030] of JP-A-9-288328.
To [0036], 9-905;
No. 50, paragraphs [0062] to [0063], U.S. Pat. No. 5,028,523 and European Patent Nos. 600,587 and 605,981;
Compounds disclosed in JP-A-631,176 and the like can be used.

It is preferable to add a toning agent to the photothermographic material of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are Research Discl
No. 17029, which includes the following:

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

The photothermographic materials of the present invention include, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455,
Nos. 4,741,966 and 4,751,175
No. 4,835,096.

Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
17643 IV-A (p. 23, December 1978), and Item 18431 (p. 437, August 1979), etc. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-806
The compounds described in No. 79 are preferably used.

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

When a mercaptan derivative is used in the present invention, it may have any structure, but it may be Ar-SM or Ar-SM.
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar represents an aromatic ring or a condensed aromatic ring having at least one nitrogen, sulfur, oxygen, selenium or tellurium atom.

As the aromatic ring, an aromatic carbon ring and a heteroaromatic ring are used. In the present invention, a heteroaromatic ring is preferably used. As the heteroaromatic ring, for example, benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, Pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, a halogen atom (eg, Br and Cl), a hydroxyl group, an amino group, a carboxy group,
Alkyl groups (e.g., those having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxyl groups (e.g., those having one or more carbon atoms, preferably 1-4 carbon atoms) )). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole,
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
2-mercaptoquinoline, 8-mercaptopurine, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like,
The present invention is not limited to these.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and it is preferable to provide a matting agent on the surface of the photosensitive material in order to prevent the image after thermal development from being damaged. It is preferable that the composition contains 0.5 to 30% by weight of the agent with respect to all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as the inorganic substance, silica described in Swiss Patent No. 330,158 or the like,
Glass powder described in French Patent No. 1,296,995,
Alkaline earth metals or carbonates such as cadmium and zinc described in British Patent No. 1,173,181 can be used as a matting agent. 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, Swiss Patent 330,15
Use of an organic matting agent such as polystyrene or polymethacrylate described in No. 8, etc., polyacrylonitrile described in U.S. Pat. No. 3,079,257, and polycarbonate described in 3,022,169 or the like. Can be.

The shape of the matting agent may be either regular or irregular, but it 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. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent has a coefficient of variation 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 used in the present invention can be contained in any constituent layer, but is preferably photosensitive in order to achieve the object of the present invention. It is a constituent layer other than the functional layer, and is more preferably the outermost layer as viewed from the support.

The method of adding the matting agent used in the present invention may be a method in which the matting agent is dispersed in a coating solution in advance, or may be sprayed after the coating solution is applied and before the drying is completed. May be used. When a plurality of types of matting agents are added, both methods may be used in combination.

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 contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.

In the present invention, US Pat.
The conductive compounds described in No. 773 columns 14 to 20 are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other constituent 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 in addition to the above. These additives and the other additives mentioned above are used in Research Disclosure.
re Item 17029 (June 1978, p. 9-
The compound described in 15) can be preferably used.

The binder suitable for the photothermographic material of the present invention is transparent or translucent, generally colorless, and includes natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (arabic gum). (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 (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), 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 non-hydrophilic. In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer may be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same or different from the binder used for the photosensitive layers.

In the present invention, the binder amount of the photosensitive layer is preferably 1.5 to 10 g / m ² , more preferably 1.7 to 8 g / m ² in order to increase the speed of thermal development.
²

The support according to the present invention is preferably a plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate) in order to prevent deformation of the image after development processing.

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.

A heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming 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 plastic used will be described. PET is made of polyethylene terephthalate in which all of the polyester components are used. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, 5-sodium sulfoisophthalic acid are used as acid components.
A polyester containing a modified polyester component of adipic acid or the like and a glycol component such as ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol or the like in an amount of 10 mol% or less of the entire polyester may be used.

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 of forming a film of the support and the method of producing the undercoat used in the present invention, known methods can be used, and preferably, paragraph [0030] of JP-A-9-50094 is used.
To [0070].

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. It is preferable that the photothermographic material contains a color-toning agent which suppresses the color tone of the present invention, usually in a dispersed state in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is exposed to high temperature (for example,
(° 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.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a 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 filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or pigment may be included in the active layer. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range, and examples thereof include JP-A-59-6481 and JP-A-59-1.
No. 82436, U.S. Pat. No. 4,271,263, U.S. Pat. No. 4,594,312, European Patent Publication 533,0
08, European Patent Publication 652,473, JP-A-2-2-2
No. 16140, JP-A-4-348339, JP-A-7-
Compounds described in JP-A-191432 and JP-A-7-301890 are preferably used.

