JP2003186140A - 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 even in storage at high temperature and high humidity. <P>SOLUTION: In the heat-developable photosensitive material having a photosensitive layer comprising photosensitive silver halide grains on at least one face of a support, an organic silver salt, a reducing agent and at least one of compounds represented by formulae (1) and (2) are comprised in the photosensitive layer or in at least one of non-photosensitive layers. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material which forms an image by heat development, and more specifically, it has a super-high contrast image and has no fog even when stored under high temperature and high humidity. The present invention relates to a photothermographic material that hardly generates.

[0002]

2. Description of the Related Art In recent years, in the fields of printing and plate making and medical treatment, a waste liquid caused by a wet process of an image forming material has become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to a photothermographic material for photographic technology that can form a clear black image with high resolution by thermal development. As this technique, for example, US Pat.
52,904, 3,487,075 and D.M. "Dry Silver Photographic" by Morgan
Materials) "(Handbook of I
maging materials, marcel d
ekker, Inc. The method described in p. 48, 1991) is well known. These photosensitive materials are usually 8
Since it is developed at a temperature of 0 ° C. or higher, it is called a photothermographic material.

By the way, it has been difficult to obtain a high-contrast image in most of the photothermographic materials of this type, and various high-contrast agents have been tried. Hydrazine and cyanovinyl compounds have been noticed and developed as useful compounds. Such a technology is called Research Disc
loss (hereinafter RD) Item 23515 (1
983 November issue, P. 346) and the references cited therein, as well as U.S. Pat.
No. 269,929, No. 4,276,364, No. 4,278,748, No. 4,385,108, No. 4,459,347, No. 4,478,928,
No. 4,560,638, No. 4,686,167
No. 4,912,016, No. 4,988,60
No. 4, No. 4,994, 365, No. 5,041, 3
55, 5,104,769, British Patent 2,0.
11,391B, European Patents 217,310, 301,799, 356,898 and 89.
7,130, JP-A-60-179734, 61-
170733, 61-270744, 62-1
78246, 62-270948, 63-29.
751, 63-2538, 63-10404.
No. 7, No. 63-121838, No. 63-129337.
No. 63-223744, No. 63-234244.
No. 63-234245, No. 63-234246.
No. 63-294552, No. 63-306438.
No. 64-10233, JP-A-1-90439,
1-100530, 1-105941, 1-
No. 105943, No. 1-276128, No. 1-280
No. 747, No. 1-283548, No. 1-283549.
No. 1, No. 1-285940, No. 2-2541, No. 2-
No. 77057, No. 2-139538, No. 2-1962.
No. 34, No. 2-196235, No. 2-198440.
No. 2, No. 2-198441, No. 2-198442, No. 2-220042, No. 2-221953, No. 2-2.
21954, 2-285342, 2-2853.
No. 43, No. 2-289843, No. 2-302750
No. 2, No. 2-304550, No. 3-37642, No. 3
-54549, 3-125134, 3-184.
039, 3-240036, 3-240037.
No. 3, No. 3-259240, No. 3-280038, No. 3-228536, No. 4-51143, No. 4-56.
No. 842, No. 4-84134, No. 2-230233.
No. 4, No. 4-96053, No. 4-216544, No. 5
-45761, 5-45762, 5-4576
No. 3, No. 5-45764, No. 5-45765, No. 6
The thing described in No. 289524, No. 9-160164, etc. can be mentioned. In addition to this,
No. 77138, a compound represented by (Chemical formula 1), specifically the compound described on pages 3 and 4 of the publication, represented by the general formula (1) described in JP-B-6-93082. Specifically, compounds 1 to 3 described on pages 8 to 18 of the publication.
Compound of formula (8), compounds represented by formulas (4), (5) and (6) described in JP-A-6-23049, specifically compound 4- 1-4
10, Compounds 5-1 to 5-4 described on pages 28 to 36
2, and compounds 6-1 to 6- described on pages 39 and 40
7, compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-17 described on pages 5 to 7 of the publication. ) And 2-
1), the compounds represented by (Chemical formula 2) and (Chemical formula 3) described in JP-A-6-313936, specifically, the compounds described on pages 6 to 19 of the publication, JP-A-6-313951. The compound represented by (Chemical formula 1) described above, specifically
Compounds described on pages 5 to 5, compounds represented by formula (I) described in JP-A-7-5610, specifically compound I-1 described on pages 5 to 10 of the publication. ~ I-3
8, compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication, JP-A-7- 10442
Compounds represented by the general formula (H) and the general formula (Ha) described in No. 6, specifically, compounds described in the compounds H-1 to H-44 described on pages 8 to 15 of the same publication; Etc.

It has been impossible to obtain a sufficiently high-contrast image with these known compounds. Meanwhile, US Pat. No. 5,54
No. 5,515, No. 5,635,339, No. 5,6
Nos. 54 and 130 describe specific alkene derivatives, and although these compounds have considerably improved the contrast, they have the problem that fog tends to occur during storage under high temperature and high humidity. Was there.

Further, JP-A-10-161270 and JP-A-10-161270.
-1095747, European Patent 897,130, and JP-A-11-133546 describe specific substituted alkene derivatives, and JP-A-11-109546 describes alkene compounds having a diffusion resistant group. JP-A-11-119373 describes a substituted alkene derivative having a specific adsorption promoting group to a silver salt via a linking group. However, these compounds are also fogged during storage under high temperature and high humidity. However, there is a problem in that

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material capable of obtaining a high contrast image and having low fog even when stored under high temperature and high humidity.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1. In a photothermographic material having a photosensitive layer containing photosensitive silver halide grains on at least one surface of a support, an organic silver salt, a reducing agent, and the above general formula ( 1) and (2)
A photothermographic material containing at least one compound represented by:

2. 2. The photothermographic material as described in 1 above, wherein the photosensitive silver halide is doped with a transition metal complex.

3. 3. The photothermographic material as described in 1 or 2 above, wherein the photothermographic material contains a hydrazine compound.

