JP2003121965A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-developable photosensitive material having high sensitivity, excellent storage stability and excellent stability of an image after development. SOLUTION: In the heat-developable photosensitive material comprising at least photosensitive silver halide, non-photosensitive organic silver salts, a reducer for silver ions and a binder on one face of a support, the silver behenate content of the non-photosensitive organic silver salts is 40 to <85 mol% and at least one compound comprising two or more dye chromophores is contained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photothermographic material. More specifically, the present invention is to provide a photothermographic material having high sensitivity, excellent storage stability, and excellent image stability after development.

[0002]

2. Description of the Related Art In recent years, in the fields of medical diagnostic films and photoengraving films, there has been a strong demand for reducing the amount of processing waste liquid from the viewpoint of environmental protection and space saving. Therefore, heat development as a film for medical diagnosis and a film for photoengraving, which can be efficiently exposed by a laser imagesetter or a laser imager and can form a clear black image having high resolution and sharpness. There is a need for technology relating to image recording materials. According to these heat-developable image recording materials, it is possible to supply a customer with a heat-development processing system that does not require a solution-type processing chemical and is simpler and does not damage the environment.

Although there are similar demands in the field of general image forming materials, particularly medical diagnostic images require fine depiction, so high image quality excellent in sharpness and graininess is required, and diagnostic images are required. There is a feature that a cold black image is preferred from the viewpoint of easiness. Currently, as general image forming systems, various hard copy systems using pigments and dyes such as ink jet printers and electrophotography are in circulation, but none are satisfactory as medical image output systems.

On the other hand, thermal image forming systems utilizing organic silver salts are disclosed in, for example, US Pat. Nos. 3,152,904, 3457075 and D.I. Cross Tabor (Kl
osterboer) "The Silver System Heat Treated (The
rmally Processed Silver Systems "(Imaging Processes & Materials (Imaging Pr
ocesses and Materials), Neblette 8th edition, J. Sturge, V.I. Walworth,
A. Edited by Shepp, Chapter 9, 279, 1
989). In particular, the photothermographic material generally has a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent, a reducible silver salt (eg, organic silver salt),
It has a photosensitive layer in which a toning agent for controlling the color tone of silver is dispersed in a binder matrix, if necessary. Photothermographic materials are exposed to high temperatures (for example, 80 ° C or higher) after image exposure.
Upon heating, the redox reaction between the reducible silver salt (which functions as an oxidizing agent) and the reducing agent forms a black silver image. The redox reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, a black silver image is formed in the exposed area. Such a heat-developable image recording material is disclosed in many documents including U.S. Pat. No. 2,910,377 and JP-B-43-4924.

In addition, a large number of silver halide spectral sensitizing dyes used in these photothermographic materials have been conventionally used, and great efforts have been made to improve sensitivity and improve storage stability. It has been done. For example, JP 2000
There are known methods using sensitizing dyes such as JP-A-98525 and JP-A-2000-122206. However, even when these sensitizing dyes are used, the storage stability and the image stability after development are improved. Was required to be further improved.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art.
That is, the object of the present invention is to provide a photothermographic material having high sensitivity and excellent storage stability and image stability after development.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the following means can be achieved. (1) A photothermographic material containing at least one photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions and a binder on one surface of a support, in the non-photosensitive organic silver salt. Content of silver behenate is 40 mol%
A photothermographic material comprising at least one compound containing two or more dye chromophores and at least 85 mol%. (2) The photothermographic material according to (1) above, wherein the compound containing two or more dye chromophores is selected from the compounds represented by the following general formula (A).

[Chemical 11] (In the formula, D ^a and D ^b each independently represent a dye chromophore.
L ^a represents a linking group or a single bond. q ^a and r ^a are each 1
Represents an integer of -100. q ^b represents an integer of 1 to 4. M ^a represents a charge balancing counter ion, m ^a represents a number necessary to neutralize a charge of the molecule. (3) The photothermographic material as described in (2) above, wherein the compound represented by the general formula (A) is selected from the compounds represented by the following general formula (I).

[Chemical 12] (In the formula, D ¹ represents a dye chromophore. L ¹ represents a linking group or a single bond. Q ¹ and r ¹ each represent an integer of 1 to 100. q ² represents an integer of 1 to 4. . M ¹ represents a charge-balancing counter ion, and m ¹ represents a number necessary for neutralizing the charge of the molecule.) (4) The dye chromophore D ¹ has the following general formulas (XI) and (XII).
Alternatively, the photothermographic material according to (3) above, which is a dye chromophore having a structure of (XIII).

[0008]

[Chemical 13]

[In the formula (XI), L ¹¹ , L ¹² , L ¹³ , L ¹⁴ ,
L ¹⁵ , L ¹⁶ and L ¹⁷ represent a methine group. p ¹¹ , and p
¹² represents 0 or 1. n ¹¹ is 0, 1, 2, 3 or 4
Represents Z ¹¹ and Z ¹² represent an atomic group necessary for forming a nitrogen-containing heterocycle, and the ring may be condensed to Z ¹¹ and Z ¹² . M ¹¹ represents a charge-balancing counterion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. ]

[0010]

[Chemical 14]

[In the formula (XII), L¹⁸, L¹⁹, L²⁰,as well as
L^{twenty one}Represents a methine group. p¹³Represents 0 or 1. q¹¹Is
Represents 0 or 1. n¹²Represents 0, 1, 2, 3 or 4
You Z¹³Is the atomic group necessary to form a nitrogen-containing heterocycle
Represents Z¹⁴And Z¹⁴'Is (N-R ¹⁴) Q¹¹Be with
To form a heterocyclic or acyclic acidic end group.
Form the necessary atomic groups, Z¹³And Z¹⁴And Z¹⁴’And a ring
It may be condensed. M¹²Represents a charge-balancing counterion,
m¹²Represents the number 0 or more required to neutralize the charge of the molecule.
You R¹³, And R¹⁴Is hydrogen atom, alkyl group, aryl
Represents a group or a heterocyclic group. ]

[0012]

[Chemical 15]

[In the formula (XIII), L^{twenty two}, L^{twenty three}, L^{twenty four},
L^{twenty five}, L²⁶, L²⁷, L²⁸, L²⁹And L³⁰Represents the methine group
You p¹⁴And p¹⁵Represents 0 or 1. q¹²Is 0 or 1
Represent. n ¹³And n¹⁴Represents 0, 1, 2, 3 or 4.
Z¹⁵, And Z¹⁷Is necessary to form a nitrogen-containing heterocycle
Represents a group of atoms. Z¹⁶And Z¹⁶'Is (N-R¹⁶) Q¹²With
Represents a group of atoms necessary to form a heterocycle,
Z¹⁵, Z¹⁶And Z¹⁶’And Z¹⁷In addition, the ring is further condensed
May be. M¹³Represents a charge-balancing counterion, m¹³Is the molecule
Represents a number of 0 or more necessary to neutralize the electric charge of. R¹⁵,
R¹⁶And R¹⁷Is a hydrogen atom, an alkyl group, an aryl group or
Represents a heterocyclic group. ] (5) The compound represented by the general formula (I) has the following general formula:
Selected from compounds represented by (XXI) or (XXII)
The photothermographic material according to (3) above,

[0014]

[Chemical 16]

[In the formula (XXI), L ¹¹ , L ¹² , L ¹³ ,
^{L 14, L 15, L 16} , L 17, p 11, p 12, n 1 1, Z 11, and Z ¹² has the same meaning as in formula (XI). L ² represents a linking group. M ¹⁴ represents a charge-balancing counterion, and m ¹⁴ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ²¹ represents an alkyl group, an aryl group, or a heterocyclic group. ]

[0016]

[Chemical 17]

[In the formula (XXII), L¹⁸, L¹⁹, L²⁰,
L^{twenty one}, P¹³, Q¹¹, N¹², Z¹³, Z¹⁴, Z ¹⁴'And R¹⁴
Is synonymous with general formula (XII). L³Represents a linking group. M
¹⁵Represents a charge-balancing counterion, m¹⁵Neutralizes the charge of the molecule
Represents a number of 0 or more required to do. ] (6) The compound represented by the general formula (I) has the following general formula:
Compound represented by (XXXIa), (XXXIb) or (XXXII)
The thermal expression according to (3) above, which is selected from
Image-sensitive material.

[0018]

[Chemical 18]

[In the formula (XXXIa), Z⁵¹, And Z⁵²Is oxygen
Atom, sulfur atom, selenium atom, nitrogen atom, or carbon atom
Represents R⁵¹Is an alkyl group, an aryl group, or a heterocyclic group
Represents L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, And L
⁵⁷Represents a methine group. V⁵¹, V ⁵², V⁵³, V⁵⁴, V⁵⁵,
V⁵⁶, V⁵⁷, And V⁵⁸Represents a hydrogen atom or a substituent.
L^FourRepresents a linking group. M⁵¹Represents a charge-balancing counterion,
m⁵¹Represents the number 0 or more required to neutralize the charge of the molecule.
You ]

[0020]

[Chemical 19]

Of the above two R ^{52 s} or R ^{53 s} , one of them jointly forms L ⁵ of the linking group. [In the formula (XXXIb), Z ⁵³ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, or a carbon atom. R ⁵² and R ⁵³
Represents an alkyl group, an aryl group, or a heterocyclic group. However, one of the two R ^{52 s} or R ^{53 s} together forms L ⁵ . L ⁵ represents a linking group. L ⁵⁸ , L ⁵⁹ ,
L ⁶⁰ , L ⁶¹ , and L ⁶² represent a methine group. V ⁵⁹ , V ⁶⁰ ,
V ⁶¹ , V ⁶² , V ⁶³ , V ⁶⁴ , V ⁶⁵ , V ⁶⁶ , V ⁶⁷ , and V ⁶⁸
Represents a hydrogen atom or a substituent. M ⁵² represents a charge-balancing counterion, and m ⁵² represents a number of 0 or more necessary for neutralizing the charge of the molecule. ]

[0022]

[Chemical 20]

[In the formula (XXXII), Z ⁵⁴ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom. Z
⁵⁵ represents an oxygen atom, a sulfur atom, or a nitrogen atom. R ⁵⁴ represents an alkyl group, an aryl group, or a heterocyclic group. L ⁶ represents a linking group. ^{L 63, L 64, L 6} 5, and L ⁶⁶ each represents a methine group. n ⁵¹ represents 1 or 2. V ⁶⁹ , V ⁷⁰ , V ⁷¹ , and V ⁷² represent a hydrogen atom or a substituent. M ⁵³ represents a charge-balancing counterion, and m ⁵³ represents a number of 0 or more necessary for neutralizing the charge of the molecule. (7) A compound containing two or more dye chromophores, a compound represented by the general formula (A), or a compound represented by the general formula (I) is adsorbed in a single layer. (1)
The photothermographic material according to any one of to (6). (8) The photothermographic material according to any one of the above (1) to (7), wherein 50% by mass or more and 100% by mass or less of the binder is polyvinyl butyral. (9) The photothermographic material according to any one of (1) to (8) above, wherein the binder has a Tg of 40 ° C to 90 ° C.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION (Part of the description of the compound of the present invention)
Hereinafter, the present invention will be described in detail. In addition, in this specification, "-" shows the range including the numerical value described before and behind that as a minimum value and a maximum value, respectively. The compounds used in the present invention will be described. First, a comprehensive definition of groups and the like of the compounds used in the present invention will be described in detail. In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or may be substituted with one or more (up to the maximum number of possible) substituents. If it is possible to substitute with a plurality of substituents, it means that the substituents may be the same or different from each other. For example, "alkyl group"
Means a substituted or unsubstituted alkyl group. Also,
Substituents that can be substituted on the groups of the compounds of the present invention include any substituents, whether or not they are themselves substituted.

When such a substituent is represented by W, the substituent represented by W may be any one, and is not particularly limited, and examples thereof include a halogen atom, an alkyl group {(cycloalkyl group, bicycloalkyl group, And a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), and an alkynyl group. }, Aryl group, heterocyclic group (sometimes referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy Group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryls. Oxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group (sometimes referred to as phosphono group) , Silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (O
H) _2), a sulfato group (-OSO ₃ H), and other known substituents.

More specifically, W is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom),
Alkyl group {Alkyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-).
Butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl,
Cyclopentyl, 4-n-dodecylcyclohexyl),
Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1, 2,
[2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [representing a linear, branched or cyclic, substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example,
Vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed. And a monovalent group such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group,
Preferred is a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl and bicyclo [2,2,2] oct-2-en-4-yl) are included. ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)}, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, heterocyclic groups (preferably 5- or 6-membered, substituted or unsubstituted, aromatic or non-aromatic) Is a monovalent group obtained by removing one hydrogen atom from the heterocyclic compound of, and more preferably
It is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2
It may be a cationic heterocyclic group such as -pyridinio or 1-methyl-2-quinolinio. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyl. Oxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-
tert-butylphenoxy, 3-nitrophenoxy,
2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms,
For example, trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-
Tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 6 to 3 carbon atoms)
A substituted or unsubstituted arylcarbonyloxy group of 0, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy,
p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyl Oxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyl). Oxy, ethoxycarbonyloxy, tert-
Butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy,
pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a carbon number of 1 to 3)
0-substituted or unsubstituted alkylamino group, carbon number 6
~ 30 substituted or unsubstituted anilino groups such as amino, methylamino, dimethylamino, anilino, N-
Methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an aryl group, an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio, diphenyl Methylammonio), acylamino group (preferably formylamino group, carbon number 1)
~ 30 substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5 -Tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N , N
-Diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n- Octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 carbon atoms)
~ 30 substituted or unsubstituted aryloxycarbonylamino groups, such as phenoxycarbonylamino, p
-Chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, and substituted having 6 to 30 carbon atoms) Or unsubstituted arylsulfonylamino, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group Preferably, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p -Chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N
-(N'-phenylcarbamoyl) sulfamoyl),
Sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl , P-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl,
Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) , A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl. , 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitro. Phenoxical Nyl, p-tert-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl). ), A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-cimethylcarbamoyl, N, N-di-n-).
Octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 1 to 30 carbon atoms) , For example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazole-2
-Ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methyl). Phenoxyphosphino), phosphinyl group (preferably substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably , A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 to 30 carbon atoms). A substituted or unsubstituted phosphinylamino group, eg dimetho Cyphosphinylamino, dimethylaminophosphinylamino), phospho group, silyl group (preferably substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl). A hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino),
It represents a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N-dimethylureido).

Further, two W's may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle). These can be further combined to form a polycyclic condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a quinoline ring, a phenanthrene ring,
Fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring , A phenoxathiin ring, a phenothiazine ring, and a phenazine ring.

Among the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above-mentioned group after removing the hydrogen atom. Examples of the substituent which is further substituted on the above-mentioned substituent W include -CONHSO ₂ -group (sulfonylcarbamoyl group, carbonylsulfamoyl group), -CONHCO-.
Group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ -
Group (sulfonylsulfamoyl group). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) may be mentioned.

Next, the compound containing two or more dye chromophores used in the present invention will be described. The compound can be preferably used as a sensitizing dye. Preferable examples of these dye chromophores include those similar to D ¹ described later. Also, even if these dye chromophores are the same,
It may be different, but preferably the same.
The number of dye chromophores contained in the compound may be any number as long as it is 2 or more, but preferably 2 to 10000, more preferably 2 to 1000, further preferably 2-1.
00, more preferably 2 to 10, more preferably 2
-5, more preferably 2-3, most preferably 2. In the compound, two or more dye chromophores are linked by a covalent bond or a coordinate bond, preferably a covalent bond. Further, in the compound, a covalent bond or a coordinate bond may be formed in advance or may be formed in the process of preparing a silver halide light-sensitive material (for example, in a silver halide emulsion), but preferably a bond Is formed in advance.

Next, the compound represented by the general formula (A) used in the present invention will be explained. In the formula, D ^a and D ^b represent dye chromophores. D ^a and D ^b may be the same dye chromophore or different dye chromophores. The same dye chromophore is preferred. As D ^a and D ^b , those similar to D ¹ described later are preferably mentioned. L ^a represents a linking group or a single bond, and preferably the same group as L ¹ described later can be mentioned. q ^a and r ^a each represent an integer of 1 to 100. It is preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and particularly preferably 1. When q ^a and r ^a are 2 or more, a plurality of L ^a included are included.
Each of D ^b and D ^b may be a different linking group, or a single bond, and a dye chromophore.

Q ^b represents an integer of 1 to 4. In addition, q ^b being 2 or more means that D ^a and D ^b , or D ^b and D ^b are linked by a plurality of linking groups, respectively. That is,
D ^a and D ^b , or D ^b and D ^b may be connected at each one position, or may be connected at a plurality of positions (2 to 4 positions, preferably 2 positions). . When q ^b is 2 or more, a plurality of L ^a may be the same or different. The case where they are the same is preferable. q ^b is preferably 1 or 2, and more preferably 1.

L ^a may be bonded at any part of D ^a and D ^b , but is preferably not a methine chain part. The case of binding at the N-position of the basic nucleus or the acidic nucleus is more preferable, and the case of binding at the N-position of the basic nucleus is more preferable.

M ^a represents ^a charge-balancing counterion, and m ^a represents a number necessary for neutralizing the charge of the molecule, and preferably the same as those described below for M ¹ and m ¹ .

The general formula (A) represents that the dye chromophores can be linked to each other in any linking manner.

