JPH08292513A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To reduce deterioration of Dmax due to pinholes and to prevent abrasion of the surface by incorporating a hydrazine derivative in an emulsion layer and incorporating a matting agent comprising particles smaller in diameter than the thickness of the protective layer and agglomerated with each other into the protective layer. CONSTITUTION: This photosensitive material is provided on a support with a photosensitive silver halide emulsion layer and its protective layer and this emulsion layer and/or another hydrophilic colloidal layer contains a hydrazine derivative, and the protective layer contains a matting agent comprising the primary particles agglomerated with each other each smaller than the thickness of this layer. This matting agent is made of particles of a polymer, such as an acrylic resin, or formed by coating the surfaces of inorganic particles with a polymer. The thickness of the protective layer is in the range of 0.1-10μm and it is preferred that the average diameter of the primary particles is in the range of 0.01-10μm and the average diameter of the agglomerated particles is in the range of 0.2-30μm. The hydrazine derivative is added, preferably, in an amount of 1×10<-6> -5×10<-2> mol/l of the silver halide.

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 suitable for producing a high contrast image, and in particular, a light-sensitive silver halide emulsion layer and a protective layer are arranged in this order on a support. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In general, a light-sensitive material has a coating layer using a hydrophilic colloid such as gelatin as a binder, so that it is easy to cause blocking particularly under high temperature and high humidity conditions. Inclusion of particles (matting agents) has been carried out. This blocking phenomenon means that when the photosensitive material is rolled into a roll, when the photosensitive material is stored, or during development processing, one surface of the photosensitive material comes into contact with an object that comes into contact therewith. . The roughening of the surface with a matting agent has the effect of preventing blocking as well as shortening the vacuuming time when image exposure is carried out in vacuum contact, imparting slipperiness and antistatic effect. It has become one of the important properties of the material.
In particular, in a photosensitive material for plate making, vacuum adhesion at the time of exposure is extremely important for producing a high-definition and high-quality image.

Recently, as a high-contrast image forming system having high definition and high image reproducibility, an image in which a silver halide light-sensitive material containing a hydrazine derivative as a nucleating agent is developed using a developing solution having a pH of about 10.5. A forming system was developed. In this image forming method, since an image having a high blackening density can be obtained, the required image density can be obtained even if the coating amount of the silver halide emulsion is smaller. This is also advantageous in that the coating thickness becomes thin and the rapid development processability and the reduction in dimensional change of the film due to temperature and humidity changes.

However, in a light-sensitive material containing a hydrazine nucleating agent, the coating amount of silver halide emulsion is 3.
It was found that pinholes due to the matting agent rapidly increased at 0 g / m ² or less. In the light-sensitive material using the hydrazine nucleating agent, the blackened density in the image area is remarkably lowered due to the white pinholes in the blackened area of the film after the development processing. This phenomenon varies depending on the type of matting agent, and relatively small pinholes are obtained when using a conventionally known inorganic amorphous matting agent such as silica particles or alumina particles, and it frequently occurs when spherical particles of organic polymer are used. A trend was recognized. However, when the inorganic particles are used, there is a problem that the coated surface becomes a polished surface, abrades other surfaces in contact, and powdery abrasion debris adheres to the photosensitive surface to cause noise.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-contrast silver halide photographic light-sensitive material containing a matting agent which causes little decrease in Dmax due to pinholes and which does not cause adverse effects such as surface abrasion. .

[0006]

The above object is to provide a silver halide light-sensitive material having at least a light-sensitive silver halide emulsion layer and a protective layer thereof on a support, the emulsion layer or another hydrophilic colloid layer. Contains a hydrazine derivative,
The problem is solved by a silver halide photographic light-sensitive material characterized in that the protective layer contains a matting agent composed of agglomerated particles in which a plurality of primary particles having a particle diameter smaller than the thickness of the protective layer are agglomerated.

Specific means of the present invention will be described in detail below. The matting agent of the present invention is formed of polymer particles or inorganic particles surface-coated with a polymer. The polymer used in the polymer matting agent of the present invention is selected from acrylic resins, vinyl chloride resins, vinyl acetate resins, styrene resins, vinylidene chloride resins, acetal resins, and fibrin resins.

Next, specific examples of the polymer used for the polymer matting agent will be given, but the present invention is not limited thereto. 1) Acrylic resin: polymethylmethacrylate, polyethylmethacrylate, polyn-propylmethacrylate, polyn-butylmethacrylate, polydimethylaminoethylmethacrylate, polymethylacrylate,
Polyethyl acrylate, polymethoxyethyl acrylate 2) Copolymer acrylic resin: Copolymerization of the resin monomers listed in 1) with vinyl chloride, vinyl acetate, vinylitene chloride, vinyl pyridine, styrene, acrylonitrile, acrylic acid, methacrylic acid. Polymerized resin 3) Vinyl chloride resin: Polyvinyl chloride, vinyl chloride and vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, maleic acid ester, copolymer resin with acrylonitrile 4) Polyvinyl acetate and its parts Saponification resin 5) Styrene resin: Copolymer resin of polystyrene, styrene and acrylonitol 6) Vinylidene chloride: Polyvinylidene chloride, Vinylidene chloride and acrylonitrile copolymer resin 7) Acetal resin: Polyvinyl formal, polyvinyl butyra 8) Fibrin resin: Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose nitrate Although only two-component copolymer resins have been exemplified, naturally, three-component or four-component copolymer resins may be used. Absent. The monomers to be combined can also be selected from the above examples.

