JPH09160166A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photosensitive material sensitive in panchromatic or infrared wavelength region and high in Dmax and sharp in the toe and high in contrast by incorporating at least an organic acid silver salt and the like, and a cyanine dye having at least one group having a thioether bond. SOLUTION: This heat-developable photosensitive material contains at least the organic acid silver salt, the silver halide, and the hydrazine derivative, and the cyanine dye having at least one group having a thioether bond. The organic acid silver salt to be used for this heat-developable photosensitive material is an organic acid silver salt and a hetero organic acid silver salt, and especially, the silver salt of a long-chain aliphatic carboxylic acid is preferably. The silver halide functions as a photosensor and it is preferred that the average grain size is small in order to restrain effectively white clouding after image formation and to obtain good image quality. An amount of the above-mentioned cyanine dye to be added is, preferably, 0.1-100mg/m<2> , especially, 1-20mg/m<2> .

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photothermographic material, and more particularly to a photothermographic material suitable for printing plate making.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials) Neblette Eighth Edition, Sturge, V. Walworth
orth), A. Edited by Shepp, page 2, 196
It was disclosed in 9 years. Such a photothermographic material is
A reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), a toning agent for controlling the color of silver and a reducing agent are usually contained in a binder matrix in a dispersed state. Although the photothermographic material is stable at room temperature, it can be reduced by a redox reaction between a silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature (for example, 80 ° C. or higher) after exposure. Produces silver. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. Such a photothermographic material has been used for micro sensitive materials and X-rays, but it is only partially used as printing sensitive materials. It has a low Dmax of the obtained image, and has poor leg leginess,
This is because the image quality is extremely poor as a printing photosensitive material due to the soft gradation. On the other hand, with the recent development of lasers and light-emitting diodes, scanners and imagesetters having an oscillation wavelength of 600 to 800 nm have become widespread, and development of sensitive materials with high sensitivity, high Dmax, and suitable for these output machines. Was strongly desired. Also, demands for simple processing and dry processing are increasing.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material having a high sensitivity in the panchromatic or infrared wavelength range, a high Dmax and a good sharpness.
An object of the present invention is to provide a photosensitive material for printing which has a good image quality. Another object of the present invention is to provide a completely dry processed photosensitive material for printing which does not require wet processing.

[0004]

The above object of the present invention is to provide at least one organic acid silver salt, a silver halide, a hydrazine derivative and a substituent having a thioether bond.
It is achieved by a photothermographic material characterized in that it contains a cyanine dye having an individual number.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The photothermographic material of the present invention contains silver organic acid. Silver salts of organic acids and heteroorganic acids, especially long-chain (10-30, preferably 15-25 carbon atoms) aliphatic carboxylic acids are preferred. The ligand is 4.0-1
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 0.0 are also useful. An example of a suitable silver salt is Rese
Described in arch Disclosure Nos. 17029 and 29963 and include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkyl thioureas. Salt (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); Silver complex of polymer reaction product of aldehyde and hydroxy-substituted aromatic carboxylic acid (For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (for example, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid,
5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene, and 3-carboxymethyl-4-). (Thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,
Complexes or salts of silver with a nitric acid selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime Silver salts such as; and silver salts of mercaptides. The preferred silver source is silver behenate. The amount of organic acid silver used is preferably 3 g / m ² or less in terms of silver amount. More preferably 2 g / m ²
It is as follows.

The silver halide in the present invention functions as an optical sensor. The silver halide preferably has a small average grain size in order to suppress white turbidity after image formation and obtains good image quality, and the average grain size is 0.20 μm or less, more preferably 0.03 μm.
m to 0.15 μm, particularly 0.03 μm to 0.11 μm is preferable. The term "grain size" as used herein refers to the length of the edges of silver halide grains when the silver halide grains are cubic or octahedral so-called normal crystals. Also, in the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it means the diameter when considering the sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grain is not particularly limited, but it is preferable that the Miller index [100] plane occupy a high proportion, and this proportion is 50% or more, and further 7
It is preferably 0% or more, and particularly preferably 80% or more. The ratio of Miller index [100] planes is based on the adsorption dependence of [111] planes and [100] planes in the adsorption of sensitizing dyes.
T. Tani, J. Imaging Sci., 29, 165 (1985).

The halogen composition is not particularly limited and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. Preferred is silver bromide or silver iodobromide. The photographic emulsion used in the present invention is P.Gl.
afkides Chimie et Physique Photographique (Paul
Montel, 1967), GF Duffin Photograph
ic Emulsion Chemistry (The Focal Press, 196
6), VL Zelikman et al, Making and Coating P
hotographic Emulsion (Published by The Focal Press, 1964
Year)). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. The silver halide may be prepared by converting a part or all of silver in the organic acid silver into a silver halide by the reaction of the organic acid silver and a halogen ion, or the silver halide may be prepared in advance. It may be added to the solution for preparing the organic silver salt, or a combination of these methods is possible. The latter is preferred. Generally, silver halide is 0.75 with respect to a reducible silver source (organic acid silver).
It is preferred to contain an amount of -30% by weight.

