JPH1115091A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material ultrahigh in contrast and superior in storage stability and processing stability and low in tendency to cause uneven development by incorporating fine polymer particles containing at least one kind of specified hydrazine derivative. SOLUTION: At least one of silver halide emulsion layer and/or another hydrophilic colloidal layer contains fine polymer particles containing at least one kind of hydrazine derivative represented by formula I in which A is a bonding group; B is a group represented by formula II; (m) is an integer of 2-6; in formula II, each of Ar1 -Ar2 is an aromatic or heterocyclic group; each of L1 -L2 is a bonding group; (n) is 0 or 1; R1 is an H atom or an alkyl, aryl, heterocyclic, alkoxy, aryl-oxy, amino, or hydrazino group; and G1 is a -CO- or -SO2 - or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a super-high contrast silver halide photographic light-sensitive material used for photolithography and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the field of photolithography, a photographic photosensitive material having good original reproducibility has been desired in order to cope with the variety and complexity of printed matter, and a reduction in processing waste liquid due to an increase in environmental awareness. A processing system that can be used has been desired. In order to improve the reproduction of a continuous tone image or the reproduction of a line image using a halftone dot image, an image forming system that exhibits photographic properties of ultra-high contrast (particularly, gamma of 10 or more) is required. As a method for obtaining high-contrast photographic characteristics, a lith developing system using a so-called "contagious developing effect" has been used for a long time, but has a drawback that a developing solution is unstable and difficult to use. There is a demand for an image forming system which can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics.
Nos. 166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,269,922,
Nos. 4,272,606 and 4,311,781
No. 4,332, 878, No. 4,618,5
No. 74, No. 4,634,661, No. 4,681,
No. 836, No. 5,650,746 and the like are disclosed. These systems treat a surface latent image type silver halide photographic material to which a hydrazine derivative is added with a stable MQ or PQ developer having a pH of 11.0 to 12.3 to obtain a super-high contrast negative image having a gamma of more than 10. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and a high concentration of sulfite can be added to the developing solution. Dramatically improved compared to liquid.

[0003] However, in the above-mentioned method, it is possible to enhance the stability of the developer by using a high-concentration sulfurous acid preservative. However, in order to obtain a super-high contrast photographic image, a relatively high p value is required.
It was necessary to use a developing solution having an H value, and therefore, the developing solution was easily oxidized by air, and a large amount of the developing solution had to be replenished. Therefore, attempts have been made to realize a super-high contrast photographic image forming system using nucleation development of a hydrazine compound with a developer having a lower pH.

[0004] US Pat. No. 4,269,929 (Japanese Unexamined Patent Publication No.
No. 1-267759), U.S. Pat. No. 4,737,452 (Japanese Unexamined Patent Publication No. 60-179733), U.S. Pat.
4,769,4,798,780, JP-A-1-1-1
No. 79939, No. 1-179940, U.S. Pat.
Japanese Patent Application Nos. 98,604, 4,994,365 and Japanese Patent Application No. 7-37817 disclose highly active hydrazine nucleation in order to obtain an ultra-high contrast image using a stable developer having a pH of less than 11.0. An agent and a method using a nucleation accelerator are disclosed.
It is also disclosed that a silver halide emulsion having a high silver chloride content and subjected to chemical sensitization has high nucleation activity.

However, when the highly active hydrazine nucleating agent, the highly active nucleation promoting agent, or the highly active emulsion is used, unevenness in density when a certain net area is output, called processing unevenness, becomes a problem. Had become.

Further, the above-mentioned highly active hydrazine nucleating agent has a disadvantage that it is easily decomposed, and there is a problem in long-term preservation of the photosensitive material.

Further, by using a stable developer having a pH of less than 11.0, the replenishment amount of the developer and the processing waste liquid are in the direction of reduction, but the demand remains unknown. Accordingly, there has been a demand for a light-sensitive material having higher processing stability, specifically, a change in light-sensitive material performance due to a change in developer pH.

The addition of a hydrazine nucleating agent in polymer fine particles to a coating solution is disclosed in Japanese Patent Application Laid-Open No. 2-948, which is intended to prevent the precipitation of the hydrazine nucleating agent. is there.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is super-hard, has excellent storage stability and processing stability, and is less likely to cause processing unevenness, and a processing method therefor. It is in.

[0010]

An object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer or another hydrophilic silver halide emulsion layer is provided. This has been attained by a silver halide photographic material characterized in that at least one of the colloid layers contains polymer fine particles containing at least one hydrazine derivative represented by the general formula (NB). General formula (NB)

[0011]

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In the formula, A represents a linking group, B represents a group represented by the following formula (B-1), and m represents an integer of 2 to 6. General formula (B-1)

[0013]

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In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents —CO—
Group, -SO ₂ - group, -SO- group,

[0015]

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Represents a -CO-CO- group, a thiocarbonyl group or an iminomethylene group. R ₂ is selected from the same range as defined for R ₁ and may be different from R ₁ .

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrazine derivative used in the present invention will be described in detail. In the present invention, a hydrazine derivative represented by the following general formula (NB) is used. General formula (NB)

[0018]

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In the formula, A represents a linking group, B represents a group represented by the following formula (B-1), and m represents an integer of 2 to 6. General formula (B-1)

[0020]

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In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents —CO—
Group, -SO ₂ - group, -SO- group,

[0022]

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Represents a -CO-CO- group, a thiocarbonyl group, or an iminomethylene group. R ₂ is selected from the same range as the groups defined in R _1, may be different from R _1.

In the general formula (B-1), Ar ₁ , Ar
_The aromatic group represented by ₂ is a monocyclic or bicyclic aryl group such as a benzene ring or a naphthalene ring. The aromatic heterocyclic group represented by Ar ₁ or Ar ₂ is a monocyclic or bicyclic aryl group. The aromatic heterocyclic group may be condensed with another aryl group, for example, 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. Ar ₁ , Ar
₂ is preferably an aromatic group, and more preferably a phenylene group.

Ar ₁ and Ar ₂ may be substituted,
Representative substituents include, for example, alkyl groups (including active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, heterocyclic groups containing quaternized nitrogen atoms (eg, pyridinio groups), hydroxy Groups, alkoxy groups (including groups that repeatedly contain ethyleneoxy or propyleneoxy group units), aryloxy groups, acyloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, urethane groups, carboxyl groups (the Salts), imide groups, amino groups,
Carbonamido group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group (including its salt), sulfamoyl group, acylsulfamoyl group, (alkyl or aryl)
Sulfonylureido group, (alkyl or aryl)
Sulfonylcarbamoyl group, halogen atom, cyano group,
Nitro group, phosphoric amide group, group containing phosphate ester structure, acylureide group, group containing selenium or tellurium atom, group having tertiary sulfonium structure or quaternary sulfonium structure, group containing quaternized phosphorus atom And the like. These substituents may be further substituted with these substituents.

Preferred substituents are those having 1 to 20 carbon atoms.
Alkyl group, aralkyl group, heterocyclic group, substituted amino group, acylamino group, sulfonamide group, ureido group,
Sulfamoylamino group, imide group, thioureido group,
Phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxyl group (including its salt), (alkyl,
An aryl or heterocycle) thio group, a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group, a nitro group and the like. Ar ₁ is preferably an unsubstituted phenylene group.

In the general formula (B-1), the alkyl group represented by R ₁ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a benzene ring. The heterocyclic group is a 5- to 6-membered ring compound containing at least one nitrogen, oxygen and sulfur atom, for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, pyridinio group, quinolinio group, quinolinyl group and so on. Pyridyl or pyridinio groups are particularly preferred. The alkoxy group has 1 carbon atom
Preferred is an alkoxy group having from 8 to 8, preferably a monocyclic aryloxy group, and an unsubstituted amino group as an amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, a saturated or unsaturated group. Is preferred. R ₁ may be substituted, and preferred substituents include those exemplified as the substituents of Ar ₁ and Ar ₂ .

Among the groups represented by R ₁ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxy group) is preferable. Tetrafluoroethyl group, pyridiniomethyl group, 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group) , O-carbamoylphenyl group, 4
-Cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom and an alkyl group. When G ₁ is a —SO ₂ — group, R ₁ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Or a substituted amino group (for example,
And a dimethylamino group. G ₁ is -CO
In the case of a CO- group, an alkoxy group, an aryloxy group,
An amino group is preferable, and an alkylamino group, an arylamino group, or a heterocyclic amino group (including a heterocyclic group containing a quaternized nitrogen atom) is particularly preferable. For example, 2,2,6,6-tetramethylpiperidine -4-ylamino group, propylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group and the like. or,
R ₁ splits the G ₁ -R ₁ moiety from the residual molecule,
₁ -R ₁ part of atoms may be such as to rise to cyclization reaction to form a cyclic structure containing, examples, include those described in, for example, JP-A-63-29751 Can be

The compound represented by formula (NB) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948 and 63-234244
And the groups described in JP-A-63-234245 and JP-A-63-234246. These adsorbing groups to silver halide may be precursors. Examples of such a precursor include groups described in JP-A-2-285344.

In the general formula (B-1), the linking groups represented by L ₁ and L ₂ are -O-, -S-, -N ( _RN )-.
(R _N represents a hydrogen atom, an alkyl group or an aryl group,.), - CO -, - C (= S) -, - SO 2 -, - S
O-, -P = O-, an alkylene group alone or a combination of these groups. If Shimese the group consisting of a combination where _{specifically, -CON (R N) -,} -
_{SO 2 N (R N) -} , - COO -, - N (R N) CON
_{(R N) -, - N} (R N) CSN (R N) -, - N (R
_{N) SO 2 N (R N} ) -, - SO 2 N (R N) CO-,
_{-SO 2 N (R N) CON} (R N) -, - N (R N) C
_{OCON (R N) -, -} CON (R N) CO -, - S Arukiren group -CONH -, - O-alkylene group -CO
And groups such as NH- and -O-alkylene-NHCO-. In addition, these groups may be connected from either side. When the linking group represented by L ₁ or L ₂ in the general formula (B-1) contains a trivalent or higher valent group, L ₁ is -Ar ₁ -in the general formula (B-1). Two or more groups represented by NHNH-G ₁ -R ₁ may be linked, and L ₂ represents -Ar ₂ -L ₁ -Ar ₁ -N in the general formula (B-1).
Two or more groups represented by HNH-G ₁ -R ₁ may be linked. In this case, the trivalent or higher valent linking group contained in L ₁ and L ₂ is specifically an amino group or an alkylene group. In the general formula (B-1), L ₁ is preferably -S
_{O 2 NH -, - NHCONH -} , - NHC (= S) NH
—, —OH, —S—, —N (R _N ) — and an active methine group, particularly preferably a —SO ₂ NH— group. L ₂ is preferably _{-CON (R N) -, -} SO 2 N (R N)
_{-, - COO -, - N} (R N) CON (R N) -, - N
_{(R N) CSN (R N} ) - a group.