Further, a bifunctional monomer or a trifunctional or more polyfunctional monomer may be copolymerized. Examples of bifunctional or polyfunctional monomers are ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth).
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trihydroxymethylethane triacrylate, 1,1,1-trishydroxymethylmethylethane triacrylate, 1,1, Mention may be made of 1-trishydroxymethylpropane triacrylate and divinylbenzene. A dispersion of these polymers is prepared by dissolving the polymer (A) in an organic solvent and mixing with water or an aqueous gelatin solution with vigorous stirring to disperse the polymer.
Alternatively, it can be prepared by (B) a method of polymerizing a monomer by emulsion polymerization, precipitation polymerization, or pearl polymerization while precipitating it into particles. Examples of the organic solvent include ethyl acetate, methylene chloride, ethylene dichloride, acetone, alcohol, chloroform, carbon tetrachloride, benzene, toluene, tetrahydrofuran, dichlorohexanone, dioxane, methyl ethyl ketone, o-chlorobenzene, and the like, which are good solvents for the polymer. Selected from solvents. After dispersion, it is desirable to remove these organic solvents by heating or desolvation under reduced pressure. In the case of an organic solvent which is partially soluble in water, it can be removed by filtering with an ultrafiltration membrane.

The method for producing aggregated particles is as follows: i) A above
Or a method of heating and drying the powder of the primary particles produced by the method B under pressure to form large agglomerates, and then pulverizing with a pulverizer, ii) stabilizing the dispersion when producing the above primary particles There is a method in which the primary particles are easily aggregated without using an agent, iii) a method in which an aggregating agent is added to the produced primary particle dispersion liquid to aggregate the particles.

These methods are generally well known,
Agglomerated matting agent particles produced according to this method are commercially available. GR-5P (trade name of Soken Chemical Industry Co., Ltd.)
Is a polymethylmethacrylate resin whose primary particles are 0.
At 1 μm, the average particle diameter of the aggregate is 4.0 μm.

In the present invention, the average particle size of the primary particles is 0.
It is in the range of 0.1 to 5 μm, preferably 0.1 to 2 μm. The average particles of the obtained aggregated particles are 0.5 to 30 μm.
m, preferably in the range of 1.0 to 15 μm. Further, it is desirable that the aggregated particles of the present invention have a particle size distribution as close to monodisperse as possible.

The primary particles of the matting agent of the present invention have a particle size smaller than the film thickness of the protective layer of the silver halide photographic light-sensitive material used. Usually 1/200 to 1 / of the protective layer thickness
The particle size is 0.9, especially 1/100 to 1 / 0.1.
The particle size of the agglomerated particles is 0.5 to 20 times the thickness of the protective layer.
It is preferably double, especially 1 to 10 times.

As the inorganic particles surface-coated with a polymer, silica, titanium white, calcium carbonate, or barium sulfate is used as a hydrophilic polymer (eg gelatin, P
VA, polyacrylamide), or those surface-coated with the above-mentioned acrylic resin.

The matting agent used in the present invention is used in the protective layer. When the protective layer comprises two or more layers, either layer may be used, but the uppermost layer is particularly preferable. The matting agent of the present invention is 5 to 600 mg, particularly 10 to 4 mg per 1 m ² of the support.
It is 00 mg. The thickness of the protective layer is usually 0.1 μm to 10 μm.
m, especially 0.2 μm to 5 μm.

The hydrazine derivative used in the present invention is
The compound represented by the following general formula (I) is preferable. In formula (I) R ₁ -N (A ₁ ) -N (A ₂ ) -G ₁ -R ₂ formula, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₂ is hydrogen. It is an atom or a blocking group. G ₁
Is -CO- group, -SO ₂ - group, -SO- group, -CO-C
O- group, thiocarbonyl group, iminomethylene group or-
_{P (O) (R 3)} - group, represents, R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

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, a substituted or 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, R ₂
May be different from. In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly 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 (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aliphatic group or aromatic group of R ₁ may be substituted, and a typical substituent is, for example, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group-containing group, pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group, sulfonamide group, ureido group 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 Group, acyl group,
Alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group,
Examples thereof include a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. Chain, branched or cyclic alkyl group (preferably having 1 carbon atom)
To 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl group 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).

The blocking group for R ₂ is an alkyl group,
There are aryl groups, unsaturated heterocyclic groups, alkoxy groups, aryloxy groups, amino groups, or hydrazino groups.

In formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
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,
Alkyl group (for example, methyl group, trifluoromethyl group, 2-carboxy-tetrafluoroethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, methyl group substituted with a pyridinium group, Etc.), aralkyl groups (eg o
-Hydroxybenzyl group), an aryl group (for example,
Phenyl group, 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.
When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, methyl group) or an aralkyl group (eg,
An o-hydroxybenzyl group), an aryl group (eg, a phenyl group), a substituted amino group (eg, a dimethylamino group), etc. are preferable. G ₁ is -COC
In the case of the O-group, an alkoxy group, an aryloxy group and a substituted or unsubstituted amino group are preferable. As G in the general formula (I), a -CO- group and a -COCO- group are preferable, and -CO
-Groups are most preferred. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms For example, Japanese Patent Laid-Open No. 63-29
751 etc. are mentioned.

