JPH0498240A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image small in occurrence of color stains due to residual dyes and black spots after processing and high in storage stability for a long time and contrast by incorporating a hydrazine compound in at least one of a photosensitive silver halide emulsion layers and a specified compound in a nonphotosensitive hydrophilic colloidal layer. CONSTITUTION:At least one of the silver halide emulsion layers contains the hydrazine compound and the nonphotosensitive hydrophilic colloidal layer on the same side contains the compound represented by formula I in which A is a 2-pyrazoline-5-one acid nucleus; B is 4-aminoaryl; each of L1-L3 is methine; (m) is 0 or 1; and it is necessary to incorporate carboxy, sulfoamido, or the like in the aminoaryl group, or a sulfamoyl group in the 2-pyrazoline-5-one acid nucleus.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material that can obtain images with high contrast using a hydrazine compound, and more specifically, it relates to a silver halide photographic material that produces fewer black spots and that improves over time. The present invention relates to a silver halide photographic material that has good storage stability and provides images with high contrast.

[Prior Art] In the field of printing plate making, excellent image quality is required of silver halide photographic materials. A method used for this purpose is to obtain high-contrast images using a developing solution containing a hydrazine compound in a silver halide photographic sensitizer, with a high concentration of sulfite ions, and with improved retention. Are known.

It is also well known that dyes are incorporated into silver halide photographic materials for the purpose of improving image quality or handling under brighter safelights. prevention,
Used in light absorption filters.

The dye used in the above [1] depends on the purpose of use; 1) it has a good absorption spectrum; 2) it does not diffuse from the colored layer to other layers; 4. It must be stable in silver halide photographic light-sensitive materials. 5. It must be easy to add. 6. It must be stable in the emulsion coating solution and not affect the solution viscosity. 7. Processing The properties required include that no color remains behind.

A large number of dyes have been proposed in the past for the purpose of satisfying these desired characteristics, including azo dyes, British Patent No. 506.385 and Japanese Patent Publication No. 39-2206.
No. 9 contains oxonol dye, U.S. Pat. No. 2,493.7
No. 47 includes merocyanine dye, US patent 1.845,
No. 404 proposes subril dye and the like. Further, heterocyclic type arylidene dyes 1 are disclosed in JP-A-1-196040 and JP-A-1-196041.

[Problem to be solved by the invention] The general method is to dissolve these dyes in water or an organic solvent that is miscible with water and add them to the photographic constituent layer. It does not stay in the desired layer but spreads to all layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye that diffuses into other layers, causing undesirable phenomena such as black spots and decreased sensitivity. Used to avoid these
Even if the amount of light is not reduced, the original light absorption effect cannot be obtained sufficiently. To solve this problem, dyes with reduced diffusivity that dye specific layers are known, for example, U.S. Pat.
．． No. 538.008, No. 2.539.009, No. 4.
Specifications of No. 420.555, JP-A-61-20463
No. 0, 6l-20593t@, 62-321160
No. 62-56958, No. 62-92949, No. 62-222248, No. 63-40143, No. 6
It is described in each publication of No. 3-1847119 and No. 63-316852.

Although these diffusion-resistant dyes have improved the above-mentioned drawbacks to some extent, new problems have arisen, such as difficulty in elution or fading during processing, and difficulty in causing color staining. . In order to solve these problems, new diffusion-resistant dyes are required.

Therefore, an object of the present invention is to provide a high-contrast image that satisfies the above-mentioned requirements for a diffusion-resistant dye, has less residual color after processing, has less black spots, and has excellent storage stability over time. The object of the present invention is to provide a silver halide photographic light-sensitive material that can be used.

A further object of the present invention is to provide a silver halide photographic material that is easier to handle under safelight.

