JPH09292674A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photosensitive material, for a printing plate, ultrahigh in contrast and high in Dmax and restrained from occurrence of black spots and good in image quality by incorporating prescribed compounds in the photosensitive material containing an organic silver salt, photosensitive silver halide, a reducing agent, and an ultrahigh contrast giving agent. SOLUTION: The heat-developable photosensitive material contains the organic silver salt, the photosensitive silver halide, the reducing agent, and the ultrahigh contrast giving agent, and moreover, a compound of formula I: C-L-D in which C is a group for promoting adsorption to silver halide; D is an acid group; and L is a divalent bonding group; and C-L-D has substantially no absorption maximum in the visible wavelength region. The ultrahigh-contrast giving agent is a hydrazine derivative, preferably, a compound represented by formula II in which R1 is an aliphatic or aromatic group; each of R2 and R3 is an H atom or an alkyl group or the like; G1 is a -CO- or -SO2 group or the like; and each of A1 and A2 an H atom or a non-substituted alkylsulfonyl group or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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.M. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials) Neblette 8th
Edition, Sturge, V.I. Walwor
th), A. It is disclosed in Shepp, pp. 2, 1969.

In such a photothermographic material, 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 tone of silver and a reducing agent are usually used as a binder. It is contained in the matrix in a dispersed state and is called dry silver. The photothermographic material is stable at room temperature, but at a high temperature (for example, 80
When heated to (° C. or higher), silver is produced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. 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.

[0004] Such photothermographic materials have been used for micro-sensitive materials and X-rays, but are only partially used as printing photosensitive materials. This is because the obtained image has a low Dmax and soft gradation, so that the image quality of the printing photosensitive material is extremely poor.

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 the sensitivity, Dmax and high contrast suitable for these output machines are high. The development of wood was strongly desired. Also, demands for simple processing and dry processing are increasing.

[0006] US Patent No. 5,647,738 describes that use of sulfonyl hydrazide as a reducing agent for dry silver provides a high-contrast image.

US Pat. No. 5,496,695 describes that a high contrast image can be obtained by using a combination of hindered phenol and formyl hydrazine or trityl hydrazine as dry silver reducing agents.

All of these image forming methods are performed at 120 ° C.
It is characterized by heat development at the above high temperature, and has some problems associated with the formation of a high contrast image. One of them is noise called peper fog when hydrazines are used. As a well-known phenomenon in normal wet development when using hydrazines, there is a black spot, but the black spot generated in a dry thermal development system has a considerably different aspect, and the thermal development temperature dependency is extremely large. It is more likely to occur at higher temperatures. In the wet development system, the developer p
H dependency is large, acidic compounds in the photosensitive emulsion layer of the light-sensitive material,
By including an acidic polymer, the generation of black dots or black spots can be suppressed. On the other hand, the thermal development system contains a large amount of organic fatty acids, aromatic carboxylic acids such as phthalic acid derivatives, and bisphenol derivatives as a reducing agent in the light-sensitive material, and is in a sufficiently acidic atmosphere. Nevertheless, black spots occur when thermally developed at high temperatures.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material having a super-high contrast and a high Dmax. Furthermore, specifically, it is to provide a photothermographic material for printing plate making which has a high image quality in which the generation of black dots is suppressed.

[0010]

The above object of the present invention is attained by the following constitutions. (1) A photothermographic material containing an organic silver salt, a photosensitive silver halide, a reducing agent and a super-high contrast agent, which contains a compound represented by the following general formula. (General Formula) C-L-D (wherein C represents a group that promotes adsorption to silver halide, D represents an acid group, L represents a divalent linking group,
C-L-D has substantially no absorption maximum in the visible region. (2) The above (1), wherein the ultrahigh contrast agent is a hydrazine derivative
Photothermographic material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The ultrahigh contrast agent used in the present invention will be described. The super-high contrast agent used in the present invention does not function alone as a developer, but can be used in combination with a reducing agent as a developer to give a super-high contrast image. Therefore, the concept and action and effect are completely different from the above-described conventional use of a reducing agent together.

The ultrahigh contrast agent can be selected from a hydrazine derivative or a compound containing a quaternary nitrogen atom.

The hydrazine derivative as an ultrahigh contrast agent is
Compounds represented by the following general formula (I) are preferred.

[0014]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, and 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,

[0016]

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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 (I), 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 (I), 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, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring,
Quinoline ring, isoquinoline ring, benzimidazole ring,
There are a thiazole ring, a benzothiazole ring and the like, and among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocycle, a pyridinium group, Has a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, a semicarbazide group, a thiosemicarbazide group, a urethane group, and a hydrazide structure. Group, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group, acyl group,
Alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group,
A nitro group, a nitrosyl group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like.
Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), An alkoxy group (preferably having 1 carbon atom)
To 20), a substituted amino group (preferably having 1 to carbon atoms)
An amino group substituted with an alkyl group of 20), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms),
Ureido group (preferably having 1 to 30 carbon atoms),
And a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In the general formula (I), 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.

The unsaturated heterocyclic group is a compound having a 5- or 6-membered ring containing at least one nitrogen, oxygen and sulfur atom, for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, pyridinium group, Examples include quinolinium group and 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 the alkylamino group having 1 to 10 carbon atoms. A group and an arylamino group are preferred.

R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable.

Preferred among the groups represented by R ₂ are hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3 and 3 when G ₁ is —CO— group. -Methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o-hydroxybenzyl group, etc.), aryl group (for example, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), —C ₂ F ₂ COOM (M: hydrogen atom, alkali metal atom) and the like.

When G ₁ is a --SO ₂ --group, R is R.
₂ is preferably 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).

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 (I), --CO-- group,-
A COCO- group is preferred, and a -CO- group is most preferred.

[0029] Also, R ₂ is be as occurring cyclization reaction to form a cyclic structure containing disrupts portion of G ₁ -R ₂ from the remainder molecule, -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751.

R ₁ is preferably a hydrazine derivative having at least one nitro group or nitrosyl group in R ₂ . Particularly, those having at least one nitro group or nitrosyl group in R ₁ are preferable.

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 (I) 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 of the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. 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 (I) may have a group incorporated therein to enhance adsorption to the surface of the silver halide grain. 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.

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

[0036]

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[0037]

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[0038]

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[0039]

[Chemical 6]

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

[Chemical 12]

[0046]

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[0047]

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[0048]

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[0049]

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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
And Japanese Patent Application No. 5-94925 can be used.

In addition to these, the compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically the compounds described on pages 3 and 4 of the 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 preferably 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per 1 mol of total silver of organic acid silver and silver halide, Especially 1 × 10 ⁻⁵ mol to 5
The preferable addition amount is in the range of ^{x10 -2} mol.

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.

By a well-known emulsification and dispersion method, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are used to dissolve and mechanically dissolve them. An emulsified dispersion 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, in combination with a hydrazine derivative,
It is preferable to use indazoles (for example, nitroindazole) as an antifoggant.

It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative to the light-sensitive material in combination with the hydrazine derivative.

As a compound example of the nucleating propellant, Japanese Patent Application No.
A-1 to A-47 described in JP-A-266204.

As the ultrahigh contrast agent containing a quaternary nitrogen atom,
The pyridinium and quinolinium compounds represented by the following general formulas (Pa), (Pb), and (Pc), or the tetrazolium compound represented by the general formula (T) described later are used.

[0059]

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Where A ¹ , A ² , A ³ , A ⁴ and A
⁵ represents a group of nonmetallic atoms for completing the nitrogen-containing heterocycle, which may contain an oxygen atom, a nitrogen atom, and a sulfur atom, and may be condensed with a benzene ring. A ¹ , A ² ,
The hetero ring composed of A ³ , A ⁴ and A ⁵ may have a substituent and may be the same and different. As the substituent, an alkyl group, an aryl group, an aralkyl group,
Alkenyl group, alkynyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, amino Represents a group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group and an arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ are 5 to 5.
Examples include a 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiozole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, and the like), and a more preferred example is a pyridine ring.

B _p represents a divalent linking group. The divalent linking group means alkylene, arylene, alkenylene, -S
_{O 2 -, - SO -,} - O -, - S -, - CO -, - N
(R ⁶⁾ - (R ⁶ is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. Preferred examples of Bp include alkylene and alkenylene.

R ¹ , R ² and R ³ have 1 or more carbon atoms and 20
The following alkyl groups are represented. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² ,
It is the same as the substituent described as the substituent for A ³ , A ⁴ and A ⁵ .

Preferred examples are R ¹ , R ² and R ³
Represents an alkyl group having 4 to 10 carbon atoms. A more preferred example is a substituted or unsubstituted aryl-substituted alkyl group. X _p represents a counter ion required to balance the charge of the entire molecule. For example, chlorine ion, bromine ion,
Represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. n _p represents the number of counter ions required to balance the charge of the entire molecule, and n _p is 0 in the case of an intramolecular salt. Next, specific examples of the pyridinium compound according to the present invention are shown below, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

[Chemical 21]

[0068]

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[0069]

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In the present invention, the substituents R ₁ , R ₂ , and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula (T) are hydrogen atoms or Hammett's sigma value (σ Those in which _p ) is negative are preferred.

