JPH08211526A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance the contrast of a negative image with a stable developing solution low in pH and to stabilize photographic performance against the fluctua tion of a developing solution composition by incorporating a hydrazine derivative and a specified compound. CONSTITUTION: A silver halide emulsion layer and/or another hydrophilic colloidal layer contains the hydrazine derivative and at least one kind of glycidyl or ketone derivative mainly represented by the formula, wherein R1 is a 1-40C aliphatic group; A is an arylene group; X1 is a divalent bonding group; Y1 is an H atom or a -(CH2 H2 O)i -H or an anionic group; (i) is an integer of 1-500; (t) is 0 or 1; and (m) is an integer of 1-50. The hydrazine derivative has an anionic group near the hydrazine group or an anionic group of forming an intermolecular hydrogen bond with the H atom of the hydrazine, thus permitting a negative image extremely high in contrast to be obtain with a stable developing solution lower than 11 in pH and moreover, and occurrence of uneven processing is reduced even with a developing machine with deteriorated rollers.

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.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system showing photographic characteristics of ultra-high contrast (especially γ of 10 or more) in order to favorably reproduce a continuous tone image or a line image by a halftone image. is required.
There is a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics. One of them is U.S. Pat.
8,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
As disclosed in Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added is added with a sulfite preservative.
A system has been proposed which forms a super-high contrast negative image in which γ exceeds 10 by processing with a developer having a pH of 11.0 to 12.3 containing 5 mol / liter or more. This new image forming system can be used with silver iodobromide and silver iodochlorobromide, while only silver chlorobromide with a high silver chloride content can be used in the conventional ultrahigh contrast image formation. There is. Another feature is that the conventional lith developer can contain a very small amount of sulfite preservative, whereas it can contain a large amount of sulfite preservative, so that it has relatively good storage stability. However, a developer having a pH of 11 or more is easily oxidized by air and is unstable, and cannot be stored or used for a long time. A silver halide light-sensitive material containing a hydrazine compound is used at a lower p
An attempt has been made to develop a high contrast image by developing with a H developing solution. JP-A-1-179939 and JP-A-1-179939
-179940 is a process of developing with a developer having a pH of 11.0 or less using a photosensitive material containing a nucleation development accelerator having an adsorption group for silver halide emulsion grains and a nucleation agent also having an adsorption group. The method is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient hardness cannot be achieved. JP-A-60-1403
No. 40 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, in the case of developing with a developer having a pH of less than 11.0, sufficient contrast cannot be expressed. JP-A-56
-106244 discloses that an amino compound is added to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

US Pat. No. 4,998,604, and US
No. 4,994,365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and the high contrast and the required Dma are required under practical development processing conditions.
Getting x is difficult.

In order to obtain a super-high contrast image using a stable developing solution having a pH of less than 11.0, various investigations have been conducted to increase the reactivity of the hydrazine nucleating agent and further promote the nucleation of a specific quaternary onium salt. It has been found that a super-high contrast image can be obtained by using the agent together. In the case of an image forming system using a hydrazine derivative, the photographic performance changes greatly with changes in the developer composition, and particularly the photographic performance changes with respect to the pH of the developer. It has been found that introduction of an electron-withdrawing group into the acyl portion of the hydrazine nucleating agent reduces the pH dependence of the developer, but it is still insufficient. Nucleating agents with electron-withdrawing groups in the acyl part decompose hydrazine during production or during storage of sensitive materials due to their high reactivity, resulting in performance variations due to differences in production lots and deterioration of performance after long-term storage. There was a problem to be solved. That is, a photographic material which is stable during manufacture or during storage, exhibits super-high contrast photographic performance when processed with a developer having a pH of less than 11.0, and is stable against fluctuations in composition of the processing solution during processing. Was desired.

Further, in a nucleating hard-tone, high-tone negative image system using a hydrazine derivative, one of the points that is desired to be improved is to cause an undesired phenomenon called flat mesh unevenness, which is a problem in the photomechanical process. ing. Here, the flat halftone unevenness refers to unevenness caused by halftone dot images that are originally the same area due to differences in the size of individual halftone dots due to variations in the nip pressure of the developing roller during development processing. Therefore, since it greatly affects the halftone or highlight finish of printed matter, improvement is strongly desired.

It is known from JP-B-43-13166 that a photographic light-sensitive material contains a compound having a polyglycerol group, but there is no description of a hydrazine derivative. An image forming system using a polyalkylene oxide or its derivative and a hydrazine derivative is disclosed in JP-B-58-941.
No. 2, but there is no description of a compound having a polyglycerol group.

[0007]

SUMMARY OF THE INVENTION Accordingly, the first object of the present invention is to obtain a very hard negative image with a stable developing solution having a pH of less than 11.0, and to stabilize the photographic property against variations in the developing solution composition. Is to provide a black and white silver halide light-sensitive material. Secondly, it is to provide a silver halide black-and-white light-sensitive material in which flat mesh unevenness and processing unevenness are less likely to occur even when processed in an automatic developing machine having a deteriorated developing roller.

[0008]

These objects of the present invention are, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, said silver halide emulsion layer and / or At least one hydrazine derivative is contained in at least one of the other hydrophilic colloid layers, and at least one compound represented by the general formula (I), (II), (III) or (IV) is contained. Achieved by a characteristic silver halide photographic light-sensitive material. General formula (I)

[0009]

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In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, and X ₁ represents a divalent linking group. Y ₁ is a hydrogen atom, — (CH ₂ CH ₂ O) _i —H (i is 1
To 500) or an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50. General formula (II)

[0011]

[Chemical 6]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, X ₂ is an oxygen atom,
Or _{- (OCH 2 CH 2) J} -O - represents a group represented by (J is from 1 represents a numerical value of 500). Y ₁ is a hydrogen atom,-(CH ₂
CH ₂ O) _i -H _(i is 1 to represent the numerical value of 500) or anionic groups. t represents a numerical value of 0 or 1, and m
Represents a numerical value of 1 to 50. General formula (III)

[0013]

[Chemical 7]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, and X ₃ represents a divalent linking group. Y ₂ represents a hydrogen atom or an anionic group. t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7. General formula (IV)

[0015]

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In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, X ₄ is an oxygen atom,
—NR ₂ — (R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms) is represented. t is a numerical value of 0 or 1, and n is 3
Represents a numerical value of 7 to 7.