The silver halide grains used in the present invention are
Those containing an ion or a complex ion of a metal belonging to Group VII or Group VIII of the periodic table are preferable. The above metals include Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re,
There are Os, Ir, Pt, Au, but among them, Rh, Re, Ru, Os, Ir,
It is preferably selected from Co and Fe, and particularly preferably Fe and Ir. One kind of these metal ions or complex ions may be used, or two or more kinds of the same kind of metal and different kinds of metal may be used in combination. The content of these metal ions or complex ions is generally 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, and preferably 1 × 10 ⁻⁸ to 1 per mol of silver halide. It is × 10 ^-4 mol. A compound providing an ion or complex ion of these metals is preferably added at the time of silver halide grain formation and incorporated into the silver halide grain. Preparation of the silver halide grain, that is, nucleation, growth, physical ripening , It may be added at any stage before and after the chemical sensitization, but it is particularly preferable to add it at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth. It is preferably added at the stage of nucleation. Upon addition, the silver halide grains may be added dividedly over several times, or may be uniformly contained in the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683.
It is also possible to have a distribution within the particles, as described in the above publication. Preferably, it can have a distribution inside the particles. These metal compounds are water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides).
Can be added by dissolving it in a water-soluble silver salt solution or a water-soluble halide solution during grain formation, for example, an aqueous solution of a metal compound powder or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together. The method of adding or when the silver salt solution and the halide solution are mixed at the same time
As an aqueous solution of the above, and a method of preparing silver halide grains by a method of simultaneous mixing with three liquids, a method of adding an aqueous solution of a metal compound in a necessary amount into a reaction vessel during grain formation, or a method of preparing a metal halide in advance at the time of preparing silver halide. Another method is to add and dissolve another silver halide grain doped with ions or complex ions. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which the metal compound and NaCl or KCl are dissolved together to a water-soluble halide solution is preferable.
When added to the particle surface, a necessary amount of an aqueous solution of a metal compound can be added to the reaction vessel immediately after particle formation, during or during physical ripening, or at the time of chemical ripening.

A water-soluble rhodium compound can be used as the rhodium compound. For example, a halogenated rhodium (III) compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaammine rhodium ( III) complex salts, trioxalatrodium (III) complex salts and the like.

Rhenium, ruthenium and osmium compounds are disclosed in European Patents (EP) 0336689A, 0336427A1, 0336425A1 and 0.
The water-soluble complex salts described in JP-A-336426A1, JP-A-63-2042, JP-A-1-285941 and JP-A-2-20855 are preferred. A hexadentate complex represented by the following formula is particularly preferable. [ML ₆ ] ^-n where M is rhenium, ruthenium, osmium,
n represents 0, 1, 2, 3 or 4. L is a ligand, preferably, a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand and the like can be mentioned. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Specific examples include the following. (ReCl ₆ ) ^-3 (ReBr ₆ ) ^-3 (ReCl ₅ (NO)) ^-2 (Re (NS) Br ₅ ) ^-2 (Re (NO) (CN) ₅ ) ^-2 (Re (O) ₂ ( CN) ₄ ) ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) ₆ ] ^{- 4} (Ru (CO) ₃ Cl ₃ ) ^-2 (Ru (CO) Cl ₅ ) ^-2 (Ru (CO) Br ₅ ) ^-2 (OsCl ₆ ) ^-3 (OsCl ₅ (NO)) ^-2 (Os ( NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

As the iridium compound, various compounds can be used. For example, hexachloroiridium (III) complex salt, hexachloroiridium (IV) complex salt, hexabromoiridium (III) complex salt, hexabromoiridium (IV) complex salt, hexaiodoiridium (III) III) Complex salt, hexaiodoiridium (IV) complex salt, hexaammineiridium (III)
Examples thereof include complex salts, hexaammineiridium (IV) complex salts, hexacyanoiridium (III) complex salts, triogizaratiridium complex salts, and the like.

Although various compounds can be used as the cobalt compound, a hexacyano complex is particularly preferable, and an example thereof is [Co (CN) ₆ ] ^-3 (a counter ion is not important but, for example, ammonium, Alkali metal ions are included).

The iron compound is a divalent or trivalent water-soluble iron ion-containing compound, and specifically, ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, citric acid. Ferrous iron, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate , Ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate, ferrous ammonium nitrate, basic ferric acetate, ferric albumin, ferric ammonium acetate, bromide Ferric, ferric chloride, ferric chlorate, ferric citrate, ferric fluoride, ferric formate, ferric glycerophosphate, ferric hydroxide, acidic phosphoric acid Ferric, ferric nitrate, ferric phosphate, ferric pyrophosphate, ferric sodium pyrophosphate, ferric thiocyanate, ferric sulfate, ferric sulfate ammonium , Ferric sulfate guanidine sulfate, ferric ammonium citrate, potassium hexanecyanoferrate (II) acid, ferric potassium benthacyanoammine, sodium ferric ethylenedinitrilotetraacetate, potassium hexacyanoferrate (III), Ferric tris (dipyridyl) chloride,
There are potassium pentacyanonitrosyl ferric and ferric hexarea chloride. Among these, hexacyanoferrate (II) and hexacyanoferrate (III) show remarkable effects.

The hydrazine derivative used in the present invention is
A compound represented by the following general formula (III) is preferable. General formula (III)

[0016]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
A —SO ₂ — group, a —SO— group,

[0018]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (III), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (III),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring,
Pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, hydrazide Group having a quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl Group, halogen atom, cyano group, phosphoric acid amide group, diacylamino group, imide group, group having an acylurea structure, group containing a selenium atom or tellurium atom, tertiary sulfonium structure, etc. Is a group having a quaternary sulfonium structure. Preferred examples of the substituent include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety having a carbon number of 1 to 20). Monocyclic or bicyclic one to three), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
0), a ureido group (preferably having 1 to 3 carbon atoms)
0), a phosphoric amide group (preferably having 1 carbon atom)
To 30).

In the general formula (III), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
A hydrogen atom, an alkyl group (eg, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (eg, an o-hydroxybenzyl group, etc.), Aryl group (for example, phenyl group, 3,5
- dichlorophenyl group, o- methanesulfonamidophenyl group, 4-methanesulfonyl phenyl, and 2-hydroxymethyl phenyl _{group), - C 2 F 4 COOM} (M: a hydrogen atom, an alkali metal atom) and the like. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferred.
As G in the general formula (III), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (III) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (III) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (III) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivative in the present invention is that R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, Or a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (as a substituent, an electron-withdrawing group or a hydroxymethyl group at the 2-position is used. Preferred) hydrazine derivative. Note that any combination of the above R ₁ and R ₂ options is possible and preferred.

Specific examples of the compound represented by the general formula (III) are shown below. However, the present invention is not limited to the following compounds.

