JP2003140297A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material having high sensitivity, is low in fogging and little in decrease in sensitivity and little in increase in fog even when the material is left under forced storage conditions, and having favorable raw preservability. SOLUTION: The heat developable photosensitive material containing a photosensitive silver halide, a nonphotosensitive organic silver salt, a reducing agent and a binder on one face of a supporting body, is characterized in containing (a) a compound containing two or more dye chromophores and (b) at least one kind of compound expressed by general formula (H): Q-(Y)n -C(Z1 )(Z2 )X. In the formula (H), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a bivalent connecting group, n is 0 or 1, each of Z1 and Z2 represents halogen atom and X represents hydrogen atom or an electron withdrawing group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photothermographic material.

[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, p. 2, 1996). In particular, the photothermographic material generally contains a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent,
It has a photosensitive layer in which a reducible silver salt (for example, an organic silver salt) and, if necessary, a color tone controlling agent for controlling the color tone of silver are dispersed in a binder matrix. The photothermographic material is
After the image exposure, it is heated to a high temperature (for example, 80 ° C. or higher), and a black silver image is formed by a redox reaction between a reducible silver salt (which functions as an oxidizing agent) and the reducing agent. 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
U.S. Pat. No. 2,910,377, JP-B-43-492
Fuji Medical Dry Imager FM-DPL has been released as a medical image forming system using a photothermographic material, which has been disclosed in many documents including Japanese Patent No. 4 publication.

In the production of a thermal image forming system using an organic silver salt, there are a method of producing by a solvent coating method and a method of applying and drying a coating solution containing polymer fine particles as a water dispersion as a main binder. . The latter method does not require steps such as solvent recovery, and thus has simple manufacturing equipment and is advantageous for mass production.

[0006]

Therefore, an object of the present invention is to provide a photothermographic material for use in medical images, photolithography, etc., which has high sensitivity, low fog, and good raw storage stability. Another object is to provide a photothermographic material.

[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) In a photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder on the same surface of a support, (a) a compound containing two or more dye chromophores, And (b) a photothermographic material containing at least one compound represented by the following general formula (H). Formula (H) Q- (Y) n -C (Z 1) (Z 2) X [ Formula (H), Q represents an alkyl group, an aryl group or a heterocyclic group, Y is a divalent linking of Represents a group, n
Represents 0 or 1, Z ₁ and Z ₂ represent a halogen atom, and X represents a hydrogen atom or an electron-withdrawing group. (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).

[0008]

[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 each represent an integer of 1 to 100.] ^b is .M ^a represents a charge balancing counter ion an integer of 1 4, m ^a is represented by represents a number necessary to neutralize the charge of the molecule.) (3) general formula (a) The photothermographic material as described in (2) above, wherein the compound is selected from the compounds represented by the following general formula (I).

[0010]

[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 ^{1 to} 10).
Represents an integer of 0. q ² represents an integer of 1 to 4. M ¹ represents a charge-balancing counterion, and m ¹ represents the number required to neutralize 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).

[0012]

[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. ]

[0014]

[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. ]

[0016]

[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. Z¹⁵And 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, m¹⁹Is 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,

[0018]

[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. ]

[0020]

[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.

[0022]

[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 ]

[0024]

[Chemical 19]

One of the above two R ^{52 s} or R ^{53 s} together forms L ⁵ of the linking group. [Expression (X
In XXIb), Z ⁵³ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, or a carbon atom. R ⁵² and R ⁵³ represent 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 represent 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. ]

[0026]

[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 melting point of the compound represented by the general formula (H) is 170.
The photothermographic material according to any one of (1) to (7) above, wherein the photothermographic material is at a temperature of not higher than ° C. (9) The photothermographic material according to any one of (1) to (8) above, wherein Q of the compound represented by formula (H) is a heterocyclic group. (10) A compound having at least one compound in which Q in the general formula (H) is a heterocyclic group, and further containing at least one compound represented by the general formula (H) having a melting point of 170 ° C. or lower. The photothermographic material according to any one of (1) to (9) above.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. (Part of Description of Compound of the Present Invention) The present invention is described in detail below. In addition, in this specification, "-" shows the range which includes the numerical value described before and after 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. Further, the substituent that can be substituted on the group of the compound in the present invention includes any substituent regardless of the presence or absence of substitution of itself.

When such a substituent is represented by W, the substituent represented by W may be any one, and is not particularly limited. For example, 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 arylsulfinyl groups, alkyl-
And arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl- and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho Group (sometimes called phosphono group), silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), 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-dimethylcarbamoyl, 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 3 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 Ws 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.

Of the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above-mentioned groups 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 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 are each 1 to 100
Represents the integer. 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 included L
Each of ^a 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 bound 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 counter ion, and m ^a represents a number necessary for neutralizing the charge of the molecule, and preferably, those similar to M ¹ and m ¹ described later are mentioned.

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

Further, in the general formula (A), D^aAnd D^bDifferent places
A more preferred range of the dye chromophore, the general formula, and
Substituents and the like are described in D below.^aAnd D^bAre the same
In the description of the general formula (I) and its preferable range, the color
Similar except that the chromophores are not the same. Sanawa
Then, in the general formula (A), D^aAnd D^bEven if the
The dye chromophores in the preferred range are those described in the general formula (I).
Formulas (XI), (XII) and (XIII) are represented by
If they are not the same. D in the general formula (A)^aAnd D^b
Further preferred dye chromophores of the general formula
(XXI) two L's¹¹, L¹², L¹³, L¹⁴, L¹⁵,
L¹⁶, L¹⁷, P¹¹, P ¹², N¹¹, Z¹¹, Z¹², And R^{twenty one}
Out of which at least one is not the same, or the general formula
(XXII) and two L¹⁸, L¹⁹, L²⁰, L^{twenty one},
p¹³, Q¹¹, N¹², Z¹³, Z¹⁴, Z¹⁴'And R¹⁴Nou
If at least one is not the same. General formula
D in (A)^aAnd D^bParticularly preferred dye
The chromophore has the general formula (XXXIa) and two Z⁵¹, Z⁵²,
R⁵¹, L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, L⁵⁷, V
⁵¹, V⁵², V⁵³, V⁵⁴, V⁵⁵, V⁵⁶, V⁵⁷, And V⁵⁸of
If at least one of them is not the same, the general formula (XX
XIb) with two Z⁵³, R⁵², R⁵³, L⁵⁸, L⁵⁹, L
⁶⁰, L⁶¹, L⁶², V⁵⁹, V⁶⁰, V⁶¹, V⁶², V⁶³,
V⁶⁴, V⁶⁵, V⁶⁶, V⁶⁷, And V⁶⁸At least of
If one is not the same or is of the general formula (XXXII)
And two Z⁵⁴, Z⁵⁵, R⁵⁴, L⁶³, L⁶⁴, L⁶⁵,
L⁶⁶, N⁵¹, V⁶⁹, V⁷⁰, V⁷¹, And V⁷²Out of
At least one 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 identical dye chromophores and is more sensitive than the compound represented by the general formula (A) (when D ^a and D ^b are different).
Further, the compound represented by the general formula (I) has the general formula (A):
It is also easier than the compound represented by (when D ^a and D ^b are different) and is excellent in that it can be manufactured at low cost.

The compound represented by the general formula (A) or (I) used in the present invention is preferably adsorbed in a single layer because of high sensitivity. 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 general formula (A) or (I) used in the present invention.
The compound represented by is preferably not adsorbed in multiple layers in terms of high sensitivity. 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.

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. More preferably, cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes,
An oxonol dye and a rhodacyanine dye are more preferable, and a group consisting of a cyanine dye, a merocyanine dye and an oxonol dye is more preferable, and a group consisting of a cyanine dye and a merocyanine dye is particularly preferable.

For details of these dyes, see FM Harmer, "Heterocyclic.
Heterocyclic Compounds-Cyanline Dy
es and Related Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer," Heterocyclic Compounds-Special Topics Inn "・ Heterocyclic Compounds-Special t
opics in heterocyclic chemistry ", Chapter 18, Section 14, 482-515, John Wiley & Sons-New York,
London, 1977, "Rodd's Chemistry of Car Compounds"
bon Compounds) "2nd.Ed.vol.IV, partB, 1977, Chapter 15, pp.369-422, Elsevier Scienc.
e Publishing Company Inc.), published in New York, etc. Preferred general formulas for dyes include the general formulas described in U.S. Pat. No. 5,994,051 pages 32 to 36, and the general formula described in U.S. Pat. No. 5,747,236 pages 30 to 34. What is represented is mentioned. Further, preferable cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,69.
General formula (XI), (XI) of the 21st column of the 4th specification
I) and (XIII) (provided that n
The number of 12, n15, n17, and n18 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 30 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene,
Hexamethylene, octamethylene, decamethylene, dodecamethylene), arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), alkenylene group having 2 to 30 carbon atoms (eg, ethenylene, propenylene), 2 to 30 carbon atoms Alkynylene groups (eg, ethynylene,
Propynylene), ether group, amide group, ester group,
It is a divalent linking group having 1 to 30 carbon atoms, which is formed by combining one or more sulfoamide groups and sulfonate groups. These may be substituted with W described above.

It is more preferable that the linking group does not contain a hetero atom other than an amide group or an ester group, and further preferably a case that does not contain a hetero atom.

Particularly preferred are the above-mentioned alkylene groups (for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene), more preferably 2 to 24, and further preferably carbon atoms. Is 4 to 20, more preferably 6 to 18, particularly preferably 8 to 15, and most preferably 12 to 14. 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. In addition, q ² being 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), and more preferably,
The methine dyes represented by the general formulas (XI) and (XII) are particularly preferable, and the methine dye represented by (XII) is particularly preferable. Hereinafter, general formulas (I), (XI), and (XI
The methine compounds represented by I) and (XIII) will be described in detail.

General formulas (XI), (XII) and (XII
In I), 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. The ring may be condensed. 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.

Examples of the nitrogen-containing heterocycle formed by Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁵ and Z ¹⁷ include, for example, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus and 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 and Z ¹⁴ 'and (N-R ¹⁴ ) q ¹¹ together represent an atomic group 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 herein are, for example, "The Theory of the Photographic Process" edited by James (The Theory).
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-thiooxazolidine-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-dioxide, 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,
It is an acidic nucleus obtained by removing an oxo group or a thioxo group from the specific examples of the heterocyclic group formed by Z ¹⁴ and Z ¹⁴ 'and (N-R ¹⁴ ) q ¹¹ , and more 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 from which an oxo group or a thioxo group has been removed, more preferably Is hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, particularly preferably 2 or 4-Thiohydantoin, 2-oxazoline-5-one, rhodanine from which an oxo group or thioxo group has been removed, and most preferably 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 (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl),
Aryloxycarbonylalkyl group (for example, 3-phenoxycarbonylpropyl), acyloxyalkyl group (for example, 2-acetyloxyethyl), acylalkyl group (for example, 2-acetylethyl), carbamoylalkyl group (for example, 2-morpholinocarbonylethyl), and sulfur. Famoylalkyl group (for example, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (eg, 2-sulfatoethyl group, 3 -Sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl) Group), an acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl group) }, C6-20, preferably C6-10, more preferably C6-8 unsubstituted aryl group (eg phenyl group, 1-naphthyl group), C6-20, preferably C6 A substituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, an aryl group substituted with the above-mentioned W mentioned as an example of the substituent can 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),
In (XII) and (XIII), R ¹¹ , R ¹² , R
¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ ), and particularly preferably the N-position of the basic nucleus (ie, general formulas (XI), (XII), ( XII
In I), it is linked with 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-ion). Chlorobenzene sulfonate ion), aryl disulfonate ion (eg 1,3-benzenesulfonate 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 having hydrogen ions as counter ions.

M ¹ , m ¹¹ , m ¹² and m ¹³ represent a number of 0 or more necessary to balance the charge, 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 (XX).
The case where it is selected from the compounds represented by II) is preferable.

In the general formulas (XXI) and (XXII)
L¹¹, L¹², L¹³, L¹⁴, L¹⁵, L¹⁶, L¹⁷,
p¹¹, P¹², N¹¹, Z¹¹, Z¹², L¹⁸, L¹⁹, L²⁰, L
^{twenty one}, P¹³, Q¹¹, N¹², Z¹³, Z¹⁴, Z¹⁴'And R¹⁴
As described in the general formulas (XI) and (XII).
Examples thereof include the same ones, and the same ones are preferable.
M ¹⁴And m¹⁴, And M¹⁵And m¹⁵Are the above M¹
And m¹The same thing as is mentioned. R^{twenty one}Is R above¹²Na
Among those explained above, alkyl groups excluding hydrogen atoms,
Examples of the aryl group or the same as the heterocyclic group include
Such a thing is preferable. L², And L³Is the above L¹The theory
Among the revealed ones, the same ones as the linking group except for the single bond
And similar ones are preferable.

Particularly preferred in formula (XXI)
The combination is n¹¹Is 2, Z¹¹, L ¹¹, L¹², P¹¹Shaped in
Formed basic nucleus, and Z¹², L¹⁶, L¹⁷, P¹²Formed by
Among the basic nuclei, one is a 4-quinoline nucleus and the other is
Benzoxazole nucleus, or benzothiazole nucleus (preferred
Benzothiazole nucleus) or n¹¹Is 3, Z
¹¹, L¹¹, L¹², P¹¹A basic nucleus formed by
Z¹², L¹⁶, L¹⁷, P¹²The basic nucleus formed by
Zoxazole nucleus or benzothiazole nucleus (preferably
At least one is a benzothiazole nucleus, more preferred
Or both benzothiazole nuclei). General
In formula (XXII), a particularly preferred combination is
n¹²Is 2, Z¹³, L¹⁸, L¹⁹, P¹³Basicity formed by
The nucleus is a benzoxazole nucleus, or a benzothiazole nucleus,
Z¹⁴, Z¹⁴', (N-R¹⁴) Q¹¹The acidic nuclei formed by
Rhodanine nucleus, or n¹²Is 3, Z¹³, L¹⁸，
L¹⁹, P¹³The basic nucleus formed by benzothiazole
Nucleus, Z¹⁴, Z¹⁴', (N-R¹⁴) Q¹¹Acidic formed by
This is the case when the nucleus is a rhodanine nucleus. General formula (XXI),
And (XXII) is preferably (XXII).
It

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

In the general formulas (XXXIAa), (XXXIb) and (XXXII), Z ⁵¹ , Z ⁵² , Z ⁵³ , and Z
⁵⁴ is an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom (N-
V ^80), or represents a carbon atom (CV ⁸¹ V ^82). here,
V ⁸⁰ , V ⁸¹ , and V ⁸² represent a hydrogen atom or a substituent (for example, W described above), and preferably an alkyl group, an aryl group, or a heterocyclic group similar to R ¹¹ and the like, more preferably an alkyl group. It is a base. 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. When n ⁵¹ is 2, it is more preferably a sulfur atom. Z ⁵⁵ represents an oxygen atom, a sulfur atom, or a nitrogen atom (N-V ⁸³ ). Here, V ⁸³ represents a hydrogen atom or a substituent (for example, W described above), and is preferably an alkyl group, an aryl group, or a heterocyclic group similar to R ¹¹ and the like,
More preferably, it is 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
Represents a hydrogen atom or a substituent (for example, W described above), and among these, two adjacent substituents may be bonded to each other to form a saturated or unsaturated condensed ring. Preferably, a hydrogen atom, an alkyl group (eg methyl), an aryl group (eg phenyl), an aromatic heterocyclic group (eg 1-pyrrolyl, 2-thienyl), an alkoxy group (eg methoxy), an alkylthio group (eg methylthio), A cyano group, an acyl group (eg acetyl), an alkoxycarbonyl group (eg methoxycarbonyl), a 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.

