JPH09138477A - Negative type black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a very stable black-and-white silver halide photographic sensitive material excellent in preservability at high temp., especially a silver halide photographic sensitive material for a printing plate by hardening at least one of silver halide emulsion layers on one face of a substrate with a specified compd. and adjusting the surface of the top layer on the emulsion layer side to a specified pH. SOLUTION: This sensitive material has a silver halide emulsion layer hardened with a compd. represented by the formula as at least one of the silver halide emulsion layers and has pH3.5-6.0 of the surface of the top layer on the emulsion layer side. In the formula, each of R12 and R13 is straight chain, branched or cyclic 1-20C alkyl or 6-20C aryl, R14 is H or a substituent, L is a single bond, 1-20C alkylene, 6-20C arylene, a divalent group obtd. by combining them, acylamino or sulfonamido and X3 is a single bond, -0-, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-working black-and-white silver halide photographic light-sensitive material, and more particularly to a very stable silver halide photographic light-sensitive material having excellent storage stability at high temperatures.

[0002]

2. Description of the Related Art Conventionally, in printing plate making films and photographic printing papers, there has been a demand for a high contrast image in which halftone is eliminated as much as possible in order to record a halftone dot image and a line image. In particular, high quality performance is required in each plate making process, such as enlargement (expansion) and reduction (contraction) of halftone pictures in the line drawing process, bright reproducibility, and character quality in the return process. Or, in the scanner process, high-definition output exceeding 400 lines / inch and minute Dot output such as FM screen method are not only hard, but also manuscripts from large points to small points. Faithful reproducibility is required.

For this reason, as a method of forming an ultrahigh contrast image, a method using a contrast enhancing agent represented by a hydrazine derivative, a pyridium derivative or a tetrazolium derivative is well known. For example, a surface latent image type silver halide photographic light-sensitive material containing a specific hydrazine derivative as a contrast-increasing agent as disclosed in U.S. Pat. No. 4,269,929 is used as a developer containing a contrast-enhancing amount of an amine compound. How to handle with
European Patent 0231850, US Patent 4975354
JP-A-63-124045 and JP-A-5-2326.
No. 16, a method of containing a hydrazine derivative as a contrast-increasing agent and containing a nucleation accelerator having a specific structure for promoting the hydrazine nucleation reaction, and a method of using a pyridinium salt derivative as a contrast-increasing agent. For example, JP-A-1-217337, JP-A-5-53231, and JP-A-6-161009 are known.

In addition to this, as a method of incorporating a tetrazolium derivative as a contrast-increasing agent, Japanese Patent Application Laid-Open No. 57-13213
7, JP-A-58-173737, JP-A-61-27.
0745 and the like. Films and prints with more faithful reproducibility, which do not satisfy the high quality requirements for printing plate making by using only the above-mentioned contrast enhancing agent, have excellent storage performance particularly at high temperature The development of paper has long been desired. On the other hand, carboxyl group-activating type hardeners known as fast-acting hardeners are disclosed in JP-A-1-198744, page 509 and JP-A-1-2835.
No. 50, general formulas (1) to (7) described on pages 453 to 457.
Examples of such compounds include the photographic light-sensitive materials that use hardeners of this type, but they are extremely unstable against forced deterioration such as heat. It turned out to be greatly desensitized.

[0005]

In view of the above problems, the object of the present invention is to provide a very stable negative-working black-and-white silver halide photographic light-sensitive material excellent in high-temperature storability, especially halogen for printing plate making. In providing silver halide photographic light-sensitive material.

[0006]

The above object of the present invention is to provide a silver halide emulsion layer on one surface of a support, and at least one of the silver halide emulsion layer side has a gelatin and a hydrazine derivative or In a silver halide photographic light-sensitive material containing a contrast-increasing agent such as a tetrazolium compound or a pyridinium compound, at least one of the silver halide emulsion layers is hardened with the compound represented by the general formula (1), and the halogen The pH of the outermost film on the silver halide emulsion side is 3.5 to
It is achieved by a silver halide photographic light-sensitive material characterized by being 6.0.

Hereinafter, the present invention will be described in detail.

The hydrazine derivative used in the present invention is not particularly limited, but a compound represented by the following general formula [H] is desirable.

[0009]

Embedded image

In the formula, A represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents-.
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₂ — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group. A carbamoyl group or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group or the like.

Of the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferred.

[0012]

Embedded image

In the formula, R ¹ is an aliphatic group (eg octyl group, decyl group), aromatic group (eg phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg pyridyl group, cenyl group, Represents a furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group having 8 or more carbon atoms is relatively inert to photographic properties, such as an alkyl group. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and m
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group. In the general formula [Ha], R ² is a hydrogen atom,
Alkyl group, alkenyl group, alkynyl group, allyl group,
It represents a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group, or an oxycarbonyl group. Most preferred R ²
Is a —COOR ³ group and —CON (R ⁴ ) (R ⁵ ).
Group (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group,
Represents an alkynyl group, an aryl group or a heterocyclic group, and R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0020]

Embedded image

[0021]

Embedded image

[0022]

[Chemical 6]

[0023]

Embedded image

[0024]

Embedded image

Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The addition amount may be any amount as long as it gives a high contrast (amount of high contrast), and the grain size of the silver halide grains, the halogen composition,
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
It is in the range of ^-1 mol, preferably in the range of ^10-5 to ^10-2 mol.

