JP2005148271A - Heat developable photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material having high sensitivity and low fog, excellent in storage stability and ensuring a good silver tone. <P>SOLUTION: In the heat developable photosensitive material having a photosensitive layer containing photosensitive halogenated grains on at least one surface of a support, a compound represented by formula (1) is contained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photothermographic material (also referred to as a photosensitive material) that forms an image by thermal development. More specifically, the present invention relates to a photothermographic material suitable for the fields of medical diagnosis, printing plate making, industrial photography, etc., with little occurrence of fogging and lowering of sensitivity even when stored at high temperature.

  In recent years, in the fields of printing plate making and medical diagnosis, reduction of processing waste liquid accompanying wet processing of image forming materials is strongly desired from the viewpoint of environmental conservation and space saving. As a technique for meeting such a demand, a technique for forming a clear black image with high resolution by heat development is well known. Since these photographic materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic materials and do not require solution-type processing chemicals. Therefore, they are simple and hardly affect the environment. Development processing system can be supplied to customers.

  Such a photothermographic material generally has a reducible non-photosensitive silver salt (for example, organic silver salt), a reducing agent (developer) and a photocatalyst (for example, photosensitive silver halide), and controls the color tone as necessary. A photosensitive layer containing a color toning agent dispersed in an organic binder matrix is provided on the support. The photothermographic material is stable at normal temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is oxidized by a redox reaction between a reducible silver salt (acting as an oxidizing agent) and the reducing agent. Is generated. This oxidation-reduction reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. As a result, a black silver image is formed, which contrasts with the unexposed areas and forms an image.

  Although there is a similar requirement in the field of general image forming materials, especially high-sensitivity images with high Dmax are required for photothermographic materials for printing plate making and medical diagnosis. Has been tried. Among these, hydrazine derivatives and vinyl cyanide compounds have been attracting attention and developed as useful compounds.

  On the other hand, as a technique based on vinyl cyanide compounds, a combined use of a hindered phenol compound and an acrylonitrile compound as a reducing agent (developer) (see, for example, Patent Document 1), and a nitrogen-containing heterocyclic group substituted as a reducing agent. Concomitant use of an acrylonitrile compound and a hindered phenol developer (see, for example, Patent Document 2), Concomitant use of hindered phenols and 1-hydroxy-2-formylethylenes as a reducing agent (see, for example, Patent Document 3) Thus, it is disclosed that a high-contrast black-and-white image can be formed.

  Combination use of a hydrazine derivative having a specific structure and a substituted alkene having a specific structure (for example, see Patent Document 4), a substituted alkene having a specific structure (for example, see Patent Document 5), an alkene compound having a non-diffusible group (for example, , And Patent Document 6), by using a substituted alkene derivative having a specific structure as a nucleating agent, all of them can provide an image having few black spots and high Dmax and gradation (for example, see Patent Document 7). ) Is disclosed.

  By incorporating a substituted alkene derivative having a specific adsorption promoting group to the silver salt via a linking group, a heat-developable recording material having high Dmax, high sensitivity, sufficient contrast, and excellent storage stability It is disclosed that it can be provided (see, for example, Patent Document 8).

  However, the photothermographic material containing these substituted alkene compounds has a problem that fog is likely to occur when stored at a high temperature.

  In order to improve this problem, attempts have been made to suppress fogging with an antifoggant for a photothermographic material. Alkene derivatives substituted with a cyano group and a hydroxy group (see, for example, Patent Document 9), alkene derivatives substituted with an electron-withdrawing group and a hydroxy group (see, for example, Patent Document 10), and alkenes substituted with an electron-withdrawing group Derivatives have been described (see, for example, Patent Document 11), but none of these compounds has a sufficient fog-inhibiting effect during storage, and has a problem with an anti-fogging effect particularly at high temperatures. .

  Further, in a photosensitive material, it is generally known that reducing the amount of silver is effective in reducing the film thickness, but simply reducing the amount of silver will reduce the image density. In order to reduce the silver amount and not reduce the image density, it is necessary to increase the number of development points per unit area. 2. Description of the Related Art Conventionally, a technology for obtaining high image density with a low silver amount has been established by using “infectious development” with a nucleating agent in a photosensitive material for printing to increase the covering power (for example, Patent Documents 12 and 13). See.)

However, many of the light-sensitive materials using a conventionally known nucleating agent have poor storage stability, and the color tone of the formed image silver is yellowish. Further, it has a drawback that it tends to cause a significant change in image density with respect to a slight change in heat development temperature and processing time.
US Pat. No. 5,545,515 (pages 5-10) US Pat. No. 5,635,339 (pages 3-7) US Pat. No. 5,654,130 (pages 3-7) JP-A-10-161270 (Claims) European Patent No. 897,130 (pages 2-4) JP 11-109546 A (Claims) JP 11-133546 A (Claims) JP-A-11-119373 (Claims) US Pat. No. 5,686,228 (pages 3-7) JP 2002-207273 A (Claims) JP 2003-140298 A (Claims) JP 10-512061 A (Claims) Japanese Patent Publication No. 11-511571 (Claims)

  It is an object of the present invention to provide a photothermographic material which improves the above-mentioned problems of the conventional invention, has high sensitivity, low fog, excellent storage stability and good silver tone.

The above object of the present invention can be achieved by the following configuration.
(Claim 1)
A photothermographic material having a photosensitive layer containing photosensitive halogenated particles on at least one surface of a support, wherein the photothermographic material contains a compound represented by the following general formula (1): .

(In formula ^(I), Q ¹ is each .W ^1, V ¹ which represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring together with W ¹ and ^{V 1> C (R 1)} - or> N- R ¹ represents a hydrogen atom, a substituent or a simple bond, and Z ¹ is condensed with a ring formed by Q ¹ , W ¹ and V ¹ to form a ring together with W ¹ and V ^1. X ¹ is a hydroxy group (or salt thereof), mercapto group (or salt thereof), amino group, alkylamino group, arylamino group, heterocyclic amino group, acylamino group, sulfonamide group Or represents a heterocyclic group, and Y ¹ represents an electron-withdrawing group.
(Claim 2)
2. The photothermographic material according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein Q ² represents> CR ²¹ R ²² ,> N—R ²³ ,> O or> S. R ²¹ , R ²² and R ²³ represent a hydrogen atom or a substituent. M ² represents ═O, = .W ^1, V ¹ .R ²⁴ is representing a hydrogen atom or a substituent represented S or ^{= N-R 24, Z 1} , X 1 and Y ^1, W ^1, V ¹ in the general formula (1) , Z ¹ , X ¹ and Y ¹ .
(Claim 3)
3. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (3):

(Wherein, R ₃₁ and R ₃₄ represents an alkyl group .R ₃₂ and R ₃₃ represents .L ₁ is> S or> CR ₃₅ R ₃₆ group represents an alkyl group having 2 or more carbon atoms, R ₃₅ and R ₃₆ represents a hydrogen atom, an alkyl group, a 3- to 10-membered non-aromatic ring group, an aryl group, or a heteroaryl group, J ₁ and J ₂ represent groups that can be substituted on the benzene ring, and n and m are 0 Represents an integer of ~ 2)

  According to the present invention, it is possible to provide a photothermographic material having high sensitivity, low fog, good storage stability and excellent silver tone. In particular, to provide a photothermographic material in which a developed sample does not rise in fog over time, and is a photothermographic photosensor for laser imagers that has high sensitivity, low fog, and good storability of the photosensitive material. It is possible to provide a photothermographic material for an image setter output film that provides a material, and has high sensitivity, low fog, and good storability of the photosensitive material.

The present invention will be described in more detail. In the general formula (1), Q ¹ represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring together with W ¹ and V ¹ . This 5- to 7-membered ring is a substituted or unsubstituted 5- to 7-membered ring. Specific examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclopentene ring, a cyclohexene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. Pyrrolidone ring, pyrrolone ring, furanone ring, thiophenone ring and the like.

As the 5- to 7-membered ring formed by Q ¹ together with W ¹ and V ¹ , a cyclopentane ring, cyclohexane ring, pyrrole ring, imidazole ring, pyrrolidone ring, pyrrolone ring, and furanone ring are preferable, and a cyclohexane ring, pyrrolidone ring, and pyrrolone A ring and a furanone ring are more preferable, and a pyrrolidone ring and a pyrrolone ring are more preferable.

The 5- to 7-membered ring formed by Q ¹ may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, Atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acylamino groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, ureido groups, acyl groups, sulfonyl groups, sulfonyloxy groups, sulfinyl groups, phosphonyl groups, Selected from the group consisting of amino, alkylamino, arylamino, imino, alkylthio, arylthio, acyloxy, cyano, nitro, sulfo, carboxy, hydroxy, oxygen, nitrogen and sulfur 3-7 membered compound containing at least one hetero atom and carbon atom Each of which may contain a ring and may be substituted, such as a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, a quaternary ammonium, a silyloxy group, and the like. It may be further substituted one or more times with a substituent.

In the general formula (1), W ¹ and V ¹ each represent> CR ¹ -or> N-. R ¹ represents a hydrogen atom, a substituent or a simple bond. Specific examples of the substituent represented by R ¹ include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, aryloxy groups. Carbonyl, acylamino, sulfonamido, carbamoyl, sulfamoyl, ureido, acyl, sulfonyl, sulfonyloxy, sulfinyl, phosphonyl, amino, alkylamino, arylamino, imino, alkylthio 3 to 7 containing at least one hetero atom selected from the group consisting of a group, an arylthio group, an acyloxy group, a cyano group, a nitro group, a sulfo group, a carboxy group, a hydroxy group, oxygen, nitrogen and sulfur, and a carbon atom Containing membered heterocycles and optionally substituted Each of them includes a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, a quaternary ammonium, and a silyloxy group, and these substituents themselves are further substituted one or more times with the above-mentioned substituents. May be.