[0028]

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[0029]

[Chemical 6]

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
Nos. 4,912,016 and 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2, No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
No. 285343, No. 2-289843, No. 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3-54549, No. 3-125134, No. 3
Nos. -184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, 3-282536, 4-51143, 4-56842, 4-84134, 2-230
No. 233, No. 4-96053, No. 4-216544
Nos. 5-45761, 5-45762, 5-
No. 45763, No. 5-45764, No. 5-45765
No. 6-289524 can be used.

In addition to these, compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by the general formula (6), specifically, Compounds 4-1 to 4- described on pages 25 and 26 of the publication.
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same publication
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
A compound represented by (Chemical Formula 1) described in No. 13951, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I described in JP-A-7-77783)
The compound represented by I), specifically, pages 10 to 2 of the same publication.
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
compounds represented by a), specifically, pages 8 to 15 of the same publication.
Compounds H-1 to H-44 described on page. It is possible to use those described in.

The addition amount of the hydrazine derivative in the present invention is 1 × 10 ^{−6 to} 1 × 10 ⁶ mol per mol of silver.
^-1 mol is preferable, and a range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.

The hydrazine derivative of the present invention is a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method. In the present invention, it is preferable to use indazoles (for example, nitroindazole) as an antifoggant in combination with a hydrazine derivative.

It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative or a hydroxyamine derivative to the light-sensitive material in combination with the hydrazine derivative. Examples of compounds for the nucleation accelerator are given below.

[0045]

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[0046]

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The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ^-6 to 2 × 10 ^-2 mol, and 1 × 10 ^-5 mol per mol of silver.
２2 × 10 ⁻² mol is more preferred, and 2 × 10 ^-5 −1 × 1
0 ^-2 mol is most preferred.

The photothermographic material of the present invention forms a photographic image by using the photothermographic processing method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan and B.A. "Thermally Processed SilverSy" by Shely
stems) "(Imaging Processors and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, Sturge, V. Walworth, A. Edited by Shepp, page 2,
1969) and the like. As described in the above documents, it is preferable to incorporate a developer in the photothermographic material of the present invention.

Examples of suitable developers are described in US Pat. No. 3,770.
448, 3773512, 3593863, and Research Disclosure Nos. 17029 and 29.
963 and include the following: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, as precursors of developers) (eg, Piperidinohexo-sridactone monoacetate); N-hydroxyurea derivatives (eg Np-
Methylphenyl-N-hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamide anilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; azines and sulfones Combination of amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
Combination of dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidephenol reducing agent; 2-phenylindane-1,3-dione, etc .; chromane; 1,4-dihydropyridines (eg 2,6-dimethoxy-3 , 5-dicarboethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,5 -Ethylidene-bis (2
-T-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Ultra-high contrast by the combination of the hydrazine derivative of the present invention and a silver halide containing a heavy metal ion or a complex ion,
Hindered phenols are particularly suitable developers for achieving the effects of high Dmax and high sensitivity without increasing fog. In this selection, dihydroxybenzenes and ascorbic acids were the developers that have been considered appropriate in the field of silver halide light-sensitive materials processed by using a developing solution to cause the hydrazine derivative to have high contrast and high sensitivity. In light of this, it can be said to be extremely unique. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0050]

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In the formula, R represents a hydrogen atom or a carbon atom number of 1 to
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group (e.g., methyl 1 to 5 carbon atoms, ethyl, t- butyl ).

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

[0053]

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[0054]

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The amount of the developer including the compound represented by the general formula (A) is preferably 1 × 10 6 per mol of silver.
^{It is -2} to 10 mol, especially 1 x 10 ^{-2 to} 1.5 mol.

As the cyanine dye containing at least one substituent having a thioether bond used in the present invention, many known cyanine dyes can be used. As an example thereof, JP-A-62-58
239, 3-138638, 3-138642, 4-2
55840, 5-72659, 5-72661, 6-2
22491, 2-230506, 6-258757, 6
-317868, 6-324425, Tokuhyo 7-500
926, Research Disclosure (Research
Disclosure), No. 173, p. 64, published in 1978.

The cyanine dye preferably used in the present invention is a cyanine dye represented by the following general formula (D). General formula (D)

[0058]

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In the formula, R ₁ and R ₂ represent an alkyl group, Z ₁ and Z ₂ represent an atomic group for completing a 5- or 6-membered nitrogen-containing heterocycle, and L represents a cyanine dye. Represents a methine chain, and X represents a counter ion for maintaining charge balance. However, at least one of R ₁ , R ₂ , Z ₁ , and Z ₂ is substituted with an alkylthio group, an arylthio group, or a substituent having a thioether bond.

Preferred as the alkylthio group in the general formula (D) are alkylthio groups having 1 to 8 carbon atoms, further aryl groups (phenyl, 4-chlorophenyl, etc.), alkylthio groups (methylthio, 2-hydroxyethyl, etc.). ), An alkoxy group (methoxy, 2-
It may be substituted with hydroxy-2-methylethyl, 2-methoxyethoxy, etc.), a hydroxyalkyl group (2-hydroxyethyl, etc.), or a halogen atom (F, Cl, Br, I). Particularly preferred among these are unsubstituted alkylthio groups having 1 to 4 carbon atoms. Preferred as the arylthio group in the general formula (D) is a phenylthio group, further including an alkyl group (methyl, t-amyl, etc.), an alkylthio group (methylthio,
2-hydroxyethylthio, etc.), alkoxy group (methoxy, 2-hydroxy-2-methylethyl, 2-methoxyethoxy, etc.), hydroxyalkyl group (2-hydroxyethyl, etc.), halogen atom (F, Cl, Br,
I) and may be substituted with a hydroxy group. Of these, particularly preferred are phenylthio group, halogen-substituted phenylthio group, phenylthio group substituted with an alkyl group having 1 to 4 carbon atoms, phenylthio group substituted with an alkoxy group having 1 to 4 carbon atoms, and number of carbon atoms. 1
A phenylthio group substituted with 4 to 4 alkylthio groups. Preferred as the substituent having a thioether bond in the general formula (D) are those having 2 to 8 carbon atoms.
An alkylthioalkyl group of 7 to 1 carbon atoms
An alkylthiophenyl group of 0 or a phenylthioalkyl group, and further includes an alkyl group (methyl, t-amyl, etc.), an alkylthio group (methylthio, 2-hydroxyethylthio, etc.), and an alkoxy group (methoxy, 2-hydroxy-2-). It may be substituted with methylethyl, 2-methoxyethoxy, etc.), hydroxyalkyl group (2-hydroxyethyl, etc.) halogen atom (F, Cl, Br, I), and hydroxy group.