Hammett's sigma value for phenyl substitution is well documented, eg, Journal of Medical Chemistry, Volume 20,
304, 1977, C.I. Hansch
And the like, and particularly preferred groups having a negative sigma value include, for example, a methyl group (σ _p = −
All values below 0.17 are σ _p values) ethyl values (-0.1
5), cyclopropyl group (-0.21), n-propyl group (-0.13), isopropyl group (-0.15),
Cyclobutyl group (-0.15), n-butyl group (-0.
16), iso-butyl group (-0.20), n-bentyl group (-0.15), cyclohexyl group (-0.2)
2), amino group (-0.66), acetylamino group (-
0.15), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.24), propoxy group (-0.25), butoxy group (-0.32), Examples thereof include a bentoxy group (-0.34), which are all useful as a substituent of the compound of the general formula (T) of the present invention.

N represents 1 or 2, and examples of the anion represented by X _r ^n- are halogen ions such as chloride ion, bromide ion and iodide ion, and inorganic acids such as nitric acid, sulfuric acid and perchloric acid. Acid radicals, organic acid radicals such as sulfonic acid and carboxylic acid, anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion and higher alkylbenzenes such as p-dodecylbenzene sulfonate anion. Higher alkyl sulfate ester anions such as sulfonate anion and lauryl sulfate anion, borate anions such as tetraphenylboron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anion, cetyl polyethenoxysulfate anions, etc. Polyether alcohol Ester anion, higher aliphatic acid such as stearic acid anion anion, those with a acid radical in a polymer of polyacrylic acid anion, and the like.

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

[0074]

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The above-mentioned tetrazolium compound is described in, for example, Chemical Reviews Vol. 55, 335.
The compound can be easily synthesized according to the method described on pages 483 to 483.

The tetrazolium compound represented by formula (T) may be used alone or in combination of two or more kinds at an appropriate ratio.

The pyridinium compound and the tetrazolium compound used in the present invention can be used in any layer on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or its adjacent layer. Is preferred. The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like.
The range is preferably from ^-6 to 10 ^-1 mol, particularly from 10 ^-5 to 10 ^-2.
A molar range is preferred.

Next, the compound represented by the general formula (II) used in the present invention has a silver halide adsorbing group and an acid group at the same time and substantially absorbs in the visible region (more specifically, in the region of 440 nm or more). A compound having no maximum will be described.

General formula (II) C-L-D

C represents a group that promotes adsorption to silver halide, D represents an acid group, and L represents a divalent linking group.

Here, the compound "having substantially no absorption maximum in the visible light region" means a compound having a color tone such that the residual color on the photographic light-sensitive material is below a level at which there is no practical problem. The residual color after development is a compound having a color tone of a level below a level at which there is no practical problem.

Preferably, the absorption maximum of the above compound in methanol is 460 nm or less, more preferably 43.
It is less than 0 nm.

The adsorbing group C to silver halide includes all those usually used, but for example, one hydrogen atom is desorbed from a compound having a thioamide component, a mercapto group, a heterocyclic group, a compound such as cyanine or merocyanine. Examples of the group include radical groups, and groups including a combination of two or more selected from these.

The thioamide adsorption promoting group represented by C is
It is characterized by containing a divalent thioamide group as shown by-(C = S) -amino-. This thioamide group is
It may be part of a 5 to 6 membered heterocycle. A useful thioamide adsorption promoting group is a conventional thioamide adsorption promoting group,
For example, U.S. Pat. Nos. 4,030,925 and 4,031,
No. 127, No. 4,080,207, No. 4,245,0
No. 37, No. 4,255,511, No. 4,266,01
3 and 4,276,364, and research
Research Disclosure No. 151
Vol., November 1976, Item 15, 162, and ibid.
It can be selected from those disclosed in Volume 170, December 1978, Item 17,626.

Particularly preferred thioamido groups are those of formula (III).

General formula (III) R ⁴ -E- (C = S) -E'-

In the formula, one of E and E'is --N (R ⁵ )-
And the other is -O-, -S-, or -N.
(R ⁶⁾ - represent. R ⁴ represents a hydrogen atom, an aliphatic group or an aromatic group, or 5 together with E or E ′
Complete a 6-membered or 6-membered heterocycle. R ⁵ or R of E
⁶ represents a hydrogen atom, an aliphatic group or an aromatic group. E '
Positions R ⁵ and R ⁶ represent hydrogen or benzyl substituents when E ′ is directly attached to the aromatic ring, and can otherwise be selected from the same substituents as in the E position. However, at least one of R ⁴ , R ⁵ and R ⁶ is a hydrogen atom. The aliphatic groups of R ⁴ , R ⁵ and R ⁶ may be the same or different and may be an alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, hexadecyl group, etc.), 2 to 18 carbon atoms. Alkenyl groups (eg, allyl group, 2-butenyl group, etc.), C2-C18 alkynyl groups (eg, propargyl group), C3
To 12 cycloalkyl groups (eg, cyclohexyl group) and the like.

The aromatic groups represented by R ⁴ , R ⁵ and R ⁶ may be the same or different and have 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

R ⁴ , R ⁵ and R ⁶ may have a suitable substituent. As the substituent, for example, an alkyl group (preferably one having 1 to 18 carbon atoms, for example, a methyl group,
An ethyl group, a hexyl group, an isobutyl group, etc.), an alkenyl group (preferably having 2 to 18 carbon atoms, for example, a vinyl group, an aryl group, a butynyl group, etc.), an alkynyl group (preferably having 2 to 18 carbon atoms) Such as ethynyl group, propargyl group, butynyl group), aralkyl group (preferably having 7 to 20 carbon atoms, such as benzyl group), aromatic group (preferably having 6 to 20 carbon atoms) And, for example, phenyl group, naphthyl group, etc., hydroxy group, aliphatic oxy group (alkoxy group, alkenyloxy group, alkynyloxy group, etc.); preferably those having 1 to 18 carbon atoms, for example, methoxy group, ethoxy group,
Aryloxy group, propargyloxy group, butynyloxy group, etc.), aromatic oxy group (preferably having 6 to 6 carbon atoms)
20 groups, such as phenyloxy groups), halogen atoms (eg, fluorine, chlorine, bromine, iodine), amino groups, substituted amino groups (preferably having 1 to 1 carbon atoms)
18 groups, such as methylamino group, dimethylamino group, hexylamino group, phenylamino group, etc., aliphatic thio groups (preferably having 1 to 18 carbon atoms, such as methylthio group, hexylthio group, etc.) An aromatic thio group (preferably having 6 to 20 carbon atoms such as phenylthio group), an acyloxy group (preferably having 1 to 18 carbon atoms such as acetoxy group, benzoxy group etc.), sulfonyloxy group Group (preferably having 1 to 1 carbon atoms)
18 groups, for example, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylamino groups (preferably, those having 1 to 18 carbon atoms, such as acetylamino group, benzoylamino group, etc.), sulfonylamino groups ( Preferably, those having 1 to 18 carbon atoms, such as methanesulfonylamino group, benzenesulfonylamino group, etc., carboxyl group, aliphatic oxycarbonyl group (preferably those having 1 to 18 carbon atoms, such as methoxycarbonyl group. , Butyloxycarbonyl group, etc.), aromatic oxycarbonyl group (preferably having 7 to 20 carbon atoms, such as phenoxycarbonyl group), acyl group (preferably having 1 to 20 carbon atoms, for example formyl Groups, acetyl groups, benzoyl groups, etc.), carbamoyl groups, N-substituted carboxylic groups. Bamoiru group (preferably 2 carbon atoms
~ 20, for example N-methylcarbamoyl group,
N-isobutylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfamoyl group, N-substituted sulfamoyl group (preferably having 1 to 18 carbon atoms, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group) Moyl group, N-butynylsulfamoyl group, N-phenylsulfamoyl group, etc.), sulfo group, cyano group, ureido group, substituted ureido group (preferably having 2 to 20 carbon atoms, for example, 3-methyl Ureido group, 3-allylureido group, 3-phenylureido group, etc., substituted urethane group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonylamino group, cyclohexyloxycarbonylamino group, phenoxycarbonylamino group, etc.) ), A carbonic acid ester group (preferably having 2 to 20 carbon atoms, such as ethoxy Ruboniruokishi group, oxycarbonyl group, phenoxy etc. aryloxycarbonyl group) or a substituted or unsubstituted imino group (preferably those of less than 18 carbon atoms, such as N- methylimino group, N-
Phenylimino group).

Further, the above substituents may be further substituted with these substituents.

R ⁵ or R ⁶ at the E'position is preferably hydrogen.

