JPH09185147A - Silver halide photographic sensitive material with glass substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass dry plate free from fog, sensitization and desensitization due to an abrasion at the time of forming or transferring an original pattern on the dry plate and giving a high contrast and high definition image. SOLUTION: This sensitive material with at least one silver halide emulsion layer on the glass substrate contains colloidal silica of <=30μm average particle diameter and a hydrazine deriv. in the emulsion layer or at least one hydrophilic colloidal layer on the upper side of the emulsion layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having a silver halide emulsion layer on a glass support, and more specifically, a photographic light-sensitive material which is less likely to be scratched on the surface and is less likely to cause fogging or increase / decrease due to scratches. It is about.

[0002]

2. Description of the Related Art A glass dry plate having a silver halide photographic emulsion layer on a glass support is excellent in dimensional stability, and therefore, a photomask for ICs, a shadow mask of a CRT, a lead frame, various displays which require high precision are required. It is used as a related photomask. Such a glass plate is printed with a fine pattern to form an original image pattern, which is used as a mask to closely expose another glass plate to duplicate the pattern, or to be exposed to a substrate having a photoresist layer to form an original image pattern. It is used to transfer and obtain a large number of photoresist patterns. However, in the conventional technology, when a fine pattern is printed by a photo plotter or the like to form an original image pattern, or when the original image pattern is transferred by contact exposure, scratches caused by adhesion of minute foreign matter or contact during handling. There was a case where a fog or a feeling of increase / decrease occurred during development, impairing the original image pattern. The fogging and increase / decrease sensation due to such scratches are more remarkable in a light-sensitive material having a high contrast, which has been an obstacle to obtaining a high-definition image having a high contrast.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-definition image with high contrast without fogging or increase / decrease feeling due to scratches generated when forming or transferring an original pattern on a glass plate. It is to provide a dry plate.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a glass support, in which at least one silver halide emulsion layer or silver halide emulsion layer is used. The average particle diameter is 30 mμ in at least one hydrophilic colloid layer on the upper side.
It is achieved by a silver halide photographic light-sensitive material characterized by containing the following colloidal silica and a hydrazine derivative. Hereinafter, the present invention will be described in detail.

The glass support used in the present invention is not particularly limited in glass composition, but soda lime glass, soda lime aluminum glass and the like are preferable. It is preferable that the surface of the support is degreased in advance before the application of the coating liquid for a hydrophilic colloid layer, and is subjected to a pretreatment for improving hydrophilicity. The end face of the support is preferably polished for handling.

The light-sensitive material of the present invention has at least one silver halide emulsion layer on a glass support, and if necessary, at least one protective layer can be provided on the emulsion layer. Is preferred. Further, an undercoat layer can be provided below the emulsion layer. Further, an antihalation layer can be provided between the emulsion layer and the undercoat layer.

The colloidal silica used in the present invention has an average particle diameter of 30 mμ or less, preferably 5 to 20 mμ. These colloidal silicas can be easily obtained as commercial products from Nissan Chemical Industries, Ltd., for example.
Colloidal silica may be added to any of the hydrophilic colloid layers of the silver halide emulsion layer and the protective layer. More preferred is an embodiment in which both the protective layer and the silver halide emulsion layer are contained and coated.

When incorporated in the protective layer, the hydrophilic colloid of the protective layer is preferably gelatin, and the weight ratio of gelatin to colloidal silica is preferably in the range of 50: 1 to 5: 1. The coating amount of colloidal silica is 5 to 5
00 mg / m ² , preferably 30-300 mg / m ² . The thickness of the protective layer is preferably in the range of 0.1 to 5 μm,
The range of 0.5 to 2 mμ is more preferable. When it is contained in the silver halide emulsion layer, gelatin is preferable as the hydrophilic colloid of the silver halide emulsion layer, and the weight ratio of gelatin to colloidal silica is preferably in the range of 50: 1 to 5: 1. Coating amount of colloidal silica is 3 ~ 3
000mg / m ^2, preferably 100-1000 mg / m ^2. The thickness of the silver halide emulsion layer is preferably in the range of 1 to 20 μm, more preferably 4 to 10 μm.