Examples of the atomic group forming a 5- or 6-membered nitrogen-containing heterocycle in Z ₁ and Z ₂ include the following. However, it is not a quaternary salt for convenience of representing the heterocycle, but is shown by a corresponding nonionic type name.

A thiazole nucleus (eg thiazole, 4-
Methylthiazole, 4-phenylthiazole, 4,5-
Dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 -Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-
6-methylbenzothiazole, 5,6-dimethylthiobenzothiazole, 5,6-dimethylbenzothiazole,
5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-
d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,2]
1-d] thiazole, 8-methoxynaphtho [2,1-
d] thiazole, 8-methylthionaphtho [1,2-d]
Thiazole, 5-methoxynaphtho [2,3-d] thiazole), thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-nitrothiazoline),

Oxazole nucleus (eg, oxazole,
4-methyloxazole, 4-nitrooxazole, 5
-Methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazole, etc., benzoxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole) , 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-
Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,2]
1-d] oxazole), an oxazoline nucleus (for example,
4,4-dimethyloxazoline),

Selenazole nucleus (eg 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (eg benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselena) Azole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]). Selenazole, naphtho [1,2-d] selenazole), 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3-, 3-diethylindolenine, 3,3-dimethyl-5-cyano) Indolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl 5-nitro-indolenine, 3,
3-dimethyl 5-methoxyindolenine, 3,3,5-
Trimethyl indolenine, 3,3-dimethyl-5-chloroindolenine),

Imidazole nucleus (eg 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Alkylnaphtho [1,2-d] imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5- Chlorobenzimidazole, 1-aryl-
5,6-dichlorobenzimidazole, 1-aryl-
5-methoxybenzimidazole, 1-aryl-5
Cyanobenzimidazole, 1-arylnaphtho [1,
2-d] imidazole (provided that the alkyl group which is a substituent of the above heterocycle has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or a hydroxyalkyl group. (For example, 2-
Hydroxyethyl, 3-hydroxypropyl) is preferred. Particularly preferred are a methyl group and an ethyl group. The above aryl group is phenyl, halogen (for example, chloro) substituted phenyl, alkyl (for example, methyl) substituted phenyl,
Represents an alkoxy (eg methoxy) substituted phenyl group},

Pyridine nuclei (eg 2-pyridine, 2-
Pyridine, 5-methyl-2-pyridine, 3-methyl-4
-Pyridine), quinoline nuclei (eg 2-quinoline, 3
-Methyl-2-quinoline, 5-ethyl-2-quinoline,
6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-
Quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-
Quinoline, 8-fluoro-4-quinoline, 8-methyl-
4-quinoline, 8-methoxy-4-quinoline, isoquinoline, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline), imida [4,5-b] quinoxaline Nuclear (eg,
1,3-Diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-
b] quinoxaline, a benzoterrazole nucleus (for example, benzoterrazole, 5-methylbenzoterrazole, 5
-Methoxybenzoterrazole), a naphthoterrazole nucleus (for example, naphtho [1,2-d] telrazole), an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

As the atomic groups forming the 5- to 6-membered nitrogen-containing heterocycle of Z ₁ and Z ₂ , benzothiazole nucleus, benzoxazole nucleus, benzimidazole nucleus, naphthoxazole nucleus, which may be substituted, respectively, An atomic group forming a naphthothiazole nucleus or a quinoline nucleus is preferable.

The atomic group forming a 5- to 6-membered nitrogen-containing heterocycle of Z ₁ and Z ₂ may have a substituent having no thioether bond, and such a substituent has a carbon number of 1-8 alkyl groups (eg, methyl, ethyl, trifluoromethyl, propyl, isopropyl), halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), aryl groups (eg, phenyl, chlorophenyl, bromo) Phenyl, methylphenyl, methoxyphenyl), alkoxy groups (eg methoxy, ethoxy, propoxy, butoxy, benzyloxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-methoxy-2-).
Methylethoxy), alkoxycarbonyl groups (eg,
Methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), cyano group, nitro group, hydroxy group and the like.

The alkyl group represented by R ₁ and R ₂ is preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, which may further have a substituent. Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms, eg, methoxycarbonyl, ethoxycarbonyl). , Benzyloxycarbonyl, etc.), an alkoxy group (preferably having 7 or less carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, benzyloxy), an alkylthio group (eg, methylthio, 2-methylthioethylthio) aryloxy group (eg, phenoxy, p-tolyloxy, α-naphthoxy), an acyloxy group (preferably having 3 or less carbon atoms,
Acetyloxy, propionyloxy), acyl group (preferably having 8 or less carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl) , A sulfamoyl group (eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl), an alkyl group substituted with an aryl group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) (preferably a carbon atom in the alkyl moiety) (6 or less atoms). However, two or more of these substituents may be substituted with an alkyl group.

The methine chain represented by L is one in which an odd number of methine groups are linked so as to form a conjugated double bond, and for example, -L ₁ =, -L ₁ = L ₂ -L ₃ =, -L _{1
= L 2 -L 3 = L 4} -L 5 =, - L 1 = L 2 -L 3 = L
_4- L ₅ = L ₆ -L ₇ =, (wherein L ₁ to L ₇ represent a methine group).