Further, when D ^a and D ^b in the general formula (A) are different from each other, the dye chromophore, the general formula, and the substituent in a more preferable range have the same D ^a and D ^{b as} described below. In the description of the general formula (I) and its preferable range in the case, the same applies except that the dye chromophores are not the same. That is, when D ^a and D ^b in the general formula (A) are different from each other, the dye chromophores in a more preferable range are the general formulas (XI), (XII) and (XIII) described in the general formula (I). , If they are not the same. When D ^a and D ^b in the general formula (A) are different from each other, more preferably, in the general formula (XXI), two L
¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , L ¹⁷ , p ¹¹ ,
When at least one of p ¹² , n ¹¹ , Z ¹¹ , Z ¹² and R ²¹ is not the same or in the general formula (XXII), two L ¹⁸ , L ¹⁹ , L ²⁰ , L ²¹ and p ^{13 are represented.} , Q ¹¹ , n ¹² , Z ¹³ , Z
^This is the case where at least one of ¹⁴ , Z ¹⁴ ′ and R ¹⁴ is not the same. When D ^a and D ^b are different from each other in the general formula (A), it is particularly preferable to use two Z ⁵¹ , Z ⁵² , R ⁵¹ , L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ and L in the general formula (XXXIa). ⁵⁵ , L
⁵⁶ , L ⁵⁷ , V ⁵¹ , V ⁵² , V ⁵³ , V ⁵⁴ , V ⁵⁵ , V ⁵⁶ ,
When at least one of V ⁵⁷ and V ⁵⁸ is not the same, two Z ⁵³ , R ⁵² , R ⁵³ and L in the general formula (XXXIb) are used.
^{58, L 59, L 6 0} , L 61, L 62, V 59, V 60, V 61,
If at least one of V ⁶² , V ⁶³ , V ⁶⁴ , V ⁶⁵ , V ⁶⁶ , V ⁶⁷ , and V ⁶⁸ is not the same, or two Z ⁵⁴ , Z ⁵⁵ , and R in the general formula (XXXII). ⁵⁴ , L ⁶³ , L ⁶⁴ ,
This is a case where at least one of L ⁶⁵ , L ⁶⁶ , n ⁵¹ , V ⁶⁹ , V ⁷⁰ , V ⁷¹ , and V ⁷² is not the same.

Among the compounds represented by the general formula (A) used in the present invention, a particularly preferred compound is the compound represented by the above general formula (I). The compound represented by the general formula (I) corresponds to the case where both D ^a and D ^b in the general formula (A) are the same dye chromophore.

The general formula (I) represents that the dye chromophores can be linked to each other in any linking manner.

The compound represented by formula (I) will be described in detail below. The compound of the general formula (I) has a plurality of the same dye chromophores, and the compound represented by the general formula (A) (where D ^a and D ^b are Better than different). In addition, the compound represented by the general formula (I) is superior to the compound represented by the general formula (A) (when D ^a and D ^b are different), and is excellent in that it can be manufactured at low cost. ing.

The compound represented by formula (A) or (I) used in the present invention is preferably adsorbed in a single layer because of high sensitivity, storage stability and image stability after development. Here, the monolayer adsorption means that the dye chromophore of the compound (sensitizing dye) is adsorbed on the surface of the silver halide grain in one layer or less. That is, it means a state in which the adsorption amount of the dye chromophore per unit particle surface area is further equal to or less than the saturated coating amount. (The one-layer saturated coating amount means the dye adsorption amount per unit particle surface area at the one-layer saturated coating.) In other words, the compound represented by the general formula (A) or (I) used in the present invention is a multi-layer. The non-adsorption is preferred in terms of high sensitivity, storage stability and image stability after development. Multilayer adsorption means that more dye chromophores of compounds (sensitizing dyes) are adsorbed on the surface of silver halide grains. That is, it means a state in which the adsorption amount of the dye chromophore per unit particle surface area is more than the saturated coating amount.
Further, the number of adsorption layers means the adsorption amount when the one-layer saturated coating amount is used as a reference.

D ¹ and L ¹ will be described. The dye chromophore represented by D ¹ may be any one, for example, a cyanine dye, a styryl dye, a hemicyanine dye,
Merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye,
Coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, Examples thereof include groups consisting of polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes and metal complex dyes.

Preferably, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye,
Examples thereof include polymethine chromophores such as hemioxonol dyes, squarylium dyes, croconium dyes, and azamethine dyes. Cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, oxonol dyes, rhodacyanine dyes, more preferably cyanine dyes, merocyanine dyes, oxonol dyes, particularly preferably cyanine dyes, A group consisting of a merocyanine dye.

For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine Soybean and Relativated Compounds-C.
yanine Dyes and Related Compounds, "John Wiley & Sons, Inc.-New York, London, 1964, DMSturmer," Heterocyclic Compounds-Special Topics. " In Heterocyclic Compounds-S
pecial topics inheterocyclic chemistry) ", 18th
Chapter, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rodd's Chemistry of Carbon Compounds".
ry of Carbon Compounds) ”2nd.Ed.vo1.IV, part B, 1
977, Chapter 15, 369-422, published by Elsevier Science Publishing Company Inc.
It is described in New York, etc. Preferred general formulas for dyes include those described in U.S. Pat. No. 5,994,051, pages 32-36, and U.S. Pat.
Examples thereof include those represented by the general formula described on pages 30 to 34 of the 47,236 specification. Preferred cyanine dyes, merocyanine dyes, and rhodacyanine dyes are those represented by the general formulas (XI), (XII), and (XIII) in US Pat. No. 5,340,694, columns 21 to 22 ( However, the number of n ¹² , n ¹⁵ , n ¹⁷ , and n ¹⁸ is not limited, and examples thereof include an integer of 0 or more (preferably 4 or less)). D ¹ is J
-It may or may not form an aggregate.

Next, L ¹ will be described. L ¹ represents a linking group (preferably a divalent linking group) or a single bond. L ¹
Is preferably a linking group. This linking group is
Preferably, it comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom.
Preferably an alkylene group (eg methylene, ethylene,
Trimethylene, tetramethylene, pentamethylene), arylene group (eg, phenylene, naphthylene), alkenylene group (eg, ethenylene, propenylene), alkynylene group (eg, ethynylene, propynylene), amide group, ester group, sulfamide group, sulfonate ester Group, ureido group, sulfonyl group, sulfinyl group,
Thioether group, ether group, carbonyl group, -N (V
^a )-(V ^a represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include W described above.) and a heterocyclic divalent group (for example, 6-chloro-1,3). , 5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group,
Quinoxaline-2,3-diyl group) is a combination of one or more of 0 to 100 carbon atoms, preferably 1 to 20 carbon atoms.

The above-mentioned linking group may further have the above-mentioned substituent represented by W. Further, these linking groups may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle).

The linking group is more preferably an alkylene group having 1 to 18 carbon atoms, and more preferably 1 to 10 carbon atoms (eg methylene, ethylene, trimethylene,
(Tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene), an arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), an alkenylene group having 2 to 10 carbon atoms (eg, ethenylene, propenylene), 2 carbon atoms. Alkenylene group of 10 to 10 (for example, ethynylene, bropinylene), an ether group, an amide group, an ester group, a sulfoamide group, a sulfonate ester group having 1 or 2 or more carbon atoms
It is a divalent linking group of 0. These may be substituted with W described above.

The linking group is more preferably a case where it does not contain a heteroatom other than an amide group or an ester group, and more preferably a case where it does not contain a heteroatom.

The above alkylene groups (eg, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene) are particularly preferable, and the number of carbon atoms is preferably 2-18, more preferably 5-10. , And particularly preferably 8 to 10. Further, it is particularly preferable that L ¹ is a linking group having a center of symmetry.

Q ¹ and r ¹ each represent an integer of 1 to 100. It is preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and particularly preferably 1. r
A plurality of L ¹ 's contained when ¹ is 2 or more may be different linking groups or single bonds, but preferably the same linking group or a single bond. q ¹ or r ¹ is 2
In the above cases, a plurality of D ¹ 's bonded to L ¹ 's must be the same dye chromophore.

Q ² represents an integer of 1 to 4, and that q ² is 2 or more means that D ¹ and D ¹ are linked by a plurality of linking groups. That is, D ¹ and D ¹ are each 1
It may be connected at several points or at a plurality of points (2 to 4 points, preferably 2 points). When q ² is 2 or more, a plurality of L ¹ may be the same or different. The case where they are the same is preferable. q ² is preferably 1 or 2, and more preferably 1.

L ¹ may be bonded at any part of D ¹ , but is preferably not a methine chain part. Preferably,
It is a case of binding at the N position of the basic nucleus or acidic nucleus, and more preferably a case of binding at the N position of the basic nucleus.

In the general formula (I), D ¹ is preferably a methine dye represented by the above general formulas (XI), (XII) and (XIII), more preferably the above general formula ( XI) and (XII) are methine dyes,
The methine dye represented by (XII) is particularly preferable.
The methine compounds represented by formulas (I), (XI), (XII) and (XIII) will be described in detail below.

In the general formulas (XI), (XII) and (XIII),
Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁵ and Z ¹⁷ represent a group of atoms necessary for forming a nitrogen-containing heterocycle, preferably a 5- or 6-membered nitrogen-containing heterocycle, and these rings are further condensed rings. You may have. Further, the condensed ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferable, and examples thereof include a hydrocarbon aromatic ring such as a benzene ring and a naphthalene ring, and a heteroaromatic ring such as a pyrazine ring and a thiophene ring.

The nitrogen-containing heterocycle formed by Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁵ and Z ¹⁷ is, for example, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline. Nuclear,
Selenazole nucleus, benzoselenazole nucleus, tellrazoline nucleus, tellurazole nucleus, benzoterrazole nucleus, 3,3-
Dialkyl indolenine nucleus (eg 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus,
2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus,
Examples thereof include a tetrazole nucleus and a pyrimidine nucleus, but preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenin), a benzimidazole nucleus, a 2-pyridine nucleus. , 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, more preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3 , 3-Dimethylindolenine) and benzimidazole nuclei, particularly preferably benzoxazole nuclei, benzothiazole nuclei, and benzimidazole nuclei, and most preferably benzoxazole nuclei and benzothiazole nuclei.

These nitrogen-containing heterocycles may be substituted or condensed with the substituent represented by W and the ring. Examples of preferable substituents include an alkyl group, an aryl group, an alkoxy group, a halogen atom, an aromatic ring condensation, a sulfo group, a carboxyl group and a hydroxyl group.

Specific examples of the heterocycle formed by Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁵ and Z ¹⁷ include US Pat.
40, 694, columns 23 to 24, Z ¹¹ , Z ¹² , and Z
^{The same} as those mentioned as examples of ¹³ , Z ¹⁴ and Z ¹⁶ can be mentioned. The substituent W on Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁵ and Z ¹⁷ is more preferably a halogen atom, an aromatic group or an aromatic ring condensation.

Z ¹⁴ , Z ¹⁴ 'and (N-R ¹⁴ ) q ¹¹ each represent a group of atoms necessary for forming a heterocyclic ring or an acyclic acidic terminal group. The heterocycle (preferably a 5- or 6-membered heterocycle) may be any, but an acidic nucleus is preferred. Here, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nuclei and acyclic acidic end groups can take the form of the acidic nuclei and acyclic acidic end groups of any common merocyanine dye. In a preferred form, Z ¹⁴ is a thiocarbonyl group, a carbonyl group,
An ester group, an acyl group, a carbamoyl group, a cyano group, and a sulfonyl group are more preferable, and a thiocarbonyl group and a carbonyl group are more preferable. Z ¹⁴ 'represents the remaining atomic group necessary for forming an acidic nucleus and an acyclic acidic end group. When forming an acyclic acidic terminal group, a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, a sulfonyl group and the like are preferable. q ¹¹ is 0 or 1, but is preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to here are, for example, "The Theory of the Photographic Process" (edited by James).
of the Photographic Process) 4th edition, Macmillan Publishing Company, 1977, pp. 198-200. Here, the acyclic acidic terminal group means an acidic or electron-accepting terminal group that does not form a ring. The acidic nucleus and the acyclic acidic terminal group are specifically described in US Pat. No. 3,567,719, 3,575,869, 3,804,634, and US Pat. No. 3,837,862, No. 4,00
No. 2,480, No. 4,925,777,
JP-A-3-167546, US Pat. No. 5,99
Examples thereof include those described in US Pat. No. 4,051 and US Pat. No. 5,747,236.

The acidic nucleus forms a heterocycle (preferably a 5- or 6-membered nitrogen-containing heterocycle) composed of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. And more preferably when forming a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Specifically, for example, 2-pyrazolin-5-one, pyrazolidine-3,5
-Dione, imidazolin-5-one, hydantoin, 2
Or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one, 2-thiooxazolicin-2,5-dione, 2-thiooxazoline-2,4-dione, isoxazoline- 5-on, 2
-Thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-
1,3-dione, thiophen-3-one, thiophene-
3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-
6,7-dihydrothiazolo [3,2-a] pyrimidine,
Cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-
Dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b ] Quinazolone, Pyrazolo [1,5-
a] benzimidazole, pyrazolopyridone, 1, 2,
3,4-tetrahydroquinoline-2,4-dione, 3-
Oxo-2,3-dihydrobenzo [d] thiophene-
1,1-sioxide, 3-dicyanomethine-2,3-
The core of dihydrobenzo [d] thiophene-1,1-dioxide may be mentioned.

Further, the carbonyl group or thiocarbonyl group forming these nuclei serves as a raw material for a nucleus having an exomethylene structure in which the active methylene position of the acidic nucleus is substituted, and an acyclic acidic terminal group. Examples include a nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene, and a nucleus obtained by repeating this, but the case where these are not substituted is preferable.

The above-mentioned substituent or ring represented by the substituent W may be substituted or condensed on the acidic nucleus and the acyclic acidic terminal group. Of the acidic nucleus and the acyclic acidic terminal group, the acidic nucleus is preferable.

The heterocyclic group formed by Z ¹⁴ and Z ¹⁴ 'and (N-R ¹⁴ ) q ¹¹ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline. -2,4-dione,
Thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-. On, rhodanine, barbituric acid, and 2-thiobarbituric acid, particularly preferably 2 or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine. Most preferably, it is rhodanine.

The heterocyclic group formed by Z ¹⁶ and Z ¹⁶ ′ and (N—R ¹⁶ ) q ¹² is the heterocyclic group formed by Z ¹⁴ and Z ¹⁴ ′ and (N—R ¹⁴ ) q ¹¹ described above. The same as those mentioned in the explanation of the ring group can be mentioned. Preferably include those excluding the above-mentioned Z ¹⁴ and Z ¹⁴ 'and ^{(N-R 1 4) q} 11 -oxo group from the acidic nuclei described in the description of the heterocyclic ring formed by, or thioxo group. More preferably,
An oxo group or a thioxo group is removed from the acidic nucleus mentioned as a specific example of the heterocyclic group formed by Z ¹⁴ and Z ¹⁴ 'and (N-R ¹⁴ ) q ¹¹ ;

More preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one,
2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4
-Dithione, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, and more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine,
Barbituric acid or 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-thiohydantoin, 2-oxazoline-
It is a 5-one or rhodanine from which a thioxo group or a thioxo group has been removed, and most preferably a rhodanine from which a thioxo group has been removed.

Q ¹² is 0 or 1, but is preferably 1.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom, an alkyl group, an aryl group,
And a heterocyclic group, preferably an alkyl group, an aryl group and a heterocyclic group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
Specific examples of the alkyl group, aryl group and heterocyclic group represented by R ¹⁵ , R ¹⁶ and R ¹⁷ include carbon atom 1
-18, preferably 1-7, particularly preferably 1-4 unsubstituted alkyl groups (e.g. methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (for example, an alkyl group in which W as the substituent is substituted) Is mentioned. Particularly, an alkyl group having an acid group described below is preferable. Preferably an aralkyl group (eg benzyl,
2-phenylethyl), unsaturated hydrocarbon group (for example, allyl group, vinyl group, that is, substituted alkyl group includes alkenyl group and alkynyl group), hydroxyalkyl group (for example, 2-hydroxy group). Ethyl, 3-hydroxypropyl), carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- ( 2-methoxyethoxy) ethyl), an aryloxyalkyl group (eg 2-
Phenoxyethyl, 2- (1-naphthoxy) ethyl),
Alkoxycarbonylalkyl groups (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl groups (eg 3-
Phenoxycarbonylpropyl), acyloxyalkyl group (eg 2-acetyloxyethyl), acylalkyl group (eg 2-acetylethyl), carbamoylalkyl group (eg 2-morpholinocarbonylethyl),
Sulfamoylalkyl group (eg N, N-dimethylsulfamoylmethyl), sulfoalkyl group (eg 2
-Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy]
Ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), Heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl groups (eg, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl groups (eg, acetylcarbamoylmethyl) Group), an acylsulfamoylalkyl group (for example, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group)}, a carbon number of 6 to 20, preferably a carbon number of 6 to 10 More preferably, an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms. (For example, the above-mentioned aryl group substituted with W mentioned as an example of the substituent may be mentioned. Specifically, p-methoxyphenyl group, p
-Methylphenyl group, p-chlorophenyl group and the like. ), 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms
0, more preferably an unsubstituted heterocyclic group having 4 to 8 carbon atoms (for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2 -Oxazolyl, 2
-Thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-
Pyrazyl, 2- (1,3,5-triazolyl), 3-
(1,2,4-triazolyl), 5-tetrazolyl),
A substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, the heterocyclic group substituted with W mentioned above as an example of the substituent is exemplified. Specific examples thereof include a 5-methyl-2-thienyl group and a 4-methoxy-2-pyridyl group.).

The groups represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are preferably unsubstituted alkyl groups,
It is a substituted alkyl group, and the substituted alkyl group is preferably an alkyl group having an acid group. Here, the acid group will be described. The acid group is a group having a dissociative proton.

Specifically, for example, sulfo group, carboxyl group, sulfato group, -CONHSO ₂ -group (sulfonylcarbamoyl group, carbonylsulfamoyl group),-
CONHCO- group (carbonylcarbamoyl group), -S
O ₂ NHSO ₂ — group (sulfonylsulfamoyl group), sulfonamide group, phosphono group, boronic acid group, phenolic hydroxyl group and the like may be a group capable of dissociating a proton depending on the pka of these and the surrounding pH. PH 5 for example
A proton-dissociable acidic group that dissociates by 90% or more between 12 and 12 is preferable. More preferably a sulfo group, a carboxyl group, -CONHSO ₂ - group, -CONHCO- group, -S
O ₂ NHSO ₂ — group, particularly preferably sulfo group,
It is a carboxyl group, most preferably a sulfo group.