The compounds represented by the above general formulas (I) to (IV) of the present invention will be described in detail. In the general formulas (I) to (IV), the aliphatic group represented by R ₁ is a linear or branched C ₁ to C 40 unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, sec-butyl group, te
rt-butyl group, n-amyl group, tert-amyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,
1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2- Decyltetradecyl group, tricosyl group and the like), linear or branched C 1 to C 40 substituted alkyl group (substituents are alkoxyl group, aryl group, halogen atom, carboxylic ester group, carbonamido group, carbamoyl group, Oxycarbonyl group, phosphoric acid ester group, etc.) (for example, benzyl group, β-phenethyl group, 2-methoxyethyl group, 4-
Phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-
Phenyl octadecyl group, heptadecyl fluorooctyl group, 12- (p-chlorophenyl) dodecyl group, 2-
(Diphenyl phosphate) ethyl group, etc., a straight-chain or branched C 2 -C 40 unsubstituted alkenyl group (for example, vinyl group, allyl group, 3-butenyl group, 2-methyl-2-butenyl group, 4- Pentenyl group, 3-pentenyl group, 3-
Methyl-3-pentenyl group, 5-hexenyl group, 4-hexenyl group, 3-hexenyl group, 2-hexenyl group, 7
-Octenyl group, 9-decenyl group, oleyl group, linoleyl group, linolenyl group, etc.), linear or branched carbon number 2
To 40 substituted alkenyl groups (eg, 2-phenylvinyl group, 4-acetyl-2-butenyl group, 13-methoxy-9-octadecenyl group, 9,10-dibromo-1).
2-octadecenyl group, etc.), straight or branched carbon number 2
To 40 unsubstituted alkynyl groups (eg, acetylene group, propargyl group, 3-butynyl group, 4-pentynyl group, 5-hexynyl group, 4-hexynyl group, 3-hexynyl group, 2-hexynyl group, etc.), straight chain Alternatively, a branched alkynyl group having 2 to 40 carbon atoms (such as an alkoxyl group and an aryl group as a substituent) (eg, 2-phenylacetylene group, 3-phenylpropargyl group, etc.) and the like are preferable.

Among these, straight chain, cyclic or branched unsubstituted alkyl groups having 6 to 24 carbon atoms (for example, n-
Hexyl group, cyclohexyl group, n-heptyl group, n-
Octyl group, 2-ethylhexyl group, n-nonyl group,
1,1,3-trimethylhexyl group, n-decyl group, n
-Dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetradecyl group, etc.), excluding the carbon number of the substituent A straight-chain, cyclic or branched substituted alkyl group having 6 to 24 carbon atoms (eg, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, heptadecylfluorooctyl group, 12- (p -Chlorophenyl) dodecyl group, 4-tert-butylcyclohexyl group, etc.), a straight-chain, cyclic or branched unsubstituted alkenyl group having 6 to 24 carbon atoms (for example, 5-hexenyl group, 3-hexenyl group, 3-cyclo Hexenyl group, 7-octenyl group, 9-decenyl group, oleyl group, linoleyl group, linolenyl group, etc.), carbon A straight chain, cyclic or branched substituted alkenyl group of the formulas 6 to 24 (eg, 9,10-dibromo-12-octadecenyl group etc.) is particularly preferable.

A is preferably an arylene group having 6 to 14 carbon atoms, and particularly preferably a phenylene group.

X ₁ is preferably a group represented by the following general formula.

[0021]

[Chemical 9]

In the formula, Y ₁ , Y ₂ and Y ₃ may be the same or different and are a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms and 6 to 4 carbon atoms.
Represents a substituted or unsubstituted arylene group of 0 (the substituents are the same as those shown in the definition of R ₁ ), the alkylene group is a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, O-as an arylene group such as a pentamethylene group, a hexamethylene group, a 1,4-cyclohexylene group, an octamethylene group, a decamethylene group, and a 2-methoxy-1,3-propylene group.
Phenylene group, m-phenylene group, p-phenylene group,
A 3-chloro-1,4-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group and the like are preferable. Of these, particularly preferred are ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,4-cyclohexylene group, octamethylene group, decamethylene group, m-phenylene group, p- It is a phenylene group.

J ₁ , J ₂ and J ₃ each represent a divalent binding unit which may be the same or different,
Single bond, -O-, -S-, -CO-, -COO-, -O
_{CO -, - CON (R 5} ) - (R 5 is a hydrogen atom, a carbon number 1
1 to 6 unsubstituted alkyl group or a substituted alkyl group having 1 to 6 carbon atoms excluding the carbon number of the substituent (the substituent is an aryl group, an alkoxyl group, a halogen atom or the like). ), -N (R ₅ ) CO- (R ₅ is the same as those shown above), -CON (R ₅ ) CO- (R ₅ is the same as those shown above), -N (R ₅ ). _{CON (R 6) - (R} 5, R 6
May be the same or different, and the above R
Same) to those defined _{5, - OCON (R 5)} - (R 5
Are the same as those shown above), -N (R ₅ ) COO- (R
₅ are the same as those shown _{above), - SO 2 -, -} SO 2
N (R ₅ )-(R ₅ is the same as the above), -N
(R ₅ ) SO ₂ — (R ₅ is the same as above), −
N (COR ₅ ) − (R ₅ is the same as the above), −
OP (= O) (OR ₁ ) O- (R ₁ is the same as defined above) and the like are preferable. Among these, single bond, -O
-, -S-, -CO-, -COO-, -OCO-, -C
ON (R ₅ )-(R ₅ is a hydrogen atom, a methyl group, an ethyl group,
Represents a propyl group. ), —N (R ₅ ) CO— (R ₅ is the same as those shown above), —SO ₂ N (R ₅ ) — (R ₅ is the same as those shown above), —N (R ₅ ) SO ₂ — (R ₅ is the same as the above) and the like are particularly preferable.

P, q and r are each independently an integer of 0 to 5. Preferably, p, q, and r are each independently an integer value of 0 to 3, and it is particularly preferable that p, q, and r are each independently an integer value of 0 or 1. s is an integer value of 1 to 10, preferably 1 to 5, and particularly preferably 1 to 3. a
And b are each independently an integer value of 0 to 50. Of these, a and b are independently 0 to 2
It is preferable to take an integer value of 0, and a and b are 0 to 1
The case of taking an integer value of 0 is particularly preferable.