L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, L
⁵⁷, L⁵⁸, L⁵⁹, L⁶⁰, L⁶¹, L⁶², L⁶³, L⁶⁴,
L⁶⁵, And L⁶⁶Represents a methine group, and the above L¹³,
L¹⁴, L¹⁵, L ²⁰, L^{twenty one}And similar ones,
The same is preferable.

L⁵¹, L⁵², L⁵³, L⁵⁴, L⁵⁵, L⁵⁶, L
⁵⁷For L⁵²And L⁵⁴, L⁵³And L ⁵⁵, L⁵⁴And L⁵⁶,
Or L⁵²And L⁵⁴And L⁵⁶At least one of them is tied together
The case where they are combined to form a ring is preferable. As a ring
, But preferably 5 or 6 membered carbonized water
It is a prime ring or a heterocycle. More preferably, 5,
Is a 6-membered hydrocarbon ring. Of the above, the methine group is 3
When two together form a ring, preferably 5 or 6 members
Is a structure in which two hydrocarbon rings or heterocycles are condensed.
And more preferably two 5- or 6-membered hydrocarbon rings
It is a condensed structure. Also, in these rings with the above W
The substituents represented may be substituted. Preferred ring structure
Is specifically shown below.

[0085]

[Chemical 21]

Particularly preferred are the following ring structures.

[0087]

[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.

Regarding L ⁵⁸ , L ⁵⁹ , L ⁶⁰ , L ⁶¹ and L ⁶² ,
L ⁵⁸ , 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, more preferably a methyl group 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 (XXXII), preferably (XXXIa),
And (XXXII), more preferably (XXX
II).

Next, 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. (The charge-balancing counterion is omitted. Any possible counterion may be present.)

[0093]

[Chemical formula 23]

[0094]

[Chemical formula 24]

[0095]

[Chemical 25]

[0096]

[Chemical formula 26]

[0097]

[Chemical 27]

[0098]

[Chemical 28]

[0099]

[Chemical 29]

[0100]

[Chemical 30]

[0101]

[Chemical 31]

[0102]

[Chemical 32]

[0103]

[Chemical 33]

[0104]

[Chemical 34]

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

[0106]

[Chemical 35]

[0107]

[Chemical 36]

[0108]

[Chemical 37]

[0109]

[Chemical 38]

[0110]

[Chemical Formula 39]

[0111]

[Chemical 40]

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

[0113]

[Chemical 41]

[0114]

[Chemical 42]

[0115]

[Chemical 43]

[0116]

[Chemical 44]

The sensitizing dye compounds represented by the general formula (A) or (I) used in the present invention are those described by FM Harmer in "Heterocyclic Compounds Cyanide-and-Related." Heterocyclic Compounds-Cyaline 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, Chapter 15, pp. 369-422, Elsevier Science Publishing Company Inc., New York, etc. .

In the present invention, the sensitizing dyes represented by formulas (A) and (I) may be used alone or in combination with other sensitizing dyes. 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 & 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 a 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 formulas (A) and (I) used in the present invention (and 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 (also 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 the general 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 preferred, and compounds described in the literature of JP-A No. 11-65021, paragraph 0030, the general formulas (II) and (III) in JP-A No. 5-313284,
The compound represented by (IV) is more preferable.

In the present invention, chemical sensitization can be carried out at any time after grain formation and before 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.

Next, the compound represented by formula (H) used in the present invention will be explained. Formula (H) Q- (Y) n -C (Z 1) (Z 2) X

In the general formula (H), Q is an alkyl group,
It represents an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, Z ₁ and Z ₂ represent a halogen atom, and X represents a hydrogen atom or an electron-withdrawing group. Q is preferably a heterocyclic group. Specific examples of the heterocycle of Q include, for example, oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring,
Thiadiazine ring, pyridine ring, quinoline ring, purine ring,
A pyrrole ring, an indole ring, an isoquinoline ring, or
A ring bonded to another carbon ring or a hetero ring, for example, a benzoxazole ring, a benzothiazole ring, a benzoselenazole ring, a benzimidazole ring, a benzotriazole ring, a naphthoxazole ring, a triazeindolidine ring, a diazaindolizine ring, Triazaindolizine ring and the like.
Preferred are a benzothiazole ring, a pyridine ring, and a quinoline ring.

In the general formula (H), Q preferably represents a phenyl group substituted with an electron-withdrawing group whose Hammett's substituent constant σp has a positive value. For Hammett's substituent constants, see Journal of Medicinal Chemistry, 1973, Vo.
You can refer to l.16, No.11, 1207-1216, etc.

Examples of such an electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.2).
3), iodine atom (σp value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp value: 0) .54)), a cyano group (σp value: 0.6)
6), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, Acetyl (σp value: 0.5
0), benzoyl (σp value: 0.43), alkynyl group (for example, C≡CH (σp value: 0.23)), aliphatic
Aryl or heterocyclic oxycarbonyl groups (eg,
Methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value:
0.57), a sulfoxide group, a heterocyclic group, a phosphoryl group and the like. The σp value is preferably 0.2 to
It is in the range of 2.0, and more preferably in the range of 0.4 to 1.0.

The above-mentioned electron-withdrawing group is particularly preferably a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an alkylphosphoryl group, of which the carbamoyl group is the most preferable.

X is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group. A group, a carbamoyl group, a sulfamoyl group,
Particularly preferred is a halogen atom. Among the halogen atoms, chlorine atom, bromine atom and iodine atom are preferable, chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable. Y is preferably -C (= O)
-, - SO- or -SO ₂ -; more preferably, -C (= O) -, - SO 2 - , and particularly preferably -S
O ₂ −. n represents 0 or 1, and is preferably 1.

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

[0135]

[Chemical formula 45]

[0136]

[Chemical formula 46]

The compound represented by formula (H) of the present invention is preferably used in the range of 10 ^-4 to 1 mol, and more preferably 1 per mol of the non-photosensitive silver salt in the image forming layer.
In the range of 0 ^{-3 to} 0.8 mol, more preferably 5 × 10
It is preferably used in the range of ^{-3 to} 0.5 mol. In the present invention, examples of the method of incorporating the compound represented by the general formula (H) into the light-sensitive material include the method described in the method of incorporating a reducing agent described below. The melting point of the compound represented by formula (H) is preferably 200 ° C. or lower, more preferably 185 ° C. or lower, and particularly preferably 170.
It is below ℃. The photothermographic material of the invention may contain two or more compounds represented by formula (H). In that case, it is particularly preferable that the compound represented by the general formula (H) contains at least one compound in which Q is a heterocyclic group, and further contains at least one compound represented by the general formula (H) having a melting point of 170 ° C. or lower. .

(Description of Organic Silver Salt) The organic silver salt that can be used in the present invention is relatively stable to light, but it is exposed to a photocatalyst (such as a latent image of a photosensitive silver halide) and reduced. A silver salt that forms a silver image when heated to 80 ° C. or higher in the presence of an agent. The organic silver salt may be any organic substance containing a source capable of reducing silver ions. Regarding such a non-photosensitive organic silver salt, JP-A-10-628
No. 99, paragraphs 0048-0049, European Patent Publication No. 08
03764A1, page 18, line 24 to page 19, page 3
7th line, European Patent Publication No. 0962812A1, JP-A-11-349591
No. 2000-7683, 2000-72711 and the like. Silver salts of organic acids, particularly silver salts of long-chain aliphatic carboxylic acids (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) are preferable.
Preferred examples of the fatty acid silver salt are silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate,
And mixtures thereof and the like. In the present invention,
Among these fatty acid silvers, it is preferable to use fatty acid silver having a silver behenate content of preferably 50 mol% or more, more preferably 85 mol% or more, still more preferably 95 mol% or more.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, and may be needle-like, rod-like, tabular or flaky. In the present invention, a flaky organic silver salt is preferred. In addition, short needle-shaped, rectangular parallelepiped, cubic or potato-shaped amorphous particles having a length ratio of the major axis to the minor axis of 5 or less are also preferably used. These organic silver particles are characterized by less fog during heat development than long needle-like particles having a major axis to minor axis length ratio of 5 or more. In the present specification, the flaky organic silver salt is defined as follows. By observing the organic acid silver salt with an electron microscope, the shape of the organic acid silver salt particles was approximated to a rectangular parallelepiped, and the sides of this rectangular parallelepiped were defined as a, b, and c from the shortest side (c is the same as b. In this case, the shorter numerical values a and b are calculated, and x is obtained as follows. x = b / a

In this way, when x is determined for about 200 particles and the average value x (average) is taken, the one satisfying the relationship of x (average) ≧ 1.5 is made into flaky shape. 30 ≧ x (average) ≧ 1.5, more preferably 20 ≧ x
(Average) ≧ 2.0. By the way, needle-shaped is 1 ≤ x (average)
<1.5.

In the scale-like particles, a can be regarded as the thickness of a tabular particle having a plane having sides b and c as a main plane. The average of a is preferably 0.01 μm or more and 0.23 μm or more.
More preferably, it is not less than μm and not more than 0.20 μm. The average of c / b is preferably 1 or more and 6 or less, more preferably 1.05 or more and 4 or less, still more preferably 1.1 or more and 3 or less, and particularly preferably
It is 1.1 or more and 2 or less.

The particle size distribution of the organic silver salt is preferably monodisperse. Monodisperse is the short axis, the standard deviation of the length of each of the major axis is the minor axis, the 100% of the value divided by the major axis is preferably 100% or less, more preferably 80% or less, and further preferably 50%. 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. Another way to measure monodispersity is:
There is a method to obtain the standard deviation of the volume-weighted average diameter of organic silver salt, and the percentage of the value divided by the volume-weighted average diameter (coefficient of variation).
Is preferably 100% or less, more preferably 80% or less, still more preferably 50% or less. As a measuring method, for example, by irradiating an organic silver salt dispersed in a liquid with a laser beam, and obtaining the autocorrelation function with respect to the time change of the fluctuation of the scattered light, the particle size (volume-weighted average diameter) is obtained. You can

Known methods and the like can be applied to the method for producing the organic silver salt used in the invention and the dispersing method thereof. For example, Japanese Unexamined Patent Publication No. 10-62899 and European Patent Publication No. 0803763A described above.
1, European Patent Publication No. 0962812A1, JP-A-11-349591,
JP 2000-7683, 2000-72711, Japanese Patent Application No. 11-348228 ~
No. 30, No. 11-203413, Japanese Patent Application No. 2000-90093, No. 2000-1956
21, 2000-191226, 2000-213813, 2000-214
Reference can be made to Nos. 155 and 2000-191226.

When a photosensitive silver salt is allowed to coexist during dispersion of the organic silver salt, fog increases and sensitivity is significantly reduced. Therefore, it is more preferable that the photosensitive silver salt is not substantially contained during dispersion. In the present invention, the amount of the photosensitive silver salt in the dispersed aqueous dispersion is 1 m per 1 mol of the organic acid silver salt in the liquid.
It is preferably ol% or less, more preferably 0.1 mol%
The following is more preferable, and more preferable is one in which the photosensitive silver salt is not positively added.

In the present invention, it is possible to produce a light-sensitive material by mixing an organic silver salt aqueous dispersion and a photosensitive silver salt aqueous dispersion. The mixing ratio of the organic silver salt and the photosensitive silver salt depends on the purpose. You can choose, but the ratio of photosensitive silver salt to organic silver salt is 1
To 30 mol% is preferable, further 2 to 20 mol%, especially 3 to
A range of 15 mol% is preferred. Mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions at the time of mixing is a method preferably used for controlling photographic characteristics.

The organic silver salt of the present invention can be used in a desired amount, but the amount of silver is preferably 0.1 to 5 g / m ² , and more preferably
It is 0.3 to 3 g / m ² , and more preferably 0.5 to ² g / m ² .

(Explanation of Reducing Agent) The photothermographic material of the present invention preferably contains a thermal developing agent which is a reducing agent for the 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. Examples of such reducing agents include those disclosed in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 080376.
It is described on page 7, line 34 to page 18, line 12 of 4A1. In the present invention, a so-called hindered phenol-based reducing agent or a bisphenol-based reducing agent having a substituent at the ortho position of the phenolic hydroxyl group is preferable as the reducing agent, and a compound represented by the following general formula (R) is more preferable. General formula (R)

[0148]

[Chemical 47]

(In the general formula (R), R ¹¹ and R ¹¹ ′ each independently represent an alkyl group having 1 to 20 carbon atoms.
R ¹² and R ¹² ′ each independently represent a hydrogen atom or a substituent capable of substituting on the benzene ring. L is -S- group or -CHR
Represents a ¹³ -group. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ and X ¹ 'each independently represent a hydrogen atom or a group capable of substituting for 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, a hydroxy group, an alkoxy group. Group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonamide group, sulfonyl group, phosphoryl group, acyl group, carbamoyl group, ester group, ureido group, urethane group,
Examples include halogen atoms.

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 include the same groups as the substituent of R ¹¹ .

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. Group, cyclohexyl group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group, methoxyethyl group and the like. More preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-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, an ethyl group, a propyl group or an isopropyl group.

When R ¹³ is a hydrogen atom, R ¹² and R
¹² 'is preferably an alkyl group having 2 to 5 carbon atoms, more preferably an ethyl group or a propyl group, and most preferably an ethyl group. When R ¹³ is a primary or secondary alkyl group having 1 to 8 carbon atoms, R ¹² and R ¹² ′ are preferably methyl groups. The primary or secondary alkyl group having 1 to 8 carbon atoms of R ¹³ is more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, further preferably a methyl group, an ethyl group or a propyl group. When R ¹¹ , R ¹¹ ′, R ¹² and R ¹² ′ are all methyl groups, R ¹³ is preferably a secondary alkyl group. In this case, the secondary alkyl group for R ¹³ is preferably an isopropyl group, an isobutyl group or a 1-ethylpentyl group, more preferably an isopropyl group. The reducing agents are R ¹¹ , R ¹¹ ′, R ¹² , R ¹² ′ and R
^{Depending on} the combination of ¹³ , the heat developability, developed silver color tone, etc. are different. Since these can be adjusted by combining two or more reducing agents, it is preferable to use two or more reducing agents depending on the purpose.

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.

[0158]

[Chemical 48]

[0159]

[Chemical 49]

[0160]

[Chemical 50]

[0161]

[Chemical 51]

In the present invention, the amount of reducing agent added is 0.1 to 3.0.
It is preferably g / m ² , more preferably 0.2 to 1.5
In g / m ^2, more preferably from 0.3 to 1.0 g / m ^2. It is preferably contained in an amount of 5 to 50% by mole, more preferably 8 to 30% by mole, and further preferably 10 to 20% by mole based on 1 mole 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 emulsion 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. In the above mills, beads such as zirconia are usually used as a dispersion medium, and Z that elutes from these beads is used.
r and the like may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1 ppm to 1000 ppm. Zr in sensitive material
If the content of is less than 0.5 mg per 1 g of silver, there is no problem in practical use. The water dispersion preferably contains a preservative (for example, benzoisothiazolinone sodium salt).

(Explanation of Development Accelerator) In the photothermographic material of the invention, the development accelerator is represented by the general formula (A) described in JP-A-2000-267222 or 2000-330234. Sulfonamidephenol-based compounds represented
Hindered phenolic compounds represented by the general formula (II) described in 2001-92075, JP-A-10-62895 and JP-A-10-62895.
11-15116 General formula (I) described in the specification, etc., Japanese Patent Application 2001-07
A hydrazine-based compound represented by the general formula (1) described in Japanese Patent No. 4278 and a phenol-based or naphthol-based compound represented by the general formula (2) described in Japanese Patent Application No. 2000-76240 Compounds are preferably used. These development accelerators are used in the range of 0.1 to 20 mol% with respect to the reducing agent, 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 development accelerators, Japanese Patent Application No. 2001
-074278 and hydrazine compounds represented by the general formula (1) and Japanese Patent Application No. 2000-7624.
The phenol-based or naphthol-based compounds represented by the general formula (2) described in No. 0 are 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.