These non-photosensitive layers preferably contain the above-mentioned binder and matting agent, and may further contain a slip 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.

The details of the photothermographic material are described in, for example, US Pat. Nos. 3,152,904 and 3,457,
No. 075, and D.A. Morgan and B.A. U.S. Pat. No. 3,152,9 by Shelly
No. 04, 3,457,075 or D.I. H Thermally Treated Silver System (Thermally Pr) by Klosterboer
processed Silver Systems),
Imaging Processes and Materials
terials) Neblette Eighth Edition, Sturge, V.A. Walworth
th), A. Editing Shepp, # 279
1989, and the like.

Among them, the present invention is characterized in that an image is formed by thermally developing a light-sensitive material at 80 to 140 ° C. without fixing. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, after the heat development processing,
The optical transmission density of the light-sensitive material containing the support at 400 nm is preferably 0.2 or less. A more preferable value of the optical transmission density is 0.02 or more and 0.2 or less.

[0132]

Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to these.

Example 1 << Preparation of Photographic Support >> Concentration: 0.170 (Konica Corporation)
8 W / m on both sides of a 175 μm-thick PET film colored blue with a densitometer PDA-65
^{A 2} -minute corona discharge treatment was performed.

<< Preparation of Photosensitive Silver Halide Emulsion 1 >> Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate, potassium bromide and potassium iodide (equimolar amounts of silver nitrate) in a molar ratio of (98/2), and iridium chloride were added at 1 × per mole of silver. 370 ml of an aqueous solution containing 10 ^-4 mol
Was added over 10 minutes by the controlled double jet method while maintaining the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the particle size was 12
%, << 100 >> cubic silver iodobromide grains having a face ratio of 87% were obtained. The emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then 0.1 g of phenoxyethanol was added.
The pH was adjusted to 5.9 and the pAg was adjusted to 7.5 to obtain a photosensitive silver halide emulsion 1.

<< Preparation of Powdered Organic Silver Salt >> 111.4 g of behenic acid and 83.8 g of arachidic acid were added to 4720 ml of pure water.
54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, a 1.5 M aqueous sodium hydroxide solution 54 was added.
After adding 0.2 ml of concentrated nitric acid and 6.9 ml of concentrated nitric acid,
It cooled to ° C and obtained the organic acid sodium solution. While maintaining the temperature of the organic acid sodium acid solution at 55 ° C., the silver halide emulsion (containing 0.038 mol of silver) and pure water 45
0 ml was added and stirred for 5 minutes. Next, 760.6 ml of a 1M silver nitrate solution was added over 2 minutes, and the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, washing with deionized water and filtration are repeated until the conductivity of the filtrate becomes 2 μS / cm, and centrifugal dehydration is performed. Then, hot air drying is performed at 37 ° C. until the mass loss does not occur. Obtained.

<< Preparation of Photosensitive Emulsion Dispersion >> Polyvinyl butyral powder (Butvar B manufactured by Monsanto)
-79) 14.57 g of methyl ethyl ketone 1457 g
And 500 g of an organic silver salt powder was gradually added thereto while stirring with a dissolver-type homogenizer, and mixed well. Thereafter, dispersion is performed at a peripheral speed of 13 m and a residence time in the mill of 0.5 minute by a media type disperser (manufactured by Gettzmann) filled with 80% of Zr beads (manufactured by Toray) having a diameter of 1 mm to prepare a photosensitive emulsion dispersion liquid. did.

<< Preparation of Coating Solution for Photosensitive Layer >> The above-mentioned photosensitive emulsion (500 g) and MEK (methyl ethyl ketone) 10
0 g was kept at 21 ° C. while stirring. Antifoggant 1
(0.20 g) was added and stirred for 1 hour. Further, calcium bromide (3.25 ml of a 10% methanol solution) was added, followed by stirring for 30 minutes. Next, as shown in Table 1, sensitizing dye 1, a mixed solution of general formula (1) or general formula (1) + (2) or general formula (1) + (3), and a supersensitizer Ratio 1: 250-450: 20, 0.1 for sensitizing dye.
(1% MEK solution, 7 ml) and stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes.
While keeping the temperature at ° C, 48 g of polyvinyl butyral was added and dissolved sufficiently, and then the following additives were added.