When both E and E'are amino groups, the adsorption promoting group is a thiourea group. In addition to hydrogen, particularly preferred R ⁴ and R ⁵ or R ^{6 at the} E position are substituted alkyl groups such as alkoxyalkyl groups (eg methoxyethyl group), haloalkyl groups (eg perhaloalkyl group, trifluoromethyl group and homologues). ), Aralkyl groups (eg phenylalkyl groups or naphthylalkyl groups) and unsubstituted alkyl groups (eg methyl groups,
Hexyl group) and aryl groups (eg phenyl group,
Naphthyl group, alkylphenyl group, cyanophenyl group,
Halophenyl group, alkoxyphenyl group, etc.) and the like.

R ⁴ , R ⁵ and R ⁶ usually contain from 1 to 18 carbon atoms, and in a particularly preferred form they contain 8 or less carbon atoms.

The thiocarbonyl group is an oxy group, for example R ⁴
When bonded to -O-, it is the resulting thiourethane group. The thiocarbonyl group is a thio group, for example R ⁴ —S—
When attached to, the resulting group is a dithiocarbamate group. If anything, among E and E ', it is generally preferred that E is -O- or -S-. Furthermore, E is more preferably -O- rather than -S-.

When E or E'and R ⁴ together form a heterocycle, it is preferably a 5- or 6-membered ring.

Preferred rings formed by E'and R ⁴ are those found as acidic nuclei in merocyanine dyes, such as 4-thiazolin-2-thione, thiazolidine-2-thione, 4-oxazoline-2-. Thione, oxazolidine-2-thione, 2-pyrazoli-5-thione,
4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-
Oxazolidinedione, thioparpituric acid, 1,3
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione and the like can be mentioned. These may be further substituted with the appropriate substituents described for R ⁴ .

When E and R ⁴ are combined to form a heterocycle, the same as the heterocycle of C described later can be mentioned. Preferable examples further include pyrrole, pyrroline, pyrrolidine, piperidine, morpholine, piperazine and indole.

Examples of the mercapto group of C include an aliphatic mercapto group, an aromatic mercapto group and a hetero group mercapto group (in this case, the nitrogen atom is not adjacent to the carbon to which the SH group is bonded).

Examples of the aliphatic mercapto group include a mercaptoalkyl group (eg, mercaptoethyl group and mercaptopropyl group), a mercaptoalkenyl group (eg, mercaptopropenyl group) and a mercaptoalkynyl group (eg, mercaptobutynyl group). can give. Examples of the aromatic mercapto group include a mercaptophenyl group and a mercaptonaphthyl group. Examples of the heterocyclic mercapto group include 4-mercaptopyridine group, 5-mercaptoquinolinyl group, 6-mercaptobenzothiazolyl group and the like.

Examples of the heterocyclic group of C include a 5-membered to 6-membered heterocyclic ring composed of a combination of nitrogen, oxygen, sulfur and carbon. Examples of preferable heterocycles include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole and triazine. These heterocycles may have a suitable substituent. As the substituent, those mentioned as the substituent of R ⁴ can be mentioned.

The heterocycle is preferably benzotriazole, triazole, tetrazole or indazole, and particularly preferably benzotriazole or indazole.

Specific preferred examples of the heterocyclic group include enzotriazol-5-yl, 6-chlorobenzotriazol-5-yl and benzotriazole-.
5-carbonyl, 5-phenyl-1,3,4-triazol-2-yl, 4- (5-methyl-1,3,4-triazol-2-yl) benzoyl, 1H-tetrazol-5-yl and 3 -Cyanoindazol-5-yl and the like can be mentioned.

The radicals of the above-mentioned compounds such as cyanine and merocyanine represented by C are those having substantially no absorption maximum in the visible region, and examples thereof include monomethinecyanine and apomerocyanine. Etc. are selected. More specifically, it is selected from cyanine represented by the general formula (IV) and merocyanine represented by the general formula (V).

Here, the above-mentioned monomethinecyanine, apomerocyanine, and the cyanine represented by the general formula (IV),
Many merocyanines represented by the general formula (V) are generally known as spectral sensitizing dyes in a broad sense for silver halide emulsions, but since they are compounds that do not substantially have an absorption maximum in the visible region, It is effectively used in the present invention.

[0105]

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Z ⁴¹ and Z ⁴² are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus and selenazoline nucleus, respectively. , Represents a non-metal atomic group necessary for completing a pyridine nucleus or a quinoline nucleus.
R ⁴¹ and R ⁴² each represent an alkyl group or an aralkyl group. X ⁴ is a charge balance counter ion, and n represents 0 or 1.

Here, when the general formula (IV) is a radical, it is preferable that one hydrogen atom be desorbed from the atom group represented by Z ⁴¹ or Z ⁴² or the group represented by R ⁴¹ or R ^42. It is preferable that one hydrogen atom be removed from R ⁴¹ and R ⁴² .

Further, in the general formula (IV), those having an acid group as a substituent (for example, R ⁴¹ and R ⁴² are alkyl groups or aralkyl groups having an acid group) are themselves represented by the general formula (II ).

In the general formula (IV), the heterocyclic ring formed by Z ⁴¹ and Z ⁴² is preferably a benzoxazole nucleus, a benzothiazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a thiazole nucleus or an oxazole nucleus, and Preferably, a benzoxazole nucleus, a benzothiazole nucleus, or a naphthoxazole nucleus,
Most preferably, it is a benzoxazole nucleus or a naphthoxazole nucleus. In formula (IV), the heterocycle formed by Z ⁴¹ or Z ⁴² may be substituted with at least one substituent, and the substituent may be a halogen atom (eg, fluorine, chlorine, bromine, iodine). , Nitro group, alkyl group (preferably having 1 to 4 carbon atoms, such as methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group), aryl group (eg phenyl group), alkoxy group (preferably carbon) Those having a number of 1 to 4, such as methoxy group, ethoxy group, propoxy group, butoxy group), carboxyl group, alkoxycarbonyl group (preferably having a carbon number of 2 to 5, such as ethoxycarbonyl group), hydroxy group, cyano group, etc. Can be mentioned.

Regarding Z ⁴¹ and Z ⁴² in the general formula (IV), the benzothiazole nucleus is, for example, benzothiazole or 4
-Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromo Benzothiazole,
6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-
Ethoxybenzothiazole, 5-propoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5-trifluoromethyl Benzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole,
Examples of the naphthothiazole nucleus include naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d]. ] Thiazole, 7-ethoxynaphtho [1,2-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, and the like, and examples of the benzoselenazole nucleus include benzoselenazole and 5-chlorobenzoselenazole. , 5-nitrobenzoselenazole,
5-methoxybenzoselenazole, 5-ethoxybenzoselenazole, 5-hydroxybenzoselenazole, 5
-Chloro-6-methylbenzoselenazole and the like can be used as the naphthoselenazole nucleus, for example, naphtho [1,2-
Examples of the thiazole nucleus include d] selenazole, naphtho [2,1-d] selenazole, and the like.
4-methylthiazole nucleus, 4-phenylthiazole nucleus,
Examples of thiazoline nuclei such as 4,5-dimethylthiazole nuclei and 4,5-diphenylthiazole nuclei include thiazoline nuclei and 4-methylthiazoline nuclei.

Regarding Z ⁴¹ and Z ⁴² in the general formula (IV), examples of the benzoxazole nucleus include a benzoxazole nucleus, a 5-chlorobenzoxazole nucleus, a 5-methylbenzoxazole nucleus, a 5-bromobenzoxazole nucleus, and a 5-bromobenzoxazole nucleus. Fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxybenzoxazole nucleus, 5-ethoxybenzoxazole nucleus, 5-trifluoromethylbenzoxazole nucleus, 5-hydroxybenzoxazole nucleus, 5-carboxybenzoxazole nucleus, 6 -Methylbenzoxazole nucleus, 6-chlorobenzoxazole nucleus, 6-methoxybenzoxazole nucleus, 6-hydroxybenzoxazole nucleus, 5,6
A naphtho [2,1-d] oxazole nucleus, a naphtha [2,1-d] oxazole nucleus, a naphtho [2,3-d] oxazole nucleus, 5- Methoxynaphtho [1,2-d] oxazole nucleus and the like can be mentioned.

Further with respect to Z ⁴¹ and Z ⁴² , examples of the oxazole nucleus include an oxazole nucleus, 4-methyloxazole nucleus, 4-ethyloxazole nucleus, 4-phenyloxazole nucleus, 4-benzyloxazole nucleus, 4-methoxyoxazole nucleus, 4,5-dimethyloxazole nucleus,
Examples of a 5-phenyloxazole nucleus or a 4-methoxyoxazole nucleus include pyridine nuclei such as a 2-pyridine nucleus, a 4-pyridine nucleus, a 5-methyl-2-pyridine nucleus,
-Methyl-4-pyridine nucleus and the like, and as a quinoline nucleus, for example, 2-quinoline nucleus, 4-quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus, 6-
Methyl-2-quinoline nucleus, 8-fluoro-4-quinoline nucleus, 8-chloro-2-quinoline nucleus, 8-fluoro-2-
Quinoline nucleus, 6-methoxy-2-quinoline nucleus, 6-ethoxy-4-quinoline nucleus, 8-chloro-4-quinoline nucleus,
Examples thereof include 8-methyl-4-quinoline nucleus and 8-methoxy-4-quinoline nucleus.