[0166]

[Chemical 52]

[0167]

[Chemical 53]

(Explanation of Hydrogen Bonding Compound) When the reducing agent in the present invention has an aromatic hydroxyl group (—OH),
Particularly in the case of the above-mentioned bisphenols, it is preferable to use a non-reducing compound having a group capable of forming a hydrogen bond with these groups in combination. Examples of the group forming a hydrogen bond with a hydroxyl group or an amino group include a phosphoryl group, a sulfoxide group, a sulfonyl group, a carbonyl group, an amide group, an ester group, a urethane group, a ureido group, a tertiary amino group, and a nitrogen-containing aromatic group. Can be mentioned. Among them, preferred are a phosphoryl group, a sulfoxide group, an amide group (provided that they do not have a> N-H group and are blocked as> N-Ra (Ra is a substituent other than H)), and a urethane group. (However, it does not have a> N-H group and is blocked as> N-Ra (Ra is a substituent other than H).), An ureido group (however, it does not have a> N-H group, and> It is a compound having N-Ra (wherein Ra is a substituent other than H) is blocked. In the present invention, a particularly preferable hydrogen-bonding compound is a compound represented by the following general formula (D).

[0169]

[Chemical 54]

In formula (D), R ²¹ to R ²³ each independently represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these groups may be unsubstituted. It may have a substituent.
When R ²¹ to R ²³ have a substituent, the substituent is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an acylamino group, an alkylthio group, an arylthio group, a sulfonamide group, an acyloxy group, Examples thereof include an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, and a phosphoryl group. Preferred substituents are an alkyl group or an aryl group such as a methyl group, an ethyl group, an isopropyl group,
Examples thereof include t-butyl group, t-octyl group, phenyl group, 4-alkoxyphenyl group and 4-acyloxyphenyl group. Specific examples of the alkyl group of R ²¹ to R ²³ include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, an isopropyl group, a t-butyl group, a t-amyl group, a t-octyl group, a cyclohexyl group, Examples thereof include a 1-methylcyclohexyl group, a benzyl group, a phenethyl group and a 2-phenoxypropyl group. As the aryl group, a phenyl group, a cresyl group, a xylyl group, a naphthyl group,
4-t-butylphenyl group, 4-t-octylphenyl group, 4-anisidyl group, 3,5-dichlorophenyl group and the like can be mentioned. As the alkoxy group, methoxy group, ethoxy group, butoxy group, octyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, dodecyloxy group, cyclohexyloxy group,
4-methylcyclohexyloxy group, benzyloxy group and the like can be mentioned. Aryloxy groups include phenoxy group, cresyloxy group, isopropylphenoxy group, 4
Examples thereof include -t-butylphenoxy group, naphthoxy group, biphenyloxy group and the like. Examples of the amino group include dimethylamino group, diethylamino group, dibutylamino group, dioctylamino group, N-methyl-N-hexylamino group, dicyclohexylamino group, diphenylamino group, N-methyl-N-phenylamino group and the like. .

As R ²¹ to R ²³ , an alkyl group, an aryl group, an alkoxy group and an aryloxy group are preferable.
From the viewpoint of the effect of the present invention, at least one or more of R ²¹ to R ²³ is preferably an alkyl group or an aryl group, and more preferably two or more are an alkyl group or an aryl group. Further, it is preferable that R ²¹ to R ²³ are the same group in that they can be obtained at low cost. Specific examples of the hydrogen-bonding compound including the compound of the general formula (D) in the present invention are shown below, but the present invention is not limited thereto.

[0172]

[Chemical 55]

[0173]

[Chemical 56]

Specific examples of the hydrogen-bonding compound are, in addition to the above, specifications of European Patent 1096310, Japanese Patent Application Nos. 2000-270498 and 2001-1.
No. 24796 is mentioned. The compound of the general formula (D) of the present invention can be used in a light-sensitive material by containing it in a coating solution in the form of a solution, an emulsified dispersion, or a solid fine particle dispersion, like a reducing agent. The compound of the present invention forms a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state, and as a complex depending on the combination of the reducing agent and the compound of the general formula (D) of the present invention. It can be isolated in crystalline form. It is particularly preferable to use the crystal powder thus isolated as a solid fine particle dispersion in order to obtain stable performance. Further, a method in which a reducing agent and the compound of the general formula (D) of the present invention are mixed in a powder form and a complex is formed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can also be preferably used. The compound of the general formula (D) of the present invention is preferably used in the range of 1 to 200 mol%, more preferably 10 to 150 mol%, based on the reducing agent.
More preferably, it is in the range of 20 to 100 mol%.

(Explanation of Silver Halide) The photosensitive silver halide used in the present invention is not particularly limited in halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and iodochloroodor. Silver iodide and silver iodide can be used. Among them, silver bromide and silver iodobromide are preferable. 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. Further, silver halide grains having a core / shell structure can be preferably used. The preferred structure is a 2- to 5-fold structure, and more preferably a 2- to 4-fold structure core / shell particles can be used. Further, a technique of localizing silver bromide or silver iodide on the surface of silver chloride, silver bromide or silver chlorobromide grains can also be preferably used.

Methods of forming photosensitive silver halide are well known in the art, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,45.
Although the method described in No. 8 can be used, specifically, a photosensitive silver halide is prepared by adding a silver-providing compound and a halogen-providing compound to gelatin or another polymer solution, and then adding A method of mixing with an organic silver salt is used. Further, the method described in paragraph Nos. 0217 to 0224 of JP-A No. 11-119374, Japanese Patent Application No.
The methods described in 11-98708 and JP-A-2000-347335 are also preferable.

The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or less.
m or more and 0.15μm or less, more preferably 0.02μm or more and 0.12μ
m or less is preferable. The grain size as used herein refers to the diameter when converted into a circular image having the same area as the projected area of silver halide grains (projected area of the principal plane in the case of tabular 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, but cubic grains are particularly preferable in the present invention. Grains with rounded corners of silver halide grains can also be preferably used. There is no particular limitation on the surface index (Miller index) of the outer surface of the photosensitive silver halide grain, but the ratio of [100] surface, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, is high. preferable. The ratio is preferably 50% or more, 6
5% 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] and [100] planes in the adsorption of sensitizing dyes. T. Tani; J.Imaging
Sci., 29, 165 (1985).

In the present invention, a silver halide grain having a hexacyano metal complex present on the outermost surface of the grain is preferred. As the hexacyano metal complex, [Fe (CN) ₆ ] ^4- , [Fe (CN) ₆ ] ^3- ,
[Ru (CN) ₆ ] ^4- , [Os (CN) ₆ ] ^4- , [Co (CN) ₆ ] ^3- , [Rh (C
^{_{N) 6] 3-, [Ir}} (CN) 6] 3-, [Cr (CN) 6] 3 -, and the like ^{_{3- [Re (CN) 6]}} . In the present invention, a hexacyano Fe complex is preferable.

Since the hexacyano metal complex exists in the form of an ion in an aqueous solution, the counter cation is not important, but it is easily miscible with water and is suitable for the precipitation operation of a silver halide emulsion. Use of alkali metal ions such as ions, rubidium ions, cesium ions and lithium ions, ammonium ions, alkylammonium ions (eg, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetra (n-butyl) ammonium ion) Is preferred.

The hexacyano metal complex is a mixed solvent with water or a suitable organic solvent miscible with water (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) and gelatin. It can be mixed with and added.

The addition amount of the hexacyano metal complex is preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less per mol of silver,
It is more preferably 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻³ mol or less.

To allow the hexacyano metal complex to be present on the outermost surface of the silver halide grain, after the addition of the hexacyano metal complex to the silver nitrate aqueous solution used for grain formation is completed, sulfur sensitization, selenium sensitization and tellurium sensitization are carried out. Of the chalcogen sensitization or gold sensitization before the chemical sensitization step before the chemical sensitization step, the washing step, the dispersion step, or the chemical sensitization step. In order to prevent silver halide fine grains from growing, it is preferable to add the hexacyano metal complex immediately after the grain formation, and preferably before the end of the charging step.

The addition of the hexacyano metal complex may be started after the addition of 96% by mass of the total amount of silver nitrate added for grain formation, or after the addition of 98% by mass. More preferably, and particularly preferably after addition of 99% by mass.

When these hexacyano metal complexes are added after the aqueous silver nitrate solution just before the completion of grain formation, they can be adsorbed on the outermost surface of the silver halide grain, and most of them are hardly soluble with silver ions on the grain surface. Form a salt. Since this hexacyanoiron (II) silver salt is a salt that is less soluble than AgI, redissolution due to fine particles can be prevented, and it has become possible to produce fine silver halide particles with a small particle size. .

The light-sensitive silver halide grain of the present invention can contain a metal or metal complex of Group 8 to Group 10 of the Periodic Table (showing Groups 1 to 18). The metal of Group 8 to 10 of the periodic table or the central metal of the metal complex is preferably rhodium, ruthenium or iridium.
One of these metal complexes may be used, or two or more of the same metal complex and different metal complexes may be used in combination. The preferred content is in the range of 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per mol of silver. Regarding these heavy metals and metal complexes and addition methods thereof, JP-A-7-225449, JP-A-11-65021, paragraph numbers 0018 to 0024, JP-A-11-119374, paragraph numbers 0227 to 024.
It is described in 0.

Further, a metal atom (eg, [Fe (CN) ₆ ]] that can be contained in the silver halide grain used in the present invention.
^4- ), desalting method and chemical sensitizing method of silver halide emulsion are disclosed in JP-A No. 11-84574, paragraphs 0046 to 0050 and JP-A No. 11-650.
No. 21, paragraphs 0025 to 0031, JP-A No. 11-119374, paragraph number 0
242-250.

Various gelatins can be used as the gelatin contained in the photosensitive silver halide emulsion used in the present invention. In order to maintain a good dispersion state of the photosensitive silver halide emulsion in a coating solution containing an organic silver salt, it is preferable to use low molecular weight gelatin having a molecular weight of 500 to 60,000. These low molecular weight gelatins may be used during grain formation or dispersion after desalting treatment, but are preferably used during dispersion after desalting treatment.

The sensitizing dye that can be used 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 the spectral characteristics of an exposure light source. The sensitizing dye having can be advantageously selected. For the sensitizing dye and the addition method, see JP-A-11
-65021, paragraph Nos. 0103 to 0109, JP-A-10-186572, compounds represented by the general formula (II), JP-A No. 11-119374, dyes represented by the general formula (I) and paragraph No. 0106, U.S. Pat. Patent No. 5,
510,236, 3,871,887, dyes described in Example 5, dyes disclosed in JP-A-2-96131 and JP-A-59-48753, European Patent Publication No. 0803764A1, page 19, line 38-
Page 20 Line 35, Japanese Patent Application No. 2000-86865, Japanese Patent Application 2000-10256
No. 0, Japanese Patent Application No. 2000-205399, etc. 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 that can be used in combination in the present invention can be a desired amount depending on 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, More preferably 10 ⁻⁴ to 10
^-1 mol.

In order to improve the spectral sensitization efficiency of the present invention,
A supersensitizer can be used. The supersensitizer used in the present invention, European Patent Publication No. 587,338, U.S. Pat.No. 3,877,943, No. 4,873,184, JP-A-5-341432,
Examples thereof include compounds described in Nos. 11-109547 and 10-111543.

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-7-128768 can be used. Particularly in the present invention, tellurium sensitization is preferred, and compounds described in the literature of paragraph No. 0030 of JP-A No. 11-65021, JP-A No. 5-31
The compounds represented by formulas (II), (III) and (IV) in 3284 are more preferable.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized by a gold sensitization method in combination with the above chalcogen sensitization or alone. The gold sensitizer preferably has a valence of gold of +1 or +3, and the gold sensitizer is preferably a gold compound usually used. Typical examples are chloroauric acid, bromioric acid, potassium chloroaurate, potassium bromoaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate and pyridyl trichlorogold. Are preferred. The gold sensitizers described in US Pat. No. 5,858,637 and Japanese Patent Application No. 2001-79450 are also preferably used.

In the present invention, chemical sensitization can be carried out at any time after grain formation and before coating. After desalting, (1) before spectral sensitization, (2) simultaneously with spectral sensitization, ( There may be 3) after spectral sensitization and (4) immediately before coating. The amount of the sulfur, selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is 10 ⁻⁸ to 10 ⁻² mol, preferably 1 ⁻⁸ mol, per mol of silver halide. About 10 ⁻⁷ to 10 ⁻³ mol is used. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 10 ^-7 to 10 ^-3 mol, and more preferably 1 mol per mol of silver halide.
It is 0 ^{-6 to} 5 x 10 ^-4 mol. The chemical sensitization conditions in the present invention are not particularly limited, but the pH is 5 to
8, 6 to 11 as pAg, 40 to 95 as temperature
It is about ℃. The silver halide emulsion used in the present invention includes
By the method shown in European Patent Publication No. 293,917,
A thiosulfonic acid compound may be added.

It is preferable to use a reduction sensitizer for the photosensitive silver halide grains in the invention. As a specific compound for the reduction sensitization method, ascorbic acid and thiourea dioxide are preferable, and stannous chloride, aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound, a silane compound, and a polyamine compound are preferably used. . The reduction sensitizer may be added at any stage of the photosensitive emulsion production process from the crystal growth to the adjustment process immediately before coating. Further, the pH of the emulsion is 7 or more or the pAg is 8.
It is preferable to carry out reduction sensitization by keeping it at 3 or less and ripening, and it is also preferable to carry out reduction sensitization by introducing a single addition portion of silver ions during grain formation.

The photosensitive silver halide emulsion in the present invention preferably contains a FED sensitizer (Fragmentable electron donating sensitaizer) as a compound capable of generating two electrons with one photon. Examples of FED sensitizers include US Pat. Nos. 5,747,235, 5,747,236, and 60.
No. 5426, No. 5940551, and Japanese Patent Application No. 2001-86.
The compounds described in No. 161 are preferable. The step of adding the FED sensitizer is preferably any step of the photosensitive emulsion production step from crystal growth to the adjustment step immediately before coating. The addition amount varies depending on various conditions, but as a guide, it is 10 ^-7 mol to 10 ^-1 mol, and more preferably 10 ^-6 mol to 5 × 10 ^-2 mol, per 1 mol of silver halide.

The photosensitive silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits). , Different chemical sensitization conditions) may be used together. Gradation can be adjusted by using a plurality of photosensitive silver halides having different sensitivities.
Techniques related to these are disclosed in JP-A-57-119341 and 53-
106125, 47-3929, 48-55730, 46-5187,
50-73627, 57-150841 and the like. As a difference in sensitivity, it is preferable that each emulsion has a difference of 0.2 logE or more.

The addition amount of the photosensitive silver halide is 1 m of the light-sensitive material.
Indicated by the amount of coated silver per ² is preferably 0.03~0.6g / m ^2, more preferably from 0.07~0.4g / m ^2, and most preferably from 0.05 to 0.3 g / m ² The photosensitive silver halide is preferably 0.01 mol or more and 0.5 mol or less, more preferably 0.02 mol or more and 0.3 mol or less, still more preferably 0.03 mol or more and 0.2 mol or less, with respect to 1 mol of the organic silver salt.

Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide grains and organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, or a vibration machine. There is a method of mixing with a mill, a homogenizer or the like, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during preparation of the organic silver salt. There is no particular limitation as long as the effect is sufficiently exhibited. In addition, mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions at the time of mixing is a preferable method for controlling photographic characteristics.