[Means for Solving the Problems] The present inventors conducted intensive research in view of the above-mentioned problems, and as a result, the above-mentioned object of the present invention was achieved by forming at least one photosensitive silver halide emulsion layer on a support and at least one light-sensitive silver halide emulsion layer. In a silver halide photographic light-sensitive material having one non-light-sensitive hydrophilic colloid layer, at least one of the light-sensitive silver halide emulsion layers contains a hydrazine compound, and the light-sensitive silver halide emulsion layer and the support This is achieved by a silver halide photographic photosensitive material characterized by containing a compound represented by the following general formula [1] in the non-photosensitive hydrophilic colloid layer on the same side.

General formula [I] △=l+-←L2=L3+-B (A represents a 2-pyrazolin-5-one acidic core, B represents a 4-aminoaryl group, and L1 to L3 each represent a methine group) , m represents O or 1, and the general formula [[1
The compound represented by satisfies at least one of the following conditions (1) to (4).

(1) The 4-aminoaryl group represented by B has at least one group selected from the group consisting of a carboxyl group, a sulfonamide group, an aminosulfonylamino group, and a sulfamoyl group.

(2) 2-pyrazolin-5-one represented by A has at least one sulfamoyl group in the acidic core.

(3) An aliphatic group or a heterocyclic group having at least one group selected from a norboxyl group, a sulfonamide group, and an aminosulfonylamino group in the 2-pyrazoline-5-71 acidic core represented by A. and at least one naphthyl group.

(4) It has at least one group selected from the group consisting of a carboxyl group, a sulfonamide group, and an aminosulfonylamino group bonded to the 2-pyrazolin-5-one acidic core represented by A. ) The present invention will be explained in detail below.

The dorazine compound used in the present invention is preferably a compound represented by the following general formula [H].

General formula "1" 1 In the formula, R1 represents a monovalent organic residue, R2 represents a hydrogen atom or a monovalent organic residue, Ql and Q2 are a hydrogen atom,
Alkylsulfonyl group (including those with substituents),
It represents an arylsulfonyl group (including those with substituents), and x1 represents an oxygen atom or 1 represents a sulfur atom. Among the compounds represented by the general formula [H], compounds in which x1 is an oxygen atom and R2 is a hydrogen atom are more preferred.

The organic residues 11i1j of R1 and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (for example, alkyl groups, alkoxy groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxy groups, nitro groups, alkylthio groups, (hydroxy group, sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide group, urea group, thiourea group, etc.).

Specific examples of those with substituents include 4-methylphenyl group, 4-ethylphenyl group, 4oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diedylaminophenyl group, 4 -octylaminophenyl group, 4-benzylaminophenyl group,
4-acetamido-2-medylphenyl group, 4-(3-
ethylthioureido) phenyl group, 4-[2-(2,4
Examples include a di-tart-butylphenoxy)butylamido]phenyl group, and a 4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl group.

The heterocyclic residue is a five- or six-membered monocyclic or fused ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and a substituent may be attached to these.

Specifically, for example, biroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzodeazole ring, naphthothiazole ring. , selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as a methyl group or an ethyl group.
Alkyl group, methoxy group, ethoxy group, etc. having 1 to 4 carbon atoms
may be substituted with an alkoxy group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, an amino group, or the like.

Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably 1 to 8 alkyl groups, and specific examples include methyl group, ethyl group, isobutyl group, and 1-octyl group.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclohexyl group, and an adamantyl group.

Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups, and cyano groups. , sulfonyl groups, halogen atoms (e.g., chlorine, bromine, fluorine, iodine, etc.), aryl groups (e.g., engineering diyl groups, halogen-substituted phenyl groups, alkyl-substituted phenyl groups), etc. Specific examples of substituted groups include Examples include 3-methoxypropyl group, ethoxylponylmethyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group, and the like.

Further, as an alkenyl group, for example, allyl
) '4. Examples of alkynyl groups include propargyl groups.