The hydrazine derivative used in the present invention is
Compounds represented by the following general formula (I) are preferred. General formula (I)

[0010]

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

[0012]

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Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both 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. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring,
Pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemitalvazide group, urethane group , A group having a hydrazide structure, a group having a quaternary ammonium structure, an alkyl or arylthio group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxycarbonyl group, a carbamoyl group , Sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, group containing selenium atom or tellurium atom, tertiary sulfonium structure or Is a group having a quaternary sulfonium structure. Preferred examples of the substituent include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety having a carbon number of 1 to 20). Monocyclic or bicyclic one to three), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
0), a ureido group (preferably having 1 to 3 carbon atoms)
0), a phosphoric amide group (preferably having 1 carbon atom)
To 30).

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

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

The substituents of R ₁ and R _{2 in} the general formula (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 polymer 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 be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, No. 61-170733
No. 61-270744, No. 62-948, No. 6
No. 3-234244, No. 63-234245, No. 63
-234246.

Particularly preferred hydrazide derivative in the present invention
The conductor is R₁Is a sulfonamide group, an acylamino group or
Indicates a ballast group via a ureide group and a silver halide grain
Groups that promote adsorption to surfaces
Or a phenyl group having an alkylthio group.
And G is a —CO— group, and R_TwoIs a hydrogen atom,
Kill group or substituted aryl group (electron withdrawing as a substituent
Or a hydroxymethyl group at the 2-position is preferred)
It is a hydrazine derivative. Note that the above R ₁and
R_TwoAny combination of each option is possible and preferred
Yes.

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

[0022]

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[0023]

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[0024]

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[0025]

[Chemical 6]

[0026]

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[0027]

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[0028]

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[0029]

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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, No. 3-228536, No. 5-51143, No. 5-56842, No. 4-84134, No. 2-230.
No. 233, No. 5-96053, No. 4-216544
No. 5, No. 5-45761, No. 5-25762, No. 5-
No. 45763, No. 5-45764, No. 5-45765
And Japanese Patent Application No. 5-94925 can be used.

More preferred hydrazine derivatives used in the present invention are those having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group. Is.

More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred hydrazine derivatives used in the present invention are those represented by the following general formulas (2) to (4).

General formula (2)

[0034]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group that forms an intramolecular hydrogen bond.)

General formula (3)

[0037]

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(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. )

General formula (4)

[0040]

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(In the formula, X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (2) to (4) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl It is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² ,
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

The alkyl groups of R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, pentamethylene, octamethylene, propylene, 2-butene-1,4-yl, 2-butyne-1,4-.
And p-xylylene. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable group include those mentioned as the substituents of R ^{1 in the} general formula (2). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler, or may have an adsorption promoting group on silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (2) to (4), radicals from which the hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (2) to (4), the general formulas (2) and (4) are preferable, and the general formula (2) is more preferable. Further, in the general formulas (2) to (4), the following general formulas (5) to (7) are more preferable, and the general formula (5) is most preferable. General formula (5)

[0053]

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(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (4), and L ⁴ , Y ^{4 and}
Has the same meaning as L ¹ and Y ^{1 in} the general formula (2). ) General formula (6)

[0055]

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(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 in the} general formula (4), and L ⁵ , Y ^{5 and}
Has the same meaning as L ² and Y ^{2 in} the general formula (3). ) General formula (7)

[0057]

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(Where R⁶¹, R⁶², X⁶, M⁶, N⁶Is
R in general formula (4)^Three, R^Three, X^Three, M ^Three, N^ThreeSynonymous with
is there. )

Specific examples of the nucleating agent used in the present invention are shown below, but the present invention is not limited thereto.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the hydrazine derivative of the present invention is 1 × with respect to 1 mol of silver halide.
10 ^-6 to 1 × 10 ^-2 mol is preferred, and 1 × 10 ^{-5 to} 5 ×
10 ^-3 mol is more preferred, and 5 × 10 ^-5 to 1 × 10 ^-3 mol is most preferred.