The hydrazine derivative used in the present invention is
It is added to the silver halide emulsion layer or an adjacent layer.

In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0030]

Embedded image

In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorptive group in the molecule.

Specific examples of these nucleation accelerators [Na] will be given below.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₁₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific compounds represented by the general formula [Nb] include the compounds shown below.

[0039]

Embedded image

[0040]

Embedded image

Specific examples of other preferable nucleation promoting compounds are described in JP-A-6-258751, page (13), “0062”.
~ (15) page "0065" (2-1)
To (2-20) and 6-258751 (1
5) Pages “0067” to (16) “3-1 to 3-6” described in “0068”.

These nucleation promoting compounds can be used in any layer on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or a layer adjacent thereto.

Next, the pyridinium salt derivative used in the present invention is represented by the following general formula [Pa], [Pb] or [Pc].

[0044]

Embedded image

In the formula, A ₁ , A ₂ , A ₃ , A ₄ and A ₅ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ₁ , A ₂ , A ₃ , A ₄
And the heterocycle composed of A ₅ may have a substituent, and they may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an aryloxy group. , Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group,
It represents a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group. As preferred examples, A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are 5- or 6-membered rings (for example, pyridine, imidazole, thiazole, oxazole, pyrazine, pyrimidine rings, etc.), and more preferred examples are given. A pyridine ring can be mentioned.

B _P represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene or --SO ₂
-, -SO-, -O-, -S-, -CO-, -N
(R ₆₎ -, it represents what is configured alone or in combination (R ₆ represents an alkyl group, an aryl group, a hydrogen atom). As a preferable example, B _p is alkylene, alkenylene,
Mention may be made of alkylene oxides.

R ₁ , R ₂ and R ₅ represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms. R ₁ and R ₂ may be the same or different. As the substituents, A ₁ , A ₂ ,
It has the same meaning as the groups mentioned as the substituents for A ₃ , A ₄ and A ₅ .

As a preferred example, R ₁ , R ₂ and R ₅ each represent an alkyl group having 4 to 10 carbon atoms. Further preferable examples are a substituted or unsubstituted aryl group and a substituted alkyl group. X _p ⁻ represents a counter ion necessary for balancing the charges of the entire molecule, and represents, for example, chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an intramolecular salt. Specific examples of the compounds are shown below.

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

Next, the tetrazolium salt used in the present invention is represented by the following general formula [T].

[0055]

Embedded image

In the present invention, the substituents R ₁ , R ₂ , and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are hydrogen atoms or Hammett's sigma value (σP) showing electron withdrawing degree. ) Is preferably negative.

Hammett's sigma value for phenyl substitution is well documented, for example, Journal of Medical Chemistry.
Chemistry) Volume 20, page 304, 1977
Year, C. As a group having a particularly preferable negative sigma value, which can be found in reports such as C. Hansch and the like, for example, a methyl group (σ _P = −0.17 or less, any σ _P value) ethyl group ( -0.15), cyclopropyl group (-0.21), n-propyl group (-0.13),
iso propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34) and the like, all of which are useful as a substituent of the compound of the general formula [T] of the present invention.

N represents 1 or 2, and examples of the anion represented by X _T ^n- are halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid,
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonate anion such as toluene sulfonate anion, higher alkylbenzene sulfonate anion such as p-dodecylbenzene sulfonate anion, higher alkyl sulfate ester anion such as lauryl sulfate anion, boric acid anion such as tetraphenylboron, di- A dialkyl sulfosuccinate anion such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion, higher aliphatic anions such as stearic acid anion, and polymers having an acid radical such as polyacrylate anion.

Specific examples of the compound represented by the general formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0060]

Embedded image

The above-mentioned tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, Volume 55, pp. 335-483.

The hydrazine derivative and nucleation accelerator, pyridinium salt derivative, or tetrazolium salt used in the present invention may be used in any layer on the silver halide emulsion layer side, preferably a silver halide emulsion layer. Alternatively, it is preferably used for the adjacent layer.

The optimum amount of addition is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but generally it is 10 per mol of silver halide. The range of ^-6 to 10 ^-1 mol is preferable, and especially 1
The range of 0 ^-5 to 10 ^-2 mol is preferable.

Next, examples of the hardener used in the present invention include compounds represented by the following general formula (1).