The simple bond, hydrogen atom or substituent represented by R ¹ is preferably a simple bond, a hydrogen atom, an alkyl group, or an aryl group, and is simply a bond, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or aryl. A group is more preferable, and a simple bond, a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms is more preferable.

In the general formula (1), Z ¹ represents a nonmetallic atom group necessary for condensing with a ring formed by Q ¹ , W ¹ and V ¹ to form a ring together with W ¹ and V ¹ . The ring formed by combining Z ¹ with the ring formed by Q ¹ , W ¹ and V ¹ together with W ¹ and V ¹ is either saturated or unsaturated, carbocyclic or heterocyclic, substituted or unsubstituted. The ring may further be condensed with another saturated or unsaturated carbocyclic or heterocyclic ring.

  Specific examples include benzene ring, naphthalene ring, cyclohexane ring, cyclopentane ring, pyridine ring, furan ring, thiophene ring, pyrrole ring, benzofuran ring, benzothiophene ring, imidazole ring, pyrazole ring, triazole ring, pyrimidine ring, benz Examples include an imidazole ring, a benzoxazole ring, a benzothiazole ring, and the like, preferably a benzene ring, a naphthalene ring, a cyclohexane ring, and a cyclopentane ring, more preferably a benzene ring, a naphthalene ring, and still more preferably a benzene ring.

The ring formed by Z ¹ may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, and an alkoxy group. , Aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, sulfonyl group, sulfonyloxy group, sulfinyl group, phosphonyl group, amino group, alkyl At least one selected from the group consisting of amino group, arylamino group, imino group, alkylthio group, arylthio group, acyloxy group, cyano group, nitro group, sulfo group, carboxy group, hydroxy group, oxygen, nitrogen and sulfur Includes 3-7 membered heterocycles containing hetero atoms and carbon atoms Each of which may be substituted, such as a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, a quaternary ammonium, and a silyloxy group. These substituents themselves are the above substituents. Further, it may be substituted one or more times.

As the condensed ring formed by Q ¹ , W ¹ , V ¹ and Z ¹ , indole, oxindole, benzofuranone and benzothiophenone are preferable, benzofuranone and oxyindole are more preferable, and oxindole is more preferable.

In the general formula (1), X ¹ represents a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an acylamino group, a sulfonamide group or a hetero group. Represents a cyclic group. The alkylamino group represented by X ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms. Specific examples include a methylamino group and a dimethylamino group.

In the general formula (1), the arylamino group represented by X ¹ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. Specific examples include an anilino group, an N-methylanilino group, and a diphenylamino group. In the general formula (1), the heterocyclic amino group represented by X ¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms. Specific examples include 1-phenyltetrazole-5-amino group. In General Formula (1), the acylamino group represented by X ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms. Specific examples include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like. In the general formula (1), the sulfonamide group represented by X ¹ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms. Specific examples include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, and a p-methylphenylsulfonylamino group. In the general formula (1), the heterocyclic group represented by X ¹ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms. Moreover, it is preferable that it is a saturated or unsaturated heterocyclic group couple | bonded with a hetero atom. Specific examples include 1-indolyl group and 1-indazolyl group.

In the general formula (1), the substituent represented by X ¹ is preferably a hydroxy group (including a salt thereof), a mercapto group (or a salt thereof), an amino group, or an alkylamino group, and a hydroxy group (a salt thereof). Or a mercapto group (or a salt thereof), more preferably a hydroxy group (including a salt thereof).

In general formula (1), Y ¹ represents an electron-withdrawing group. The electron withdrawing group represented by Y ¹ is a substituent whose Hammett's substituent constant σp can take a positive value. Here, Hammett's substituent constant used in the present specification will be described briefly. Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. This is a rule of thumb advocated by Hammett. The σ value is known as σo at the ortho position, σm at the meta position, and σp at the para position, based on the substitution position of the phenolic hydroxyl group. A positive Hammett value (σp) indicates that the group is electron withdrawing. In the present specification, the σp value is substituted as a measure of the electronic effect. These substituent constants are described in C.I. Hansch, A.M. Leo, “Substitutants Constants for Correlation Analysis in Chemistry and Biology,” Jhon Wiley & Sons, Inc. , New York, 1979.

The electron-withdrawing group represented by Y ¹ is preferably a group having a σp value of 0.1 or more, more preferably a σp value of 0.2 or more. Specific examples of the electron withdrawing group represented by Y ¹ include a halogen atom (chlorine atom (σp value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18). ), Trihalomethyl group (for example, tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp value: 0.54), etc.), cyano group (σp value) : 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl group (σp value: 0.72), etc.), aliphatic / aryl or heterocyclic ring Acyl groups (for example, acetyl group (σp value: 0.50), benzoyl group (σp value: 0.43), etc.), aliphatic / aryl or heterocyclic oxycarbonyl groups (for example, methoxycarbonyl group (σp value: 0) .45), Fe Alkoxycarbonyl group (.sigma.p value: 0.45), etc.), a carbamoyl group (.sigma.p value: 0.36), a sulfamoyl group (.sigma.p value: 0.57), and the like, preferably as a substituent represented by Y ¹ Is a trihalomethyl group, a cyano group, an aliphatic / aryl or heterocyclic acyl group, more preferably a trihalomethyl group, still more preferably a trifluoromethyl group.

In the general formula (2), Q ² is preferably> N—R ²³ ,> O or> S, and more preferably> N—R ²³ .

R ²¹ and R ²² represent a hydrogen atom or a substituent. Specific examples of the substituent represented by R ²¹ and R ²² include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, and an alkoxycarbonyl group. , Aryloxycarbonyl group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, sulfonyl group, sulfonyloxy group, sulfinyl group, phosphonyl group, amino group, alkylamino group, arylamino group, imino Including at least one heteroatom selected from the group consisting of a group, an alkylthio group, an arylthio group, an acyloxy group, a cyano group, a nitro group, a sulfo group, a carboxy group, a hydroxy group, oxygen, nitrogen and sulfur, and a carbon atom Contains 3-7 membered heterocycles and is also substituted Each of which may be a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, a quaternary ammonium, a silyloxy group, etc., and these substituents themselves are further substituted one or more times by the above-mentioned substituents. It may be.

The hydrogen atom or substituent represented by R ²¹ and R ²² is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group, a hydrogen atom, carbon A C1-C6 alkyl group is more preferable.

R ²³ represents a hydrogen atom or a substituent. Specific examples of the substituent represented by R ²³ include the substituents exemplified as R ²¹ and R ²² .

The hydrogen atom or substituent represented by R ²³ is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or a carbon number of 1 to 12 alkyl groups are mentioned.
In the general formula (2), M ² represents ═O, ═S or ═N—R ²⁴ . R ²⁴ represents a hydrogen atom or a substituent. As M ² , ═O or ═S is preferable, and ═O is more preferable. Specific examples of the substituent represented by R ²⁴ include the substituents exemplified as R ²¹ and R ²² . The hydrogen atom or substituent represented by R ²⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom or an alkyl having 1 to 12 carbon atoms. More preferred are groups.

In the present invention, Y ¹ may contain a diffusion-resistant group. The anti-diffusion group is called a ballast group in a photographic coupler or the like, and has a bulky molecular weight so that the added compound does not move in the film of the photosensitive material.

In the present invention, Y ¹ may contain an adsorption promoting group for silver salt. Adsorption promoting groups for silver salts include thioamide groups, aliphatic mercapto groups, aromatic mercapto groups, heterocyclic mercapto groups and benzotriazoles, triazoles, tetrazoles, indazoles, benzimidazoles, imidazoles, benzothiazoles, thiazoles, benzoxazoles, Examples include groups represented by 5- to 6-membered nitrogen-containing heterocycles such as oxazole, thiadiazole, oxadiazole, and triazine.

In the present invention, the alkene compounds represented by the general formulas (1) and (2) include all isomers when they can take an isomer structure with respect to the double bond substituted by X ¹ and Y ^1. In addition, all isomers are included when tautomeric structures such as keto-enol can be taken.

  Specific examples of the compounds represented by general formula (1) and general formula (2) are shown below, but the present invention is not limited thereto.

  The compounds represented by general formula (1) and general formula (2) of the present invention can be synthesized by various methods. The synthesis example is shown below.

<Synthesis of Exemplified Compound 41>
15 ml of methanol was added to 15.0 g of oxindole and cooled with an ice-water bath. Sodium methoxide (28% methanol solution) (23.9 g) was added dropwise, and the mixture was stirred for 1 hour under ice-water cooling. After 17.6 g of trifluoroacetic acid ethyl ester was added dropwise, the mixture was further stirred for 1 hour. After warming to room temperature and stirring for 1 hour, 36 ml of water was added and stirred for 30 minutes. Concentrated hydrochloric acid 11.3 ml was added dropwise and acetonitrile 25 ml was added. After stirring for 1 hour under ice-water cooling, the precipitated solid was collected by filtration and recrystallized from acetonitrile to obtain 14.4 g of Exemplified Compound 41. Yield 56%. Identification was carried out using MASS and NMR spectra, and it was confirmed to be Exemplified Compound 41.