In the general formula (NB), the linking group represented by A is a divalent to hexavalent linking group capable of linking a group represented by 2 to 6 represented by B; -S-, -N
( _RN ′)-( _RN ′ represents a hydrogen atom, an alkyl group, or an aryl group), —N ⁺ ( _RN ′) ₂ — (the two _RN ′s may be the same or different; And may be linked to form a ring), -CO-, -C (= S)-,
—SO ₂ —, —SO—, —P ＝ O—, an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group,
It is an arylene group, a heterocyclic group alone, a group composed of a combination of these groups, or a single bond. Here, the heterocyclic group may be a heterocyclic group containing a quaternized nitrogen atom such as a pyridinio group.

In the general formula (NB), the linking group represented by A may be substituted.
Examples of the substituents that may be possessed by Ar ₁ and Ar _{2 in} -1) are the same.

When n is 0, the linking group represented by A includes a benzene ring, a naphthalene ring, a saturated or unsaturated hetero ring, a hetero ring containing a quaternized nitrogen atom such as a pyridinio group, It preferably contains at least one of a quaternized nitrogen atom such as an ammonio group and a cycloalkylene group. When n is 1, the linking group represented by A includes a single bond, a benzene ring, a naphthalene ring, a saturated or unsaturated heterocyclic ring, a heterocyclic ring containing a quaternized nitrogen atom such as a pyridinio group, It preferably contains at least one of a quaternized nitrogen atom such as an ammonio group and a cycloalkylene group.

In the general formula (NB), m represents an integer of 2 to 6, preferably 2, 3 or 4, particularly preferably 2 or 3.

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

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

The hydrazine derivative of the present invention may be added to any of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. 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 preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably from 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, per mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

The polymer used in the present invention will be described in detail.

The following are preferred as the water-insoluble and organic solvent-soluble polymer used in the present invention, but the present invention is not limited thereto. (A) Vinyl polymer As monomers forming the vinyl polymer of the present invention, acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, sec-butyl acrylate,
tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
Octyl acrylate, tert-octyl acrylate,
2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate,
Dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl Acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxy) Ethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9) 1
-Bromo-2-methoxyethyl acrylate, 1-1-
And dichloro-2-ethoxyethyl acrylate. In addition, the following monomers can be used.

Methacrylic esters: Specific examples thereof include methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl Methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl Methacrylate, naphthyl methacrylate, 2- Mud methacrylate,
4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy Examples thereof include polyethylene glycol methacrylate (addition mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt, and the like.

Vinyl esters: Specific examples thereof include:
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate,
Vinyl chloroacetate, vinyl methoxy acetate,
Vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc .; acrylamides: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide , Dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl)
Acrylamide, diacetone acrylamide, tert-octylacrylamide and the like;

Methacrylamides: For example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl acrylamide, methoxyethyl methacrylamide , Dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like;

Olefins: styrenes such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene; and styrenes; , Dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate;

Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like;

Others include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate,
Dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylene malon nitrile,
And vinylidene. As the monomer (for example, the above-mentioned monomer) used in the polymer of the present invention, two or more kinds of monomers are used as comonomers for various purposes (for example, for improving the solubility).

For the purpose of adjusting the solubility, etc., monomers having an acid group such as those described below are also used as comonomers as long as the copolymer does not become water-soluble.

Acrylic acid; methacrylic acid; itaconic acid;
Maleic acid; monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate; citraconic acid; styrene sulfonic acid;
Vinylbenzylsulfonic acid; vinylsulfonic acid; acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, and the like; methacryloyloxyalkylsulfonic acid, such as methacryloyloxymethylsulfonic acid; Methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc .; acrylamidoalkylsulfonic acids, for example, 2-acrylamido-2-methylethanesulfonic acid-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid Methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-me Le propanesulfonic acid, 2-methacrylamide-2-methyl butanoic acid; These acids alkali metal (e.g., Na, K, etc.) may also be a salt or an ammonium ion.

Among the above-mentioned vinyl monomers and other vinyl monomers used in the present invention, hydrophilic monomers (here, those which become water-soluble when formed into a homopolymer) are used as comonomers. If used,
As long as the copolymer does not become water-soluble, the ratio of the hydrophilic monomer in the copolymer is not particularly limited, but is usually preferably 40 mol% or less, more preferably 20 mol% or less, and further preferably, 10 mol% or less.

When the hydrophilic comonomer copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol% or less, preferably 10 mol% or less. Mol% or less, and most preferably when such a comonomer is not contained.

The monomers of the present invention in the polymer are preferably methacrylate, acrylamide and methacrylamide. Particularly preferred are acrylamide and methacrylamide.

It is also possible to use polymers, cellulose derivatives, polyesters and polyamides obtained by ring-opening polymerization described in pages 13 and 14 of JP-A-2-948, etc. it can.

Two or more of the above-mentioned polymers of the present invention may be used in combination. The water-insoluble polymer in the present invention is a polymer having a solubility of 3 g in 100 g of distilled water.
The polymer is preferably 1 g or less. The oil-soluble polymer used in the present invention contains components having a molecular weight of 40,000 or less.
Those containing 30 to 70% are preferred.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited to these. Specific examples Polymer type P-1) Polyvinyl acetate P-2) Polyvinyl propionate P-3) Polymethyl methacrylate P-4) Polyethyl methacrylate P-5) Polyethyl phthalate P-6) Vinyl acetate-vinyl alcohol Copolymer (95: 5) P-7) Poly n-butyl acrylate P-8) Poly n-butyl methacrylate P-9) Polyisobutyl methacrylate P-10) Polyisopropyl methacrylate P-11) Polydecyl methacrylate P-12 ) N-butyl acrylate-acrylamide copolymer (95: 5) P-13) polychloromethyl acrylate P-14) 1,4-butanediol-adipate polyester P-15) ethylene glycol-sebacate polyester P-16 ) Polycaprolactone P-17) Poly (2-tert-butylphenyl acrylate) P-18) Poly (4-tert-butylphenyl acrylate) P-19) n-butyl methacrylate -N- vinyl-2-pyrrolidone copolymer (90: 10) P-20) Methyl methacrylate - vinyl chloride copolymer (70:30)

P-21) Methyl methacrylate-styrene copolymer (90:10) P-22) Methyl methacrylate-ethyl acrylate copolymer (50:50) P-23) n-butyl methacrylate-methyl methacrylate-stainless steel Polymer (50:30:20) P-24) Vinyl acetate-acrylamide copolymer (85:15) P-25) Vinyl chloride-vinyl acetate copolymer (65:35) P-26) Methyl methacrylate-acryl Nitrile copolymer (65:35) P-27) Diacetone acrylamide-methyl methacrylate copolymer (50:50) P-28) Vinyl methyl ketone-isobutyl methacrylate copolymer (55:45) P-29) Ethyl Methacrylate-n-butyl acrylate copolymer (70:30) P-30) Diacetone acrylamide-n-butyl acrylate copolymer (60:40) P-31) Methyl methacrylate-cyclohexyl methacrylate Copolymer (50:50) P-32) n-butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) P-33) N-tert-butyl methacrylamide-methyl Methacrylate-acrylic acid copolymer (60:30:10) P-34) Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10) P-35) Methyl methacrylate-phenylvinylketone copolymer (70:30) P-36) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:30) P-37) n-butyl acrylate-pentyl methacrylate-N-vinyl-2- Pyrrolidone copolymer (38:38:24) P-38) Methyl methacrylate-n-butyl methacrylate-isobutyl methacrylate-acrylic acid polymer (37: 29: 25: 9) P-39) n-butyl methacrylate Acrylic acid (95: 5) P-40) Methyl methacrylate - acrylic acid copolymer (95: 5)

P-41) Benzyl methacrylate-acrylic acid copolymer (90:10) P-42) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35: 35: 25: 5) P-43) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (35:35:30) P-44) poly-3-pentyl acrylate P-45) cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate Polymer (37:29:34) P-46) Polypetinyl methacrylate P-47) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-48) Vinyl acetate-vinyl propionate copolymer (75:25) P-49) n-butyl methacrylate-3-acryloxybutane-1-sodium sulfonate copolymer (97: 3) P-50) n -Butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-51) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-52) n-butyl methacrylate -Styrene copolymer (90:10) P-53) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-54) n-butyl methacrylate-vinyl chloride copolymer (90:19) ) P-55) n-butyl methacrylate-styrene copolymer (70:30) P-56) poly (N-sec-butylacrylamide) P-57) poly (N-tert-butylacrylamide) P-58) di Acetone acrylamide-methyl methacrylate copolymer (62:38) P-59) Polycyclohexyl methacrylate-methyl methacrylate copolymer (60:40) P-60) N-tert-butylacrylamide-methyl methacrylate Copolymer (60:40)

P-61) Poly (Nn-butylacrylamide) P-62) Poly (tert-butyl methacrylate) -N-tert-butylacrylamide copolymer (50:50) P-63) tert-butyl methacrylate -Methyl methacrylate copolymer (70:30) P-64) Poly (N-tert-butyl methacrylamide) P-65) N-tert-butyl acrylamide-methyl methacrylate copolymer (60:40) P-66 ) Methyl methacrylate-acrylonitrile copolymer (70:30) P-67) Methyl methacrylate-vinyl methyl ketone copolymer (38:62) P-68) Methyl methacrylate-styrene copolymer (75:25) P- 69) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-70) Poly (benzyl acrylate) P-71) Poly (4-biphenyl acrylate) P-72) Poly (4-butoxycarbonylphenyl acryl) Rate) P-73) Poly (sec-butyl acrylate) P-74) Poly (tert-butyl acrylate) P-75) Poly [3-chloro-2,2- (chloromethyl) propyl acrylate] P-76) Poly (2-Chlorophenyl acrylate) P-77) Poly (4-chlorophenyl acrylate) P-78) Poly (pentachlorophenyl acrylate) P-79) Poly (4-cyanobenzyl acrylate) P-80) Poly (cyanoethyl acrylate) )