Particularly preferred as X ₁ is an oxygen atom or a group represented by-(OCH ₂ CH ₂ ) _j --O--. In the formula, j preferably takes a value of 1 to 50,
A value of 3 to 20 is particularly preferable.

X ₂ is preferably an oxygen atom or-(O
CH ₂ CH ₂ ) _j —O— is a group (j is a value of 1 to 50), and an oxygen atom or a group represented by — (OCH ₂ CH ₂ ) _j —O— (j is Three
To 20).

X ₃ is preferably a group represented by the following general formula.

[0028]

[Chemical 10]

In the formula, Y ₁ , Y ₂ , Y ₃ , J ₁ , J ₂ ,
J ₃ , p, q, r, s, a, and b are the same as defined in X ₁ above. X ₃ is preferably an oxygen atom or —NR ₂ — (R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms), particularly preferably an oxygen atom or —NH.
_{-, - N (CH 3)} - it is.

X ₄ is preferably an oxygen atom, --NH--,-.
N (CH ₃ )-and particularly preferred is -NH-.

In the formula, glycidyl represents a repeating unit obtained by ring-opening polymerization of glycidol, and is specifically a group represented by the following structure.

[0032]

[Chemical 11]

Y ₁ is a hydrogen atom,-(CH ₂ CH ₂ O) _i
-H (i represents a value of 1 to 500, preferably 3 to 100, particularly preferably 5 to 50),
Or represents an anionic group. Preferred anionic groups _{-COOM, -SO 3 M, -OSO 3} M, -PO
(OM) ₂ and -OPO (OM) ₂ (M represents a counter cation, preferably an alkali metal ion or an ammonium ion), particularly preferably -SO ₃ M,
It is a -OSO ₃ M. Particularly preferred as Y ₁ is a hydrogen atom, —SO ₃ Na, or —SO ₃ NH ₄ .

Y ₂ represents a hydrogen atom or an anionic group, preferably a hydrogen atom, --OSO ₃ M, --OPO (O
M) ₂ (M is the same as defined for Y ₁ above), and particularly preferably a hydrogen atom.

L represents 0 or 1, and is preferably 1. m represents a value of 1 to 50, preferably 2 to 30, particularly preferably 3 to 15. n is 3
Represents a numerical value of 1 to 7, preferably 4 to 6, and particularly preferably 4 to 5.

Specific examples of preferable surface-active compounds used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

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[0040]

[Chemical 15]

[0041]

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[0042]

[Chemical 17]

The compounds represented by the general formulas (I) to (IV) of the present invention can be synthesized by a general synthetic method. Detailed synthetic methods are described in JP-A-2-96643, International Patent 90/12782, European Patent 314,425 and the like.

The compounds represented by formulas (I) to (IV) of the present invention may be added anywhere in the emulsion layer or another hydrophilic colloid layer (preferably a layer provided on the emulsion layer side). It is preferably added to the uppermost layer on the emulsion layer side. The amount used is not particularly limited, but is generally 0.1 mg / m ^{2 to 1} g / m ² , preferably 0.2 mg / m ^{2 to} 300 mg / m ² , and particularly preferably 0.3 mg / m ² Used in the range of 150 mg / m ² .

The hydrazine derivative used in the present invention is
It is represented by the following general formula (N). General formula (N)

[0046]

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

[0048]

[Chemical 19]

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

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

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

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

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

R ₁ or R ₂ of the general formula (N) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (N) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in US Pat.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of a silver halide grain, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group, G
Is a —CO— group and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

In the present invention, a hydrazine derivative characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group is particularly preferably used.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means that an atom 2 to 5 selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is present between the nitrogen atom close to the anionic group of hydrazine and the anionic group.
It means that there is an intervening bond chain formed by individuals. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and contains at least an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (1) to (3). General formula (1)

[0059]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group that forms an intramolecular hydrogen bond.) General formula (2)

[0061]

[Chemical 21]

(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (3)

[0063]

[Chemical formula 22]

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

The general formulas (1) to (3) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

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

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

[0068] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethyl and phenylethynyl. The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include methoxy, isopropoxy and benzyloxy. The amino group has 0 to 16 carbon atoms, preferably 1 to 1 carbon atoms.
10 of them are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ = 2
At this time, R ³ is preferably an amino group or an alkoxy group.

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

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

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

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

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

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

In the general formulas (1) to (3), radicals from which hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (1) to (3), the general formulas (1) and (2) are preferable, and the general formula (1) is more preferable. Furthermore, in the general formulas (1) to (3), the following general formulas (4) to (6) are more preferable, and the general formula (4) is most preferable. General formula (4)

[0076]

[Chemical formula 23]

(In the formula, R ⁴ , X ⁴ and m ⁴ are synonymous with R ³ , X ³ and m ^{3 in the} general formula (3), respectively, and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ^{1 in} the general formula (1). ) General formula (5)

[0078]

[Chemical formula 24]

(In the formula, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in} formula (3), respectively, and L ⁵ and Y ⁵
Is synonymous with L ² and Y ^{2 in} the general formula (2). ) General formula (6)

[0080]

[Chemical 25]

(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ or Y in the general formula (3).
Synonymous with ³ . )

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

[0083]

[Chemical formula 26]

[0084]

[Chemical 27]

[0085]

[Chemical 28]

[0086]

[Chemical 29]

[0087]

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[0088]

[Chemical 31]

[0089]

Embedded image

[0090]

[Chemical 33]

[0091]

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[0092]

Embedded image

[0093]

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[0094]

Embedded image

[0095]

[Chemical 38]

[0096]

[Chemical Formula 39]

[0097]

[Chemical 40]

[0098]

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[0099]

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[0100]

[Chemical 43]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, and particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method. Further, as described in JP-A-2-948, it can be used by being contained in fine polymer particles.