L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , L
¹⁷ , L ¹⁸ , L ¹⁹ , L ²⁰ , L ²¹ , L ²² , L ²³ , L ²⁴ ,
L ²⁵ , L ²⁶ , L ²⁷ , L ²⁸ , L ²⁹ and L ³⁰ each independently represent a methine group. The methine group represented by L ^{11 to} L ³⁰ may have a substituent, and examples of the substituent include W described above. For example, substituted or unsubstituted C1 to C15, preferably C1 to C10, and particularly preferably C1 to C5.
Alkyl group (for example, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted carbon number 6 to 20, preferably carbon number 6 to 15, and more preferably carbon number 6 to 10.
Aryl group (e.g., phenyl, o-carboxyphenyl), a substituted or unsubstituted C3-20, preferably C4-15, more preferably C6-10 heterocyclic group (e.g., N, N-). Dimethyl barbituric acid group), halogen atom (for example, chlorine, bromine, iodine, fluorine),
An alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms (eg, methoxy,
Ethoxy), having 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (eg, methylamino, N, N-dimethylamino, N-methyl-
N-phenylamino, N-methylpiperazino), C1-15, preferably C1-10, more preferably C1-5 alkylthio groups (eg methylthio, ethylthio), C6-20, preferably 6 to 1 carbon atoms
2, and more preferably, an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. It may form a ring with another methine group, or may form a ring together with Z ^{11 to} Z ¹⁷ and R ^{11 to} R ¹⁷ . L ¹¹ , L ¹² , L ¹⁶ , L ¹⁷ , L ¹⁸ ,
L ¹⁹ , L ²² , L ²³ , L ²⁹ and L ³⁰ are preferably unsubstituted methine groups.

N ¹¹ , n ¹² , n ¹³ and n ¹⁴ each independently represent 0, 1, 2, 3 or 4. Preferably 0,
1, 2, 3 and more preferably 1, 2, 3
It is particularly preferably 2 or 3. Most preferably, n ¹¹ is 3, and most preferably n ¹² is 2.
When n ¹¹ , n ¹² , n ¹³ and n ¹⁴ are 2 or more, the methine group is repeated. Even if these methine groups are the same as each other,
It may be different. p ¹¹ , p ¹² , p ¹³ , p ¹⁴ and p ¹⁵
Each independently represent 0 or 1. It is preferably 0.

The position at which the dye chromophore D ¹ is linked to L ¹ may be any of the carbon atom portion or the N position of the basic nucleus of the dye chromophore, the N position of the acidic nucleus, the methine chain, etc.
It is preferably the carbon atom portion or N position of the basic nucleus, or the N position of the acidic nucleus, and more preferably the N position of the basic nucleus.
Position, or the N position of the acidic nucleus (ie, general formula (XI), (XI
In I) and (XIII), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ , R ¹⁶ or R ¹⁷ ), particularly preferably the N-position of the basic nucleus (ie,
In the general formulas (XI), (XII) and (XIII), R ¹¹ ,
R ¹² , R ¹³ , R ¹⁵ or R ¹⁷ ).

M ¹ , M ¹¹ , M ¹² and M ¹³ are included in the formula to indicate the presence of a cation or anion when required to neutralize the ionic charge of the dye. .
Typical cations are inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg calcium ion), ammonium ions (eg, Ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion,
1,8-diazabicyclo [5,4,0] -7-undecenium ion) and the like. The anion may be an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-chloro ion). Benzenesulfonate ion), aryldisulfonate ion (eg 1,3-hensensulfonate ion,
1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion,
Examples thereof include picrate ion, acetate ion, and trifluoromethanesulfonate ion. In addition, ionic polymers or other dyes having an opposite charge to the dye may be used.
Further, CO ₂ and SO ₃ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

M ¹ , m ¹¹ , m ¹² and m ¹³ represent a number of 0 or more necessary for balancing charges, preferably 0 to 4, more preferably 0 to 2 and in the molecule. It is 0 when forming a salt.

Further, in the present invention, the compound represented by the general formula (I) is a compound represented by the above general formula (XXI) or (XXII).
It is preferable that it is selected from the compounds represented by

In the general formulas (XXI) and (XXII), L
¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ , L ¹⁶ , L ¹⁷ , p ¹¹ ,
P ¹² , n ¹¹ , Z ¹¹ , Z ¹² , L ¹⁸ , L ¹⁹ , L ²⁰ , L ²¹ , p
Examples of ¹³ , q ¹¹ , n ¹² , Z ²³ , Z ¹⁴ , Z ¹⁴ ′, and R ¹⁴ include the same as those described in the general formulas (XI) and (XII). preferable. Examples of M ¹⁴ and m ¹⁴ and M ¹⁵ and m ¹⁵ are the same as those of M ¹ and m ¹ described above. Examples of R ²¹ are the same as those of the alkyl group, aryl group, or heterocyclic group excluding a hydrogen atom among those described for R ^{12 and the} like, and the same group is preferable. Examples of L ² and L ³ include the same groups as those described for L ¹ above except for a single bond,
The same is preferable.

Particularly preferred groups in the general formula (XXI)
The combination is n¹¹Is 2, Z¹¹, L¹¹, L¹², P¹¹Formed by
Basic nucleus, and Z¹², L¹⁶, L¹⁷, P¹²Formed by
Among the basic nuclei, one is the 4-quinoline nucleus and the other is the base nucleus.
Nzoxazole nucleus or benzothiazole nucleus (preferred
Or benzothiazole nucleus), or n¹¹Is 3,
Z ¹¹, L¹¹, L¹², P¹¹A basic nucleus formed by Z, and Z
¹², L¹⁶, L¹⁷, P¹²The basic nucleus formed by
Oxazole nucleus, or benzothiazole nucleus (preferably
At least one benzothiazole nucleus, more preferably
Are both benzothiazole nuclei). General formula
In (XXII), a particularly preferred combination is n¹²But
2, Z¹³, L¹⁸, L¹⁹, P¹³The basic nucleus formed in
Nzoxazole nucleus, or benzothiazole nucleus, Z¹⁴，
Z¹⁴', (N-R¹⁴) Q¹¹The acidic nuclei formed by
In the case of nin nucleus, or n¹²Is 3, Z¹³, L¹⁸, L¹⁹, P¹³
The basic nucleus formed by is a benzothiazole nucleus, Z¹⁴, Z
¹⁴', (N-R¹⁴) Q¹¹The acidic nuclei formed in
This is the case for nuclear weapons. General formulas (XXI) and (XXII)
It is preferably (XXII).

In the present invention, the compound represented by the general formula (I) is a compound represented by the above general formula (XXXIa), (XXXIb).
Alternatively, the case where it is selected from the compounds represented by (XXXII) is particularly preferable.

General formulas (XXXIa), (XXXIb) and (XXXI
In ^{I), Z 51, Z 52} , Z 53, Z 5 4 and Z ⁵⁵ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom (N-V ^80),
Or represents a carbon atom (CV ⁸¹ V ⁸² ). Where V ⁸⁰ and V
⁸¹ and V ⁸² represent a hydrogen atom or a substituent (for example, W described above), preferably an alkyl group similar to R ¹¹ and the like,
An aryl group or a heterocyclic group, more preferably an alkyl group. Z ⁵¹ and Z ⁵² are preferably oxygen atoms or sulfur atoms, more preferably at least one is a sulfur atom, and particularly preferably both are sulfur atoms. Z ⁵³ is preferably an oxygen atom or a sulfur atom, and more preferably a sulfur atom. Z ⁵⁴ is preferably an oxygen atom or a sulfur atom, and when n ⁵¹ is 1, more preferably an oxygen atom, and when n ⁵¹ is 2, further preferably a sulfur atom. Z ⁵⁵ is an oxygen atom, a sulfur atom, or a nitrogen atom (NV
⁸³ ). Here, V ⁸³ represents a hydrogen atom or a substituent (for example, W described above), preferably an alkyl group, an aryl group, or a heterocyclic group similar to R ¹¹ and the like, and more preferably an alkyl group.

'V ⁵¹ , V ⁵² , V ⁵³ , V ⁵⁴ , V ⁵⁵ , V ⁵⁶ ,
V ⁵⁷ , V ⁵⁸ , V ⁵⁹ , V ⁶⁰ , V ⁶¹ , V ⁶² , V ⁶³ , V ⁶⁴ , V
⁶⁵ , V ⁶⁶ , V ⁶⁷ , V ⁶⁸ , V ⁶⁹ , V ⁷⁰ , V ⁷¹ , and V ⁷² represent a hydrogen atom or a substituent (for example, W described above), and two adjacent substituents are They may be linked to each other to form a saturated or unsaturated condensed ring. Preferably,
Hydrogen atom, alkyl group (eg methyl), aryl group (eg phenyl), aromatic heterocyclic group (eg 1-pyrrolyl, 2-thienyl), alkoxy group (eg methoxy), alkylthio group (eg methylthio), cyano group, Acyl group (eg acetyl), alkoxycarbonyl group (eg methoxycarbonyl), halogen atom (eg fluorine, chlorine, bromine, iodine) or adjacent 2
In this case, the two substituents are linked to each other to form an unsaturated condensed ring (for example, a benzene ring).

R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ represent an alkyl group, an aryl group, or a heterocyclic group. However, two R
^{One of 52} and R ⁵³ cooperates to form L ⁵ . Preferable examples of R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ are the same as those of R ¹¹ and the like, and the similar ones are preferable. R ⁵⁴ is more preferably a carboxyalkyl group, and most preferably a carboxymethyl group.

L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ , L
⁵⁷ , L ⁵⁸ , L ⁵⁹ , L ⁶⁰ , L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ ,
L ⁶⁵ and L ⁶⁶ each represent a methine group, and L ¹³ and
Examples thereof include those similar to L ¹⁴ , L ¹⁵ , L ²⁰ , L ²¹ and the like,
The same is preferable.

L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ , L
^{For 57} , L ⁵² and L ⁵⁴ , L ⁵³ and L ⁵⁵ , L ⁵⁴ and L ⁵⁶ ,
Alternatively, it is preferable that at least one of L ⁵² , L ⁵⁴ and L ⁵⁶ is bonded to each other to form a ring. The ring may be any ring, but is preferably a 5- or 6-membered hydrocarbon ring or a heterocycle. More preferably, it is a 5- or 6-membered hydrocarbon ring. Of the above, the methine group is 3
When two together form a ring, it preferably has a structure in which two 5- or 6-membered hydrocarbon rings or heterocycles are fused, and more preferably two or five- or 6-membered hydrocarbon rings are fused. It is a structure. Further, these rings may be substituted with the above-mentioned substituent represented by W. Specific preferred ring structures are shown below.

[0082]

[Chemical 21]

The above-mentioned ring structure may be substituted with a substituent (eg, W) at any position. The following ring structures are particularly preferred.

[0084]

[Chemical formula 22]

L ⁵¹ , L ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ , L
Of ^57, the methine group that does not form a ring is preferably an unsubstituted methine group.

For L ⁵⁸ , L ⁵⁹ , L ⁶⁰ , L ⁶¹ and L ⁶² ,
L ⁵⁶ , L ⁵⁹ , L ⁶¹ and L ⁶² are preferably unsubstituted methine groups, L ⁶⁰ is preferably an unsubstituted methine group or a methine group substituted with an alkyl group, and more preferably a methyl group is substituted. It is a methine group. L ⁶³ , L ⁶⁴ ,
Regarding L ⁶⁵ and L ⁶⁶ , when n ⁵¹ is 1, L ⁶³ and L ^66
64 and L ⁶⁶ are preferably unsubstituted methine groups, and L ⁶⁵
Is preferably an unsubstituted methine group or a methine group substituted with an alkyl group, and more preferably a methine group substituted with a methyl group. When n ⁵¹ is 2, L ⁶⁴ and L ⁶⁵
Are repeated but need not be the same, and are preferably all unsubstituted, or L ^{64 to} L ⁶⁶ are the above L ⁵¹ , L
^{This is a} case where at least one ring described as a preferable case for ⁵² , L ⁵³ , L ⁵⁴ , L ⁵⁵ , L ⁵⁶ , and L ⁵⁷ is formed, and the methine group not forming a ring is an unsubstituted methine group. n ⁵¹ represents 1 or 2, but is preferably 1.

M ⁵¹ and m ⁵¹ , M ⁵² and m ⁵² , and M ⁵³ and m ⁵³
Are the same as the above M ¹ and m ¹ , respectively. Examples of L ⁴ , L ⁵ , and L ^{6 which} are the same as the linking group excluding the single bond among those described for L ¹ above, and the same ones are preferable.

General formulas (XXXIa), (XXXIb), and (XXXI
Among I), (XXXIa) and (XXXII) are preferable, and (XXXII) is more preferable.

Specific examples of particularly preferable dye compounds represented by formulas (A) and (I) used in the present invention are shown below, but the present invention is not limited thereto. First, specific examples of the dye chromophore D ¹ , D ^a or D ^b will be shown. (Charge-balancing counterions are omitted. Any possible counterion may be present.)

[0090]

[Chemical formula 23]

[0091]

[Chemical formula 24]

[0092]

[Chemical 25]

[0093]

[Chemical formula 26]

[0094]

[Chemical 27]

[0095]

[Chemical 28]

[0096]

[Chemical 29]

[0097]

[Chemical 30]

[0098]

[Chemical 31]

[0099]

[Chemical 32]

[0100]

[Chemical 33]

Next, specific examples of the linking group —L ¹ — or —L ^a — will be shown. (Charge-balancing counterions are omitted. Any possible counterion may be present.)

[0102]

[Chemical 34]

[0103]

[Chemical 35]

[0104]

[Chemical 36]

[0105]

[Chemical 37]

[0106]

[Chemical 38]

[0107]

[Chemical Formula 39]

Specific examples of the compounds represented by formula (A) or (I) used in the present invention are shown below.

Specific examples of D ¹ -L ¹ -D ¹ M ¹ m ¹ (when q ¹ and r ¹ are both 1 in the general formula (I)) are shown below. It is linked to L ¹ at the position of * in each structural formula of DS shown in [Chemical Formula 13] to [Chemical Formula 29].

[0110]

[Table 1]

[0111]

[Table 2]

The following two D¹Is two L¹Connected by
(In the general formula (I), q ²Is 2, q¹And r¹
When 1 is 1). The DS-44 is *
It is connected to L-55 at the position.

[0113]

[Chemical 40]

Specific examples of the case where there are three or more D ^1's (in the general formula (I), q ² is 1, one of q ¹ and r ¹ is 1 and the other is 2) Show. It is linked to L ¹ at the position of * in the structural formula of DS shown in [Chemical Formula 13] to [Chemical Formula 29].

[0115]

[Chemical 41]

[0116] (In the general formula (A), q ^a, when q ^b and r ^a are both 1) below ^{D a -L a -D b M a} m a a specific example of. D shown in [Chemical Formula 13] to [Chemical Formula 29]
It is linked to L ^a at the position of * in the structural formula of S.

[0117]

[Table 3]

The sensitizing dye compounds represented by the general formula (A) or (I) used in the present invention are those described by FM Harmer, "Heterocyclic Compounds-Cyanine Soybean and Relativated." Heterocyclic Compounds-Cyanine Dyes and Re
Compounded Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer (DMStur)
mer) "Heterocyclic Compounds-Special topics in h
eterocyclic chemistry ", Chapter 18, Section 14, pages 482-515, John Wiley & Sons-New York, London, 1977," Rods Chemistry of Carbon. " Compounds (Rodd's Chemistry of Carbon C
ompounds) ”2nd. Ed. vol.IV, part B, 1977, first issue
Chapter 5, Pages 369-422, Elsevier, Science Public Company, Inc. (Elisevier Scienc
ePublishing Company Inc.), published by New York, and the like.

In the present invention, the sensitizing dyes represented by formulas (A) and (I) may be used alone, or other sensitizing dyes may be used in combination. Preferable examples of the dye used in combination include a cyanine dye, a merocyanine dye, a rhodacyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye and a styryl dye. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are particularly preferred. For more information on these dyes, see FMHarm.
er), “Heterocyclic Compounds-Cyanine and Relative Compounds (Hetero
cyclic Compounds-Cyanine Dyes and Related Compound
s) ", John Wile and Sons
y &amp; Sons) -New York, London, 196
DMSturmer, 4th edition, "Heterocyclic Compounds-Special topics in heteroc"
yclic chemistry), Chapter 18, Section 14, pp. 482-515.

Specific examples of dyes preferably used in combination include US Pat. No. 5,994,051 Nos. 32-4.
The sensitizing dyes described on page 4 and the general formulas on pages 30 to 39 of US Pat. Further, preferable cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat.
General formula (X
I), (XII) and (XIII) (however, n
^{The number of 12} , n ¹⁵ , n ¹⁷ , and n ¹⁸ is not limited and is an integer of 0 or more (preferably 4 or less). ) Is mentioned.

These sensitizing dyes to be used in combination may be used alone or in combination of two or more, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. A typical example thereof is US Pat. No. 2,688,545.
No. 2,977,229, No. 3,
397,060, 3,522,052, 3,527,641 and 3,61.
No. 7,293, No. 3,628,964, No. 3,666,480, and No. 3,67.
No. 2,898, No. 3,679,428, No. 3,303,377, No. 3,76.
No. 9,301, No. 3,814,609, No. 3,837,862, No. 4,02
6,707, British Patent 1,344,281, 1,507,803, and Japanese Examined Patent Publication No. 43.
-49336, 53-12375, 52-110618, 52-109925.

In addition to the above-mentioned sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. Supersensitizers useful in spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts), and strong. A combination of a color sensitizer and a sensitizing dye is described in, for example, US Pat. No. 3,511,664.
No. 3,615,613, No. 3,
No. 615,632, No. 3,615,641, No. 4,596,767, No. 4,94.
No. 5,038, No. 4,965,182, No. 4,965,182, No. 2,93.
No. 3,390, No. 3,635,721, No. 3,743,510, No. 3,61.
No. 7,295, No. 3,635,721 and the like, and the method described in the above-mentioned patent is also preferable for its usage.