P-81) Poly (4-cyanoethyl acrylate) P-82) Poly (4-cyano-3-mercaptobutyl acrylate) P-83) Poly (cyclohexyl acrylate) P-84) Poly (2-ethoxycarbonyl) P-85) Poly (3-ethoxycarbonylphenyl acrylate) P-86) Poly (4-ethoxycarbonylphenyl acrylate) P-87) Poly (2-ethoxyethyl acrylate) P-88) Poly (2) -Ethoxypropyl acrylate) P-89) Poly (1H, 1H, 5H-octafluoropentyl acrylate) P-90) Poly (heptyl acrylate) P-91) Poly (hexadecyl acrylate) P-92) Poly (hexyl acrylate) P-93) Poly (isobutyl acrylate) P-94) Poly (isopropyl acrylate) P-95) Poly (3-meth) (Cybutyl acrylate) P-96) poly (2-methoxycarbonylphenyl acrylate) P-97) poly (3-methoxycarbonylphenyl acrylate) P-98) poly (4-methoxycarbonylphenyl acrylate) P-99) Poly (2-methoxyethyl acrylate) P-100) Poly (4-methoxyphenyl acrylate)

P-101) Poly (3-methoxypropyl acrylate) P-102) Poly (3,5-dimethyladamantyl acrylate) P-103) Poly (3-dimethylaminophenyl acrylate) P-104) Polyvinyl-tert -Butyrate P-105) poly (2-methylbutyl acrylate) P-106) poly (3-methylbutyl acrylate) P-107) poly (1,3-dimethylbutyl acrylate) P-108) poly (2-methylpentyl) Acrylate) P-109) Poly (2-naphthyl acrylate) P-110) Poly (phenyl methacrylate) P-111) Poly (propyl acrylate) P-112) Poly (m-tolyl acrylate) P-113) Poly (o) -Tolyl acrylate) P-114) Poly (p-tolyl acrylate) P-115) Poly (N, N-dibutylacrylamide) P-116) Poly (isohexylacrylamide) P-117) Poly (a Octylacrylamide) P-118) Poly (N- methyl -N- phenylalanine acrylamide) P-119) Poly (adamantyl methacrylate) P-120) Poly (benzyl methacrylate)

P-121) Poly (2-bromoethyl methacrylate) P-122) Poly (2-tert-butylaminoethyl methacrylate) P-123) Poly (sec-butyl methacrylate) P-124) Poly (tert-butyl) (Methacrylate) P-125) poly (2-chloroethyl methacrylate) P-126) poly (2-cyanoethyl methacrylate) P-127) poly (2-cyanomethylphenyl methacrylate) P-128) poly (4-cyano) P-129) Poly (cyclohexyl methacrylate) P-130) Poly (dodecyl methacrylate) P-131) Poly (diethylaminoethyl methacrylate) P-132) Poly (2-ethylsulfinylethyl methacrylate) P-133 ) Poly (hexadecyl methacrylate) P-134) Poly (hexyl methacrylate) P-135) Poly (2-hydroxypropyl methacrylate) G) P-136) poly (4-methoxycarbonylphenyl methacrylate) P-137) poly (3,5-dimethyladamantyl methacrylate) P-138) poly (dimethylaminoethyl methacrylate) P-139) poly (3,3 -Dimethylbutyl methacrylate) P-140) Poly (3,3-dimethyl-2-butyl methacrylate)

P-141) Poly (3,5,5-trimethylhexyl methacrylate) P-142) Poly (octadecyl methacrylate) P-143) Poly (tetradecyl methacrylate) P-144) Poly (4-butoxycarbonylphenyl) Methacrylamide) P-145) Poly (4-carboxyphenyl methacrylamide) P-146) Poly (4-ethoxycarbonylphenyl methacrylamide) P-147) Poly (4-methoxycarbonylphenyl methacrylamide) P- 148) Poly (butylbutoxycarbonyl methacrylate) P-149) Poly (butylchloroacrylate) P-150) Poly (butylcyanoacrylate) P-151) Poly (cyclohexylchloroacrylate) P-152) Poly (chloroethylacrylate) P -153) Poly (ethylethoxycarbonyl methacrylate) P-154) Poly (ethyl ethacrylate) P-155 ) Poly (fluoroethyl methacrylate) P-156) Poly (hexylhexyloxycarbonyl methacrylate) P-157) Poly (chloroisobutyl acrylate) P-158) Poly (isopropylchloroacrylate) P-159) Trimethylenediamine-glutaric acid polyamide P-160) Hexamethylenediamine-adipate polyamide

P-161) Poly (α-pyrrolidone) P-162) Poly (ε-caprolactam) P-163) Hexa tolylene diisocyanate-1,4-ditandiolpolyurethane P-164) p-Phenylene diisocyanate Ethylene glycol polyurethane P-165) Poly (vinyl hydrogenated phthalate) P-166) Poly (vinyl acetal phthalate) P-167) Poly (vinyl acetal) P-168) 2-hydroxypropyl methylcellulose hexahydrophthalate (2-hydroxypropyl) Group: 0.28, methyl group: 1.65, hexahydrophthalyl group: 0.60) P-169) 2-hydroxypropylmethylcellulose hexahydrophthalate (2-hydroxypropyl group: 0.33, methyl group: 1.60) , Hexahydrophthalyl group ・ ・ ・ 0.69) P-170) 2-Hydroxypropylmethylcellulose hex Hydrophthalate (2-hydroxypropyl group: 0.22, methyl group: 1.81, hexahydrophthalyl group: 0.84) P-171) Cellulose acetate hexahydrophthalate (acetyl group: 1.23, hexahydrophthalyl group) 0.67) P-172) 2-Hydroxypropyl 4-hydroxybutylmethylcellulose hexadrophthalate (2-hydroxypropyl group 0.28, 4-hydroxybutyl group 0.06, methyl group 1.53, Hexahydrophthalyl group ... 0.39)

These compounds can be produced by known methods, for example, the methods described in US Pat. No. 3,392,022 and JP-B-49-17367.

As a method for incorporating the hydrazine derivative of the present invention into polymer fine particles, the hydrazine derivative is dissolved in a water-miscible organic solvent, and this solution is mixed with a loadable polymer latex to impregnate the polymer with the hydrazine derivative ( loading), a hydrazine derivative and a polymer are dissolved in a low boiling organic solvent insoluble in water (having a solubility of 30% or less in water), and emulsified and dispersed in an aqueous phase (at this time, if necessary, such as a surfactant, etc.) Emulsifying aids and gelatin may be used). In both cases, it is preferable from the viewpoint of storage stability that an unnecessary organic solvent is removed after the hydrazine derivative is contained in the polymer fine particles. Also, when the former method is used, when the hydrazine derivative is contained in the polymer fine particles, there is an advantage that a large amount of power is not required as in the case of emulsification and dispersion, but a large amount of the hydrazine derivative is contained per polymer. It is difficult. On the other hand, in the latter method, a large amount of power is required for emulsification and dispersion, but a large amount of a hydrazine derivative can be contained per polymer, and the reactivity of the hydrazine derivative can be increased by adjusting the size of the polymer particles. Is advantageous over the former method in that a plurality of hydrazine derivatives having different photographic performances can be uniformly contained in the polymer fine particles at an arbitrary ratio, and the dispersion method is preferable. . The dispersion of polymer fine particles containing the hydrazine derivative of the present invention is prepared as follows.

After completely dissolving the hydrazine derivative and the polymer together in a low-boiling organic solvent, the solution is added to water, preferably to an aqueous hydrophilic colloid solution, more preferably to an aqueous gelatin solution, and if necessary, a surfactant. Using a suitable dispersing agent, the particles are dispersed into fine particles by an ultrasonic wave, a colloid mill, a dissolver, or the like, and contained in the coating solution. Removing the low-point organic solvent from the prepared dispersion is effective for the stability of the dispersion, particularly for preventing the precipitation of the hydrazine derivative during storage. Examples of the method for removing the low boiling point organic solvent include distillation under reduced pressure with heating, distillation under normal pressure with heating under a gas atmosphere such as nitrogen or argon, washing with noodle, or ultrafiltration.

The term "low-boiling organic solvent" as used herein means an organic solvent which is useful at the time of emulsifying and dispersing, and which is finally removed from the photosensitive material by a drying step at the time of coating or the above-mentioned method. And a solvent having low solubility in water or a certain degree of solubility in water, which can be removed by washing with water or the like. Examples of low-boiling organic solvents include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol,
Examples include methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, and the like. Further, if necessary, an organic solvent which is completely mixed with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran or the like can be partially used. These organic solvents can be used in combination of two or more.

The pH of the emulsion may be 0.3 or more preferably 0.5 or more higher than the isoelectric point of the gelatin when the gelatin is used for the dispersion in which the chemical stability of the compound itself and the stability of the dispersion are preferably neutral to acidic. It is preferable that the gel be left unattended so that the so-called syneresis water, which naturally separates and contracts the liquid, can be prevented. For adjusting the pH, an organic acid such as citric acid, oxalic acid, acetic acid, tartaric acid, succinic acid, malic acid, or the like may be used.

In the present invention, when the hydrazine derivative is contained in the polymer latex particles, it is extremely preferable to use a melting point depressant. The melting point depressant used in the present invention is a substantially water-insoluble organic compound that has a function of lowering the melting point when mixed with a hydrazine derivative that is substantially diffusion-resistant and oil-soluble. Means

The melting point depressants used in the present invention include:
General formula (II) described on page 18 of JP-A-2-948
And a compound of the general formula (II ′) described on page 20 of the publication,
Specifically, the compounds II-
1) to II-14) and II'-1) to II'-10) are preferably used.

The average particle size of the particles in the emulsion thus obtained is preferably from 0.02 μm to 2 μm, more preferably from 0.04 μm to 0.4 μm. The particle size of the particles in the emulsion can be measured, for example, with a measuring device such as Nanosizer manufactured by Coulter, USA.