The silver halide of the present invention is preferably added to the coating solution for the image forming layer 180 minutes before to immediately before coating, preferably 60 minutes to 10 seconds before coating. The mixing method and the mixing conditions are as follows. Is not particularly limited as long as the effects of the present invention are sufficiently exhibited. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount sent to the coater is set to a desired time, and N. Harnby, MF Edwards, AW Nienow, translated by Koji Takahashi. Eighth of "Liquid mixing technology" (published by Nikkan Kogyo Shimbun, 1989)
There is a method of using a static mixer described in chapters and the like.

(Description of Binder) As the binder of the organic silver salt-containing layer of the present invention, any polymer may be used, and a suitable binder is transparent or translucent, and generally colorless, natural resins, polymers and copolymers, Synthetic resins, polymers and copolymers, other film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrate,
Poly (vinylpyrrolidone) s, casein, starch, poly (acrylic acid) s, poly (methylmethacrylic acid) s,
Poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, poly (vinyl acetal) s (for example, poly (vinyl acetal)) (Vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resin, poly (vinylidene chloride) s, poly (epoxide)
, Poly (carbonates), poly (vinyl acetate) s,
There are poly (olefins), cellulose esters, and poly (amides). The binder may be formed by coating with water, an organic solvent or an emulsion.

In the present invention, the glass transition temperature of the binder that can be used in combination with the layer containing the organic silver salt is 10 ° C. or higher and 80 ° C. or higher.
The following (hereinafter sometimes referred to as high Tg binder)
The temperature is preferably 20 ° C. to 70 ° C., more preferably 23 ° C. or higher and 65 ° C. or lower.

In this specification, Tg was calculated by the following formula. 1 / Tg = Σ (Xi / Tgi) Here, the polymer is i = 1
It is assumed that n monomer components from 1 to n are copolymerized. Xi is the weight fraction of the i-th monomer (ΣXi = 1), Tgi
Is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum of i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer is shown in Polymer Handbook (3rd Edition) (J. Brandrup,
The values from EHImmergut (Wiley-Interscience, 1989)) were adopted.

The polymer serving as the binder may be used alone or in combination of two or more as required.
Further, those having a glass transition temperature of 20 ° C. or higher and those having a glass transition temperature of less than 20 ° C. may be used in combination.
When two or more polymers having different Tgs are blended and used, the weight average Tg is preferably within the above range.

In the present invention, when the organic silver salt-containing layer is formed by coating with a coating solution in which 30% by mass or more of the solvent is water and drying, a binder for the organic silver salt-containing layer is further added. The performance is improved when the polymer is soluble or dispersible in an aqueous solvent (water solvent), particularly when the polymer latex has an equilibrium water content of 2% by mass or less at 25 ° C. and 60% RH. The most preferable form is one prepared to have an ionic conductivity of 2.5 mS / cm or less, and such a preparation method includes a method of purifying using a separation functional membrane after polymer synthesis.

The aqueous solvent in which the polymer is soluble or dispersible as used herein is water or a mixture of water and 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide.

[0206] The term "aqueous solvent" is used here also in the case of a system in which a polymer is not thermodynamically dissolved and exists in a so-called dispersed state.

"Equilibrium water content at 25 ° C 60% RH" means the weight W1 of the polymer in humidity controlled equilibrium in the atmosphere of 25 ° C 60% RH and the weight W0 of the polymer in an absolutely dry state at 25 ° C. It can be expressed as follows. Equilibrium water content at 25 ° C 60% RH = [(W1-W0) / W0] × 100 (mass%)

For the definition and measurement method of the water content, for example, Polymer Engineering Course 14, Polymer Material Testing Method (Polymer Society,
You can refer to Jijijinkan.

25 ° C. 60% RH of the binder polymer of the present invention
The equilibrium water content in is preferably 2% by mass or less, more preferably 0.01% by mass or more and 1.5% by mass or less,
More preferably, 0.02 mass% or more and 1 mass% or less is desirable.

In the present invention, a polymer dispersible in an aqueous solvent is particularly preferable. Examples of the dispersed state may be latex in which fine particles of a water-insoluble hydrophobic polymer are dispersed or those in which polymer molecules are dispersed in a molecular state or forming micelles, but latex dispersed particles are more preferable. preferable. Average particle size of dispersed particles is 1-50,000n
m is preferable, and more preferably in the range of 5 to 1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may be a wide particle size distribution or a monodisperse particle size distribution. Mixing and using two or more kinds having a monodisperse particle size distribution is also a preferable use method for controlling the physical properties of the coating solution.

In the present invention, preferred examples of the polymer dispersible in an aqueous solvent include acrylic polymers, poly (esters), rubbers (eg SBR resin), poly (urethane) s, poly (vinyl chloride) s, Hydrophobic polymers such as poly (vinyl acetate) s, poly (vinylidene chloride) s, and poly (olefins) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more kinds of monomers. The copolymer may be a random copolymer or a block copolymer. The number average molecular weight of these polymers is 5,000 to 100,000, preferably 10,000.
~ 200,000 is good. If the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and if it is too large, the film formability is poor and it is not preferred.

(Specific Examples of Latex) Specific examples of preferable polymer latex include the following. In the following, the raw material monomers are used, and the numerical values in parentheses are mass% and the molecular weights are number average molecular weights. When a polyfunctional monomer is used, the concept of molecular weight cannot be applied because a crosslinked structure is formed, so the term "crosslinkable" is used and the description of molecular weight is omitted. Tg represents a glass transition temperature.

P-1; -MMA (70) -EA (27) -MAA (3) -latex (molecular weight 37,000, Tg 61 ° C.) P-2; -MMA (70) -2EHA (20) -St (5 ) -AA (5) -latex (Mw 40,000, Tg59 ℃) P-3; -St (50) -Bu (47) -MAA (3) -latex (crosslinkable, Tg-
17 ℃) P-4; -St (68) -Bu (29) -AA (3) -latex (crosslinkable, Tg17
℃) P-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg24
℃) P-6; -St (70) -Bu (27) -IA (3) -latex (crosslinkable) P-7; -St (75) -Bu (24) -AA (1) -latex (Crosslinkability, Tg29
℃) P-8; -St (60) -Bu (35) -DVB (3) -MAA (2) -latex (crosslinkable) P-9; -St (70) -Bu (25) -DVB ( 2) -AA (3) -latex (crosslinkable) P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5) -latex (molecular weight 80,000) P-11; -VDC (85) -MMA (5) -EA (5) -MAA (5) -latex (molecular weight 67000) P-12; -Et (90) -MAA (10) -latex (molecular weight 12000) P-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130
000, Tg43 ℃) P-14; -MMA (63) -EA (35) -AA (2) latex (molecular weight 330
00, Tg47 ℃) P-15; -St (70.5) -Bu (26.5) -AA (3) -latex (crosslinking,
Tg23 ℃) P-16; -St (69.5) -Bu (27.5) -AA (3) -latex (crosslinkable,
(Tg20.5 ° C)

The abbreviations for the above structures represent the following monomers.
MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2-ethylhexyl acrylate, St; styrene, Bu; butadiene, AA; acrylic acid, DVB; divinylbenzene, VC; vinyl chloride, AN;
Acrylonitrile, VDC; vinylidene chloride, Et; ethylene, IA; itaconic acid.

The polymer latexes described above are commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635,471
8,4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 8
FINETEX ES650, 611, 67 are examples of poly (ester) s such as 14, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.).
5,850 (manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, WMS
Polyurethane (such as Eastman Chemical)
Examples of rubbers include HYDRAN AP10, 20, 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.), and examples of rubbers include LACSTAR.
7310K, 3307B, 4700H, 7132C (below Dainippon Ink and Chemicals
Nipol Lx416, 410, 438C, 2507 (Nippon Zeon)
G35 is an example of poly (vinyl chloride)
Examples of poly (vinylidene chloride) such as 1, G576 (all manufactured by Nippon Zeon Co., Ltd.) are L502, L513 (all Asahi Kasei Corporation)
Examples of poly (olefin) s such as (made by Mitsui Petrochemical Co., Ltd.) include Chemipearl S120 and SA100.

These polymer latices may be used alone, or may be used by blending two or more kinds as required.

(Preferable Latex) As the polymer latex used in the present invention, a latex of styrene-butadiene copolymer is particularly preferable. The weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably 40:60 to 95: 5. Further, the proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is 60-
It is preferably 99% by mass. Further, the polymer latex of the present invention preferably contains 1 to 6 mass% of acrylic acid or methacrylic acid with respect to the sum of styrene and butadiene, and more preferably 2 to 5 mass%. The polymer latex of the present invention preferably contains acrylic acid.

Styrene preferably used in the present invention-
As the latex of the butadiene acid copolymer, the above-mentioned P-
3 to P-8,15, LACSTAR-3307B, 7132C, Nipol which are commercial products
Lx416 etc. are mentioned.

If desired, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose or the like may be added to the organic silver salt-containing layer of the light-sensitive material of the present invention. The addition amount of these hydrophilic polymers is preferably 30% by mass or less, more preferably 20% by mass or less based on the total amount of the binder in the organic silver salt-containing layer.

The organic silver salt-containing layer (that is, the image forming layer) of the present invention is preferably formed by using a polymer latex. The amount of the binder in the organic silver salt-containing layer is such that the total binder / organic silver salt weight ratio is in the range of 1/10 to 10/1, more preferably 1/3 to 5/1, and further preferably 1/1 to 3 It is in the range of / 1.

Such an organic silver salt-containing layer is also usually a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt. The weight ratio of / silver halide is in the range of 400-5, more preferably 200-10.

The total amount of binder in the image forming layer of the present invention is preferably in the range of 0.2 to 30 g / m ² , more preferably 1 to 15 g / m ² , and even more preferably ² to 10 g / m ² . A cross-linking agent for cross-linking, a surfactant for improving coatability, and the like may be added to the image forming layer of the present invention.

(Preferred Solvent for Coating Liquid) In the present invention, the solvent of the coating liquid for the organic silver salt-containing layer of the light-sensitive material (for simplicity, the solvent and the dispersion medium are collectively referred to as the solvent) is water in an amount of 30 parts by mass. A water-based solvent containing at least 100% is preferable. As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide or ethyl acetate may be used. The water content of the solvent of the coating liquid is
It is preferably 50% by mass or more, more preferably 70% by mass or more. As an example of a preferable solvent composition, in addition to water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30,
Water / methyl alcohol / dimethylformamide = 80/15/5,
Water / methyl alcohol / ethyl cellosolve = 85/10/5, water /
Methyl alcohol / isopropyl alcohol = 85/10/5, etc. (numerical value is% by mass).

(Explanation of Antifoggant) Antifoggants, stabilizers and stabilizer precursors which can be used in combination with the compound of the general formula (H) of the present invention are disclosed in paragraph No. 0070 of JP-A-10-62899. 20th of European Patent Publication No. 0803764A1
Patents described on page 57, line 57 to page 21, line 7, JP-A-9-
281637, compounds described in 9-329864, U.S. Pat.
The compounds described in No. 681, No. 6,083,681 and European Patent No. 1048975 can be mentioned. However, it is particularly preferable to be selected from the compounds represented by the above general formula (H) of the present invention.

(Other Antifoggants) Other antifoggants include mercury (I) disclosed in paragraph No. 0113 of JP-A No. 11-65021.
I) Salt, benzoic acids of paragraph No. 0114 of the same item, JP 2000-20664 A
No. 2, a salicylic acid derivative, a formalin scavenger compound represented by the formula (S) of JP-A-2000-221634, JP-A-11-3
Triazine compound according to claim 9 of 52624, JP-A-6-16-1
A compound represented by the general formula (III) of 1791, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene and the like can be mentioned.

The photothermographic material of the invention may contain an azolium salt for the purpose of preventing fog. The azolium salt, the general formula (XI) described in JP-A-59-193447
And compounds described in JP-B-55-12581 and compounds represented by the general formula (II) described in JP-A-60-153039. The azolium salt may be added to any part of the light-sensitive material, but the addition layer is preferably added to the layer on the side having the photosensitive layer, more preferably to the organic silver salt-containing layer. The azolium salt may be added at any step of the coating solution preparation, but when it is added to the organic silver salt-containing layer, it may be any step from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable that it is applied afterward and immediately before application. The azolium salt 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. In the present invention, the amount of the azolium salt added may be any
It is preferably 1 × 10 ^-6 mol or more and 2 mol or less per 1 mol, 1 ×
It is more preferably 10 ⁻³ mol or more and 0.5 mol or less.

In the present invention, a mercapto compound, a disulfide compound or a thione compound is contained for the purpose of suppressing or accelerating the development to control the development, improving the spectral sensitization efficiency, and improving the storage stability before and after the development. Paragraph Nos. 0067 to 0069 of JP-A No. 10-62899, Compounds represented by the general formula (I) of JP-A No. 10-186572 and Paragraph Nos. 0033 to 0052 as specific examples thereof, European Patent Publication No. 0803
No. 764A1, page 20, lines 36-56. Among them, JP-A-9-297367, JP-A-9-304875,
JP 2001-100358, Japanese Patent Application 2001-104213, Japanese Patent Application 2001-104
The mercapto-substituted heteroaromatic compounds described in No. 214 and the like are preferable.

(Explanation of Color Tone Agent) In the photothermographic material of the present invention, it is preferable to add a color tone agent, and the color tone agent is described in JP-A No. 10-62899, paragraphs 0054 to 0055, European Patent Publication No. 08
No. 03764A1, page 21, lines 23 to 48, JP-A-2000-356317
No. 2000-187298 and particularly phthalazinones (phthalazinone, phthalazinone derivatives or metal salts; for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazide Non and 2,
3-dihydro-1,4-phthalazinedione); phthalazinones and phthalic acids (eg phthalic acid, 4-methylphthalic acid, 4
-Nitrophthalic acid, diammonium phthalate, sodium phthalate, potassium phthalate and tetrachlorophthalic anhydride); phthalazines (phthalazine, phthalazine derivatives or metal salts; eg 4- (1-naphthyl))
Phthalazine, 6-isopropylphthalazine, 6-t-butylflatazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine); a combination of phthalazines and phthalic acids is preferable, A combination of phthalazines and phthalic acids is particularly preferable. Among them, a particularly preferable combination is a combination of 6-isopropylphthalazine and phthalic acid or 4-methylphthalic acid.

(Other Additives) The plasticizers and lubricants that can be used in the photosensitive layer of the present invention are described in JP-A-Hei.
No. 11-65021, paragraph 0117, regarding the ultra-high contrast agent for forming ultra-high contrast image and the addition method and amount thereof, the same paragraph No. 01
18, JP-A-11-223898, paragraph numbers 0136 to 0193, JP-A-200
Compounds of formula (H), formulas (1) to (3), formulas (A) and (B) of 0-284399, compounds of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652 (Specific compounds: Chemical formula 21 to Chemical formula 24), for the contrast enhancing accelerator, JP-A No. 11-65021, paragraph No. 0102, JP-A No. 11-22389.
No. 8, paragraphs 0194 to 0195.

To use formic acid or formate as a strong fogging substance, 5 mmol or less, more preferably 1 mol or less, per mol of silver on the side having an image forming layer containing a photosensitive silver halide.
It is preferable that the content is not more than mmol.

When the ultrahigh contrast agent is used in the photothermographic material of the present invention, it is preferable to use an acid formed by hydration of diphosphorus pentaoxide or a salt thereof in combination. Examples of the acid formed by hydration of diphosphorus pentoxide or a salt thereof include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline. Acid (salt)
And so on. Particularly preferably used as an acid formed by hydration of phosphorus pentoxide or a salt thereof,
Examples thereof include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and the like. The amount of the acid or salt thereof formed by hydration of diphosphorus pentoxide (coating amount per 1 m ^{2 of the} light-sensitive material) may be a desired amount according to the performance such as sensitivity and fog, but it is 0.1 to 500 m.
g / m ² is preferable, and 0.5 to 100 mg / m ² is more preferable.