<Synthesis of Exemplary Compound 58>
100 ml of methylene chloride was added to 25.8 g of 2-diazo-4,4,4-trifluoro-3-oxobutyric acid phenyl ester, 2.2 g of dirhodium tetraacetate was added, and the mixture was stirred at room temperature for 1 hour. 150 ml of water was poured into the reaction solution, and extracted with 100 ml of methylene chloride. The organic layer was dried over magnesium sulfate and the solvent was distilled off. The obtained pale yellow crystals were recrystallized from hexane-ethyl acetate to obtain 20.9 g of Exemplified Compound 58. Yield 91%. Identification was carried out using MASS and NMR spectra, and it was confirmed to be Exemplified Compound 58.

<Synthesis of Exemplary Compound 64>
31.5 g of 1,4-epoxy-1-cyano-4-methyl-1,4-dihydronaphthalene was dissolved in 300 ml of methylene chloride, and 60.0 g of 50% m-chloroperbenzoic acid was added. 10 ml of saturated multistory water was added and stirred at room temperature for 2 hours. The reaction solution was poured into 400 ml of water and extracted by adding 100 ml of methylene chloride. The organic layer was dried over magnesium sulfate and the solvent was distilled off. The residue was purified by a silica gel column (hexane-ethyl acetate) to obtain 28.4 g of exo-1,4: 2,3-diepoxy-1-cyano-4-methyl-1,2,3,4-tetrahydronaphthalene. . Yield 82%.

  300 ml of toluene was added to 28.4 g of exo-1,4: 2,3-diepoxy-1-cyano-4-methyl-1,2,3,4-tetrahydronaphthalene, and 1.5 g of lithium perchlorate (anhydrous) was added. The mixture was heated to reflux for 1 hour. After confirming the disappearance of the raw materials by reaction with TLC, the reaction solution was allowed to cool and extracted by adding 300 ml of water. The organic layer was dried over magnesium sulfate and the solvent was distilled off. The obtained yellow crystals were recrystallized from heptane to obtain 27.3 g of Exemplified Compound 64. Yield 96%. Identification was carried out by MASS and NMR spectra, and it was confirmed to be Exemplified Compound 64.

In the general formula (3), R ₃₁ and R ₃₄ each independently represents an alkyl group. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, and a decyl group. Group, dodecyl group, pentadecyl group, trifluoromethyl group, perfluorooctyl group, cycloalkyl group, cyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, alkynyl group, propargyl group and the like.

  These groups may be further substituted, and examples of the substituent include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.) , Halogenated alkyl groups (eg, trifluoromethyl group, perfluorooctyl group, etc.), cycloalkyl groups (eg, cyclohexyl group, cyclopentyl group, etc.), alkynyl groups (eg, propargyl group), glycidyl groups, acrylate groups, methacrylates Group, aryl group (for example, phenyl group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sriphoranyl group, Piperidinyl group, pyrazolyl group, tetrazoli group Group), halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, Cyclohexyloxy group etc.), aryloxy group (eg phenoxy group), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group) ), Sulfonamide groups (for example, methanesulfonamide groups, ethanesulfonamide groups, butanesulfonamide groups, hexanesulfonamide groups, cyclohexanesulfonamide groups, benzenesulfonamide groups, etc.), sulfamoyl groups (for example, Minosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), urethane group (for example, methylureido group) , Ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, etc.), acyl group (for example, acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, Pyridinoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclo Hexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), amide group (eg, acetamido group, propionamide group, butanamide group, hexaneamide group, benzamide group etc.), sulfonyl group (eg, methylsulfonyl group) , Ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino) Group, 2-pyridylamino group and the like), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, oxamoyl group and the like.

R ₃₁ and R ₃₄ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a secondary or tertiary alkyl group, and particularly preferably a tert-butyl group or a 1-methylcyclohexyl group.

In the general formula (3), R ₃₂ and R ₃₃ represent an alkyl group having 2 or more carbon atoms. Specific examples of the alkyl group having 2 or more carbon atoms include ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, decyl group, dodecyl group, pentadecyl group, pentafluoroethyl group, perfluorooctyl. Group, cyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, propargyl group and the like. These groups may be further substituted, and examples of the substituent include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.) , Halogenated alkyl groups (eg, trifluoromethyl group, perfluorooctyl group, etc.), cycloalkyl groups (eg, cyclohexyl group, cyclopentyl group, etc.), alkynyl groups (eg, propargyl group), glycidyl groups, acrylate groups, methacrylates Group, aryl group (for example, phenyl group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sriphoranyl group, Piperidinyl group, pyrazolyl group, tetrazoli group Group), halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, Cyclohexyloxy group etc.), aryloxy group (eg phenoxy group), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group) ), Sulfonamide groups (for example, methanesulfonamide groups, ethanesulfonamide groups, butanesulfonamide groups, hexanesulfonamide groups, cyclohexanesulfonamide groups, benzenesulfonamide groups, etc.), sulfamoyl groups (for example, Minosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), urethane group (for example, methylureido group) , Ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, etc.), acyl group (for example, acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, Pyridinoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclo Hexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), amide group (eg, acetamido group, propionamide group, butanamide group, hexaneamide group, benzamide group etc.), sulfonyl group (eg, methylsulfonyl group) , Ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino) Group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxy group, oxamoyl group, ether group (ethoxy group, tert-butoxy group, allyloxy group, benzyloxy group, triphenyl group) Rumethoxy group, trimethylsilyloxy group, etc.), hemiacetal group (tetrahydropyranyloxy group, etc.), ester group (benzoyloxy group, p-nitrobenzoyloxy group, formyloxy group, trifluoroacetyloxy group, pivaloyloxy group, etc.), Carbonate groups (ethoxycarbonyloxy group, phenoxycarbonyloxy group, tert-butyloxycarbonyloxy group, etc.), sulfonate groups (p-toluenesulfonyloxy group, benzenesulfonyloxy group, etc.), carbamoyloxy groups (phenylcarbamoyloxy group, etc.) Thiocarbonyloxy group (benzylthiocarbonyloxy group etc.), nitrate ester group, sulfenate group (2,4-dinitrobenzenesulfenyloxy group etc.) and the like.

The alkyl group having 2 or more carbon atoms represented by R ₃₂ and R ₃₃ is preferably an alkyl group having 2 to 6 carbon atoms substituted by an ethyl group, an isopropyl group, a tert-butyl group or a hydroxy group, more preferably It is a C2-C4 alkyl group substituted by a hydroxy group, more preferably a 2-hydroxyethyl group.

In the general formula (3), L ₁ represents> S or> CR ₃₅ R ₃₆ . L ₁ is preferably> CR ₃₅ R ₃₆ . R ₃₅ and R _{36 each} represents a hydrogen atom, an alkyl group, a 3- to 10-membered non-aromatic ring group, an aryl group, or a heteroaryl group.

  Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, an undecyl group, an isopropyl group, a 1-ethylpentyl group, and a 2,4,4-trimethylpentyl group.

  Specific examples of 3 to 10-membered non-aromatic ring groups include cyclopropyl, aziridyl, oxiranyl as 3-membered rings, cyclobutyl, cyclobutenyl, oxetanyl, azetidinyl as 4-membered rings, and cyclopentyl, cyclopentenyl, cyclohexane as 5-membered rings Pentadienyl, tetrahydrofuranyl, pyrrolidinyl, tetrahydrothienyl, 6-membered ring is cyclohexyl, cyclohexenyl, cyclohexadienyl, tetrahydropyranyl, pyranyl, piperidinyl, dioxanyl, tetrahydrothiopyranyl, norcaranyl, norpinanyl, norbornyl, 7-membered ring As cycloheptyl, cycloheptynyl, cycloheptadienyl, 8-membered ring as cyclooctanyl, cyclooctenyl, cyclooctadienyl, cyclooctatrienyl, 9-membered ring Te is cyclononanyl, cyclononenyl, shea chrono Nagy enyl, cyclononatrienyl enyl, as the 10-membered ring cyclooctyl, Shikurodekeniru, cycloalkyl decadienyl include the group such as cyclopropyl tetradecatrienyl.

  Preferably it is a 3-6 membered ring, More preferably, it is a 5-6 membered ring, Most preferably, it is a 6 membered ring, Among these, the hydrocarbon ring which does not contain a hetero atom is preferable.

  The ring may form a spiro bond with another ring through a spiro atom, or may be condensed in any way with another ring including an aromatic ring.

  Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group.

  Specific examples of heteroaryl groups include imidazole groups, pyrazole groups, pyridine groups, pyrimidine groups, pyrazine groups, pyridazine groups, triazole groups, triazine groups, indole groups, indazole groups, purine groups, thiadiazole groups, oxadiazole groups, and quinolines. Group, phthalazine group, naphthyridine group, quinoxaline group, quinazoline group, cinnoline group, pteridine group, acridine group, phenanthroline group, phenazine group, tetrazole group, thiazole group, oxazole group, benzimidazole group, benzoxazole group, benzthiazole group, Indolenine group and tetrazaindene group can be mentioned.

These groups can further have an optional substituent. Specifically for the substituent it is the same as the substituents of the groups represented by R ₃₁ to R _34.

R ₃₅ is preferably a hydrogen atom, an isopropyl group, a 2,4,4-trimethylpentyl group, or a 5- to 6-membered non-aromatic ring group (a cyclohexyl group, a cyclohexenyl group, or the like).
R ₃₆ is preferably a hydrogen atom.