The sensitizing dyes represented by the general formulas (A) and (I) used in the present invention (also other sensitizing dyes,
The same applies to the supersensitizer) may be added to the silver halide emulsion used in the present invention at any step in the preparation of an emulsion which has heretofore been found to be useful. For example, US Pat. Nos. 2,735,766, 3,628,960, and 4,18.
No. 3,756, No. 4,225,666, JP-A No. 58-184142, and No. 60-196.
As disclosed in Japanese Patent Publication No. 749, etc., the time before the grain formation step and / or desalting of the silver halide, the time during the desalting step and / or after the desalting until the start of chemical ripening, As disclosed in Japanese Laid-Open Patent Publication No. 58-113920, the compound may be added at any time or step immediately before chemical ripening or during the step, or after the chemical aging and before the emulsion is coated. Good. Also, US Pat. No. 4,22
No. 5,666, JP-A No. 58-7629, etc., the same compound alone or in combination with a compound having a different structure, for example, during the grain forming step and the chemical aging step. Alternatively, it may be added in a divided manner such as after completion of the chemical aging or before or after the chemical aging or after completion of the process, and the compound to be added in a divided manner and the kind of the combination of compounds may be changed. May be added.

The sensitizing dyes represented by the general formulas (A) and (I) used in the present invention (and other sensitizing dyes,
The same applies to the supersensitizer), but the addition amount can be a desired amount depending on the sensitivity and fog performance, and the shape and size of the silver halide grains. The amount is preferably 10 ^-6 to 1 mol, more preferably 10 ^-4 to 10 ^-1 mol.

The sensitizing dyes represented by formulas (A) and (I) used in the present invention (and other sensitizing dyes,
The same applies to the supersensitizer) can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method for adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. A method of adding a dispersion to an emulsion, a method of dispersing in a water-soluble solvent and adding this dispersion to an emulsion as described in JP-B-46-24185, US Pat. No. 3,822,135 JP-A-51-74624, wherein a compound is dissolved in a surfactant and the solution is added to an emulsion as described in JP-A-51-74624.
As disclosed in JP-A No. 6-187242, a method of dissolving using a compound for red-shifting and adding the solution to an emulsion, JP-A-5-58138.
As described in JP-A-0-80826, a method of dissolving the compound in an acid containing substantially no water and adding the solution to the emulsion is used. Other additions to the emulsion are described in U.S. Pat. Nos. 2,912,343 and 3,34.
The methods described in No. 2,605, No. 2,996,287, No. 3,429,835, etc. are also used.

The method of using the sensitizing dye that can be used in combination with the sensitizing dye compounds represented by the general formulas (A) and (I) has been described above, but will be further described. The sensitizing dye that can be used in combination in the present invention is capable of spectrally sensitizing silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for spectral characteristics of an exposure light source. A sensitizing dye having a can be advantageously selected. Regarding the sensitizing dye and the addition method, JP-A-11-65
Paragraph Nos. 0103 to 0109 of Japanese Patent Application No. 021, JP-A-1
No. 0-186572, the compound represented by the general formula (II), the dye represented by the general formula (I) in JP-A No. 11-119374 and paragraph No. 0106, US Patent No. 5,5.
No. 10,236, No. 3,871,887, the dye described in Example 5, the dyes disclosed in JP-A-2-96131 and JP-A-59-48753, and European patents. No. 19 of Publication No. 0803764A1
Page 38, Line 38 to Page 20, Line 35, Japanese Patent Application No. 2000-868.
No. 65, Japanese Patent Application No. 2000-102560, and the like. These sensitizing dyes may be used alone or in combination of two or more kinds. In the present invention, the sensitizing dye is added to the silver halide emulsion preferably after the desalting step and before coating, more preferably after the desalting step and before the start of chemical ripening. The addition amount of the sensitizing dye used in the present invention can be a desired amount according to the sensitivity and the performance of fog, but it is preferably 10 ^-6 to 1 mol per 1 mol of silver halide in the photosensitive layer. , And more preferably 10 ⁻⁴ to 10 ⁻¹ mol.

In the present invention, a supersensitizer can be used in order to improve the spectral sensitization efficiency. Examples of the supersensitizer used in the present invention include European Patent Publication No. 587,3.
38, US Pat. No. 3,877,943,
No. 4,873,184, JP-A-5-3414.
No. 32, No. 11-109547, No. 10-1
Examples thereof include the compounds described in Japanese Patent No. 11543. The photosensitive silver halide grains in the present invention are preferably chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method or a tellurium sensitizing method. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds, for example, the compounds described in JP-A No. 7-128768 can be used. In the present invention, tellurium sensitization is particularly preferable, and compounds described in the literature of paragraph No. 0030 of JP-A No. 11-65021, and the general formulas (II) and (II in JP-A No. 5-313284 are described.
The compounds represented by I) and (IV) are more preferred.

In the present invention, the chemical sensitization can be carried out at any time after the grain formation and before the coating, (1)
After desalting, (2) before spectral sensitization, (3) simultaneously with spectral sensitization,
There may be (4) after spectral sensitization, (5) immediately before coating, and the like. In particular, (4) it is preferably performed after spectral sensitization.

The photothermographic material of the invention contains an organic silver salt. The organic silver salt that can be used in the present invention is relatively stable to light, but at 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated above. The organic silver salt may be any organic substance containing a source capable of reducing silver ions, but is characterized by containing 40 mol% or more and 85 mol% or less of silver behenate, and 53 mol% or more and 8 mol% or more.
It is preferable to contain 0 mol% or less, and 58 mol% or more 75
It is particularly preferable that the content is not more than mol%. As the silver salt of other organic acid, a silver salt of a long-chain fatty carboxylic acid having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms is particularly preferable. Complexes of organic or inorganic silver salts in which the ligand has a complex stability constant in the range of 4.0 to 10.0 are also preferable. Regarding such a non-photosensitive organic silver salt, JP-A-10-62899, paragraphs 0048 to 0049, European Patent Publication No. 0803.
No. 1864, line 24 to page 19, line 37, European Patent Publication No. 0962812A1, JP-A-11-349591, JP-A-2000-7683, and JP-A-2000-72711. There is. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. As preferred examples of the silver salt of an aliphatic carboxylic acid, in addition to the above-mentioned silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, It includes silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof. The organic silver salt as the silver supplying substance can preferably constitute about 5 to 30% by mass of the image forming layer.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, and may be cubic, rectangular parallelepiped, rod-shaped, needle-shaped, flat plate-shaped, and flaky. Are relatively preferable. Cubic, rectangular parallelepiped, rod-shaped, and needle-shaped organic silver salts are defined as follows. The organic acid silver salt is observed with an electron microscope, the shape of the organic silver salt particles is approximated to a rectangular parallelepiped, and the sides of the rectangular parallelepiped are defined as a, b, and c (a ≦ b ≦ c). Cube is 0.9
Particles in the range of ≦ a / c ≦ 1.0. Rectangular particles mean 0.2 ≦ a / c <0.9 and 0.2 ≦ b / c <1.
Refers to particles in the 0 range. Rod-shaped particles mean 0.1 ≦ a / c <
It refers to particles in the range of 0.2 and 0.1 ≦ b / c <0.3. Needle-shaped particles mean a / c <0.1 and b / c <0.1
Say particles. The shape of the organic silver salt more preferable in the present invention is acicular particles or rod-shaped particles, and acicular particles are most preferable.
The inversely proportional relationship between the size of silver salt crystal grains and their covering power is well known in the field of silver halide photographic light-sensitive materials. This relationship also holds true for the photothermographic material of the present invention, which means that if the organic silver salt particles forming the image forming portion of the photothermographic material are large, the covering power is small and the image density is low. Therefore, it is preferable to reduce the size of the organic silver salt. In the present invention, the minor axis is 0.01 μm or more and 0.20 μm or less, and the major axis is 0.10 μm or more and 5.0 μm
The short axis is preferably 0.01 μm or more and 0.15 μm or less, and the long axis is 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodisperse. Monodisperse is preferably 100% or less, more preferably 80% or less, still more preferably 50%, of 100% of the value obtained by dividing the standard deviation of the length of each of the minor axis and the major axis by each of the minor axis and the major axis. It is the following. The shape of the organic silver salt can be measured by a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the 100 fraction (variation coefficient) of the value divided by the volume-loaded average diameter is preferably 100% or less. , More preferably 80% or less, further preferably 50% or less. As a measuring method, for example, the particle size (volume-weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with a laser beam and obtaining an autocorrelation function for the time change of the scattered light fluctuation You can

The organic silver salt which can be used in the present invention is prepared by forming particles in a water solvent, followed by drying and dispersing in a solvent such as MEK. Oxygen partial pressure is 15 vol% in air flow type flash jet dryer
It is preferably 0.01 vol% or more, more preferably 10 vol% or less and 0.01 vol% or more.

[0132] While the organic silver salt can be used in a desired amount, preferably 0.1-5 g / m ² of silver coating amount, more preferably from 1 to 3 g / m ^2.

The photothermographic material of the present invention contains a photosensitive silver halide. The method of forming the photosensitive silver halide used in the present invention is well known in the art, and described in, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458. Can be used. As a specific method which can be used in the present invention, a method of converting a part of silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin, Alternatively, a method can be used in which a photosensitive silver halide grain is prepared by adding a silver-providing compound and a halogen-providing compound into another polymer solution and then mixed with an organic silver salt. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is
It is preferably small for the purpose of suppressing white turbidity after image formation, and specifically, it is 0.0001 μm or more and 0.15 μm or more.
m or less, more preferably 0.02 μm or more and 0.10 μm
The following is good. If the silver halide grain size is too small, the sensitivity may be insufficient, and if it is too large, the haze of the light-sensitive material may increase. The term "grain size" as used herein means the length of the edges of silver halide grains when the silver halide grains are cubic or octahedral so-called normal crystals. Further, when the silver halide grains are tabular grains, it means the diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other non-normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it means the diameter when considering a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Examples thereof include octahedra, tabular grains, spherical grains, rod-shaped grains and potato-shaped grains. In the present invention, cubic grains and tabular grains are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1.
1 is good. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (Miller index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the {100} plane, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, may be high. preferable. The ratio is preferably 50% or more, and 65
% Or more is more preferable, and 80% or more is further preferable. The ratio of Miller index {100} planes is based on the adsorption dependence of {111} planes and {100} planes in the adsorption of sensitizing dyes.
T. Tani; J. Imaging Sci., 29, 165 (1985). The halogen composition of the photosensitive silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide, In the present invention, silver bromide or silver iodobromide can be preferably used. Silver iodobromide is particularly preferred, and the silver iodide content is 0.1.
The content is preferably in the range of mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%. The distribution of the halogen composition in the grain may be uniform, the halogen composition may be changed stepwise, or the halogen composition may be continuously changed, but a preferable example is the silver iodide content in the grain. High silver iodobromide grains can be used. Further, preferably, silver halide grains having a core / shell structure can be used. As the structure, core / shell particles having preferably a 2- to 5-fold structure, more preferably a 2- to 4-fold structure, can be used.

The photosensitive silver halide grains used in the present invention preferably contain at least one metal complex selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt, mercury or iron. One kind of these metal complexes may be used, or two or more kinds of the same metal complex and different metal complexes may be used in combination. Preferred content is silver 1
The range of 1 nanomol (nmol) to 10 mmol (mmol) is preferable, and 10 nanomol (nmo) is preferable.
More preferably, the range is from 1) to 100 micromolar (μmol). As a specific structure of the metal complex, JP-A-7-
A metal complex having a structure described in Japanese Patent No. 225449 or the like can be used. A hexacyano metal complex can be preferably used as the compound of cobalt or iron. Specific examples thereof include, but are not limited to, ferricyanate ion, ferrocyanate ion, and hexacyanocobaltate ion. The metal complex-containing phase in the silver halide may be uniform, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration, and is not particularly limited.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method, but in the present invention, they may or may not be desalted. .

The photosensitive silver halide grain in the invention is preferably chemically sensitized. As a preferable chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, or a tellurium sensitization method can be used as well known in the art. Further, a noble metal sensitization method such as a gold compound, platinum, palladium, or iridium compound or a reduction sensitization method can be used. Known compounds can be used as the compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, and the compounds described in JP-A No. 7-128768 can be used.

The amount of the photosensitive silver halide used in the present invention is preferably 0.01 mol or more and 0.5 mol or less, and 0.02 or less, with respect to 1 mol of the organic silver salt.
The amount is more preferably 0.3 mol or more and 0.3 mol or less, particularly preferably 0.03 mol or more and 0.25 mol or less. Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and the organic silver salt, the prepared silver halide grains and the organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer, etc. Or a method of preparing an organic silver salt by mixing the photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, but the effect of the present invention is sufficient. There is no particular limitation as long as it appears.

As a method for preparing silver halide used in the present invention, a so-called halide method in which a part of silver of an organic silver salt is halogenated with an organic or inorganic halide is also preferably used. The organic halide used here may be any compound as long as it is a compound which reacts with an organic silver salt to produce a silver halide, but may be N-halogenoimide (N-bromosuccinimide or the like), halogenated quaternary nitrogen compound ( (Tetrabutylammonium bromide, etc.), an association of a quaternary nitrogen salt with a halogen molecule (pyridinium perbromide), and the like. The inorganic halogen compound may be any compound as long as it is a compound capable of reacting with an organic silver salt to form a silver halide, and an alkali metal halide or ammonium (sodium chloride, lithium bromide, potassium iodide, ammonium bromide, etc.). ), An alkaline earth metal halide (calcium bromide, magnesium chloride, etc.), a transition metal halide (ferric chloride, cupric bromide, etc.), a metal complex having a halogen ligand (sodium iridate bromide). , Ammonium rhodate, etc.), halogen molecules (bromine, chlorine, iodine), etc. Further, a desired organic / inorganic halide may be used in combination. The amount of the halide added during the halidation is preferably 1 mmol to 500 mmol as a halogen atom per mol of the organic silver salt, and 10 mmol to 25 mmol.
0 mmol is more preferred.

In the heat-developable light-sensitive material of the present invention, it is preferable to add a color tone agent, and the color tone agent is described in JP-A-10-6289.
No. 9, paragraphs 0054-0055, European Patent Publication No. 0
No. 803764A1, page 21, lines 23 to 48, Japanese Patent Application No. 10-213487, particularly phthalazinones, phthalazines, phthalazinone derivatives or metal salts such as 4- (1-naphthyl) phthalazinone, 6
-Chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione); phthalazinones and phthalic acids (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and Tetrachlorophthalic anhydride); phthalazines (phthalazine, phthalazine derivatives or metal salts; for example, 4- (1-naphthyl) phthalazine, 6-isopropylphthalazine, 6-t-butylflatadine, 6-chlorophthalazine. , 5,7-dimethoxyphthalazine and 2,3
-Dihydrophthalazine); a combination of phthalazines and phthalic acids is preferable, and a combination of phthalazines and phthalic acids is particularly preferable. The toning agent is preferably contained in an amount of 0.1 to 50% mol, and more preferably 0.5 to 20% mol, per mol of silver on the surface having the image forming layer.

The photothermographic material of the invention contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt may be any substance (preferably organic substance) that reduces silver ions to metallic silver. Such a reducing agent is disclosed in JP-A-11-
65021, paragraphs 0043 to 0045, and European Patent Publication No. 0803764A1, page 7, line 34.
It is listed on page 18, line 12. In the present invention, the reducing agent is preferably a hindered phenol reducing agent or a bisphenol reducing agent, more preferably a compound represented by the following general formula (R).

[0142]

[Chemical 42]

(In the general formula (R), R ¹¹ and R ¹¹ ′ each independently represents an alkyl group having 1 to 20 carbon atoms. R ¹² and R ¹² ′ can each independently be replaced by a hydrogen atom or a benzene ring. Do .L representing the substituent, -S- group, or, CHR ¹³ - .X ¹ and X ¹ .R ¹³ represents a group represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms' are each independently hydrogen Represents a group capable of substituting on an atom or a benzene ring.)

The general formula (R) will be described in detail. R
¹¹ and R ¹¹ 'each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the substituent of the alkyl group is not particularly limited, but preferably an aryl group,
Hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonamide group, sulfonyl group, phosphoryl group, acyl group,
Examples thereof include a carbamoyl group, an ester group and a halogen atom.

R ¹² and R ¹² ′ each independently represent a hydrogen atom or a substituent capable of substituting on a benzene ring, and X ¹ and X ¹ ′ each independently represent a hydrogen atom or a group capable of substituting on a benzene ring. Preferable examples of the group capable of substituting on the benzene ring include an alkyl group, an aryl group, a halogen atom, an alkoxy group and an acylamino group.

L represents a --S-- group or a --CHR ¹³ -group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may have a substituent. R ¹³
Specific examples of the unsubstituted alkyl group of are methyl group, ethyl group,
Examples thereof include 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. Examples of the substituent of the alkyl group are the same as the substituents of R ¹¹ , and include a halogen atom, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acylamino group, a sulfonamide group, a sulfonyl group, a phosphoryl group, an oxycarbonyl group, Examples thereof include a carbamoyl group and a sulfamoyl group.

R¹¹And R¹¹'Preferably as carbon number
It is a secondary or tertiary alkyl group of 3 to 15,
Include isopropyl group, isobutyl group, t-butyl group, t
-Amyl group, t-octyl group, cyclohexyl group, cyclo
Lopentyl group, 1-methylcyclohexyl group, 1-methyl
Examples thereof include a rucyclopropyl group. R¹¹and
R ¹¹More preferably as', a tertiary alkane having 4 to 12 carbon atoms.
Kill groups, among them, t-butyl group, t-amyl group, 1
-Methylcyclohexyl group is more preferable, and t-butyl is
Groups are most preferred.