The present invention will be described in detail below. The compound represented by the general formula (1) of the present invention will be further described. Specific substituents represented by X include substituted alkyl groups (halogen-substituted alkyl, etc.), substituted alkenyl groups (cyanovinyl, etc.), substituted and unsubstituted alkynyl groups (trifluoromethylacetylenyl, cyanoacetylenyl, formylacetyl). (Renyl etc.), a substituted or unsubstituted aryl group (phenyl, cyanophenyl etc.), a substituted or unsubstituted heterocyclic group (pyridyl, triazinyl, benzoxazolyl etc.),
Halogen atom, acyl group (acetyl, trifluoroacetyl, formyl, etc.), thioacyl group (thioformyl, thioacetyl, etc.), oxalyl group (methyloxalyl, etc.), oxyoxalyl group (ethoxalyl, etc.), -S-
Oxalyl group (ethylthiooxalyl etc.), oxamoyl group (methyloxamoyl etc.), oxycarbonyl group (ethoxycarbonyl, carboxyl etc.), -S-carbonyl group (ethylthiocarbonyl etc.), carbamoyl group, thiocarbamoyl group, sulfonyl group , Sulfinyl group, oxysulfonyl group (ethoxysulfonyl etc.),-
S-sulfonyl group (ethylthiosulfonyl etc.), sulfamoyl group, oxysulfinyl group (methoxysulfinyl etc.), -S-sulfinyl group (methylthiosulfinyl etc.), sulfinamoyl group, phosphoryl group, nitro group, imino group (imino, N- Methylimino, N-phenylimino, N-pyridylimino, N-cyanoimino, N
-Nitroimino, etc.), N-carbonylimino group (N-acetylimino, N-ethoxycarbonylimino, N-ethoxallylimino, N-formylimino, N-trifluoroacetylimino, N-carbamoylimino, etc.), N
-Sulfonylimino group (N-methanesulfonylimino,
N-trifluoromethanesulfonylimino, N-methoxysulfonylimino, N-sulfamoylimino, etc.),
Examples thereof include an ammonium group, a sulfonium group, a phosphonium group, a pyrylium group, an immonium group, and the like, and a heterocyclic group in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, or the like forms a ring is also included.
As X, an electron withdrawing group whose Hammett's substituent constant σp value can take a positive value, as well as a substituted or unsubstituted aryl group and a heterocyclic group are preferable.

W is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, cyclohexyl, trifluoromethyl, methoxymethyl, methylthiomethyl, ethanesulfonylmethyl, etc.), or an aryl group (unsubstituted or substituted with an electron donating group) Phenyl, naphthyl, methylphenyl,
Methoxyphenyl, etc.), oxy group (hydroxy, alkoxy, aryloxy, heterocycleoxy, acyloxy, alkenyloxy, alkynyloxy, alkoxycarbonyloxy, aminocarbonyloxy, sulfonyloxy, etc.), thio group (mercapto, alkylthio, arylthio, hetero) Ring thio, alkenylthio, alkynylthio, acylthio, alkoxycarbonylthio, aminocarbonylthio, sulfonylthio, etc.), amino group (amino, alkylamino, arylamino, heterocyclic amino, alkenylamino, alkynylamino, acylamino, oxycarbonylamino) , Ureido, sulfonamide, etc.), non-aromatic heterocyclic group (pyrrolidine, piperidine, piperazine, tetrahydrofuran, succinimide, etc.), silyl group ( Trimethylsilyl, etc.) and the like.

As the nitrogen-containing aromatic heterocyclic group represented by A, a 5- or 6-membered nitrogen-containing heteroaromatic ring is preferable, and a group forming a bond ring is also preferable. The nitrogen-containing heteroaromatic ring, pyrrole, diazole, triazole,
It is represented by tetrazole and the like, and specifically, imidazole, benzotriazole and the like are preferable.

Next, the compound represented by the general formula (2) of the present invention will be further described. Y is a hydrogen atom, an alkyl group (methyl, ethyl, trifluoromethyl, etc.), an alkenyl group (vinyl, halogen-substituted vinyl, cyanovinyl, etc.), an alkynyl group (acetylenyl, cyanoacetylenyl, etc.), an aryl group (phenyl, Chlorophenyl, nitrophenyl, cyanophenyl, pentafluorophenyl, etc.), heterocyclic groups (pyridyl, pyrimidyl,
Pyrazinyl, quinoxalinyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl,
Benzoxazolyl, furyl, thienyl, piperidinyl, pyrrolidinyl, etc.), cyano group, etc., and the general formula (1)
A halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxyoxalyl group, an —S-oxalyl group, an oxamoyl group, an oxycarbonyl group,
S-carbonyl group, carbamoyl group, thiocarbamoyl group, sulfinyl group, sulfonyl group, oxysulfonyl group, -S-sulfonyl group, sulfamoyl group, oxysulfinyl group, -S-sulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, Imino group, N-carbonylimino group, N-sulfonylimino group, ammonium group, sulfonium group, phosphonium group, pyrylium group,
Examples thereof include an immonium group, and further include an oxy group, a thio group, an amino group, a silyl group and the like as described for W in the general formula (1). Y is Hammett's substituent constant σ
In addition to the electron withdrawing group whose p value can take a positive value, an aryl group and a heterocyclic group are also preferable.

Examples of the nitrogen-containing aromatic heterocyclic group represented by A include the same ones as those described in the general formula (1).