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferable examples thereof include those exemplified as the 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 (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. 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 (I) may be one in which a group for enhancing adsorption to the surface of the silver halide grain 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.

In the present invention, a particularly preferred hydrazine derivative is a group 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 silver halide grains, a group having a quaternary ammonium structure, or a phenyl group having an alkylthio group, G is -CO- group or -COCO- group, hydroxymethyl R ₂ is the electron withdrawing group or 2-position as a substituent alkyl group or a substituted aryl group (substituent Group), or a hydrazine derivative which is a substituted or unsubstituted amino group. Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

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

[0025]

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[0026]

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[0027]

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[0028]

[Chemical 4]

[0029]

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[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

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[0033]

[Chemical 9]

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, 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, dimethylsulfoxide, 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.

The silver halide photographic light-sensitive material of the present invention comprises a silver halide emulsion layer or at least one other hydrophilic colloid layer formed of an amine derivative, an onium salt, a disulfide derivative and a hydroxymethyl derivative. It is preferable to contain a nuclear promoter. These nucleation accelerators may be used alone or in combination of two or more.

As the amine derivative, for example, JP-A-60 is used.
-140,340, 62-50,829, 62
-222, 241, 62-250, 439, 6
2-280,733, 63-124,045, 63-133,145, 63-286,840,
JP-A-2-170,155 and 4-114,150
No. 3-206445, etc. can be mentioned. The amine derivative is more preferably JP-A-63-124,045 and JP-A-63-133,145.
No. 63-286,840, etc., or a compound having a group capable of adsorbing to silver halide, or JP-A-6-63.
It is a compound having 20 or more carbon atoms, which is described in, for example, No. 2-222,241. The onium salt is preferably an ammonium salt, a pyridinium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A Nos. 62-250,439 and 62-280,733.
And the compounds described in JP-A-6-242,534 and the like. Examples of preferable phosphonium salts include compounds described in JP-A-61-167,939, JP-A-62-280,733, and Japanese Patent Application No. 5-123,273. Examples of disulfide derivatives include, for example, JP-A-61-198,
The compound described in No. 147 can be mentioned. Examples of hydroxymethyl derivatives include, for example, US Pat.
3,956, 4,777,118, EP231.
Examples thereof include compounds described in JP-A No. 850 and JP-A No. 62-50,829, and more preferably a diarylmethanol derivative.

Specific examples of the nucleation accelerator are shown below.

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

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[0045]

[Chemical 15]

[0046]

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[0047]

[Chemical 17]

[0048]

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[0049]

[Chemical 19]

[0050]

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The optimum addition amount of these compounds varies depending on the kind thereof, but 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is desirable to use it in the range of 10 ⁻¹ mol to 1.0 × 10 mol. These compounds are dissolved in a suitable solvent (H ₂ O) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

The coated silver amount of the light-sensitive emulsion layer of the present invention is preferably as small as possible in order to facilitate rapid processing and reduce the amount of silver accumulated in the fixing solution. In the light-sensitive material using the nucleating agent of the present invention, the required blackening density can be obtained when the coated silver amount is 3.0 g / m ² or less.

The light-sensitive material of the present invention may contain a polymer latex in the silver halide emulsion layer and / or other hydrophilic colloid layer. By using the polymer latex, the coating amount of the hydrophilic colloid such as gelatin can be reduced, and the expansion and contraction of the film due to changes in temperature and humidity can be reduced. Polymer latex
It can be used by mixing 10% by weight to 130% by weight with respect to gelatin. As the polymer latex, various conventionally known latexes can be used.
Particularly preferred is a polymer latex having a repeating unit derived from an ethylenically unsaturated monomer having an active methylene group. Such a polymer latex is represented by the following general formula (V). In formula (V)-(C) _x- (A) _y- (B) _{z-, in the} formula, C represents a repeating unit derived from an ethylenically unsaturated monomer containing an active methylene group, and A represents C And the glass transition temperature of the homopolymer is 35 ° C.
The following represents a repeating unit derived from an ethylenically unsaturated monomer, and B represents a repeating unit derived from an ethylenically unsaturated monomer other than C and A.

X, y and z represent the weight percentage ratio of each component, x is 0.5 to 40, y is 60 to 99.5,
z takes a value of 0 to 50. Where x + y + z = 10
Represents 0.

Explaining in more detail, the ethylenically unsaturated monomer containing an active methylene group represented by C is represented by the following general formula.