In the present invention, the silver halide emulsion may be spectrally sensitized. In order to add the sensitizing dyes used in the present invention to the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or they may be water, methanol, ethanol, propanol, acetone or methyl cell. Sorb, 2,2,3,3-tetrafluoropropanol,
2,2,2-trifluoroethanol, 3-methoxy-
1-propanol, 3-methoxy-1-butanol, 1
It may be added to the emulsion by dissolving it in a solvent such as -methoxy-2-propanol, N, N-dimethylformamide or the like alone or in a mixed solvent. Also, US Pat. No. 3,469,98
No. 7, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. 44-23389, 44-25555, 57-
As disclosed in 22091 and the like, a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexistent to be added to the emulsion as an aqueous solution, US Pat. No. 135, No. 4,006,025, etc., a method of adding an aqueous solution or colloidal dispersion in which a surfactant coexists into an emulsion, as disclosed in JP-A-53-102733. , Ibid. 58-105
No. 141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion, as disclosed in JP-A-51-74624, a compound for redshift To dissolve the dye,
A method of adding the solution into the emulsion can also be used.
Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been found to be useful so far. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666 and JP-A-58-184142,
As disclosed in the specification of JP-A-60-196749 and the like, the period before the grain forming step or / and desalting of the silver halide, during the desalting step and / or after the desalting to before the start of chemical ripening. No., as disclosed in the specification of JP-A-58-113920, immediately before or during chemical ripening, at any time before the emulsion is coated, until the coating after chemical ripening. , May be added in the step. In addition, as disclosed in the specifications of US Pat. No. 4,225,666 and JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure. It may be added dividedly by dividing into medium and during the chemical aging step or after completion of the chemical aging, or before chemical aging or during the step and after completion of the chemical aging. The kind of combination may be changed and added.

The silver halide photographic light-sensitive material of the present invention comprises
It is preferable that the silver halide emulsion layer or other hydrophilic colloid layer contains a nucleation accelerator such as an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. As the amine derivative, for example, JP-A-60-140340, JP-A-62-50829,
62-222241, 62-250439, 62-280733, 63-124045, 6
The compounds described in 3-133145, 63-286840 and the like can be mentioned. More preferred as amine derivatives are JP-A-63-124045 and 63-
Compounds having a group capable of adsorbing to silver halide described in JP-A-133145 and JP-A-63-286840, or compounds having a total carbon number of 20 or more described in JP-A-62-222241. As an onium salt,
Ammonium salts or phosphonium salts are preferred. Examples of preferable ammonium salts include JP-A-62-250.
The compounds described in No. 439, No. 62-280733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167939 and JP-A-6-167939.
The compounds described in 2-280733 and the like can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198147. Examples of hydroxymethyl derivatives include, for example, U.S. Pat. Nos. 4,693,956 and 4,777,118.
No. EP, 231,850, JP-A No. 62-50829 and the like can be mentioned, and a diarylmethanol derivative is more preferable.

As a particularly useful nucleation accelerator, Japanese Patent Application No.
General formulas (IV) to (VII described in No. 103,272)
Compounds of I), specifically IV-1 to IV-36, V-1 to
V-22, VI-1 to VI-36, VIII-1 to VIII-41, and the general formula (A) described in the patent.
To (D), specifically A-101 to A-14
7, exemplified compounds A-201 to A-255 can be mentioned. Specific compound examples are shown below. However, the present invention is not limited to the following compounds.

[0073]

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The optimum addition amount of these compounds varies depending on the kind, but is 1.0 × per mol of the hydrazine compound.
It is preferably used in the range of 10 ⁻² mol to 1.0 × 10 ² mol. These compounds are dissolved in a suitable solvent (H ₂ O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. Two or more of these compounds may be used in combination.

In the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide or silver iodobromide is used as the silver halide. However, silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. Silver iodide content is 3 mol%
Or less, more preferably 0.5 mol% or less. The shapes of silver halide grains are cubic, tetrahedral, octahedral,
Any of an irregular shape and a plate shape may be used, but a cube is preferable. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.2 to 0.5 μm,
It is preferable that the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less, with a narrow particle size distribution. The silver halide grains may have a uniform inner layer and a different surface layer, or may have different layers. The photographic emulsion used in the present invention is
P. Chimieet Phy by Glafkides
sique Photographie (Pau
Montel, 1967), G.I. F. Duf
by in Photographic Emulsion
Chemistry (The Forcal Pres
S., 1966), V.I. L. Zelikman et
Al by Making and Coating P
photographic Emulsion (TheF
Ocal Press, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 5,163,364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,242,44.
No. 5, JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Preferably. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably in the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and those described in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545, and JP-A-4-167545 can be used.
No. 76534, No. 6-110146, Japanese Patent Application No. 4-68
As described in JP-A No. 305 and the like, the particles can be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having halogen, amines, oxalate, etc. as a ligand, for example, hexachlororhodium (III)
Examples thereof include complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent.
That is, a method of adding an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁶ mol, and particularly preferably 5 × 10 ⁻⁸ mol to 1 × 1 mol, per mol of silver halide.
0 ^-6 mol. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1.
Nos. -285941 and 2-20852 and 2-208
No. 55, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (CN) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) _6] ^-4 [Ru (CO) ₃ Cl _3] ^-2 [Ru (CO) Cl _5] ^-2 [Ru (CO) Br _5] ^-2 [OsCl _6] ^-3 [OsCl ₅ (NO)] ^-2 [Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