[0065]

Embedded image

In the compound represented by the general formula (1),
R ₁₂ and R ₁₃ have a linear, branched or cyclic carbon number of 1 to
Examples thereof include 20 alkyl groups (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group) and aryl groups having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group). Also R ₁₂ and R
₁₃ may have a substituent, and examples of the substituent include those mentioned as the substituents of R _{1 to} R ₁₁ in the general formulas [1] to [6] described in JP-A-5-289219. Can be mentioned. It is also preferable that R ₁₂ and R ₁₃ are combined to form a ring together with the nitrogen atom, and a particularly preferable example is the case of forming a morpholine ring or a pyrrolidine ring. R ₁₄ represents a hydrogen atom or a substituent, and examples of the substituent include JP-A 5-2.
R _{1 in} General Formula [1] to General Formula [6] described in No. 89219.
Although the examples of the substituents for R ₁₁ to R ₁₁ are mentioned, a hydrogen atom is particularly preferable. L represents a single bond and has 1 carbon atom
To 20 alkylene groups (for example, methylene group, ethylene group, trimethylene group, propylene group), C6 to 20
An arylene group (for example, a phenylene group) and a divalent group (for example, a baraxylene group) obtained by combining them, an acylamino group (for example, a -NHCOCH ₂₂ group),
It represents a divalent group such as a sulfonamide group (eg, —NHSO ₂ CH ₂ — group). Preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group. X ₃
Represents a single bond or —O—, —N (R ₁₅ ) —, and R ₁₅
Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (e.g., a methyl group, an ethyl group, a benzyl group, etc.);
20 aryl groups (for example, phenyl group), having 1 to 1 carbon atoms
20 alkoxy groups (eg, methoxy group, etc.),
Hydrogen atoms are particularly preferred. Specific examples of preferred hardeners are given below.

[0067]

Embedded image

Other preferable compounds as the hardener are
Compounds (1) to (17) described on pages 11 to 13 of Japanese Patent Application No. 6-144823.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer of the present invention are used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

In addition to the above, an inorganic or organic hardener can be added to the photographic emulsion of the present invention as a crosslinking agent for hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro). -S-triazine, bis (vinylsulfonyl)
Methyl ether, N, N′-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, Phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used in combination. These hardeners are used by Research Disclosure.
rch Disclosure) Volume 176 17643
(Issued December 1978), page 26, paragraphs A to C.

The film surface pH on the silver halide photographic emulsion layer side used in the present invention is the pH measured after coating and drying,
The measurement is performed by dropping 1 cc of pure water per 1 cm ^{2 of the} measured portion with a pH meter. In the present invention, when lowering the film surface pH, citric acid, oxalic acid, succinic acid, sulfuric acid,
An acid such as nitric acid, acetic acid or carbonic acid, or an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or sodium acetate can be used when increasing the film surface pH, but more preferably Organic acids such as citric acid, oxalic acid and succinic acid are preferably used. Further, these acids can be present in any layer on the silver halide emulsion layer side, such as a layer adjacent to the emulsion layer or another layer via the adjacent layer in the silver halide emulsion layer. The same method can be applied when adjusting the pH when using a photographic additive. Further, the pH of the film surface on the silver halide emulsion layer side of the present invention is preferably 3.5 to 6.0, more preferably 4.5 to 5.5. A big effect was seen.

The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, but preferably, silver chlorobromide containing 60 mol% or more of silver chloride or 60 mol% or more of silver chloride. It is silver chloroiodobromide containing silver chloride.

The average grain size of silver halide is 0.7 μm.
m, particularly 0.5 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. Gives a silver halide emulsion having a substantially uniform grain size.

The silver halide grains used in the silver halide emulsion include cadmium salt, zinc salt, lead salt, thallium salt, ruthenium salt, osmium salt and iridium salt in at least one of the grain forming process and the growing process. Alternatively, a Group 8 transition metal such as a rhodium salt, or a complex salt containing these elements is preferably added.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As methods for chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these methods may be used alone or in combination. A preferred chemical sensitization method is sulfur sensitization. Examples of the sulfur sensitizer include, in addition to a sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, rhodanines, and polysulfide compounds. Can be used.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of reduction sensitizers include stannous salts, amines,
Formamidine sulfinic acid, silane compounds, ascorbic acid and the like can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. In addition to the present invention, the sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, and the like. A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus,
A 5- to 6-membered heterocyclic ring such as a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, Research Disclosure No. 176
Volume RD-17643 (December 1978 issue) No. 23 to 2
P. 4, RD34686 (1993) U.S. Pat. No. 4,42
Those described in Nos. 5,425 and 4,425,426 can be used. In the present invention, 600n
The effect of stabilizing the performance was great in the sensitizing dye which is sensitive to light having a relatively long wavelength of m or more. As a sensitizing dye having a particularly large effect, JP-A-6-194771,
JP-A-6-194774, JP-A-6-242533
JP-A-5-119425, JP-A-5-15818
No. 1, Japanese Patent Application No. 6-195578, JP-A No. 6-2304
The sensitizing dyes described in No. 97 are mentioned. Particularly preferred are compounds represented by the general formulas [1] to [6] described in JP-A-6-250327, page 24.