Preferred specific examples of the hydrazine compound of the present invention are shown below, but the present invention is not limited thereby in any way. 33 ShirI3 The hydrazine compound represented by the general formula [I4] is added to the silver halide emulsion layer.The amount added is from 10-5 to
10-1 mol/silver 1 mol is preferable, more preferably 1
It is 0-4 to 10-2 mol/1 mol of silver.

Next, the compound represented by the general formula [I] used in the present invention will be explained.

General formula [I] A=1+→L2-L3-)-B (A represents a 2-pyrazolin-5-one acidic core, B represents a 4-aminoaryl group, and 1 to [3 are each methine represents a group, l represents O or 1, and has the general formula [I]
The compound represented by satisfies at least one of the following conditions (1) to (4).

(1) The 4-aminoaryl group represented by B has at least one group selected from the group consisting of a carboxyl group, a sulfonamide group, an aminosulfolamino group, and a sulfamoyl group.

(2) The 2-pyrazolin-5-one acidic core represented by Δ has at least one sulfamoyl group.

(3) An aliphatic group having at least one group selected from the group consisting of a carboxylic group, a sulfonamide group, and an aminesulfonylamino group in the 2-pyrazolin-5-one acidic core represented by A; It has at least one ring group and naphthyl group.

(4) It has at least one group selected from the group consisting of a carboxyl group, a sulfonamide group, and an aminosulfonylamino group bonded to the 2-pyrazolin-5-one acidic core. ) In the above general formula [IJ, the amino moiety attached to the 4-aminoaryl group represented by B includes those having a substituent and cyclic ones, and the @ substituent includes, for example, alkyl group, cycloalkyl group, aryl group, alkenyl group,
Examples include heterocyclic groups.

Examples of the alkyl group as a substituent include methyl group, ethyl group, n-propyl group, 15O-propyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, Examples include n-dodecyl group, n-pentadecyl group, and icosyl group. The alkyl group includes those having a substituent, and the substituent includes:
For example, halogen atoms (e.g., chlorine, bromine, iodine, fluorine, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), cycloalkyl groups (e.g., cyclopentyl, cyclohexyl), heterocyclic groups (e.g., pyrrolidyl, pyridyl group, etc.), sulfinic acid group, carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (e.g. amino group, diethylamino group, etc.), alkyloxy group (e.g. medyloxy group, ethyloxy group, n-butyloxy group, n- Octyloxy group, isopropyl tertiary
), aryloxy groups (phenyloxy, naphthyloxy, etc.), carbamoyl groups (e.g., aminocarbonyl, methylcarbamoyl, n-pentylcarbamoyl, phenylcarbamoyl, etc.), amide groups (e.g., methylamide, benzamide group, n-octylamide group, etc.), aminosulfonylamino group (e.g. aminosulfonylamino group, ) group, methylaminosulfonylamino group, anilinosulfonylamino group, etc.), sulfamoyl group (e.g. sulfamoyl group, methylsulfamoyl group) , phenylsulfamoyl group, n-butylsulfamoyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, n-hebutanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl group (e.g. methylsulfinyl group, ■Alkylsulfinyl groups such as delsulfinyl group, phenylsulfinyl group, octylsulfinyl group, arylsulfinyl group such as phenylsulfinyl group), alkyloxycarbonyl group (e.g. methyloxycarbonyl group, ethyloxycarbonyl group,
-Hydroxyethyl A oxycarbonyl group, n-octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (e.g. mebrudio group, edildio group, n-hexylthio group) etc.), arylthio groups (e.g. phenylthio group, naphthylthio group, etc.),
Alkylcarbonyl groups (e.g. acedel group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group, etc.), arylcarbonyl groups (e.g. benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group) etc.), cyan group,
Examples include ureido groups (eg, methylureido group, phenylureido group, etc.), thioureido groups (eg, methylthioureido group, phenylthioureido group, etc.), and the like.