Each compound is added in the following amounts. A-3 (reducing agent) 15 g Desmodu N3300 (Mobay, Inc., aliphatic isocyanate) 1.10 g Printout inhibitor 1.55 g Phthalazine 1.5 g Tetrachlorophthalic acid 0.5 g 4-Methylphthalic acid 0.5 g

[0139]

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[0140]

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After preparing the coating solution for the photosensitive layer, the solution was kept at 13 ° C. and applied by the following method. The following layers were sequentially formed on a support to prepare a sample. In addition, each drying is 75
C. for 5 minutes.

<< Back surface side coating >> (Preparation of back surface coating solution) 830 g of methyl ethyl ketone
While stirring the cellulose acetate butyrate (E
astman Chemical, CAB 381-2
0) 84.2 g, polyester resin (Bostic,
(VitelPE2200B) 4.5 g was added and dissolved. To the dissolved solution, 0.30 g of infrared dye 1 was added,
Further, 4.5 g of an F-based activator (Asahi Glass Co., Ltd., Surflon KH40) dissolved in 43.2 g of methanol and 2.3 g of an F-based activator (Dainippon Inc., Megafag F120K)
Was added and the mixture was sufficiently stirred until it was dissolved. Finally, silica (WR Grac) dispersed in methyl ethyl ketone at a concentration of 1% by mass with a dissolver-type homogenizer.
(Company e, Syloid 64 × 6000) was added and stirred to prepare a coating solution for the back surface. (Coating of Back Surface) The coating solution for the back surface thus prepared was extruded so as to have a dry film thickness of 3.5 μm, and was applied and dried by a coater. Drying was performed for 5 minutes using a drying air having a drying temperature of 100 ° C. and a dew point of 10 ° C.

The coating solution for the photosensitive layer and the coating solution for the surface protective layer were simultaneously coated with an extrusion coater. The photosensitive layer was coated at a rate of 20 m / min so that the coated silver amount was 2.0 g / m ² and the surface protective layer was 2.5 μm in dry film thickness. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C.

<< Coating of Photosensitive Layer Surface Side >> A solution having a composition equal to or less than that of the photosensitive layer was applied so that the coating amount of silver was 2.0 g / m ² and polyvinyl butyral as a binder was 8.5 g / m ^2. Applied.

<< Surface Protective Layer >> (Preparation of Coating Solution for Surface Protective Layer) Acetone 5 ml / m ² Methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² Matting agent: Monodisperse silica having a degree of monodispersity of 10% and an average particle size of 4 μm 70 mg / m ² CH ₂ ＣＨCH—SO ₂ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ SO ₂ —CH 2CH ₂ 35 mg / m ² C ₉ F ₁₉ -C ₆ H ₄ -SO ₃ Na 10 mg / m ² << Exposure and development treatment >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800 nm to 820 was superposed by high frequency superposition.
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a multi-nm vertical semiconductor mode as an exposure source. At this time, an image was formed by setting the angle between the exposure surface of the photosensitive material and the exposure laser beam to 75 degrees (the unevenness was smaller than when the angle was set to 90 degrees, and the sharpness and the like were unexpectedly good). Image was obtained.).

Thereafter, heat development was performed at 123 ° C. for 16.5 seconds using an automatic developing machine having a heat drum so that the protective layer of the photosensitive material was in contact with the drum surface. that time,
Exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. The obtained image was evaluated using a densitometer. The results of the measurement are the sensitivity (S) (the reciprocal of the ratio of the exposure dose that gives a density 1.0 higher than the unexposed portion) and the fog
The relative values are shown in Table 1 with the sensitivity of photosensitive material sample 1 being 100.

<< Evaluation of Storage Property of Film >> One of the two samples was exposed and developed immediately after coating, and the other was
After storing at 5 ° C. and 55% RH for 3 days under light shielding, exposure and development were performed, and the sensitivity and the density of the fog portion were measured. Table 1 shows the obtained results.

Increase in sensitivity (ΔS) = relative sensitivity of development after light-shielded storage—relative sensitivity of immediate development Increase in fog (Δfog) = fog in development after light-shielded storage
Immediate development fog The storage stability of the photothermographic material was evaluated from the increase in sensitivity and the increase in fog described above. Here, the exposure, development, and evaluation methods are as described above.