In the present invention, the method of dissolving or dispersing the sensitizing dye and adding it to the emulsion is described in US Pat.
482,981, 3,585,195, 3,4
No. 69,987, No. 3,425,835, No. 3,34
2,605, British Patent 1,271,329,
Nos. 038,029 and 1,121,174, and U.S. Pat. Nos. 3,660,101 and 3,658,546 can be used. US Patent 3,48
The dissolution may be carried out using ultrasonic vibration described in US Pat. No. 5,634.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resea).
rch Disclosure) Volume 176 17643
(Published December 1978), page 23, IV, paragraph J.

The addition amount of the sensitizing dye used in the present invention varies depending on the shape and size of silver halide grains, but is 4 × 10 ⁻⁶ to 8 per mol of silver halide.
It can be used at × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the surface area of the silver halide grain is 2 × 10 ⁻⁷ to 1 m ² per m ^2.
The addition amount of 3.5 × 10 ^-6 mol is preferable, and 6.5 × 10.
The addition amount of ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

In the silver halide photographic light-sensitive material of the present invention,
Various compounds can be contained for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, azoles,
For example, benzothiazolium salts, nitroindazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles ( 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1) , 3,3a, 7-tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. It can be added a number of compounds known as such antifoggants or stabilizers.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The silver halide emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, Methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used.

The silver halide photographic light-sensitive material of the present invention comprises
Various other additives are used. For example, desensitizers,
Examples include plasticizers, slip agents, development accelerators, oils and dyes.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure 176
No. 6, pages 22 to 31, etc. can be used.

In the silver halide photographic light-sensitive material of the present invention, the emulsion layer and the protective layer may be a single layer or multiple layers composed of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Those useful as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

Further, in the present invention, it is desirable to use a DIR compound which releases a development inhibitor by being oxidized during development processing.

For the silver halide photographic light-sensitive material of the present invention, it is desirable to use a DIR compound which releases a development inhibitor by being oxidized during development processing. Specifically, it can be represented by the following general formula [D].

General Formula [D] A- (Tm) _n -X In the formula, A represents a redox mother nucleus, and-(Tm) n-X can be released by being oxidized during development processing. Represents an atomic group that can be trained. As such an atomic group, hydroquinone, catechol, naphthohydroquinone, aminophenol, pyrazolidone, hydrazine, hydroxylamine, reductones and the like are preferably used. T
m represents a divalent linking group and may have a timing adjusting mechanism. n represents 0 or 1. X represents a development inhibitor, and is specifically a known development inhibitor having a hetero atom. Specific preferred examples of these A, Tm and X include those described in JP-A-3-174143 and JP-A-3-29643. The DIR compound particularly preferably used in the present invention includes the following general formulas (2) and (3)
Alternatively, the compound represented by (4) may be mentioned.

[0098]

Embedded image

In the general formula (2), R ₁ represents an aliphatic group or an aromatic group. G _l is -C (= N-G ₂ -R ₂ )-, -P
(O) (= N-G 2 -R 2) - or -CO- group, -CO
-CO- group, -CS- group, -S0- group, -SO ₂ - represents a group. G ₂ is a mere bond, —O—, —S— or —N
(R ₂ )-, wherein R ₂ represents a group having the same definition as R ₁ or a hydrogen atom.

A _l and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. At least one of A ₁ and A ₂ is a hydrogen atom.

Tm represents a divalent linking group, and n represents 0 or 1. PUG represents a development inhibitor.

General formula (2) will be further described. R
_The aliphatic group represented by _l 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. This alkyl group may have a substituent.

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 an aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring and the like. Among them, those containing a benzene ring are preferred. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group for R _l may be substituted,
Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group,
Sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, carboxyl group, phosphoric acid amide group, and the like, As a preferable substituent, a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 1)
20), aralkyl group (preferably having 7 to 3 carbon atoms)
0), an alkoxy group (preferably having a carbon number of 1 to 30)
Group), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 carbon atom). To 40), a ureido group (preferably having 1 to 40 carbon atoms), a phosphoric acid amide group (preferably having 1 to 40 carbon atoms) and the like.