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

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[0106]

[Chemical 44]

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

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide, silver iodobromide. However, silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol% or less. The shape of the silver halide grains may be any of a cube, a tetradecahedron, an octahedron, an irregular shape and a plate shape, but a cube is preferable. The average grain size of silver halide is from 0.05 μm
0.7 μm is preferable, but more preferably 0.08 to
It is 0.5 μm, and the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less, and a narrow particle size distribution is preferable. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is a Chimie et Physi by P. Glafkides.
que Photographique (published by Paul Montel, 1967
), GFDufin Photographic Emulsion Chemistry
(The Forcal Press, 1966), VL Zelikman e
Making and Coating Photographic Emulsion by t al
(Published by The Focal Press, 1964) and the like.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, 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 preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
As described in No. 0 and No. 52-16364,
A method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,4
It is preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-45-58-158124, and to grow it quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. Preferably. This content is preferably in the range of 1 × 10 ⁻⁹ to 4 × 10 ⁻⁴ mol, and more preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol, per mol of silver. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545 and JP-A-4-167453.
No. 76534, No. 6-110146, and Japanese Patent Application No. 4-68.
As described in No. 305, etc., it may be contained in the particles having a distribution.

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

The addition amount of these rhodium compounds is preferably in the range of 1 × 10 ^-8 mol to 1 × 10 ^-4 mol, and particularly preferably 5 × 10 ^-8 mol to 8 × 1 per mol of silver halide.
It is 0 ^-5 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and JP-A-1.
-2859451, 2-20852, 2-208
It is added in the form of a water-soluble complex salt described in No. 55, etc. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands and thionitrosyl ligands. 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 (Os (NO) (CN) ₅ ) ^-2 (OsCl ₆ ) ^-3 (OsCl ₅ (NO)) ^-2 (Os (O) ₂ (CN) ₄ ) ^-4 (Os (NS) Br ₅ ) ^-2 (Os (CN)) ₆ ^-4

The addition amount of these compounds is 1
The range of 1 × 10 ⁻⁹ mol to 4 × 10 ⁻⁴ mol is preferable, and the range of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol is particularly preferable. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. . To incorporate these compounds into the silver halide grains by adding them during silver halide grain formation, a metal complex powder or NaC is used.
1, a method in which an aqueous solution dissolved together with KCl is added to a water-soluble salt or a water-soluble halide solution during grain formation, or when a silver salt and a halide solution are simultaneously mixed, a third solution is added. There are a method of preparing silver halide grains by a three-liquid simultaneous mixing method, a method of charging a necessary amount of an aqueous solution of a metal complex into a reaction vessel during grain formation, and the like. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium and hexacyanoiridium.
These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, 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 iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

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

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

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, thiazoles, rhodanins and the like can be used. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The addition amount of the sulfur sensitizer changes under various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 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 unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
No. 3489, Japanese Patent Application Nos. 2-130976 and 2-229.
The compounds described in No. 300, No. 3-121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, 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, J. Chem. Soc. Chem. Commun.,
635 (1980), 1102 (1979), 645 (1979), J. Chem. Soc.
Perkin.Trans., 1,2191 (1980), edited by S. Patai, The Chemi
stry of Organic Serenium and Tellurium Compounds, V
The compounds described in ol1 (1986) and Vol2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use molar amounts. 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. It is 85 ° C.

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

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

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

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

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, further, JP-A Nos. 1-112235, 2-124560, 3-79928, 5-11389, Japanese Patent Application Nos. 6-103272 and 3 -41 1064 spectral sensitizing dye. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538 Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12, lower left column, and EP452772A. 12) Redox compounds Compounds represented by the general formula (I) of JP-A No. 2-301743 (particularly compound examples 1 to 50), and compounds described in JP-A 3-174143, pages 3 to 20 Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, compounds described in Japanese Patent Application No. 3-69466 and JP-A No. 4-278939. 13) Organic desensitizers Compounds described in Japanese Patent Publication No. 3-76450, Japanese Patent Application Laid-Open No. 63-64039, Japanese Patent Application No. 6-117454, or the like or the description thereof.

The developer used in the development processing of the light-sensitive material according to the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any known method can be used for the development processing of the present invention, and a known development processing solution can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable that the developing agent contains dihydroxybenzenes or an ascorbic acid derivative. Further, in view of developing ability, dihydroxybenzenes and 1-phenyl-3- Combination of pyrazolidones, combination of dihydroxybenzenes and p-aminophenols, combination of ascorbic acid derivative and 1-phenyl-3-pyrazolidones, or ascorbic acid derivative and p-
A combination of aminophenols is preferred.

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

Examples of the preservative 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 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly 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.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole and its derivatives; mercapto compounds, indazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black spots.
pper) May be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6
-Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4
-Thiadiazol-2-yl) thio] butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. it can. The amount of these antifoggants is usually 0.01 to 10 mmol per liter of developer.
And more preferably 0.1 to 2 mmol.

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

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (197)
Compounds described in May 9). Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

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

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

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid and adipic acid, and inorganic buffers such as boric acid, phosphate and sulfite. Agents can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH rise of the fixing agent due to the carry-in of the developing solution,
1.0 mol / liter, more preferably 0.02 to 0.
Use about 6 mol / liter. The pH of the fixer is 4.0
6.5 is preferable, and the range of 4.5 to 6.0 is particularly preferable. Further, as a dye elution accelerator, JP-A-64-
The compounds described in No. 4739 can also be used.

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

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, addition of various oxidizing agents and filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents can also be used in this stabilizing bath. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time is 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be powdered or solidified. As the method, known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533 and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Instead of the water washing step, four stable steps may be used.

[0142]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited to these examples. Example 1 <Preparation of silver halide light-sensitive material> Emulsion preparation [Emulsion A] 1 part Water 750 ml Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium thiosulfonate 10 mg 2 parts Water 300 ml Silver nitrate 150 g 3 liquid Water 300 ml Sodium chloride 38 g Potassium bromide 32 g K ₃ IrCl ₆ 0.25 mg K ₂ Rh (H ₂ O) Cl ₅ 0.07 mg One liquid kept at 38 ° C., pH 4.5 To 90% of each of the second and third liquids was added simultaneously with stirring for 20 minutes to form 0.19 μm core particles. Subsequently, the following 4 liquids and 5 liquids were added over 8 minutes, and the remaining 10% amounts of 2 liquids and 3 liquids were added over 2 minutes to obtain a silver chloride content of 70 mol% with an average particle size of 0.22 μm.
To obtain silver chlorobromide grains. 4-liquid water 100 ml Silver nitrate 50 g 5-liquid water 100 ml Sodium chloride 14 g Potassium bromide 11 g