[0149]

[Table 1]

From Table 1, it is clear that the sample of the present invention has low fog, high sensitivity, and improved storage stability as compared with the comparative sample. In the area of the present invention, a photothermographic material having low fog, high initial sensitivity, and excellent storage stability over time was obtained.

Example 2 Photothermographic materials 1 to 11 shown in Table 1 of Example 1
Was exposed and developed in the same manner as described in Example 1 and then stuck inside a glass window exposed to direct sunlight and left for one month. Were visually evaluated for light fastness, and shown as Samples 12 to 22, respectively. Table 2 shows the obtained results.

<< Evaluation Criteria of Image Preservation during Light Irradiation >> ：: Almost no change ：: Slight change in color tone, but no problem in practical use Δ: Discoloration in image portion, but practically acceptable × : Dmin is discolored to increase the density, making it impractical. In the present invention, Dmin is defined as in the following general formula.

Dmin = density of unexposed area + base (support) density

[0154]

[Table 2]

From Table 2, it is clear that the sample of the present invention has improved light fastness of the image as compared with the comparative sample.

Example 3 << Preparation of Subbed Photographic Support >> (Preparation of PET Subbed Photographic Support) Commercially available biaxially-stretched heat-fixed thickness 175 μm, optical density 0.170
(Measured by Konica Densitometer PDA-65) was subjected to a corona discharge treatment of 8 W / m ² · min on both sides of a blue-colored PET (polyethylene terephthalate) film, and the following undercoating solution a-1 was applied to one surface. The dry film thickness 0.8
μm, and dried to form an undercoat layer A-1,
On the other side, the following undercoating coating solution b-1 was dried to a dry film thickness of 0.
It was applied so as to have a thickness of 8 μm and dried to obtain an undercoat layer B-1.

(Composition of Undercoat Coating Solution a-1) A copolymer latex solution of butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (30/20/25/25% by mass) (solid 270 g Compound C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water (composition of undercoat coating solution b-1) Butyl acrylate / styrene / glycidyl Acrylate (40/20/40 mass%) copolymer latex liquid (solid content 30%) 270 g Compound C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g To 1 liter with water Finishing The surface of the undercoat layer A-1 and the undercoat layer B-1 is then 8 W
/ M ² · min. Of corona discharge, and on the undercoating layer A-1, the following undercoating upper layer coating solution a-2 is formed as the undercoating upper layer A-2 so as to have a dry film thickness of 0.1 μm. On the undercoat layer B-1, the undercoat upper layer coating solution b-2 shown below was applied as an undercoat upper layer B-2 having an antistatic function so as to have a dry film thickness of 0.8 μm.

(Composition of Undercoating Upper Layer Coating Solution a-2) Gelatin Mass of 0.4 g / m ² Compound C-1 0.2 g Compound C-2 0.2 g Compound C-3 0.1 g Silica particles (average) 0.1 g Finished to 1 liter with water (composition of the undercoating upper layer coating solution b-2) Compound C-4 60 g Latex liquid containing compound C-5 as a component (solid content 20%) 80 g Ammonium sulfate 0. 5 g Compound C-6 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

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(Coating on Back Side) While stirring 830 g of methyl ethyl ketone (MEK), 84.2 g of cellulose acetate butyrate (manufactured by Eastman Chemical: CAB381-20) and polyester resin (Vitel PE2200B manufactured by Bostic).
4.5 g were added and dissolved. Next, in the dissolved solution,
0.30 g of the following infrared dye 2 was added, and further, 4.5 g of a fluorine-based activator (Surflon KH40 manufactured by Asahi Glass Co., Ltd.) and 4 g of a fluorine-based activator dissolved in 43.2 g of methanol (MegaFag F120K manufactured by Dainippon Ink Inc.) ) 2.3 g was added and stirred well until dissolved. Finally, MEK 1
Silica (manufactured by WR Grace, Inc .: Syloid 64 × 60) dispersed by a dissolver type homogenizer at a concentration of mass%
(00) was added and stirred to prepare a coating solution for the back surface side.

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The thus prepared back surface coating solution was extruded so as to have a dry film thickness of 3.5 μm, and was applied and dried by a coater. Drying temperature 100 ° C, dew point 10 ° C
And dried for 5 minutes using a drying air.