As G ₁ , a —CO— group and a —SO ₂ — group are preferable, and a —CO— group is the most preferable. A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula (2), Tm represents a divalent linking group and may have a timing adjusting function. T
The two linking groups represented by m represent groups that release PUG from Tm-PUG released from the oxidant of the redox mother nucleus through one or more steps of reaction.
Examples of the divalent linking group represented by Tm include U.S. Pat. No. 4,248,962 (JP-A-54-145135).
Releasing PUG by an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat.
310,612 (JP-A-55-53330) and 4,358,525, which release PUG by an intramolecular ring closure reaction after ring cleavage, US Pat.
No. 30,617, No. 4,446,216, No. 4,48
No. 3,919, JP-A-59-121328, and the like, with the formation of an acid anhydride by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its chloroplast, PU
G-releasing agent: US Pat. No. 4,409,323,
No. 4,421,845, Research Disclosure No. 21,228 (December 1981), U.S. Pat. No. 4,416,977 (JP-A-57-135944).
No.), JP-A-58-209736 and JP-A-58-2097.
No. 38, etc. to produce quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG: US Pat. No. 4,420, No. 554 (JP-A-57-57)
136640), JP-A-57-135945, 5
7-188035, 58-98728 and 58.
No. 209737, etc., which releases PUG from the 7-position of the enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle: Nitrogen atom of the nitrogen-containing heterocycle described in JP-A-57-56837. Releasing PUG by an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group conjugated with U.S. Pat. No. 4,146,3
96 (JP-A-52-90932), JP-A-59-9
3442, 59-75475, 60-2491.
No. 48, No. 60-249149, etc., which release PUG with the formation of aldehydes;
No. 146828, No. 57-179842, No. 59-1
Releasing PUG with decarboxylation of the carboxyl group described in 04641; -O-COOCR _a R _b -PUG
(R _a and R _b represent a monovalent group) and releases PUG with decarboxylation and subsequent formation of aldehydes; isocyanate described in JP-A-60-7429. And the like, which release PUG with the formation of the following: those which release PUG by the coupling reaction with the oxidant of the color developing agent described in US Pat. No. 4,438,193 and the like. Specific examples of these divalent linking groups represented by Tm are described in JP-A-61-236549.
And JP-A-1-269936. PUG represents a group having a development inhibiting effect as (Tm) _n -PUG or PUG.

Development inhibitors represented by PUG or (Tm) _n -PUG are known development inhibitors which have a heteroatom and are linked via a heteroatom, these are, for example, CK・ MEEs (CEK Mees)
And T. H. James (TH james)
Written by The Theory of the Photographic Process (The Theory of the Photographic Process)
3rd Edition, 196
6 years, published by Macmillan, 344
Pp. 346 and the like.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those enumerated as the substituents of R ₁ , and these groups may be further substituted. Preferred substituents are nitro group, sulfo group, carboxyl group, sulfamoyl group, phosphono group, phosphinic acid group and sulfonamide group.
As the development inhibitor represented by PUG, there can be used a development inhibitor that can react with a developer component when it flows out into the developer to be converted into a compound having less inhibitory properties. A redox compound using such a development inhibitor is disclosed in JP-A-4-1330.
51, the same 4-13639, the same 4-136840, the same 4
-136841, 4-136843, 4-2789
39, 4-283743, and Japanese Patent Application No. 3-69466.

In the general formula (2), R _l or-(T
m) _n- PUG incorporates therein a ballast group which is commonly used in a non-moving photographic additive such as a coupler and a group which promotes adsorption of a compound represented by the general formula (2) to silver halide. It may be. The ballast group is an organic group giving a molecular weight sufficient to prevent the compound represented by the general formula (2) from substantially diffusing into another layer or the treatment liquid, and an alkyl group, an aryl group, a heterocyclic group, It comprises one or more combinations of ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption-promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid and tetrazoline-5. -Thion,
1,2,4-triazoline-3-thione, 1,3,4-
Oxazoline-2-thione, benzimidazoline-2-
Cyclic thioamide group such as thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, Heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom next to it is synonymous with a cyclic thioamide group having a tautomer relationship with this, specific examples of this group are those listed above. Group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzthiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine. , Nitrogen, like azaindene, oxygen Such as sulfur and heterocyclic quaternary salts such as 5- to 6-membered nitrogen-containing heterocyclic group and base lens imidazolinium, a combination of carbon and the like. It may be further substituted with a suitable substituent. Examples of the substituent include those mentioned as the substituent of R ₁ .

In the general formulas (3) and (4), R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃
Represents a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group, or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. Tm represents a timing group. , N represents 0 or 1. PUG represents a development inhibitor residue. X represents O or NH. Z represents an atomic group necessary for constituting a 5- or 6-membered heterocycle.

An alkyl group represented by R ₁ , an aryl group,
Alternatively, the heterocyclic group is preferably a methyl group, a p-methoxyphenyl group, a pyridyl group or the like. Among the acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group represented by R ₂ and R ₃ , preferably an acyl group and carbamoyl group. And a cyano group. The total number of carbon atoms in these groups is preferably 1-20. R _{1 to} R ₃ may further have a substituent, and as the substituent, for example,
Halogen atom (chlorine atom, bromine atom etc.), alkyl group (eg methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group etc.), cycloalkyl group (eg cyclopentyl) Group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p
-Chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, n-butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino). Groups, etc.), alkylthio groups (eg methylthio group, ethylthio group, n-butylthio group etc.), arylthio groups (eg phenylthio group etc.), sulfonylamino groups (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido groups ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group etc.), sulfamoylamino group (eg dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethyl Carbamoyl group, dimethyl calc Moyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), Sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (eg methylamino group, ethylamino group, dimethylamino group etc.) , A hydroxyl group, a nitro group, an imide group (for example, a phthalimido group, etc.), and a heterocyclic group (for example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group, etc.).