The amounts of these compounds added are silver halide 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. The addition of these compounds was
Appropriate at the time of manufacturing the baby and at each stage before applying the emulsion
Can be carried out, but especially when added during emulsion formation,
It is preferably incorporated into silver halide grains. these
Halogen was added by adding the compound during grain formation of silver halide.
For incorporation into silver halide particles, powder of metal complex or N
The aqueous solution dissolved together with aCl and KCl
In water-soluble salt or water-soluble halide solution
Method or silver salt and halide solution are mixed at the same time
When added as a third solution, add
How to prepare silver logenide grains or during grain formation
A method of charging the required amount of metal complex aqueous solution into the reaction vessel
There is a throat. Especially with powder or NaCl, KCl
Method of adding a dissolved aqueous solution to a water-soluble halide solution
Is preferred. To add to the particle surface, immediately after particle formation
Or during or after physical ripening or during chemical ripening
It is also possible to pour the required amount of aqueous solution of metal complex into the reaction vessel.
it can.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium and hexacyanoiridium.
These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg KCl,
NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The silver halide grains in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (C
N) ₆ ] is preferably used for doping the Fe salt. Further, in the silver halide grain used in the present invention, cobalt,
Nickel, palladium, platinum, gold, thallium, copper, lead,
It may contain a metal atom such as chromium. The amount of the metal is preferably 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of silver halide. Further, in order to incorporate the metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added at the time of preparing particles.

The silver halide emulsion of the present invention is preferably subjected to chemical sensitization. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, the sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Known compounds can be used as the sulfur sensitizer.Examples include sulfur compounds contained in gelatin, and various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, usually, an unstable type and / or an unstable type selenium compound is added, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, Japanese Patent Application No. 2-130976, 2-229
Compounds described in JP-A Nos. 300, 3-121798 and the like can be used. In particular, it is preferable to use the compounds represented by the general formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride presumed to be a sensitizing nucleus on the surface or inside of the silver halide grain. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patents 235,211 and 1,121,496. No. 1,295,462, No. 1,396,696
No., Canadian Patent No. 800,958, Japanese Patent Application No. 2-333.
No. 819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Comm.
un., 635 (1980), ibid. 1102 (1979), ibid.645 (1979), J. Che
m.Soc. Perkin.Trans., 1,2191 (1980), edited by S.Patai, T
he Chemistry of Organic Serenium and Tellurium Com
The compounds described in pounds, Vol1 (1986) and Vol2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use about moles. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physically ripening them. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

Gelatin is advantageously used as a binder for the protective colloid of the photographic emulsion or the other hydrophilic colloid layer of the emulsion layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during production process of the light-sensitive material, storage during storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) tetrazaindenes), pentaazaindenes and the like; hydroquinone and its derivatives; disulfides such as thioctic acid; Alternatively, many compounds known as stabilizers can be added. Among these, preferred are benzotriazoles (for example, 5
-Methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Also,
These compounds may be contained in the processing solution.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to right lower column, line 7 and JP-A-2-18542, page 2, lower left column 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538 Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. The syndiotactic polystyrene support described in Japanese Patent Application No. 6-44606. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to category 12, page 12, lower left column, and EP 452772A.