[0056]

[Chemical 21]

In the formula, R ¹ represents a hydrogen atom, a carbon number of 1 to 4 (eg, methyl, ethyl, n-propyl, n-butyl) or a halogen atom (eg, chlorine atom, bromine atom), preferably hydrogen. Represents an atom, a methyl group, and a chlorine atom.
L represents a single bond or a divalent linking group, and is specifically represented by the following formula. _{^{- (L 1) m - (}} L 2) n - L 1 is ^{-CON (R 2) - (R} 2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms Represents), -COO-, -NHCO-, -OCO-,

[0058]

[Chemical formula 22]

(R ³ and R ⁴ each independently represent hydrogen, hydroxyl, halogen atom or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² is a link connecting L ¹ and X. Represents a group, m represents 0 or 1, and n represents 0 or 1. The linking group represented by L ² is specifically represented by the following general formula.

[0060] - ^{[X 1 - (J 1 -X 2} ) p - (J 2 -X 3) q - (J 3) r ] _s -

J ¹ , J ² and J ³ may be the same or different, and -CO-, -SO _2- , -CON (R ⁵ )-(R ⁵ is a hydrogen atom, an alkyl group (having 1 to 1 carbon atoms). 6), substituted alkyl group (having 1 carbon atom
~ 6), -SO ₂ N (R ⁵ )-(R ⁵ is as defined above), -N (R ⁵ ) -R ^6-
(R ⁵ is as defined above, R ⁶ is an alkylene group having 1 to about 4 carbon atoms), -N (R ⁵ ) -R ⁶ -N (R ⁷ )-(R ⁵ and R ⁶ are as defined above,
R ⁷ represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms) or a substituted alkyl group (having 1 to 6 carbon atoms). ), -O-, -S-,
-N (R ⁵ ) -CO-N (R ⁷ )-(R ⁵ and R ⁷ are as defined above), -N (R ⁵ ).
-SO ₂ -N (R ⁷ )-(R ⁵ and R ⁷ are as defined above), -COO-, -O
CO-, -N (R ⁵ ) CO _2- (R ⁵ is as defined above), -N (R ⁵ ) CO-
(R ⁵ is as defined above) and the like.

P, q, r and s represent 0 or 1.
X ¹ , X ² and X ³ may be the same or different from each other and represent an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or a phenylene group,
The alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene group such as benzylidene, and phenylene group such as p-phenylene, m-phenylene and methyl. There is phenylene etc.

X represents a monovalent group containing an active methylene group, and preferable specific examples thereof include R ⁸ -CO-CH ₂ -COO-, NC-CH _{2
^{-COO-, R 8 -CO-CH 2}} -CO-, R 8 -CO-CH 2 -CON (R 5) - , and the like. Where R ⁵ is the same as above and R ⁸
Is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl,
t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl etc.), a substituted or unsubstituted aryl group (eg phenyl, p-methylphenyl, p-methoxyphenyl,
o-chlorophenyl etc.), an alkoxy group (eg methoxy, ethoxy, methoxyethoxy, n-butoxy etc.),

Cycloalkyloxy groups (eg cyclohexyloxy), allyloxy (eg phenoxy, p-
Methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.), amino group, and substituted amino group (eg, methylamino, ethylamino, dimethylamino, butylamino, etc.).

Particularly preferred polymer latex having an active methylene group is one having a core / shell structure and having an active methylene group in the shell part. A detailed description of such a core / shell latex is described in Japanese Patent Application No. 7-3.
296.

Specific examples of the monomer having an active methylene group which gives the repeating unit constituting the shell in the latex of the present invention are shown below, but the present invention is not limited thereto.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamidoethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate

M-7 2-Cyanoacetoxyethyl Methacrylate M-8 2-Cyanoacetoxyethyl Acrylate M-9 N- (2-Cyanoacetoxyethyl) acrylamide M-10 2-Propionylacetoxyethyl Acrylate M-11 N- (2 -Propionylacetoxyethyl) methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide

M-13 Ethyl acryloyl acetate M-14 Acryloyl methyl acetate M-15 N-methacryloyloxymethyl acetoacetamide M-16 Ethyl methacryloyl acetoacetate M-17 N-allyl cyanoacetamide M-18 2-cyanoacetylethyl acrylate

M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloylpiperazine M-22 ethyl-α-acetate Acetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetamide M-24 p- (2-acetoacetoxy) ethylstyrene

The preferred examples of the compounds of the core / shell latex of the present invention are shown below, but the present invention is not limited thereto. The structures of the latex compounds below are described in the order of the core polymer structure, the shell polymer structure, and the core / shell ratio, and the copolymerization composition ratio and the core / shell ratio of each polymer are expressed as weight percentage ratios. .

P-1 to 12 core: styrene / butadiene copolymer (37/63) P-1 shell = styrene / M-1 (98/2) core / shell = 50/50 P-2 shell = styrene / M-1 (96/4) core / shell = 50/50 P-3 shell = styrene / M-1 (92/8) core / shell = 50/50 P-4 shell = styrene / M-1 (84 / 16) Core / Shell = 50/50 P-5 Shell = Styrene / M-1 (68/32) Core / Shell = 50/50 P-6 Shell = Styrene / M-1 (84/16) Core / Shell = 67/33 P-7 shell = styrene / M-1 (84/16) core / shell = 85/15 P-8 shell = n-butyl acrylate / M-1 (96/4) core / shell = 50/50 P-9 shell = n-butyl acrylate / M-1 (92/8) core / shell = 50/50 P-10 shell = n-butyl acrylate / M- 1 (84/16) core / shell = 50/50 P-11 shell = methyl acrylate / M-7 (84/16) core / shell = 50/50 P-12 shell = styrene / methyl acrylate / M-3 ( 21/63/16) Core / Shell = 50/50