J ₁ and J ₂ in the general formula (3) represents a group substitutable on a benzene ring, n and m represents an integer of 0 to 2. Specific examples of the substituent represented by J ₁ and J ₂ include methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, trifluoromethyl group, perfluoro group. Octyl, cyclohexyl, cyclopentyl, propargyl, etc., glycidyl, acrylate, methacrylate, phenyl, pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl Group, selenazolyl group, sliphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group , Cyclohexyloxy group, phenoxy group, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, phenyloxycarbonyl group, etc., methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfone Amide group, benzenesulfonamide group, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, methylureido Group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group, acetyl group, pro Onyl group, butanoyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, pyridinoyl group, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, phenyl Aminocarbonyl group, 2-pyridylaminocarbonyl group, acetamide group, propionamide group, butanamide group, hexaneamide group, benzamide group, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridyl group Sulfonyl group, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino group, 2-pyridylamino group, cyano group Nitro group, a sulfo group, a carboxyl group, a hydroxyl group, can be exemplified Okizamoiru group. Further, these groups may be further substituted with these groups.

  n and m represent an integer of 0 to 2, and most preferably n and m are 0.

  Specific examples of the compound represented by the general formula (3) are listed below, but the present invention is not limited thereto.

  The compound represented by the general formula (3) of the present invention can be synthesized by various methods. The general synthesis method is shown below.

  Preferably 2 equivalents of phenol and 1 equivalent of aldehyde are dissolved or suspended in the absence of solvent or in a suitable organic solvent and a catalytic amount of acid or alkali is added, preferably at a temperature of -20 ° C to 180 ° C. The target compound can be obtained in good yield by reacting for 0.5 to 60 hours.

  The organic solvent is preferably a hydrocarbon organic solvent, and specific examples include benzene, toluene, xylene, dichloromethane, chloroform and the like. Preferred are toluene and xylene. Furthermore, it is most preferable to make it react without a solvent from the point of a yield. Although any inorganic acid and organic acid can be used as the acid catalyst, concentrated hydrochloric acid, p-toluenesulfonic acid, and phosphoric acid are preferably used. As the alkali catalyst, caustic soda, caustic potash, triethylamine, DBU, and sodium methylate are preferably used. The catalyst amount is preferably 0.001 to 1.5 equivalents relative to the corresponding aldehyde. The reaction temperature is preferably (15 ° C. to 150 ° C.), and the reaction time is preferably 3 to 20 hours.

The compounds represented by the general formula (1) and the general formula (2) may be contained in at least one of the photosensitive layer of the photothermographic material or the non-photosensitive layer on the photosensitive layer side. It is to be included in the layer. The amount of the compound represented by the general formula (1) and the general formula (2) is preferably 1 × 10 ⁻⁸ to 1 mol per 1 mol of silver, and 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol. Is more preferable, and 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol is most preferable.

  The compounds represented by the general formula (1) and the general formula (2) can be added to the photosensitive layer and the non-photosensitive layer according to a known method. That is, it can be dissolved in an alcohol such as methanol or ethanol, a ketone such as methyl ethyl ketone or acetone, or a polar solvent such as dimethyl sulfoxide or dimethylformamide, and added to the coating solution for the photosensitive layer or the non-photosensitive layer. Further, fine particles of 1 μm or less can be dispersed and added in water or an organic solvent. Many techniques for fine particle dispersion are disclosed, but they can be dispersed according to these techniques.

  Although the reducing agent represented by General formula (3) used with General formula (1) and General formula (2) may be used independently, you may use it in combination of 2 or more types. The reducing agent may be contained in the coating solution by any method such as a solution form, an emulsified dispersion form, a solid fine particle dispersion form, or the photosensitive material.

  The amount of reducing agent used varies depending on the type of organic silver salt, reducing agent, and other additives, but is generally 0.05 to 10 moles, preferably 0.1 to 3 moles per mole of organic silver salt. Mole is appropriate. In the present invention, it may be preferable that the reducing agent is added to and mixed with a photosensitive emulsion solution composed of photosensitive silver halide and organic silver salt grains and a solvent immediately before coating, because photographic performance fluctuation due to stagnation time is small. is there.

  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 aliphatic carboxylic acid, carbocyclic carboxylic acid, heterocyclic carboxylic acid, heterocyclic compound and the like, but particularly long chain (10-30, preferably 15-25). The aliphatic carboxylic acid having the number of carbon atoms) and the heterocyclic carboxylic acid having a nitrogen-containing heterocyclic ring are preferably used. An organic silver salt complex having a total stability constant with respect to silver ions having a ligand of 4.0 to 10.0 is also useful.

  Examples of such organic acid silver salts are described in Research Disclosure (hereinafter abbreviated as RD) 17029 and 29963. Of these, silver salts of fatty acids are preferably used, and silver behenate, silver arachidate, and silver stearate are particularly preferably used.

  The organic silver salt compound described above can be obtained by mixing a water-soluble silver compound and a compound that forms a complex with silver, and a normal mixing method, a back mixing method, a simultaneous mixing method, and the like are preferably used. It is also possible to use a controlled double jet method as described in JP-A-9-127643.

  In the present invention, the organic silver salt preferably has an average particle size of 1 μm or less and is monodispersed. The average particle diameter of the organic silver salt is, for example, when the organic silver salt particles are spherical, rod-shaped, or tabular, the diameter when considering a sphere equivalent to the volume of the organic silver salt particles. Say. The average particle size is preferably 0.01 to 0.8 μm, particularly preferably 0.05 to 0.5 μm. Moreover, monodispersion is synonymous with the case of the below-mentioned silver halide, Preferably monodispersion degree is 1 to 30%. In the present invention, the organic silver salt is more preferably monodisperse particles having an average particle size of 1 μm or less, and an image having a high density can be obtained by setting the content within this range. Further, the organic silver salt preferably has tabular grains of 60% by number or more of the total organic silver. In the present invention, the tabular grains mean those having an average grain diameter / thickness ratio, that is, an aspect ratio (abbreviated as AR) represented by the following formula of 3 or more.

AR = average particle diameter (μm) / thickness (μm)
Such organic silver particles are preferably preliminarily dispersed together with a binder, a surfactant or the like, if necessary, and then dispersed and ground with a media disperser or a high-pressure homogenizer. As the disperser that can be used in the preliminary dispersion, for example, a general stirrer such as an anchor type or a propeller type, a high-speed rotating centrifugal radiation stirrer (dissolver), or a high-speed rotating shear stirrer (homomixer) may be used. it can. Examples of the media disperser include a rolling mill such as a ball mill, a planetary ball mill, and a vibration ball mill, a bead mill that is a medium agitation mill, an attritor, and other basket mills, and a high-pressure homogenizer. For example, various types such as a type that collides with a wall, a plug, etc., a type that allows liquids to collide with each other at high speed after dividing the liquid, and a type that allows a thin orifice to pass through can be used.

  In the apparatus used when dispersing the organic silver particles used in the present invention, for example, ceramics such as zirconia, alumina, silicon nitride, boron nitride, or diamond is used as the material of the member in contact with the organic silver particles. It is preferable to use zirconia, in particular.

  The organic silver particles used in the present invention preferably contain 0.01 to 0.5 mg of Zr per 1 g of silver, particularly preferably 0.01 to 0.3 mg of Zr. When carrying out the above dispersion, optimizing the binder concentration, the preliminary dispersion method, the dispersing machine operating conditions, the number of times of dispersion, etc. is very preferable as a method for obtaining the organic silver salt particles used in the present invention.

  The photosensitive silver halide according to the present invention preferably has a smaller average grain size, and preferably has an average grain size of 0.1 μm or less, more preferably, in order to suppress white turbidity after image formation and to obtain good image quality. 0.01-0.1 micrometer, especially 0.02-0.08 micrometer are preferable. The particle size here refers to the diameter (equivalent circle diameter) of a circle having the same area as each particle image observed with an electron microscope. The silver halide is preferably monodispersed. The monodispersion here means that the monodispersity obtained by the following formula is 40% or less. The particles are more preferably 30% or less, and particularly preferably 20% or less.

Monodispersity = (standard deviation of particle size) / (average particle size value) × 100
The shape of the photosensitive 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, further 70% or more, particularly 80% or more. Preferably there is. The ratio of the Miller index [100] plane is calculated by using the adsorption dependency between the [111] plane and the [100] plane in the adsorption of the sensitizing dye. Tani, J .; Imaging Sci. 29, 165 (1985).

  In the present invention, another preferred shape of the photosensitive silver halide is a tabular grain. The term “tabular grain” as used herein refers to those having an aspect ratio (r / h) of 3 or more when the square root of the projected area is the grain size r μm and the thickness in the vertical direction is h μm. Among them, the aspect ratio is preferably 3 to 50. Moreover, it is preferable that the particle size of a tabular grain is 0.1 micrometer or less, Furthermore, 0.01 micrometer-0.08 micrometer are preferable. These tabular grains are described in US Pat. Nos. 5,264,337, 5,314,798, 5,320,958, etc., and the desired tabular grains can be easily obtained. it can.

  The photosensitive 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 emulsion used in the present invention is P.I. Chifie et Physique Photographic (published by Paul Montel, 1967) by Glafkides. F. Duffin's Photographic Emission Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared based on the method described in Making and Coating Photographic Emulsion (published by The Focal Press, 1964) by Zelikman et al.

  The photosensitive silver halide according to the present invention preferably contains a metal ion belonging to Groups 6 to 11 of the periodic table. As the metal, W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, and Au are preferable.