R ¹² and R ¹² ′ are preferably alkyl groups having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, isopropyl group, t-
Butyl group, t-amyl group, cyclohexyl group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group,
Examples include methoxyethyl group. More preferably, methyl group, ethyl group, propyl group, isopropyl group, t-
It is a butyl group. X ¹ and X ¹ ′ are preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom.

L is preferably a --CHR ¹³ --group. R
¹³ is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and the alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a 2,4,4-trimethylpentyl group. Particularly preferred as R ¹³ is a hydrogen atom, a methyl group, a propyl group or an isopropyl group.

R¹³When is a hydrogen atom, R¹²And R
¹²'Is preferably an alkyl group having 2 to 5 carbon atoms,
A tyl group and a propyl group are more preferable, and an ethyl group is the most preferable.
Good R¹³Is a primary or secondary alky having 1 to 8 carbon atoms
R is a radical¹²And R ¹²'Is preferably a methyl group
Yes. R¹³A C1-C8 primary or secondary alkyl group
Are methyl group, ethyl group, propyl group, isopropyl group
Group, more preferably a methyl group, an ethyl group, a propyl group
Is more preferable. R¹¹, R¹¹’、 R¹²And R¹²’Gay
When the shift is also a methyl group, R¹³Is a secondary alkyl
It is preferably a group. In this case R¹³Secondary alkyl
As the group, isopropyl group, isobutyl group, 1-ethyl group
Pentyl group is preferable, and isopropyl group is more preferable.
Yes.

The specific examples of the reducing agent of the present invention including the compounds represented by the general formula (R) of the present invention are shown below.
The present invention is not limited to these.

[0152]

[Chemical 43]

[0153]

[Chemical 44]

[0154]

[Chemical formula 45]

In the present invention, the reducing agent is added in an amount of 0.01
~ 5.0 g / m ² , preferably 0.1 ~ 3.0
It is more preferably g / m ² , and is 0.2 to 1.8 g.
/ M ² is more preferable, and 0.5 to 1.5 g /
It is particularly preferably m ² . It is preferably contained in an amount of 5 to 50% by mol, and more preferably 10 to 40% by mol, based on 1 mol of silver on the surface having the image forming layer. The reducing agent is preferably contained in the image forming layer.

The reducing agent may be contained in the coating solution and contained in the light-sensitive material by any method such as a solution form, an emulsified dispersion form and a solid fine particle dispersion form. Well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion A method of producing the same can be given.

As the solid fine particle dispersion method, a reducing agent powder is dispersed in a suitable solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves to obtain a solid dispersion. There is a method of creating. At that time, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three different isopropyl group substitution positions) or the like) may be used. Good. The water dispersion may contain a preservative (for example, benzoisothiazolinone sodium salt).

Next, the development accelerator that can be contained in the photothermographic material of the invention will be described. As the development accelerator, any compound can be used as long as it is a compound that accelerates development in thermal development. So-called reducing agents can be used. The development accelerator is 90% with respect to the case where the exposure amount required to obtain a blackening density = 1.0 when added in a molar ratio of 10% with respect to the main reducing agent is not added.
The following compounds. It is preferably a compound in which the molar ratio to the main reducing agent is 5%, more preferably 2%, and the exposure amount required to obtain a blackening density = 1.0 is 90% or less compared to the case where no addition is made. .

As a development accelerator, JP-A-2000-2672.
No. 22, JP-A-2000-330234, etc., a sulfonamidephenol-based compound represented by the general formula (A), and a hinder represented by the general formula (II) described in JP-A No. 2001-92075. Dephenol compounds, JP-A-10-62895 and JP-A-11-1
General formula (I) described in Japanese Patent No. 5116, etc., Japanese Patent Application No. 200
A hydrazine compound represented by the general formula (I) described in JP-A-1-074278, Japanese Patent Application No. 2000-76240.
Phenol-based or naphthol-based compounds represented by the general formula (2) described in the specification are preferably used. These development accelerators are used in an amount of 0.1-2 with respect to the reducing agent.
It is used in the range of 0 mol%, preferably in the range of 0.5 to 10 mol%, and more preferably in the range of 1 to 5 mol%. The method of introducing into the light-sensitive material may be the same as that of the reducing agent, but it is particularly preferable to add it as a solid dispersion or an emulsion dispersion. When added as an emulsified dispersion, it is added as an emulsified dispersion dispersed using a high-boiling solvent and a low-boiling auxiliary solvent that are solid at room temperature, or as a so-called oilless emulsified dispersion that does not use a high-boiling solvent. It is preferable to add. In the present invention, among the above-mentioned development accelerators, the hydrazine-based compound represented by the general formula (1) described in Japanese Patent Application No. 2001-074278 and the general one described in Japanese Patent Application No. 2000-76240. The phenol-based or naphthol-based compound represented by the formula (2) is particularly preferable. Preferred specific examples of the development accelerator of the invention are to be described below. The present invention is not limited to these.

[0160]

[Chemical formula 46]

[0161]

[Chemical 47]

The binder of the photosensitive layer in the photothermographic material of the present invention is a natural or synthetic resin such as gelatin, polyvinyl butyral, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene, polyacrylonitrile. , Polycarbonate, butylethyl cellulose, methacrylate copolymers, maleic anhydride copolymers, polystyrene and butadiene-styrene copolymers, etc. can be used. It is preferable to use 50% by mass or more of polyvinyl butyral. Of course, copolymers and terpolymers are also included. A preferable amount of polyvinyl butyral as a binder is 50% by mass or more and 100% by mass or less, and more preferably 7% by mass or less.
It is 0 mass% or more and 100 mass% or less. The Tg of the binder in the photosensitive layer is preferably in the range of 40 ° C to 90 ° C, more preferably 50 ° C to 80 ° C. The total amount of binder in the photosensitive layer according to the invention is used in an amount sufficient to hold the components therein. That is, it is used within a range effective to function as a binder. The effective range can be appropriately determined by those skilled in the art. As a guide for holding at least the organic silver salt, the ratio of the binder to the organic silver salt is 15: 1 to 1: 3 by mass ratio, and particularly 8:
The range of 1 to 1: 2 is preferable.

The silver halide emulsion used in the present invention or /
And the organic silver salts can be further protected against the formation of additional fog and stabilized against loss of sensitivity during storage by antifoggants, stabilizers and stabilizer precursors. Suitable antifoggants, stabilizers and stabilizer precursors which can be used alone or in combination are the thiazoniums described in US Pat. Nos. 2,131,038 and 2,694,716. salt,
U.S. Pat. Nos. 2,886,437 and 2,
Azaindene described in Japanese Patent No. 444,605, JP-A-9-329865 and US Pat. No. 6,083,68.
Compounds described in US Pat. No. 1,728,6
63, the mercury salt described in US Pat. No. 3,287,
Urazol as described in US Pat. No. 135, US Pat.
35,652, sulfocatechol, British Patent 623,448, oxime, nitrone, nitroindazole, U.S. Pat. No. 2,839,4.
Polyvalent metal salts described in No. 05, US Pat. No. 3,22
No. 0,839, the thiuronium salt, US Pat. Nos. 2,566,263 and 2,597,
915, palladium, platinum and gold salts,
U.S. Pat. No. 4,108,665 and 4,
Halogen-substituted organic compounds described in US Pat. No. 4,128,557 and US Pat. No. 4,128,557.
The triazines described in 137,079, 4,138,365 and 4,459,350, and the phosphorus compounds described in US Pat. No. 4,411,985, etc. is there.

The antifoggants preferably used in the present invention are organic halides, of which polyhalomethyl compounds, especially trihalomethylsulfone compounds are preferable. Organic halides are described in, for example, JP-A-50-119624, JP-A-50-120328, and JP-A-51-1213.
No. 32, No. 54-58022, No. 56-70.
No. 543, No. 56-99335, and No. 59-9.
0842, 61-129642, and 62.
No. 129845, No. 6-208191, No. 7-5621, No. 7-2781, No. 8-15809, No. 9-160167, No. 9-244177, No. 9 -244178 gazette,
No. 9-258367, No. 9-265150, No. 9-319022, and No. 10-171063.
No. 11-212211, No. 11-231
Compounds such as those disclosed in Japanese Patent No. 460, No. 11-242304, US Pat. Nos. 5,340,712, 5,336,000, and 5,464,737 are mentioned, and specifically, 2 -(Tribromomethylsulfone) quinoline, 2- (tribromomethylsulfone) pyridine, tribromomethylphenyl sulfone,
Examples include tribromomethylnaphthyl sulfone.

Although not required to practice the invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the photosensitive layer. Mercury (II) preferred for this purpose
Salts are mercury acetate and mercury bromide. The addition amount of mercury used in the present invention is preferably 1 nanomol (nmol) to 1 mmol (mmo) per 1 mol of coated silver.
l), more preferably 10 nanomolar (nmol) to 1
It is in the range of 00 micromol (μmol).

The photothermographic material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acid used in the present invention may be any benzoic acid derivative, but as an example of a preferable structure, US Pat.
4,939,4,152,160, JP-A-9-281637 and 9-32986.
Examples thereof include compounds described in JP-A No. 4 and JP-A No. 9-329865. The benzoic acid used in the present invention may be added to any part of the light-sensitive material, but as an addition layer, it is preferable to add it to the layer having the photosensitive layer, and further to the organic silver salt-containing layer. preferable. The benzoic acid may be added at any step of the coating solution preparation, and when it is added to the organic silver salt-containing layer, it may be any step from the organic silver salt preparation to the coating solution preparation, but after the organic silver salt preparation. Therefore, immediately before coating is preferable. The benzoic acid may be added by any method such as powder, solution and fine particle dispersion. Also, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a toning agent. The amount of the benzoic acid added may be any amount, but 1 micromol (μmol) or more and 2 mol (mo) per 1 mol of silver.
l) or less is preferable and 1 mmol or more and 0.1.
It is more preferably 5 mol or less.

In the present invention, a mercapto compound, a disulfide compound or a thione compound is contained in order to suppress or accelerate the development and control the development, to improve the spectral sensitization efficiency, or to improve the storage stability before and after the development. be able to. When the mercapto compound is used in the present invention, it may have any structure, but Ar-SM, Ar
Those represented by -SS-Ar are preferable. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, nafusuimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine. , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring is, for example, halogen (eg Br and Cl), hydroxy, amino, carboxy, alkyl (eg having 1 or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy ( For example, it may have one selected from the group of substituents consisting of one or more carbon atoms, preferably having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimithazole, 6-ethoxy-2-mercaptopentazothiazole, 2,2'-dithiobis- (benzothiazole, 3
-Mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolthiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto -4 (3H) -quinazolinone, 7
-Trifluoromethyl-4-quinolinethiol, 2,
3,5,6-tetrachloro-4-pyridinethiol, 4
-Amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,
3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,
6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2
-Mercapto-4-phenyloxazole and the like, but the present invention is not limited thereto. The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the photosensitive layer, and more preferably in the range of 0.01 to 0.3 mol per mol of silver. Is.

Regarding the plasticizer and lubricant which can be used in the photosensitive layer of the present invention, paragraph No. 0117 of JP-A No. 11-65021, the super-high contrast agent for forming a super-high contrast image and the addition method and amount thereof are described. , Paragraph No. 011 of the same issue
8, JP-A No. 11-223898, paragraph numbers 0136 to 0
193, compounds of formula (H), formulas (1) to (3), formulas (A) and (B) of Japanese Patent Application No. 11-87297, Japanese Patent Application No.
The compounds of the general formulas (III) to (V) described in JP-A No. 1-91652 (specific compounds: Chemical formula 21 to Chemical formula 24), and the contrast enhancing accelerator are described in JP-A No. 11-65021, Dan Clan No. 0102,
JP-A No. 11-223898, paragraph numbers 0194 to 019
5 are described.

The light-sensitive silver halide grain-containing layer in the present invention preferably has an absorption at an exposure wavelength of 0.1 or more and 0.6 or less, and more preferably 0.2 or more and 0.5 or less. If the absorption is large, Dmin is increased, making it difficult to distinguish the image. If the absorption is small, the sharpness is deteriorated.
Any method may be used to impart absorption to the photosensitive silver halide layer in the present invention, but it is preferable to use a dye. As the dye, any dye may be used as long as it satisfies the absorption conditions described above, for example, a pyrazoloazole dye,
Examples thereof include anthraquinone dye, azo dye, azomethine dye, oxonol dye, carbocyanine dye, styryl dye, triphenylmethane dye, indoaniline dye, indophenol dye and squarylium dye.
Preferred dyes used in the present invention include anthraquinone dyes (for example, compounds 1-9 described in JP-A-5-341441, compounds 3-6-18 and 3-23-38 described in JP-A-5-165147). , Azomethine dye (Compound 1 described in JP-A-5-341441)
7-47), indoaniline dye (for example, Japanese Patent Laid-Open No.
Compounds 11 to 19 described in JP-A-289227, compound 47 described in JP-A-5-341441 and JP-A-5-341441.
Compounds 2-10 to 11 described in JP 165147), azo dyes (compounds 10 to 16 described in JP-A-5-341441), and squarylium dyes (compounds 1 to 20 described in JP-A-10-104779), US Compounds 1a to 3 described in Japanese Patent No. 5,380,635
d). As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state of being mordanted with a polymer mordant may be used. The amount of these compounds used depends on the target absorption amount, but is generally 1 m ²
It is preferable to use it in the range of 1 μg or more and 1 g or less.

In the present invention, it is preferable that any portion other than the photosensitive silver halide grain-containing layer has an absorption at an exposure wavelength of 0.1 or more and 3.0 or less, and 0.3 or more and 2.0 or less. It is more preferable to prevent halation. As the portion having absorption at the exposure wavelength, a layer of the photosensitive silver halide grain-containing layer on the opposite side of the support (back layer, back surface undercoat or undercoat layer, back layer protective layer) or photosensitive layer Between the layer containing the functional silver halide grains and the support (undercoat or undercoat layer) is preferred.
When the light-sensitive silver halide grains are spectrally sensitized in the infrared region, any method may be used to make the region other than the layer containing the light-sensitive silver halide grains absorb, but absorption in the visible region The maximum is preferably 0.3 or less. The dye used for coloring may be the same dye as that used for absorbing the light-sensitive silver halide layer, and may be the same as or different from the dye used for the light-sensitive silver halide layer. .

When the light-sensitive silver halide grains are spectrally sensitized in the visible region, any method may be used to make the portion other than the light-sensitive silver halide grain-containing layer absorb light. It is preferable to use a dye which is decolorized or a combination of a compound which is decolorized by heat treatment and a dye which is decolorized. Examples of the colored layer that is erased include the following, but the present invention is not limited thereto. JP-A-52-139136 and JP-A-53-132
No. 334, No. 56-501480, No. 57-
16060, 57-68831, 57.
No. 101835, No. 59-182436,
JP-A-7-36145, JP-A-7-199409, JP-B-48-33692 and JP-A-50-1664.
No. 8, Japanese Patent Publication No. 2-41734, US Pat. No. 4,088,497, and No. 4,283,487.
No. 4,548,896, No. 5,548,896
No. 187,049 is disclosed. The amount of these compounds used is determined depending on the intended amount of absorption, but it is generally preferable to use in the range of 1 μg or more and 1 g or less per 1 m ² .

The light-sensitive material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the light-sensitive layer (image-forming layer). Any polymer may be used as the binder of the surface protective layer. Examples of the binder include polyester, gelatin, polyvinyl alcohol,
Although there are cellulose derivatives and the like, cellulose derivatives are preferable. Examples of the cellulose derivative are shown below, but the invention is not limited thereto. For example, cellulose acetate,
There are cellulose acetate butyrate, cellulose propionate, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like and mixtures thereof. The thickness of the surface protective layer in the present invention is preferably 0.1 to 10 μm, and 1 to 5 μm.
Is particularly preferable.

Any anti-adhesion material may be used for the surface protective layer. Examples of anti-adhesion materials are waxes, liquid paraffin, silica particles, styrene-containing elastomeric block copolymers (eg styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate. And mixtures of these.

The photosensitive layer or the protective layer for the photosensitive layer in the present invention includes US Pat. Nos. 3,253,921, 2,274,782 and 2,52.
It can be used in photographic elements containing light absorbing materials and filter dyes such as those described in US Pat. Nos. 7,583,2,956,879.
Further, a dye can be mordanted as described in, for example, US Pat. No. 3,282,699. The amount of filter dye used is 0.1 as the absorbance at the exposure wavelength.
-3 are preferable and 0.2-1.5 are especially preferable. For the photosensitive layer or the protective layer of the photosensitive layer in the present invention, a matting agent such as starch, titanium dioxide, zinc oxide, silica, US Pat. Nos. 2,992,101 and 2,701,245. It may contain polymeric beads and the like, including beads of the type described in the specification. Also, the matteness of the emulsion surface may be anything as long as stardust failure does not occur, but the Beck smoothness is 200 seconds or more 100
00 seconds or less is preferable, and 300 seconds or more and 10,000 seconds or less is particularly preferable.

In the photothermographic material of the present invention, the photosensitive layer is composed of one or more layers on the support. The one-layer construction must contain organic silver salts, silver halides, reducing agents and binders, and optionally additional materials such as toning agents, coating aids and other auxiliaries. The two layer construction is the first photosensitive layer (usually the layer adjacent to the substrate).
It must contain an organic silver salt and a silver halide therein, and some other ingredients in the second layer or both layers.
A bilayer construction comprising a mono-photosensitive layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor light sensitive photothermographic material may include a combination of these two layers for each color and is also described in US Pat. No. 4,708,928.
All components may be included in a single layer as described in the specification. In the case of multi-dye multi-color light-sensitive photothermographic materials, each light-sensitive layer is generally described in US Pat.
As described in US Pat. No. 0,681, a functional or non-functional barrier layer is used between each photosensitive layer to keep them distinct from each other.

The photothermographic material of the present invention is a so-called single-sided photosensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of a support and a back layer on the other side. Is preferred.