The polymer fine particles in the emulsion of the present invention may contain various photographic hydrophobic substances as long as the hydrazine derivative can sufficiently fulfill the purpose of use. Examples of hydrophobic materials for photography include high boiling organic solvents, colored couplers, colorless couplers, developers, developer precursors, development inhibitors, development inhibitor precursors, ultraviolet absorbers, nucleation accelerators, and development accelerators. Agents, gradation regulators such as hydroquinones, dyes, dye releasing agents, antioxidants, optical brighteners, fog inhibitors, and the like. Further, these hydrophobic substances may be used in combination with each other.

In the present invention, the above-mentioned hydrazine derivatives may be used alone or in combination of two or more.
In the present invention, the above melting point depressant is preferably used in an amount of usually 10 to 200% by weight, particularly 20 to 100% by weight, based on the hydrazine derivative. In the present invention, the above-mentioned polymer is usually used in an amount of 10 to 2000% by weight, especially
It is preferable to use 50 to 1000 wt%.

In the present invention, it is preferable to incorporate a nucleation accelerator in the light-sensitive material. Examples of the nucleation accelerator used in the present invention include an amino compound, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58.
(Chem. 21) and (Chem. 2) described in JP-A-7-84331.
Compounds represented by 2) and (Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. JP-A-7-1044
No. 26, compounds represented by general formula [Na] and general formula [Nb], specifically, compounds of Na-1 to Na-22 and Nb-1 described on pages 16 to 20 of the same publication. ~
Compound of Nb-12. The general formulas (1), (2), (3), (4), (5), (6) and (7) described in Japanese Patent Application No. 7-37817. ), Specifically, the compounds of 1-1 to 1-19, the compounds of 2-1 to 2-22, the compounds of 3-1 to 3-36, and the 4-, Compounds of 1-4 to 5-5, compounds of 5-1 to 5-41, compounds of 6-1 to 6-58 and compounds of 7-1 to 7-38. Japanese Patent Application 8-70
No. 908.

In the present invention, general formula (A-1):
Onium salt compounds represented by (A-2), (A-3) or (A-4) are most preferably used as nucleation accelerators.

First, the general formula (A-1) will be described in detail.

[0083]

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In the formula, R ₁₀ , R ₂₀ and R _{30 each} represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group, which further has a substituent. May be combined with each other to form a ring. L represents an m-valent organic group bonded to Q ⁺ and its carbon atom, wherein m
Represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. Where R ₁₀ , R ₂₀ , R
_{When 30} or L has an anionic group in its substituent and forms an inner salt with Q ⁺ , X ^n- is not necessary.

Examples of the groups represented by R ₁₀ , R ₂₀ and R ₃₀ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Linear or branched alkyl groups such as -butyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group; aralkyl groups such as substituted or unsubstituted benzyl groups; cyclopropyl group, cyclopentyl group And cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group and phenanthryl group; alkenyl groups such as allyl group, vinyl group and 5-hexenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group. An alkynyl group such as a phenylethynyl group; a heterocyclic group such as a pyridyl group, a quinolyl group, a furyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, a benzothiazolyl group, a morpholyl group, a pyrimidyl group, or a pyrrolidyl group. No.

Examples of the substituents on these groups include, in addition to the groups represented by R ₁₀ , R ₂₀ and R ₃₀ , halogen atoms such as fluorine, chlorine, bromine and iodine; Group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, sulfonamido group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group (Including carboxylate), sulfonic acid group (including sulfonate), cyano group, oxycarbonyl group, and acyl group.

Examples of the group represented by L include groups having the same meanings as R ₁₀ , R ₂₀ and R ₃₀ when m represents 1. m
When represents an integer of 2 or more, trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, polymethylene group such as dodecamethylene group,
Arylene groups such as phenylene group, biphenylene group and naphthylene group, polyalkylene groups such as trimethylenemethyl group and tetramethylenemethyl group, phenylene-1,3,3
A polyvalent arylene group such as a 5-toluyl group, a phenylene-1,2,4,5-tetrayl group, or these groups and-
SO _2- , -SO-, -O-, _-S- , -N ( _RN )
-, -C = O-, -P = O- and the like, which are formed by a combination thereof (that is, for example, -COO-, -OCO
O -, - NHCONH -, - CONH -, - SO 2 -,
-O-, -CONHCO-, -S- or other alkylene group or arylene group). ( _RN is as defined above).

Examples of the counter anion represented by X ^n- include a chloride ion, a bromine ion, a halogen ion such as an iodine ion, an acetate ion, an oxalate ion, and the like.
Examples include carboxylate ions such as fumarate ions and benzoate ions, sulfonate ions such as p-toluenesulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate; sulfate ions; perchlorate ions; carbonate ions; and nitrate ions.

In the general formula (A-1), R ₁₀ , R ₂₀ ,
R ₃₀ is preferably a group having 20 or less carbon atoms, and when Q represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferred. When Q represents a nitrogen atom, an alkyl group having 15 or less carbon atoms, aralkyl And aryl groups are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, an aralkyl group, or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group, an aralkylene group, or a combination of these groups with a —CO— group, a —O— group,
—N ( _RN ′) — group ( _RN ′) is a hydrogen atom or R ₁₀ ,
Represents a group having the same meaning as R ₂₀ and R _30, and has a plurality of _RN ′ in the molecule.
When they are present, they may be the same or different and may be further bonded to each other), -S-
₂ formed by a combination with a group, -SO2-
Is a valence group. When m represents 2, L is preferably a divalent group having a total carbon number of 20 or less bonded to Q ⁺ at its carbon atom. When m represents an integer of 2 or more, R
_10, R _20, R ₃₀ are present in plural, but a plurality of R _10, R _20, R ₃₀ may be different even in the same, respectively.

The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion or a sulfate ion, and n is preferably 1 or 2.

Many of the compounds represented by formula (A-1) of the present invention are known and are commercially available as reagents. As a general synthesis method, when Q is a phosphorus atom, a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. is there. When Q is a nitrogen atom, there is a method of reacting a primary, secondary or tertiary amino compound with an alkylating agent such as an alkyl halide or a sulfonic acid ester.

Specific examples of the compound represented by formula (A-1) are shown below. However, the present invention is not limited to the following compounds.

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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Next, the general formula (A-2) and the general formula (A-
3) will be described in detail.

[0100]

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In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent an organic residue for completing a substituted or unsubstituted unsaturated hetero ring containing a quaternary nitrogen atom, and a carbon atom ,
It may contain a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and the benzene ring may be condensed. A ₁ , A
Examples of the unsaturated hetero ring formed by ₂ , A ₃ and A ₄ include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring, a pyrimidine ring and a pyrazole ring. And the like. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.

The divalent groups represented by B and C include alkylene, arylene, alkenylene, alkynylene, -SO
_2- , -SO-, -O-, _-S- , -N ( _RN )-,-
What is constituted by C = O- and -P = O- alone or in combination is preferable. Here, RN represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -C = O
-, -O-, _-S- , and -N ( _RN )-alone or in combination. ( _RN is as defined above).

R ₁ and R ₂ are preferably an alkyl group or an aralkyl group having 1 to 20 carbon atoms, and may be the same or different. R ₁ and R ₂ may be substituted. Examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), a substituted or unsubstituted alkyl group (eg, a methyl group, a hydroxyethyl group, etc.), Alternatively, an unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), (alkyl or aryl ) Oxycarbonyl, sulfo (including sulfonate), carboxy (including carboxylate), hydroxy,
Alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group, carbonamido group, sulfonamido group, sulfamoyl group, carbamoyl group, ureido group, thioureido group, (alkyl or aryl)
Examples include an amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group.

Particularly preferably, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Preferred examples of the substituent include a carbamoyl group, an oxycarbonyl group, an acyl group, an aryl group, a sulfo group (including sulfonate), a carboxy group (including carboxylate), and a hydroxy group.

The unsaturated heterocyclic ring formed by A ₁ , A ₂ , A ₃ and A ₄ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include the examples of the substituent which R ₁ and R ₂ may have. The substituent is preferably an aryl group having 0 to 10 carbon atoms, an alkyl group, a carbamoyl group, an (alkyl or aryl) amino group, an oxycarbonyl group, an alkoxy group, an aryloxy group, an (alkyl or aryl) thio group, or a hydroxy group. Carbonyl groups, sulfonamide groups, sulfo groups (including sulfonates), carboxy groups (including carboxylate) and the like.

With respect to the counter anion represented by X ^n- ,
It is the same as the general formula ((A-1)), and its preferred range is also the same.

The compounds of the present invention can be easily synthesized by generally well-known methods, but reference is made to the following documents. (See Quart. Rev., 16, 163 (19
62). )

Specific compounds of the general formulas (A-2) and (A-3) are shown below, but the invention is not limited thereto.

[0109]

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[0110]

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[0111]

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[0112]

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Next, the general formula (A-4) will be described in detail.

[0114]

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The nitrogen-containing unsaturated hetero ring containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom, and may further have a benzene ring fused thereto.
Further, it may have a substituent. Examples of the hetero ring formed include general formulas (A-2) and (A-3)
And the same as the examples of the nitrogen-containing unsaturated heterocyclic ring formed by A ₁ , A ₂ , A ₃ and A ₄ . The preferred range is also the same, and a pyridine ring, a quinoline ring and an isoquinoline ring are preferred. When the nitrogen-containing unsaturated heterocyclic ring containing Z has a substituent, examples of the substituent include A ₁ , A ₂ , A ₃ , and A _{4 in the} general formula (A-2) and the general formula (A-3). Examples of the substituent which the nitrogen-containing unsaturated hetero ring to form may have may be the same as those mentioned above, and the preferred range is also the same.

R ₃ represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, which has 1 to 20 carbon atoms and is substituted or unsubstituted and may be linear or branched or cyclic. Good. Examples of the substituent include the same as the examples of the substituent which R ₁ and R _{2 in} formula (A-2) may have, and the preferable range is also the same.

For the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compound represented by formula (A-4) of the present invention can be easily synthesized by a generally well-known method. (See, Quar
t. Rev., 16, 163 (1962). )

Next, specific examples of the compound represented by formula (A-4) of the present invention are shown below, but the present invention is not limited thereto.

[0120]

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[0121]

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The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto.

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

The silver halide emulsion according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, and silver iodobromide. It is preferably at least 50 mol%, more preferably at least 50 mol%.
The content of silver iodide is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be any one of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular.