Examples of the cycloalkyl group as a substituent for the amino moiety include a cyclopropyl group, a cyclobutyl group, a cyclopendel group, a cyclohexyl group, and the cycloalkyl group includes those having a substituent. Examples of the alkyl group and substituents for the alkyl group include IC.

Placement of amino part! Examples of the aryl group represented by m include a phenyl group and a naphthyl group.

The aryl group includes those having a substituent, and examples of the substituent include the above-mentioned alkyl group or the above-mentioned groups listed as substituents for the alkyl group.

Examples of the alkenyl group as a substituent for the amino moiety include a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group, a 2-benzonyl group, and the alkenyl group includes those having a substituent. Examples of the substituent include those listed above as the alkyl group and the substituent for the alkyl group.

Examples of the heterocyclic group as a substituent for the amino moiety include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-carboxy-2-pyridyl Ii, 3.5-
Dichloro-2-pyridyl group, 4,6-dimethyl-2-pyridyl group, 6-hydroxy-2-pyridyl group, 2,3.
5.6-tetrafluoro-4-pyridyl group, 3-2!・
oxasilyl group (5-carboxyl-2-benzoxasilyl group, 2-benzoxasilyl group, 2-oxasilyl group, etc.), deazolyl group (5-carboxyl-2-benzoxasilyl group, 2-benzoxasilyl group, 2-oxasilyl group, etc.),
-sulfamoyl-2-benzthiazolyl group, 2-benzdeazolyl group, 2-deazolyl group, etc.), imidazolyl group (1-methyl-2-imidazolyl group, 1-methyl-5
-carboxy-2benzimidazolyl group, etc.), Furyl W
(3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.)
, thienyl group (2-thienyl group, etc.), pyrazinyl group (2-thienyl group, etc.)
-pyrimidinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloroo-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxacylyl group ( 3-isoxasilyl group, etc.), selenazolyl group (5-carboxy-2-lerenazoly difluor group, etc.), sulfolanyl group (3-sulfolanyl group, etc.),
Piperidinyl group (1-methyl-3-piperidinyl group, etc.)
, pyrazolyl group (3-pyrazolyl group, etc.), tetrazolyl group (1-methyl-5-terazolyl group, etc.)? +7, and the heterocyclic group includes those having a substituent, and the substituent includes those exemplified as the alkyl group and the substituent of the alkyl group described above.

Examples of cyclic amine moieties include piperidine, piperazine, and morpholine from which the hydrogen atom bonded to the nitrogen atom is removed, and cyclic amino groups include those having substituents, such as those mentioned above. Examples of the alkyl group and substituents for the alkyl group include those exemplified.

As the aryl part of the 4-aminoaryl group represented by B, phenyl is preferred. In addition to the 4-amino group, the aryl part includes those having a substituent,
Examples of the substituent include those exemplified as the alkyl group and the substituent for the alkyl group described above.

The 4-aminoaryl group also includes those in which a substituent on the amino moiety is bonded to a carbon atom on the aryl moiety to form a ring (for example, a piperidine ring or a julolidyl ring).

The methine groups represented by +, 12, and La include those having a substituent, and the substituent is an alkyl group
Examples include methyl, ethyl, 3-hydroxypropyl, benzyl, etc.), halogen atoms (e.g., fluorine, chlorine, bromine atoms, etc.), aryl groups (e.g., phenyl group), alkoxy groups (e.g., methoxy, ethoxy, etc.), Each of these weights further includes those having, as substituents, those exemplified as substituents for the alkyl group shown as the substituent for the amino moiety described above.

The 2-pyrazolin-5-one acidic core represented by A includes those having a substituent, and examples of the substituent at the 1-position include alkyl, alkenyl, cycloalkyl, aryl, and heterocycle. , and as a substituent at position 3,
For example, alkyl, alkenyl, cycloalkyl, aryl, heterocycle, ',) [,1 carboxyl, carbamoyl, oxycarbonyl, amino, amido, ureido, sulfonamide, aminosulfonylamino, human0xy, alkyloxy, aryloxy, acyl , cyano, sulfamoyl, sulfonyl, and alkylna A1 arylthio.