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,
323, No. 3,674,478, Research
Disclosure No. 21228 (December 1981), JP-A-57-56837, JP-A-4-43
No. 8 and the like.

The 5- or 6-membered heterocycle represented by Z may be a single ring or a condensed ring, and is a 5- or 6-membered heterocycle having at least one O, S, or N atom in the ring. Can be mentioned. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

Preferred development inhibitor residues for PUG include, for example, US Pat. No. 4,477,563, JP-A-60-218644, JP-A-60-221750, and JP-A-60-221750.
The development inhibitor residues described in 0-233650 or 61-11743 are mentioned. General formula (2),
Specific examples of the compound represented by (3) or (4) will be given.
In addition to these, JP-A-3-174143 and JP-A-3-24
Examples thereof include those described in JP-A-9643 and JP-A-7-5629, but the present invention is not limited thereto.

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

In the present invention, it is preferable to use an F type activator. As a specific compound example, JP-A-5-22
No. 4328, pages 14 to 18 can be mentioned.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone), 3-pyrazolidones (eg 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol,
1-aryl-3-pyrrolodins (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p
-Methylaminophenyl) -3-aminopyrazoline, 1
-(P-aminophenyl) -3-aminopyrazoline, 1
-(P-amino-N-methylphenyl) -3-aminopyrazoline, etc.), and transition metal complexes (Ti, V, Cr, M
It is a complex salt of a transition metal such as n, Fe, Co, Ni or Cu, and may be in a form having a reducing power for use as a developing solution thereof, for example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , Fe ²⁺
In the form of a complex salt such as, and as a ligand, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and The salt etc. are mentioned. ) Or the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, amino It is preferable to use a combination of phenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844,
4-26838, 4-362942, 1-3
Examples thereof include compounds described in No. 19031.

The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. Sulfurous acid is preferably 0.25 mol / liter or more. Particularly preferably, it is at least 0.4 mol / liter.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 8.5-10.5.

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, in an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.
In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing liquid, those having a generally used composition can be used. Fixing is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium amber, etc. can be added to the fixing solution.

If desired, the fixer may contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid),
Compounds such as a pH adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. Further, it may be diluted before use, or may be used as it is.

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C.

The silver halide photographic light-sensitive material of the present invention is preferably processed using an automatic processor. At this time, the processing is performed while replenishing a fixed amount of a developing solution proportional to the area of the photosensitive material. The development replenishment amount is 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably it is 75 to 200 ml per m ² .

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from when the leading edge of the film is inserted into the automatic developing machine to when it is removed from the insertion zone when the processing is performed using the automatic developing machine. It is preferably -60 seconds. The total processing time referred to here includes the total process time required for processing the black-and-white light-sensitive material, and specifically, for the processing, such as development, fixing, bleaching, washing, stabilizing, and drying. Time including all process time, that is, Dr
It is the time of y to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
More preferably, the total processing time (Dry to Dry) is 15 to 50 seconds.

In the automatic processor, a heat transfer member having a temperature of 90 ° C. or higher (for example, a heat roller of 90 to 130 ° C.) or 15
Radiating object of 0 ° C or higher (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.), and direct heat generation to radiate heat, or heat energy from a resistance heating element to copper, stainless, nickel It emits infrared rays by transmitting heat to various types of radiators such as ceramics, and emits infrared rays.

[0135]

EXAMPLES The effects of the present invention will be specifically illustrated by examples.

Example 1 (Preparation of Silver Halide Emulsion) An aqueous silver nitrate solution and a mixed aqueous solution of NaCl and KBr were controlled so as to have a silver halide composition of 70 mol% silver chloride and 30 mol% silver bromide by the controlled double jet method. To grow silver halide grains. At this time, the mixture was 36 ° C., pAg 7.8, pH 3.
Under conditions of 0, and Na ₃ RhCl ₆ was added to silver 1 during grain formation.
2 × 10 ^-7 mol was added per mol. After the completion of mixing, 80 mg of the following S-1 was added per mol of silver. Thereafter, desalting was carried out with modified gelatin treated with phenylisocyanate, and a bactericide composed of a mixture of the following compounds [A] [B] [C] and ossein gelatin were added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%. The emulsion thus obtained contained 4-hydroxy-6-methyl-per mole of silver.
60 mg of 1,3,3a, 7-tetrazaindene was added,
Further, 5 mg of chloroauric acid and 0.5 mg of sulfur flower were added to 1 mol of silver, and the pH was adjusted to 5.8 and pAg was adjusted to 60.
Chemical aging was performed at 80 ° C. for 80 minutes. After the ripening, 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver, and KI300 was further added.
mg, S-2 350 mg, and then S-3 40
mg was added.