The developer used in the development processing of the light-sensitive material according to the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffer, preservative, chelating agent). . In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes or an ascorbic acid derivative, and in view of developing ability, dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones, a combination of dihydroxybenzenes and p-aminophenols,
A combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or a combination of an ascorbic acid derivative and p-aminophenols is preferable.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. Ascorbic acid derivative developing agents used in the present invention include ascorbic acid, its stereoisomer erythorbic acid, and its alkali metal salts (sodium and potassium salts). 1 used in the present invention
As a developing agent for phenyl-3-pyrazolidone or a derivative thereof, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3- There is pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , But especially N-methyl-p
-Aminophenol is preferred. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably,
It is in the range of 0.6 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 to 0.6 mol / liter, more preferably 0.2 to 0.5 mol. / L, the latter is preferably used in an amount of 0.06 mol / L or less, more preferably 0.03 mol / L or less. The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably 0.2
Is in the range of to 0.6 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 to 0.6 mol / liter, more preferably 0.2 to 0.5 mol. / L, the latter is preferably used in an amount of 0.06 mol / L or less, more preferably 0.03 mol / L or less.

Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. Additives other than those described above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine; A development accelerator such as imidazole or a derivative thereof; a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound as an antifoggant or black pep
per) may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Sodium thiadiazol-2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-
Examples thereof include 2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, a compound described in JP-A-62-212651 can be used as a development unevenness inhibitor, and a compound described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, sugars (eg saccharose) and oximes described in JP-A-60-93433. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is preferably 9.5 to 11.0, particularly preferably 9.8 to 11.0. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 500 ml or less, preferably 400 ml or less. Processing liquid transportation cost, packaging material cost,
For the purpose of saving space, it is preferable to concentrate the treatment liquid and dilute it before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / l. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing promoters. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. As the pH buffer, for example, acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid, organic acids such as adipic acid, boric acid,
Inorganic buffers such as phosphates and sulfites can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to bringing in a developing solution, and is 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / l.
Use about 1 liter. The pH of the fixing solution is preferably 4.0 to 6.5, particularly preferably 4.5 to 6.0. Further, as a dye elution accelerator, JP-A-64-473 is used.
The compound described in No. 9 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, more preferably 0.03 to 0.08 mol / l. Fixing temperature is
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds at about 20 ° C to about 50 ° C, preferably 25 to 45 ° C. The replenishing amount of the fixing solution is 600 ml / per processing amount of the light-sensitive material.
m ² or less, particularly preferably 500 ml / m ² or less.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed.

[0108]

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

Example 1 <Preparation of silver halide photographic material> 1-liquid water 750 ml gelatin 20 g sodium chloride 2 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium thiosulfonate 10 mg 2-liquid water 300 ml silver nitrate 150 g 3-liquid water 300 ml Sodium chloride 38 g Potassium bromide 32 g K ₃ IrCl ₆ 0.25 mg K ₂ Rh (H ₂ O) Cl ₅ 0.07 mg 38%, 90% of 2 and 3 liquids in 1 liquid kept at pH 4.5. Was added simultaneously with stirring for 20 minutes to form 0.19 μm core particles. Subsequently, the following 4 liquids and 5 liquids were added over 8 minutes, and the remaining 10% amounts of 2 liquids and 3 liquids were added over 2 minutes to obtain a silver chloride content of 70 mol% with an average particle size of 0.22 μm.
Of silver chlorobromide particles were obtained. 4 liquid water 100 ml silver nitrate 50 g 5 liquid water 100 ml sodium chloride 14 g potassium bromide 11 g

Then, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added per mol of silver, and benzenethio was added per mol of silver. 7 mg sodium sulfonate and 2 benzenesulfinic acid
After adding mg, the pH was adjusted to 5.7 and pAg 7.5,
1 mg of sodium thiosulfate, a compound (CS-A) and 5 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity. Then, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
150 mg of tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains were silver iodochlorobromide cubic grains having an average grain size of 0.22 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

[0111]

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<Preparation of coating sample> Coating was performed on the glass support in this order from the support side so as to have a layer constitution of an undercoat layer, an emulsion layer and a protective layer, and a back side was formed on the side opposite to the emulsion layer of the support. The layers were applied to make samples. The preparation method and application amount of each layer are shown below. (Undercoat layer) As an undercoat layer, 50 mg / m ^{2 of} gelatin and 150 mg / m ² of colloidal silica having an average particle diameter of 8 mμ were applied.