The halogen atom represented by R includes atoms such as fluorine, chlorine, bromine and iodine, and the oxy group includes hydroxy, alkoxy (methoxy, ethoxy, etc.), aryloxy (phenoxy, etc.) and hetero. Ring oxy (tetrahydropyranyloxy etc.), acyloxy (acetyloxy etc.), alkenyloxy, alkynyloxy, oxycarbonyloxy (t-butoxycarbonyloxy etc.), aminocarbonyloxy (anilinocarbonyloxy etc.), sulfonyloxy (methane Sulfonyloxy etc.), silyloxy (trimethylsilyloxy etc.) and the like. Examples of the thio group include mercapto, alkylthio (methylthio, benzylthio etc.), arylthio (phenylthio etc.), heterocyclic thio (pyridylthio etc.), alkenylthio. , Alkynylthio, acylthio (acetylthio, etc.), oxycarbonylthio, aminocarbonylthio, sulfonylthio (methanesulfonylthio, etc.), silylthio (trimethylsilylthio, etc.), thiuronium, etc., and the amino group includes amino, alkylamino ( Methylamino, etc.), arylamino (anilino, etc.), alkenylamino, alkynylamino, acylamino (acetylamino, etc.), oxycarbonylamino, sulfonylamino (methanesulfonamide, etc.), ureido, etc., and the heterocyclic group includes Pyrrolidino, morpholino, succinimide, piperidino, imidazolyl, benzotriazolyl and the like can be mentioned, and the silyl group can be trimethylsilyl and the like. R is preferably an oxy group.

In the present invention, it is preferable that X in the general formula (1) and Y in the general formula (2) have a formyl group. It is also preferable that X in the general formula (1) and Y in the general formula (2) have the following alkene groups.

-C (R ₁ ) = C (Z ₁ ) (Z ₂ ) R ₁ represents a hydrogen atom and a substituent, Z ₁ and Z ₂ represent a hydrogen atom and a substituent, and Z ₁ and Z ₂ At least one of them represents an electron-withdrawing group.

Of the substituents represented by Z ₁ and Z ₂ , examples of the electron-withdrawing group include a cyano group and a formyl group, and the above-mentioned X.
The electron-withdrawing group mentioned above can be used.

As X and Y represented by the above general formula,
For example, the following groups can be mentioned.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

It is also preferable that X and Y have the following alkyne groups.

[0024]

[Chemical 5]

R ₂ represents a hydrogen atom or a substituent, and the substituent is preferably an electron-withdrawing group as mentioned in the above X. Examples of X and Y represented by the above general formula include the following groups.

[0026]

[Chemical 6]

It is also preferable that X and Y have an acyl group selected from a substituted alkylcarbonyl group, an alkenylcarbonyl group and an alkynylcarbonyl group. Examples of X and Y include the following groups.

[0028]

[Chemical 7]

[0029]

[Chemical 8]

It is also preferable that X and Y have an oxalyl group. Examples of X and Y include the following groups.

--COCOCH ₃ , --COCOOC ₂ H ₅ ,
_{-COCONHCH 3, -COCOSC 2 H 5,} -COC
OOC ₂ H ₄ SCH ₃ , —COCONHC ₂ H ₄ SCH ₃ , and those in which X and Y have a substituted or unsubstituted aryl group or a nitrogen-containing heterocyclic group are also preferable, and X and Y are, for example, the following groups. Is mentioned.

[0032]

[Chemical 9]

In the present invention, the alkene compound represented by the general formula (1) or the general formula (2) is isomerized with respect to the double bond substituted by X, W, A and H or Y, A, R and H. When the body structure can be taken, it includes all the isomers, and when the tautomeric structure such as keto-enol can be taken, it also includes all the isomers.

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

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

The compounds represented by the general formulas (1) and (2) of the present invention can be synthesized by various methods. For example, US Pat. Nos. 5,545,515 and 5,635. No. 5,339, No. 5,654,130, No. 2,824,121, JP-A No. 11-84576,
11-109546, 11-119373, C
hem. Ber. 103, 1982-1991 (197)
0). Chem. Pharm. Bull. 28 (5),
1408-1414 (1980), J. Org. Che
m. 47.2216-2217 (1982), Tetr
ahedron 28 (10), 2783-2798 (1
It can be synthesized with reference to the synthesis method described in 972) and the like.

The exemplified compound (1) -6 can be synthesized, for example, by the following route.

[0046]

[Chemical 19]

The exemplified compound (2) -5 can be synthesized, for example, by the following route.

[0048]

[Chemical 20]

Other compounds of the present invention can be similarly synthesized. The compounds represented by the general formulas (1) and (2) of the present invention can be added to the photothermographic material according to known addition methods. It can be added by dissolving it in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, polar solvents such as dimethyl sulfoxide and dimethylformamide, and the like. It is also possible to add fine particles of 1 μm or less dispersed in water or an organic solvent. Although many techniques for fine particle dispersion have been disclosed, they can be dispersed according to these techniques.

The photosensitive silver halide used in the photothermographic material of the present invention can be prepared by any method known in the photographic art such as a single jet method or a double jet method, for example, an ammonia method emulsion, a neutral method, It can be prepared by any method such as an acidic method. It can thus be pre-prepared and then mixed with the other components of the invention and incorporated into the composition used according to the invention. In this case, in order to sufficiently bring the photosensitive silver halide into contact with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 are used as protective polymers when preparing the photosensitive silver halide. , 56
No. 5, No. 3,713,833, No. 3,748,1
43, means for using polymers other than gelatin such as polyvinyl acetals described in British Patent No. 1,362,970, and photosensitive halogens described in British Patent No. 1,354,186. Means for enzymatically decomposing gelatin in silver halide emulsions, or US Pat. No. 4,076,5
By preparing the photosensitive silver halide grains in the presence of a surfactant as described in No. 39, various means such as a means for omitting the use of a protective polymer can be applied.

The silver halide functions as an optical sensor, and preferably has a small grain size in order to suppress white turbidity after image formation and to obtain a good image quality. The average particle size is 0.1 μm or less, preferably 0.1 μm.
01 to 0.1 μm, particularly 0.02 to 0.08 μm is preferable. Further, the shape of the silver halide is not particularly limited, and so-called cubic or octahedral so-called normal crystal or non-normal crystal spherical shape,
There are rod-shaped, flat-shaped particles, and the like. The silver halide composition is also not particularly limited, and silver chloride, silver chlorobromide, silver chloroiodobromide,
It may be any of silver bromide, silver iodobromide and silver iodide.