Then, 1 × 10 ^-3 mol of KI solution was added to each emulsion for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added per mol of silver, and benzenethio was added per mol of silver. 7 mg sodium sulfonate and 2 mg benzenesulfinic acid
PH was adjusted to 5.7 and pAg 7.5, and silver 1 was added.
1 mg / mol of sodium thiosulfate and compound (CS-
A) and 5 mg of chloroauric acid were added and chemically sensitized at 55 ° C. for optimum sensitivity. Then, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained particles have an average particle size of 0.
The silver iodochlorobromide cubic grains had a size of 22 μm and a silver chloride content of 70 mol%. (Variation coefficient 10%)

[0144]

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<Preparation of coating sample> On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, a UL layer, an EM layer, and a support layer were sequentially formed from the support side.
A sample was prepared by coating so as to have a PC layer and an OC layer. The preparation method and coating amount of each layer are shown below. As a (UL) UL layer, 0.5 g / m ^{2 of} gelatin, 150 mg / m ² of a dispersion of polyethyl acrylate, and 5 mg / m ^{2 of the following} dye [a] were applied.

(EM) The above emulsion contains (S
-1) and (S-2) sensitizing dyes were added in an amount of 5 × 10 ^-4 mol, and further, 5 mg of KBr, 3 × 10 ^-4 , per mol of silver.
Molar mercapto compound represented by the following (a), 4 × 1
0 ⁻⁴ mol of the mercapto compound represented by (b), 4 × 1
0 ⁻⁴ mol of the triazine compound represented by (c), 2 × 1
0 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added, and 1 × 10 ⁻⁴ mol of the hydrazine nucleating agent shown in Table 1 was added,
4 × 10 ⁻⁴ mol of the following compound A-1 as a nucleation accelerator,
4 × 10 ⁻⁴ mol of A-2 was added. Further, hydroquinone 100 mg / m ² , N-oleyl-N-methyltaurine sodium salt 20 mg / m ² , dodecylbenzenesulfonic acid sodium salt 20 mg / m ² , and the compound of (d) 15 mg / m ² .
200 m ² of colloidal silica with an average particle size of 0.02 μm
mg / m ² was added so as to be applied, and the water-soluble latex shown in (e) was 200 mg / m ² , the dispersion of polyethyl acrylate was 200 mg / m ² , methyl acrylate and 2-acrylamido-2-methylpropane. 200 mg / l of latex copolymer of sodium sulfonate and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7)
m ² , and 1,3-divinylsulfonyl-as a hardening agent
200 mg / m ² of 2-propanol was added. PH of solution
Was adjusted to 5.5 with acetic acid. They were coated such that the coated silver amount was 3.5 g / m ² and gelatin was 1.5 g / m ² .

(PC) Gelatin 0.5 g / m ² , polyethyl acrylate dispersion 250 mg / m ² , sodium ethylsulfonate 5 mg / m ² , 1,5-dihydroxy-2-
Benzaldoxime was applied at 10 mg / m ² . (OC) gelatin 0.3 g / m ² , average particle size about 3.
An amorphous SiO ₂ matting agent 40 mg / m ² of 5 [mu] m, an average particle diameter of the colloidal silica 100 mg / m ² of 0.02 [mu] m, Methanol Silica 100 mg / m ^2, polyacrylamides 100
mg / m ² , silicone oil 20 mg / m ² and a compound represented by (f) 30 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (g) as a coating aid and dodecylbenzene sulfone. 50 mg / m ² of sodium acid was applied.
Further, the compounds represented by the general formulas (I) to (IV) of the present invention and the comparative compounds (1) and (2) were added as shown in Table 1.

[0148]

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[0149]

[Chemical 47]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Methyl acrylate, 2-acrylamido-2-methyl propanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7) 200 mg / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound (h) 110 mg / m ²

[0151]

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SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² Mixture of dye, dye [b], dye [c], dye [d] Dye [b] 100 mg / m ² dye [c] 30 mg / m ² dye [d] 60 mg / m ²

[0153]

[Chemical 49]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfone Sodium acid salt 15 mg / m ² Sodium acetate 40 mg / m ²

<Exposure and development> (1) Evaluation of photographic performance The above sample was exposed to xenon flash light with an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 488 nm, and Fuji Film Co., Ltd. Company-made FG
Using a -680AG automatic processor, development (30 ° C, 30 seconds), fixing, washing with water and drying were performed. As the developing solution and the fixing solution, the developing solution and the fixing solution having the following compositions were used.

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

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

The sensitivity S _1.5 is represented by the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the higher the value, the higher the sensitivity. As an index (γ) representing the contrast of the image, a point of fog + density 0.3 to a point of fog + density 3.0 of the characteristic curve was connected by a straight line, and the slope of this straight line was expressed as a γ value. That is, γ = (3.0-0.3) / [log
(Exposure amount that gives a density of 3.0) -log (exposure amount that gives a density of 0.3)], and the larger the γ value, the harder the photographic characteristics.

(2) Evaluation of Dependence on Developer Composition The pH was measured by adding potassium hydroxide or acetic acid to the above developer A.
Was adjusted to 10.75 or 10.15 to prepare Developers B and C, and the same evaluation as in (1) was performed. Developer A
_{ΔS ba} (S _b1.5 −) between the sensitivity (S _a1.5 ) in the case of using the developer and the sensitivity (S _b1.5 ) in the case of using the developing solution B.
S _a1.5 ), and similarly, the difference in sensitivity when developers A and C (S _c1.5 ) are used is _{ΔS ca} (S _c1.5 −S _a1.5 ).
In each case, the smaller the difference in sensitivity, the more stable the photographic properties are with respect to the pH fluctuation of the developer.

(3) Evaluation of flat screen unevenness [0160] A flat screen having a screen% of 93% was exposed at 500 lines / inch by using Magnascan M-656 (manufactured by Crossfield) on the above sample, and the sample was placed in a developing rack. Roll each roller to 0.
Development was carried out with an FG-680A automatic developing machine decentered by 3 mm, and the level of flat mesh unevenness of the processed sample was evaluated.
“5” represents a good level with no flat mesh unevenness.
"1" represents a quality in which the occurrence of flat mesh unevenness is extremely bad.
“3” is the limit level at which the occurrence of flat mesh unevenness can be substantially allowed.