The photographic emulsion used in the present invention is P. Glafki.
by des Chimie et Physique Photographique (Paul Mo
ntel, 1967), GFDufin Photographi
c Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
graphic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a double-mixing method, and a combination thereof. Is also good. A method of forming grains in the presence of excess silver ions (a 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. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added depends on the type of the compound used, the intended grain size, and the halogen composition, but is preferably from 10 ^-5 to 10 ^-2 mol per mol of silver halide.

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 is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, or the like. Further, it is preferable to contain an iron compound for higher sensitivity. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds,
Or rhodium complex salts having halogens, amines, oxalates and the like as ligands, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium (III) complex salt, trizalatrodium (III) ) Complex salts and the like. These rhodium compounds are used after being dissolved in water or a suitable solvent.
A method commonly used for stabilizing a solution of a rhodium compound, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr)
Etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-Hei.
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 where M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counter ion is not important 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 addition amount of these compounds is as follows.
The range is preferably from 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol per mol, and particularly preferably from 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol. The iridium compound used in the present invention includes hexachloroiridium, hexabromoiridium, and hexaammineiridium. Examples of the ruthenium compound used in the present invention include hexachlororuthenium and pentachloronitrosylruthenium. Examples of the iron compound used in the present invention include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, 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 these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, and sulfur sensitization, tellurium sensitization and gold sensitization 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 period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. 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, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. 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, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. 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, palladium, and iridium, and gold sensitization is particularly preferable. 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 can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. 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 according to the method described in European Patent Application (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, different crystal habits, different chemical sensitization conditions, and different sensitivities) may be used in combination. Above all, in order to obtain a high contrast, Japanese Patent Application Laid-Open
As described in JP-A-324426, it is preferable to coat an emulsion having a higher sensitivity as it is closer to the support.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention are described, for example, in the literature described or cited in RESEARCH DISCLOSURE Item 17643 IV-A (p. 23, December 1978) and Item 18341X (p. 437, August 1979). Have been. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected.

For example, A) for an argon laser light source, (I) -1 described in JP-A-60-162247.
To (I) -8, compounds of I-1 to I-28 described in JP-A-2-48653, JP-A-4-3304
Compounds I-1 to I-13 described in No. 34, Examples 1 to E described in U.S. Pat. No. 2,161,331.
Xample 14 compound, compounds 1 to 7 described in German Patent 936,071, B) For helium-neon laser light source, compounds I-1 to I-38 described in JP-A-54-18726, Compounds of I-1 to I-35 described in JP-A-6-75322 and JP-A-7-75322
No. 287338, compounds of I-1 to I-34,
C) For LED light sources, compounds of Dyes 1 to 20 described in JP-B-55-39818, compounds of I-1 to I-37 described in JP-A-62-284343, and JP-A-7-2
No. 87338, compounds of I-1 to I-34,
D) Japanese Patent Laid-Open No. 59-191 discloses a semiconductor laser light source.
No. 032, compounds of I-1 to I-12 described in JP-A-60-80841, compounds of I-1 to I-22 described in JP-A-60-80841, and compounds of I-1 to I- described in JP-A-4-335342.
Compound No. 29 and compounds I-1 to I-18 described in JP-A-59-192242;
Compounds (1) to (19) represented by the general formula [I] described in JP-A-5015, and I described in Japanese Patent Application No. 7-346193.
-1 to I-97 and JP-A-6-24254
The compound of 4-A to 4-S described in No. 7, 5-A to 5
Compounds of -Q, compounds of 6-A to 6-T and the like are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any stage of the emulsion preparation which has been recognized to be useful. 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 specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step, during the chemical ripening step, or when the chemical ripening is completed. May be divided and added before or after chemical ripening or during the process and after completion, or may be added by changing the kind of compound and compound combination to be divided and added. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, and the type of antifoggant. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5; Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-118832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right line, line 19 to page 18, upper right line, line four.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. General formula (I) described in Japanese Patent Application No. 8-13592.
A polymer latex having an active methylene group represented by the following formula:
6. Polymer latex having a core / shell structure described in Japanese Patent Application No. 8-13592, specifically, compounds P-1 to P-55 described in the same specification. JP-A-7-10441
The acidic polymer latex described on page 14 left line 1 to right 30 line of JP-A No. 3 (Publication 3), specifically, compounds II-1) to II-9) described on page 15 of the same publication.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardeners described in JP-A-2-103536, page 18, upper right line, 5th line to upper right line, 17th line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, right lower second line to page 10 lower right line, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18;

Solid disperse dyes represented by formulas (FA), (FA1), (FA2) and (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112. Solid disperse dyes described in JP-A-2-29638 and JP-A-3-185773.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right 1
The binder described in the second to 20th lines.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material. Further, a support made of a styrene polymer having a syndiotactic structure described in JP-A-7-234478 and US Pat. No. 5,589,795 is also preferably used.

Hereinafter, the processing agents such as the developing solution and the fixing solution and the processing method in the present invention will be described, but it is needless to say that the present invention is not limited to the following description and specific examples.

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 developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonates, and may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone or a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol is preferable. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred.

The ascorbic acid derivative developing agent preferably used in the present invention is a compound of the formula (1).

[0164]

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In the general formula (1), R ₁ and R ₂ each represent a hydroxy group or an amino group (substituents having 1 carbon atom)
To 10 alkyl groups such as methyl group, ethyl group, n-
Includes those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group, an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, and an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, hydroxyalkyl, carboxyl, carboxyalkyl, sulfo, sulfoalkyl, amino, aminoalkyl,
Represents an alkyl group, an alkoxy group, a mercapto group,
Or an atom group necessary for bonding P and Q to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted with R ₁ and R ₂ and a carbon atom substituted with Y. Represents
Specific examples of the ring structure, -O -, - C (R 4) (R 5) -,
_{-C (R 6) =, -} C (= O) -, - N (R 7) -, - N
= And are combined. Where R ₄ , R ₅ , R
₆ , R ₇ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a substituent may be a hydroxy group, a carboxy group, a sulfo group), a hydroxy group,
Represents a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring and a uracil ring. And as an example of a preferred 5- to 7-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azasiloxhexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or ＮN—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Hereinafter, specific examples of the compound of the general formula (1) are shown, but the present invention is not limited thereto.

[0169]

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[0170]

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[0171]

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Of these, preferred is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid).

The ascorbic acids used in the developer used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol), an endamine type (Endiamin), a thiol-enol type (Thiol-Enol) and an enamine thiol type (E
namin-Thiol) is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549 and JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known, and are described, for example, in Tsukio Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Lao Tsuruhoshinsha 1969). The ascorbic acids used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt and a potassium salt.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone and others.

The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- ( N-methylamino) phenol, N-methyl-p-aminophenol, or the aminophenols described in Japanese Patent Application Nos. 8-70908 and 8-70935 are used. The represented p-aminophenols are most preferred. General formula (A)

[0176]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. R ₅ and R ₆ may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.

The p-aminophenol represented by formula (A) will be described in detail. Where R ₁ , R ₂ , R
₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a mercapto group, a hydroxy group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyloxy group. Group, amino group, alkylamino group, carbonamido group, sulfonamido group, sulfamoylamino group, ureido group, acyl group,
Oxycarbonyl group, carbamoyl group, sulfonyl group,
Examples include a sulfinyl group, a sulfamoyl group, a carboxyl group (including a salt), and a sulfo group (including a salt). These include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, an ammonium group, a carbonamide group, and a sulfonamide group. , A sulfamoylamino group,
It may be substituted with a ureido group, a carbamoyl group, a sulfamoyl group, a carboxyl group (including a salt), a sulfo group (including a salt), or another substituent formed by an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom. .

More specific examples of the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are shown below. The alkyl group has 1 carbon atom
10 to 10 linear, branched or cyclic alkyl groups,
For example, methyl, ethyl, propyl, isopropyl, t
-Butyl, cyclopentyl, cyclohexyl, benzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl,
-Methoxyethyl and the like.

The aryl group is an aryl group having 6 to 10 carbon atoms, for example, phenyl, naphthyl, p-methoxyphenyl and the like. The aralkyl group has 7 to 7 carbon atoms.
And 10 aralkyl groups such as benzyl.
The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and the ring may comprise at least one hetero element. It may be plural, for example, 2-furyl, 2-pyrrolyl, 2-imidazolyl, 1-pyrazolyl, 2-pyridyl, 2-pyrimidyl, 2-thienyl and the like. Examples of the halogen atom include a fluorine atom and a chlorine atom. The alkoxy group has 1 to 10 carbon atoms,
Preferably an alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, 2-hydroxyethoxy, 3-hydroxypropoxy, 2-methoxyethoxy, hydroxyethoxyethoxy, 2,3
-Dihydroxypropoxy, 2-hydroxypropoxy, 2-methanesulfonylethoxy and the like. The aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and examples thereof include phenoxy, p-carboxyphenoxy, and o-sulfophenoxy. The alkylthio group is an alkylthio group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methylthio and ethylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms, such as phenylthio and 4-methoxyphenylthio. The acyloxy group is an acyloxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as acetoxy and propanoyloxy.

The alkylamino group has 1 to 1 carbon atoms.
0, preferably an alkylamino group having 1 to 6 carbon atoms, such as methylamino, diethylamino and 2-hydroxyethylamino. The carbonamido group is a carbonamido group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as acetamido and propionamido.
The sulfonamide group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and is, for example, methanesulfonamide. The sulfamoylamino group is a sulfamoylamino group having 0 to 10 carbon atoms, preferably 0 to 6 carbon atoms, such as methylsulfamoylamino and dimethylsulfamoylamino. The ureido group is a ureido group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as ureide, methylureide, and N, N-dimethylureide. The acyl group has 1 to 1 carbon atoms.
An acyl group having 0, preferably 1 to 6 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group is an oxycarbonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. The carbamoyl group has 1 to 1 carbon atoms.
0, preferably a carbamoyl group having 1 to 6 carbon atoms, for example, carbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl. The sulfonyl group is a sulfonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and ethanesulfonyl. The sulfinyl group is a sulfinyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfinyl. The sulfamoyl group has 0 to 0 carbon atoms.
10, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl and dimethylsulfamoyl.