The amount of silver halide is 50% or less, preferably 25 to 50% based on the total amount of silver halide and the organic silver salt described below.
It is 0.1%, more preferably between 15 and 0.1%.

The light-sensitive silver halide used in the photothermographic material of the present invention can also be a halide ion in preparing an organic silver salt, as described in British Patent 1,447,454. By coexisting the halogen component of (3) with the organic silver salt-forming component and injecting silver ions into this component, the organic silver salt can be produced almost at the same time.

As still another method, a solution or dispersion of an organic silver salt prepared in advance or a sheet material containing the organic silver salt is allowed to act with a silver halide forming component to expose a part of the organic silver salt to light. It can also be converted into a polar silver halide.
The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable effect. The silver halide-forming component is a compound capable of reacting with an organic silver salt to form a photosensitive silver halide, and what kind of compound corresponds to this compound and is effective is determined by the following simple test. I can do things. That is, the organic silver salt and the compound to be tested are mixed and, if necessary, heated and then examined by X-ray diffractometry for the presence of a peculiar peak to silver halide. The silver halide-forming components which have been confirmed to be effective by such a test include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds and other halogen-containing compounds. Are US Pat. Nos. 4,009,039 and 3,45.
7,075, 4,003,749, British Patent 1,498,956 and the like and JP-A-53-27027,
This is explained in detail in No. 53-25420, and one example thereof is shown below. (1) Inorganic halide: For example, a halide represented by MX _n (wherein M represents H, NH ₄ , or a metal atom, X represents a halogen atom, and n represents H or NH ₄ ). Represents 1, and when M is a metal atom, its valence is represented by lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, Manganese, iron, cobalt, nickel, rhodium,
There is cerium etc.). Further, halogen molecules such as bromine water are also effective. (2) Onium halides: for example, quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, trimethylsulfuric acid. There are tertiary sulfonium halides such as phonium iodide. (3) Halogenated hydrocarbons: for example, iodoform,
Bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like. (4) N-halogen compound: for example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazone, N-bromooxazolinone , N-chlorophthalazone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, N-bromourazole and the like. (5) Other halogen-containing compounds: For example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.

These silver halide-forming components are used stoichiometrically in small amounts with respect to the organic silver salt. Usually, the range is 0.001 mol to 0.7 mol, preferably 0.03 mol to 0.5 mol, per mol of the organic silver salt. Two or more kinds of silver halide-forming components may be used in combination within the above range. Although various conditions such as reaction temperature, reaction time and reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above silver halide-forming component can be appropriately set according to the purpose of production. Usually, the reaction temperature is −20 ° C. to 70 ° C., the reaction time is 0.1 second to 72 hours,
The reaction pressure is preferably set to atmospheric pressure. This reaction is also preferably carried out in the presence of the polymer used as the binder described below. In this case, the amount of the polymer used is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass, per 1 part by mass of the organic silver salt.

The photosensitive silver halide prepared by the above-mentioned various methods is, for example, a sulfur-containing compound, a gold compound,
Platinum compound, palladium compound, silver compound, tin compound,
Chemical sensitization can be performed with a chromium compound or a combination thereof. Regarding the method and procedure of this chemical sensitization, for example, US Pat. No. 4,036,650, British Patent No. 1,518,850, JP-A-51-22430,
No. 51-78319 and No. 51-81124. Further, when a part of the organic silver salt is converted into a photosensitive silver halide by the silver halide-forming component, as described in U.S. Pat. No. 3,980,482, a low sensitization is required to achieve sensitization. An amide compound having a molecular weight may coexist.

In addition, these photosensitive silver halides are added to groups 6 to 10 of the Periodic Table of the Elements in order to adjust the illuminance and adjust the gradation.
Group metals such as Rh, Ru, Re, Ir, O
Ions such as s and Fe, or a complex or complex ion thereof can be contained. In particular, it is preferable to contain an ion or a complex ion of a metal belonging to Groups 6 to 10 of the Periodic Table of the Elements. The above metals include W, Fe, Co, Ni,
Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u is preferable, and when it is used in a photosensitive material for printing plate making, it is preferably selected from Rh, Re, Ru, Ir and Os.

These metals can be introduced into the photosensitive silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a hexacoordinated complex represented by the following general formula (3).

[0059] Formula (3) [ML _6] ^m wherein the transition metal M is selected from Groups 6-10 elements of the Periodic Table of the Elements, L is bridging ligand, m is 0, -, 2- or 3-
Represents Specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and aco. Examples include ligands, nitrosyl, thionitrosyl, and the like, with preference given to ako, nitrosyl, thionitrosyl, and the like. When an aco ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

Specific examples of sodium salts of transition metal coordination complexes are shown below. Sodium is not shown for convenience,
It is a salt composed of three sodium atoms in the case of trivalent and two sodium atoms in the case of divalent.