In the general formula (IV), the alkyl group represented by R ⁴¹ and R ⁴² includes an unsubstituted group and a substituent, and the unsubstituted alkyl group has 18 or less carbon atoms, particularly 8 carbon atoms.
The following are preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-octadecyl group. The substituted alkyl group preferably has 6 or less carbon atoms in the alkyl moiety, and particularly preferably 4 or less carbon atoms. For example, an alkyl group substituted with a sulfo group (a sulfo group is They may be bonded via an alkoxy group, an aryl group, etc. For example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
(-3-Sulfopropoxy) ethyl group, 2- [2- (3
-Sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, p-sulfophenethyl group, p-sulfophenylpropyl group, etc.) Alkyl group substituted with a carboxy group (wherein the carboxy group is an alkoxy group or an aryl group) And the like, for example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc.), hydroxyalkyl group (eg, 2-hydroxyethyl group, 3 -Hydroxypropyl group, etc.), acyloxyalkyl group (eg, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (eg, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxy Carbonylalkyl group (for example, 2-
Methoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), vinyl group-substituted alkyl group (eg, allyl group), cyanoalkyl group (eg, 2-cyanoethyl group), carbamoylalkyl group (eg, 2-carbamoylethyl group, etc.), aryloxyalkyl group (eg, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.), aralkyl group (eg, 2-phenethyl group, 3-phenylpropyl group, etc.), or aryloxyalkyl group. (Eg 2
-Phenoxyethyl group, 3-phenoxypropyl group, etc.) and the like.

It is particularly preferable that at least one of the substituents represented by R ⁴¹ and R ⁴² is an alkyl group having a sulfo group or a carboxyl group.

The charge balance counter ion X ⁴ is any anion capable of canceling out the positive charge generated by the quaternary ammonium salt in the heterocycle, and examples thereof include bromide ion, chloride ion, iodine ion and p- ion. Toluene sulfonate ion,
Examples thereof include ethyl sulfonate ion, perchlorate ion, trifluoromethane sulfonate ion, and thiocyanate ion. In this case, n is 1.

When the heterocyclic quaternary ammonium salt further contains an anionic substituent such as a sulfoalkyl substituent,
The salt may take the form of betaine, in which case no counterion is needed and n is 0. When the heterocyclic quaternary ammonium salt has two anion substituents, for example two sulfoalkyl groups, X ⁴ is a cationic counterion, such as an alkali metal ion (sodium ion, potassium ion). Etc.) and ammonium salts (such as triethylammonium).

[0117]

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Z ⁵ is a thiazoline nucleus, thiazolidine nucleus, selenazoline nucleus, selenazolidine nucleus, pyrrolidine nucleus, dihydropyridine nucleus, oxazoline nucleus, oxazolidine nucleus,
To complete the imidazoline nucleus, indoline nucleus, tetrazoline nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benzimidazoline nucleus, benzoxazoline nucleus, naphthothiazoline nucleus, naphthoselenazoline nucleus, naphthaloxazoline nucleus, naphthimidazoline nucleus or dihydroxynoline nucleus Represents a group of non-metal atoms required for. Q is to complete a rhodamine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thioselenazoline-2,4-dione nucleus, a 2-thiohydantoin nucleus, a barbituric acid nucleus or a 2-thiobarzbyric acid nucleus. Represents the necessary non-metallic atomic group. R ⁵¹ and R ⁵² each represent a hydrogen atom, an alkyl group, or an aryl group.

P represents 0 or 1.

Here, when the compound of the general formula (V) is in the form of a radical, preferably, one hydrogen atom is selected from the group of atoms represented by Z ⁵ and Q or the groups represented by R ⁵¹ and R ^52. It has been released, and in particular 1 hydrogen atom from R ⁵¹ and R ^52.
Those separated from each other are preferable.

In the compound of the general formula (V) having an acid group as a substituent (for example, R ⁵¹ and R ⁵² are an alkyl group or an aralkyl group having an acid group), the compound itself has the general formula (II). Can be a compound represented by.

Here, Z ⁵ is a thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-phenylthiazoline, 4,5-dimethylthiazoline, 4,5-diphenylthiazoline, etc.) and a benzothiazoline nucleus (eg, Benzothiazoline, 4-chlorobenzothiazoline,
5-chlorobenzothiazoline, 6-chlorobenzothiazoline, 7-chlorobenzothiazoline, 5-nitrobenzothiazoline, 6-nitrobenzothiazoline, 4-methylbenzothiazoline, 5-methylbenzothiazoline, 6-
Methylbenzothiazoline, 5-bromobenzothiazoline, 6-bromobenzothiazoline, 5-iodobenzothiazoline, 5-methoxybenzothiazoline, 6-methoxybenzothiazoline, 5-ethoxybenzothiazoline,
5-propoxybenzothiazoline, 5-butoxybenzothiazoline, 5-carboxybenzothiazoline, 5-ethoxycarbonylbenzothiazoline, 5-phenethylbenzothiazoline, 5-fluorobenzothiazoline, 5-
Chloro-6-methylbenzothiazoline, 5-trifluoromethylbenzothiazoline, 5,6-dimethylbenzothiazoline, 5-hydroxy-6-methylbenzothiazoline, tetrahydrobenzothiazoline, 4-phenylbenzothiazoline, 5-phenylbenzothiazoline, Etc.), a naphthothiazoline nucleus (for example, naphtho [2,1-
d] thiazoline, naphtho [1,2-d] thiazoline, naphtho [2,3-d] thiazoline, 5-methoxynaphtho [1,2-d] thiazoline, 7-ethoxynaphtho [2,2]
1-d] thiazoline, 8-methoxynaphtho [2,1-
d] thiazoline, 5-methoxynaphtho [2,3-d] thiazoline, etc., thiazolidine nucleus (eg, thiazolidine, 4-methylthiazolidine, 4-nitrothiazolidine, etc.), oxazoline nucleus (eg, oxazoline, 4-
Methyloxazoline, 4-nitrooxazoline, 5-methyloxazoline, 4-phenyloxazoline, 4,5
-Diphenyloxazoline, 4-ethyloxazoline, etc.), a benzoxazoline nucleus (benzoxazoline, 5
-Chlorobenzoxazoline, 5-methylbenzoxazoline, 5-bromobenzoxazoline, 5-fluorobenzoxazoline, 5-phenylbenzoxazoline, 5-methoxybenzoxazoline, 5-nitrobenzoxazoline, 5-trifluoromethylbenzoxazoline, 5 -Hydroxybenzoxazoline, 5-carboxybenzoxazoline, 6-methylbenzoxazoline, 6-chlorobenzoxazoline, 6-nitrobenzoxazoline, 6-methoxybenzoxazoline, 6
-Hydroxybenzoxazoline, 5,6-dimethylbenzoxazoline, 5-ethoxybenzoxazoline, etc.), naphthooxazoline nucleus (for example, naphtho [2,1
-D] oxazoline, naphtho [1,2-d] oxazoline, naphtho [2,3-d] oxazoline, 5-nitronaphtho [1,2-d] oxazoline, etc.), oxazolidine nucleus (eg, 4,4-dimethyloxazolidine, etc.) ),
The selenazoline nucleus (e.g., 4-methyl selenazoline, 4
-Nitroselenazolin, 4-phenylselenazolin, etc.), selenazolidine nucleus (for example, selenazolidine, 4-
Methyl selenazolidine, 4-phenyl selenazolidine riddle, benzoselenazoline nucleus (for example, benzoselenazoline, 5-chlorobenzoselenazoline, 5-nitrobenzoselenazoline, 5-methoxybenzoselenazoline, 5
-Hydroxybenzoselenazoline, 6-nitrobenzoselenazoline, 5-chloro-6-nitrobenzoselenazoline riddle), naphthoselenazoline nucleus (for example, naphtho [2,1-d] selenazoline, naphtho [1,2-d] ] Selenazoline, etc.), 3,3-dialkylindoline nucleus (for example, 3,3-dimethylindoline, 3,3-diethylindoline, 3,3-dimethyl-5-dianoindoline, 3,3-dimethyl-6-nitroindoline) , 3, 3
-Dimethyl-5-nitroindoline, 3,3-dimethyl-5-methoxyindoline, 3,3-dimethyl-5-methylindoline, 3,3-dimethyl-5-chloroindoline, etc.), imidazoline nucleus (e.g., 1- Alkyl imidazoline, 1-alkyl-4-phenyl imidazoline, 1-aryl imidazoline, etc.), benzimidazoline nucleus (for example, 1-alkyl benzimidazoline, 1-
Alkyl-5-chlorobenzimidazoline, 1-alkyl-5,6-dichloro-benzimidazoline, 1-alkyl-5-methoxybenzimidazoline, 1-alkyl-5-cyanobenzimidazoline, 1-alkyl-5
Fluorobenzimidazoline, 1-alkyl-5-trifluoromethylbenzimidazoline, 1-allyl-5
6-dichlorobenzimidazoline, 1-allyl-5-chlorobenzimidazoline, 1-arylbenzimidazoline, 1-aryl-5-chlorobenzimidazoline,
1-aryl-5,6-dichlorobenzimidazoline,
1-aryl-5-methoxybenzimidazoline, 1-
Aryl-5-cyanobenzimidazoline, etc.), naphthoimidazoline nucleus (for example, 1-alkylnaphtho [1,
2-d] imidazoline, 1-arylnaphtho [1,2-
d] imidazoline etc.), said alkyls being especially those of 1 to 8 carbon atoms, for example methyl, ethyl, propyl,
Unsubstituted alkyl groups such as isopropyl and butyl and hydroxyalkyl groups (eg, 2-hydroxyethyl group, 3-
And hydroxypropyl. The aforementioned aryl group represents phenyl, halogen (for example, chloro) -substituted phenyl, alkyl (for example, methyl) -substituted phenyl, alkoxy (for example, methoxy) -substituted phenyl and the like. ),
Pyrrolidine nucleus (for example, 2-pyrrolidine), dihydropyridine nucleus (for example, 1,4-dihydropyridine, 5-methyl-1,2-dihydropyridine, 3-methyl-1,4)
-Dihydropyridines, etc.), dihydroquinoline nuclei (eg 1,4-dihydroquinoline, 3-methyl-1,2-
Dihydroquinoline, 5-ethyl-1,2-dihydroquinoline, 6-methyl-1,2-dihydroquinoline, 6-nitro-1,2-dihydroquinoline, 8-fluoro-1,
2-dihydroquinoline, 6-methoxy-1,2-dihydroquinoline, 6-hydroxy-1,2-dihydroquinoline, 8-chloro-1,2-dihydroquinoline, 6-ethoxy-1,4-dihydroquinoline, 6 -Nitro-1,4
-Dihydroquinoline, 8-chloro-1,4-dihydroquinoline, 8-fluoro-1,4-dihydroquinoline, 8
-Methyl-1,4-dihydroquinoline, 8-methoxy-
1,4-dihydroquinoline, dihydroisoquinoline, 6
-Nitro-1,2-isoquinoline, 6-hitoro-2,3
-Dihydroisoquinoline, etc.) and tetrazoline represent nonmetallic atomic groups necessary for completing the nucleus.