(Explanation of Layer Structure) The photothermographic material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer. The surface protective layer may be a single layer,
It may have multiple layers. For the surface protective layer, see
No. 11-65021, paragraph numbers 0119 to 0120, and Japanese Patent Application No. 2000-171936. Gelatin is preferred as the binder for the surface protective layer of the present invention, but polyvinyl alcohol (PV
It is also preferable to use or use A) together. As gelatin, inert gelatin (for example, Nitta gelatin 75
0), phthalated gelatin (eg, Nitta gelatin 801) and the like can be used. As PVA, Japanese Patent Laid-Open No. 2000-171
Those described in paragraph numbers 0009 to 0020 of No. 936,
Completely saponified PVA-105, partially saponified PVA
Preferred examples thereof include -205, PVA-335, and modified polyvinyl alcohol MP-203 (these are trade names of Kuraray Co., Ltd.). The coating amount of polyvinyl alcohol (per 1 m ^{2 of} support) of the protective layer (per layer) is 0.
3 to 4.0 g / m ² is preferable, and 0.3 to 2.0 g / m ² is more preferable.

When the photothermographic material of the present invention is used for printing in which dimensional change is a problem, it is preferable to use polymer latex for the surface protective layer and the back layer.
Regarding such polymer latex, "Synthetic resin emulsion (Taira Okuda, edited by Hiroshi Inagaki, published by Kobunshi Kogyokai (1978))", "Application of synthetic latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Takashi) Molecular Publishing (1993)), "Chemistry of Synthetic Latex (Souichi Muroi, Polymer Publishing (1970))", and more specifically, methyl methacrylate (33.5% by mass).
/ Ethyl acrylate (50% by mass) / Methacrylic acid (16.5% by mass) copolymer latex, methyl methacrylate (4
7.5% by mass / butadiene (47.5% by mass) / itaconic acid (5% by mass)
%) Copolymer latex, ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate (58.9% by mass) / 2-ethylhexyl acrylate (2
5.4% by mass) / styrene (8.6% by mass) / 2-hydroxyethyl methacrylate (5.1% by mass) / acrylic acid (2.0% by mass) copolymer latex, methyl methacrylate (64.0% by mass) / styrene (9.0% by mass) / butyl Acrylate (20.0
Mass%) / 2-hydroxyethyl methacrylate (5.0 mass
%) / Acrylic acid (2.0 mass%) copolymer latex. Further, as a binder for the surface protective layer, a combination of polymer latexes of Japanese Patent Application No. 11-6872, paragraph Nos. 0021 to 0 of Japanese Patent Application No. 11-143058.
Paragraph number 00 of the technology described in 025, Japanese Patent Application No. 11-6872
The techniques described in paragraphs 0023 to 0041 of the specification of Japanese Patent Application No. 10-199626 may be applied. The ratio of polymer latex in the surface protection layer is 10 of the total binder.
Mass% or more and 90 mass% or less are preferable, and especially 20 mass% or more
It is preferably 80% by mass or less. The total coating amount (including water-soluble polymer and latex polymer) of the surface protective layer (per layer) is 0.3 to 5.0 per 1 m ^{2 of the} support.
preferably ^{g / m 2, 0.3~2.0g / m} 2 is more preferable.

The preparation temperature of the coating solution for the image forming layer of the present invention is 30
℃ or more and 65 ℃ or less is preferable, more preferable temperature is 35 ℃ or more
The temperature is lower than 60 ° C, more preferably 35 ° C or higher and 55 ° C or lower. Further, the temperature of the coating liquid for the image forming layer immediately after the addition of the polymer latex is preferably maintained at 30 ° C. or higher and 65 ° C. or lower.

The image forming layer of the present invention comprises one or more layers on a support. When it is composed of a single layer, it consists of an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, and optionally contains additional materials such as a toning agent, a coating aid and other auxiliary agents. When composed of two or more layers, the first image forming layer (usually a layer adjacent to the support) contains an organic silver salt and a photosensitive silver halide, the second
Some other component must be included in the imaging layer or layers. The composition of the multicolor photothermographic material is
Combinations of these two layers for each color may be included and all ingredients may be included in a single layer as described in US Pat. No. 4,708,928. In the case of multi-dye multicolor light-sensitive photothermographic materials, each emulsion layer generally comprises a functional or non-functional barrier layer between each light-sensitive layer as described in U.S. Pat.No. 4,460,681. By being used, they are retained separately from each other.

The photosensitive layer of the present invention contains various dyes and pigments (for example, CI Pigment Blue 60, C.I., etc.) from the viewpoint of improving color tone, preventing interference fringes during laser exposure, and preventing irradiation.
I.Pigment Blue 64, CI Pigment Blue 15: 6) can be used. About these, WO98 / 36322, JP
It is described in detail in Nos. 10-268465 and 11-338098.

In the photothermographic material of the invention, the antihalation layer can be provided on the side farther from the light source than the photosensitive layer.

The photothermographic material generally has a non-photosensitive layer in addition to the photosensitive layer. The non-photosensitive layer is (1) a protective layer provided on the photosensitive layer (the side farther than the support) from the arrangement, (2) between a plurality of photosensitive layers or between the photosensitive layer and the protective layer. Can be classified into an intermediate layer provided in (3), (3) an undercoat layer provided between the photosensitive layer and the support, and (4) a back layer provided on the opposite side of the photosensitive layer. The filter layer is
The layer (1) or (2) is provided on the photosensitive material.
The antihalation layer is provided on the photosensitive material as the layer (3) or (4).

Regarding the antihalation layer, Japanese Patent Application Laid-Open No. 11-1999
-65021, paragraph numbers 0123 to 0124, JP-A Nos. 11-223898 and 9
-230531, 10-36695, 10-104779, 11-23145
No. 7, No. 11-352625, No. 11-352626, etc. The antihalation layer contains an antihalation dye having absorption at the exposure wavelength. When the exposure wavelength is in the infrared region, an infrared absorbing dye may be used, and in that case, a dye having no absorption in the visible region is preferable. When using a dye having absorption in the visible region to prevent halation, it is preferable that the color of the dye does not substantially remain after image formation, and a means for erasing by heat of heat development is used. It is particularly preferable to add a heat-decolorizable dye and a base precursor to the non-photosensitive layer so that the non-photosensitive layer functions as an antihalation layer. These techniques are described in JP-A-11-231457 and the like.

The addition amount of the decolorizing dye is determined depending on the use of the dye. Generally, it is used in such an amount that the optical density (absorbance) when measured at a target wavelength exceeds 0.1. The optical density is preferably 0.15 to 2, and 0.2 to 1
Is more preferable. The amount of dye used for obtaining such an optical density is generally about 0.001 to 1 g / m ² .

By decoloring the dye in this way, the optical density after thermal development can be lowered to 0.1 or less. Two or more kinds of decolorizable dyes may be used together in the thermally decolorizable recording material or the photothermographic material. Similarly, two or more kinds of base precursors may be used in combination. In thermal erasing using such an erasing dye and a base precursor,
A substance (eg, diphenyl sulfone, 4-chlorophenyl (phenyl) sulfone), 2-naphthyl benzoate, etc. which lowers the melting point by 3 ° C. (deg) or more when mixed with a base precursor as described in JP-A-11-352626 is used in combination. It is preferable from the viewpoint of thermal decoloring property.

In the present invention, a colorant having an absorption maximum at 300 to 450 nm can be added for the purpose of improving the silver tone and the change with time of the image. Such colorants are disclosed in JP-A Nos. 62-210458, 63-104046, 63-103235 and 63-
208846, 63-306436, 63-314535, JP 01-6
1745, JP 2001-100363, etc. Such a colorant is usually added in the range of 0.1 mg / m ^{2 to 1} g / m ² , and the layer to be added is preferably a back layer provided on the opposite side of the photosensitive layer.

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. Preferably there is.

(Explanation of Matting Agent) In the present invention, it is preferable to add a matting agent in order to improve transportability. As for the matting agent, JP-A No. 11-65021, paragraphs 0126 to 01 can be used.
27. The matting agent is preferably 1 to 400 mg / m ² , and more preferably 5 to 300 mg / m ² when expressed as the coating amount per 1 m ² of the light-sensitive material. Also, the matteness of the emulsion surface may be anything as long as stardust failure does not occur, but the Beck smoothness is preferably 30 seconds or more and 2000 seconds or less, particularly 40 seconds or more.
It is preferably 1500 seconds or less. Beck's smoothness can be easily determined by Japanese Industrial Standards (JIS) P8119 "Smoothness test method for Beck tester of paper and board" and TAPPI standard method T479.

In the present invention, the matteness of the back layer preferably has a Bekk smoothness of 1200 seconds or less and 10 seconds or more,
It is preferably 20 seconds or less and 20 seconds or more, more preferably 500 seconds or less and 40 seconds or more.

In the present invention, the matting agent is preferably contained in the outermost surface layer or the layer functioning as the outermost surface layer of the light-sensitive material, or in the layer close to the outer surface, and in the layer acting as a so-called protective layer. It is preferably contained.

The back layer applicable to the present invention is described in paragraph Nos. 0128 to 0130 of JP-A No. 11-65021.

The photothermographic material of the present invention preferably has a film surface pH of 7.0 or less before heat development, and more preferably 6.6 or less. The lower limit is not particularly limited, but is about 3. Most preferred pH range is 4 to
The range is 6.2. From the viewpoint of reducing the film surface pH, it is preferable to use an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia for adjusting the film surface pH. Ammonia is particularly volatile so that it can be removed before the coating step or heat development, which is preferable for achieving a low film surface pH. It is also preferable to use a non-volatile base such as sodium hydroxide, potassium hydroxide or lithium hydroxide in combination with ammonia. The film surface pH is measured by Japanese Patent Application No. 11-87297.
No. 0123 of the specification.

A hardener may be used in each layer such as the photosensitive layer, the protective layer and the back layer of the present invention. An example of a hardener is T.
"THE THEORY OF THE PHOTOGRAPHIC PROCESS" by H. James
FOURTH EDITION ”(Macmillan Publishing Co., Inc.
, 1977) each method described on pages 77 to 87, chromium alum, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N , N-propylene bis (vinyl sulfone acetamide), polyvalent metal ions described on page 78 of the same book, polyisocyanates such as U.S. Pat. Vinyl sulfone compounds such as those disclosed in JP-A-62-89048 are preferably used.

The hardener is added as a solution, and the timing of adding this solution to the protective layer coating solution is from 180 minutes before to immediately before coating, preferably from 60 minutes before to 10 seconds before coating. The mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount sent to the coater is set to a desired time, and N. Harnby, MF Edwards, AW Nienow, translated by Koji Takahashi. "Liquid mixing technology" (published by Nikkan Kogyo Shimbun, 1989)
There is a method of using the static mixer described in Chapter 8 etc.

The surfactant applicable to the present invention is described in JP-A No. 11-65021, paragraph 0132, the solvent is paragraph 0133, the support is paragraph 0134, the antistatic or conductive layer is the same. No. 0135, No. 0136 of the same item for a method of obtaining a color image, and JP-A No. 11-84573, paragraphs 0061 to 0064 and Japanese Patent Application No.
No. 11-106881, paragraph numbers 0049 to 0062 are described.

In the present invention, it is preferable to have a conductive layer containing a metal oxide. As the conductive material of the conductive layer, a metal oxide in which oxygen defects and foreign metal atoms are introduced into the metal oxide to enhance the conductivity is preferably used. As an example of the metal oxide, ZnO, TiO ₂ , and SnO ₂ are preferable, and ZnO
Addition of Al and In for _{2 and} S for SnO2
It is preferable to add b, Nb, P, a halogen element, or the like, and to TiO ₂ , add Nb, Ta, or the like. SnO ₂ containing Sb is particularly preferable. The addition amount of the heteroatom is 0.01 to
30 mol% range is preferable, 0.1 to 10 mol
The range of% is more preferable. The shape of the metal oxide may be spherical, acicular, or plate-like, but acicular particles having a major axis / uniaxial ratio of 2.0 or more, preferably 3.0 to 50, are preferable in terms of the effect of imparting conductivity. The amount of metal oxide used is preferably 1 mg / m ^{2 to} 1000 m
in the range of g / m ^2, more preferably from ^{10mg / m 2 ~500mg / m 2} , more preferably in the range of ^{20mg / m 2 ~200mg / m 2} . The conductive layer of the present invention may be provided on either the emulsion surface side or the back surface side, but it is preferably provided between the support and the back layer. Specific examples of the conductive layer of the present invention are described in JP-A-7-29.
5146 and JP-A No. 11-223901.

In the present invention, it is preferable to use a fluorinated surfactant. Specific examples of the fluorine-based surfactant are JP-A-10-197985, JP-A-2000-19680, and JP-A-2000-21.
Examples thereof include compounds described in No. 4554 and the like. Further, a polymeric fluorine-based surfactant described in JP-A-9-281636 is also preferably used. In the present invention, it is particularly preferable to use the fluorine-based surfactant described in Japanese Patent Application No. 2000-206560.

The transparent support is a polyester heat-treated in the temperature range of 130 to 185 ° C. in order to alleviate the internal strain remaining in the film during biaxial stretching and to eliminate the heat shrinkage strain generated during the heat development treatment. Especially, polyethylene terephthalate is preferably used. In the case of a heat-developable photosensitive material for medical use, the transparent support has a blue dye (for example, JP-A-8-
It may be colored with the dye-1) described in Example No. 240877 or may be uncolored.

As the support, a water-soluble polyester described in JP-A No. 11-84574, a styrene-butadiene copolymer described in JP-A No. 10-186565, JP-A No. 2000-39684 and paragraph No. 0 of Japanese Patent Application No. 11-106881 can be used.
It is preferable to apply an undercoating technique such as a vinylidene chloride copolymer of 063 to 0080. Further, regarding the antistatic layer or undercoat, JP-A-56-143430, JP-A-56-143431,
58-62646, 56-120519, JP-A-11-84573, paragraph numbers 0040 to 0051, U.S. Pat.No. 5,575,957, JP-A-11-22
The technique described in paragraph numbers 0078 to 0084 of No. 3898 can be applied.

The photothermographic material is preferably a monosheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material).

The photothermographic material may further contain an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber or a coating aid. Various additives are added to either the photosensitive layer or the non-photosensitive layer. About them WO98
/ 36322, EP803764A1, JP-A-10-186567, 10-18
You can refer to No. 568 etc.

The photothermographic material in the invention may be coated by any method. Specifically, extrusion coating, slide coating, curtain coating, dip coating, knife coating,
Various coating operations are used, including flow coating, or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294, Stephen F. Kis.
"LIQUID FILM COATING" by tler, Petert M. Schweizer
(CHAPMAN & HALL, 1997) Extrusion coating described on pages 399 to 536, or slide coating is preferably used, and slide coating is particularly preferably used. For an example of the shape of the slide coater used for slide coating, see Figure 427 of the same book.
It is in 11b.1. If desired, the method described on pages 399 to 536 of the same document, U.S. Pat.No. 2,761,791 and British Patent 83.
Two or more layers can be coated simultaneously by the method described in 7,095.

The coating solution for the organic silver salt-containing layer in the present invention comprises
It is preferably a so-called thixotropic fluid. Regarding this technique, reference can be made to JP-A-11-52509. The organic silver salt-containing layer coating solution of the present invention has a viscosity at a shear rate of 0.1 S ⁻¹ of 400 mPa · s or more and 100,000 mPa · s.
The following is preferable, and more preferably 500 mPa · s or more 20,00
It is 0 mPa · s or less. Further, at a shear rate of 1000 S ^−1, it is preferably 1 mPa · s or more and 200 mPa · s or less, and more preferably 5 mPa · s or more and 80 mPa · s or less.