[0137]

Embedded image

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides. The following prescriptions (1) to (4) were simultaneously applied onto the undercoat layer in the order close to the undercoat layer. On the other undercoat layer on the opposite side, a backing layer was applied according to the following prescription (5) so that the amount of gelatin would be 3.1 g / m ^2, and the protection of the following prescription (6) was further applied thereon. A sample was obtained by coating the layer so that the amount of gelatin was 1 g / m ² .

Formulation (1) composition of antihalation layer Gelatin 0.3 g / m ² sodium dodecylbenzenesulfonate 50 mg / m ² DIR compound: No. 14 80 mg / m ² Formulation (2) Emulsion layer composition Gelatin 1.7 g / m ² Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² Hardening agent: Table 1 3 × 10 ⁻⁵ mol / m ² Nucleation accelerator: Na-3 1 × 10 ⁻⁴ mol / m ² Polymer latex 1 0.7 g / m ² Colloidal silica 0.5 g / m ² Compound K 45 mg / m ² Water-soluble polymer V-1 20 mg / m ² Surfactant: saponin 0.1 g / m ² : sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² formulation (3) intermediate layer composition gelatin 0.5 g / m ² dodecyl sodium benzenesulfonate 50 mg / m ² polymer latex 2 0.3 g / m ² formulation (4) emulsion protective layer composition gelatin 0.5 g / m ² polymer latex 2 0.1 g / m ² matting agent The average particle diameter 3.5μm silica 20 mg / m ² Surfactant: Sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² Surfactant ^F-2 2mg / m 2 promoter: hydroquinone 50 mg / m ^2: 1 -Phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5 mg / m ² Acid: shown in Table 1 Hardener: shown in Table 1 Formulation (5) Backing layer composition Gelatin 2.8 g / m ² Surfactant Agent: Sodium dodecylbenzenesulfonate 50 mg / m ² Colloidal silica 0.5 g / m ² Formulation (6) Backing protective layer composition Gelatin 0.6 g / m ² Matting agent: Polymethyl methacrylate 50 mg / m with an average particle size of 4.0 μm ² Surfactant: sodium sulfosuccinate: di (2-ethylhexyl) ester 10 mg / m ² Hardener: Glyoxer 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3,5-triazine 35 mg / m ²

[0140]

Embedded image

(Developer formulation) Pure water (ion exchanged water) 800 ml Potassium carbonate 55 g Hydroquinone 15 g Dimezone S (1-phenyl-4-hydroxymethyl-4-methylpyrazolidone) 1.0 g DTPA-5Na (diethylenetriamine pentaacetic acid) 5 sodium) 1.45 g potassium bromide 5 g 5-methylbenzotriazole 0.2 g 1-phenyl-5-mercaptotetrazole 0.03 g sodium sulfite 40 g diethylene glycol 40 g pH adjustment with potassium hydroxide pH 9.8 Finally, 1 l with pure water Finished.

(Fixing solution formulation) Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50%) W / V aqueous solution) 15.7 g Gluconic acid (50% W / V aqueous solution) 8.55 g Aluminum sulfate (48% aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid Amount to bring pH to 4.6 when using Finished to 1 liter.

(Processing conditions) In the above processing, GR
An automatic developing machine of 26SR (manufactured by Konica Corporation) was used.

Development: 35 ° C., 20 seconds, replenishment amount 100 ml / m ² fixing; 33 ° C., 10 seconds, replenishment amount 40 ml / m ² water washing; normal temperature, 10 seconds Squeeze; 2 seconds drying; 40 ° C., 8 seconds All treatments It took 50 seconds.

For replenishment, a new solution having the above-described formulation was used for both the developing solution and the fixing solution.

(Evaluation method) High temperature stability was determined by the following method.

The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and developed and fixed according to the above-mentioned prescription to obtain an optical densitometer Konica Corporation.
Sensitivity was determined using PDA-65 manufactured by K.K. The sensitivity was determined by the reciprocal of the exposure amount giving a fog density + 3.0 transmission density.

Two same samples were prepared under light shielding, one was stored at 40 ° C. for 7 days, and the other was stored at 23 ° C. for 7 days (both under humidity 55%), and then exposed by the same method as above. 40 when the sensitivity of the sample stored at 23 ° C is set to 100.
The sensitivity of the sample stored at ℃ was determined. In other words, this value is 100
It can be considered that the nearer to, the better the high temperature storability of the light-sensitive material is.

[0149]

[Table 1]

[0150]

Embedded image

From the results shown in Table 1, it is understood that the samples of the present invention have good stability at high temperature storage.