P-13,14 core: styrene / butadiene copolymer (22/78) P-13 shell = styrene / M-2 (84/16) core / shell = 50/50 P-14 shell = n- Butyl acrylate / M-8 (84/16) core / shell = 50/50

P-15 to 20 core: polybutadiene homopolymer (100) P-15 shell = styrene / M-1 (84/16) core / shell = 50/50 P-16 shell = ethyl acrylate / M-7 / Methacrylic acid (65/15/20) core / shell = 75/25 P-17 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-18 shell = n-butyl Acrylate / M-2 (84/16) core / shell = 50/50 P-19 shell = 2-ethylhexyl acrylate / M-24 (84/16) core / shell = 50/50 P-20 shell = n-butyl Acrylate / M-18 (84/16) core / shell = 50/50

P-21 to 23 Core: polyisoprene homopolymer (100) P-21 shell = styrene / acrylonitrile / M-1 (63/21/16) core / shell = 90/10 P-22 shell = methyl Methacrylate / Ethyl acrylate / M-2 / 2- Sodium acrylamido-2-methylpropanesulfonic acid (15/65/15/5) Core / Shell = 75/25 P-23 Shell = Styrene / M-1 (84/16) ) Core / shell = 20/80

P-24 to 26 core: styrene / butadiene copolymer (49/51) P-24 shell = styrene / butyl acrylate / M-1 (25/60/15) core / shell = 50/50 P- 25 Shell = M-1 (100) Core / Shell = 90/10 P-26 Shell = Lauryl Methacrylate / Butyl Acrylate / M-7 (30/55/15) Core / Shell = 40/60 P-27 Core: Acrylonitrile / Styrene / Butadiene Copolymer (25/25/50) Shell: Butyl Acrylate / M-1 (92/8) Core / Shell = 50/50 P-28 Core: Ethyl Acrylate / Butadiene Copolymer (50 / 50) Shell: Styrene / divinylbenzene / M-1 (79/5/16) Core / shell = 50/50

P-29 to 33 Core: poly (n-dodecyl methacrylate) homopolymer P-29 shell = styrene / M-1 (92/8) core / shell = 50/50 P-30 shell = styrene / M -1 (84/16) Core / Shell = 50/50 P-31 Shell = Ethyl Acrylate / M-1 (96/4) Core / Shell = 50/50 P-32 Shell = Ethyl Acrylate / M-1 (92 / 8) Core / shell = 50/50 P-33 Shell = styrene / methyl acrylate / M-3 (21/63/16) Core / shell = 50/50

P-34 core: poly (n-butyl acrylate) homopolymer shell: styrene / M-2 (84/16) core / shell = 50/50 P-35,36 core: poly (ethylene glycol dimethacrylate) / N-butyl acrylate) copolymer (10/90) P-35 shell = styrene / M-1 (84/16) core / shell = 50/50 P-36 shell = methyl acrylate / M-7 / methacrylic acid (65/15/20) Core / Shell = 75/25

P-37 to 40 core: poly (ethylene glycol dimethacrylate / n-butyl acrylate) copolymer (20/80) P-37 shell = styrene / M-1 (84/16) core / shell = 50 / 50 P-38 shell = styrene / M-1 (84/16) core / shell = 75/25 P-39 shell = methyl acrylate / M-8 / 2-acrylamido-2-sodium methylpropanesulfonate (80 / 15/5) Core / shell = 75/25 P-40 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50

P-41 to 43 Core: Polyvinyl acetate homopolymer (100) P-41 Shell = styrene / M-1 (84/16) Core / shell = 50/50 P-42 Shell = styrene / divinylbenzene / M-24 (79/5/16) core / shell = 50/50 P-43 shell = n-dodecyl methacrylate / butyl acrylate / M-7 (30/55/15) core / shell = 40/60

P-44 to 46 core: poly (divinylbenzene / 2-ethylhexyl acrylate) copolymer (10/90) P-44 shell = methyl acrylate / M-1 (84/16) core / shell = 50 / 50 P-45 shell = methyl acrylate / styrene / M-1 (74/10/16) core / shell = 50/50 P-46 shell = M-1 (100) core / shell = 90/10 P-47 ~ 49 core: poly (divinylbenzene / styrene / 2-ethylhexyl acrylate) copolymer (10/23/67) P-47 shell = methyl acrylate / M-1 (84/16) core / shell = 50/50 P- 48 shell = methyl acrylate / styrene / M-1 (74/10/16) core / shell = 50/50 P-49 shell = ethyl acrylate / 2-hydroxyethyl methacrylate / M-5 (65/15/20) core / Shell = 85 15