(Emulsion layer) To the above emulsion, the following sensitizing dyes [A] and [B] were added at 8 mg / m ² , 2 mg / m ² and K, respectively.
Br of 17 mg / m ² , mercapto compounds of the following (a) and (b) of 2 mg / m ² , 1 mg / m ² , triazine compounds of the following (c) of 5 mg / m ² , and nucleation. the compound a-6 to 6 mg / m ² as a promoter, a hydroquinone 100 mg / m ^2, sodium 8 mg / m ² dodecylbenzenesulfonic acid, polystyrenesulfonic acid potassium 80 mg / m ^2, a dispersion of polyethyl acrylate and 40mg
/ M ² , the compound (d) is 7 mg / m ² , the polyacrylamide derivative represented by the compound (e) is 1.3 mg / m ² , the compound (f) is 20 mg / m ² , 1,5-dihydroxy-2-. Benzaldoxime was added at 4 mg / m ² , and as a hardening agent, 1,3-divinylsulfonyl-2-propanol was added at 200 mg / m ² . Further, 2 mg / m ^{2 of} the hydrazine derivative shown in Table 1 and colloidal silica having an average particle diameter of 20 mμ were added so as to be applied in the amounts shown in Table 1. The pH of the solution was adjusted to 5.5 with acetic acid, gelatin was added, and the amount of coated silver was 5.1 g / m ² and the amount of gelatin was 4.9 g.
/ M ² so as to be coated to prepare Samples 1 to 12.

[0114]

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(Back layer) The following backing solution was prepared, and the coating amount was 15 cc / on the side opposite to the emulsion layer of the glass support.
It was coated so as to be in m ^2. Binder (compound C-1 below) 30 g Dye (compound C-2 below) 5 g (〃 C-3) 5 g (〃 C-4) 6 g (〃 C-5) 1.2 g Ethanol 420 ml Methanol 550 ml

[0116]

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[0117]

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In Samples 9 to 12, the following protective layer was further provided on the emulsion layer. (Protective layer) 0.9 g / m ^{2 of} gelatin, 7 mg / m ^{2 of} 1,5-dihydroxy-2-benzaldoxime, 70 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of 3.5 μ,
Compound (f) a 40 mg / m ^2, compound a fluorine surfactant 5 mg / m ² with a compound represented by (g) (d) a 40 mg / m ^2,
Colloidal silica having an average particle diameter of 20 mμ was added to the amount shown in Table 1 so as to be applied, and applied.

<Evaluation Method> (Evaluation of Photographic Property) The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁵ seconds through a step wedge through an interference filter having a peak at 488 nm and developed (20 ° C., 3 ° C.). Min), fixing, washing with water, and drying. The density of each step was measured with a Macbeth densitometer, and the density was 0.
Gamma values between 3 and 3.0 were measured. The developer and fixer used had the following formulations.

Developer Formulation Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfate 40.0 g Potassium carbonate 40.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.08 g 2,3,5 , 6,7,8-Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.15 g hydroquinone 25.0 g 4-hydroxymethyl-4-methyl- 1-Phenyl-3-pyrazolidone 0.45 g sodium erythorbate 3.0 g diethylene glycol 20.0 g potassium hydroxide is added, water is added to 1 liter and the pH is adjusted to 10.45.

Fixing Solution Formulation Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Gluconic acid Sodium 6.6g Aluminum sulphate 25.3g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add 3 liters of water

(Evaluation of Scuffing) A diamond needle having a diameter of 0.2 mm was weighed while changing its weight, the surface of the sample was scratched, and development was performed. The evaluations are summarized in Table 1.

[0123]

[Table 1]

As is clear from the results shown in Table 1, the sample containing the hydrazine derivative has a high gamma value and high contrast. Further, it can be seen that the sample containing colloidal silica has a large amount of load that causes abrasion and is less likely to suffer abrasion.

Claims (3)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a glass support, in at least one silver halide emulsion layer or in at least one hydrophilic colloid layer above the silver halide emulsion layer. To
A silver halide photographic light-sensitive material comprising colloidal silica having an average particle diameter of 30 mμ or less and a hydrazine derivative. 2. The hydrazine derivative contained in the hydrophilic colloid layer has an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group. Item 1. A silver halide photographic light-sensitive material of item 1. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the amount of colloidal silica contained in the hydrophilic colloid layer is 100 mg / m ² or more.