Of these, Z ⁵ is preferably oxazoline nucleus, oxazolidine nucleus, thiazoline nucleus, benzothiazoline nucleus, thiazolidine nucleus, benzoxazoline, naphthoxazoline nucleus, selenazoline nucleus, selenazolidine nucleus, benzoselenazoline nucleus, benzimidazoline nucleus, This is the case with pyrrolidine nuclei, dihydropyrrolidine nuclei and tetrazoline nuclei. Particularly preferred are oxazoline nucleus of Z ^5, oxazolidine nucleus, benzoxazoline nucleus, a thiazoline nucleus, a thiazolidine nucleus, a selenazoline nucleus, Serenazorijin nucleus, benzimidazoline nucleus, pyrrolidine nucleus, even more preferred as Z ⁵ is a dihydropyridine nucleus,
They are an oxazoline nucleus, an oxazolidine nucleus, a benzoxazoline nucleus, a thiazoline nucleus, a thiazolidine nucleus, a benzimidazoline nucleus and a pyrrolidine nucleus.

R ⁵¹ and R ⁵² are each a hydrogen atom, an unsubstituted alkyl group (an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, dothesyl, Octadecyl etc.), substituted alkyl group [eg aralkyl group (eg,
Benzyl, β-phenylethyl etc.), hydroxyalkyl group (eg 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyethoxyethyl etc.), carboxyalkyl group (eg carboxymethyl, 2-
Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.), an alkyl group substituted with a sulfo group (the sulfo group may be bonded to the alkyl group via an alkoxy group, an aryl group, etc., for example, 2-sulfoethyl, Three
-Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, p-sulfophenethyl Etc.), a sulfate alkyl group (eg, 3-sulfatepropyl, 4-sulfatebutyl, etc.), a mercapto group, a vinyl group-substituted alkyl group (eg, an allyl group),
Acyloxyalkyl group (for example, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (for example, 2- Methoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), cyanoalkyl group (eg, 2-cyanoethyl group, etc.), carbomoylalkyl group (eg, 2
-Carbamoylethyl group, etc.), aryloxyalkyl group (eg, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.), aryloxyalkyl group (eg,
2-phenoxyethyl group, 3-phenoxypropyl group, etc.), mercaptoalkyl group (eg, 2-mercaptoethyl group, 3-mercaptopropyl group, etc.), alkylthioalkyl group (eg, 2-methylthioethyl group), or aryl Groups (eg phenyl, tolyl,
Naphthyl group, methoxyphenyl group, chlorophenyl group, etc.). Among them, at least one of R ⁵¹ and R ⁵² is preferably an alkyl group having a sulfo group or a carboxyl group.

Q is a rhodanine nucleus, 2-thiooxazoline-2,4-dione nucleus, 2-thioselenazoline-2,
4-dione nucleus, barbituric acid nucleus or thiobarbituric acid nucleus [eg 1-alkyl group (eg 1-methyl, 1-
Ethyl, 1-propyl, 1-butyl, etc.), 1,3-dialkyl group (for example, 1,3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl,
1,3 dicyclohexyl, 1,3-di (β-methoxyethyl), etc., 1,3-diaryl group (eg, 1,3
-Diphenyl, 1,3-di (pchlorophenyl), 1,
3-di (p-ethoxycarbonylphenyl) and the like), 1
-Sulfoalkyl group (for example, 1- (2-sulfoethyl), 1- (3-sulfopropyl), 1- (4-sulfobutyl), etc.), 1,3-disulfoalkyl group (for example, 1,3-di ( 2-sulfoethyl), 1,3-di (3-
Sulfopropyl), 1,3-di- (4-sulfocyclohexyl etc.), 1,3-di- (sulfoaryl group (eg 1,3-di- (4-sulfophenyl) etc.), or 1-sulfo. A barbitur nucleus or a thiobarbituric acid nucleus containing an aryl group (eg 1- (4-sulfophenyl) etc.), or a thiohydantoin nucleus (wherein the substituent at the 1-position is synonymous with the 3-position (R ⁵² )) Both may be the same or different) represents a non-metal atomic group necessary to complete the above.

The heterocycle formed by Q is preferably a rhodamine nucleus or a thiohydantoin nucleus, more preferably a rhodamine nucleus.

C is preferably a radical composed of cyanine and merocyanine, and most preferably a radical composed of cyanine.

D represents an acid group. Examples of the acid group include those capable of being dissociated into anions during development processing.
Some examples thereof have already been described as the substituent of C, but a more detailed description will be made, for example, with a sulfonic acid group,
Carboxylic acid group, phosphonic acid group, sulfinic acid group, sulfoamino group, phosphinic acid group, sulfuric acid monoester group, sulfonamide group, sulfamoyl group, hydroxyimino group, hydroxyaminocarbonyl group, sulfinamide group, sulfinamoyl group, or hydroxyamino group Examples thereof include a sulfonyl group.

D is preferably a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, a sulfinic acid group, a sulfoamino group, or a sulfuric acid monoester group, more preferably a sulfonic acid group, a carboxylic acid group, or a phosphonic acid group. Acid groups, most preferably sulfonic acid groups.

The acid group represented by D may be in the form of an acid anion. In this case, it may have a suitable cation as a charge balance counter ion. Examples of such cations include ammonium salts (eg, triethylammonium and pyridinium) and alkali metal ions (eg, sodium ion and potassium ion).

L is a divalent linking group. The divalent linking group represented by L is an atom or an atomic group containing at least one of C, N and SO.

Specific examples of L include alkylene group, alkenylene group, alkynylene group, arylene group,
-O -, - S -, - NH -, - N =, - CO-, or -SO ₂ - (which may have these groups the substituent)
Etc., or a combination of two or more. More specifically, as L, for example, (3)
Alkylene group (preferably having 1 to 12 carbon atoms, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, etc.), (2) alkenylene group (preferably having 2 to 12 carbon atoms, for example, vinylene group) , Butenylene group, etc.), (3) alkynylene group (preferably having 2 to 12 carbon atoms, for example, ethynylene group, butynylene group, etc.), (4) arylene group (preferably having 6 to 1 carbon atoms).
0, for example, phenylene group, naphthylene group, etc.), (5) -O-, (6) -S-, (7) -NH-,
(8) -N =, (9 ) -CO -, (10) -SO 2 - and the like, further, for example, as a combination thereof

[0133]

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And (1) to (4) and (5) to (16)
An appropriate combination of (for example,

[0135]

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And the like. As the compound represented by the general formula (II) used in the present invention, a compound of the general formula (IV) or the general formula (V) having an acid group is particularly preferable. Among them, the former is preferable in terms of black spots and residual color.

Specific examples in the case where C is a mercapto group or a heterocyclic group in the general formula (II) are shown below.
However, the present invention is not limited to the following compounds.