[0062] (1): [RhCl _6] ^3- (2): [RuCl _6] ^3- (3): [ReCl _6] ^3- (4): [RuBr _6] ^3- (5): [OsCl ₆ ^3- (6): [CrCl _6] ^3- (7): [Ru (NO) Cl _5] ^2- (8): [RuBr ₄ (H ₂ O)] ^2- (9): [Ru (NO ) (H ₂ O) Cl ₄ ] ^- (10): [RhCl ₅ (H ₂ O)] ^2- (11): [Re (NO) Cl ₅ ] ^2- (12): [Re (NO) CN ₅ ] ^2- (13): [Re (NO) ClCN ₄ ] ^2- (14): [Rh (NO) ₂ Cl ₄ ] ^- (15): [Rh (NO) (H ₂ O) Cl ₄ ] ^- ( 16): [Ru (NO) CN ₅ ] ^2- (17): [Fe (CN) ₆ ] ^3- (18): [Rh (NS) Cl ₅ ] ^2- (19): [Os (NO) Cl _5] ^2- (20): [Cr (NO) Cl _5] ^2- ( 1): [Re (NO) Cl _5] ^- (22): _{[Os (NS) Cl 4 (TeCN} ) ] ^2- (23): [Ru (NS) Cl _5] ^2- (24): [Re ( NS) Cl ₄ (SeCN)] ^2- (25): [Os (NS) Cl (SCN) ₄ ] ^2- (26): [Ir (NO) Cl ₅ ] ^2- One kind may be used, or two or more kinds of the same kind of metal and different kinds of metals may be used in combination. In addition to sodium salt, potassium salt or lithium salt may be used, and cesium salt or the like may be arbitrarily selected.
The content of these metal ions or complex ions is generally from 1 × 10 ⁻⁹ to 1 mol per mol of silver halide.
1 × 10 ⁻² mol is suitable, and preferably 1 × 10 ⁻⁸ to
It is 1 × 10 ⁻⁴ mol. Compounds providing ions or complex ions of these metals 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,
It may be added at any stage before and after physical ripening and chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth. , Most preferably at the stage of nucleation. At the time of addition, it may be added dividedly over several times, or may be uniformly contained in the silver halide grains,
JP-A-63-29603, JP-A-2-306236
No. 3, No. 3-167545, No. 4-76534, No. 6
As described in JP-A-110146, JP-A-5-273683 and the like, the particles can be contained with a distribution. Preferably, it can have a distribution inside the particles. These metal compounds are water or a suitable organic solvent (for example, alcohols, ethers, glycols,
(Ketones, esters, amides), for example, an aqueous solution of a powder of a metal compound or an aqueous solution of a metal compound and NaCl or KCl is dissolved in water-soluble silver during grain formation. A silver halide grain is prepared by a method in which it is added to a salt solution or a water-soluble halide solution, or when a silver salt solution and a halide solution are simultaneously mixed, added as a third aqueous solution Method, a method in which a necessary amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or another silver halide grain previously doped with a metal ion or a complex ion during preparation of silver halide is added and dissolved. There is a method to make it. In particular, an aqueous solution of a metal compound powder or a metal compound and N 2
A method of adding an aqueous solution in which aCl and KCl are dissolved together to a water-soluble halide solution is preferable. When added to the surface of the particles, a necessary amount of an aqueous solution of the metal compound may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the end of chemical ripening.

A hydrazine compound can be contained in the photothermographic material of the present invention. The following can be mentioned as preferable hydrazine compounds.

The hydrazine compound is a compound having a —NHNH— group, and can be represented by the following general formula (4) as a typical one.

Formula (4) T-NHNH-CO-V In the formula, T is an optionally substituted alkyl group, aryl group,
Represents a heterocyclic group. V represents a hydrogen atom or a block group.

Examples of the alkyl group represented by T include linear, branched, and cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, and cyclohexyl, and various alkyl groups such as aryl, heterocycle, acyl, and cyano. The substituent may be substituted, and specific examples thereof include a trityl group and a benzyl group.

The aryl group represented by T includes a benzene ring and a naphthalene ring, and this ring may be substituted with various substituents, and a preferable substituent is a straight chain,
Branched alkyl group (preferably having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, dodecyl, etc.), alkoxy group (preferably having 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, dodecyl) Oxy), an aliphatic acylamino group (preferably having an alkyl group having 1 to 21 carbon atoms, such as an acetylamino group, a heptylamino group, etc.), an aromatic acylamino group, and the like. A substituted or unsubstituted aromatic ring is -CONH-, -O-,-
Including those linked by a linking group such as SO ₂ NH-, -NHCONH-, and -CH ₂ CH = N-.

Examples of the heterocyclic group represented by T include pyridyl, furyl, thienyl and the like, which may be substituted with the above-mentioned substituents for the aryl group. As T, a substituted or unsubstituted phenyl group and a trityl group are preferable, and a trityl group is more preferable.

V represents a hydrogen atom or a blocking group, and examples of the blocking group include alkyl, aryl, heterocycle, carbamoyl, oxycarbonyl, oxy, amino and the like, and these groups have been described above. The substituents listed as the substituents for T may be similarly substituted.

Specific examples of the blocking group other than hydrogen atom represented by V include, for example, methyl, methoxymethyl, methylthiomethyl, trifluoromethyl, phenyl, naphthyl, pyridyl, thienyl, furyl, ethoxy, t-butoxy, N. -Methylcarbamoyl, ethoxycarbonyl,
Each group such as anilino may be mentioned.

Hydrazine compounds are described in US Pat.
No.9,929, No.5,545,515, Tokuhyo 10
It can be synthesized with reference to the description of No. 512061 or the like. The hydrazine compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in another hydrophilic colloid layer. The hydrazine compound can be added after being dissolved in alcohols such as methanol and ethanol, ethylene glycols, ethers, ketones such as methyl ethyl ketone and acetone, polar solvents such as dimethyl sulfoxide and dimethylformamide, and the like. It is also possible to add fine particles of 1 μm or less dispersed in water or an organic solvent. Although many techniques for fine particle dispersion have been disclosed, they can be dispersed according to these techniques. The amount thereof added is in the range of 10 ⁻⁶ to 10 ⁻¹ mol, and preferably in the range of 10 ⁻⁴ to 10 ⁻² mol, per mol of silver halide.

The hydrazine compound preferably used in the present invention is, for example, US Pat. No. 5,545,515.
And the hydrazine compounds described in JP-A-10-512061.

Specific examples of the hydrazine compound will be given below.

[0074]

[Chemical 21]

[0075]

[Chemical formula 22]

[0076]

[Chemical formula 23]

A reducing agent is preferably incorporated in the photothermographic material of the present invention. Examples of suitable reducing agents include U.S. Pat. Nos. 3,770,448, 3,773,512,
No. 3,593,863 and RD Nos. 17029 and 29963, which are as follows.