The number of methine groups constituting L is preferably selected according to the wavelength of light for exposing the photographic light-sensitive material of the present invention. Generally, the greater the number of methine groups, the longer the spectral sensitivity distribution becomes. Therefore, L containing 5 or more methine groups is preferred for exposure to infrared light, and the wavelength of 600 to 7 is preferable.
L containing 3 or 5 methine groups is preferable for exposure to light of about 00 nm, wavelength 400 to 600 nm
L containing 1 or 3 methine groups is preferred for exposure to moderate light.

The methine group represented by L ₁ to L ₇ may have a substituent, and examples of the substituent include alkyl (preferably having 1 to 6 carbon atoms), aryl (eg phenyl), Aralkyl (eg benzyl),
Examples include alkoxy (eg, methoxy, ethoxy), alkylthio (eg, methylthio, ethylthio) and the like. These groups may further have a substituent. L ₂ and L ₄ , L ₃ and L ₅ , and L ₄ and L ₅ may be connected to each other to form a ring. This ring is preferably a 5- or 6-membered carbon ring. More specifically, the skeleton is represented by the following (a), (b), (c) and (d), and may further have a substituent.

[0073]

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M1 is preferably 1, 2, or 3.
The counter ion represented by X is a cation or an anion selected so that the total charge of the compound represented by formula (I) becomes 0, and X is Z ₁ , Z ₂ , R ₁ , R _{2, and the} like. May form an inner salt as a substituent. Examples of cations include Na ⁺ , K ⁺ , NH ₄ ⁺ , (n-C ₄ H ₉ ) ₄ N
⁺ , And the like. Examples of anions include acid anions (eg chloride, bromide, iodide, tetfluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfone). Nato, 4-nitrobenzene sulfonate,
Trifluoromethane sulfonate, perchlorate, etc.).

The compound represented by the general formula (I) of the present invention can be easily synthesized by referring to the matters described in a series of patent specifications in which the above-mentioned cyanine dye having a thioether group is described. You can Furthermore, the synthesis methods of various cyanine dyes described in the following books can be referred to. For example, F.M.Harmer, "The Cyanine Soybean and Related Compounds" (Interscience Publishers, NY).
(1964) from page 55 onwards, Nikolai Tyuturkov, Jurgen Fabian, Akim Merhorn, Fritz Dietz, Nikolai Tyut
yulkov, Jurgen Fabian, Achim Ulehlhorn, Fritz Dietz, A
lia Tadjer) "Polymethine soybean", St. Kliment Ohridski University Press, Sophia,
23 to 38 pages, Research Disclosure, Volume 152, 48 pages (1976).

Specific examples of the cyanine dye having a substituent having a thioether bond used in the present invention are shown below, but the scope of the present invention is not limited to these.

[0077]

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[0078]

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[0079]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085] The addition amount of the cyanine dye having a substituent having a thioether bond is preferably from ^{0.1mg / m 2 ~100mg / m 2} , preferably more ^{1mg / m 2 ~20mg / m 2} .

The present invention preferably contains at least one compound represented by the following general formula (I) or a conjugate thereof and at least one compound represented by the following general formula (II). Each of them will be explained.

[0087]

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The present invention preferably contains at least one compound represented by the following general formula (I) or a conjugate thereof. General formula (I)

[0089]

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(In the formula, R ₁ and R ₂ each represent _a hydrogen atom or a substituent. R _a and R _b each represent _a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a halogen atom, Carboxy group, alkoxy group, aryloxy group, amino group, hydrazino group, carboxy group, acylamino group, carbamoyl group, sulfonylamino group, sulfamoyl group, ureido group, acyl group, acyloxy group, oxycarbonyl group, oxycarbonylamino group,
Represents an alkylthio group or an arylthio group. Note that R ₁ ,
If possible, R ₂ , R _a , and R _b may combine to form a ring. )

First, the compound represented by formula (I) will be described in detail. The substituent represented by R ₁ and R ₂ is, for example, an aliphatic hydrocarbon group (for example, an alkyl group (preferably having a carbon number of 1 to 30, more preferably having a carbon number of 1).
To 12, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl,
Examples thereof include n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl. ), An alkenyl group (preferably having 2 to 3 carbon atoms).
It has 0, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl and 3-pentenyl. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl). ), An aryl group (preferably having 6 carbon atoms)
To 30, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, a monocyclic or bicyclic aryl group,
For example, phenyl, p-methylphenyl, naphthyl and the like can be mentioned. ), An amino group (preferably having a carbon number of 0 to 3)
It has 0, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably having 1 to carbon atoms)
30, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 16 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms,
For example, acetyl, benzoyl, formyl, pivaloyl and the like can be mentioned. ), An oxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, and phenyloxycarbonyl). An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy,
Examples thereof include benzoyloxy. ), An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). (Preferably has 2 to 30 carbon atoms, more preferably has 2 to 16 carbon atoms, and particularly preferably has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino, phenyloxycarbonylamino and the like.), Sulfonylamino group (preferably Has 1 to 1 carbon atoms
30, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenylsulfonylamino. ),
Sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 16 carbon atoms, and particularly preferably having 0 to 1 carbon atoms).
2, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, carbamoyl,
Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like can be mentioned. ), An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably having 1 carbon atom)
To 16, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio. ), An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio and the like), a sulfonyl group (preferably having 1 carbon atom). -30, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, mesyl, tosyl and the like can be mentioned. ), A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms,
For example, methanesulfinyl, benzenesulfinyl and the like can be mentioned. ), An ureido group (preferably having a carbon number of 1 to
30, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like. ), A phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms,
For example, diethylphosphoramide, phenylphosphoramide and the like can be mentioned. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom,
(Iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) and the like can be mentioned. . These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, and sulfamoyl. Group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoramide group, hydroxy group, mercapto group, sulfo group, hydroxamic acid group, sulfino group, hydrazino group, halogen atom, heterocyclic group Is.

R ₁ and R ₂ may be linked to each other to form a ring, or may be linked to R _a and R _b to form a ring. The ring formed by linking is a hydrocarbon ring or a hetero ring, and examples thereof include a cyclohexene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and a pyrazole ring, and preferably a benzene ring.