Alkyl, alkenyl as substituents at the 1st and 3rd positions,
The six groups of cycloalkyl, aryl, and heterocycle are:
Examples of the substituents on the 4-amine moiety of the above-mentioned 4-aminoaryl group include those having 1=, each of which further includes those having a substituent. Examples of the substituent include those exemplified by IC as the substituent for the aryl group as the substituent for the 4-amino moiety described above.

Examples of the amino group as a substituent at the 3-position include an alkylamino group, a dialkylamino group, and an arylamino group. Examples of the alkyl and aryl include the above-mentioned 4-
Examples of the alkyl group and aryl group as a substituent for the amino moiety include those exemplified, including those each having a substituent, such as the aryl group as a substituent for the 4-amino moiety described above. Examples of substituents for the group include those exemplified.

Examples of the oxycarbonyl group at the 3-position substituent include an alkyloxycarbonyl group, an aryloxycarbonyl group, and a heterocyclic oxycarbonyl group; examples of the acyl group include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group. The carbamoyl group includes, for example, a carbamoyl group, an alkylcarbamoyl group,
Arylcarbamoyl group, heterocyclic carbamoyl group, 1
Nitrogen-containing heterocyclic carbonyl groups such as -piperidinocarbonyl group and 4-morpholinocarbonyl group, etc.; ureido groups include, for example, alkylureido groups, arylureido groups, and heterocyclic treido groups; amide groups include, Examples of the sulfonamide group include an alkylcarbonylamino group, an arylcarbonylamino group, a heterocyclic carbonylamino group, and an alkylsulfonylamino group.
Examples of the aminesulfonylamino group include an arylsulfonylamino group, a heterocyclic sulfonylamino group, and an alkylaminosulfonylamino group, a dialkylaminosulfonylamino group, an arylaminosulfonylamino group, and a heterocyclic aminosulfonylamino group. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a heterocyclic sulfamoyl group, and examples of the sulfonyl group include an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, and the like. Examples of the sulfinyl group include an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, and the like. Examples of alkyl and aryl include the above-mentioned 4-
Examples of the alkyl group, aryl group, and heterocyclic group as substituents for the amino moiety include those exemplified, including those each having a substituent. Examples of the substituent include the substituents for the 4-amino moiety described above. Examples of substituents for the aryl group include those exemplified.

The compound represented by the general formula [I] is under the conditions (1) to
It satisfies at least one of (4), but conditions (1) to (4) (for sulfonamide, aminosulfonylamino and sulfamoyl groups, 2-pyrazolin-5-one acidic core) 6 shown as a substituent at position 3
Examples of aliphatic groups and heterocyclic groups having a carboxyl group, aminosulfonylamino group, or sulfonamido group include the alkyl groups, alkenyl groups, and heterocyclic groups exemplified as substituents for the 4-amino moiety described above. can be mentioned.

Specific examples of the compounds of the present invention are listed below, including the wood specific compound CH2COOH 3 (-i 3J CH2C) + 20CH.

(Z9) CH.

しF12N ti b U 2 し+13(CH,)3
SO2NH2 4° C, H5 C, H.

(CH2), C00H Ha 51 CH, CH, OH 5) J U to H2C(J()H OCH2CUUl( CH.

Goose ni L) (Jl-1 CC) (J l-1 Satoshi CH3 C(J (Jl-1) Specific synthesis examples of the compound represented by the general formula [il are shown below, but other compounds can also be synthesized by the same method. can be easily synthesized.

Synthesis Example 1 Synthesis of Exemplified Compound (1) 1-(4-carboxymethylphenyl)-3methyl-2
-Pyrazolin-5-one 23.2(+,4) A mixture of 14.9111 dimethylaminobenzaldehyde and 300 d of ethanol was heated and stirred under reflux for 3 hours. After the reaction mixture was allowed to cool, the product was collected by filtration.