A matting agent may be added to the photothermographic material of the present invention in order to improve transportability. Matting agents are generally fine particles of water-insoluble organic or inorganic compounds.
Any matting agent can be used, for example, US Pat. Nos. 1,939,213 and 2,701,24.
5, No. 2,322,037, No. 3,2
62,782, 3,539,344, 3,767,448 and the like, organic matting agents described in the respective specifications, 1,260,772 and 2 No. 192,241, No. 3,257,206, No. 3,370,951 and No. 3,52.
Those well known in the art such as the inorganic matting agents described in the respective specifications such as the specifications of Nos. 3,022 and 3,769,020 can be used. For example, specifically as an example of an organic compound that can be used as a matting agent, as an example of a water-dispersible vinyl polymer, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc. Examples of cellulose derivatives are methyl cellulose, cellulose acetate, cellulose acetate propionate, etc. Examples of starch derivatives are carboxy starch, carboxynitrophenyl Starch, urea-formaldehyde-starch reaction product, etc.
Gelatin which has been hardened with a known hardener and hardened gelatin which has been made into microcapsules hollow particles by hardening coacervate can be preferably used. As examples of inorganic compounds, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth and the like can be preferably used. The above matting agents can be used by mixing different kinds of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In carrying out the present invention, it is preferable to use particles having a particle size of 0.1 μm to 30 μm. The particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent has a great influence on the haze and surface gloss of the light-sensitive material, the particle size, shape and particle size distribution can be adjusted to a necessary state when preparing the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, examples of the layer that can contain a matting agent include the outermost layer (which may be a photosensitive layer or a back layer) on the photosensitive layer surface and the back surface, a protective layer, an undercoat layer, and the like. It is preferably contained in a layer functioning as an outer surface layer or an outermost surface layer, or a layer close to the outer surface, and preferably contained in a layer acting as a so-called protective layer. In the present invention, the matteness of the back surface is, as Bekk smoothness, preferably 250 seconds or less and 10 seconds or more, and more preferably 180 seconds or less and 50 seconds or more.

Suitable binders for the back layer in the present invention are transparent or translucent, generally colorless, and include natural polymers such as synthetic resins, polymers and copolymers, and 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), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, Poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be formed by coating with water, an organic solvent or an emulsion.

Backside resistive heating layers such as those shown in US Pat. Nos. 4,460,681 and 4,374,921.
r) can also be used in a photothermographic image system.

A hardener may be used in each of the layers such as the photosensitive layer, the protective layer and the back layer in the present invention. Examples of the hardener include polyisocyanates described in U.S. Pat. No. 4,281,060, JP-A-6-208193, U.S. Pat. No. 4,791,042 and the like. Epoxy compounds described, JP-A-62-1
The vinyl sulfone compounds described in Japanese Patent No. 89048 and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coatability and charging. As an example of the surfactant, any of nonionic, anionic, cationic, and fluorine-based can be appropriately used. Specifically, JP-A-62-170950 and US Pat. No. 5,380,6.
No. 44, etc., a fluorine-containing polymer surfactant,
JP-A-60-244945, JP-A-63-188
No. 135, etc., fluorine-based surfactants, US Pat. No. 3,885,965, etc., polysiloxy acid-based surfactants, JP-A-6-301140, etc., and polyalkylene oxides. Examples include anionic surfactants.

Examples of the solvent used in the present invention include New Edition Solvent Pocket Book (Ohm Co., 1994), but the present invention is not limited thereto. The boiling point of the solvent used in the present invention is 40 ° C.
It is preferably above 180 ° C. Examples of the solvent used in the present invention include hexane, cyclohexane, toluene,
Methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, 1,1,1-trichloroethane, tetrahydrofuran, triethylamine, thiophene, trifluoroethanol, perfluoropentane, xylene, n-butanol, phenol,
Examples thereof include methyl isobutyl ketone, cyclohexanone, butyl acetate, diethyl carbonate, chlorobenzene, dibutyl ether, anisole, ethylene glycol diethyl ether, N, N-dimethylformamide, morpholine, propane sultone, perfluorotributylamine, and water.

The photosensitive layer in the present invention can be coated on various supports. Typical supports include polyester films, subbed polyester films, poly (ethylene terephthalate) films, polyethylene naphthalate films, cellulose nitrate films, cellulose ester films, poly (vinyl acetal) films, polycarbonate films and related or resinous. Including materials, as well as glass, paper, metal and the like.
Coated with a flexible substrate, especially a partially acetylated, or baryta and / or α-olefin polymer, especially a C 2-10 α-olefin polymer, such as polyethylene, polypropylene, ethylene-butene copolymers. A coated paper support is typically used. The support may be transparent or opaque, but is preferably transparent.

The photothermographic material of the present invention comprises an antistatic or conductive layer such as a soluble salt (eg chloride, nitrate, etc.), a vapor-deposited metal layer, US Pat. No. 2,861,056 and the same. Ionic polymers as described in US Pat. No. 3,206,312 or US Pat.
It may have a layer containing an insoluble inorganic salt or the like as described in Japanese Patent No. 451.

A method for obtaining a color image using the photothermographic material of the present invention is described in JP-A-7-13295, No. 1
There is a method described in page 0, left column, line 43 to 11 left column, line 40. Further, examples of stabilizers for color dye images include British Patent No. 1,326,889 and US Pat. No. 3,43.
No. 2,300, No. 3,698,909 ', No. 3,574,627, No. 3,57.
Those exemplified in 3,050, 3,764,337 and 4,042,394 can be used.

The heat-developable photographic emulsions of the present invention can be prepared by a variety of coating operations including dip coating, air knife coating, flow coating or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. Can be coated.
If desired, two or more layers can be coated simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

In the photothermographic material of the invention, additional layers can be used, such as dye-receiving layers for receiving transfer dye images, opacifying layers when reflective printing is desired, protective topcoat layers and photothermographic techniques. Known primer layers and the like can be included. The light-sensitive material of the present invention is preferably capable of forming an image with only one light-sensitive material, and it is preferable that a functional layer necessary for image formation such as an image receiving layer does not serve as another light-sensitive material.

The light-sensitive material of the present invention may be developed by any method, but it is usually developed by heating the light-sensitive material exposed imagewise. The preferred developing temperature is 80
To 250 ° C, more preferably 100 to 140 ° C
Is. The developing time is preferably 1 to 180 seconds, and 1
0 to 90 seconds is more preferable. Also as the developing method, it is preferable to perform development using a heat drum. The light-sensitive material of the present invention may be exposed by any method, but a laser beam is preferable as an exposure light source. The laser light according to the present invention is preferably a gas laser, a dye laser, a semiconductor laser or the like. Further, a semiconductor laser, a YAG laser, a second harmonic generating element or the like can be used.

[0190]

Example 1 <Preparation of photosensitive silver halide emulsion> In 5429 ml of water,
Phenylcarbamoyl gelatin 88.3 g, PAO compound _{(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) of 10% aqueous methanol solution 10 ml, into which was kept added dissolved 45 ° C. Potassium bromide 0.32 g, silver nitrate 0.67 mol / l 659 ml of aqueous solution and 0.703 m per liter
and KBr of 0.013 mol and KI of 0.013 mol are dissolved in JP-B-58-58288 and 58-58289.
Nucleation was carried out for 4 minutes and 45 seconds by the simultaneous mixing method while controlling the pAg to 8.09 by using the mixing stirrer shown in No. After 1 minute, 20 ml of 0.63 N potassium hydroxide solution was added. After 6 minutes, 0.67 mol /
l 1976 ml of an aqueous silver nitrate solution and 0.1 liter per liter.
A solution containing 657 mol of KBr, 0.013 mol of potassium iodide, and 30 μmol of dipotassium hexachloroiridate was added by a simultaneous mixing method over 14 minutes and 15 seconds while controlling the temperature at 45 ° C. and pAg at 8.09. did. After stirring for 5 minutes, the temperature was lowered to 40 ° C. To this
18 ml of a 6% aqueous acetic acid solution was added to precipitate the silver halide emulsion. The supernatant was removed, leaving 2 liters of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was precipitated again. Further, the supernatant was removed, leaving 1.5 liters of the sedimented portion, 10 liters was added, and after stirring, the silver halide emulsion was allowed to settle. After removing the supernatant liquid, leaving 1.5 liters of sedimentation water,
A solution of 1.72 g of anhydrous sodium carbonate dissolved in 51 ml was added, and the temperature was raised to 60 ° C. It was stirred for another 120 minutes. Finally, the pH was adjusted to 5.0, and water was added so that the amount was 1161 g per mol of silver. This emulsion is
The particles were monodisperse cubic silver iodobromide grains having an average grain size of 0.058 μm, a grain size variation coefficient of 12%, and a [100] plane ratio of 92%.

<< Preparation of Powdered Organic Silver Salts A to E >> 4720 m
Behenic acid, arachidic acid, and stearic acid were added in a total amount of 0.7552 mol to 1 l of pure water at a ratio shown in Table 1, dissolved at 80 ° C., and then 540.2 ml of 1.5N sodium hydroxide aqueous solution was added. Then, after adding 6.9 ml of concentrated nitric acid, 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., 45.3 g of the above silver halide emulsion and 450 of pure water.
ml, and add IKA JAPAN homogenizer (ULTRA
-TURRAX T-25) was stirred at 13200 rpm (mechanical vibration frequency was 21.1 KHz) for 5 minutes. next,
702.6 ml of a 1 mol / l silver nitrate solution was added over 2 minutes and stirred for 10 minutes to obtain an organic silver salt dispersion. After that, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and then allowed to stand to separate the organic silver salt dispersion by flotation to remove the water-soluble salts below. After that, washing with deionized water and drainage were repeated until the conductivity of the drainage reached 2 μS / cm, and after centrifugal dehydration, 40 ° C
Was dried with a circulating dryer with warm air having an oxygen partial pressure shown in Table 1 until the weight loss was eliminated.

<< Preparation of Photosensitive Emulsion Dispersion >> 14.57 g of polyvinyl butyral powder (Butvar B-79 manufactured by Monsant Co.) was dissolved in 1457 g of methyl ethyl ketone (MEK) to prepare VM.
500 g of the powdered organic silver salt was gradually added while stirring with a dissolver DISPERMAT CA-40M type manufactured by A-GETZMANN and mixed sufficiently to form a slurry. A photosensitive emulsion dispersion was prepared by dispersing the above slurry for 2 passes using a GH-2 type pressure homogenizer manufactured by SMT. On this occasion,
The processing pressure during one bath was 280 kg / cm ² , and the processing pressure during two passes was 560 kg / cm ² . The Tg of the binder was 68 ° C.

<Preparation of Coating Solutions 1 to 50 for Photosensitive Layer> 15.1 g of MEK was added to the photosensitive emulsion dispersion (50 g), and the mixture was kept at 21 ° C. while stirring at 1000 rpm with a dissolver type homogenizer to obtain N, N- 390 μl of a 10 mass% methanol solution of an association of 2 molecules of dimethylacetamide / 1 molecule of bromic acid / 1 molecule of bromine was added, and the mixture was stirred for 1 hour.
Further, a 10 mass% methanol solution of calcium bromide 49
4 μl was added and stirred for 20 minutes. Then 15.9
Wt% dibenzo-18-crown-6 and 4.9 wt%
After adding 167 mg of a methanol solution containing potassium acetate and stirring for 10 minutes, the sensitizing dye A, for comparison,
B, C and D are 1.0 × 10 ⁻³ mol / mol silver, the sensitizing dyes DD-35, DD-36, DD-38 and DD of the present invention.
-39, DD-43 and DD-44 to 0.5 × 10 ^-2
Mol / mol Ag (Ag of photosensitive silver halide) was added as shown in Table 2, and 18.3% by mass of 2-chlorobenzoic acid, 3
2.6 g of salicylic acid-p-toluenesulfonate of 4.2 mass% and 4.5 g of MEK solution of 5-methyl-2-mercaptobenzimidazole were added and stirred for 1 hour. After that, the temperature is lowered to 13 ° C and further 30
Stir for minutes. While keeping the temperature at 13 ° C, 13.31 g of polyvinyl butyral (Butvar B-79, manufactured by Monsant Co.) was added and stirred for 30 minutes, and then 1.08 g of 9.4 mass% tetrachlorophthalic acid solution was added for 15 minutes. It was stirred.
With continued stirring, 20% by weight of reducing agent R-1 10.
0 g, 1.1% by weight of 4-methylphthalic acid and 12.4 g of MEK solution of dye A were added, and 10% by weight of D
1.5 g of esmodur N3300 (aliphatic isocyanate from Mobay Corp.) was continuously added, and further, 4.27 g of MEK solution containing 7.4% by mass of tribromomethyl-2-azaphenylsulfone and 7.2% by mass of phthalazine was added. By doing so, a photosensitive layer coating liquid was obtained.

<< Preparation of coating liquid for surface protective layer >> MEK865
96 g of cellulose acetate butyrate (Eastman Chemical Co., CAB171-15) with stirring.
4.5 g of polymethylmethacrylic acid (Rohm & Haas Company, Paraloid A-21), 1.5 g of 1,3-di (vinylsulfonyl) -2-propanol, 1.0 g of benzotriazole, fluorinated activator (Asahi Glass Co., Ltd., Surflon KH
40) 1.0 g of cellulose acetate butyrate (Eastman Chemical) was added and dissolved.
CAB171-15) and 9 mass% calcium carbonate (Speciality Minerals, Super-pflex200) MEK
Then, 30 g of the substance dispersed in a dissolver type homogenizer at 8000 rpm for 30 minutes was added and stirred to prepare a surface protective layer coating liquid.

<< Preparation of Support >> Concentration of 0.170 (measured with a Macbeth densitometer TD-904) was colored blue.
8W / m ^{2 on} both sides of 175 μm thick PET film
A corona discharge treatment of min was applied.

<< Back side coating >> While stirring 830 g of MEK, cellulose acetate butyrate (Eastma
n chemical company, CAB381-20) 84.2 g and polyester resin (Bostic company, Vitel PE2200)
B) 4.5 g was added and dissolved. To this dissolved liquid, 0.30 g of Dye B was added, and further 43.2 g of methanol was added.
Fluorine activator dissolved in (Asahi Glass Co., Surflon KH
4Q) (4.5 g) and a fluorine-based activator (Dainippon Ink and Chemicals, Megafac F120K) (2.3 g) were added, and the mixture was sufficiently stirred until it was dissolved. Finally, silica dispersed in methyl ethyl ketone with a dissolver type homogenizer having a concentration of 1% by mass (WR Grace, Syroid 64).
X6000) (75 g) was added and stirred to prepare a coating solution for the back surface. 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. Drying temperature 100 ℃, Open-air temperature 10 ℃
It was dried for 5 minutes using the drying air of.

<< Preparation of Photosensitive Material >> The photosensitive layer coating solutions 1 to
50 and the surface protective layer coating solution are extruded by a coater to form a multilayer coating on the back surface coated support at the same time.
Photosensitive materials 1 to 50 were prepared. The photosensitive layer was coated with an amount of coated silver of 1.9 g / m ² , and the surface protective layer had a dry film thickness of 2.5 μm.
I went to. Then, it was dried for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C. The solvent content was defined as the sum of MEK and methanol content of the photosensitive material thus obtained under the following conditions. A film area of 46.3 cm ² is cut out, finely cut to a size of about 5 mm, stored in a dedicated vial bottle, sealed with a septum and an aluminum cap, and then headspace of Hewlett Packard's gas chromatography (GC) 5971 type. It was set on the sampler HP7694 type. In addition, G
A hydrogen flame ionization detector (FID) was used as the C detector, and J & W DB-624 was used as the column. As the main measurement conditions, the headspace sampler heating condition is 120 ° C,
20 minutes, GC introduction temperature is 150 ℃, 8 ℃ / min 4
The temperature was raised from 5 ° C for 3 minutes to 100 ° C. The calibration curve was prepared by using a peak area of a chromatogram obtained by storing a fixed amount of the butanol diluted solution of each solvent in a dedicated vial and measuring the same as above. The solvent content of the light-sensitive material was 40 mg / m ² . A photosensitive material (100 cm ²⁾ was cut out and the photosensitive layer was peeled off in MEK. Pro-Lab Micro Digest A300 type microwave wet decomposition equipment decomposes sulphate and nitric acid, VG Elemental PQ-Ω
Type ICP-MS (inductively coupled plasma mass spectrometer) was used to analyze by a calibration curve method, Zr in the light-sensitive material was analyzed.
The content was 10 μg or less per 1 mg of Ag.

[0198]

[Chemical 48]

<< Evaluation >> (i) Evaluation of Photographic Performance Fuji Medical Dry Laser Imager FM-DP
The photothermographic material prepared by L (equipped with a 660 nm semiconductor laser with a maximum output of 60 mW) was exposed and heat-developed (about 1
20 ° C). However, for a photothermographic material using sensitizing dyes C, D DD-43 and DD-44, 810 n
m semiconductor laser was used for exposure. The obtained image was evaluated with a densitometer. The measurement results were evaluated by Dmin (fog) and sensitivity. The sensitivity was obtained from the ratio of the reciprocal of the exposure amount that gives a density 1.0 higher than Dmin, and was expressed as a relative value with the photothermographic material 25 as 100. (2) Evaluation of Storage Stability Each photothermographic material was aged under conditions of 50 ° C. and 70% relative humidity for 10 days (forced aging). This heat-developable photosensitive material was used in the same manner as in (1) Evaluation method of photographic performance, and the decrease in sensitivity and the increase in Dmin were measured, and the results are shown in Table 2. (3) Evaluation of Image Preservability After the photosensitive material was exposed and heat-developed by the above method,
After sufficiently irradiating light and adjusting the humidity at 70% RH for 3 hours, the bag was sealed in a light-shielding bag and left in an environment of 60 ° C. for 72 hours. Table 2 shows the increment of Dmin at this time. The results obtained are shown in Table 2. The photothermographic material of the present invention has high sensitivity and good storability with time (small decrease in sensitivity due to forced aging, little increase in Dmin) and good image storability (little increase in Dmin after exposure / heat development). Give good results.