P-50 Core: Poly (ethylene glycol dimethacrylate / vinyl palmitate / n-butyl acrylate) copolymer (20/20/60) Shell: Ethylene glycol dimethacrylate / styrene / n-butyl methacrylate / M-1 (5/40/40/15) core / shell = 50/50 P-51 core: poly (trivinylcyclohexane / n-butyl acrylate / styrene) copolymer (10/55/35) shell: methyl acrylate / M -1 / 2-Acrylamido-2-methylpropanosulfonic acid sodium (88/7/5) core / shell = 70/30 P-52,53 core: poly (divinylbenzene / styrene / methylmethacrylate) copolymer (10 / 45/45) P-52 shell = n-butyl acrylate / M-1 (84/16) core / shell = 50/50 P-53 shell = - dodecyl acrylate / ethyl acrylate / M-21 (60/30/10) Core / shell = 50/50

P-54,55 Core: Poly (p-vinyltoluene / n-dodecyl methacrylate) Copolymer (70/30) P-54 Shell = Methyl Acrylate / n-Butyl Methacrylate / M-2 / Acrylic Acid ( 30/55/10/5) core / shell = 50/50 P-55 shell = n-butyl acrylate / M-19 (84/16) core / shell = 70/30

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver iodobromide and salts. Silver iodobromide or the like can be used. 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 preferably 0.01 μm to 0.7 μm, more preferably 0.05 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100 It is preferable that the variation coefficient is 15% or less, more preferably 10% or less and the particle size distribution is narrow. 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 described by P. Glafkides C
himie et Physique Photographique (Paul Montel, 1967), GFDufin, Photographic Emulsi
on Chemistry (The Focal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c Emulsion (The Focal Press, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in 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 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 such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. 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.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. It is particularly preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

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 Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem. Soc. Perkin.Trans., 1,
2191 (1980), edited by S. Patai, The Chemistry of
OrganicSerenium and Tellurium Compounds, Vol1 (１
986) and the same Vol2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. 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 used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, 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 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.

The silver halide photographic light-sensitive material of the present invention preferably contains a rhodium compound in order to achieve high contrast and low fog. 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 a halogen, an amine, oxalate, etc. as a ligand, such as hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium ( III) complex salts, trizalatrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the rhodium 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, Na
A method of adding Br or the like) 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 total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-3 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-4 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Although various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. 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 (for example, 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 total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ^-5 mol is suitable, and preferably 5 × 10 ^-8 to 1 ×.
It is 10 ^-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. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. 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.

Further, contact films and contact papers that can be handled in a bright room are generally called bright room reversing sensitizers, and silver chloride emulsions are preferable for such sensitizers.

The developing solution used in the present invention will be described. The developing agent to be used is not particularly limited, but it is preferable to contain dihydroxybenzenes or ascorbic acid from the viewpoint of easily obtaining good halftone dot quality. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, hydroquinone monosulfonic acid and salts thereof, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3- Examples include dibromohydroquinone and 2,5-dimethylhydroquinone. Ascorbic acids used in the present invention include ascorbic acid or a salt thereof, erythorbic acid or a salt thereof, and the like. Particularly preferred developing agents are ascorbic acid, erythorbic acid, hydroquinone monosulfonic acid, and salts thereof. The developing agent is 0.01 mol to 1.5 mol in 1 liter of development,
Preferably, 0.05 mol to 0.8 mol is added. The developer of the present invention preferably contains an auxiliary developing agent.

As the auxiliary developing agent, 3-pyrazolidones, phenylenediamines, and aminophenols can be used. As 3-pyrazolidones,
For example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-
4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone,
1- (2-benzothiazolyl) -3-pyrazolidone, 3
-Acetoxy-1-phenyl-3-pyrazolidone, etc.), 3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p
-Methylaminophenyl) -3-aminopyrazoline, 1
-(P-amino-m-methylphenyl) -3-aminopyrazoline and the like are used. Examples of the phenylenediamines include 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-Methoxyethylaniline and the like can be added.

As aminophenols, 4-aminophenol, 4-amino-3-methylphenol, 4-aminophenol
(N-methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine,
N- (2'-hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-4-aminophenol, 2
-Hydroxymethyl-4- (N-methyl) aminophenol and hydrochlorides and sulfates of these compounds can be mentioned.

The amount of these auxiliary developing agents used is generally in the range of 5 × 10 ⁻⁴ to 0.5 mol, preferably 10 ⁻³ to 0.1 mol, per liter of the developing solution.

The developer of the present invention preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative. Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The larger the amount of preservative added, the better the preservability of the developer, but on the other hand, the amount of silver ions dissolved from the photosensitive material into the developer increases, so silver sludge gradually accumulates in the developer. It has an adverse effect. Since the developer of the present invention has high stability, it is possible to obtain sufficient preservability by reducing the amount of sulfite added. Therefore, the amount of sulfite added is preferably 0.5 mol or less per liter of the developing solution. More preferably 0.0
3 to 0.3 mol / liter is preferable.

The pH of the developer of the present invention is 8.5 to 12.8.
Is. It is preferably used in the range of 9.0 to 11.0. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, lithium 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 pep
per) inhibitor may be included. 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. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.05 to 2 mmol, per liter of the developing solution.

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 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

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.

If necessary, a toning agent, a surfactant,
You may also contain a defoaming agent, a hardening agent, etc.