<< Preparation of Photosensitive Silver Halide Emulsion A >> (Solution A1) Phenylcarbamoylated gelatin 88.3 g Compound A (10% aqueous methanol solution) 10 ml Potassium bromide 0.32 g Finish with water to 5429 ml (solution B1) 0 2.635 mol / L silver nitrate aqueous solution 2635 ml (solution C1) Potassium bromide 51.55 g potassium iodide 1.47 g Make up to 660 ml with water (solution D1) Potassium bromide 154.9 g potassium iodide 4.41 g iridium chloride (1% solution) ) Make up to 1982 ml with 0.93 ml water (Solution E1) 0.4 mol / L aqueous solution of potassium bromide Controlled silver potential below (Solution F1) 0.71 g of potassium hydroxide Make up to 20 ml with water (Solution G1) 56% acetic acid aqueous solution 18.0 ml (solution H1) anhydrous sodium carbonate Finish 151ml with 2g water _{A: HO (CH 2 CH 2} O) n (CH (CH 3) CH 2 O) 17 (CH 2 CH 2 O) m H (m + n = 5~7) Japanese Patent Publication No. 58-58288 The solution (B1) was added to the solution (A1) using a mixing stirrer shown in JP-A-58-58289.
Of the solution (C1) at 45 ° C. and pAg
While controlling at 8.09, the mixture was added by the simultaneous mixing method in 4 minutes and 45 seconds to form nuclei. One minute later, the solution (F
The whole amount of 1) was added. During this time, pAg was appropriately adjusted using the solution (E1). After 6 minutes, the solution (B
3/4 amount of 1) and the total amount of solution (D1) were added at 45 ° C.
14 minutes 1 by the simultaneous mixing method while controlling to Ag 8.09
The addition took 5 seconds. After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (G1) was added to precipitate a silver halide emulsion. The supernatant was removed, leaving 2000 ml of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. Leaving 1500 ml of sedimentation,
The supernatant was removed, and 10 liters of water was further added. After stirring, the silver halide emulsion was settled. Settling part 1500
After removing the supernatant liquid while leaving the ml, the solution (H1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and the pH was adjusted to 1 per mole of silver.
Water was added so as to be 161 g to obtain a photosensitive silver halide emulsion A. This emulsion had an average grain size of 0.058
The particles were monodispersed cubic silver iodobromide grains having a particle size of 12 μm, a coefficient of variation of grain size of 12% and a [100] face ratio of 92%.

<< Preparation of Powdered Organic Silver Salt A >> In 4720 ml of pure water, 130.8 g of behenic acid and 67.7 g of arachidic acid were added.
g, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 mol / L sodium hydroxide aqueous solution was added, and 6.9 m of concentrated nitric acid was added.
After adding 1 liter, the mixture was cooled to 55 ° C. to obtain a sodium fatty acid solution.

The temperature of the fatty acid sodium solution was 55 ° C.
, 45.3 g of the photosensitive silver halide emulsion A and 450 ml of pure water were added, and the mixture was stirred for 5 minutes. Then 1
702.6 ml of an aqueous silver nitrate solution (mol / L) was added over 2 minutes and stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. After that, washing with deionized water and drainage are repeated until the conductivity of the wastewater becomes 2 μS / cm, and centrifugal dehydration is performed. The obtained organic silver salt in a cake form is washed with a flash-type drier flash jet drier (Seisin). (Manufactured by a company), under the operating conditions of the nitrogen gas atmosphere and the hot air temperature at the dryer entrance,
The dried organic silver salt A was obtained by drying until the water content became 0.1%. An infrared moisture meter was used for measuring the water content of the organic silver salt composition.

<< Preparation of Preliminary Dispersion A >> Polyvinyl butyral powder (manufactured by Monsanto: Butvar B-
79) Dissolve 14.57 g in 1457 g MEK and add VM
Dissolver DISPERMA manufactured by A-GETZMANN
Powdered organic silver salt A5 while stirring with TCA-40M type
Preliminary dispersion liquid A was prepared by gradually adding 00 g and thoroughly mixing.

<< Preparation of Photosensitive Emulsion Dispersion 1 >> Zirconia beads having a diameter of 0.5 mm (manufactured by Toray Industries: Treceram Co., Ltd.) using a preparatory dispersion A with a pump so that the residence time in the mill becomes 1.5 minutes. ) Filled with 80% of the internal volume of the media type disperser DISPERMAT SL-C12EX (VM
A-GETZMANN) and mill peripheral speed 8m /
s to prepare a photosensitive emulsion dispersion liquid 1.