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

General formula [ML ₆ ] ⁿ
In the formula, M represents a transition metal selected from Group 6 to 11 elements of the periodic table, L represents a ligand, and m represents 0,-, 2-, 3-, or 4-. Specific examples of the ligand represented by L include, for example, halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and acos. Each ligand includes nitrosyl, thionitrosyl, and the like, preferably aco, nitrosyl, thionitrosyl, and the like. When an acoligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

M is preferably rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os). Specific examples of transition metal complex ions containing these include [RhCl ₆ ] ^-3 [RhCl ₅ (H ₂ O)] ⁻² , [RhBr ₅ (NO)] ⁻² , [RhCl ₅ (NS)] ⁻² , [RhCl ₄ (NO) (CN)] ⁻¹ , [RhCl (NO) ) (CN) ₄ ] ⁻² , [ReCl ₆ ] ⁻³ , [ReBr ₆ ] ⁻³ , [ReCl ₅ (NO)] ⁻² , [Re (NS) Br ₃ ] ⁻² , [Re (NO) ( CN) _5] ^-2, [RuCl _6] ^-3, [RuCl ₄ (H ₂ O) _2] ^-1, [RuCl ₅ (NO)] ^-2, [RuBr ₅ (NS)] ^-2, [RuCl ₅ (NS)] ^-2, [OsCl _6] ^-3, [OsCl ₅ (NO)] ^-2, [Os (NO) (CN) _5] ^-2, [ Os (NO) (CN)] ⁻¹ , [Os (NS) Br ₅ ] ⁻² , [IrCl ₆ ] ⁻³ , [IrCl ₅ (H ₂ O)] ⁻² , [IrBr ₅ (NO)] ⁻² , [IrCl ₅ (NS)] ^{-2 and the} like.

One kind of metal ion, metal complex or metal complex ion described above may be used, or two or more kinds of the same kind of metal and different kinds of metals may be used 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 ^{- 8} to 1 × 10 ⁻⁴ mol.

  These metal-providing compounds are preferably added at the time of silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, chemical sensitization It may be added at any stage before or after, but is preferably added at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, most preferably Add at the stage of formation.

  In addition, it may be divided and added several times, or it can be uniformly contained in the silver halide grains. JP-A-63-29603, JP-A-2-306236, 3 As described in No. 167545, No. 4-76534, No. 6-110146, No. 5-273683, etc., it can also be contained with distribution in the particles. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving in water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides). A method of adding an aqueous solution or a metal compound and an aqueous solution in which NaCl and KCl are dissolved together to a water-soluble silver salt solution or a water-soluble halide solution during particle formation, or a silver salt solution and a halide solution are simultaneously mixed. When adding a third aqueous solution, a method of preparing silver halide grains by a three-liquid simultaneous mixing method, a method of adding an aqueous solution of a required amount of a metal compound to the reaction vessel during grain formation, or silver halide There is a method of adding another silver halide grain previously doped with a metal ion or complex ion at the time of preparation and dissolving it. In particular, a method of adding an aqueous solution of a metal compound powder or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together is added to the water-soluble halide solution.

  When added to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during physical ripening, or at the end or chemical ripening.

  In the present invention, the photosensitive silver halide grains may or may not be desalted after grain formation. However, when desalting is performed, for example, the noodle method, the flocculation method, etc. are known in the art. Can be washed with water and desalted.

  The silver halide grains used in the present invention are preferably chemically sensitized. As a preferable chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and the like well known in the art can be used. Further, noble metal sensitization methods such as gold compounds, platinum, palladium, iridium compounds, and reduction sensitization methods can be used.

  As the compound preferably used in the above-described sulfur sensitization method, selenium sensitization method, and tellurium sensitization method, known compounds can be used. For example, compounds described in JP-A-7-128768 are used. be able to. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Compound having Te bond, tellurocarboxylates, Te-organyl tellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having P-Te bond Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used.

  Examples of the compound preferably used for the noble metal sensitization include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, U.S. Pat. No. 2,448,060 and British Patent 618,061. The compounds described in No. etc. can be preferably used.

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

Next, components of the photothermographic material of the present invention excluding the above-described items will be described.
The photothermographic material of the present invention is obtained by laminating an image forming layer and a protective layer containing the above-described organic silver salt, photosensitive silver halide, and the reducing agent of the present invention on a support in this order. Further, it is preferable that an intermediate layer is provided between the support and the image forming layer as necessary.

  Further, a photothermographic material in which a backing layer is provided on the surface opposite to the image forming layer to ensure transportability and prevent blocking with the protective layer can be suitably used. Each layer may be a single layer, or may be composed of two or more layers having the same or different composition.

  In the present invention, a binder resin is preferably used to form each of the above layers. As such a binder resin, a conventionally used transparent or translucent binder resin can be selected and used as appropriate. Examples of such a binder resin include polyvinyl formal, polyvinyl acetoacetal, and polyvinyl butyral. Polyvinyl acetal resins such as ethyl cellulose, hydroxyethyl cellulose, cellulose resins such as cellulose acetate butyrate, styrene resins such as polystyrene, styrene-acrylonitrile copolymers, styrene-acrylonitrile-acrylic rubber copolymers, polyvinyl chloride, chlorine Vinyl chloride-based resins such as modified polypropylene, polyester, polyurethane, polycarbonate, polyarylate, epoxy resin, acrylic resin, and the like. These may be used alone or in combination of two or more. It may be used in combination with fat.

  In addition, the said binder resin can be suitably selected and used for each layer of a protective layer, an intermediate | middle layer, or the backcoat layer provided when needed, unless the objective of this invention is impaired. In addition, you may use an epoxy resin, an acrylic monomer, etc. which can be hardened | cured with an active energy ray as a layer formation binder resin for an intermediate | middle layer and a backcoat layer. In the present invention, the following aqueous binder resins are also preferably used.

  As a preferable resin, a water-soluble polymer or a water-dispersible hydrophobic polymer (latex) can be used. For example, polyvinylidene chloride, vinylidene chloride-acrylic acid copolymer, vinylidene chloride-itaconic acid copolymer, sodium polyacrylate, polyethylene oxide, acrylic acid amide-acrylic acid ester copolymer, styrene-maleic anhydride copolymer Examples thereof include acrylonitrile-butadiene copolymer, vinyl chloride-acetic acid part nyl copolymer, and styrene-butadiene-acrylic acid copolymer. These constitute an aqueous coating solution, but form a uniform resin film at the stage of drying after coating and forming a coating film. When these are used, an organic silver salt, silver halide, reducing agent, etc. as an aqueous dispersion, mixed with these latexes to form a uniform dispersion, and then applied to form a heat-developable image forming layer Can be formed. By drying, the latex coalesces and forms a uniform film. Further, a polymer having a glass transition point of −20 ° C. to 80 ° C. is preferable, and −5 ° C. to 60 ° C. is particularly preferable. This is because if the glass transition point is high, the temperature at which heat development is carried out becomes high, and if it is low, fogging tends to occur, leading to a reduction in sensitivity and softening. The water-dispersed polymer is preferably dispersed in the form of fine particles having an average particle diameter in the range of 1 nm to several μm. The water-dispersed hydrophobic polymer is called a latex, and is preferably a latex that improves water resistance among widely used binders for aqueous coating. The amount of latex used for the purpose of obtaining water resistance as a binder is determined in consideration of applicability, but is preferably as large as possible from the viewpoint of moisture resistance. The ratio of latex to the total binder mass is preferably 50 to 100%, particularly preferably 80 to 100%.

In the present invention, as these binder resins, the amount of solids is 0.25 to 10 times the amount of silver attached, for example, when the amount of silver attached is 2.0 g / m ² , the amount of polymer attached is It is preferable that it is 0.5-20 g / m < ² >. Further, more preferably 0.5 to 7 times the grain-weight, for example, the amount with silver, if 2.0 g / m ^2, a 1.0~14g / m ^2. If the amount of binder resin is less than 0.25 times the amount of silver, the silver color tone may be significantly deteriorated and may not endure use, and if the amount is more than 10 times the amount of silver, it may become soft and endure use. is there.

  Further, the image forming layer according to the present invention includes, in addition to the above-described essential components and binder resin, an antifoggant, a toning agent, a sensitizing dye, and a substance that exhibits supersensitization (supersensitization). Various additives may also be added.

In the present invention, examples of the antifogging agent include compounds disclosed in US Pat. Nos. 3,874,946 and 4,756,999, —C (X ₁ ) (X ₂ ) ( X ₃ ) (wherein X ₁ and X ₂ represent a halogen atom, and X ₃ represents hydrogen or a halogen atom), a heterocyclic compound having one or more substituents, JP-A-9-288328, No. 9-90550, US Pat. No. 5,028,523 and European Patent Nos. 600,587, 605,981, 631,176, etc. be able to.

  Examples of toning agents added for the purpose of improving the silver tone after development include imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (for example, succinimide, 3-phenyl- 2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (eg N-hydroxy-1,8-naphthalimide); cobalt complexes (eg cobalt hexamine trifluoro) Acetate), mercaptans (eg, 3-mercapto-1,2,4-triazole); N- (aminomethyl) aryl dicarboximides (eg, N- (dimethylaminomethyl) phthalimide); blocked pyrazoles , Isothiuronium ) Derivatives and certain photobleaching agents (eg, N, N′-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothione) Uronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); merocyanine dyes (eg 3-ethyl-5- (2- (3-tyl-2-benzothiazolinylidene) ethylidene) ) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (eg, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalate) Radinone and 2,3-dihydro-1,4-phthalazinedione); phthalazinone and sulfinic acid derivatives Combinations (eg 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalic acid combinations; phthalazine (including adducts of phthalazine) and maleic anhydride And phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) In combination with at least one compound; quinazolinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric- Triazines (eg 2,4-dihydroxy Pyrimidine) and tetraazapentalene derivatives (for example, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene), and preferred toning agents As phthalazone and phthalazine. In addition, as long as it is a range which does not inhibit the objective of this invention, you may add a toning agent to the protective layer mentioned later.