Aminohydroxycycloalkenone compounds (eg 2-hydroxypiperidino-2-cyclohexenone); aminoreductones (eg piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
-Hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg,
Hydroquinone, t-butylhydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl)
Methyl sulfone); sulfhydroxamic acids (eg,
Benzenesulfhydroxamic acid); sulfonamide anilines (for example, 4- (N-methanesulfonamide) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) ) Hydroquinone); tetrahydroquinoxalines (for example, 1,2,3,4-tetrahydroquinoxaline); amidoxines; azines (for example, combinations of aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzenes Hydroxylamine combination, reductone and / or hydrazine;
Hydroxane acids; Combination of azines and sulfonamide phenols; α-Cyanophenylacetic acid derivative; Combination of bis-β-naphthol and 1,3-dihydroxybenzene derivative; 5-Pyrazolones; Sulfonamidephenol reducing agent; 2-Phenyl Indane-1,3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-
1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tolyl) mesitol, 2,2- Screw (4
-Hydroxy-3-methylphenyl) propane, 4,5
-Ethylidene-bis (2-t-butyl-6-methyl) phenol), UV-sensitive ascorbic acid derivative and 3
-Pyrazolidones. Among them, particularly preferable reducing agents are hindered phenols.

The amount of reducing agent used is preferably 1 × 10 ^-2 to 10 mol, and particularly 1 × 10 ^{-2 to} 5 mol per mol of silver.

As the binder of the photothermographic material of the present invention, the following may be added. That is, transparent or translucent, generally colorless, natural polymers, synthetic resins and polymers and copolymers, other film-forming media such as: gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose. Acetate butyrate,
Poly (vinylpyrrolidone), casein, starch, poly (acrylic acid ester) s such as poly (methylmethacrylic acid), poly (acrylic acid), poly (methacrylic acid),
Poly (vinyl chloride), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(For example, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resin, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. It may be hydrophilic or non-hydrophilic.

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

In the present invention, it is preferable to contain a matting agent on the photosensitive layer side, and in order to improve the accuracy of repeating the dimensions of the present invention, a polymer matting agent or an inorganic matting agent is added to all binders on the emulsion layer side. 0.5 to 10% by mass
It is preferable to contain.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as the inorganic substance, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, and alkali described in British Patent No. 1,173,181, etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in US Pat. No. 2,322,037, Belgian patent 625,451 and British patent 981,19
No. 8, etc., starch derivative, Japanese Examined Patent Publication No.
Polyvinyl alcohol described in Swiss Patent No. 33
Polystyrene or polymethacrylate described in US Pat. No. 0,158, polyacrylonitrile described in US Pat. No. 3,079,257, US Pat. No. 3,022,16
Organic matting agents such as polycarbonate described in No. 9 can be used.

The shape of the matting agent may be either a fixed shape or an amorphous shape, but it is preferably a fixed shape, and a spherical shape is preferably used. The size of the matting agent is represented by the diameter when the volume of the matting agent is converted into a spherical shape. In the present invention, the particle size of the matting agent refers to the spherically converted diameter.

The matting agent used in the present invention preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. The coefficient of variation of the particle size distribution is preferably 50% or less,
It is more preferably 40% or less, and particularly preferably 30.
It is a matting agent whose content is less than or equal to%.

Here, the variation coefficient of the particle size distribution is a value represented by the following formula. (Standard deviation of particle size) / (Average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably a photosensitive layer in order to achieve the object of the present invention. It is a constituent layer other than the above, and more preferably the outermost layer as viewed from the support.

The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed in a coating solution in advance and then applied.
A method of spraying the matting agent after applying the coating solution and before the completion of drying may be used. When a plurality of types of matting agents are added, both methods may be used together.

The heat-developable light-sensitive material of the present invention forms a photographic image by heat-development processing, and comprises a reducible silver source (organic silver salt), a catalytically active amount of silver halide, a specific alkene derivative, and a reduced alkene derivative. The photothermographic material preferably contains an agent and, if necessary, a color toning agent for suppressing the color tone of silver in a state of being normally dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is developed by being heated to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. When heated, silver is produced through a redox reaction between an organic silver salt (which functions as an oxidizing agent) and a reducing agent. This redox reaction is promoted by the catalytic action of the latent image generated on the silver halide upon exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms an image. This reaction process proceeds without supplying a treatment liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side as or on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. As the dye, the compound of Japanese Patent Application No. 7-11184 is preferable. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitive layer / low sensitive layer or a low sensitive layer / high sensitive layer for adjusting gradation. Various additives may be added to any of the light-sensitive layer, the non-light-sensitive layer, and other forming layers. The photothermographic material of the present invention includes, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber,
A coating aid or the like may be used.

A color tone agent is preferably added to the photothermographic material of the present invention. Examples of suitable toning agents are RD No. 17
No. 029, and includes the following.

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2). , 4-thiazolidinedione); naphthalimides (for example, N-hydroxy-1,8-naphthalimide); cobalt complexes (for example, hexaminetrifluoroacetate of cobalt), mercaptans (for example, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (e.g.,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
iuronium) derivative and certain photobleaching agents (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
(Combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); merocyanine dye (for example, 3-ethyl-5-((3-ethyl 2-Benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthal Acid combination; phthalazine (including phthalazine adduct) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and their anhydrides (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride)
A combination of two compounds; quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-diones (for example, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines. (For example, 2,4-dihydroxypyrimidine), and a tetraazapentalene derivative (for example, 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). A preferable color tone agent is phthalazone or phthalazine.

An antifoggant may be contained in the photothermographic material of the invention. The most known antifoggant is mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is disclosed, for example, in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfavorable. Examples of non-mercury antifoggants include US Pat. No. 4,546,
075 and 4,452,885 and JP-A-59.
Antifoggants such as those disclosed in -57234 are preferred.

Particularly preferred non-mercury antifoggants are US Pat. Nos. 3,874,946 and 4,756,99.
A compound as disclosed in No. 9, --C (X ₁ ).
A heterocyclic compound having one or more substituents represented by (X ₂ ) (X ₃ ), where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen. Examples of suitable antifoggants include JP-A No. 9-90550, paragraph number [0062] to
The compounds described in [0063] are preferably used.