R ₁ and R ₂ are particularly preferably those in which R ₁ and R ₂ are linked to form a benzene ring.

The aliphatic hydrocarbon group represented by R _a and R _b is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 12 carbon atoms). And, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl,
Examples include cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 2 carbon atoms).
30, more preferably 2 to 20, still more preferably 2 to 1
2, for example vinyl, allyl, 2-butenyl, 3-
Examples include pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 12 carbon atoms, for example, propargyl, 3-pentenyl, etc.) and having a substituent. May be. As the substituent, those mentioned as the substituents represented by R ₁ and R ₂ can be applied. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group.

The aryl group represented by R _a and R _b is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably 6 to carbon atoms. 20 phenyl groups, more preferably 6-12 phenyl groups. The aryl group may have a substituent, and as the substituent, those exemplified as the substituents represented by R ₁ and R ₂ can be applied.

The heterocyclic group represented by R _a and R _b is N,
It is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one O or S atom, which may be a single ring or may form a condensed ring with another ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, and more preferably 5 containing a nitrogen atom.
A 5- to 6-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing 1 to 2 nitrogen atoms.

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Examples thereof include pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole and the like. The heterocycle is preferably thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine, and more preferably pyridine and quinoline.

Halogen atom represented by R _a and R _b , carboxy group, alkoxy group, aryloxy group, amino group, hydrazino group, carboxy group, acylamino group, carbamoyl group, sulfonylamino group, sulfamoyl group, ureido group, The acyl group, acyloxy group, oxycarbonyl group, oxycarbonylamino group, alkylthio group, and arylthio group have the same meanings as the substituents represented by R ₁ and R ₂ , respectively, and the preferred ranges are also the same.

If possible, R _a and R _b are R
_It may combine with ₁ or R ₂ to form a ring.

R _a and R _b are preferably hydrogen atoms,
It is an alkyl group, an aryl group or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a chlorine atom, and particularly preferably a hydrogen atom.

Among the compounds represented by the general formula (I), the compounds represented by the following general formula (Ia) are preferable. General formula (Ia)

[0102]

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(In the formula, R _a and R _b have the same meanings as those in formula (I), and the preferred ranges are also the same. R _a1 , R _a2 , R _a3 and R _a4 are each hydrogen. Representing an atom or a substituent.) _Examples of the substituent represented by R _a1 , R _a2 , R _a3 , and R _a4 include those enumerated as the substituents represented by R ₁ and R ₂ in the general formula (I). Applicable. R _a1 , R _a2 , R _a3 and R _a4 are preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a chlorine atom, particularly preferably hydrogen. Is an atom.

Among the compounds represented by the general formula (I), the compounds represented by the following general formula (Ib) are preferable. General formula (Ib)

[0105]

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(In the formula, R _a1 , R _a2 , R _a3 and R _a4 have the same _{meanings as} those in formula (Ia),
The preferred range is also the same. )

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

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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If possible, the above compounds may be used in the form of salts. As the compound represented by the general formula (I) of the present invention, a commercially available compound may be used. Also, for example, K. Dur
y, Angew.Chem., Int.Ed., 4,292 (1965),
J. Druey, A. Marxer, J. Med. Pharm. Chem., 1, 1 (19
59) and the like according to the method described therein. The addition amount of the compound represented by the general formula (I) is 1 per mol of Ag.
0 ^-3 mol to 1 mol is preferred. More preferably, it is 10 ^-2 mol to 5 x 10 ^-1 mol.

Next, the compound represented by formula (II) will be described. General formula (II)

[0117]

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(In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents a carbonyl group or a sulfonyl group. A represents A Represents a hydrogen atom, a halogen atom or an electron-withdrawing group, and n represents 0 or 1.)

The aliphatic hydrocarbon group represented by Q is a straight chain,
Branched or cyclic alkyl group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 20, even more preferably 1 to 12
And, for example, methyl, ethyl, iso-propyl, t
Examples include ert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl and cyclohexyl. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 12 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group. (It preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and further preferably 2 to 12 carbon atoms, and examples thereof include propargyl and 3-pentenyl.) And may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group,
Examples thereof include a sulfamoyl group, an oxycarbonylamino group or a ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group. The aryl group represented by Q is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably 6 to 6 carbon atoms.
20 phenyl groups, more preferably 6-12 phenyl groups. The aryl group may have a substituent, and examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and an ureido group. The heterocyclic group represented by Q is N, O or S
It is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one atom, which may be a single ring or may form a condensed ring with another ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom, and even more preferably 1 or 2 nitrogen atoms. And a 5- or 6-membered aromatic heterocyclic group including. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, Examples thereof include quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole and benzthiazole. The heterocycle is preferably thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine, more preferably triazine,
Quinoline, thiadiazole, benzthiazole,
Particularly preferred are quinoline and thiadiazole. Q
Is preferably an aromatic nitrogen-containing heterocyclic group.
The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably Chlorine atom and bromine atom are preferred, and bromine atom is particularly preferred. Y represents a carbonyl group or a sulfonyl group, preferably a sulfonyl group. The halogen atom represented by A is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably bromine. Is an atom. The electron withdrawing group represented by A is preferably σp
It is a substituent having a value of 0.01 or more, and more preferably 0.1.
One or more substituents. Examples of the electron-withdrawing group include a trihalomethyl group, a cyano group, a nitro group, a sulfonyl group, a carbonyl group, an alkenyl group, an alkynyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group. Is a sulfonyl group, a carbonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. A is preferably a halogen atom, more preferably a chlorine atom, a bromine atom or an iodine atom, still more preferably a chlorine atom or a bromine atom, and particularly preferably a bromine atom. n represents 0 or 1, and is preferably 1 when Y is a sulfonyl group. Among the compounds represented by the general formula (II), the compounds represented by the following general formula (II-a) are preferable. General formula (II-a)

[0120]