R ₅ and R ₆ may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. The details thereof are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . Where R ₅ and R
_{When 6} is an alkyl group, it is linked to 5
A 6-membered ring may be formed. In this case, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring can be mentioned. When at least one of R ₅ and R ₆ is an alkyl group and at least one of R ₃ and R ₄ is an alkyl group or an alkoxy group, these are linked to form a condensed heterocyclic ring together with a nitrogen atom and a benzene ring. The 5- or 6-membered ring condensed with the formed benzene ring may include, for example, indole, indoline, dihydroquinoline, tetrahydroquinoline, and benzoxazine. The compound represented by the general formula (A) may be a dimer to form a bis-type structure.

Among the compounds represented by the general formula (A),
Compounds represented by the following general formula (B) are preferred. General formula (B)

[0184]

Embedded image

In the formula, R ₁₁ and R ₂₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₅₅ , R ₆₆
May be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.

In the general formula (B), R ₁₁ , R ₂₂ and R ₅₅ , R
_{66 is} described below regarding preferred combinations thereof. R ₁₁ and R ₂₂ are a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, a carbonamido group, a sulfonamido group, a sulfamoylamino group, a ureido group, and R ₅₅ and R ₆₆ are Combinations that are alkyl groups are preferred. Here, the alkyl group, the alkoxy group, and the alkylamino group include those substituted with another substituent. In this combination, R ₅₅ , R
₆₆ is more preferably an unsubstituted alkyl group or an alkyl group substituted with a water-soluble group. Here, the water-soluble group includes a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an ammonio group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a ureido group, a carbamoyl group, a sulfamoyl group, a carboxyl group ( And a sulfo group (including a salt).

More preferably, in the formula (B), R ₁₁ is a hydrogen atom, and R ₂₂ is an alkyl group, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a ureido group. Yes, R
₅₅ and R ₆₆ are compounds wherein the alkyl group is an alkyl group. Here, an alkyl group, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, and a ureido group are a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an ammonium group, a carbonamide group, and a sulfonamide group. Or those substituted by a ureido group.

As still more preferred compounds, in the general formula (B), R ₁₁ is a hydrogen atom, and R ₂₂ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
A carbonamide group having 1 to 3 carbon atoms, a sulfonamide group having 1 to 3 carbon atoms, a ureido group having 1 to 3 carbon atoms,
A compound in which R ₅₅ and R ₆₆ are an unsubstituted alkyl group having 1 to 3 carbon atoms. Wherein the alkyl group, alkoxy group represented by R ₂₂ includes those substituted hydroxy group, an alkoxy group, a carbonamido group, the sulfonamido group.

As the most preferred compound, in the general formula (B), R ₁₁ is a hydrogen atom, and R ₂₂ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a C 1 to 3 carbon atom. A sulfonamide group having 1 to 3 carbon atoms, a ureido group having 1 to 3 carbon atoms, and R ₅₅ ,
A compound in which R ₆₆ is a methyl group. Here, the alkyl group and the alkoxy group represented by R ₂₂ include those substituted with a hydroxy group or an alkoxy group.

Examples of specific compounds of the present invention include, but are not limited to, the following compounds.
Since the compound represented by the general formula (A) may be unstable as a free aniline, it is generally produced and stored as a salt with an inorganic acid or an organic acid, and is added with a free amine only after being added to the treatment solution. Preferably. Examples of the inorganic and organic acids that form the salt of the compound of the formula (A) include hydrochloric acid, hydrobromic acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid. Is preferably a salt of sulfuric acid or naphthalene-1,5-disulfonic acid.

[0191]

[Table 9]

[0192]

[Table 10]

[0193]

[Table 11]

[0194]

[Table 12]

[0195]

[Table 13]

[0196]

[Table 14]

[0197]

[Table 15]

[0198]

[Table 16]

[0199]

[Table 17]

The compound represented by formula (A) is, for example,
Photographic Science and Engineering, 10, 306 (196
According to a general synthesis method such as 6), refer to Japanese Patent Application No.
It can be easily synthesized according to the synthesis example described in No. 0908.

The dihydroxybenzene-based developing agent is usually 0.1.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / L to 0.6 mol / L, preferably 0.23 mol / L to 0.5 mol / L, It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.1
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or p-aminophenol is used, the ascorbic acid derivative is used in an amount of 0.01 to 0.5 mol / l, and the 1-phenyl-3-pyrazolidone or p-aminophenol is used. The aminophenols are preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-9
The sugars described in 3433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonates , Boric acid is used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular from 0.2 to
1.5 mol / l.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is used in an amount of 0.2 mol / l or more, especially 0.3 mol / l or more. However, if added in an excessively large amount, silver stain in a developing solution may be caused.
It is desirable to use liters. Particularly preferably, 0.35 to
0.7 mole / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide.
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol,
Examples thereof include methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these additives is usually 0.01 to 10 mmol per liter of developer, more preferably 0.1 to 10 mmol.
~ 2 mmol.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelinic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632, 55-67747, 57-1
02624 and compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Patent Publication No. 2,227,369, and Research Disclosure, Vol. 181, Item 18170 (19).
May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Other examples include the compounds described in Research Disclosure 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include, for example, those described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127 and JP-A-55-102127.
-4024, 55-4025, 55-126241, 55-65955, 55
-65956 and the aforementioned Research Disclosure 1817
0 and the like.

These organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-46585, JP-B-62
849, JP-A-4-362942 and JP-A-8-6215, as well as triazines having at least one mercapto group (for example, JP-B-6-23830, JP-A-3-282457, JP-A-7-175178).
And the pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-
Dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine and the like pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5 -Dimercaptopyridine, 2,4,6 trimercaptopyridine,
7-248587), the same pyrazine (for example,
2-mercaptopyrazine, 2,6-dimercaptopyrazine,
2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, and the like pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-
Dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), the compounds described in JP-A-7-175177, and the polyoxyalkylphosphonic acid esters described in US Pat. These silver stain inhibitors can be used alone or in combination of two or more. The addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer. In addition, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, a color tone agent, a surfactant, an antifoaming agent, a hardener and the like may be contained as necessary.

The preferred pH of the developer is from 8.0 to 12.0, particularly preferably from 9.0 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As the cation of the developer, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution was per 1 m ² of the photosensitive material.
390 ml or less, preferably 325-30 ml, most preferably 180-120 ml. The development replenisher may have the same composition and / or concentration as the development initiator, or may have a different composition and / or
Alternatively, it may have a concentration.

It is preferable to concentrate the processing liquid and dilute it at the time of use for the purpose of transporting the processing liquid, packaging material cost, space saving, and the like.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are used as an aluminum ion concentration of 0.01 to 0.15 mol /
It is preferably contained in liters. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If necessary, a preservative (eg, sulfite, bisulfite, metabisulfite, etc.)
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / L to 1 mol / L, preferably 0.2 mol / L to 0.7 mol / L of phosphoric acid, succinic acid, adipic acid, and the like, and compounds having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodi Acetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediamine Acetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.1 mol / l
005 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxide, polyethylene-based surfactants, and amphoteric surfactants described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in the above 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat. No. 4,216,459, JP-A-64-4739, JP-A-1-4739, JP-A-1-4739
159645 and the mercapto compounds described in 3-101728,
The mesoionic compound described in 4-170539 and a thiocyanate can be included.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. The pH of the fixer is increased by mixing with a developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment amount of the fixing solution is per 1 m ² of the photosensitive material.
500 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be regenerated and used by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

The photosensitive material which has been subjected to development and fixing is then subjected to washing or stabilizing treatment (hereinafter referred to as washing including stabilizing treatment unless otherwise specified, and the liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. These replenishing amounts are generally 1 m ² of photosensitive material.
From about 17 liters to about 8 liters per volume, although lower replenishment rates can be used. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Also, various oxidizing agents (eg, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect is achieved by the independent multi-stage method (a method of replenishing a new liquid individually in a multi-stage washing tank without countercurrent)
But it can be obtained as well.

Further, in the method of the present invention, means for preventing water scale may be provided in the washing step. Known means can be used as the scale preventive means, and is not particularly limited, but a method of adding a sunscreen (a so-called scale preventive agent), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed according to the processing of the photosensitive material, may be performed at regular intervals irrespective of the state of use, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method of energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, JP-A-4-18
980 or the like can be used.

In addition, known water-soluble surfactants and defoamers may be added to prevent unevenness of water bubbles and transfer of dirt. In addition, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by dyes eluted from the light-sensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver, or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment, and examples thereof include JP-A-2-201357, JP-A-2-132435,
A bath containing the compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains ammonium compounds, metal compounds such as Bi and Al, fluorescent brighteners, various chelating agents, membrane pH regulators,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are described, for example, in Japanese Patent Publication No. 7-83867, US Pat.
It is also possible to dispose it after concentrating it into a liquid or solidifying it with a concentrating device as described in O.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stopping step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, the dry-to-dry processing
160 seconds is preferred, development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is preferably 25 to 50 ° C.
30-40 ° C is preferred. Washing temperature and time are 0-50 ℃
And preferably 40 seconds or less. According to the method of the present invention, development,
The fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. As the drying method, any known method can be used, and there is no particular limitation.
Heat roller drying and far-infrared drying as disclosed in 4-15534, 5-2256 and 5-289294 may be used, and a plurality of methods may be used in combination.

When the developing and fixing processing agent in the present invention is a liquid, it is preferable to store it in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Furthermore, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained. However, the solid processing agent will be described below. As the solid preparation in the present invention, known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, stick, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3
You can refer to the 13th line.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The solid processing agent has a bulk density of 0.5 to 6.0 g / c.
m ³ is preferred, especially 1.0 to 5.0 g / cm ³ for tablets, and 0.5 to 1.5 g / cm ^{3 for} granules.

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-
32837, 4-78848, 5-93991, JP-A-4-85533,
4-85534, 4-85535, 5-134362, 5-97070, 5-
204098, 5-224361, 6-138604, 6-138605, Japanese Patent Application
7-89123 etc. can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, Japanese Patent Application 5-30664
Also, it is preferable to make it a foldable shape as disclosed in JP-A-7-5664 and JP-A-7-5666 to 7-5669, in order to reduce the storage space of the waste packaging material. These packaging materials
A screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used without any particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function,
A method of dissolving with a dissolving apparatus having a dissolving portion and a portion for storing a completed solution as described in 7-235499 and replenishing from the stock portion, JP-A-5-119454, JP-A-6-19102,
A method of dissolving and replenishing by introducing a processing agent into the circulating system of an automatic developing machine as described in 7-261357, and inputting a processing agent according to the processing of the photosensitive material with an automatic developing machine having a built-in dissolving tank. Although there is a dissolving method and the like, any other known method can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method disclosed in JP-A-6-19102
And 6-95331.