[0161]

[Table 1]

As can be seen from Table 1, compounds (w-9), (w-17), (w-24) and (w-2) of the present invention.
7) and the sample to which (w-28) was added showed less flat mesh unevenness. Further, as a hydrazine compound (I-5
5), the sample to which (I-56) was added, the developer pH
The sensitivity is small and stable with respect to the fluctuation of.

Example 2 <Emulsion preparation> Emulsion A: pH containing sodium chloride kept at 40 ° C. and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate and sodium benzenethiosulfinate per mol of silver
Double jet of an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 3.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver in a 1.5% gelatin aqueous solution of 2.0 According to the method, half of the silver amount of the final particles was simultaneously added at a potential of 95 mV for 3 minutes and 30 seconds to prepare 0.12 μm of core particles.
After that, 10.5 × 10 ^-5 per mol of silver nitrate aqueous solution and silver
An aqueous sodium chloride solution containing moles of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added in the same manner as above for 7 minutes to give an average particle size of 0.15.
Cubic silver chloride cubic grains were prepared. (Coefficient of variation 12
%) Then 4-hydroxy-6-methyl-1,3,3a,
1.5 × 10 ^{−3 of} 7-tetrazaindene per 1 mol of silver
Mole was added. After this, after further washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added to adjust pH = 5.7 and pAg = 7.5, and further, per mol of silver, 2 × 10 ^-5 mol sodium thiosulfate and 4 × 10 ^-5 mol chloroauric acid were added,
After chemical sensitization by heating at 60 ° C. for 60 minutes, compound- (i) and phenoxyethanol as preservatives were each 50 mg per mol of silver, and 4-hydroxy-6-as stabilizer.
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 3 × 10 ⁻³ mol per mol of silver.
H = 5.7, pAg = 7.5, Rh = 7 × 10 ⁻⁵ mol /
Ag mol).

Emulsion B: The metal species doped in grain formation was K ₂ Ru (NO) Cl ₅ , and the doping amount was 6.0 × 10 ^-5 mol / Ag mol (dope specific core part: shell part =
It was prepared in exactly the same way as Emulsion A, except that it was 1: 3).

<Preparation of Coating Solution for Emulsion Layer and Coating Thereof> The following compounds were added to the emulsions shown in Table 2 and the coating amount of gelatin was 1.1 g / m ² on the following support including the subbing layer, coated silver. The silver halide emulsion layer was coated so that the amount was 2.5 g / m ² . 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² compound- (j) 10 mg / m ² compound -(K) 20 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² compound- (h) (hardener) 150 mg / M ² Further, the nucleation accelerator and the hydrazine derivative of the present invention were added so as to be coated as shown in Table 2.

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer.

<Preparation and Coating of Emulsion Protecting Lower Layer Coating Solution>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.7 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound- (i) 5 mg / m ² compound- (l) 10 mg / m ² compound- (m ) 20 mg / m ²

<Preparation of Emulsion Protection Upper Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.8 g / m ² . Further, the compounds represented by the general formulas (I) to (IV) of the present invention and the comparative compounds (1) and (2) were added as shown in Table 2. Gelatin (Ca ⁺⁺ content 2700ppm) 0.8 g / m ² Amorphous silica matting agent 40 mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700 m ² / g) Amorphous silica matting agent 10 mg / M ² (average particle diameter 2.5μ, pore diameter 170Å, surface area 300m ² / g) N-perfluorooctanesulfonyl-N-propylglycine sympototadium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound -(I) 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 77.
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 77 〃 Sodium dodecylbenzene sulfonate 10 〃 Dihexyl-α-sulfosuccinate sodium 40 〃 Sodium polystyrene sulfonate 9〃 Compound- (i) 7〃

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 2.92 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Dye [e] 140 〃 Dye [b] 140 〃 Dye [d] 40 〃 Dodecyl Sodium benzene sulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound- (n) 5 〃 N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following composition. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25〃 polystyrene fine particles (average particle size 3μ) 0.05〃 compound- (o) 0.20〃 colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 〃 Water added 100 〃 Further, 10% by weight KOH was added to adjust the pH = 6, and the coating solution was dried at 180 ° C for 2 minutes. And the dry film thickness is 0.
It was applied so as to be 9μ.

<Second Layer of Undercoat Layer> Gelatin 1 Methylcellulose 0.05 〃 Compound- (p) 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound- (i) 3.5 × 10 ^-3 〃 Acetic acid 0.2 〃 water was added 100 〃 This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness would be 0.1µ. Sample 1
15 was produced.

[0174]

Embedded image

[0175]

[Chemical 51]

[0176]

Embedded image

<Evaluation Method> (1) Evaluation of Photographic Properties The sample thus obtained was exposed through an optical wedge with an FPA-800FX printer manufactured by Fuji Photo Film Co., Ltd., and automatically developed by Fuji Photo Film Co., Ltd. Machine FG-68
It was treated with 0 AG and the developer A at 38 ° C. for 20 seconds, fixed, washed with water and dried. The fixer used was the above fixer A. The following items were evaluated for these samples. 1) Sensitivity (S _1.5 ); logarithmic value of exposure amount giving a density of 1.5 (the smaller the value, the higher the sensitivity) 2) γ; (1.5-0.1) / {log (giving a density of 1.5) Exposure dose) -log (exposure dose that gives a density of 0.1)}

(2) Evaluation of Dependence on Composition of Developer The evaluation was carried out in the same manner as in Example 1 except that the exposure and treatment were carried out in the same manner as the evaluation in (1).

(3) Evaluation of flat screen unevenness 50 was obtained by using Magnascan M-656 (manufactured by Crossfield) on LS-5500 manufactured by Fuji Photo Film Co., Ltd.
FG-6 is exposed with a flat screen with 0% / inch and a net% of 10%.
Development was performed with an 80AG automatic developing machine to prepare a document for evaluation. Through this document, the sample used in the evaluation (1) was exposed to the sample so that the dot percentage was 93%, and the rollers in the developing rack used in Example 1 were each exposed to 0.3%.
Development was carried out with an FG-680A automatic processor with eccentricity of mm, and the level of flat mesh unevenness of the processed sample was evaluated in the same manner as in Example 1.

[0180]

[Table 2]

As in Example 1, the compound of the present invention (w-
The samples to which (9), (w-23), (w-24), and (w-26) were added were good with less flat mesh unevenness. Further, the sample to which (I-61) was added as the hydrazine compound is stable with little sensitivity fluctuation with respect to the fluctuation of the developer pH.