The product was purified by slurrying it in ethanol under reflux and filtering it to remove the dye. This treatment was repeated to obtain compound (1) 19.20.

The structure of the compound was confirmed by NMR, IR and MASS spectra.

Synthesis Example 2 Synthesis of Exemplified Compound (55) 1-(4-carboxymethylphenyl)-3=methyl-
A mixture of 2.5° of 2-pyrazolin-5-one, 1.8 g of 4-dimethylaminocinnamaldehyde and 10° of glacial acetic acid was heated and stirred under reflux for 10 minutes. After the reaction mixture was allowed to cool, ethanol was added thereto, and the mixture was again heated and stirred under reflux to cool it. The product was taken out by filtration, first slurried in ethanol under reflux, filtered, and then slurried in methanol under reflux, filtered for purification. 1.8o of compound (55) was obtained.

The structure of the compound was confirmed by NMR, IR and MΔSS spectra.

The compound represented by the general formula [I] of the present invention may be added to a silver halide photographic material with an optical density of 0.05 to 3 depending on the purpose.
．． It is used so that it is in the range of 0.

The method of adding the solid fine particle dispersion of the compound represented by the general formula [I] of the present invention into a light-sensitive material is not particularly limited, and for example, US Pat. No. 4,857,4
The method described in No. 46 can be mentioned.

In the present invention, examples of the photosensitive silver halide emulsion layer include a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer, and examples of the non-photosensitive hydrophilic colloid layer include an intermediate layer, a protective layer, and a filter layer. layer, antihalation layer, antiirradiation layer, etc.

The compound represented by the general formula [I] of the present invention is contained in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer located on the same side of the support, and is particularly suitable for W retention! It is preferable to contain it in a layer or an intermediate layer.

As the silver halide emulsion used in the silver halide photographic material of the present invention, any conventional silver halide emulsion can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

If the silver halide photographic material is for color photography,
A coupler is used in the emulsion layer.

Furthermore, by coupling with a colored coupler having a color correction effect, a competing coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent,
Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and sensitizers are used.

A photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, etc., but these layers and/or emulsion layers contain substances that may flow out of the photosensitive material during development. Alternatively, a bleaching dye may be included.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support for photosensitive UPI, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain an image using the photosensitive material of the present invention, commonly known photographic processing can be performed after exposure.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any of those used in emulsions can be used.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is formed mainly inside the particle.

A hydrophilic colloid used with particular advantage in the present invention is gelatin.

Developing agents used in developing the silver halide photographic material according to the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2
．． 3-dibromohydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-
Phenyl-catechol, 3-methoxy-catechol, 4
Examples include acetyl-pyrogallol and sodium ascorbic acid.

The silver halide photographic material according to the present invention can be processed under various conditions. As for the processing temperature, for example, the development temperature is preferably 50°C or lower, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, particularly preferably 10 seconds to 50 seconds. often has positive effects. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual image processing such as plate development or frame image processing, or mechanical development such as roller development or hanger development.

[Example] The present invention will be specifically explained below in Examples.

Note that the present invention is not limited to the embodiments described below.

Example 1 (Preparation of emulsion) An iridium salt was prepared by the Chondral double jet method in an acidic atmosphere of pl-13.0 at a concentration of 10 iridium salts per mole of silver.
Silver iodobromide grains containing -7 mol, average grain size 0.20 μm, silver halide composition monodispersity 15, and 0.5 mol % silver iodide were prepared. Particle growth is based on benzyladenine
% geladine aqueous solution 1! The experiment was conducted using a system containing 30 mg per sample. After mixing silver and halide, 6-methyl-4-hydroxy-1,3,38,7-chitrazaindene was added in an amount per mole of silver halide, followed by washing with water and desalting.