<< Preparation of Stabilizer Liquid >> 1.0 g of stabilizer
1. 0.31 g of potassium acetate was added to 4.97 g of methanol.
To prepare a stabilizer solution.

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<< Preparation of Infrared Sensitizing Dye Solution A >>
As shown in Table 2, general formula (1) or general formula (1) +
(2) or a mixed solution of the general formula (1) + (3) and 5-methyl-2-mercaptobenzimidazole (mixing ratio 1: 250 to 450: 20, 0.1% by sensitizing dye)
MEK solution (31.3 ml) was dissolved in a dark place to prepare an infrared sensitizing dye solution A.

<< Preparation of Additive Solution a >> 1,1 as a developer
-Bis (2-hydroxy-3,5-dimethylphenyl)
27.98 g of 2-methylpropane and 1.54 g of 4
-Methylphthalic acid, 0.48 g of the infrared dye 1
Dissolved in 110 g of K to obtain an additive liquid a.

<< Preparation of Additive Solution b >> 1.78 g of antifoggant 1 and printout inhibitor, further 3.43 g
Was dissolved in 40.9 g of MEK to prepare an additive solution b.

<< Preparation of Additive Solution c >> 5.0 g of silver saving agent H
-94 was dissolved in 45.0 g of MEK to obtain an additive liquid c.

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<< Preparation of Photosensitive Layer Coating Solution A >> The photosensitive emulsion dispersion 1 was prepared under an inert gas atmosphere (nitrogen: 97%).
While stirring 50 g of MEK and 15.11 g of MEK.
, And 1000 μl of a chemical sensitizer S-5 (0.5% methanol solution) was added. Two minutes later, the antifoggant 1 (1
(0% methanol solution) (390 μl) was added and stirred for 1 hour. Further, calcium bromide (10% methanol solution) 49
After adding 4 μl and stirring for 10 minutes, a gold sensitizer Au-5 equivalent to 1/20 mol of the above-mentioned chemical sensitizer was added, and further 2 parts were added.
Stirred for 0 minutes. Subsequently, 167 ml of a stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the infrared sensitizing dye solution A was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C., polyvinyl butyral (Butvar B-79:
After adding 13.31 g and stirring for 30 minutes, 1.084 g of tetrachlorophthalic acid (9.4% MEK solution)
Was added and stirred for 15 minutes. While continuing stirring,
12.43 g of additive solution a, 1.6 ml of isocyanate compound (Desmodur N330, manufactured by Mobay Corporation)
A 10% MEK solution of 0) and 4.27 g of an additive solution b were sequentially added and stirred to obtain a photosensitive layer coating solution A.

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<< Preparation of Photosensitive Layer Coating Solution B >> The photosensitive emulsion dispersion 1 was prepared under an inert gas atmosphere (nitrogen: 97%).
While stirring 50 g of MEK and 15.11 g of MEK.
, And 1000 μl of a chemical sensitizer S-5 (0.5% methanol solution) was added. Two minutes later, the antifoggant 1 (1
(0% methanol solution) (390 μl) was added and stirred for 1 hour. Further, calcium bromide (10% methanol solution) 49
After adding 4 μl and stirring for 10 minutes, a gold sensitizer Au-5 equivalent to 1/20 mol of the above-mentioned chemical sensitizer was added, and further 2 parts were added.
Stirred for 0 minutes. Subsequently, after adding 167 ml of a stabilizer solution and stirring for 10 minutes, 1.32 g of the infrared sensitizing dye solution A was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C, polyvinyl butyral (Butvar B-79;
After adding 13.31 g and stirring for 30 minutes, 1.084 g of tetrachlorophthalic acid (9.4% MEK solution)
Was added and stirred for 15 minutes. While continuing stirring,
12.43 g of additive solution a, 1.6 ml of isocyanate compound (Desmodur N330, manufactured by Mobay Corporation)
0) 10% MEK solution, 4.27 g of additive solution b, 10.
By adding 0 g of the additive liquid c in sequence and stirring, a photosensitive layer coating liquid B was obtained.

<< Preparation of Matting Agent Dispersion >> Cellulose acetate butyrate (Eastman Chemical)
7.5 g of MEB42.5
g of calcium carbonate (Specia)
manufactured by lite Minerals: Super-Pfl
ex200), and dispersed by a dissolver-type homogenizer at 8000 rpm for 30 minutes to prepare a matting agent dispersion.