Techniques that can be used for the photothermographic material of the present invention include EP803764A1, EP883022A1 and WO98.
/ 36322, JP-A-56-62648, JP-A-58-62644, JP-A-9-
43766, 9-281637, 9-297367, 9-304869, 9
-311405, 9-329865, 10-10669, 10-62899
No. 10, No. 10-69023, No. 10-186568, No. 10-90823, No. 1
0-171063, 10-186565, 10-186567, 10-186
569 ~ 10-186572, 10-197974, 10-197982
No. 10, No. 10-197983, No. 10-197985 ~ No. 10-197987,
10-207001, 10-207004, 10-221807, 10-
282601, 10-288823, 10-288824, 10-30736
No. 5, No. 10-312038, No. 10-339934, No. 11-7100, No.
11-15105, 11-24200, 11-24201, 11-30832
No. 11, No. 11-84574, No. 11-65021, No. 11-109547, No. 1
1-125880, 11-129629, 11-133536 ~ 11-133
No. 539, No. 11-133542, No. 11-133543, No. 11-223898
No. 11, No. 11-352627, No. 11-305377, No. 11-305378,
11-305384, 11-305380, 11-316435, 11-
327076, 11-338096, 11-338098, 11-33809
No. 9, No. 11-343420, Japanese Patent Application No. 2000-187298, No. 2000-1022
No. 9, 2000-47345, 2000-206642, 2000-98530
No. 2000, No. 2000-98531, No. 2000-112059, No. 2000-112060
No. 2000-112104, 2000-112064, 2000-17193
No. 6 is also mentioned.

(Explanation of Packaging Material) The light-sensitive material of the present invention has a low oxygen permeability and / or a low moisture permeability in order to suppress fluctuations in photographic performance during raw storage or to improve curl, curl and the like. It is preferable to wrap with a packaging material. Specific examples of the packaging material having a low oxygen transmission rate and / or a water transmission rate include, for example, JP-A-8-25479.
No. 3. The packaging material is described in JP-A-2000-206653.

(Explanation of Thermal Development) The photothermographic material of the present invention may be developed by any method, but it is usually developed by raising the temperature of the imagewise exposed photothermographic material.
The preferred developing temperature is 80 to 250 ° C, preferably 100 to 140 ° C, more preferably 110 to 130 ° C. The development time is preferably 1 to 60 seconds, more preferably 3 to
30 seconds, more preferably 5 to 25 seconds and 7 to 15 seconds are particularly preferable.

As a method of heat development, a drum type heater,
Any plate type heater may be used, but the plate heater system is more preferable. The heat development method using the plate heater method is preferably the method described in JP-A-11-133572, and a heat treatment for obtaining a visible image by bringing the heat-developable photosensitive material on which a latent image is formed into contact with a heating means in the heat development section. In the developing device, the heating means is composed of a plate heater, and a plurality of pressing rollers are arranged to face each other along one surface of the plate heater, and the heat roller is provided between the pressing roller and the plate heater. It is a thermal developing device characterized by performing thermal development by passing a developing photosensitive material. Divide the plate heater into 2 to 6 stages and
It is preferable to lower the temperature by about 10 ° C. For example, there is an example in which four sets of plate heaters that can be independently temperature controlled are used and are controlled to 112 ° C., 119 ° C., 121 ° C. and 120 ° C., respectively. Such a method is disclosed in JP-A-54
-30032, water and organic solvent contained in the photothermographic material can be excluded from the system,
Further, it is possible to suppress the change in the shape of the support of the photothermographic material due to the rapid heating of the photothermographic material.

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 includes a gas laser (Ar ⁺ ,
He-Ne), YAG laser, dye laser, semiconductor laser and the like are preferable. Alternatively, a semiconductor laser and a second harmonic wave generating element may be used. Preferred is a gas of red to infrared emission or a semiconductor laser.

Fuji Medical Dry Laser Imager FM-DP L can be mentioned as a medical laser imager having an exposure section and a heat development section.
Regarding FM-DP L, Fuji Medical Review No.
It is needless to say that those techniques are applied as a laser imager of the photothermographic material of the present invention. It can also be applied as a photothermographic material for a laser imager in "AD network" proposed by Fuji Medical System as a network system adapted to the DICOM standard.

The photothermographic material of the present invention forms a black and white image by a silver image, and is used for medical diagnosis, photothermographic material for industrial photography, photothermographic material for printing, COM.
It is preferably used as a photothermographic material.

[0267]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1

(Preparation of PET support) Using terephthalic acid and ethylene glycol, an intrinsic viscosity IV = 0.66 (phenol / tetrachloroethane = 6/4 (weight ratio) was measured at 25 ° C.) according to a conventional method. Got PET. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., and contained 0.04 wt% of the dye BB having the following structure. Then, it was extruded from a T-die and rapidly cooled to prepare an unstretched film having a thickness such that the film thickness after heat setting was 175 μm.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C and 130 ° C, respectively.
After that, heat setting was carried out at 240 ° C. for 20 seconds, and then 4% relaxation was carried out in the lateral direction at the same temperature. After slitting the chuck part of the tenter, both ends were knurled and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

(Surface corona treatment) Both sides of the support were treated at 20 m / min at room temperature using a solid state corona treatment machine 6KVA model manufactured by Pillar Co. From the current and voltage readings at this time, it was found that the support had been treated at 0.375 kV · A · min / m ² . The processing frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[0271] (Preparation of undercoat support) (1) Preparation of coating liquid for undercoat layer Prescription (for undercoat layer on photosensitive layer)   Takamatsu Yushi Co., Ltd. pestle resin A-520 (30 mass% solution) 59g   Polyethylene glycol monononyl phenyl ether (Average number of ethylene oxide = 8.5) 10 mass% solution 5.4g Soken Chemical Co., Ltd. MP-1000 (polymer fine particles, average particle size 0.4 μm) 0.91 g   Distilled water 935ml

[0272] Prescription (for back surface first layer)   Styrene-butadiene copolymer latex 158g   (Solid content 40 mass%, styrene / butadiene weight ratio = 68/32)   2,4-Dichloro-6-hydroxy-S-triazine sodium salt 20 g of 8 mass% aqueous solution   10 ml of 1% by mass aqueous solution of sodium laurylbenzene sulfonate   Distilled water 854ml

Formulation (for second layer on back side) SnO ₂ / SbO (9/1 mass ratio, average particle size 0.038 μm, 17 mass% dispersion) 84 g Gelatin (10 mass% aqueous solution) 89.2 g Shin-Etsu Chemical Co., Ltd. ) Made by Metroses TC-5 (2% by mass aqueous solution) 8.6 g Soken Chemical Industry Co., Ltd. MP-1000 0.01 g 1% by mass aqueous solution of sodium dodecylbenzenesulfonate 10 ml NaOH (1% by mass) 6 ml Proxel (manufactured by ICI) 1 ml Distilled water 805ml

After subjecting both surfaces of the biaxially stretched polyethylene terephthalate support having a thickness of 175 μm to the corona discharge treatment, one side (the photosensitive layer side) of the undercoat coating solution formulation was coated with a wire bar to give a wet coating amount of 6.6. ml /
m ² (per surface) and dry at 180 ° C for 5 minutes, then apply the above-mentioned undercoat solution formulation to the back surface (back surface) with a wire bar to achieve a wet application amount of 5.7 ml / m ^2. And dry it at 180 ° C for 5 minutes, and then apply the above-mentioned undercoating liquid formulation on the back surface (back surface) with a wire bar so that the wet coating amount is 7.7 ml / m ² .
An undercoat support was prepared by drying at 6 ° C for 6 minutes.

(Preparation of coating liquid for back surface) (Preparation of solid fine particle dispersion liquid (a) of base precursor) 1.5 kg of base precursor compound 1 and a surfactant (trade name: DEMOL N, manufactured by Kao Corporation) ) 225 g, diphenyl sulfone 937.5 g, para-hydroxybenzoic acid butyl ester (trade name Plating: Ueno Pharmaceutical Co., Ltd.) 15
g and distilled water were added to make a total amount of 5.0 kg and mixed, and the mixture was dispersed in beads using a horizontal sand mill (UVM-2: manufactured by AIMEX Co., Ltd.). The dispersion method is as follows: The mixed solution is sent to UVM-2 filled with zirconia beads with an average diameter of 0.5 mm by a diaphragm pump, and the internal pressure is 50 hP.
In a state of a or above, dispersion was performed until a desired average particle size was obtained. The dispersion was dispersed until the ratio (D450 / D650) of the absorbance at 450 nm and the absorbance at 650 nm (D450 / D650) in the spectral absorption of the dispersion was measured to be 2.2 or more. The obtained dispersion was diluted with distilled water so that the concentration of the base precursor was 20% by weight, filtered for removing dust (a polypropylene filter having an average pore diameter of 3 μm), and put into practical use.

(Preparation of Dye Solid Fine Particle Dispersion) 6.0 kg of cyanine dye compound-1 and 3.0 kg of sodium p-dodecylbenzene sulfonate, 0.6 kg of surfactant Demol SNB manufactured by Kao Corporation, and defoaming Agent (trade name:
Surfynol 104E, manufactured by Nisshin Chemical Co., Ltd. 0.15
kg was mixed with distilled water to give a total liquid volume of 60 kg. The mixed solution is a horizontal sand mill (UVM-2: IMEX Co., Ltd.)
Manufactured by K.K.) and dispersed with 0.5 mm zirconia beads. The dispersion was dispersed until the ratio (D650 / D750) of the absorbance at 650 nm and the absorbance at 750 nm in the spectral absorption of the dispersion was 5.0 or more. The resulting dispersion has a cyanine dye concentration of 6
The mixture was diluted with distilled water so as to have a mass% and filtered with a filter (average pore size: 1 μm) to remove dust and put to practical use.

(Preparation of coating liquid for antihalation layer) Gelatin 30 g, polyacrylamide 24.5 g, 1 mol /
L caustic 2.2 g, monodisperse polymethylmethacrylate fine particles (average particle size 8 μm, particle size standard deviation 0.4)
2.4 g, benzoisothiazolinone 0.08 g, the above dye solid fine particle dispersion 35.9 g, the above base precursor solid fine particle dispersion (a) 74.2 g, sodium polyethylenesulfonate 0.6 g, blue dye compound- 1 was mixed with 0.21 g, yellow dye compound-1 was mixed with 0.15 g and acrylic acid / ethyl acrylate copolymer latex (copolymerization ratio 5/95) 8.3 g, and the whole was mixed with water to 8183 ml.
The anti-halation layer coating liquid was prepared.

(Preparation of Back Surface Protective Layer Coating Solution)
Keeping the temperature at 0 ° C., gelatin 40 g, liquid paraffin emulsion as liquid paraffin 1.5 g, benzoisothiazolinone 35 mg, 1 mol / L caustic 6.8 g, t-octylphenoxyethoxyethane sulfonate sodium 0.5
g, sodium polystyrene sulfonate 0.27 g, fluorine-based surfactant (F-1: N-perfluorooctylsulfonyl-N-propylalanine potassium salt) 37
mg, fluorinated surfactant (F-2: polyethylene glycol mono (N-perfluorooctylsulfonyl-N-
Propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide 15]) 150 mg, fluorosurfactant (F-3) 64 mg, fluorosurfactant (F-4) 3
2 mg, acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) 6.0 g, and N, N-ethylene bis (vinyl sulfone acetamide) 2.0 g were mixed and made to be 10 liters with water. It was used as a coating liquid.

(Preparation of Silver Halide Emulsion) << Preparation of Silver Halide Emulsion 1 >> To 1421 ml of distilled water was added 3.1 ml of 1% by mass potassium bromide solution.
3.5 ml of sulfuric acid having a concentration of 1 / L, phthalated gelatin 31.
The solution to which 7 g was added was stirred in a reaction vessel made of stainless steel, the solution temperature was kept at 30 ° C., distilled water was added to 22.22 g of silver nitrate, and the solution A and potassium bromide 1 were diluted to 95.4 ml.
5.3 g and potassium iodide 0.8 g with distilled water to a volume of 9
The total amount of Solution B diluted to 7.4 ml was added at a constant flow rate over 45 seconds. Then, 10 ml of a 3.5 mass% hydrogen peroxide aqueous solution was added, and further, 10.8 ml of a 10 mass% aqueous solution of benzimidazole was added. Furthermore, silver nitrate 5
Solution C prepared by adding distilled water to 1.86 g to dilute it to 317.5 ml, potassium bromide 44.2 g and potassium iodide 2.2.
Solution C prepared by diluting g with distilled water to a volume of 400 ml was added to Solution C at a constant flow rate over 20 minutes.
A controlled double jet method was added while maintaining Ag at 8.1. The total amount of potassium hexachloroiridium (III) acid salt was added 10 minutes after the addition of Solution C and Solution D was started so that the amount was 1 × 10 ⁻⁴ mol per mol of silver. In addition, 5 seconds after the addition of the solution C was completed, iron hexacyanide (I
I) An aqueous potassium solution was added in a total amount of 3 × 10 ⁻⁴ mol per mol of silver. The pH was adjusted to 3.8 with sulfuric acid having a concentration of 0.5 mol / L, the stirring was stopped, and the precipitation / desalting / water washing steps were performed. P using 1 mol / L concentration of sodium hydroxide
The mixture was adjusted to H5.9 and a silver halide dispersion having pAg 8.0 was prepared.

While stirring the above silver halide dispersion, 3
While maintaining the temperature at 8 ° C, 5 ml of 0.34% by mass of 1,2-benzisothiazolin-3-one in methanol was added, and 4
Spectral sensitizing dye A and spectral sensitizing dye B for comparison after 0 minutes
Of a methanol solution having a molar ratio of 1: 1 was added in an amount of 1.2 × 10 ⁻³ mol as the total amount of A and B per 1 mol of silver and the spectral sensitizing dyes DD-35 and DD-38 of the present invention were 1: 1. And a ratio of DD-36 to DD-39 of 1: 1 in methanol solution, 0.6 × 10 6 per mol of silver.
^A photothermographic material containing ^-3 mol was prepared as shown in Tables 1 and 2. After 1 minute, the temperature was raised to 47 ° C. After 20 minutes of heating, 7.6 × 10 ⁻⁵ mol of sodium benzenethiosulfonate was added to 1 mol of silver with a methanol solution, and 5 minutes later, tellurium sensitizer C was added with a methanol solution to 2.10 per mol of silver. 9 × 10 ⁻⁴ mol was added and the mixture was aged for 91 minutes. N, N '
1.3 ml of 0.8 mass% methanol solution of -dihydroxy-N "-diethylmelamine was added, and after 4 minutes, 5
-Methyl-2-mercaptobenzimidazole in methanol solution at 4.8 x 10 ^-3 moles per mole silver and 1-
Phenyl-2-heptyl-5-mercapto-1,3,4
A silver halide emulsion 1 was prepared by adding triazole in a methanol solution at 5.4 × 10 ⁻³ mol per mol of silver.

The grains in the prepared silver halide emulsion are
Average equivalent sphere diameter 0.042 μm, coefficient of variation of equivalent sphere diameter 20
% Silver iodobromide grains uniformly containing 3.5 mol% of iodine. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The {100} plane ratio of this grain was determined to be 80% using the Kubelka-Munk method.