Further, more preferred antifoggants are US Pat. No. 5,028,523 and British patent application No. 92221.
383.4, No. 9300147.7, No. 931
No. 1790.1.

The photothermographic material of the present invention includes, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651, and 6-63.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455,
No. 4,741,966, No. 4,751,175
The sensitizing dyes described in No. 4,835,096 can be used. Useful sensitizing dyes used in the present invention are, for example, RD No. 17643IV-A (December 1978 p. 2).
3), Item 1831X (P.437, August 1978).
It is described in the literature described or cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-80.
The compounds described in No. 679 are preferably used.

[0096]

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

Example 1 [Preparation of undercoated photographic support] Both sides of a polyethylene terephthalate support having a thickness of 130 μm were subjected to a corona discharge treatment of 8 W / m ² · min. a
-1 is applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1, and the undercoating coating solution b described below is provided on the opposite surface.
-1 was applied so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoat layer B-1. << Undercoating liquid a-1 >> Copolymer latex liquid of butyl acrylate (30 mass%), t-butyl acrylate (20 mass%) styrene (25 mass%), 2-hydroxyethyl acrylate (25 mass%) Solid content 30%) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Make up to 1 L with water. << Subbing coating liquid b-1 >> Copolymer latex liquid of butyl acrylate (40% by mass), styrene (20% by mass) and glycidyl acrylate (40% by mass) (solid content 30%) 270 g Hexamethylene-1,6 -Bis (ethylene urea) 0.8 g Make up to 1 L with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
8 W / m ² · min of corona discharge is applied to the upper surface of the undercoat layer A-1, and the undercoating upper layer coating solution a-2 below is undercoated onto the undercoating layer A-1 to a dry film thickness of 0.1 μm. Underlayer B as layer A-2
-1, the following undercoating upper layer coating solution b-2 was dried to a film thickness of 0.
It was applied as an undercoating upper layer B-2 having an antistatic function so as to have a thickness of 8 μm. << Undercoating Upper Layer Coating Liquid a-2 >> Gelatin 0.4 g / m ² Mass Silica Particles (Average Particle Size 3 μm) 0.1 g Water to 1 L. << Undercoating Upper Layer Coating Liquid b-2 >> Styrene-butadiene copolymer latex liquid (solid content 20%) 80 g Polyethylene glycol (weight average molecular weight 600) 6 g Water is used to make 1 L. <Preparation of silver halide grain emulsion A> 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water to adjust the temperature to 35 ° C. and pH to 3.0, and then 370 ml of an aqueous solution containing 74 g of silver nitrate ( An aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 98/2) (equivalent to silver nitrate) was added over 10 minutes by the controlled double jet method while keeping pAg at 7.7. Then 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (0.3 g) was added, and the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8%. ] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
By adjusting to H5.9 and pAg7.5, a silver halide grain emulsion A was obtained. (Preparation of powdered organic silver salt) 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, while stirring at high speed, 540.2 ml of a 1.5 M sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain an organic acid sodium salt solution. While maintaining the temperature of the above-mentioned sodium salt of organic acid at 55 ° C., 450 ml of pure silver halide grain emulsion A (containing 0.038 mol of silver) and pure water
Was added and stirred for 5 minutes. Next, 1M silver nitrate solution 76
0.6 ml was added over 2 minutes and stirred for another 20 minutes,
Water-soluble salts were removed by filtration. After that, washing with deionized water and filtration were repeated until the electric conductivity of the filtrate reached 2 μS / cm, centrifugal dehydration was carried out, and then hot air drying was carried out at 37 ° C. until there was no loss of mass, to obtain the powdered organic silver salt. Obtained. <Preparation of Coating Solution for Photosensitive Layer> Samples were prepared by sequentially forming the following layers on the support having the undercoat layer formed thereon. The drying was carried out at 75 ° C. for 1 minute. Back surface side coating back layer: A coating solution prepared by adding an aqueous solution or water dispersion of the following composition to water was coated and dried in the following coating amounts.

Gelatin 7.0 g / m ² Dye: Dye A of Example 1 of JP-A-10-161270 70 mg / m ² Back layer protective film Gelatin 1.5 g / m ² Matting agent (polymethylmethacrylate) 0.03 g / m ² active agent _{(C 8 F 17 SO 2 N} (C 3 H 7) CH 2 COOK) 0.02g / m 2 active agent _{(p-C 8 H 17 C} 6 H 4 O (C 2 H 4 O) ₄ H) 0.02 g / m ² Photosensitive layer side coating photosensitive layer: An aqueous dispersion of the following composition was added to water to prepare a coating solution. Keeping this coating solution at 40 ° C, the silver electrode (purity 9
After measuring the silver potential using a silver electrometer formed from a reference electrode consisting of an Ag / AgCl electrode in a 3M solution through a salt bridge consisting of a 0.99% or more) and 10% KNO ₃ salt solution,
The coating amount was adjusted to the following coating amount and dried.

Polymer binder with an amount of 2.0 g / m ² as silver amount 5.0 g / m ² (The polymer has a copolymer composition ratio of styrene / methyl methacrylate / ethyl acrylate / acrylic acid of 60: 30: 8: Sensitizing dye-1: Sensitizing dye D of Example 3 of JP-A-10-161270 20 mg / m ² antifoggant-1: Pyridinium hydrobromide perbromide 0.3 mg / m ² antifoggant- 2: Isothiazolone 1.2 mg / m ² antifoggant -3: 2-tribromomethylsulfonylquinoline 120 mg / m ² phthalazone 360 mg / m ² Developer: 1,1-bis (2-hydroxy-3,5dimethylphenyl) -3,5,5-Trimethylhexane 1300 mg / m ² Hardening agent: General formula (1), (2) or comparative compound Table 1 Description 3 x 10 ^-5 m / M ² surface protective layer: An aqueous solution of the following composition or a coating solution prepared by adding an aqueous dispersion to water was coated and dried to give the following coating amounts.