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

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[0141]

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The heterocyclic compounds represented by the general formulas (II) to (III) are described in "Compre" by A.Katritzky and CWReese.
hensive Heterocyclic Chemistry, The Structure, React
ions, Synthesis and Use of Heterocyclic Compounds ”
Pergamon Press, Oxford (1984), Volumes 2-6, and thioamide compounds, edited by E. Miiller, "Method.
en der Organischen Chemie ”, Georg Thieme Verlag, S
It can be easily synthesized by referring to tuttgart (1955) Vol. 9, and those not described can be synthesized by a similar method.

Specific examples of compounds in which C in the general formula (II) has a radical of the compounds represented by the general formulas (IV) and (V) are shown below, but the present invention is limited to the following compounds: is not.

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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The compounds represented by the above general formulas (IV) to (V) are described in US Pat. Nos. 2,852,385 and 2,6.
No. 94,638, No. 3,615,635, No. 2,91
2,329, 3,314,031, 3,39
7,060, 3,506,443, British Patent 1,
339,833 and the like, which are described in the above specification or "The Cyanine Dyes and Related Com" by FM Hamer.
pounds ”, IntersciencePublishers, New York (196
With reference to 4), those skilled in the art can easily synthesize the compounds, and those not described can be synthesized by a similar method.

In the present invention, when the compound represented by the general formula (II) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers ( For example, protective layer, intermediate layer,
Filter layer, antihalation layer, etc.). Specifically, when the compound to be used is water-soluble, it is used as an aqueous solution.
It may be added to a hydrophilic colloid solution as a solution of an organic solvent miscible with water such as esters and ketones. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the end of chemical ripening and before coating. Particularly, it is preferable to add it to a coating solution prepared for coating.

In the present invention, the compound represented by the general formula (II) is preferably contained in an amount of 1 × 10 ^-6 to 1 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
It is preferable to contain 0 ^-5 to 1 x 10 ^-3 mol.

The following known compounds may be used as the black spot preventing agent. These compounds may be used alone or in addition to the black spot preventing agent of the present invention.

WO93 / 02388, WO93 / 085
Thiourea compound described in WO 03/08504,
An isothiourine compound described in JP-A-4-258,951;
JP-A-8-43985, 6-180, 480, 4-
316, 042, the same 2-120, 850, the same 2-10
3,532 nitrogen-containing heterocyclic compounds, 4-6
7,140, the purine compound described in 3-44,630, the mercapto compound described in 4-190,227,
Precursor compounds described in JP-A-62-30,243, tetrazaindene compounds described in US Pat. No. 5,256,519, JP-A-61-223,834, JP-A-61-222.
The acid compound described in 8,437 can be used.

The reducing agent for the organic silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent should be present as 1 to 10% by weight of the imaging layer. In multi-layer constructions, a slightly higher percentage, about 2-15%, tends to be more desirable when the reducing agent is added to layers other than the emulsion layer.

A wide range of reducing agents have been disclosed in the photothermographic materials using organic silver salts. For example, amidoximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2'-bis (hydroxymethyl) propionyl. A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of -β-phenylhydrazine and ascorbic acid; polyhydroxybenzene and hydroxylamine,
A combination of reductone and / or hydrazine, such as a combination of hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine;
Hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-anilinehydroxamic acid; combinations of azines with sulfonamide phenols (eg phenothiazine and 2,6-dichloro-
Α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-
Binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis-β as exemplified by bis (2-hydroxy-1-naphthyl) methane.
-Naphthol; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (eg, 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl-
5-pyrazolone, such as 5-pyrazolone; reductone as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4 Sulfonamidophenol reducing agents such as -benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7
Chromans such as -t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-
1,4-dihydropyridines such as 1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 2,
2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6)
-Methylphenol), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4)
Ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones. and so on.

Particularly preferred reducing agents in the present invention are the following general formula (R-I), general formula (R-II) and general formula (R-II).
I) and compounds represented by the general formula (R-IV).

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In the general formula (R-III), the ring structure formed by Z is as follows.

[0161]

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In the general formula (R-IV), the ring structure formed by Z is as follows.

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In the formula, L ₁ and L ₂ are a group represented by CH-R ₆ or a sulfur atom. n represents a natural number.

R (R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R ₁₁ to
Including _{R 13, R 11 '~R 13} ', R 21 ~R 26, R 21 '~R 24') is a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms),
An aryl group, an aralkyl group, a halogen atom, an amino group, or a substituent represented by -OA. However, R ₁
At least one of the at least one and R ₇ to R ₁₀ in at least to R ₅ one and R ₁ '~R _5' is a group represented by -O-A. Further, R may form a ring with each other.
A and A 'each represent a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms).
0), an acyl group (1 to 30 carbon atoms), an aryl group, a phosphate group, and a sulfonyl group. R, A and A 'may be substituted, and typical substituents include, for example, alkyl groups (including active methine groups), nitro groups, alkenyl groups, alkynyl groups, aryl groups, groups containing heterocycles, A group containing a quaternary heterocycle containing a nitrogen atom (for example, a pyridinio group), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group Group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group A hydrazino group, a quaternary ammonium group, a mercapto group, an (alkyl, aryl, or heterocycle) thio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group, Sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, phosphoric amide group, group containing a phosphoric ester structure, acyl Group having a rare structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. R,
The substituents of A and A'may be further substituted, and preferable examples thereof include those exemplified as the substituent of R. Further, the substituents, the substituents of the substituents, the substituents of the substituents of the substituents, etc. may be multiply substituted, and preferable examples are also the substituents of R, A and A ′. The examples given apply.

Hereinafter, the general formula (R-I) and the general formula (R-
Illustrative examples of the compounds represented by II), general formula (R-III) and general formula (R-IV) are shown below. However, the present invention is not limited to the following compounds.

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[Table 1]

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[0169]

[Table 2]

[0170]

[Table 3]

[0171]

[Table 4]

[0172]

[Table 5]

[0173]

[Table 6]

[0174]

[Table 7]

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The amount of the reducing agent used in the present invention is preferably silver 1.
1 × 10 ⁻² to 10 mol per mol, particularly 1 × 10 ⁻² to 1.
5 moles.

Further, in the present invention, it is preferable to set the molar ratio of the reducing agent to the contrast increasing agent in the range of 1:10 ^-3 to 1:10 ^-1 .

The photothermographic material of the present invention forms a photographic image using a heat development processing method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan
(Morgan) and B. “Themally Processed Silver System” by Shely.
ms) "(Imaging Processes and Materials Neblette
Eighth Edition, Sturge, V.I. Walwo
rth), A. Edited by Shepp, page 2, 1969
Year).

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) and a catalytically active amount of a photocatalyst (eg, halogenated compound). It is preferable that the photothermographic material contains silver), a toning agent that suppresses the color tone of silver, and a reducing agent, usually in a state of being 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, 60 ° C. or lower, without supplying a post-exposure treatment liquid).
(Preferably 80 ° C or higher, and preferably 120 ° C or lower)
It is developed by heating to. Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. 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.

In the present invention, it is considered that a high contrast agent is involved in this image forming process to form an ultrahigh contrast image. The super-high contrast connection formation by the contrast-increasing agent is known in the system for liquid treatment, but it is not known in the thermal development system using the organic silver salt, which is unexpected.

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 the opposite side of the photosensitive layer in order to suppress the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. . As the dye, the compound of Japanese Patent Application No. 7-1184 is preferable.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitive layer / low sensitive layer or a low sensitive layer / high sensitive layer for adjusting gradation.

Various additives may be added to any of the light-sensitive layer, 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, a coating aid and the like.

Suitable binders are transparent or translucent, generally colorless, and include natural polymeric synthetic resins, polymers and copolymers, and other film-forming media such as:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, cellulose acetate,
Cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione); naphthalimides (eg, , N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles, incuronium (isoth
iuronium) combinations of derivatives and certain photobleaches (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); a merocyanine dye (for example, 3-ethyl-5-((3-ethyl-2-benzothia Zorinilidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
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 (eg, ,
6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); combination of phthalazine + phthalic acid; phthalazine (including adduct of phthalazine), maleic anhydride, and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) in combination with at least one compound; quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-dione (Eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg
3,6-dimerocapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene.

A preferable toning agent is phthalazone.

A silver halide useful as a catalytically active amount of a photocatalyst is any light sensitive 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 neat silver salt complexes in which 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-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, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4- Complexes or salts of silver with a nitric acid selected from triazole and benzotriazole; silver salts such as saccharin, 5-chlorosalicylaldoxime; and silver salts of mercaptides, preferred silver salt is silver behenate. The preferable silver source is 3 g / m ^{2 in} terms of silver amount.
It is as follows. More preferably, it is 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, antifoggants such as those disclosed in U.S. Pat. Nos. 4,454,075 and 4,452,885 and Japanese Patent Publication No. 59-57234 are preferred.