[0200]

[Table 4]

[0201]

[Table 5]

[0202]

[Table 6]

Example 2 << Preparation of silver halide emulsion A >>
Re-processed gelatin (calcium content of 2700 pp
m or less) 11 g, potassium bromide 30 mg and 4-meth
Dissolve 1.3 g of sodium rubenzenesulfonate,
The pH was adjusted to 6.5 at 40 ° C. Then silver nitrate 1
159 ml of an aqueous solution containing 8.6 g and 1 part of potassium bromide
mol / L (NH_Four)₂RhCl_Five(H₂O) 5 x 10^-6m
ol / L and K₃IrCl₆2 x 10 ^-Fivemol / L
Control the aqueous solution containing pAg at 7.7
It was added by the double jet method over 6 minutes and 30 seconds. Just
Then, bromide with 476 ml of an aqueous solution containing 55.5 g of silver nitrate
1 mol / L potassium and K₃IrCl₆2 x 10
^-FiveA halogen salt aqueous solution containing mol / L was added to pAg77.
28 minutes 30 by control double jet method while keeping
Added over seconds. After that, lower the pH to cause aggregation and sedimentation.
Desalination treatment was performed to obtain a low molecular weight gel with an average molecular weight of 15,000.
Latin (20ppm or less as calcium content) 5
The pH was adjusted to 5.9 and pAg 8.0 by adding 1.1 g.
The obtained particles have an average particle size of 0.08 μm and a projected area.
Cubic particles with a coefficient of variation of 9% and a (100) face ratio of 90%
there were. The temperature of the obtained silver halide grains is raised to 60 ° C.
Benzenethiosulfonic acid sodium salt per mol of silver
76 μmol was added, and after 3 minutes, triethylthiourea
After adding 71 μmol, aging for 100 minutes,
Droxy 6-methyl-1,3,3a, 7-tetrazai
5 x 10^-Fourmol, 0.17 g of compound A added
After that, the temperature was lowered to 40 ° C. After that, keep the temperature at 40 ° C.
Then, it is 4.7 × 10 with respect to 1 mol of silver halide.^-2mo
l potassium bromide (added as an aqueous solution), for comparison
Spectral sensitizing dye E (as ethanol solution) 1.4 × 10
^-3Addition of mol Ag, similarly the spectral sensitizing dye DD-1 of the present invention
0, DD-11, DD-31, DD-32, DD-33
And DD-45 0.7 x 10^-3Mol / mol Ag, addition
Then, the photothermographic materials 101 to 135 as shown in Table 6
Created. 6.4 x 10^-3mol of compound B (methano
Added as a solution) with stirring, and after 20 minutes
The preparation of silver halide emulsion A was completed by rapid cooling to 30 ° C.
It was The silver halide emulsion A thus obtained was prepared as follows.
Used for manufacturing.

[0204]

[Chemical 49]

<< Preparation of Fatty Acid Silver Dispersion >> The fatty acid silver dispersion was prepared according to the preparation of the powdered organic silver salts A to E and the preparation of the photosensitive emulsion dispersion. << Preparation of Solid Fine Particle Dispersion of Retransfer Agent >> Reducing Agent [1,1-
Bis (2-hydroxy-3,5-dimethylphenyl)-
3,5,5-Trimethylhexane] 10 kg and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP20
1) Surfynol 1 was added to 10 kg of a 20% by mass aqueous solution of 3).
04E (manufactured by Nissin Chemical Co., Ltd.) 400 g, methanol 64
0 g and 16 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed for 3 hours and 30 minutes in a horizontal bead mill (UVM-2, manufactured by Aimex Co., Ltd.) filled with zirconia beads having an average diameter of 05 mm, and then 4 g of benzoisothiazolinone sodium salt was added. Water was added to adjust the concentration of the reducing agent to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the obtained dispersion had a median diameter of 0.44 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of average particle diameter of 19%. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and then used for the preparation of the following coating solution.

<< Preparation of Solid Particle Dispersion of Organic Polyhalogen Compound A >> 10 kg of organic polyhalogen compound A [tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone], modified polyvinyl alcohol ( Kuraray Co., Ltd., Poval MP203) 20 wt% aqueous solution 10 kg, sodium triisopropylnaphthalene sulfonate 20 wt% aqueous solution 639 g,
Surfynol 104E (Nissin Chemical Co., Ltd.) 400
g, 640 g of methanol and 16 kg of water are added,
Mix well to form a slurry. A horizontal bead mill (IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm by sending this slurry with a diaphragm pump.
Manufactured by UVM-2) and dispersed for 5 hours, and then water was added to adjust the concentration of the organic polyhalogen compound A to 25% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound A. The organic polyhalogen compound particles contained in the obtained dispersion had a median diameter of 0.36 μm, a maximum particle diameter of 2.0 μm or less, and an average particle diameter variation coefficient of 18%. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and then used for the preparation of the following coating solution.

<Preparation of Solid Fine Particle Dispersion of Organic Polyhalogen Compound B> 5 kg of organic polyhalogen compound B [tribromomethylnaphthyl sulfone], modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 20
A 2.5% by weight aqueous solution, 213 g of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate and 10 kg of water were added and mixed well to obtain a slurry. This slurry was sent by a diaphragm pump and dispersed for 5 hours in a horizontal bead mill (UVM-2, manufactured by Aimex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 2. 5 g and water were added to adjust the concentration of the organic polyhalogen compound B to be 23.5% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound B. The organic polyhalogen compound particles contained in the obtained dispersion had a median diameter of 0.38 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of average particle diameter of 20%. The resulting dispersion is
After filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, it was used for the preparation of the following coating solution.

<< Preparation of Organic Polyhalogen Compound C Aqueous Solution >> While stirring at room temperature, 75.0 ml of water and sodium tripropylnaphthalenesulfonate (20% aqueous solution)
8.6 ml, sodium dihydrogen orthophosphate dihydrate (5% aqueous solution) 6.8 ml, potassium hydroxide (1 mol
/ L aqueous solution) was sequentially added, and the mixture was stirred and mixed for 5 minutes after the addition was completed. Further, 4.0 g of a powder of the organic polyhalogen compound C [3-tribromomethanesulfonylbenzoylaminoacetic acid] was added with stirring and uniformly dissolved to obtain 100 g of a transparent solution. The resulting aqueous solution is 20
After filtering with a 0 mesh polyester screen to remove foreign matters such as dust, it was used for the preparation of the following coating liquid.

<< Preparation of Emulsified Dispersion of Compound-Z >> 10 kg of R-054 (manufactured by Sanko Co., Ltd.) containing 85% by mass of compound Z was mixed with 11.66 kg of MIBK, and the mixture was replaced with nitrogen at 80.degree. Dissolved for 1 hour. Add 25.
52 kg, MP polymer (Kuraray Co., Ltd., MP-20)
12.76 kg of 20% by weight aqueous solution of 3) and 20% by weight of sodium triisopropylnaphthalene sulfonate
Add 0.44 kg of aqueous solution and add 36 at 20-40 ° C.
It was emulsified and dispersed at 00 rpm for 60 minutes. Furthermore, Surfinol 104E (manufactured by Nisshin Chemical Co., Ltd.) 0.08
kg and 47.94 kg of water were added and distilled under reduced pressure to obtain MIBK.
Was removed, and then the concentration of the compound Z was adjusted to be 10% by mass. Compound Z contained in the dispersion thus obtained
The particles had a median diameter of 0.19 μm, a maximum particle diameter of 1.5 μm or less, and a coefficient of variation of particle diameter of 17%.
The obtained dispersion was filtered with a polypropylene filter having a pore size of 30 μm to remove foreign matters such as dust, and then used for the preparation of the coating liquid described below.

<< Preparation of dispersion of 6-iso-propylphthalazine compound >> While stirring 62.35 g of water at room temperature, 2.0 g of denatured polyvinyl alcohol (POVAL MP203, manufactured by Kuraray Co., Ltd.) was prevented from forming a lump. Add 1
Stir and mix for 0 minutes. After that, the mixture was heated to raise the internal temperature to 50 ° C., and then stirred at an internal temperature of 50 to 60 ° C. for 90 minutes to uniformly dissolve it. The inner temperature is lowered to 40 ° C. or lower, and polyvinyl alcohol (Kuraray Co., Ltd., PVA-
217, 10 mass% aqueous solution) 25.5 g, sodium tripropylnaphthalene sulfonate (20 mass% aqueous solution)
3.0 g and 6-isopropylphthalazine (70% by mass aqueous solution) 7.15 g were added, and the mixture was stirred for 30 minutes and the transparent dispersion liquid 1 was added.
00g was obtained. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and then used for the preparation of the following coating solution.

<< Preparation of Solid Fine Particle Dispersion of Hardening Agent >> Polyvinyl alcohol (Poval PVA-2 manufactured by Kuraray Co., Ltd.) was added to 4 kg of the hardening agent X-1 or X-2.
1 kg of 17) and 36 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump, and a horizontal bead mill filled with zirconia beads having an average diameter of 0.5 mm (UVM- manufactured by Aimex Co., Ltd.).
After dispersing for 12 hours in 2), 4 g of benzoisothiazolinone sodium salt and water were added to adjust the nucleating agent concentration to be 10% by mass to obtain a solid fine particle dispersion. The nucleating agent particles contained in the thus obtained dispersion had a median diameter of 0.34 μm, a maximum particle diameter of 3.0 μm or less, and a coefficient of variation of particle diameter of 19%. The obtained dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and then used for the preparation of the following coating solution.

<< Preparation of Solid Particle Dispersion of Development Accelerator >>
10 kg of development accelerator W-1 or W-2, modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP20
10 kg of 20% by mass aqueous solution of 3) and 20 kg of water were added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed for 5 hours in a horizontal bead mill (UVM-2 manufactured by Aimex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then water was added to the development accelerator W. Was adjusted to 20% by mass to obtain a solid fine particle dispersion of development accelerator W. The development accelerator particles contained in the thus obtained dispersion had a median diameter of 0.5 μm, a maximum particle diameter of 2.0 μm or less, and a coefficient of variation of average particle diameter of 18%. The resulting dispersion is
After filtering with a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, it was used for the preparation of the following coating solution. << Preparation of Coating Solution for Image Forming Layer >> To 1 mol of silver of the fatty acid silver dispersion prepared above, the following binder, material and silver halide emulsion were added, and water was added to apply the image forming layer. It was a liquid. After completion, depressurize degassing under pressure 0.54a
It was carried out at tm for 45 minutes. The coating solution had a pH of 7.7 and a viscosity of 50 mPa · s at 25 ° C.

[0213]   Binder: SBR Latex 397 g as solid content (St / Bu / AA = 68/29/3 (mass%), glass transition temperature 17 ° C. (calculation Value), as a polymerization initiator, (NH_Four)₂S₂O₈, PH: NH_Four6 with OH ． Adjusted to 5, average particle size; 118 nm) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-to Limethylhexane 149.5g as solid content Organic polyhalogen compound B 36.3 g as solid content Organic polyhalogen compound C 2.34 g as solid content Sodium ethylthiosulfonate 0.47 g Benzotriazole 1.02g Polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 10.8 g 6-iso-propylphthalazine 12.8 g Compound Z 9.7g as solid content Hardening agent X-1 10.0 g Hardening agent X-2 2.7 g Dye A (added as a mixture with low molecular weight gelatin having an average molecular weight of 15,000)   Coating amount that gives an optical density of 0.3 at 783 nm (as a standard, solid content 0.40 g) Silver halide emulsion A Ag amount 0.06 mol Compound-A as a preservative 40 ppm in the coating liquid (2.5 mg / m 2 as the coating amount) ² ) 1% by mass as the total amount of solvent in the coating solution of methanol 2 mass% as the total amount of solvent in the coating solution of ethanol It adjusted using NaOH as a pH adjuster. (The glass transition temperature of the coating film was 17 ° C.)

[0214]

[Chemical 50]

<< Preparation of Coating Solution for Protective Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2
-Hydroxyethyl methacrylate / acrylic acid = 5
8.9 / 8.6 / 25.4 / 5.1 / 2 (mass%) polymer latex solution (copolymer glass transition temperature 46
° C (calculated value), solid content concentration 21.5% by mass, compound A contained at 100 ppm, and compound D as a film-forming auxiliary
Was added to the latex solid content in an amount of 15% by mass based on the solid content of the latex to give a solution having a glass transition temperature of 24 ° C .;
62 g of an organic polyhalogen compound C aqueous solution of 114.8
g, organic polyhalogen compound A as solid content 17.0
g, sodium dihydrogen orthophosphate dihydrate as a solid content of 0.69 g, and development accelerator W-1 as a solid content of 1
0.0 g, development accelerator W-2 as solid content 2.5 g,
1.58 g of a matting agent (polystyrene particles, average particle size 7 μm, coefficient of variation of average particle size 8%) and polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 29.3.
g, and then water to prepare a coating liquid (containing 0.8% by mass of a methanol solvent). After preparation, pressure 0.47
Vacuum degassing was performed for 60 minutes at atm. The protective layer coating liquid obtained had a pH of 5.5 and a viscosity of 45 mPa · s at 25 ° C.

<< Preparation of Coating Solution for Lower Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) of polymer latex solution (copolymer glass transition temperature 46 ° C. (calculated value), solid content concentration of 21.5 mass%, compound A of 100 ppm, and compound D of latex as a film-forming assistant) Water was added to 625 g of a coating solution having a glass transition temperature of 24 ° C. to obtain a solid content of 15% by mass;
Compound C 0.23 g, compound E 0.13 g, compound F 11.7 g, compound H 2.7 g and polyvinyl alcohol (Kuraray Co., Ltd., PVA-235) 1
1.5 g was added and further water was added to prepare a coating solution (containing 0.1% by mass of a methanol solvent). After preparation, pressure 0.
Vacuum degassing was performed at 47 atm for 60 minutes. The obtained lower layer overcoat layer coating solution had a pH of 2.6 and a viscosity of 25 ° C.
Was 30 mPa · s.

<< Preparation of Coating Solution for Upper Overcoat Layer >> Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Mass%) of polymer latex solution (copolymer glass transition temperature 46 ° C. (calculated value), solid content concentration of 21.5 mass%, compound A of 100 ppm, and compound D of latex as a film-forming assistant) The content was 15% by mass with respect to the solid content, and the coating solution had a glass transition temperature of 24 ° C. to obtain a solution; 18.4 g of a 30 mass% solution having a silicone content of less than 5 ppm), 0.23 g of compound C, and compound E
1.85 g, compound G 1.0 g, matting agent (polystyrene particles, average particle size 7 μm, average particle size variation coefficient 8
%) And 26.5 g of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.), and water was further added to prepare a coating solution (containing 1.1% by mass of a methanol solvent). After the preparation, vacuum degassing was performed for 60 minutes at a pressure of 0.47 atm. The obtained coating liquid for the upper overcoat layer had a pH of 5.3 and a viscosity of 25 mPa · s at 25 ° C.

[0218]

[Chemical 51]

<< Preparation of Polyethylene Terephthalate (PET) Support Rest with Back / Undercoat Layer >> (1) Preparation of PET Support Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 (phenol / Tetrachloroethane = 6/4 (mass ratio) at 25 ° C) PET
Got This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., and then extruded from a T-die. Then, it was rapidly cooled to prepare an unstretched film having a thickness such that the film thickness after heat setting was 120 μm. This was longitudinally stretched 3.3 times at 110 ° C. using rolls having different peripheral speeds, and then horizontally stretched 4.5 times at 130 ° C. using a tenter. After that, after heat setting at 240 ° C. for 20 seconds, 4% was relaxed in the lateral direction at the same temperature. After this, after slitting the chuck part of the tenter, both ends were knurled and 4.8 kg /
I wound it up in cm ² . Thus, a roll-shaped PET support having a width of 2.4 m, a length of 3500 m and a thickness of 120 μm was obtained.

(2) Preparation of Undercoat Layer and Back Layer Undercoat First Layer The above PET support was subjected to a corona discharge treatment of 0.375 kV · A · min / m ² and then a coating solution of the following composition 0.2 ml / m ² on the support to give 125
℃ 30 seconds, then 150 ℃ 30 seconds, then 185 ℃
And dried for 30 seconds. Latex-A 280 g KOH 0.5 g Polystyrene fine particles (average particle size 2 μm, coefficient of variation of average particle size 7%) 0.03 g 2,4-dichloro-6-hydroxy-s-triazine 1.8 g Compound-Bc-C 0. 97g distilled water

Undercoating second layer A coating solution having the composition shown below was applied on the undercoating first layer so as to have a concentration of 5.5 ml / m ^2, and was applied at 125 ° C. for 30 seconds, then 150 ° C. for 30 seconds, and then 170 It was dried at 30 ° C. for 30 seconds. Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly, strength 230 g) 10 g Acetic acid (20% by mass aqueous solution) 10 g Compound-Bc-A 0.04 g Methylcellulose (2% by mass aqueous solution) 25 g Polyethyleneoxy compound 0.3 g Distillation Amount of water totaling 1000g

Back first layer 0.375 kV · on the surface opposite to the surface coated with the undercoat layer.
A corona discharge treatment of A · min / m ² was applied, and a coating solution having the composition shown below was applied to the surface so as to be 13.8 ml / m ^2, and the temperature was 125 ° C. for 30 seconds, then 150 ° C. for 30 seconds. Further, it was dried at 185 ° C. for 30 seconds. Julimer ET410 (Nippon Pure Chemicals Co., Ltd., 30% by mass aqueous dispersion) 23 g Alkali-treated gelatin (molecular weight about 10,000, Ca ²⁺ content 30 ppm) 4.44 g Deionized gelatin (Ca ²⁺ content 0.6 ppm) ) 0.84 g Compound-Bc-A 0.02 g Dye-Bc-A (adjusted to have an optical density of 783 nm of 1.3 to 14) 0.88 g Polyoxyethylene phenyl ether 1.7 g Water-soluble melamine Compound (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3, 8 mass% aqueous solution) 15 g Sb-doped SnO ₂ needle-like particle water dispersion (Ishihara Sangyo Co., Ltd., FS-10D) 24 g Polystyrene fine particles (Average particle size; 2 μm, coefficient of variation of average particle size 7%) 0.03 g Distilled water Total amount is 1000 g

Back 2nd layer A coating solution having the composition shown below was applied on the back 1st layer so as to have a concentration of 5.5 ml / m ^2, and the mixture was applied at 125 ° C. for 30 seconds and then 1 layer.
It was dried at 50 ° C for 30 seconds and further at 170 ° C for 30 seconds. Julimer ET410 (Nippon Pure Chemical Industries, Ltd., 30% by mass aqueous dispersion) 57.5 g Polyoxyethylene phenyl ether 1.7 g Water-soluble melamine compound (Sumitomo Chemical Co., Ltd., Sumitex Resin M-3) 8 mass% aqueous solution) 15 g Cerosol 524 (manufactured by Chukyo Yushi Co., Ltd., 30 mass% aqueous solution) 6.6 g Distilled water Total amount becomes 1000 g

Back 3rd layer Undercoat The same coating solution as the 1st layer was applied onto the back 2nd layer so as to have a volume of 6.2 ml / m ^2, and was applied at 125 ° C. for 30 seconds, then 150 ° C. for 30 seconds, and further 185 It was dried at 30 ° C. for 30 seconds.