In the developer used in the present invention, carbonate, boric acid and borate as a buffer (for example, boric acid, borax, sodium metaborate, potassium borate) are disclosed in JP-A-6-61.
0-93433 sugars (eg saccharose), oximes (eg acetoxime), phenols (eg 5-sulfosalicylic acid), tertiary phosphates (eg sodium salt, potassium salt), aluminates (eg sodium). Etc. are used, and preferably carbonates and borates are used. 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
Second to 1 minute and 30 seconds. When processing 1 square meter of silver halide black and white photographic light-sensitive material, the replenisher amount of the developer is 5
The amount is 00 ml or less, preferably 400 ml or less. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. 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 adjuster (eg, ammonia, sulfuric acid). ), A chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536, thiourea derivatives, alcohol having triple bond in the molecule, US Pat.
A thioether compound described in JP-A-126459, JP-A-4-
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, and inorganic acids such as boric acid, phosphate, and sulfite. A buffer can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developer, and 0.01 to 1.
The amount used is 0 mol / liter, more preferably about 0.02 to 0.6 mol / liter. The pH of the fixer is 4.0 to 6.
5 is preferable, and the range of 4.5 to 6.0 is particularly preferable. Further, as a dye elution accelerator, JP-A-64-47
The compounds described in No. 39 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 to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds at about 20 ° C to about 50 ° C, preferably 25 to 45 ° C. The replenishing amount of the fixing solution is 600 ml / per processing amount of the light-sensitive material.
m ² or less, particularly preferably 500 ml / m ² or less.

The 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. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. 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 treatment 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.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention and the development processing method. For example, those described in the following sections can be preferably used. Item 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formula (II-m) to (II-p) ) And compound examples II-1 to II-22, and compounds described in JP-A No. 1-179939. 2) Silver Halide Emulsion JP-A-2-97937, page 20, lower right column, line 12 and its manufacturing method to page 21, left lower column, line 14; JP-A-2-122336, page 7, upper right column 19 The selenium sensitization method described in the second to the lower left column 12th line of the same page and Japanese Patent Application No. 3-189532. 3) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17 The lower left column, line 20, and further, the spectroscopy described in JP-A Nos. 1-112235, 2-124560, 3-79928, Japanese Patent Application Nos. 3-189532, 6-103272, and 3-411064. Sensitizing dye. 4) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, right Lower column, line 18, Japanese Patent Application No. 5-204325. 5) Antifoggants 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; further JP-A 1-237538 The thiosulfinic acid compounds described in Japanese Patent Publication No. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 8) Matting agent, slip agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 10) Dyes Dyes from the lower right column, lines 1 to 18 of page 17, JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 11) Emulsion layers, protective layers, etc. JP-A-2-18542, page 3, lower right column, line 1 to binder layer, line 20. 12) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 13) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to first benzene, page 2, lower left column, and EP452772A. 15) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0117]

【Example】

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
A halogen salt aqueous solution containing (H ₂ O) Cl ₅ was added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method while stirring to obtain an average particle size of 0.25 μm. ,
Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

Then, after washing with water by a flocculation method according to a conventional method, gelatin for dispersion was added, and further 7 mg of sodium benzenethiosulfonate was added per mol of silver.
And benzenesulfinic acid (2 mg) were added, and the pH was adjusted to 6.
Adjusted to 0, pAg 7.5, and added with 2 mg of sodium thiosulfate and 4 mg of chloroauric acid per mol of silver to 60
Chemical sensitization was performed to obtain optimum sensitivity at ° C. Then, 4-hydroxy-6-methyl-1,3,3 as a stabilizer
150 mg of a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains were cubic chlorobromide grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol%. (Variation coefficient 10%)

Preparation of coated sample On the support, from the support side, the UL layer, the EM layer, and the P layer were sequentially formed.
A sample was prepared by coating so as to have a layer structure of a C layer and an OC layer. The preparation method and coating amount of each layer are shown below.

(UL layer) Latex P having 30% by weight of active methylene groups based on gelatin in an aqueous gelatin solution.
-4 was added, and gelatin was coated at 0.5 g / m ² .

[0121] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Furthermore, hydroquinone 100 mg and N-oleyl-N-methyltaurine sodium salt 30 mg / m ²
Added as applied. Hydrazine derivative (compound
No.17) The ^{1 × 10 -5 mol / m 2} , the water-soluble latex to 200 mg / m ^2, the latex P-4 to 200 mg / m ² having an active methylene group, polyethyl acrylate latex represented by (d) 200 mg / m ² and 200 mg / m ² of colloidal silica having an average particle size of 0.02 μm
m ² , sodium dodecyl benzene sulfonate 30 mg /
m ² , and 1,3-divinylsulfonyl-as a hardening agent
2-Propanol was added to the total gelatin on one side of 0.
3 mmol / g was added. The pH of the solution was 5.6 with acetic acid.
5 was prepared. They were coated so that the coated silver amount was 2.7 g / m ² . The coating amount of gelatin was adjusted by changing the amount of gelatin for dispersion so as to be 1.2 g / m ² .

(PC layer) Gelatin 0.5 g / m ² , ethyl acrylate latex (125 mg / m ² ) and the following surfactant (w) 5 mg / m ² , 1,5-dihydroxy-2-benzald The kimme was applied so that it was applied at 10 mg / m ² .