Particularly preferred non-mercury antifoggants are compounds such as those disclosed in US Pat. Nos. 3,874,946 and 4,756,999, --C (X ¹ ) (X ² ) (X ³ ).
(Where X ¹ and X ² are halogens (eg, F, Cl,
In Br and I), X ³ is represented by hydrogen or halogen) 1
It is a heterocyclic compound having the above substituents. Examples of suitable antifoggants include:

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Even more preferred antifoggants are US Pat. No. 5,028,523 and British Patent Application No. 9222138.
3.4, 9300147.7, 93111790.1
Issue.

The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651 and JP-A-6-259435.
3-304242, 63-15245, U.S. Pat. Nos. 4639414, 4740445 and 47419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used.

Useful sensitizing dyes used in the present invention are described in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (Dec. 1978, p. 23) and I tem Item 1831X (Aug. 1978, p. 437). It is described in the cited documents.

Especially, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For example, as for A) an argon laser light source, Japanese Patent Laid-Open No. 60-1
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
Trinuclear cyanine dyes described in JP-A-102229, merocyanines described in Japanese Patent Application No. 6-103272, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
32, the tricarbocyanines described in JP-A-60-80841, and the tricarbocyanines described in JP-A-59-192242 and JP-A-3-67242, the general formula (IIIa) and the general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Exposure of the photothermographic material of the present invention is carried out by Ar laser (488 nm), He-Ne laser (633n).
m), red semiconductor laser (670 nm), infrared semiconductor laser (780 nm, 830 nm) and the like are preferable.

The photothermographic material of the invention may be provided with a layer containing a dye as an antihalation layer.
For Ar laser, He-Ne laser, and red semiconductor laser, a 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 400 nm to 750 nm. 75 for infrared semiconductor lasers
In the range of 0 nm to 1500 nm, the exposure wavelength is at least 0.1 nm.
The dye is added so as to have an absorption of 3 or more, preferably 0.8 or more. 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 the plastic film is passed through a heat developing machine, 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, polyarylate and the like can be used.

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. be able to.

When a mercapto compound is used in the present invention, it may have any structure, but Ar-SM, Ar
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, nafusuimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine. , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring is, for example, halogen (eg Br and Cl), hydroxy, amino, carboxy, alkyl (eg having 1 or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy ( For example, it may have one selected from the group of substituents consisting of one or more carbon atoms, preferably having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobis- (benzothiazole, 3
-Mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolthiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto -4- (3H) -quinazolinone,
7-trifluoromethyl-4-quinolinethiol, 2,
3,5,6-tetrachloro-4-pyridinethiol, 4
-Amino-6-hydroxy-2-mercaptopyridine monohydrate, 2-amino-5-mercapto-1,3
4-thiadiazole, 3-amino-5-mercapto-
1,2,4-triazole, 4-hydrocicy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6
-Diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-
Examples include mercapto-4-phenyloxazole, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, and more preferably 0.01 to 0.3 mol per mol of silver. Is the amount of.

The method of forming the photosensitive silver halide in the present invention is well known in the art and described in, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458. Can be used. As a specific method that can be used in the present invention, a method of converting a part of silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin, Alternatively, a method in which a photosensitive silver halide grain is prepared by adding a silver-supplying compound and a halogen-supplying compound to another polymer solution and mixed with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation to be low, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.01 μm or less
The thickness is preferably 2 μm or more and 0.12 μm or less. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3:
1 is good. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited. However, the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high. preferable. The ratio is preferably 50% or more.
% Or more, more 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.
It can be determined by the method described in T. Tani; J. Imaging Sci., 29, 165 (1985). The halogen composition of the photosensitive silver halide is not particularly limited, and silver chloride,
It may be any of silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide and silver iodide, but in the present invention, silver bromide or silver iodobromide is preferably used. it can. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%,
More preferably, it is at least 20 mol% and not more than 20 mol%. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously, but as a preferable example, the silver iodide content inside the grains is High silver iodobromide grains can be used. Preferably, silver halide grains having a core / shell structure can be used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used.

The photosensitive silver halide grain of the present invention preferably contains at least one metal complex selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt or iron. These metal complexes are 1
One kind may be used, or two or more kinds of same metal and different metal complexes may be used in combination. The preferred content is 1 per mol of silver
The range is preferably from nmol to 10 mmol, more preferably from 10 nmol to 100 μmol. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used. cobalt,
For the iron compound, a hexacyano metal complex can be preferably used. Specific examples thereof include, but are not limited to, ferricyanate ion, ferrocyanate ion, and hexasiacobaltate ion. Even if the phase containing the metal complex in the silver halide is homogeneous,
It may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration without any particular limitation.

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

The photosensitive silver halide grain in the invention is preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyl tellurocarboxylic acid esters, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, and Te
Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium and the like can be used. Compounds preferably used in the noble metal sensitization method are described in, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, or US Pat. No. 2,448,060 and British Patent 618,061. The compounds described above can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Further, reduction sensitization can be carried out by ripening while maintaining the pH of the emulsion at 7 or more or pAg at 8.3 or less. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation.

The photosensitive silver halide of the present invention is used in such an amount that the photosensitive silver halide is 0.0 per mol of the organic silver salt.
1 mol is preferably 0.5 mol or less, more preferably 0.02 mol or more and 0.3 mol or less, and 0.03 mol or more and 0.1 mol or less.
Particularly preferred is 25 mol or less. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. Etc., or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt. There is no particular limitation as long as it appears in.

Organic silver salts usable in the present invention are
Relatively stable to light, but forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially silver salts of long-chain fatty carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Ligands 4.0-10.0
Also preferred are complexes of organic or inorganic silver salts having a complex stability constant in the range of The silver donor can preferably comprise about 5 to 30% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group.
Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate,
Silver maleate, silver fumarate, silver tartrate, silver linoleate,
Includes silver butyrate and camphorate, mixtures thereof and the like.

Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used.
Preferred examples of these compounds include 3-mercapto-4
-Silver salt of phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamido) benzothiazole, S- Alkyl thioglycolic acid (
Wherein the alkyl group has 12 to 22 carbon atoms), such as silver salts of thioglycolic acid, silver salts of dithiocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamide, 5-carboxyl-1 -Methyl-2-phenyl-4-thiopyridine silver salt,
Silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt described in U.S. Pat. No. 4,123,274,
For example, a silver salt of a 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole,
Includes silver salts of thione compounds such as the silver salt of 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione described in US Pat. No. 3,301,678. Furthermore, compounds containing an imino group can be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazoles such as silver 5-chlorobenzotriazole, U.S. Pat. No. 4,220,709, and silver salts of 1,2,4-triazole or 1-H-tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, US Pat.
Various silver acetylide compounds such as those described in 61361 and 4775613 can also be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but needle crystals having a short axis and a long axis are preferable. As is well known in photosensitive silver halide photosensitive materials, the inversely proportional relationship between the size of silver salt crystal grains and their covering power also holds in the photothermographic material of the present invention, that is, the photothermographic material When the size of the organic silver salt particles in the image forming section is large, it means that the covering power is small and the image density is low. Therefore, it is necessary to reduce the size of the organic silver salt. In the present invention, the minor axis is 0.
01 μm or more and 0.20 μm or less, long axis 0.10 μm or more and 5.0 μm or less, short axis 0.01 1 μm or more and 0.15 μm or less, long axis
It is more preferably 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse is the percentage of the value obtained by dividing the standard deviation of the length of each of the short axis and the long axis by each of the short axis and the long axis, preferably 100% or less, more preferably 80% or less, further preferably 50% or less. is there. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the 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 It is preferably at most 80%, more preferably at most 50%. As a measuring method, for example, the organic silver salt dispersed in a liquid is irradiated with laser light, and the particle size (volume weight average diameter) obtained by obtaining an autocorrelation function with respect to a time change of the fluctuation of the scattered light is obtained. Can be.

The heat-developable photographic light-sensitive material of the present invention comprises
A so-called one-sided light-sensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of a support and a backing layer on the other side is preferred.

In the present invention, a matting agent may be added to the one-sided photosensitive material in order to improve transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, US Pat. Nos. 1,939,213 and 2,701,245.
No. 2,322,037, No. 3,262,782
No. 3,539,344, No. 3,767,448 and the like, organic matting agents described in each specification, Nos. 1,260,7.
72, 2,192,241, 3,257,20
No. 6, No. 3,370,951, No. 3,523,022
Nos. 3,769,020 and the like, which are well known in the art, such as the inorganic matting agents described in the respective specifications can be used. For example, specific examples of organic compounds that can be used as a matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile as examples of water-dispersible vinyl polymers.
α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate,
Examples of known cellulose derivatives such as polyethylene carbonate and polytetrafluoroethylene, such as methylcellulose, cellulose acetate and cellulose acetate propionate, and examples of starch derivatives such as carboxy starch, carboxynitrophenyl starch and urea-formaldehyde-starch reactants Gelatin hardened with a hardener and hardened gelatin obtained by coacervate hardening to form hollow microcapsules can be preferably used. Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by known methods,
Similarly, silver bromide, glass, diatomaceous earth and the like can be preferably used. The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, 0.1 μm to 3 μm
It is preferable to use one having a particle size of 0 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent has a great influence on the haze and surface gloss of the light-sensitive material, the particle size, shape, and particle size distribution can be adjusted to the required state during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, the Bekk smoothness of the backing layer is preferably 250 seconds or less and 10 seconds or more, and more preferably 180 seconds or less and 50 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.