[0243]

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

Example 1 An emulsified dispersion of a hydrazine derivative was prepared by the following method. 1 g of the hydrazine derivative shown in Table 18, 6.0 g of the polymer shown in Table 18, 48 ml of ethyl acetate, and 2 ml of water
After heating and dissolving the solution consisting of gelatin 1
2 g and sodium dodecylbenzenesulfonate 0.7 g
Was dispersed finely by a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisaku-sho, Ltd.) to obtain a fine particle emulsified dispersion having an average particle diameter of 0.3 μm. Further, 2000 ppm of proxel was added to gelatin as a preservative, and finally, pH was adjusted to 5.0 by adding ascorbic acid. Adding the hydrazine derivative to the coating solution in this state is referred to as polymer dispersion addition. On the other hand, dissolving the hydrazine derivative in methanol and adding it to the coating solution is called adding a methanol solution.

Example 2 <Preparation of silver halide photographic light-sensitive material> Preparation of emulsion A 1 liquid water 1 liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2nd liquid 400ml Silver nitrate 100g 3rd liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Ammonium hexachloroiridium (III) ammonium (0.001% aqueous solution) 20ml Potassium hexachlorodium (III) acid (0.001% aqueous solution) 6ml

Solution 2 and solution 3 were added simultaneously to solution 1 maintained at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, water was washed by flocculation according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion A containing 70 mol% of silver chloride and having an average grain size of 0.25 μm.
I got

Preparation of Coated Sample Emulsion A was subjected to spectral sensitization by adding 3.8 × 10 ^-4 mol / mol Ag of sensitizing dye (1). Furthermore, KBr 3.4 × 10 ^-4
Mol / mol Ag, compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, 3.0 × 10 ⁻³ mol / mol Ag of citric acid and a hydrazine derivative shown in Table 18 were added in the amounts and methods shown in Table 18. Further, compound (4) was added at 6.0 × 10 ⁻⁴ mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, and 20 wt% based on gelatin.
Colloidal silica having a particle size 10mμ of, 4 wt% of the compound with respect to the gelatin (5) was added, Ag2.7g / m ² on a polyester support was coated to a gelatin 1.6 g / m ^2. On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied.

Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Underlayer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2 - benzaldoxime 10 mg / m ² of polyethyl acrylate latex 150 mg / m ² UL layer gelatin 0.5 g / m ² of polyethyl acrylate latex 150 mg / m ² compound (5) 40mg / m ² compound (10) 10mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0252]

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[0253]

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The following compounds were used as comparative compounds of the hydrazine derivative of the present invention.

[0255]

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A developer A was prepared according to the following formulation. (Developer A) Diethylenetriamine-5 acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl-5 -Mercaptotetrazole 0.02 g Sodium sulfite 5 g Add water to 1 liter and adjust pH to 9.7.

Further, a developer B was adjusted to pH 9.2 by adding acetic acid to the developer A, and a developer C was adjusted to pH 10.2 by adding sodium hydroxide to the developer A. did.

<Evaluation of photographic performance> (1) Exposure and development treatment The above sample was exposed to xenon flash light having a light emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 633 nm. Using A, B, and C, an AP-560 automatic developing machine manufactured by Fuji Photo Film Co., Ltd. developed at 38 ° C. for 15 seconds, and then fixed, washed with water,
A drying process was performed.

As a fixing solution, a fixing solution having the following formulation was used. (Fixing solution composition) Ammonium thiosulfate 120 g Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Sodium thiosulfate / pentahydrate 11 g Sodium metasulfite 19 g Sodium hydroxide 12.4 g Acetic acid (100%) 30 g Tartaric acid 2.9 g Glucone Sodium acid 1.7g Aluminum sulfate 8.4g Water is added to make 1 liter, and the pH is adjusted to 4.8.

(2) Evaluation (Gamma) As an index (gamma) indicating the contrast of an image, a point is connected from a point of fog + density of 0.1 to a point of fog + density of 3.0 on the characteristic curve, and the slope of this line is represented by gamma. Expressed as a value. That is, gamma = (3.0−0.1) /
(Log (exposure dose giving a density of 3.0)-log (density of 0.1
), Which indicates that the higher the gamma value, the harder the photographic characteristics. In practice, the gamma value needs to be 15 or more.

(Dependence of Sensitivity on pH of Developing Solution) Development processing was carried out under the above-mentioned conditions using the above-mentioned photosensitive material and developing solutions B and C.
The developer pH dependence (ΔS _1.5 ) of the sensitivity was calculated using the following equation. As the sensitivity (S _1.5 ), a logarithmic value of an exposure amount giving a density of 1.5 was used. Dependence of sensitivity on developer pH (ΔS _1.5 ) = S _1.5 (Developer B)
The higher the -S _1.5 (developer C) value, the greater the developer pH dependence of sensitivity. Practically, ΔS _1.5 needs to be 0.10 or less, and more preferably 0.05 or less.

(Storage Stability of Hydrazine Derivative in Sensitive Material) A sensitizing material which was frozen and stored after coating, was subjected to a temperature of 60 ° C. and a humidity of 65
The hydrazine derivative was extracted from each of the photosensitive materials with an organic solvent and quantified using HPLC, and the storage stability of the hydrazine derivative was evaluated by the following formula. Storage stability of hydrazine derivative (%) = {(amount of hydrazine derivative extracted from thermosensitive photosensitive material) / (amount of hydrazine derivative extracted from frozen stored photosensitive material)} x 100 In order to guarantee the performance of the photosensitive material for a period, this value needs to be 90% or more.

Table 18 shows the results. Only a light-sensitive material satisfying the requirements of the present invention was able to obtain an ultra-high-contrast light-sensitive material having extremely low pH dependency of a developer and high storage stability of a hydrazine derivative.

[0264]

[Table 18]

Example 3 The following photosensitive material was used, and development and evaluation were conducted in the same manner as in Example 2 except for the exposure method. As a result, only the photosensitive material satisfying the requirements of the present invention was specific as in Example 2. In addition, it was possible to obtain a super-high contrast sensitive material having extremely low pH dependence of the developer and high storage stability of the hydrazine derivative.

Preparation of Emulsion B 1 solution 1 liter water 20 g gelatin 20 g sodium chloride 1.5 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 solutions water 400 ml sodium chloride 27 0.1 g Potassium bromide 21.0 g Ammonium hexachloroiridate (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 10 ml

Solution 1 and Solution 3 were added simultaneously to Solution 1 maintained at 40 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the product was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion containing 70 mol% of silver chloride and having an average particle diameter of 0.22 μm B
I got

Preparation of Coated Samples Emulsion B was added with sensitizing dye (1) 8.0 × 10 ⁻⁵ mol / mol Ag and subjected to spectral sensitization. Furthermore, Kbr 3.4 × 10 ^-4
Mol / mol Ag, compound (1) 2.0 × 10 ⁻⁴ mol / mol Ag, compound (2) 1.0 × 10 ⁻³ mol / mol Ag, hydroquinone 2.0 × 10 ⁻² mol / mol Ag, 2.0 × 10 ⁻³ mol / mol Ag of citric acid and hydrazine derivatives shown in Table 18 were added in the amounts and methods shown in Table 18. Further, the compound (4) was 9.0 × 10 ⁻⁴ mol / mol Ag, the compound (5) was 2.3 × 10 ⁻⁴ mol / mol Ag, and the compound (6) was 1.4 × 10 ⁻⁴ mol / mol Ag. Mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% colloidal silica having a particle size of 10 μm based on gelatin, 4 wt% compound based on gelatin
(7) and 2.6 g of Ag on the polyester support
/ M ² and gelatin at 1.4 g / m ² . An upper protective layer and a lower protective layer having the following composition were applied thereon.

Upper layer of protective layer Gelatin 0.3 g / m ² 3.5 μm average silica matting agent 25 mg / m ² Compound (8) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (9) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (10) 20 mg / m

Lower layer of protective layer Gelatin 0.8 g / m ² Compound (11) 20 mg / m ² Compound (12) 7 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.0 g / m ² Sodium dodecylbenzenesulfonate 40 mg / m ² Compound (12) 60 mg / m ² Compound (13) 30 mg / m ² 1,3-Divinylsulfonyl-2-propanol 60 mg / m ² Polymethyl Methacrylate fine particles (average particle size 6.5 μm) 6 mg / m ² Polymethyl methacrylate fine particles (average particle size 3.5 μm) 25 mg / m ² Sodium sulfate 150 mg / m ² Compound (7) 110 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0274]

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[0275]

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(Exposure Method) The above sample was exposed to xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 780 nm.

Example 4 Developers D, E, and F were prepared according to the following formulation. (Developer D) Potassium hydroxide 40 g Diethylenetriamine / pentaacetic acid 2 g Potassium carbonate 60 g Sodium metabisulfite 70 g Potassium bromide 7 g Hydroquinone 40 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidone 1.5 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.3 g 3- (5-Mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g Sodium erythorbate 6 g Diethylene glycol 5 g Add water to 1 liter And adjust the pH to 10.65.

Further, acetic acid was added to the developer D to adjust the pH to 1
Sodium hydroxide was added to developer E and developer A adjusted to 1.15, and developer F adjusted to pH 10.15.

Developer D, developer A, B, C
Except for using E and F, the photographic material was prepared, developed, and evaluated in the same manner as in Example 2. As a result, only the photographic material satisfying the requirements of the present invention was specifically developed in the same manner as in Example 2. A very high contrast sensitive material having extremely low pH dependency and high storage stability of the hydrazine derivative was obtained.