  As the sensitizing dye, for example, for an argon ion laser light source, JP-A-60-162247, JP-A-2-48635, US Pat. No. 2,161,331, West German Patent 936,071 Simple merocyanines described in JP-A-5-11389, etc., and trinuclear compounds described in JP-A-50-62425, JP-A-54-18726, and JP-A-59-102229 with respect to a helium neon laser light source. Cyanine dyes, merocyanines described in JP-A-7-287338, Japanese Patent Publication Nos. 48-42172, 51-9609, 55-39818, Thiacarbocyanines described in JP-A-62-284343 and JP-A-2-105135 are not suitable for infrared semiconductor laser light sources. Tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841, and 4-carbon compounds described in general formulas (IIIa) and (IIIb) in JP-A-59-192242 and JP-A-3-67242. Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. Further, in the case where the wavelength of the infrared laser light source is 750 nm or more, more preferably 800 nm or more, in order to cope with a laser in such a wavelength range, JP-A-4-18239, JP-A-5-341432, JP-B-6 Nos. -52387, 3-10931, U.S. Pat. No. 5,441,866, and JP-A-7-13295 are preferably used.

  Further, examples of supersensitizers include RD 17643, JP-B Nos. 9-25500, 43-4933, JP-A-59-19032, 59-192242, JP-A-5-341432, and the like. In the present invention, a heteroaromatic mercapto compound represented by the following general formula (M), which is a general formula (Ma) that substantially forms the mercapto compound, can be used. The disulfide compounds represented can be used.

General formula (M)
Ar-SM
General formula (Ma)
Ar-SS-Ar
In the general formula (M), M represents a hydrogen atom or an alkali metal atom, and Ar represents a heteroaromatic ring or condensed heteroaromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. The heteroaromatic ring is preferably benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, triazine, pyrimidine, pyridazine, pyrazine, Pyridine, purine, quinoline or quinazoline. Moreover, in general formula (Ma), Ar is synonymous with the said general formula (M).

  The heteroaromatic ring includes, for example, a halogen atom (for example, Cl, Br, I), a hydroxy group, an amino group, a carboxyl group, and an alkyl group (for example, one or more carbon atoms, preferably 1 to 4 carbon atoms). And a substituent selected from the group consisting of an alkoxy group (for example, one having 1 or more carbon atoms, preferably 1 to 4 carbon atoms).

  The supersensitizer used in the present invention is preferably used in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer containing the organic silver salt and silver halide grains, and particularly 1 mol of silver. The range is preferably 0.01 to 0.5 mol per unit.

  The image recording layer according to the present invention may contain a macrocyclic compound containing a hetero atom. A 9-membered or larger macrocyclic compound containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom as a heteroatom is preferred, a 12-24 membered ring is more preferred, and a 15-21 membered ring is still more preferred. is there.

  A typical compound is crown ether, which was synthesized by Pederson in 1967 and has been synthesized many times since its unique report. These compounds are C.I. J. et al. Pederson, Journal of American chemical society vol, 86 (2495), 7017-7036 (1967), G.P. W. Gokel, S.M. H, Korzenowski, “Macrocyclic polyethr synthesis”, Springer-Vergal (1982) and the like.

  In addition to the additives described above, for example, surfactants, antioxidants, stabilizers, plasticizers, ultraviolet absorbers, coating aids and the like may be used for the image forming layer according to the present invention. As these additives and the other additives described above, compounds described in RD Item 17029 (June 1978, p. 9-15) are preferably used.

  In the present invention, the image forming layer may be a single layer or a plurality of layers having the same or different compositions. The film thickness of the image forming layer is usually 10 to 30 μm.

  Next, the support and the protective layer, which are essential as the layer structure of the photothermographic material of the invention, are described in detail.

  Examples of the support used in the photothermographic material of the invention include acrylic ester, methacrylic ester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene. , Nylon, aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, triacetylcellulose, and other resin films, as well as resin films obtained by laminating two or more layers of the above resins. be able to.

  In the image recording method described later, the support according to the present invention is developed with heat after forming a latent image to form an image. Therefore, a support that has been stretched into a film and heat-set is preferable in terms of dimensional stability. In addition, you may add fillers, such as a titanium oxide, a zinc oxide, barium sulfate, a calcium carbonate, in the range which does not inhibit the effect of this invention. In addition, the thickness of a support body is about 10-500 micrometers, Preferably it is 25-250 micrometers.

  As the protective layer used in the photothermographic material of the present invention, the binder resin described in the above image forming layer can be selected and used as necessary.

  As an additive to be added to the protective layer, it is preferable to contain a filler for the purpose of ensuring damage prevention and transportability of the image after heat development, and the content when the filler is added is in the layer forming composition. It is preferable to contain 0.05-30 mass%.

  Furthermore, in order to improve slipperiness and chargeability, the protective layer may contain a lubricant and an antistatic agent. Examples of such lubricants include fatty acids, fatty acid esters, fatty acid amides, and polyoxyethylene. , Polyoxypropylene, (modified) silicone oil, (modified) silicone resin, fluororesin, carbon fluoride, wax and the like, and antistatic agents include cationic surfactants, anionic surfactants Agents, nonionic surfactants, polymer antistatic agents, metal oxides or conductive polymers, etc., "11290 Chemical Products", Chemical Industry Daily, p. 875-876 etc., the compound described in US Patent No. 5,244,773 columns 14-20, etc. can be mentioned. Furthermore, various additives added to the image forming layer may be added to the protective layer as long as the object of the present invention is not hindered. About 20 mass% is preferable, More preferably, it is 0.05-10 mass%.

  In the present invention, the protective layer may be a single layer or may be composed of a plurality of layers having the same or different composition. In addition, the film thickness of a protective layer is 1.0-5.0 micrometers normally.

  In the present invention, in addition to the above-mentioned image forming layer, support and protective layer, an intermediate layer for improving film attachment between the support and the image forming layer is provided, and a back coat layer is provided for the purpose of transportability and antistatic. In the case of installation, the thickness of the intermediate layer is usually 0.05 to 2.0 μm, and the thickness of the backing layer is usually 0.1 to 10 μm.

  The coating solution for the image forming layer, the coating solution for the protective layer, and the coating solution for the intermediate layer and the backing layer that are installed according to the present invention respectively dissolve or disperse the above-described components in a solvent. Can be prepared.

  Solvents that can be used in the above preparation may be those having a solubility parameter value in the range of 6.0 to 15.0 shown in “Solvent Pocket Book” edited by the Society of Synthetic Organic Chemistry. Examples of the solvent that can be used in the coating solution for forming each layer according to the invention include ketones such as acetone, isophorone, ethyl amyl ketone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, cyclohexanol, and benzyl alcohol. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, hexylene glycol and the like. Examples of ether alcohols include ethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Examples of ethers include ethyl ether, dioxane, isopropyl ether and the like. Examples of the esters include ethyl acetate, butyl acetate, amyl acetate, isopropyl acetate and the like. Examples of hydrocarbons include n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene and the like. Examples of the chlorides include methyl chloride, methylene chloride, chloroform, dichlorobenzene and the like, but are not limited to these as long as the effects of the present invention are not impaired.

These solvents can be used alone or in combination of several kinds. The residual amount of the solvent in the photothermographic material can be adjusted by appropriately setting the temperature conditions of the drying step after coating, and the residual solvent amount is preferably 5 to 1000 mg / m ^{2 in} total. preferably, a 10-300 mg / m ^2.

  When dispersion is necessary when preparing the coating liquid, for example, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder, a Sqgvari attritor, a high-speed impeller disperser, a high-speed stone Conventionally known dispersers such as a mill, a high-speed impact mill, a disper, a high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, and a continuous kneader can be selected and used as appropriate.

  To apply the coating solution prepared as described above, for example, extrusion-type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, bar coater, Various known coater stations such as transfer roll coaters, kiss coaters, cast coaters, spray coaters and the like can be selected and used as appropriate. Among these coaters, it is preferable to use a roll coater such as an extrusion type extrusion coater or a reverse roll coater in order to eliminate unevenness in the thickness of the formation layer.

  Further, when the protective layer is applied, there is no particular limitation as long as the image forming layer is not damaged, but the solvent used in the protective layer forming coating solution may dissolve the image forming layer. In the above-described coater station, an extrusion-type extrusion coater, a gravure roll coater, a bar coater or the like can be used. Of these, when using a coating method such as a gravure roll coater or bar coater, the rotation direction of the gravure roll or bar may be forward or reverse with respect to the transport direction. A constant speed or a peripheral speed difference may be provided.

  Furthermore, when laminating each constituent layer, coating and drying may be repeated for each layer, but simultaneous multilayer coating may be performed by a wet-on-wet method and dried. In that case, for example, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, bar coater, transfer roll coater, kiss coater, cast coater, spray coater, etc. and extrusion type extrusion coater. In such a wet-on-wet multi-layer coating, the upper layer is applied while the lower layer is in a wet state. improves.