<< Preparation of Silver Halide Emulsion 2 >> In the preparation of silver halide emulsion 1, the liquid temperature at the time of grain formation was set to 4 ° C.
The temperature was changed to 7 ° C., the solution B was changed to 15.9 g of potassium bromide diluted with distilled water to a volume of 97.4 ml, and the solution D was changed.
Changed to diluting 45.8 g of potassium bromide with distilled water to a volume of 400 ml, adding solution C for 30 minutes, and removing potassium hexacyanoferrate (II) in the same manner as above. A silver halide emulsion 2 was prepared. Precipitation / desalting / washing / dispersion were carried out in the same manner as in the silver halide emulsion 1. For comparison, a methanol solution of the spectral sensitizing dye A and the spectral sensitizing dye B having a molar ratio of 1: 1 was added in an amount of 8 × 10 ⁻⁴ mol as a total amount of A and B per mol of silver, and The sensitizing dyes DD-35 and DD-38 have a molar ratio of 1: 1 and DD.
Photothermographic materials were prepared as shown in Tables 1 and 2 in which 4 × 10 ⁻⁴ mol per mol of silver was added as a total of a methanol solution containing −36 and DD-39 in a molar ratio of 1: 1. Tellurium sensitizer C is added in an amount of 1.1 × 10 ⁻⁴ mol per mol of silver, 1
-Phenyl-2-heptyl-5-mercapto-1,3
Spectral sensitization, chemical sensitization and 5-methyl-2-mercaptobenzimidazole, 1-phenyl were carried out in the same manner as in Emulsion 1 except that 4-triazole was changed to 3.3 × 10 ^-3 mol per mol of silver. -2-heptyl-5-mercapto-
Silver halide emulsion 2 was obtained by adding 1,3,4-triazole. The emulsion grains of the silver halide emulsion 2 were pure silver bromide cubic grains having an average equivalent sphere diameter of 0.080 μm and a variation coefficient of the equivalent sphere diameter of 20%.

<< Preparation of Silver Halide Emulsion 3 >> In the preparation of Silver Halide Emulsion 1, the liquid temperature at the time of grain formation was set to 2 ° C.
Silver halide emulsion 3 was similarly prepared except that the temperature was changed to 7 ° C.
Was prepared. Further, precipitation / desalting / washing / dispersion were carried out in the same manner as in the silver halide emulsion 1. For comparison, the molar ratio of the spectral sensitizing dye A to the spectral sensitizing dye B is 1: 1 and the addition amount as a solid dispersion (gelatin aqueous solution) is 6 × 10 ⁻³ mol as the total amount of A and B per mol of silver. In the same manner as those added, the spectral sensitizing dyes DD-35 and DD-38 of the present invention were in a molar ratio of 1: 1 and DD-36 and DD-39 were in a molar ratio of 1 :.
3 × 10 ⁻³ per mol of silver as a total of 1 solid dispersion
A photothermographic material having a mole added was prepared as shown in Tables 1 and 2. The amount of the tellurium sensitizer C added is 5.2 × per mol of silver.
10 changed to ^-4 mol, bromide aurate to a 5 × 10 ^-4 mol of potassium thiocyanate per mole of silver was added 2 × 10 ^-3 mol per mol of silver after the addition thirds of tellurium sensitizer A silver halide emulsion 3 was obtained in the same manner as the emulsion 1 except for the above. The emulsion grains of Silver Halide Emulsion 3 have an average equivalent spherical diameter of 0.03.
The silver iodobromide grains were 4 μm and uniformly contained 3.5 mol% of iodine having a coefficient of variation of equivalent spherical diameter of 20%.

<< Preparation of Mixed Emulsion A for Coating Solution >> 70% by mass of silver halide emulsion 1, 15% by mass of silver halide emulsion 2 and 15% by mass of silver halide emulsion 3 were dissolved, and benzothiazolium iodine was dissolved. Id was added as an aqueous solution of 1% by mass at 7 × 10 ⁻³ mol per mol of silver. Further, the content of silver halide is 38.2 g as silver per 1 kg of the mixed emulsion for coating liquid.
Was added so that

<< Preparation of Fatty Acid Silver Dispersion A >> 87.6 kg of behenic acid (product name Edenor C22-85R) manufactured by Henkel, distilled water 423 L, 5 mol / L concentration NaOH aqueous solution 49.2
L and t-butyl alcohol 120L were mixed and stirred at 75 ° C. for 1 hour to cause a reaction to obtain a sodium behenate solution A. Separately, 206.2 L of an aqueous solution of 40.4 kg of silver nitrate
(PH 4.0) was prepared and kept at 10 ° C. 635
The reaction vessel containing L of distilled water and 30 L of t-butyl alcohol was kept at 30 ° C., and while stirring sufficiently, the total amount of the sodium behenate solution A and the total amount of the silver nitrate aqueous solution were maintained at a constant flow rate for 93 minutes 15 respectively. Add over seconds and 90 minutes. At this time, only the silver nitrate aqueous solution was added for 11 minutes after the addition of the silver nitrate aqueous solution was started, and then the sodium behenate solution A was started to be added, and after the addition of the silver nitrate aqueous solution was completed, only the sodium behenate solution A was added for 14 minutes and 15 seconds. Was added. At this time, the temperature inside the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The pipe of the addition system of the sodium behenate solution A was kept warm by circulating hot water outside the double pipe, and the liquid temperature at the outlet of the addition nozzle tip was adjusted to 75 ° C. Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution A and the addition position of the silver nitrate aqueous solution were symmetrically arranged with the stirring axis as the center, and the height was adjusted so as not to come into contact with the reaction solution.

After the addition of the sodium behenate solution A was completed,
Stir for 20 minutes at the same temperature for 3 minutes over 3 minutes
The temperature was raised to 5 ° C., and then aged for 210 minutes. Immediately after completion of the aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without being dried.

The morphology of the obtained silver behenate particles was evaluated by electron microscopic photography, and the average value was a = 0.14 μ.
It was a flaky crystal having m, b = 0.4 μm, c = 0.6 μm, an average aspect ratio of 5.2, an average equivalent sphere diameter of 0.52 μm, and a variation coefficient of the equivalent sphere diameter of 15%. (A, b, c are the rules of the text)

[0288] To a wet cake having a dry solid content of 260 kg, polyvinyl alcohol (trade name: PVA-21
7) Add 19.3kg and water, the total amount is 1000kg
Then, it was slurried with a dissolver blade and further preliminarily dispersed with a pipeline mixer (manufactured by Mizuho Industry: PM-10 type).

Next, the pressure of the pre-dispersed stock solution was set to 1 by a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidex International Corporation, using Z type interaction chamber).
It was adjusted to 260 kg / cm ² and treated three times to obtain a silver behenate dispersion. For the cooling operation, a spiral heat exchanger was attached before and after the interaction chamber, and the dispersion temperature was set to 18 ° C. by adjusting the temperature of the refrigerant.

<< Preparation of Silver Fatty Acid Dispersion B >><Preparation of Recrystallized Behenic Acid> 100 kg of behenic acid (product name Edenor C22-85R) manufactured by Henkel was mixed with 1200 kg of isopropyl alcohol and dissolved at 50 ° C. to 10 μm. After filtering with a filter of No. 3, it was cooled to 30 ° C. and recrystallized. The cooling speed during recrystallization was controlled at 3 ° C./hour. The crystals obtained are centrifugally filtered and subjected to 10
After washing with 0 kg of isopropyl alcohol, the product was dried. The obtained crystals are esterified to GC
-The FID measurement showed that the silver behenate content was 96.
%, And other than that, 2% of lignoceric acid and 2% of arachidic acid were contained.

<Preparation of Silver Fatty Acid Dispersion B> 88 kg of recrystallized behenic acid, 422 L of distilled water, 5 mol / L concentration of NaOH
49.2 L of aqueous solution and 120 L of t-butyl alcohol were mixed and stirred at 75 ° C. for 1 hour for reaction to obtain a sodium behenate solution B. Separately, 206.2 L of an aqueous solution of 40.4 kg of silver nitrate (pH 4.0) was prepared and kept at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of t-butyl alcohol was kept at 30 ° C., and while sufficiently stirring, the total amount of the sodium behenate solution B and the total amount of the silver nitrate aqueous solution were maintained at a constant flow rate for 93 minutes 15 respectively. Add over seconds and 90 minutes. At this time, 11
Only the aqueous solution of silver behenate was added for 1 minute, and then the addition of sodium behenate solution B was started, and only the solution of sodium behenate B was added for 14 minutes and 15 seconds after the addition of the aqueous solution of silver nitrate was completed. At this time, the temperature inside the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The pipe of the addition system of the sodium behenate solution B was kept warm by circulating hot water outside the double pipe, and the liquid temperature at the outlet of the addition nozzle tip was adjusted to 75 ° C. Further, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double tube. The addition position of the sodium behenate solution B and the addition position of the silver nitrate aqueous solution are symmetrically arranged around the stirring axis,
The height was adjusted so that it would not come into contact with the reaction solution.

After the addition of the sodium behenate solution B was completed,
Stir for 20 minutes at the same temperature for 3 minutes over 3 minutes
The temperature was raised to 5 ° C., and then aged for 210 minutes. Immediately after completion of the aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of the filtered water reached 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without being dried.

The morphology of the obtained silver behenate particles was evaluated by an electron microscopic photography. As a result, the average value was a = 0.21 μm.
m, b = 0.4 μm, c = 0.4 μm, average aspect ratio 2.1, average sphere equivalent diameter 0.51 μm, and variation coefficient of sphere equivalent diameter 11%. (A, b, c are the rules of the text)

For a wet cake having a dry solid content of 260 kg, polyvinyl alcohol (trade name: PVA-21
7) Add 19.3kg and water, the total amount is 1000kg
Then, it was slurried with a dissolver blade and further preliminarily dispersed with a pipeline mixer (manufactured by Mizuho Industry: PM-10 type).

Next, the pressure of the pre-dispersed stock solution is set to 1 by a disperser (trade name: Microfluidizer M-610, manufactured by Microfluidex International Corporation, using Z type interaction chamber).
It was adjusted to 150 kg / cm ² and treated three times to obtain a silver behenate dispersion. For the cooling operation, a spiral heat exchanger was attached before and after the interaction chamber, and the dispersion temperature was set to 18 ° C. by adjusting the temperature of the refrigerant.

(Preparation of Reducing Agent Dispersion) << Preparation of Reducing Agent Complex-1 Dispersion >> Reducing Agent Complex-1 (6
6'-di-t-butyl-4,4'-dimethyl-2,2 '
-Butylidene diphenol) and 1: 1 complex of triphenylphosphine oxide) 10 kg, triphenylphosphine oxide 0.12 kg and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10% by mass.
10 kg of water was added to 16 kg of the aqueous solution and mixed well to form a slurry. This slurry was sent by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm (UVM-2: manufactured by IMEX Co., Ltd.).
After dispersing for 4 hours and 30 minutes, 0.2 g of benzoisothiazolinone sodium salt and water are added to reduce the concentration of the reducing agent to 2
The reducing agent complex-1 dispersion was prepared by adjusting the amount to 2% by mass. The reducing agent complex particles contained in the thus obtained reducing agent complex dispersion had a median diameter of 0.45 μm and a maximum particle diameter of 1.4.
It was less than μm. The obtained reducing agent complex dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Reducing Agent-2 Dispersion >> Reducing Agent-2
(6,6'-di-t-butyl-4,4'-dimethyl-
2,2'-butylidene diphenol) 10 kg and denatured polyvinyl alcohol (Kuraray Co., Ltd., Poval MP20)
10 kg of water was added to 16 kg of the 10% by weight aqueous solution of 3) and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt. 0.2 g and water were added to prepare a reducing agent having a concentration of 25% by mass to obtain a reducing agent-2 dispersion. The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 1.5 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Hydrogen Bonding Compound-1 Dispersion >> Hydrogen Bonding Compound-1 (Tri (4-t-butylphenyl))
Phosphine oxide) 10Kg and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10 mass% aqueous solution 16K
10 g of water was added to g and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed for 3 hours and 30 minutes by a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a solid content concentration of 25% by mass to obtain a hydrogen-bonding compound-1 dispersion. The particles contained in the thus obtained dispersion had a median diameter of 0.35 μm and a maximum particle diameter of 1.5 μm or less. The obtained hydrogen-bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

<< Preparation of Development Accelerator-1 Dispersion >> 10 kg of development accelerator-1 and modified polyvinyl alcohol (Kuraray Co., Ltd.)
Manufactured by Poval MP203), 20 kg of 10 mass% aqueous solution, 10 kg of water
Was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and dispersed for 3 hours and 30 minutes by a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a solid concentration of 20% by mass to obtain a development accelerator-1 dispersion. The particles contained in the dispersion thus obtained had a median diameter of 0.48 μm and a maximum particle diameter of 1.4 μm or less. The resulting development accelerator-1 dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored.

The solid dispersions of Development Accelerator-2, Development Accelerator-3 and Color Tone Adjuster-1 were also dispersed in the same manner as in Development Accelerator-1 to obtain a 20% by mass dispersion.

(Preparation of Polyhalogen Compound) << Preparation of Dispersion of Compound Represented by General Formula (H) of Present Invention >> Compound Represented by General Formula (H) of the Present Invention 2) 10 kg and 20% by mass of denatured polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203)
10 kg of aqueous solution, 0.4 kg of 20 mass% aqueous solution of sodium triisopropylnaphthalene sulfonate, and 16 kg of water
Was added and mixed well to form a slurry. This slurry was sent by a diaphragm pump and filled with zirconia beads having an average diameter of 0.5 mm.
2: 5 as standard dispersion time by IMEX Co., Ltd.
After dispersion for a period of time, 0.2 g of benzoisothiazolinone sodium salt and water were added to prepare an organic polyhalogen compound having a concentration of 23.5% by mass, which is represented by the general formula (H) of the present invention. A dispersion of compounds was obtained. The compound particles contained in the dispersion thus obtained had a median diameter of 0.36 μm.
m and the maximum particle diameter was 2.0 μm or less. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust and stored. The dispersion time was adjusted so that the particle diameter of each compound was 0.38 μm.

<< Preparation of Phthalazine Compound-1 Solution >> 8 kg
Denatured polyvinyl alcohol MP203 manufactured by Kuraray Co., Ltd. in water 1
Dissolve in 74.57Kg, and then add 3.15Kg of 20 mass% aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28Kg of 70 mass% aqueous solution of phthalazine compound-1 (6-isopropylphthalazine), and add 5 mass of phthalazine compound-1. % Solution was prepared.

(Preparation of mercapto compound) << Preparation of mercapto compound-1 aqueous solution >> 7 g of mercapto compound-1 (1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt) was dissolved in 993 g of water, and
A 7 mass% aqueous solution was prepared.

<< Preparation of Mercapto Compound-2 Aqueous Solution >> Mercapto Compound-2 (1- (3-methylureido) -5
-Mercaptotetrazole sodium salt) 20 g water 980
g to give a 2.0 mass% aqueous solution.

<< Preparation of Pigment-1 Dispersion >> CI Pigment Bl
64 g of ue 60, 6.4 g of Demol N manufactured by Kao Corporation, and 250 g of water were added and mixed well to form a slurry. Prepare 800 g of zirconia beads with an average diameter of 0.5 mm, put them in a vessel together with the slurry, and use a disperser (1/4 G sand grinder mill:
It was dispersed for 25 hours with IMEX Co., Ltd. to obtain a pigment-1 dispersion. The pigment particles contained in the thus-obtained pigment dispersion had an average particle diameter of 0.21 μm.

<< Preparation of SBR Latex Liquid >> Tg = 22 ° C.
The SBR latex of was prepared as follows. Ammonium persulfate was used as a polymerization initiator, an anionic surfactant was used as an emulsifier, and 70.0 mass of styrene and 2 parts of butadiene were used.
After emulsion polymerization of 7.0 mass and 3.0 mass of acrylic acid, aging was carried out at 80 ° C. for 8 hours. Then 40
The mixture was cooled to 0 ° C., adjusted to pH 7.0 with aqueous ammonia, and further added with SANDET BL manufactured by Sanyo Kasei Co., Ltd. so that the concentration was 0.22%. Next, a 5% aqueous sodium hydroxide solution was added to adjust the pH to 8.3, and the pH was adjusted to 8.4 with aqueous ammonia. The molar ratio of Na ⁺ ion and NH ₄ ⁺ ion used at this time was 1: 2.3. Furthermore, this liquid 1
Benzisothiazolinone sodium salt 7% against Kg
An SBR latex liquid was prepared by adding 0.15 ml of the aqueous solution.