<< Preparation of Coating Solution for Surface Protective Layer >> While 865 g of MEK (methyl ethyl ketone) was stirred, 96 g of cellulose acetate butyrate (CAB171-15: supra) and polymethyl methacrylic acid (manufactured by Rohm & Haas Co., Ltd .: Paraloid) A-21) 4.5 g, vinyl sulfone compound (HD-1) 1.5 g, benzotriazole 1.0 g, fluorine-based activator (Surflon KH40: supra)
Was added and dissolved. Next, 30 g of the above matting agent dispersion was added and stirred to prepare a coating solution for the surface protective layer.

HD-1: (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ CHOH << Preparation of Samples 101 to 111 >> The photosensitive layer coating solution A, the photosensitive layer coating solution B, and the surface protective layer coating solution are shown in FIGS. A sample was prepared by simultaneously coating a total of three layers, photosensitive layer A, photosensitive layer B and one protective layer, using an extrusion (extrusion) coater as shown in Table 2. ), (2), and (3) were prepared by changing the amount of addition, to prepare samples 101 to 111. Application is
The photosensitive layer A has a coated silver amount of 0.7 g / m ² , the photosensitive layer B has a coated silver amount of 0.3 g / m ² , and the surface protective layer has a dry film thickness of 2.5 μm.
I went in such a way. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 50 ° C and a dew point temperature of 10 ° C. The same method as described in Example 1 was used for the exposure, development processing, evaluation method, and the like of the obtained sample.

Table 3 shows the obtained results.

[0183]

[Table 3]

From Table 3, it is apparent that the sample of the present invention has low fog, high sensitivity, and improved storage stability as compared with the comparative sample.

[0185]

According to the present invention, a photothermographic material having low fog, high sensitivity and improved storability, and an image recording method and an image forming method using the same can be provided.

[Brief description of the drawings]

FIG. 1 shows a schematic configuration diagram of a coating apparatus used in the present invention.

FIG. 2 is a diagram schematically showing a method of discharging and stacking from three slits of an extrusion type die coater, and applying the solution onto a support having a back surface supported.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 coating backup roll 3 coating die 4 coating liquid P liquid sending pump

Claims (12)

[Claims] 1. A photothermographic material containing at least an organic silver salt, a photosensitive silver halide, a reducing agent and a binder on a support, comprising a compound represented by the following general formula (1). Characteristic photothermographic material. General formula (1) R ₁ -SO ₂ -OL ₁ -COOM ₁ [wherein R ₁ is a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a nitro group, a sulfino group, a hydrazino group, It represents a heterocyclic group, a hydrocarbon group or a group which can be formed from a combination thereof, and M ₁ represents a cation. L ₁ represents a divalent group. ] 2. The photothermographic material according to claim 1, wherein L ₁ is an alkylene group or an arylene group. 3. The photothermographic material according to claim 1, wherein L ₁ is a phenylene group. 4. The photothermographic material according to claim 1, wherein L ₁ is an orthophenylene group. 5. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (2). Formula (2) R ₂ —COOM _{2 wherein} R ₂ is a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a nitro group, a sulfino group, a hydrazino group, a heterocyclic group, a hydrocarbon group or , A group that can be formed from these combinations, and M ₂ represents a cation. ] 6. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (3). General formula (3) R ₃ —CO—L ₂ —COOM ₃ [wherein R ₃ is a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a nitro group, a sulfino group, a hydrazino group, a heterocyclic group. , A hydrocarbon group or a group which can be formed from a combination thereof, and M ₃ represents a cation. L ₂ represents a divalent group. ] 7. The photothermographic material according to claim 6, wherein L ₂ is an alkylene group or an arylene group. 8. The photothermographic material according to claim 6, wherein L ₂ is a phenylene group. 9. The photothermographic material according to claim 6, wherein L ₂ is an orthophenylene group. 10. The photothermographic method according to claim 1, wherein an angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular. An image recording method comprising exposing a material. 11. A laser scanning exposure apparatus in which a scanning laser beam for recording on a photosensitive material is a vertical multi-scan.
10. An image recording method, comprising exposing the photothermographic material according to any one of items 9 to 9. 12. An image forming method, wherein the photothermographic material according to claim 1 is heat-developed in a state where the photothermographic material contains a solvent in an amount of 1 to 1000 mg / cm ² .