Example 3 (Preparation of emulsion) Aqueous silver nitrate solution 2 in which 64 g of silver nitrate was dissolved
50 cc and 20 g of potassium bromide containing K ₂ Rh (H ₂ O) Cl ₅ corresponding to 1 × 10 ^-7 mol and 2 × 10 ^-7 mol of K ₃ IrCl ₆ per mol of silver in the whole emulsion. Halogen salt aqueous solution 25 in which 14 g of sodium chloride is dissolved
0 cc to a 2% gelatin aqueous solution containing sodium chloride (0.3%), 1,3-dimethyl-2-imidazolithione (0.002%) and citric acid (0.05%) at 38 ° C. with stirring. Nucleation was carried out for 12 minutes by the double jet method to obtain silver chlorobromide grains having an average grain size of 0.16 μm and a silver chloride content of 55 mol%. Subsequently, 300 cc of silver nitrate aqueous solution in which 106 g of silver nitrate is dissolved
Then, 300 cc of a halogen salt aqueous solution in which 28 g of potassium bromide and 26 g of sodium chloride were dissolved was added by the double jet method over 20 minutes to form particles.

Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, and the product was washed with water by a flocculation method according to a conventional method. Then, 40 g of gelatin was added per 1 mol of silver, pH was 5.9, pAg was
After adjusting to 7.5, 3 mg of sodium benzenethiosulfonate, 1 mg of sodium benzenesulfinate, 2 mg of sodium thiosulfate, 2 mg of the compound represented by the following structural formula (q) and 8 mg of chloroauric acid were added per mol of silver. , 60
Chemical sensitization was performed by heating at 70 ° C. for 70 minutes. Then, 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer
After adding 150 mg of tetrazaindene and 100 mg of proxel as a preservative, 400 mg of the dye represented by the following structural formula (S-3) was added, and the temperature was lowered after 10 minutes. The obtained grains have an average grain size of 0.22 μm and a silver chloride content of 6
It was 0 mol% of silver iodochlorobromide cubic grains. (Variation coefficient 10%)

(Preparation of emulsion layer coating solution) To this emulsion, silver 1
2 × 10 ⁻⁴ mol of a short-wave cyanine dye represented by the following structural formula (S-4) per mol, 5 × 10 ⁻³ mol of potassium bromide, 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercapto Tetrazole, 2 × 10 ⁻⁴ mol of the mercapto compound represented by the compound (b), 3 × 10 ⁻⁴ mol of the triazine compound represented by the compound (c), and 6 × 10 ⁻⁴ mol of the compound (A -2), the compound represented by 8 x 10 ^-4 mol of the compound (A-1), and the hydrazine compound are added as shown in Table 3, and further hydroquinone 100 mg / m ² , p is added. - sodium dodecylbenzenesulfonate 10 mg / m ^2, colloidal silica (manufactured by Nissan chemical Industries, Ltd. Snowtex C) 150 mg / m ^2, dispersion 500 mg / m ² of polyethyl acrylate, 1,2-bis (vinylsulfonyl acetamide) ethanone In addition, as it is 80 mg / m ² applied to an emulsion layer coating solution. The pH of the coating solution was adjusted to 5.6.

[0185]

Embedded image

[0186]

[Chemical 54]

(Preparation of Coating Solution for Lower Layer of Protective Layer and Coating Solution for Upper Layer) In a gelatin solution containing proxel as a preservative, the compound represented by the above (m) was added at 10 mg / m ² and the dye (e) was added.
100 mg / m ^{2 of} the compound represented by the formula, and 300 mg / m ² of the dispersion of polyethyl acrylate are added so as to be applied,
A lower layer liquid for the protective layer was prepared. Furthermore, in a gelatin solution containing proxel as a preservative, an average particle size of about 3.5 μm
Amorphous SiO ₂ matting agent of 50 mg / m ² , colloidal silica (Nissan Chemical's Snowtex C) 100 mg / m ² , liquid paraffin 30 mg / m ² , and fluorine represented by the following structural formula (γ) as a coating aid. A surfactant (5 mg / m ²⁾ and p-dodecylbenzenesulfonic acid sodium salt (30 mg / m ²⁾ were added so as to be applied, and further, the compound of the general formula (I) to
The compound represented by (IV) and the comparative compound (1) were added so as to be coated as shown in Table 3 to prepare a protective layer upper layer liquid.

[0188]

[Chemical 55]

These coating solutions were applied to a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides, and an emulsion layer (silver content 3.0 g / m ² , gelatin 1.
5 g / m ² ) as the lowermost layer, and the protective layer lower layer liquid (gelatin 0.5
g / m ² ) The protective layer upper layer liquid (gelatin 0.4 g / m ² ) was applied. The pH of the emulsion surface of the obtained sample was 5.8.

The back layer was coated according to the following formulation. (Back layer) Gelatin 1.5 g / m ² Surfactant p-Dodecylbenzenesulfonic acid sodium salt 30 mg / m ² Gelatin hardening agent 1,2-bis (vinylsulfonylacetamide) ethane 100 mg / m ² Dye Mixture of b), (f), (c) and (d) Dye (b) 50 mg / m ² dye (f) 100 mg / m ² dye (c) 30 mg / m ² dye (d) 50 mg / m ² Proxel 1 mg / m ²

[0191]

[Chemical 56]

(Back protective layer) Gelatin 1.5 g / m ² polymethylmethacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² p-dotecilbenzenesulfonic acid sodium salt 15 mg / m ² dihexyl-α-sulfosuccinate Nato sodium salt 15 mg / m ² Sodium acetate 50 mg / m ² Proxel 1 mg / m ²

<Evaluation Method> (1) Evaluation of Photographic Properties The sample thus obtained was exposed to tungsten light at 3200 ° K through an optical wedge, and processed and evaluated in the same manner as in Example 1.

(2) Evaluation of Dependence on Composition of Developer The evaluation was carried out in the same manner as in Example 1 except that the exposure was carried out in the same manner as the evaluation in (1).

(3) Evaluation of flat mesh unevenness Dainippon Screen Co., Ltd. plate-making camera Fine Zoom C
The evaluation sample was exposed by setting the original used in Example 2 on a -880 (camera integrated type self-developing machine LD-281Q processing) so that the stretching magnification was equal, and then irradiating a halogen lamp. . At this time, 10% of the flat net is 93
The exposure was carried out so that it became%, and the same treatment and evaluation as in Example 1 were carried out.