Suitable binders for the backing layer in the present invention are transparent or translucent, generally colorless, and include natural polymers such as synthetic resins, polymers and copolymers and other film forming media such as: gelatin, gum arabic, poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral), poly (ester) s, poly Urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
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.

In the present invention, the backing layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range, more preferably 0.5 or more and 2 or less of IR absorption, and in the visible region. Is preferably 0.001 or more and less than 0.5, and more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3.

When the antihalation dye is used in the present invention, the dye has a desired absorption in a desired wavelength range and has a sufficiently small absorption in the visible region, and a preferable absorbance spectrum shape of the backing layer can be obtained. Any compound can be used. For example, compounds described in JP-A-7-13295, U.S. Pat. No. 5,380,635, and JP-A-2-68.
Compounds described in JP-A-539 / 1993, page 13, lower left column, line 1 to page 14, lower left column, line 9 and JP-A-3-24539, page 14, lower left column to page 16, right lower column can be mentioned. The invention is not limited to this.

A backside resistive heating layer such as those shown in US Pat. No. 4,460,681 and 4,374,921, may also be used in the photothermographic image system. it can.

The light-sensitive material of the present invention may be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.
Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials include waxes, silica particles, styrene-containing elastomeric block copolymers (eg, styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and the like. And mixtures.

The emulsion layer or the protective layer for the emulsion layer according to the present invention is described in US Pat.
It can be used in photographic elements containing light absorbing materials and filter dyes such as those described in U.S. Pat. Nos. 274,782, 2,527,583 and 2,956,879. See also, for example, U.S. Pat.
The dye can be mordant as described in 2,699.

In the emulsion layer or the protective layer of the emulsion layer in the present invention, a matting agent such as starch, titanium dioxide, zinc oxide, silica, US Pat. Nos. 2,992,101 and 2,701,245. Polymer beads, including beads of the type described in 1., and the like can be included. Further, the matt degree of the emulsion surface may be any value as long as stardust failure does not occur.
0 second or less is preferable, and especially 2000 to 10000 second is preferable.

As the binder for the emulsion layer in the invention, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride,
Any one can be selected from polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral, butylethyl cellulose, methacrylate copolymers, maleic anhydride copolymers, polystyrene and butadiene-styrene copolymers. If necessary, two or more of these polymers can be used in combination. Such a polymer is used in an amount sufficient to hold the components therein. That is, it is used in a range effective to function as a binder. The curable range can be appropriately determined by those skilled in the art. As a guide when at least the organic silver salt is retained, the ratio of the binder to the organic silver salt is 1
The range of 5: 1 to 1: 2, particularly 8: 1 to 1: 1 is preferred.

As a binder for the silver halide emulsion layer and other hydrophilic colloid layers, JP-A-2-18542 is known.
The binders described in the lower right line 1st to 20th lines of page 3 of the publication are used.

[0231]

[Effect] Ultra-high contrast, high Dmax, and generation of black spots is prevented.

[0232]

【Example】

Example 1 << Preparation of Organic Acid Silver Emulsion >> 840 g of behenic acid and 95 g of stearic acid were added to 12 liters of water and 48 g of sodium hydroxide and 63 g of sodium carbonate were dissolved in 1.5 liters of water while maintaining the temperature at 90 ° C. Stuff was added. After stirring for 30 minutes, the temperature is raised to 50 ° C. and N-bromosuccinimide 1%
An aqueous solution (1.1 L) was added, and then 2.3 L of a 17% silver nitrate aqueous solution was gradually added with stirring. Further, the liquid temperature was set to 35 ° C., and potassium bromide 2% while stirring.
An aqueous solution (1.5 L) was added over 2 minutes, and the mixture was stirred for 30 minutes, and a 1% aqueous solution of N-bromosuccinimide (2.4%) was added.
One liter was added. While stirring this aqueous mixture, 3300% by weight of a solution of polyvinyl acetate in butyl acetate
After adding g, the mixture was allowed to stand for 10 minutes to separate into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. The gel-like mixture of behenic acid / silver stearate and silver bromide thus obtained was mixed with 2.6% of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo KK).
Dispersed with 1800 g of isopropyl alcohol solution, and further dispersed with 600 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) and 300 g of isopropyl alcohol, an organic acid silver salt emulsion (average minor axis 0.05 μm, average major axis 1) 0.2 μm, coefficient of variation 25%
Needle-shaped particles).

<< Preparation of Emulsion Layer Coating Solution >> Each chemical was added to the organic acid silver emulsion obtained above in the following amount per mol of silver. At 25 ° C., sodium phenylthiosulfonate 10 mg, 70 mg of dye a, 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-
21.5 g of 2-carboxylic acid, 580 g of 2-butanone and 220 g of dimethylformamide were added with stirring, and the mixture was left for 3 hours. Next, 8 g of 5-tribromomethylsulfonyl-2-methylthiadiazole, 6 g of 2-tribromomethylsulfonylbenzothiazole, 5 g of 4,6-ditrichloromethyl-2-phenyltriazine, 2 g of disulfide compound a, and R- as a reducing agent I-5 to 0.
3 mol, 6.5 × 10 ⁻³ mol of I-65 as an ultra-high contrast agent, 5.0 × 10 ⁻⁴ mol of the black dot suppressor of the present invention shown in Table 8 were further added, and Tetrachlorophthalic acid 5 g, Megafax F-176P (Dainippon Ink and Chemicals, Inc. fluorinated surfactant) 1.1 g, 2-
Butanone (590 g) and methyl isobutyl ketone (10 g) were added with stirring.

<< Emulsion Surface Protective Layer Coating Solution >> CAB171-1
75 g of 5S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.), 5.7 g of 4-methylphthalic acid, 1.5 g of tetrachlorophthalic anhydride, 12.5 g of phthalazine,
0.3 g of Megafax F-176P, Sildex H31 (average size of spherical silica manufactured by Dokai Chemical Co., Ltd., 3 μm)
2 g, 7 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) dissolved in 3070 g of 2-butanone and 30 g of ethyl acetate were prepared.

<< Preparation of Support Having Back Surface >> On a polyethylene terephthalate film consisting of a moistureproof undercoat containing vinylidene chloride on both sides, a back layer and a back surface surface protective layer were prepared with an aqueous solution so that the coating amount was 1 m ² or less. Was simultaneously multilayer coated. Back layer coating amount is 1.5 g of gelatin,
30 mg sodium p-dodecylbenzenesulfonate,
1,2-bis (vinylsulfonylacetamide) ethane 100 mg, dye a 50 mg, dye b 100 mg, dye c30
mg, dye d50 mg, proxel 1 mg, and the back surface protective layer is 1.5 g of gelatin, 20 mg of polymethylmethacrylate having an average particle size of 2.5 μm, 15 mg of sodium p-dodecylbenzenesulfonate, sodium dihexyl-α-sulfosuccinate. 15 mg, sodium acetate 50 mg,
It is 1 mg of proxel.

The emulsion layer coating solution was coated on the support prepared as described above so that the silver content was 2 g / m ^2, and then the emulsion surface protective layer coating solution was dried on the emulsion surface to a dry thickness of 2 μm. Applied.

[0237]

Embedded image

<< Evaluation of Photographic Performance >> After exposing the photographic material with a 633 nm He-Ne laser sensitometer, the photographic material was subjected to 12
The image was processed (developed) at 0 ° C. for 20 seconds, and the obtained image was evaluated by a densitometer. The result of the measurement is shown by Dmax and the gradient of the straight line connecting the points of density 0.3 and 3.0 in the characteristic curve as the gradation γ.

The number of black dots is the number of black dots observed in a circle with a diameter of 3 mm when observed with a 25-fold magnifying glass.
The number of black spots was evaluated at 120 ° C. for 20 seconds and 120 ° C. for 30 seconds.

The results are shown in Table 8. It can be seen that the compound of the present invention suppresses the generation of black dots.

[0241]

[Table 8]

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[Procedure amendment]

[Submission date] February 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0205

[Correction method] Change

[Correction contents]

On the other hand, when the plastic film is passed through a heat developing machine, 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 polyester. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyarylate and the like can be used.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0237

[Correction method] Change

[Correction contents]

[0237]

Embedded image

Claims (2)

[Claims] 1. A photothermographic material containing an organic silver salt, a photosensitive silver halide, a reducing agent and a super-high contrast agent, which contains a compound represented by the following general formula. . (General Formula) C-L-D (wherein C represents a group that promotes adsorption to silver halide, D represents an acid group, L represents a divalent linking group,
C-L-D has substantially no absorption maximum in the visible region. ) 2. The photothermographic material according to claim 1, wherein the ultrahigh contrast agent is a hydrazine derivative.