  Furthermore, in the present invention, it is preferable that the temperature at which the coating film is dried is in the range of 65 to 100 ° C. in order to effectively draw out the object of the present invention after at least applying the coating solution for the image forming layer. When the drying temperature is lower than 65 ° C., the reaction is insufficient, and thus the sensitivity may vary with time. When the drying temperature is higher than 100 ° C., the photothermographic material itself immediately after production may be changed. Since fogging (coloring) may occur, it is not preferable. The drying time cannot be generally defined by the air volume at the time of drying, but it is usually preferable to dry in the range of 2 to 30 minutes.

  The above-mentioned drying temperature may be dried immediately after coating at a drying temperature in the above-mentioned temperature range, or the vicinity of the surface caused by the marangony of the coating liquid generated during drying or the drying air of warm air is initially dried. For the purpose of preventing unevenness (scratch skin) caused by this, the initial drying temperature may be lower than 65 ° C., and then drying may be performed at a drying temperature in the above-described temperature range.

  As described above, the object of the present invention can be achieved by the photothermographic material of the present invention and the preferred production method thereof, but further, a clear image without interference fringes can be obtained by optimizing the image recording method. be able to.

  Next, an image recording method suitable for the photothermographic material of the present invention will be described in detail.

  The image recording method that can be used in the present invention is roughly divided into three modes depending on the angle formed between the exposure surface and the laser beam, the wavelength of the laser, and the number of lasers used, and they may be performed alone, Two or more types may be combined, and by using such an image forming method, a clear image without interference fringes can be obtained.

  In the present invention, as a preferred aspect of the image recording method, an image is formed by scanning exposure using a laser beam in which the angle formed by the exposure surface of the photothermographic material and the laser beam is not substantially perpendicular. Can be mentioned. In this way, by shifting the incident angle from the vertical, even if reflected light at the interlayer interface is generated, the optical path difference reaching the image forming layer becomes large, so that the scattering and attenuation of the laser light in the optical path is reduced. It occurs and interference fringes are less likely to occur. Here, “substantially not perpendicular” means that the angle that is closest to the vertical during laser scanning is preferably 55 ° to 88 °, more preferably 60 ° to 86 °, and still more preferably. It means 65 degrees or more and 84 degrees or less.

  Further, a more preferable aspect of the image recording method of the present invention is to form an image by scanning exposure using a vertical multi-laser having a non-single exposure wavelength. When scanning with such a vertical multi-laser beam having a width in wavelength, the generation of interference fringes is reduced as compared with a scanning laser beam of a vertical single mode. The term “vertical multi” as used herein means that the exposure wavelength is not single, and the normal exposure wavelength distribution is 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

Furthermore, in the above-described image recording method, lasers used for scanning exposure are generally well-known solid lasers such as ruby laser, YAG laser, and glass laser; He—Ne laser, Ar ion laser, Kr ion laser, Gas lasers such as CO ₂ laser, CO laser, He—Cd laser, N ₂ laser, and excimer laser; semiconductor lasers such as InGaP laser, AlGaAs laser, GaAsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, and GaSb laser; A laser, a dye laser, or the like can be selected and used in a timely manner. However, in the image forming method according to claim 5, among these, a semiconductor laser having a wavelength of 600 to 1200 nm due to maintenance and the size of the light source. Is preferably used.

  In a laser used in a laser imager or laser image setter, the beam spot diameter on the exposed surface of the photothermographic material when scanned with the photothermographic material is generally from 5 to 75 μm as the minor axis diameter. The shaft diameter is in the range of 5 to 100 μm, and the laser beam scanning speed can be set to an optimum value for each photothermographic material depending on the sensitivity and laser power at the laser oscillation wavelength inherent to the photothermographic material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
[Preparation of subtracted photographic support]
<Preparation of PET undercoated photographic support>
Corona of 8 W / m ² · min on both sides of a commercially available biaxially stretched heat-fixed thickness of 175 μm and blue-colored PET film having an optical density of 0.170 (measured with a Densitometer PDA-65 manufactured by Konica Corporation) Discharge treatment is performed, and the following undercoat coating liquid a-1 is applied on one surface so as to have a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1, and on the opposite surface, The undercoating liquid b-1 was applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer B-1.

<< Undercoat coating liquid a-1 >>
Butyl acrylate (30% by mass)
t-Butyl acrylate (20% by mass)
Styrene (25% by mass)
2-Hydroxyethyl acrylate (25% by mass)
270 g of copolymer latex liquid (solid content 30%)
C-1 0.6g
Hexamethylene-1,6-bis (ethylene urea) 0.8g
Finish to 1 liter with water 《Undercoating liquid b-1》
Butyl acrylate (40% by mass)
Styrene (20% by mass)
Glycidyl acrylate (40% by mass)
270 g of copolymer latex liquid (solid content 30%)
C-1 0.6g
Hexamethylene-1,6-bis (ethylene urea) 0.8g
Finish to 1 liter with water Subsequently, the upper surface of the undercoat layer A-1 and the undercoat layer B-1 was subjected to a corona discharge of 8 W / m ² · min. The undercoat layer coating liquid a-2 is used as an undercoat layer A-2 so that the dry film thickness is 0.1 μm. It was coated as an undercoating upper layer B-2 having an antistatic function so as to be 8 μm.

<< Undercoating upper layer coating liquid a-2 >>
Mass to become gelatin 0.4g / m ² C-1 0.2g
C-2 0.2g
C-3 0.1g
Silica particles (average particle size 3μm) 0.1g
Finish to 1 liter with water << Undercoating upper layer coating liquid b-2 >>
C-4 60g
Latex liquid containing C-5 as a component (solid content 20%) 80g
Ammonium sulfate 0.5g
C-6 12g
Polyethylene glycol (mass average molecular weight 600) 6g
Finish to 1 liter with water

<Back side application>
While stirring 830 g of methyl ethyl ketone (MEK), 84.2 g of cellulose acetate butyrate (Eastman Chemical Co., CAB381-20) and 4.5 g of a polyester resin (Bostic Co., VitelPE 2200B) were added and dissolved. Next, 0.30 g of infrared dye 1 was added to the dissolved liquid, and 4.5 g of F-type active agent (Asahi Glass Co., Surflon KH40) dissolved in 43.2 g of methanol and F-type active agent (Dainippon) 2.3g of Ink Co., MegaFag F120K) was added and stirred well until dissolved. Finally, 75 g of silica (WR Grace, Syloid 64X6000) dispersed in methyl ethyl ketone at a concentration of 1% by mass with a dissolver type homogenizer was added and stirred to prepare a coating solution for the back surface side.

  The back surface coating solution thus prepared was applied and dried by an extrusion coater so that the dry film thickness was 3.5 μm. It dried for 5 minutes using the drying air with a drying temperature of 100 degreeC, and dew point temperature of 10 degreeC.

<< Preparation of photosensitive silver halide emulsion A >>
A1
Phenylcarbamoylated gelatin 88.3g
Compound (A) (10% methanol aqueous solution) 10 ml
Potassium bromide 0.32g
Finish to 5429 ml with water B1
0.67 mol / L silver nitrate aqueous solution 2635 ml
C1
Potassium bromide 51.55g
Potassium iodide 1.47g
Finish to 660ml with water D1
Potassium bromide 154.9g
4.41 g of potassium iodide
Iridium chloride (1% solution) 0.93ml
Finish up to 1982ml with water E1
0.4 mol / L potassium bromide aqueous solution The following silver potential control amount F1
Potassium hydroxide 0.71g
Finish to 20ml with water G1
56% acetic acid aqueous solution 18.0 ml
H1
Anhydrous sodium carbonate 1.72 g
Finish to 151 ml with water Compound (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)
Using the mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289, the solution (A1) is controlled to 1/4 of the solution (B1) and the total amount of the solution (C1) to 45 ° C. and pAg 8.09. While adding 4 minutes 45 seconds by the simultaneous mixing method, nucleation was performed. After 1 minute, the entire amount of solution (F1) was added. During this time, pAg was adjusted appropriately using (E1). After 6 minutes, 3/4 amount of the solution (B1) and the whole amount of the solution (D1) were added over 14 minutes and 15 seconds by the simultaneous mixing method while controlling the temperature at 45 ° C. and pAg 8.09. After stirring for 5 minutes, the temperature was lowered to 40 ° C., the whole amount of the solution (G1) was added, and the silver halide emulsion was precipitated. The supernatant was removed leaving 2000 ml of the sediment, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. The remaining portion of 1500 ml was left, the supernatant was removed, 10 liters of water was further added, and after stirring, the silver halide emulsion was precipitated. After leaving 1500 ml of the sedimented portion and removing the supernatant, 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 water was added so that the amount of silver was 1161 g per mole of silver, whereby photosensitive silver halide emulsion A was obtained.

  This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.058 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 92%.

<< Preparation of powdered organic silver salt A >>
130.8 g of behenic acid, 67.7 g of arachidic acid, 43.6 g of stearic acid, and 2.3 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, 540.2 ml of a 1.5 M / L sodium hydroxide aqueous solution was added, and 6.9 ml of concentrated nitric acid was added, followed by cooling to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the fatty acid sodium solution at 55 ° C., 45.3 g of the photosensitive silver halide emulsion A and 450 ml of pure water were added and stirred for 5 minutes.

  Next, 702.6 ml of 1 M / L silver nitrate solution 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 and stirred, and then allowed to stand to float and separate the organic silver salt dispersion, thereby removing the lower water-soluble salts. Thereafter, washing with deionized water and drainage were repeated until the electrical conductivity of the drainage reached 2 μS / cm, and centrifugal dehydration was carried out. Then, the resulting cake-like organic silver salt was converted into an airflow dryer flash jet dryer (stock) The product was dried until the water content became 0.1% according to the operating conditions of nitrogen gas atmosphere and dryer inlet hot air temperature to obtain a dried organic silver salt A of organic silver salt.