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(In the formula, X ₁ , X ₂ , A and n have the same meanings as those in formula (II), respectively, and the preferred ranges are also the same. Q ′ represents an aromatic nitrogen-containing heterocyclic group. The aromatic nitrogen-containing heterocyclic group represented by Q ′ is preferably a 5- to 6-membered aromatic heterocycle containing 1 to 3 nitrogen atoms, such as pyrrole, imidazole, pyrazole, pyridine and pyrazine. , Pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,
Examples include cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole and indolenine, and more preferably pyridine, triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole. ,
Thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole and indolenine are more preferable, triazine, thiadiazole, quinoline and benzothiazole are more preferable, and quinoline and thiadiazole are particularly preferable. Among the compounds represented by the general formula (II), the compounds represented by the following general formula (II-b) are preferable. General formula (II-b)

[0122]

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(In the formula, X ₁ and X ₂ have the same meanings as those in formula (II), and the preferred ranges are also the same. Q ′ has the same meaning as that in formula (II-a). And the preferred range is also the same. X ₃ represents a halogen atom.) The halogen atom represented by X ₃ is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom. , And particularly preferably a bromine atom. Specific examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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If possible, the above compounds may be used in the form of salts. The compound represented by the general formula (II) of the present invention is, for example, US Pat. Nos. 5,340,712 and 38749.
46, European Patent Nos. 622666A1 and 60598.
1A1, JP-A-7-2781, JP-B-54-165
Can be synthesized according to the method described in No. The addition amount of the compound represented by the general formula (II) is 10 ⁻⁴ to 1 per mol of Ag.
Molar is preferred. More preferably, it is 10 ⁻³ mol to 0.3 mol.

In the present invention, the addition of a toning agent is highly desirable. Examples of suitable toning agents are disclosed in Research Report 17029 and include: imides (eg phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg succinimide, 3-
Phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (eg N-hydroxy-
1,8-naphthalimide); cobalt complex (for example,
Cobalt hexamine trifluoroacetate), mercaptans (eg, 3-mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl))
Phthalimide); a combination of blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole),
A combination of 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); a merocyanine dye (for example, 3-ethyl-5-
((3-Ethyl-2-benzothiazolinylidene (benzpt
hiazolidene))-1-Methylethylidene) -2-thio-
2,4-oxazolidinedione
); Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1, 4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; phthalazine (Including phthalazine adduct), maleic anhydride, and phthalic acid, 2,3-
Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinedione , Benzoxazine, naltoxazine derivatives; benzoxazine-2,4-diones (for example, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (for example,
2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (for example, 3,6-dimerocapto-1,
4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene. Preferred toning agents include phthalazone and phthalazine, and in the present invention, the above-mentioned compound general formula (I) was found to be specifically good in the constitution of the present invention.

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, including a reducible silver source (organic silver salt), a catalytically active amount of the above silver halide, It is preferable that the photothermographic material contains a hydrazine derivative, a developer, and, if necessary, a color tone suppressing agent for controlling the color tone of silver in a state of being normally dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but at a high temperature (for example, 80 ° C or higher) after exposure.
It is developed by heating to. By heating, silver is produced through a redox reaction between the organic acid silver (which functions as an oxidizing agent) and the developer. This redox reaction is promoted by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a treatment liquid such as water from the outside.

The photothermographic material of the invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side or on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitive layer / low sensitive layer or a low sensitive layer / high sensitive layer for adjusting gradation. Various additives may be added to any of the light-sensitive layer, non-light-sensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. Suitable binders are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film forming media such as: gelatin, gum arabic,
Poly (vinyl alcohol), Hydroxyethyl cellulose, Cellulose acetate, Cellulose acetate butyrate, Poly (vinyl pyrrolidone), Casein, Starch, Poly (acrylic acid), Poly (methimemethacrylic acid), Poly (vinyl chloride), Poly (methacrylic) Acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly ( Ester), poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver silver, silver chlorobromide, silver iodobromide, chloroiodo). However, it is preferable that the iodide ion is contained. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

Reducible silver sources are silver salts of organic and heteroorganic acids containing a source of reducible silver ions, especially long chain (10
Aliphatic carboxylic acids of up to 30 (preferably 15 to 25 carbon atoms) are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Dis
closures described in 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1-
(3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids) (Eg, salicylic acid,
Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiadisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2). -Thioene, and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4- Complexes and salts of silver with a nitric acid selected from triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides, the preferred silver source being silver behenate. The amount of silver is preferably 3 g / m ² or less, and more preferably 2 g / m ² or less.

An antifoggant may be contained in such a light-sensitive material. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 03. However, mercury compounds are environmentally unfavorable. As the non-mercury antifoggant, for example, the antifoggants disclosed in U.S. Pat. Nos. 4,456,075 and 4,458,885 and JP-A-59-57234 are preferable.

The exposure of the photothermographic material of the present invention is performed with He-
Ne laser (633 nm), red semiconductor laser (67
0 nm) and infrared semiconductor lasers (780 nm, 830 nm).

A layer containing a dye may be provided as an antihalation layer in the photothermographic material of the invention.
400 for He-Ne laser and red semiconductor laser
The dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range of nm to 750 nm. 750nm ~ 1500 for infrared semiconductor laser
The dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the nm range. One or more dyes may be used in combination. The dye can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the side opposite to the photosensitive layer.

The support used in the present invention is paper, synthetic paper, paper laminated with synthetic resin (eg polyethylene, polypropylene, polystyrene), plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate). A metal plate (for example, aluminum, aluminum alloy, zinc, iron, copper), paper or plastic film laminated or vapor-deposited with the above metals is used. On the other hand, when a plastic film is passed through a heat processor, the size of the film expands and contracts. When used as a printing photosensitive material, this expansion and contraction is a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having a small dimensional change. For example, there are a styrene-based polymer having a syndiotactic structure and a heat-treated polyethylene. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyaclate and the like can be used.