Next, 60n+g of 6methyl-4-hydroxy-1,3,3a,7-titrazaindene per mole of silver halide was added, followed by addition of 15mg of sodium thiosulfate per mole of silver halide, and sulfur sensitization was carried out at 60°C. Did. After sensitization, 6-methyl-4-hydroxy-1,3,3a,7-tetraIF indene was added as a stabilizer in an amount of 1C per mole of silver halide.

Additives were added to the obtained emulsion in the amounts shown below, and the mixture was coated on a 100 μm thick polyethylene terephthalate support that had been subjected to latex subbing treatment according to Example 1 of JP-A-59-19941. .

The support had previously been coated with a backing layer.

Latex polymer: styrene-butyl acrylate
Acrylic acid ternary copolymer polymer 1.0 g/z Tetraphenylphosphonium chloride 30 m<1/i
'Saponin 200ml/i2
Polyethylene glycol 100m! 1/w' Hydroquinone 200m (1/n' Styrene-maleic acid copolymer 20II1g/l? Hydrazine compound (not shown in Table 1) 50111 (1/n'
*'5-Methylbenzo I-lyazole 30m, Mr
Sensitizing dye A 6mO/l' Alkali-treated gelatin (isoelectric point 4.9) 1.5CI/m' Bis(vinylsulfonylmethyl)ether 15mMv? Silver amount 2., 80/11'' sensitizing dye Δ (emulsion layer protective film) The following coating amount was prepared as one emulsion layer image film, and multilayer coating was carried out simultaneously with the emulsion.

Fluorinated dioctyl sulfosuccinate ester 200111
CI/m' Sodium dodecylbenzenesulfonate 100m<1/
m' Matting agent: Polymethyl methacrylate (average particle size 3.5μm1) 100mQ
/i'Lithium nitrate m 30mg/
112 gallic acid propyl ester 300mG/v
'2-Mercaptobenzimidazole-5-sulfonic acid sodium 30+11 (1/u' Alkali-treated geladine (isoelectric point 4.9) 1.3 (1/*') Colloidal silica 30 mCl/n' Styrene-maleic acid copolymer 100mg/i' Compound of general formula [I] (shown in Table 1) 150ml/i' Bis(vinylsulfonylmethyl)ether 15m0/1
' The samples thus obtained were processed using a developing solution and a fixing solution having the following compositions in an ordinary roller type automatic developing machine under the following conditions, and residual color was evaluated.

The residual color was evaluated in 10 stages. 10 is the best;
Levels 1 to 4 are unusable, and levels 5 and above are usable.

In addition, in order to examine the storage stability of the above samples over time, the samples were conditioned at 23°C with relative humidity of 48%, sealed in a moisture-proof material laminated with polyvinyl acetate with a thickness of 100 μm, and heated in a constant temperature bath at 40°C for 10 days. Processed. This sample and the frozen sample were passed through an optical wedge and a 630 nm interference filter and exposed to a xenon flash for 1.0 xio-s seconds/υ
After being exposed to light, the samples were processed in the same manner under the following conditions, and black spots and relative sensitivity were evaluated.

Kurobo is evaluated on a five-point scale (), with 5 being the best and 1 being the best.
~2 is an unusable level, and 3 or higher is a usable level.

In addition, the halftone dot quality was evaluated by exposing the halftone dots to light. Halftone quality is evaluated on a scale of 10, with 10 being the best and 1 to 4.
is unusable, and level 3 or higher is usable.

Furthermore, in order to evaluate the laylight property, fog was measured under 1 m of Konica Safelight No. 50 (EL) after 5 minutes of safelight irradiation, and the difference in fog from that without irradiation is shown in the table.
Shown in 1.