(SBR latex: -St (70.0) -Bu (27.0) -AA
(3.0) -Latex) Tg22 ℃, average particle size 0.1μm, concentration 43 mass%, equilibrium water content 0.6 mass% at 25 ℃ 60% RH, ionic conductivity 4.2mS / cm (Ion conductivity is measured by Toa Denpa Kogyo) Conductivity meter CM-30S manufactured by Co., Ltd. was used to measure the latex stock solution (43% by mass) at 25 ° C), and the SBR latex with different pH 8.4 Tg was changed in the same manner by appropriately changing the ratio of styrene and butadiene. Can be adjusted by.

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1 >>
1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, 33.2 g of pigment-1 dispersion, 173 g of phthalazine compound-1 solution, 1082 g of SBR latex (Tg: 22 ° C.) liquid, 299 g of reducing agent complex-1 dispersion,
Development accelerator-1 dispersion 6 g, mercapto compound-1 aqueous solution
9 ml, 27 ml of mercapto compound-2 aqueous solution were sequentially added,
The dispersion of the compound represented by formula (H) of the present invention was added so as to have the contents shown in Tables 1 and 2. Immediately before coating, 117 g of silver halide mixed emulsion A was added and well mixed, and the emulsion layer coating solution was sent directly to the coating die for coating.

The viscosity of the emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki Co., Ltd. and measured at 2 ° C. at 40 ° C. (No. 1 rotor, 60 rpm).
It was 5 [mPa · s]. The viscosity of the coating solution at 25 ° C using a Rheometrics Far East Co., Ltd. RFS fluid spectrometer has shear rates of 0.1, 1, 10, 10
230, 60, 46, 24, 18 [m at 0, 1000 [1 / sec] respectively
Pa · s].

The amount of zirconium in the coating solution was 0.38 mg per 1 g of silver.

<< Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-2 >>
1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, 32.8 g of pigment-1 dispersion, 173 g of phthalazine compound-1 solution, 1082 g of SBR latex (Tg: 20 ° C.) liquid, 155 g of reducing agent-2 dispersion, hydrogen bonding property. Compound-1 dispersion 55g, development accelerator-1 dispersion 6
g, development accelerator-2 dispersion 2g, development accelerator-3 dispersion 3
g, a color tone adjusting agent-1 dispersion 2 g, and a mercapto compound-2 aqueous solution 6 ml are sequentially added so that the dispersion of the compound represented by the general formula (H) of the present invention has the contents shown in Tables 1 and 2. Was added to. Immediately before coating, 117 g of silver halide mixed emulsion A was added and well mixed, and the emulsion layer coating solution was sent directly to the coating die for coating. The viscosity of the emulsion layer coating solution is measured with a Tokyo Keiki B-type viscometer at 40 ° C (No. 1 rotor, 6
It was 40 [mPa · s] at 0 rpm. Using a Rheometrics Far East Co., Ltd. RFS Fluid Spectrometer, the viscosity of the coating solution at 25 ° C has a shear rate of 0.1,
530, 144, 9 at 1, 10, 100, 1000 [1 / sec] respectively
It was 6, 51, 28 [mPa · s].

The amount of zirconium in the coating solution was 0.25 mg per 1 g of silver.

<< Preparation of Emulsion Surface Intermediate Layer Coating Liquid >> Polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) 1000 g, 5% by weight pigment dispersion 272 g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid Copolymer (copolymerization weight ratio 64/9/20/5/2) Latex 19
To 4200 ml of a mass% liquid, 27 ml of a 5 mass% aqueous solution of aerosol OT (manufactured by American Cyanamid), 135 ml of a 20 mass% aqueous solution of diammonium phthalate salt, and water were added so that the total amount becomes 10,000 g, and the pH was 7.5. Was adjusted with NaOH to obtain a coating solution for the intermediate layer, and the solution was fed to the coating die at 9.1 ml / m ² . The viscosity of the coating solution was 58 [mPa · s] at 40 ° C. with a B type viscometer (No. 1 rotor, 60 rpm).

<< Preparation of Emulsion Surface Protective Layer First Layer Coating Solution >> 64 g of inert gelatin was dissolved in water to prepare methyl methacrylate.
/ Styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20
/ 5/2) Latex 27.5% by weight liquid 80 g, phthalic acid 10% by weight methanol solution 23 ml, 4-methylphthalic acid 10% by weight
23 ml of aqueous solution, 28 ml of 0.5 mol / L sulfuric acid, aerosol
5m of 5 mass% aqueous solution of OT (American Cyanamid)
l, phenoxyethanol 0.5g, benzisothiazolinone 0.1g, water was added to make a total amount of 750g to make a coating solution, and 48.6% by mass of chromium alum 26ml was mixed with a static mixer immediately before coating 18.6ml. The solution was fed to the coating die so that it became / m ² . The viscosity of the coating liquid was 20 [mPa · s] at 40 ° C. (B-type viscometer, No. 1 rotor, 60 rpm).

<< Preparation of Coating Solution for Second Layer of Emulsion Protecting Layer >> 80 g of inert gelatin was dissolved in water to prepare methyl methacrylate.
/ Styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20
/ 5/2) 102 g of latex 27.5% by mass liquid, fluorosurfactant (F-1: N-perfluorooctylsulfonyl-N-
3.2 ml of a 5 mass% solution of propylalanine potassium salt),
Fluorine-based surfactant (F-2: polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2
-Aminoethyl) ether [ethylene oxide average degree of polymerization =
15]) 2% by mass aqueous solution 32 ml, aerosol OT (manufactured by American Cyanamid) 23% by mass solution, polymethylmethacrylate fine particles (average particle size 0.7 μm) 4 g, polymethylmethacrylate fine particles (average particle size) Diameter 4.5 μm) 21 g, 4-
Methylphthalic acid (1.6 g), phthalic acid (4.8 g), 0.5 mol / L sulfuric acid (44 ml), benzisothiazolinone (10 mg) were added with water to a total amount of 650 g, and 4% by mass of chromium alum and 0.67
445 ml of an aqueous solution containing phthalic acid by mass was mixed with a static mixer immediately before coating to form a coating solution for the surface protective layer, which was fed to the coating die at 8.3 ml / m ² . The viscosity of the coating liquid is B type viscometer 40 ℃ (No.1 rotor, 60rp
It was 19 [mPa · s] in m).

<< Preparation of Photothermographic Materials-1 to 15 >> An antihalation layer coating solution was applied to the back side of the undercoat support so that the coating amount of gelatin was 0.44 g / m ² and the back side protective layer was used. The coating solution was simultaneously multilayer-coated so that the gelatin coating amount was 1.7 g / m ^2, and dried to form a back layer.

Simultaneous multi-layer coating by the slide bead coating method in the order of the emulsion layer (emulsion layer coating solution-1), the intermediate layer, the protective layer first layer and the protective layer second layer from the undercoating surface to the surface opposite to the back surface. Then, a sample of the photothermographic material was prepared. At this time, the emulsion layer and the intermediate layer were adjusted to 31 ° C, the protective layer first layer was adjusted to 36 ° C, and the protective layer first layer was adjusted to 37 ° C. The coating amount (g / m ² ) of each compound in the emulsion layer is as follows.

[0318] Fatty acid silver dispersion A (as fatty acid Ag) 5.55 Pigment (C.I.Pigment Blue 60) 0.036 Phthalazine compound-1 0.19 SBR latex 9.97 Reducing agent complex-1 1.41 Development accelerator-1 0.024 Mercapto compound-1 0.002 Mercapto compound-2 0.012 Silver halide (as Ag) 0.091 The compound of the general formula (H) of the present invention

The coating and drying conditions are as follows. The coating was performed at a speed of 160 m / min, the gap between the tip of the coating die and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set to 196 to 882 Pa lower than the atmospheric pressure. Prior to coating, the support was neutralized with an ionic wind. In the subsequent chilling zone,
After the coating liquid is cooled with a wind with a dry-bulb temperature of 10 to 20 ° C, it is transported in a non-contact type, and in a spinning type non-contact type drying device, a dry-bulb temperature of 23 to 45 ° C and a wet-bulb temperature of 15 to 21. It was dried with a drying air of ° C.
After drying, condition the humidity at 40 to 60% RH at 25 ° C, and
Heated to ~ 90 ° C. After heating, the film surface was cooled to 25 ° C.

The matteness of the prepared photothermographic material was Bekk smoothness of 550 seconds on the photosensitive layer side and 130 seconds on the back side. Also, when the pH of the film surface on the photosensitive layer side was measured
It was 6.0.

<< Preparation of Photothermographic Materials-16 to 30 >> For the photothermographic materials-1 to 15, emulsion layer coating solution-1 was changed to emulsion layer coating solution-2, and the halation prevention layer was changed to yellow. Except for the dye compound 15, fluorine-containing surfactants for the back surface protective layer and the emulsion surface protective layer are F-1, F-2 and F.
-3 and F-4 to F-5, F-6, F-7, respectively.
Further, the photothermographic materials-16 to 30 were produced in the same manner as the photothermographic material-1 except that the photothermographic material-1 was changed to F-8. The coating amount (g / m ² ) of each compound in the emulsion layer at this time is as follows.

Fatty Acid Silver Dispersion B (as Fatty Acid Ag) 5.55 Pigment (CIPigment Blue 60) 0.036 Phthalazine Compound-1 0.19 SBR Latex 9.67 Reducing Agent-2 0.81 Hydrogen Bonding Compound-1 0.30 Development Accelerator-1 0.024 Development Accelerator-2 0.010 Development Accelerator-3 0.015 Color Tone Adjuster-1 0.010 Mercapto Compound-2 0.002 Silver Halide (as Ag) 0 0.091 Compounds of General Formula (H) of the Present Invention Amounts shown in Table 2 The chemical structures of the compounds used in Examples of the present invention are shown below.

[0323]

[Chemical 57]

[0324]

[Chemical 58]

[0325]

[Chemical 59]

[0326]

[Chemical 60]

[0327]

[Chemical formula 61]

(Evaluation of Photographic Performance) The obtained sample was cut into half-size pieces, packaged in the following packaging materials in an environment of 25 ° C. and 50%, stored at room temperature for 2 weeks, and then evaluated as follows. It was (Packaging material) PET 10 μm / PE 12 μm / Aluminum foil 9 μm / Ny 15 μm / Polyethylene 50 μm containing 3% carbon Oxygen permeability: 0.02 ml / atm · m ² · 25 ° C · day, Moisture permeability: 0.10 g / atm · m ²・ 25 ℃ ・ day

The sample was exposed and developed by the Fuji Medical Dry Laser Imager FM-DPL (equipped with a 660 nm semiconductor laser with a maximum output of 60 mW (IIIB)) (112 ° C.-119 ° C.).
Photodevelopable photosensitive materials-1 to 15 with a total of 24 seconds with four panel heaters set at -121 ° C-121 ° C, photodevelopable photosensitive material-1
The total of 6 to 30 was 14 seconds), and the obtained image was evaluated by a densitometer. The sensitivity was shown as a relative value with the reciprocal of the exposure amount required to give a fog plus blackening density of 1.0 of the photothermographic material of the invention being 100. The larger the value, the higher the sensitivity.

(Evaluation of Raw Preservability-1) The photothermographic material prepared above was used in a room at a temperature and humidity of 25 ° C. and 40%.
101 sheets of 4 × 17 inch size samples were stacked, sandwiched between polypropylene sheets, and then placed in a packaging material A and sealed. Packaging material A has an oxygen transmission rate of 0.02 ml /
Atm · m ² · 25 ° C. · day, moisture permeability =
0.1 g / atm · m ² · 25 ° C. · day, and the material is nylon (15 μm) / aluminum foil (9 μm) / carbon black mixed polyethylene (80 μm). The sample contained in the packaging material A was further placed in a paper cosmetic box and packaged in a cardboard. This sample at 40 ℃ 30
Photographic performance was evaluated after the passage of time.

(Raw storability evaluation-2) Instead of the packaging material A, the packaging material B (oxygen permeability = 50 ml / atm · m ² ·
25 ° C ・ day, moisture permeability = 15 g / atm ・ m ²・
Evaluation was carried out in the same manner as in Raw Preservation Evaluation-1 using 25 ° C./day). The material of the packaging material B is polyethylene (50 μm) mixed with carbon black.

As is clear from the results shown in Tables 1 and 2, the photothermographic material having the constitution of the present invention realizes high sensitivity and low fog, and shows little deterioration in sensitivity even after aging under forced storage conditions. It had little increase and had good raw preservation properties. Further, in a particularly preferred embodiment of the present invention, a compound of the general formula (H) in which Q is a heterocyclic group is included, and a compound of the general formula (H) having a melting point of 170 ° C. or lower is In particular, the evaluation of the raw storage stability showed a higher sensitivity and a lower fog value, and the raw storage stability was better.

[0333]

[Table 1]

[0334]

[Table 2]

[0335]

INDUSTRIAL APPLICABILITY The photothermographic material of the present invention has a high sensitivity and a low fog by combining a specific antifoggant and a sensitizing dye, and has a small decrease in sensitivity even after aging under forced storage conditions. It is possible to provide a heat-developable light-sensitive material that has a small increase in fog and has good raw storage stability.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Eiichi Okuzu             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H123 AB00 AB01 AB03 AB18 AB23                       AB25 BB00 BB09 BB21 BB23                       BB27 CB00 CB03

Claims (10)

[Claims] 1. A photothermographic material containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent, and a binder on the same surface of a support, which comprises (a) two or more dye chromophores. A photothermographic material comprising a compound, and (b) at least one compound represented by the following general formula (H). Formula (H) Q- (Y) n -C (Z 1) (Z 2) X [ Formula (H), Q represents an alkyl group, an aryl group or a heterocyclic group, Y is a divalent linking of Represents a group, n
Represents 0 or 1, Z ₁ and Z ₂ represent a halogen atom, and X represents a hydrogen atom or an electron-withdrawing group. ] 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 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 Z¹⁵And 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, m¹⁹Is 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 above two R⁵²Each other or R⁵³One of the two is joint
And the linking group L^FiveTo form. [In the formula (XXXIb), Z⁵³
Is an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, or charcoal.
Represents an elementary atom. R⁵², And R⁵³Is an alkyl group, aryl
Represents a group or a heterocyclic group. However, two R⁵²Each other, or
R⁵³One of them is jointly L^FiveTo form. L^FiveIs
Represents a linking group. L⁵⁸, L⁵⁹, L⁶⁰, L⁶¹, And L⁶²Hame
Represents a tin group. V⁵⁹, V⁶⁰, V⁶¹, V⁶², V⁶³, V⁶⁴,
V⁶⁵, V⁶⁶, V⁶⁷, And V⁶⁸Is a hydrogen atom or a substituent
Represent M⁵²Represents a charge-balancing counterion, m⁵²Is the electric charge of the molecule
Represents a number greater than or equal to 0 required to neutralize a load. ] [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 the compound represented by formula (H) has a melting point of 170 ° C. or lower. 9. The photothermographic material according to claim 1, wherein Q in the compound represented by formula (H) is a heterocyclic group. 10. A compound having at least one compound in which Q in the general formula (H) is a heterocyclic group and having a melting point of 170.
10. The photothermographic material according to claim 1, further comprising at least one compound represented by the general formula (H) having a temperature of not higher than C.