Inert gelatin 2.0 g / m ² phthalazine 1.0 g / m ² 4-methylphthalic acid 0.72 g / m ² tetrachlorophthalic acid 0.22 g / m ² tetrachlorophthalic anhydride 0.5 g / m ² Silica matting agent (average particle size 5 μm) 0.5 g / m ² 1,2- (bisvinylsulfoneacetamide) ethane 0.3 g / m ² << exposure and heat development treatment >> Exposed surface of the photothermographic material prepared above The angle of the exposure laser beam was 76 degrees. The room temperature and normal humidity test is for 25 hours for the photothermographic material after coating and drying.
The test was performed after placing in an atmosphere of 48 ° C. and 48% RH. As a high temperature and high humidity test, the same evaluation as above was carried out after storage for 3 days in an atmosphere of 45 ° C. and 80% RH.

The photothermographic materials prepared as the room temperature and normal humidity test sample and the high temperature and high humidity test sample were exposed with a laser sensitometer having a semiconductor laser of 810 nm, and then heat developed at 120 ° C. for 8 seconds using a heat drum. Processed. At that time, exposure and development were performed in a room where the humidity was adjusted to 25 ° C. and 48% RH. << Evaluation of Photographic Performance >> The obtained images were evaluated (sensitivity and fog) with a densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the exposure dose that gives a density 0.3 higher than the fog (minimum) density (Dmin). The relative sensitivity was expressed based on the value in the room temperature and normal humidity test of 1.

The evaluation results are shown in Table 1.

[0104]

[Table 1]

[0105]

[Chemical formula 24]

As is clear from the results shown in Table 1, the photothermographic material of the present invention has high sensitivity and low fog even during storage at high temperature and high humidity.

Example 2 A photothermographic material was prepared in the same manner as in Example 1, except that a hexacoordinated complex (metal complex compound) represented by the general formula (3) was prepared during preparation of a silver halide emulsion. As described in 2, added 10 ⁻⁶ mol per mol of silver halide. Further, perfluorooctylsulfonic acid sodium salt as a fluorine-containing surfactant is added in an amount of 0.2 g / m in the emulsion protective layer and the protective layer of the backing layer in order to improve the charging property and the surface smoothness.
^It was added to be ² . The sensitivity of the coated sample No. The relative sensitivity was expressed with reference to the value of 21 normal temperature and normal humidity test. The results are shown in Table 2.

[0108]

[Table 2]

[0109]

[Chemical 25]

As is clear from the results of Table 2, the photothermographic material of the present invention has high sensitivity and low fog even at the time of storage at high temperature and high humidity.

Example 3 A photothermographic material was prepared in the same manner as in Example 1. However, as shown in Table 3, the hydrazine compound represented by the general formula (4) was added to the emulsion layer coating solution with halogen. 3 × 10 ⁻⁵ mol was added per mol of silver halide, and as shown in Table 3, a hexacoordinated complex represented by the general formula (3) (metal complex compound) was added to an arbitrary sample when preparing a silver halide emulsion. 10 ^-6 mol was added per mol of silver halide.

Further, in order to improve the charging property and the surface smoothness in the emulsion layer protective layer and the protective layer of the backing layer, perfluorooctyl sulfonic acid sodium salt as a fluorosurfactant is adjusted to 0.2 g / m ^2. Was added to. The sensitivity of the coated sample No. Relative sensitivity was expressed based on the value of 41 in the normal temperature and normal humidity test. The results are shown in Table 3.

[0113]

[Table 3]

[0114]

[Chemical formula 26]

As is clear from the results shown in Table 3, the photothermographic material of the present invention has high sensitivity and low fog even during storage at high temperature and high humidity.

[0116]

According to the present invention, even when stored at high temperature and high humidity,
The photothermographic material of high sensitivity and low fog is remarkably excellent.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H123 AB00 AB03 AB05 AB23 AB28                       BB00 BB02 BB27 BB31 CB00                       CB03 EA07

Claims (3)

[Claims] 1. A photothermographic material having a photosensitive layer containing photosensitive silver halide grains on at least one surface of a support, wherein an organic silver salt, a reducing agent, and an organic silver salt are provided on at least one of the photosensitive layer and the non-photosensitive layer. And a photothermographic material containing at least one of compounds represented by the following general formulas (1) and (2). [Chemical 1] [In the formula, X represents a substituted alkyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom,
Acyl group, thioacyl group, oxalyl group, oxyoxalyl group, -S-oxalyl group, oxamoyl group, oxycarbonyl group, -S-carbonyl group, carbamoyl group,
Thiocarbamoyl group, sulfonyl group, sulfinyl group,
Oxysulfonyl group, -S-sulfonyl group, sulfamoyl group, oxysulfinyl group, -S-sulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, ammonium group, It represents a sulfonium group, a phosphonium group, a pyrylium group, or an immonium group. W represents a hydrogen atom, an alkyl group, an unsubstituted or substituted electron donating group-substituted aryl group, an oxy group, a thio group, an amino group, a non-aromatic heterocyclic group, or a silyl group. A represents an aromatic heterocyclic group containing a nitrogen atom, and is bonded through the nitrogen atom in the ring. In addition, X and H are displayed in the form of cis,
X and H also include the transformer form. ] [Chemical 2] [In the formula, Y represents a hydrogen atom or a substituent. A represents an aromatic heterocyclic group containing a nitrogen atom, and is bonded through the nitrogen atom in the ring. R represents a halogen atom, an oxy group, a thio group, an amino group, a heterocyclic group, or a silyl group.
Although Y and H are shown in cis form, Y and H also include trans form. ] 2. The photothermographic material according to claim 1, wherein the photosensitive silver halide is doped with a transition metal complex. 3. The photothermographic material according to claim 1, wherein the photothermographic material contains a hydrazine compound.