Back 4th layer A coating solution having the composition shown below was applied onto the back 3rd layer so that the concentration was 13.8 ml / m ^2, and the temperature was 125 ° C. for 30 seconds, then 150 ° C. for 30 seconds, and 170 ° C. And dried for 30 seconds. Latex-B 286g Compound-Bc-B 2.7g Compound-Bc-C 0.6g Compound-Bc-D 0.5g 2,4-dichloro-6-hydroxy-s-triazine 2.5g Polymethylmethacrylate (10 mass % Water dispersion, average particle diameter 5 μm, coefficient of variation of average particle 7%) 7.7 g distilled water Total amount of 1000 g

[0226]

[Chemical 52]

Latex-A Core part 90% by mass, shell part 10% by mass, core-shell type latex core part, vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 93
/3/3/0.9/0.1 (mass%) copolymer shell part, vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 8
8/3/3/3/3 (mass%) copolymer weight average molecular weight 38,000 Latex-B methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 59/9/26/5/1

(3) Heat Treatment for Transporting (3-1) Heat Treatment PE thus prepared and having a back / undercoat layer
The T support was placed in a heat treatment zone having a total length of 200 m and set at 160 ° C., and was transported at a tension of 2 kg / cm ² and a transport speed of 20 m / min. (3-2) Post-heat treatment Subsequent to the above heat treatment, it was passed through a zone at 40 ° C for 15 seconds to perform post-heat treatment and wound. The winding tension at this time was 10 kg / cm ² .

<< Preparation of Photothermographic Material >> for PET support
On the second layer of the undercoat layer, the one disclosed in JP-A-2000-2964
Using the slide beat applicator shown in FIG.
The image forming layer coating solution was coated with fatty acid silver in an amount of 1.42.
g / m²Was applied. On top of that, the
The coating amount of the polymer latex solids of the protective layer coating liquid is
1.29 g / m²Together with the image forming layer coating liquid
Simultaneous multilayer coating was performed. Then, on the protective layer, the lower layer
Application of bar coat layer coating liquid to solid content of polymer latex
The amount is 1.97 g / m ²And the upper overcoat layer
The coating amount of the polymer latex solid content is 1.07.
g / m²Together with the lower layer overcoat coating liquid
Simultaneous multilayer coating was performed to prepare a photothermographic material. At the time of application
Drying is performed with a dew point of 14 to 25 ° C in both the constant rate process and the deceleration process.
When the film surface temperature is in the range of 35 to 40 ° C, the flow of the coating solution is almost
Horizontal drying zone (water of coating machine
The support is at an angle of 1.5 ° to 3 ° with respect to the horizontal direction)
It was After drying, the winding temperature is 23 ± 5 ℃ and relative humidity is 45 ±.
Performed under the condition of 5%, and the winding shape is the subsequent processing form (image
The outer surface of the image forming surface was rolled, and the image forming surface was placed outside. In addition,
The relative humidity of the heat-developable photosensitive material is 20-40% (25 ° C).
Measurement), the film surface of the image forming surface of the photothermographic material obtained
pH is 5.0, Beck's smoothness is 850 seconds, film surface on the opposite side
The pH was 5.9 and the Bekk smoothness was 500 seconds.

Regarding the sample manufactured as described above,
The following performance evaluation was performed. << Exposure >> Beam diameter (FWHM of 1/2 of beam intensity) 1
2.56 μm, laser output 50 mW, output wavelength 780
Using a single-channel cylindrical inner surface type laser exposure device equipped with a semiconductor laser of nm, the number of rotations of the mirror is 640.
Exposure was performed at 00 rpm and a main scanning speed of 633 m / sec. The overlap coefficient at this time is 0.449, and the laser energy density on the surface of the photothermographic material is 70 μJ /
It was set to cm ² .

<< Heat Development Process >> The photothermographic material was transferred online from the above-mentioned exposure apparatus through an auto carrier to obtain the image shown in FIG.
The heat development treatment was performed with the processor (heat processor) shown in. The thermal developing machine shown in FIG. 1 includes a preliminary heating section A, a thermal development processing section B, and a slow cooling section C. The preheating unit A is provided with a plurality of preheating means (for example, the lower portion of the carry-in roller 11 is a heat roller), and a pair of carry-in rollers 11 that sandwich the heat-developable image recording material 10 and carry it into the heat-development processing unit B. The heat development processing section B is provided with a smooth surface 14 and a roller 13 that sandwich and convey the heat development recording material 10, and a heater 15 that heats the heat development image recording material 10. Gradual cooling part C
Holds the heat-developable image recording material 10 in between and the heat-development processing section B
A pair of carry-out rollers 12 for carrying out the heat-developable image recording material 10 are provided between the pair of carry-out rollers 12. In the heat developing machine shown in FIG. 1, the heat-developable image recording material 10 passes through a preheating section A, a heat development processing section B, and a slow cooling section C in this order, and is subjected to preheating, heat development processing, and slow cooling (air cooling). ) Are sequentially performed, and heat development processing is performed.
The roller surface material of the heat development processing section was silicone rubber, and the smooth surface was Teflon (registered trademark) non-woven fabric, and the line speed of conveyance in the heat development processing section was set to 25 mm / sec.
Preheating section 12.2 seconds (The driving system of the preheating section and the heat development processing section are independent, and the speed difference with the heat development section is -0.5%.
Set to -1%, the speed difference from the preheating part of the auto carrier set to 0% to -1.0%, the temperature setting of the metal roller of each preheating part, the time is the first roller temperature 67 ° C, 2. 0
Seconds, second roller temperature 82 ° C, 2.0 seconds, third roller temperature 98 ° C, 2.0 seconds, fourth roller temperature 107
℃, 2.0 seconds, the fifth roller temperature 115 ℃, 2.0 seconds,
The sixth roller temperature was 120 ° C. for 2.0 seconds), and the heat development processing section 120 ° C. (heat development photosensitive material surface temperature) was 17.2.
Second, the heat-development process was performed in the slow cooling part for 13.6 seconds. The temperature accuracy in the width direction was ± 0.5 ° C. The temperature of each roller was set to be 5 cm longer on both sides than the width of the photothermographic material (for example, 61 cm in width), and the temperature was also applied to that portion to obtain temperature accuracy. Since the temperature drops sharply at both end portions of each roller, the portion that is longer than the width of the photothermographic material by 5 cm is 1 to 10 times wider than the central portion of the roller.
The temperature was set to be higher at 3 ° C., and care was taken so that the image density of the photothermographic material (for example, within a width of 61 cm) was uniform. Further, a guide plate 16 is installed downstream of the heat development processing section B, and a slow cooling section C having a carry-out roller pair 12 and a guide plate 16 is installed. The guide plate 16 is preferably made of a material having a low thermal conductivity, and it is preferable to gradually cool it. Cooling rate is 0.5-10 ° C / sec
Is preferred.

<< Evaluation of Storage Stability >> The obtained images were evaluated with a Macbeth TD904 densitometer (visible density). The measurement result was evaluated by the relative value of the ratio of the reciprocal of the exposure amount that gives a density higher than Dmin (fog) and the sensitivity Dmin by 1.5, and the photothermographic material 109 shown in Table 6 was set to 100. The prepared sample was stored in a roll form at 50 ° C., and then exposed and heat-developed in the same manner to increase Dmin ΔDmin
Is the change in sensitivity (indicating a decrease in sensitivity). << Evaluation of image storability >> After exposing and heat-developing the light-sensitive material according to the above-mentioned method, it is fully exposed to light, conditioned for 3 hours at 70% RH, enclosed in a bag which can be shielded from light, and stored in an environment of 60 ° C for 7 hours.
It was left for 2 hours. Table 6 shows the increment of Dmin at this time.

As is clear from Table 6, the photothermographic material of the present invention has high sensitivity and excellent storability, and also has excellent image storability after development.

[0234]

[Table 7]

[0235]

INDUSTRIAL APPLICABILITY The photothermographic material of the present invention has high sensitivity, excellent storage stability and excellent image stability after development by using a specific compound as a spectral sensitizing dye. A heat-developable image recording material can be provided as a film for medical diagnosis and a film for photoengraving capable of forming a clear black image having high resolution and sharpness.

[Brief description of drawings]

FIG. 1 is a side view showing an example of the configuration of a heat developing machine used for heat developing processing of a photothermographic material of the present invention.

[Explanation of symbols]

10 Thermal development image forming material 11 Carry-in roller pair 12 Delivery roller pair 13 roller 14 smooth surface 15 heating heater 16 Guide plate A Preheating section B heat development processing section C Slow cooling unit

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H123 AB00 AB03 AB25 AB28 BA00                       BA12 BA14 BB00 BB23 CB00                       CB03                 4H056 CA02 CA05 CB01 CB06 CC08                       CE03 CE06 DD19 FA05

Claims (9)

[Claims] 1. A photothermographic material containing at least one photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions and a binder on one side of a support, the non-photosensitive organic silver. The content of silver behenate in the salt is 4
A photothermographic material, which is 0 mol% or more and less than 85 mol% and contains at least one compound containing two or more dye chromophores. 2. The photothermographic material according to claim 1, wherein the compound containing two or more dye chromophores is selected from the compounds represented by the following general formula (A). [Chemical 1] (In the formula, D ^a and D ^b each independently represent a dye chromophore.
L ^a represents a linking group or a single bond. q ^a and r ^a are each 1
Represents an integer of -100. q ^b represents an integer of 1 to 4. M ^a represents a charge balancing counter ion, m ^a represents a number necessary to neutralize a charge of the molecule. ) 3. The photothermographic material according to claim 2, wherein the compound represented by the general formula (A) is selected from the compounds represented by the following general formula (I). [Chemical 2] (In the formula, D ¹ represents a dye chromophore. L ¹ represents a linking group or a single bond. Q ¹ and r ¹ each represent an integer of 1 to 100. q ² represents an integer of 1 to 4. M ¹ represents a charge-balancing counterion, and m ¹ represents the number necessary to neutralize the charge of the molecule.) 4. A dye chromophore D¹Is the following general formula (XI),
A dye chromophore having a structure of (XII) or (XIII)
4. The photothermographic material according to claim 3, wherein [Chemical 3] [In the formula (XI), L¹¹, L¹², L¹³, L¹⁴, L¹⁵, L¹⁶,
And L¹⁷Represents a methine group. p¹¹, And p¹²Is 0 or
Represents 1. n¹¹Represents 0, 1, 2, 3 or 4. Z¹¹
And Z¹²Is the atomic group necessary to form a nitrogen-containing heterocycle
Represents Z¹¹And Z¹²The ring may be condensed. M¹¹
Represents a charge-balancing counterion, m¹¹Neutralizes the charge of the molecule
Represents a number of 0 or more required to R¹¹And R¹²Is hydrogen
Represents a child, an alkyl group, an aryl group, or a heterocyclic group. ] [Chemical 4] [L in Formula (XII)¹⁸, L¹⁹, L²⁰, And L^{twenty one}Is methine
Represents a group. p¹³Represents 0 or 1. q¹¹Represents 0 or 1
Forget n¹²Represents 0, 1, 2, 3 or 4. Z¹³Is nitriding
Represents a group of atoms necessary to form a prime heterocycle. Z¹⁴When
Z¹⁴'Is (N-R ¹⁴) Q¹¹Together with a heterocycle, or
The atomic groups necessary to form an acyclic acidic end group
Then Z¹³And Z¹⁴And Z¹⁴’, The ring is further condensed
Good. M¹²Represents a charge-balancing counterion, m¹²Is the molecular
It represents a number of 0 or more necessary to neutralize the charge. R¹³, And
And R¹⁴Is a hydrogen atom, alkyl group, aryl group or heterocycle
Represents a group. ] [Chemical 5] [In Formula (XIII), L^{twenty two}, L^{twenty three}, L^{twenty four}, L^{twenty five}, L²⁶,
L²⁷, L²⁸, L²⁹And L³⁰Represents a methine group. p¹⁴as well as
p¹⁵Represents 0 or 1. q¹²Represents 0 or 1. n ¹³
And n¹⁴Represents 0, 1, 2, 3 or 4. Z¹⁵, And Z
¹⁷Is a group of atoms necessary to form a nitrogen-containing heterocycle.
You Z¹⁶And Z¹⁶'Is (N-R¹⁶) Q¹²Together with
Represents an atomic group necessary for forming a prime ring, Z¹⁵, Z¹⁶
And Z¹⁶’And Z¹⁷In addition, the ring may be condensed.
M¹³Represents a charge-balancing counterion, m¹³Is the charge of the molecule
Represents a number of 0 or more required for summing. R¹⁵, R¹⁶And R
¹⁷Is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
Represent ] 5. A compound represented by the general formula (I) is
Selected from compounds represented by the general formula (XXI) or (XXII)
The photothermographic material according to claim 3, wherein
Fee. [Chemical 6] [In the formula (XXI), L¹¹, L¹², L¹³, L¹⁴, L¹⁵,
L¹⁶, L¹⁷, P¹¹, P¹², N^{1 1}, Z¹¹, And Z¹²Is general
It is synonymous with formula (XI). L²Represents a linking group. M¹⁴Is electric
Represents the counterbalance ion, m¹⁴Is to neutralize the charge of the molecule
Represents a number of 0 or more required for. R^{twenty one}Is an alkyl group, aryl
Group or heterocyclic group. ] [Chemical 7] [In Formula (XXII), L¹⁸, L¹⁹, L²⁰, L^{twenty one}, P¹³,
q¹¹, N¹², Z¹³, Z¹⁴, Z ¹⁴'And R¹⁴Is the general formula (XI
Synonymous with I). L³Represents a linking group. M¹⁵Is the charge balance
Represents a counter ion, m¹⁵Needed to neutralize the charge on the molecule
Represents a number of 0 or more. ] 6. A compound represented by the general formula (I) is as follows:
Represented by the general formula (XXXIa), (XXXIb) or (XXXII)
The compound according to claim 3, wherein the compound is selected from compounds.
Photothermographic material. [Chemical 8] [In the formula (XXXIa), Z⁵¹, And Z⁵²Is oxygen atom, sulfur source
Represents a child, a selenium atom, a nitrogen atom, or a carbon atom. R⁵¹
Represents an alkyl group, an aryl group, or a heterocyclic group.
L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, And L⁵⁷Is meth
Represents a group. V⁵¹, V ⁵², V⁵³, V⁵⁴, V⁵⁵, V⁵⁶, V
⁵⁷, And V⁵⁸Represents a hydrogen atom or a substituent. L^FourIs
Represents a group. M⁵¹Represents a charge-balancing counterion, m⁵¹Is a minute
Represents a number of 0 or greater required to neutralize the charge of the offspring. ] [Chemical 9] The two Rs above⁵²Each other or R⁵³One of the two
Similarly, the linking group L^FiveTo form. [In the formula (XXXIb), Z⁵³Is oxygen atom, sulfur atom, selenium
Represents an atom, a nitrogen atom, or a carbon atom. R⁵², And R⁵³
Represents an alkyl group, an aryl group, or a heterocyclic group. However
And two R⁵²Each other or R⁵³One of the two is joint
Then L^FiveTo form. L^FiveRepresents a linking group. L⁵⁸, L⁵⁹,
L⁶⁰, L⁶¹, And L⁶²Represents a methine group. V⁵⁹, V⁶⁰,
V⁶¹, V⁶², V⁶³, V⁶⁴, V⁶⁵, V⁶⁶, V⁶⁷, And V⁶⁸
Represents a hydrogen atom or a substituent. M⁵²Is the charge balance vs.
And m⁵²Is less than 0 necessary to neutralize the charge of the molecule
Represents the number above. ] [Chemical 10] [In the formula (XXXII), Z⁵⁴Is oxygen atom, sulfur atom, selenium
Represents an atom, a nitrogen atom, or a carbon atom. Z⁵⁵Is oxygen source
Represents a child, a sulfur atom, or a nitrogen atom. R⁵⁴Is alkyl
Represents a group, an aryl group, or a heterocyclic group. L⁶Is a linking group
Represent L⁶³, L⁶⁴, L^{6 Five}, And L⁶⁶Represents a methine group.
n⁵¹Represents 1 or 2. V⁶⁹, V⁷⁰, V⁷¹, And V⁷²Is
Represents a hydrogen atom or a substituent. M⁵³Is a charge-balanced counterion
Represents m⁵³Is 0 or more necessary to neutralize the charge of the molecule
Represents the number of. ] 7. A compound containing two or more dye chromophores, a compound represented by the general formula (A), or a compound represented by the general formula (I) is adsorbed in a single layer. The photothermographic material according to claim 1. 8. The photothermographic material according to claim 1, wherein 50% by mass or more and 100% by mass or less of the binder is polyvinyl butyral. 9. The photothermographic material according to claim 1, wherein Tg of the binder is 40 ° C. to 90 ° C.