  An infrared moisture meter was used to measure the moisture content of the organic silver salt composition.

<< Preparation of Preliminary Dispersion A >>
14.57 g of polyvinyl butyral powder (Monsanto, Butvar B-79) was dissolved in 1457 g of methyl ethyl ketone, and 500 g of powdered organic silver salt A was gradually added while stirring with a dissolver DISPERMAT CA-40M manufactured by VMA-GETZMANN. Preliminary dispersion A was prepared by thorough mixing.

<< Preparation of photosensitive emulsion dispersion 1 >>
Media type disperser DISPERMAT SL- filled with 80% of the internal volume of 0.5 mm diameter zirconia beads (Torayserum manufactured by Toray) so that the residence time in the mill is 1.5 minutes using a pump. Photosensitive emulsion dispersion 1 was prepared by supplying to C12EX type (VMA-GETZMANN) and dispersing at a mill peripheral speed of 8 m / s.

<< Preparation of stabilizer liquid >>
A stabilizer solution was prepared by dissolving 1.0 g of Stabilizer 1 and 0.31 g of potassium acetate in 4.97 g of methanol.

<< Preparation of infrared sensitizing dye liquid A >>
19.2 mg of sensitizing dye 1, 1.488 g 2-chloro-benzoic acid, 2.7779 g stabilizer 2 and 365 mg 5-methyl-2-mercaptobenzimidazole in 31.3 ml MEK in the dark It melt | dissolved and the infrared sensitizing dye liquid A was prepared.

<< Preparation of Additive Liquid a >>
31.7 g and 1.54 g of 4-methylphthalic acid, 0.48 g of dye 1 and a compound represented by the general formula (1) or general formula (2) shown in Table 1 (8 × 10 ⁻³⁾ mol) was dissolved in 110 g of MEK to obtain an additive solution a.

<< Preparation of additive liquid b >>
9 × 10 ⁻³ mol of antifoggant 2, 3.43 g of phthalazine was dissolved in 40.9 g of MEK to obtain additive liquid b.

<< Preparation of photosensitive layer coating solution >>
In an inert gas atmosphere (97% nitrogen), the photosensitive emulsion dispersion 1 (50 g) and 15.11 g of MEK were kept at 21 ° C. with stirring, and the chemical sensitizer S-5 (0.5% methanol solution) was kept. ) 1000 μl was added, and after 2 minutes, 390 μl of antifoggant 1 (10% methanol solution) was added and stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added and stirred for 10 minutes, then gold sensitizer Au-5 corresponding to 1/20 mole of the above organic chemical sensitizer was added, and further stirred for 20 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 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., 13.31 g of polyvinyl butyral (Monsanto Butvar B-79) was added and stirred for 30 minutes, and then 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added. Stir for 15 minutes. While continuing to stir, 12.43 g of additive a (containing the additives shown in Table 1), 1.6 ml of Desmodur N3300 / Mobayic aliphatic isocyanate (10% MEK solution), 4.27 g of addition The solution b was sequentially added and stirred to obtain a photosensitive layer coating solution.

<Preparation of matting agent dispersion>
Cellulose acetate butyrate (Eastman Chemical Co., 7.5 g CAB171-15) was dissolved in 42.5 g of MEK, and 5 g of calcium carbonate (Speciality Minerals, Super-Pflex 200) was added thereto, and a dissolver type homogenizer was used. A matting agent dispersion was prepared by dispersing at 8000 rpm for 30 minutes.

<< Preparation of surface protective layer coating liquid >>
While stirring 865 g of MEK (methyl ethyl ketone), 96 g of cellulose acetate butyrate (Eastman Chemical Co., CAB171-15), 4.5 g of polymethylmethacrylic acid (Rohm & Haas Co., Paraloid A-21), vinyl sulfone compound ( VSC) (1.5 g), benztriazole (1.0 g), and F-based activator (Asahi Glass Co., Surflon KH40) (1.0 g) were added and dissolved. Next, 30 g of the above matting agent dispersion was added and stirred to prepare a surface protective layer coating solution.

<Photosensitive layer side coating>
The photosensitive material was prepared by simultaneously applying the photosensitive layer coating solution and the surface protective layer coating solution using an extrusion coater. The coating was carried out so that the photosensitive layer had an applied silver amount of 1.9 g / m ² and the surface protective layer had a dry film thickness of 2.5 μm. 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. to obtain coated samples 1 to 10 (photothermographic materials).

<Evaluation of photographic performance>
The angle between the exposure surface of the photothermographic material sample prepared above and the exposure laser beam was 76 degrees. The room temperature test was conducted after the photothermographic material after coating and drying was placed in an atmosphere of 25 ° C. and 48% RH for 24 hours. As a high temperature test, the same evaluation as described above was carried out after storage for 3 days in an atmosphere of 45 ° C. and 48% RH.

  The photothermographic materials prepared as a normal temperature test sample and a high temperature test sample were exposed with a 810 nm semiconductor laser photometer, and then heat developed at 120 ° C. for 8 seconds using a heat drum. At that time, exposure and development were performed in a room adjusted to 25 ° C. and 48% RH. The obtained image was evaluated (sensitivity and fogging) using a densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the exposure amount giving a density 0.3 higher than the fog density (Dmin). It was expressed by relative evaluation with 1 as a reference. The evaluation results are shown in Table 1.

  From Table 1, it can be seen that the present invention can provide a photothermographic material having high sensitivity and low fog even when stored at a high temperature.

Example 2
A photothermographic material was prepared in the same manner as in Example 1. Here, in the photosensitive layer coating solution (additive solution a), instead of the developer 1, the compound of the general formula (3) shown in Table 2 was added in 1 mol of silver halide. 8 × 10 ⁻² mol was added per unit. The photosensitivity was measured using photothermographic material sample No. The relative sensitivity was expressed with reference to 21. The results are shown in Table 2.

≪Evaluation of photographic performance≫
The sample prepared above (photothermographic material) was exposed to xenon flash light having a light emission time of 10 ⁻³ seconds through an interference filter having a peak at 633 nm. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. Then, the fog value at that time was measured. Further, the reciprocal of the exposure amount giving a density of 3.0 is defined as sensitivity, and sample No. The sensitivity is expressed as a relative sensitivity with 21 as 100.

  In addition, three coated samples were placed in a sealed container maintained at 25 ° C. and 55% relative humidity, and then aged for 7 days at 50 ° C. (forced aging). The second sample and the comparative sample (stored in a light-shielding container at room temperature) were subjected to the same process as the sensitometric evaluation, and the fog density was measured. The increase in fog 1 was determined and evaluated as raw storage stability.

(Increase in fog) = (Fog during forced aging)-(Fog over time for comparison)
Further, a sample that was exposed and developed so that the density after development was 1.5 ± 0.05 was prepared for evaluation of silver tone. This sample was irradiated for 10 hours with a light source stand having a color temperature of 7700 Kelvin and an illuminance of 11600 lux, and the color tone of silver was evaluated according to the following criteria. The rank with no problem in quality assurance is 4 or more.

Evaluation criteria 5: Pure black tone does not feel yellow at all 4: Although it is not pure black, almost does not feel yellow 3: Partially feels slightly yellow 2: Feels slightly yellow on the entire surface 1 : Table 2 shows the course and results more than yellowish at first glance.

  From Table 2, it can be seen that the sample of the present invention has excellent storage stability, sufficient sensitivity, little fogging, and excellent silver tone.

Claims (3)

A photothermographic material having a photosensitive layer containing photosensitive halogenated particles on at least one surface of a support, wherein the photothermographic material contains a compound represented by the following general formula (1): .

(In formula ^(I), Q ¹ is each .W ^1, V ¹ which represents a non-metallic atomic group necessary for forming a 5- to 7-membered ring together with W ¹ and ^{V 1> C (R 1)} - or> N- R ¹ represents a hydrogen atom, a substituent or a simple bond, and Z ¹ is condensed with a ring formed by Q ¹ , W ¹ and V ¹ to form a ring together with W ¹ and V ^1. X ¹ is a hydroxy group (or salt thereof), mercapto group (or salt thereof), amino group, alkylamino group, arylamino group, heterocyclic amino group, acylamino group, sulfonamide group Or represents a heterocyclic group, and Y ¹ represents an electron-withdrawing group. 2. The photothermographic material according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein Q ² represents> CR ²¹ R ²² ,> N—R ²³ ,> O or> S. R ²¹ , R ²² and R ²³ represent a hydrogen atom or a substituent. M ² represents ═O, = .W ^1, V ¹ .R ²⁴ is representing a hydrogen atom or a substituent represented S or ^{= N-R 24, Z 1} , X 1 and Y ^1, W ^1, V ¹ in the general formula (1) , Z ¹ , X ¹ and Y ¹ . 3. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (3):

(Wherein, R ₃₁ and R ₃₄ represents an alkyl group .R ₃₂ and R ₃₃ represents .L ₁ is> S or> CR ₃₅ R ₃₆ group represents an alkyl group having 2 or more carbon atoms, R ₃₅ and R ₃₆ represents a hydrogen atom, an alkyl group, a 3- to 10-membered non-aromatic ring group, an aryl group, or a heteroaryl group, J ₁ and J ₂ represent groups that can be substituted on the benzene ring, and n and m are 0 Represents an integer of ~ 2)