Example 5 <Preparation of Emulsion C> 1 solution 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 solutions Water 0.4 L Sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachlorodium (III) acidate (0.001% aqueous solution) 6 ml

Solution 2 and Solution 3 were added simultaneously to Solution 1 kept at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4 liquid water 0.4 liter Silver nitrate 100g 5 liquid water 0.4 liter sodium chloride 27.1 g potassium bromide 21.0 g potassium hexacyanoferrate (II) (0.1% aqueous solution) 10 ml

Thereafter, water was washed by flocculation according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion C containing 70 mol% of silver chloride and having an average grain size of 0.25 μm.
I got

<Method of adding hydrazine nucleating agent> An emulsified dispersion of a hydrazine derivative was prepared by the following method. 1.0 g of the hydrazine derivative shown in Table 20, 6.0 g of poly (N-tert-butylacrylamide), and 48 m of ethyl acetate
After heating and dissolving a solution consisting of 1 ml of water and 2 ml of water at 60 ° C., the solution was added to 120 ml of an aqueous solution containing 12 g of gelatin and 0.7 g of sodium dodecylbenzenesulfonate, and finely dispersed with a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho). Thus, a fine particle emulsified dispersion having an average particle diameter of 0.3 μm was obtained.
Furthermore, proxel was added as a preservative to gelatin.
000ppm, and finally add ascorbic acid and add pH
Was adjusted to 5.0. Adding the hydrazine derivative to the coating solution in this state is referred to as polymer dispersion addition. On the other hand, dissolving the hydrazine derivative in methanol and adding it to the coating solution is called adding a methanol solution.

<Preparation of Coated Sample> Sensitizing dye (1) was added to Emulsion A.
3.8 × 10 -4 mol / mol Ag was added for spectral sensitization. Further, KBr (3.4 × 10 ⁻⁴ mol / mol Ag), compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.
0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 1
0 ^-2 mol / mol Ag and 3.0 × 10 ^-3 mol / mol Ag of citric acid were added. The hydrazine derivative of the compound (3) was added in an amount of 1.0 × 10 ⁻⁴ mol / mol Ag by the above-described addition method, and the compound (4) was converted to 6.0 × 10 ⁻⁴ mol / mol A.
g, 35% by weight of polyethyl acrylate latex with respect to gelatin, 20% by weight of colloidal silica having a particle size of 10 μm with respect to gelatin, and 4% with respect to gelatin.
The compound (5) was added in an amount of wt%, and the mixture was coated on a polyester support so that Ag was 2.9 g / m ² and gelatin was 1.6 g / m ² . On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied.

Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle diameter of 10 to 20 μm 30 mg / m ² Compound (7) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ²

Lower layer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ²

UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0290]

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[0291]

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Table 20 shows the types and amounts of the compounds (3) and (4) in the light-sensitive material, which were appropriately changed.

<Composition of developer>

[0294]

[Table 19]

<Fixing solution> Formulations per liter of the fixing solution concentrated solution are shown below. Ammonium thiosulfate 360 g Ethylenediamine, tetraacetic acid, 2Na, dihydrate 0.09 g Sodium thiosulfate, pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Sulfuric acid Aluminum 25.2 g pH 4.85 For use, dilute 2 parts of water with 1 part of the above concentrate. The pH of the working solution is 4.8.

The evaluation was performed by the following method. Evaluation of photographic properties was performed using an optical wedge on the prepared sample and an emission time of 10 ⁻⁵ sec through an interference filter having a peak at 633 nm.
With a xenon flash light. Processing was performed at a development time and temperature of 35 ° C. for 20 seconds. The sensitivity was shown as a relative value with 100 being the reciprocal of the exposure required to obtain a density of 1.5 when processed in No. 1 of Table 19. Higher values indicate higher sensitivity. The gradation (gamma) was represented by the following equation. The larger this value, the harder the photographic characteristics. * Gamma = (3.0-0.3) / [log (exposure to give density 3.0)-log (exposure to give density 0.3)]

(Processing unevenness) Using a helium-neon light source color scanner SG-608 manufactured by Dainippon Screen Co., Ltd., a flat screen of 96% was output to the sample at 175 lines and developed under the above conditions. Was. Processing unevenness is (good) 5 to 1
The sensory evaluation was performed according to the (bad) 5-point method. "3" and below are practically unacceptable or unacceptable.

(Running Test) A running test was performed using AP-560 manufactured by Fuji Photo Film Co., Ltd. The running conditions were a large paper size (50.
Sixteen (8 × 61.0 cm) samples were processed, and six rounds were performed, in which one round of running, which was activated for six days and rested for one day. The replenishing amount of the fixing solution during the running was 1.5 times the replenishing amount of the developing solution.

The processing conditions were as follows: developing time = 20 seconds, developing temperature = 35 ° C., fixing temperature = 34 ° C. The developing solution shown in Table 19 was used as the mother liquor, and the pH of the replenisher was as shown in Table 20. Was adjusted. It is practically necessary that the sensitivity to the running fatigue fluid is 95 to 105. After the running, using a helium light source color scanner SG-608 manufactured by Dainippon Screen Co., Ltd., a flat screen of 50% was output to the coated photosensitive material at 175 lines, and developed under the above processing conditions. Then, the sharpness of halftone dots was visually evaluated with a 200-fold loupe. The evaluation results were (good) 5 to 1 (bad)
The results are shown in the table by the five-point method. Practically, three or more points are required.

The evaluation results are shown in Table 20.

[0301]

[Table 20]

When combined with the compounds of the present invention,
It can be seen that the processing unevenness is small, the sensitivity during running and the gradation change are small, and the dot quality is excellent.

Example 6 Development and evaluation were performed in the same manner as in Example 5 except that the following photosensitive materials were used, the exposure method thereof, and the output device used for the processing unevenness test. Only when the light-sensitive material and the developing solution were used, it was possible to obtain a super-high contrast image with little sensitivity during running, little change in gradation, excellent dot quality, and little processing unevenness.

Preparation of Emulsion D 1 solution 1 liter of water 20 g gelatin 20 g sodium chloride 1.5 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 solutions water 400 ml sodium chloride 27 0.1 g Potassium bromide 21.0 g Ammonium hexachloroiridate (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 10 ml

Solution 2 and Solution 3 were added simultaneously to Solution 1 maintained at 40 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and a silver chloroiodobromide cubic emulsion D containing 70 mol% of silver chloride and having an average particle size of 0.22 μm.
I got

Preparation of Coated Sample Emulsion D was added with 8.0 × 10 ⁻⁵ mol / mol Ag of sensitizing dye (1) and subjected to spectral sensitization. Furthermore, Kbr 3.4 × 10 ^-4
Mol / mol Ag, compound (1) 2.0 × 10 ⁻⁴ mol / mol Ag, compound (2) 1.0 × 10 ⁻³ mol / mol Ag, hydroquinone 2.0 × 10 ⁻² mol / mol Ag, 2.0 × 10 ⁻³ mol / mol Ag of citric acid and the hydrazine derivative of the compound (3) were added in an amount of 1.0 × 10 ⁻⁴ mol / mol Ag by the above-mentioned addition method, and the compound (4) was converted to the compound (4). 6.0 × 10 ^-4 mol / mol Ag, compound (5) 2.3 × 10 ^-4 mol / mol Ag, compound (6) 1.4 × 10 ^-4 mol / mol Ag, and gelatin 35 wt% polyethyl acrylate latex, 20 wt% particle size 10 based on gelatin
mμ colloidal silica, 4 wt% of compound (7) based on gelatin were added, and Ag was added on a polyester support.
Coating was performed so that 3.25 g / m ² and gelatin were 1.4 g / m ² . An upper protective layer and a lower protective layer having the following composition were applied thereon. The types and amounts of the compounds (3) and (4) in the light-sensitive material were changed in the same manner as in Example 5.

Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (8) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (9) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (10) 20 mg / m

Lower layer of protective layer Gelatin 0.8 g / m ² Compound (11) 20 mg / m ² Compound (12) 7 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.0 g / m ² Sodium dodecylbenzenesulfonate 40 mg / m ² Compound (12) 60 mg / m ² Compound (13) 30 mg / m ² 1,3-Divinylsulfonyl-2-propanol 60 mg / m ² Polymethyl Methacrylate fine particles (average particle size 6.5 μm) 6 mg / m ² Polymethyl methacrylate fine particles (average particle size 3.5 μm) 25 mg / m ² Sodium sulfate 150 mg / m ² Compound (7) 110 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ²

[0312]

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[0313]

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(Exposure method) 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 780 nm.

(Output machine for processing unevenness test) Semiconductor laser scanner MTR-110 manufactured by Dainippon Screen Co., Ltd.
Output using 0. The sample of the embodiment of the present invention had little processing unevenness.

Claims (5)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of said silver halide emulsion layer and another hydrophilic colloid layer is provided on at least one of said layers. General formula (N
A silver halide photographic light-sensitive material containing polymer fine particles containing a hydrazine derivative represented by B). General formula (NB) In the formula, A represents a linking group, B represents a group represented by the following formula (B-1), and m represents an integer of 2 to 6. General formula (B-1) In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents a —CO— group, —SO ₂ —
Group, -SO- group, Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group. R ₂ is selected from the same range as the groups defined in R _1, may be different from R _1. 2. A silver halide photographic material according to claim 1, wherein at least one of said silver halide emulsion layer and said other hydrophilic colloid layer contains a nucleation accelerator. Silver photographic photosensitive material. 3. A method for developing the silver halide photographic material according to claim 1 or 2 after image exposure while replenishing a developing solution, wherein the developing solution is substantially a dihydroxybenzene-based developing agent. Does not contain the general formula (1)
Developing a silver halide photographic light-sensitive material, comprising developing with a developer containing a developing agent represented by the formula: General formula (1) In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group. P and Q are a hydroxy group, a hydroxyalkyl group, a carboxyl group,
Carboxyalkyl group, sulfo group, sulfoalkyl group,
Represents an amino group, an aminoalkyl group, an alkyl group, an alkoxy group, or a mercapto group, or P and Q are bonded to each other, and two vinyl carbon atoms substituted by R ₁ and R ₂ are substituted with Y. Represents a group of atoms forming a 5- to 7-membered ring together with the carbon atoms. Y represents = 0 or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. 4. A method for developing a silver halide photographic light-sensitive material according to claim 1 or 2, after image exposure, while replenishing a developing solution, wherein the developing solution contains a dihydroxybenzene-based developing agent. A method for developing a silver halide photographic light-sensitive material, comprising developing with a developer. 5. The method for developing a silver halide photographic light-sensitive material according to claim 3, wherein said developer contains a compound represented by the general formula (A). A method for developing a silver halide photographic material. General formula (A) In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. R ₅ , R ₆
May be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.