Example 2 (Preparation of silver halide emulsion) A silver halide composition of 70 mol% silver chloride and 30 mol% silver bromide was mixed by the controlled double jet method in the same manner as in Example 1. The silver halide grains were grown. In this case, mixing is 40 ° C, pA
g of 7.5 and pH of 3.0, N during the particle formation
a ₃ RhCl ₆ was added in an amount of 7 × 10 ^-7 mol per mol of silver. After the mixing was completed, desalting was carried out in the same manner as in Example 1, and a bactericide and ossein gelatin were added in the same manner and redispersed.
The resulting emulsion was an emulsion composed of cubic grains having an average grain size of 0.3 μm and a coefficient of variation of 10%. To the emulsion thus obtained, 60 mg of 1-phenyl-5-mercaptotetrazole was added per mol of silver, and 5 mol per mol of silver was further added.
pH 5.8, pA with the addition of 0.3 mg of chloroauric acid, 0.2 mg of sulfur flower and 0.3 mg of triphenylphosphine selenide
Chemical aging was performed at 60 ° C. for 30 minutes under the condition of g 6.5.
After completion of aging 4-hydroxy-6-methyl-1,3,3
900 mg of a, 7-tetrazaindene per 1 mol of silver
In addition, 350 mg of S-2 and 40 mg of S-3 were added.

(Preparation of silver halide photographic light-sensitive material) The same as in Example 1 except for the formulation described below.

Formulation (2) Emulsion layer composition Gelatin 1.7 g / m ² Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² Hardening agent: Compound of Table 2 3 × 10 ⁻⁵ mol / m ² polymer latex 1 0.7 g / m ² colloidal silica 0.5 g / m ² compound K 45 mg / m ² water-soluble polymer V-1 20 mg / m ² surfactant: saponin 0.1 g / M ² : sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² formulation (4) emulsion protective layer composition gelatin 0.2 g / m ² polymer latex 2 0.1 g / m ² matting agent: average particle size 3.5 μm silica 20 mg / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² surfactant ^F-2 2mg / m 2 promoter: Haidoroki Emissions 50 mg / m ^2: 1-phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5 mg / m ² Acid: hardener shown in Table 2: Evaluation method shown in Table 2, the method of Example 1 It was carried out according to. Table 2 shows the results.

[0155]

[Table 2]

From the results of Table 2, good results were obtained as in Example 1 even when the tetrazolium compound was used.

Example 3 (Preparation of silver halide emulsion) The same emulsion as in Example 2 was used.

(Preparation of silver halide photographic light-sensitive material) The same as in Example 1 except for the formulation described below.

Formulation (2) Emulsion layer composition Gelatin 1.7 g / m ² Silver halide emulsion Silver amount 3.3 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² Hardening agent: Compound of Table 3 Polymer latex 1 0.7 g / m ² Colloidal silica 0.5 g / m ² Compound K 45 mg / m ² Water-soluble polymer V-1 20 mg / m ² Surfactant: Saponin 0.1 g / m ² : Sodium sulfosuccinate isopentyl Normal decyl ester 8 mg / m ² formulation (4) Emulsion protective layer composition Gelatin 0.2 g / m ² Polymer latex 2 0.1 g / m ² Matting agent: Silica having an average particle diameter of 3.5 μm 20 mg / m ² Surfactant: Sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Surfactant F-2 2 mg / m ² Accelerator: Hydroquinone 50 mg / m ² : 1-phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5 mg / m ² acid: shown in Table 3 hardener: shown in Table 3 The evaluation method is based on the method of Example 1. Table 3 shows the results.

[0160]

[Table 3]

From the results shown in Table 3, even when the pyridinium compound was used, the samples of the present invention showed good results as in Example 1.

[0162]

According to the present invention, excellent high temperature storage stability,
It was possible to provide a very stable negative-working black-and-white silver halide photographic light-sensitive material, particularly a silver halide photographic light-sensitive material for printing plate making.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on one surface of a support and containing a gelatin and a hydrazine derivative in at least one layer on the silver halide emulsion layer side. At least one of the silver halide emulsion layers is hardened with a compound represented by the following general formula (1), and the film surface pH of the outermost surface on the silver halide emulsion layer side is 3.5 to 6.0. A silver halide photographic light-sensitive material characterized by: Embedded image [In the formula, R ₁₂ and R ₁₃ are linear, branched or cyclic carbon atoms 1
Represents an alkyl group having 20 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and R ₁₂ and R ₁₃ may be bonded to each other to form a ring with a nitrogen atom. R
₁₄ represents a hydrogen atom or a substituent. L represents a single bond, and also represents a divalent group such as an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms and a divalent group obtained by combining them, an acylamino group or a sulfonamide group. . X ₃ represents a single bond or —O—, —N (R ₁₅ ) —, and R ₁₅ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Indicates an alkoxy group. ] 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer on one side of a support and containing gelatin and a tetrazolium derivative in at least one layer on the silver halide emulsion layer side. At least one of the silver halide emulsion layers is hardened with the compound represented by the general formula (1), and the outermost film surface p on the silver halide emulsion layer side.
A silver halide photographic light-sensitive material, wherein H is 3.5 to 6.0. 3. A silver halide photographic light-sensitive material having a silver halide emulsion layer on one surface of a support and containing gelatin and a pyridinium compound in at least one layer on the silver halide emulsion layer side, At least one of the silver halide emulsion layers is hardened with the compound represented by the general formula (1), and the pH of the outermost surface of the emulsion layer is 3.5 to
A silver halide photographic light-sensitive material characterized by having a value of 6.0.