[0196]

[Table 3]

As can be seen from Table 3, the samples of the present invention are excellent in that they do not cause unevenness in the flat screen. Further, the sample to which (I-55) was added as a hydrazine compound has a small sensitivity variation with respect to the variation of the developer pH and is stable.

Example 4 Sample of Example 1 except that the sensitizing dye is (S-4)
Samples were prepared in the same manner as Nos. 8, 10, and 20. The interference filter has a peak at 633 nm in the evaluation of photographic performance, and SG-60 in the evaluation of the flat screen unevenness.
Evaluation was performed in the same manner as in Example 1 except that 8 (manufactured by Dainippon Screen Co., Ltd.) was used. The obtained results are exactly the same as in Example 1, and it was found that the present invention is effective also in this case.

[0199]

[Chemical 57]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 5, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

Embedded image In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, and X ₁ represents a divalent linking group. Y
₁ is a hydrogen atom, - to _{(CH 2 CH 2 O) i} -H (i is 1 to 500
Represents the numerical value of) or represents an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50. General formula (III)

Embedded image In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, and X ₃ represents a divalent linking group. Y
₂ represents a hydrogen atom or an anionic group. t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7.

Embedded image In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, X ₂ is an oxygen atom, or — (OCH ₂ C
It represents a (group J is represented by from 1 represents a numerical value of _{500) - H 2) J -O} . Y ₁ is a hydrogen atom,-(CH ₂ CH ₂ O) _i -H
(i represents a numerical value of 1 to 500) or an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50.

[Chemical 4] In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, X ₄ is an oxygen atom, —NR ₂ —
(R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[0008]

These objects of the present invention are, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, said silver halide emulsion layer and / or A silver halide photographic light-sensitive material comprising at least one hydrazine derivative and at least one compound represented by the general formula (I) or (III) in at least one other hydrophilic colloid layer. Achieved by the material. General formula (I)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, and X ₁ represents a divalent linking group. Y ₁ is a hydrogen atom, — (CH ₂ CH ₂ O) _i —H (i is 1
To 500) or an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

[Chemical 6]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, and X ₃ represents a divalent linking group. Y ₂ represents a hydrogen atom or an anionic group. t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7. Among the compounds of the general formula (I), the compounds of the following general formula (II) are preferable.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013]

[Chemical 7]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, X ₂ is an oxygen atom,
Or _{- (OCH 2 CH 2) J} -O - represents a group represented by (J is from 1 represents a numerical value of 500). Y ₁ is a hydrogen atom,-(CH ₂
CH ₂ O) _i -H _(i is 1 to represent the numerical value of 500) or anionic groups. t represents a numerical value of 0 or 1, and m
Represents a numerical value of 1 to 50. Among the compounds of the general formula (III), the compound of the following general formula (IV) is preferable.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

[0015]

Embedded image

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A represents an arylene group, X ₄ is an oxygen atom,
—NR ₂ — (R ₂ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms) is represented. t is a numerical value of 0 or 1, and n is 3
Represents a numerical value of 7 to 7.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

[0106]

[Chemical 44]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0162

[Correction method] Change

[Correction content]

As can be seen from Table 1, compounds (w-9), (w-17), (w-24) and (w-2) of the present invention.
7) and the sample to which (w-28) was added showed less flat mesh unevenness. Also, as a hydrazine compound (N-5
5), the sample to which (N-56) was added, the developer pH
The sensitivity is small and stable with respect to the fluctuation of.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0181

[Correction method] Change

[Correction content]

As in Example 1, the compound of the present invention (w-
The samples to which (9), (w-23), (w-24), and (w-26) were added were good with less flat mesh unevenness. Further, the sample to which (N-61) was added as a hydrazine compound is stable with a small sensitivity variation with respect to the variation of the developer pH.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0197

[Correction method] Change

[Correction content]

As can be seen from Table 3, the samples of the present invention are excellent in that they do not cause unevenness in the flat screen. Further, the sample to which (N-55) was added as the hydrazine compound is stable with little sensitivity variation with respect to the variation of the developer pH.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0198

[Correction method] Change

[Correction content]

Example 4 Sample of Example 1 except that the sensitizing dye is (S-5)
Samples were prepared in the same manner as Nos. 8, 10, and 20. The interference filter has a peak at 633 nm in the evaluation of photographic performance, and SG-60 in the evaluation of the flat screen unevenness.
Evaluation was performed in the same manner as in Example 1 except that 8 (manufactured by Dainippon Screen Co., Ltd.) was used. The obtained results are exactly the same as in Example 1, and it was found that the present invention is effective also in this case.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0199

[Correction method] Change

[Correction content]

[0199]

[Chemical 57]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one hydrazine derivative is contained in at least one of the silver halide emulsion layer and / or other hydrophilic colloid layer, and the following general formulas (I), (II) and (III)
Alternatively, a silver halide photographic light-sensitive material containing at least one compound represented by (IV). General formula (I) In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, and X ₁ represents a divalent linking group. Y
₁ is a hydrogen atom, - to _{(CH 2 CH 2 O) i} -H (i is 1 to 500
Represents the numerical value of) or represents an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50. General formula (II) In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, X ₂ is an oxygen atom, or — (OCH ₂ C
It represents a (group J is represented by from 1 represents a numerical value of _{500) - H 2) J -O} . Y ₁ is a hydrogen atom,-(CH ₂ CH ₂ O) _i -H
(i represents a numerical value of 1 to 500) or an anionic group. t represents a numerical value of 0 or 1, and m represents a numerical value of 1 to 50. General formula (III): In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, and X ₃ represents a divalent linking group. Y
₂ represents a hydrogen atom or an anionic group. t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7. General formula (IV): In the formula, R ₁ represents an aliphatic group having 1 to 40 carbon atoms. A
Represents an arylene group, X ₄ is an oxygen atom, —NR ₂ —
(R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). t represents a numerical value of 0 or 1, and n represents a numerical value of 3 to 7. 2. The hydrazine derivative is at least one kind of a hydrazine derivative having a group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine or an anionic group not forming an intramolecular hydrogen bond in the vicinity of the hydrazine group. The silver halide photographic light-sensitive material according to claim 1.