Disaster, Takasaka ■ Mode Temperature Time Development 34℃ 15 seconds Fixing 32℃ 10 seconds Wash with water, room temperature, 10 seconds developer prescription hydroquinone 1- Fuco. Ni-4゜ Pyrazolidone Sodium bromide 1) 5-methylbenzotriazole 5-nitroindazole Diethylamine propane-1° 4-dimethyl 0.4 g g o, 30 0.05(1 2-diol 10 mouths 75! lI potassium sulfite Sodium 5-sulforilycylate Sodium ethylenediaminetetraacetate I made it to 11 with water.

The pH was adjusted to 11.5 with caustic soda.

Constant JLjL reading (composition A) Ammonium thiosulfate (72.5w% aqueous solution) sulfite]-lium 171J Sodium acetate trihydrate 6°5g boric acid
6g sodium citrate/2 water j!
i 20 acetic acid (90W% aqueous solution)
13.6d (composition) Pure water (ion-exchanged water) 17iI2 sulfuric acid (50w% aqueous solution) 4.70 Aluminum sulfate (Aj! 20s equivalent content is 8.1w% aqueous solution) 26.50 When using fixer Dissolve the above composition A in the order of composition in 500n12 of water, 1
2 and used it. Comparative Dye 1 Comparative Dye 2 As can be seen from the combinations in Table 1, the silver halide photographic material of the present invention has less residual color of the dye after development, less occurrence of black spots, and has excellent storage stability. Because it is good, there is little loss of sensitivity or occurrence of fog.

Furthermore, even when irradiated under safelight, there is little fogging and the handling is easy.

Example 2 In Example 1, the following emulsion lower layer liquid was prepared, and the dye of the present invention was added to the emulsion lower layer liquid instead of the protective layer in the same manner as in Example 1, so that the gelatin content was 0.5 g/i'. The emulsion layer and the backing layer were simultaneously coated on the support (no backing layer was coated) so that the emulsion layer and the backing layer were coated simultaneously.

[Preparation of emulsion lower layer liquid] After dispersing the dye of the present invention shown in Table 2 into an aqueous solution of 250 g of gelatin in the same manner as in Example 1, 50 g of solid fine particles were added, 25 g of saponin, and styrene as a thickener. - The maleic acid polymer was adjusted to U4 by adding 4 g of a copolymer latex of 1001 methyl acrylate and butyl acrylate.

The above sample was evaluated for residual color and storage stability over time in the same manner as in Example 1, and was further subjected to halftone exposure to evaluate halftone dot quality.

It has also been found that when the dye of the present invention is added to the emulsion underlayer solution, it is more advantageous in halftone dot quality than when it is added to the backing layer.

Comparative dye 3 Comparative dye 4 J as seen from the results in Table 2: Sea urchin, the sample of the present invention is Example 1
Similarly, the dye has little residual color and black spots, and has good storage stability.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support, at least one of the light-sensitive silver halide emulsion layers One layer contains a hydrazine compound, and a non-photosensitive hydrophilic colloid layer on the same side of the support as the photosensitive silver halide emulsion layer contains a compound represented by the following general formula [I]. A silver halide photographic material characterized by: General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (A represents a 2-pyrazolin-5-one acidic core, B represents a 4-aminoaryl group, and L_1 to L_3 each represent a methine group. , m represents 0 or 1, and the general formula [
The compound represented by I] satisfies at least one of the following conditions (1) to (4). (1) The 4-aminoaryl group represented by B has at least one group selected from the group consisting of a carboxyl group, a sulfonamide group, an aminosulfonylamino group, and a sulfamoyl group. (2) 2-pyrazolin-5-one represented by A has at least one sulfamoyl group in the acidic core. (3) An aliphatic group, a heterocyclic group, or a naphthyl group having at least one group selected from a carboxyl group, a sulfonamide group, and an aminosulfonylamino group in the 2-pyrazolin-5-one acidic core represented by A. at least 1
have one. (4) It has at least one carboxyl group, sulfonamide group, or aminosulfonylamino group bonded to the 2-pyrazolin-5-one acidic core represented by A. )