(OC layer) Gelatin 0.3 g / m ² , matting agents of the present invention and comparative examples (shown in Table 1), methanol silica 0.1 g / m ² , polyacrylamide 100 mg /
m ² and 20 mg / m ^{2 of} silicone oil, and a fluorosurfactant 5 represented by the following structural formula (e) as a coating aid.
mg / m ² and sodium dodecylbenzene sulfonate 1
00 mg / m ² was applied.

[0124]

[Chemical formula 23]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin (amount shown in Table 1) Latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0126]

[Chemical formula 24]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0128]

[Chemical 25]

[Back protective layer] Gelatin (amount shown in Table 1) 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

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 488 nm and a light emission time of 10 ⁻⁵ se through a step wedge.
Exposed with xenon flash light of c, automatic developing machine FG-
After developing with 680AS (manufactured by Fuji Photo Film Co., Ltd.) for 30 seconds at 35 ° C. using the following developing solution and fixing solution, fixing,
It was washed with water and dried.

(Developer formulation) Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0. 08 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2 -Sodium mercaptobenzimidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide is added and water is added to 1 liter to adjust the pH to 10.5.

The fixing solution used had the following formulation. (Fixer formulation) Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.03 g Sodium thiosulfate pentahydrate 10.9 g Sodium sulfite 25.0 g NaOH 13.4 g Glacial acetic acid 29.1 g Tartaric acid 2.92 g Sodium gluconate 1.74 g Aluminum sulphate 84 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.8 Add water to 1 liter

The maximum optical density of the obtained image is shown in Table 1 as Dmax.

(2) Evaluation of Becksec, vacuum time, and susceptibility to scratches Becksec was measured according to JIS-P-8119-1976 "Smoothness test method for paper and board by Beck tester". Vacuum time Using a halftone dot original film with a halftone dot image of 10%, the original film (35 cm x 45 cm) and the sample (40 cm x 50 cm) are combined and brought into close contact with each other with a vacuum degree of 650 mmHg by a printer for contact exposure, and development processing is performed after exposure. After that, the vacuuming time required to make the halftone image printed as 90% halftone dots uniform was determined. The shorter the evacuation time is, the better the vacuum adhesion is. Evaluation of Vulnerability (A) 10 μg of gelatin on 100μ polyester support
Make a sample coated so that it becomes / m ² . (B) The sample of this example is entirely exposed to light and developed to prepare a solid black sample. The samples of (A) and (B) are left in an atmosphere of 25 ° C. and 30% RH for 2 hours, and then the gelatin surface of (A) and the matting agent surface of (B) are put together and rubbed back and forth 5 times with a load of 50 g. . The amount of gelatin powder scraped off by the matting agent was evaluated on a 5-point scale from (bad) to 1 (good) by sensory evaluation. The results of these evaluations are shown in Table 1.

[0135]

[Table 1]

As is clear from the results shown in Table 1, when the matting agent A of the present invention is used, the Beck second and the vacuum time are short, the scratch resistance is strong, and a high Dmax can be maintained. On the other hand, the comparative matting agents B and C are strong against scratches, but have a drawback that when the Beck second and the vacuum time are shortened, the decrease in Dmax is extremely large. Inorganic silica particles have a relatively small decrease in Dmax, but have the drawback of being extremely inferior in scratchability.

Example 2 In Example 1, except for the sensitizing dyes S-1 and S-2 in the EM layer, the following S-3 was replaced by 2.1 × per mol of silver.
A sample was prepared in the same manner as in Example 1 ^{except that} 10 ⁻⁴ mol was added. Similar to Example 1, the sample of the present invention maintained a high Dmax and showed good performance with a short Beck second and a short vacuum time.

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[Procedure amendment]

[Submission date] June 6, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

[0032]

Embedded image

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

These compounds are optimally added depending on their types.
1.0 x 1 per 1 mol of hydrazine compound, although the amount added is different
0^-2Mol ~ 1.0 x 10²Mole, preferably 1.0 x
10 ^-1Desirable to use in the range of 1.0 to 10 mol
New These compounds are suitable solvents (H₂O methanol
And alcohols such as ethanol, acetone, dimethyl
Dissolve in formamide, methyl cellosolve, etc.) and apply
Is added to the liquid.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, n
-Butyl) or a halogen atom (for example, a chlorine atom or a bromine atom), preferably a hydrogen atom, a methyl group or a chlorine atom. L represents a single bond or a divalent linking group,
Specifically, it is expressed by the following formula. _{^{- (L 1) m - (}} L 2) n - L 1 is ^{-CON (R 2) - (R} 2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms Represents), -COO-, -NHCO-, -OCO-,

Claims (2)

[Claims] 1. A silver halide light-sensitive material having a photosensitive silver halide emulsion layer and a protective layer thereof on a support, wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative, A silver halide photographic light-sensitive material, wherein the layer contains a matting agent composed of agglomerated particles in which a plurality of primary particles having a particle diameter smaller than the thickness of the protective layer are agglomerated. 2. The thickness of the protective layer is in the range of 0.1 to 10 μm, and the average particle size of the primary particles is 0.01 to 1.
Within the range of 0 μm, the average particle size of the aggregated particles is 0.2.
The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is in the range of -30 μm.