[0141]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (Preparation of Photosensitive Silver Halide Grain A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the temperature was adjusted to 35 ° C. and pH was adjusted to 3.0, followed by silver nitrate. 7
370 ml of an aqueous solution containing 4 g and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) were pAg 7.7.
While maintaining the above, the addition was performed by the controlled double jet method over 10 minutes. At this time, 5
Over 1 minute, 1 × 10 ⁻⁵ mol / Ag mol of hexacyanoferrate (III) and hexachloroiridium (III) complex salt are added. Then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added to 0.3 g, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average grain size of 0.06 μm, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87%. Silver particles were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5.

(Preparation of Photosensitive Emulsion A Containing Silver Organic Fatty Acid) 10.6 g of behenic acid was put in 300 ml of water, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was added with sufficient stirring. , It was left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.13 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, silver halide grains A prepared in advance were added while stirring at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was left for 1 hour with stirring. While stirring the aqueous mixture, 37 g of a 1.2 wt% solution of polyvinyl acetate in n-butyl acetate was gradually added to form flocs of the dispersion, water was removed, and water was washed twice and water was removed. Then, 20 g of a 1: 2 mixed solution of 2.5 wt% of butyl acetate and isopropyl alcohol of polyvinyl butyral (average molecular weight: 3000) was added with stirring, and the thus obtained gel-like behenic acid and silver halide were added. 12.5 g of polyvinyl butyral (average molecular weight: 4000) was added to the mixture.
7 g was added and dispersed.

The following layers were sequentially formed on a heat-treated polyethylene terephthalate support to prepare a photothermographic material 1.
-1 to 1-4 were created. The drying was carried out at 75 ° C. for 5 minutes.

Backside coating: A liquid having the following composition was coated on the base surface opposite to the photosensitive layer so that the wet thickness was 100 μm. Polyvinyl butyral # 4000-2 (manufactured by Denki Kagaku Kogyo Co., Ltd.) in 10% isopropyl alcohol 60 g isopropyl alcohol 10 g 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) 8g solution of ethyl acetate in 8g Add dye S-1 to the above solution Add 0.2g of dye S-1 to 10g of methanol + acetone 2
The product dissolved in 0 g is added so that the absorption at the exposure wavelength becomes 0.8. (633 nm in Example 1)

[0146]

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Photosensitive layer surface side coating Photosensitive layer: A liquid having the following composition was coated so that the coating silver amount was 1.5 g / m ² . Photosensitive emulsion A 73 g Sensitizing dye (sensitizing dyes 1 to 4 shown in Table 1 0.05% methanol solution) 2 ml Antifoggant-1 (0.01% methanol solution) 3 ml Antifoggant-2 (1.5% methanol) Solution) 8 ml Antifoggant-3 (2.4% DMF solution) 5 ml Phtharazone (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 13 ml Hydrazine derivative H-1 (1% methanol solution) 2 ml

[0148]

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[0149]

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Surface protective layer: Wet a liquid having the following composition with a thickness of 10
It was applied to be 0 microns. Acetone 175 ml Methanol 15 ml Cellulose acetate 8.0 g 4-methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g

Photothermographic materials 2-1 to 2-4 were prepared in the same manner except that the content of the photosensitive layer was changed as follows. Photosensitive emulsion A 73 g Sensitizing dye (sensitizing dyes 1 to 4 shown in Table 1 0.05% methanol solution) 2 ml Toning agent I-11 (5% methanol solution) 2.5 ml Antifoggant II-44 (1.7% DMF) Solution) 2.5 ml Developer-1 (10% acetone solution) 13 ml Hydrazine derivative H-1 (1% methanol solution) 2 ml

[0152]

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Photothermographic materials 3-1 to 3-4 were prepared in the same manner except that the comparative sensitizing dyes shown in Table 1 (2 ml each of 0.05% methanol solution) were used.

[0154]

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Sensitometry The photothermographic material prepared above was exposed to xenon flash light with an emission time of 10 ⁻³ seconds through an interference filter having a peak at 633 nm. After that, heat development treatment was performed at 115 ° C. for 15 seconds using a heat drum. The reciprocal of the exposure dose giving a density of 3.0 was taken as the sensitivity and shown as relative sensitivity. In addition, the slope of the straight line connecting the points of density 0.1 and 1.5 on the characteristic curve is shown as the gradation (γ) representing the leg break. The dye in the back layer was erased by irradiating a halogen lamp for 15 seconds after the heat development treatment. Image quality evaluation The image quality was evaluated by generating halftone dots with the same exposure machine as in sensitometry. The quality of halftone dots when our scanner film LS5500 was exposed by our color scanner MAGNASCAN was set to 4 and, if it was better than that, 5, 6
point. If it is bad, the evaluation is made by a 6-point method of 3, 2, and 1. mainly,
The sharpness of the points was evaluated. It should be noted that three or more points are at a practical level as a photosensitive material for printing.

[0156]

[Table 1]

As can be seen from Table 1, the dyes of the present invention have high sensitivity and Dmax and very good image quality. Further, it can be seen that the compounds using the compounds I and II of the present invention are more excellent in sharpness and image quality.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Toshi City, San 210, Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. An organic acid silver salt, a silver halide,
A photothermographic material comprising a hydrazine derivative and a cyanine dye having at least one substituent having a thioether bond. 2. The composition according to claim 1, which contains at least one compound represented by the following general formula (I) or a conjugate thereof and at least one compound represented by the following general formula (II). Photothermographic material. Embedded image In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substituent. R _a and R _b are each a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a halogen atom, a carboxy group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carboxy group, an acylamino group, a carbamoyl group. Represents a sulfonylamino group, a sulfamoyl group, a ureido group, an acyl group, an acyloxy group, an oxycarbonyl group, an oxycarbonylamino group, an alkylthio group or an arylthio group. Note that R ₁ , R ₂ ,
R _a and R _b may combine with each other to form a ring, if possible. Embedded image In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents a carbonyl group or a sulfonyl group.
A represents a hydrogen atom, a halogen atom or an electron-withdrawing group. n represents 0 or 1.