JPH08286305A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photosensitive material treatable under a bright safe light and having a highly contrasty photographic characteristic by including a specified silver halide particle in a silver halide emulsion layer, and including a specified hydrazine compound in the silver halide emulsion layer and/or other hydrophilic colloid layers. CONSTITUTION: A silver halide particle with a silver chloride content of 95mol% or more which contains cyanochromium complex ions represented by [Cr(CN)6-n Ln ]<m-> (wherein L represents H2 O or OH) or 1×10<-7> per mole of silver halide is included in a silver halide emulsion layer, and at least one of a hydrazine compound having an anionic group or a nonionic group forming an intermolecular hydrogen bond with the hydrogen atom of hydrazine near the hydrazine group and a hydrazine compound represented by the formula is included in the silver halide emulsion layer and/or the other hydrophilic colloid layer. In the formula, A0 represents a difluoromethyl group or a monofluoromethyl group, and R0 represents an aromatic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide black and white photographic light-sensitive material for forming a silver image as a final image, and more specifically, it is handled in an environment which can be called a bright room. The present invention relates to a reversal silver halide black-and-white photographic light-sensitive material suitable for use in the field of photoengraving, capable of forming a negative tone silver image having high contrast.

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print reproduction, particularly in the work processes of collecting and returning plates, the work efficiency and work environment are improved by working in a brighter environment. That is, there is provided a silver halide light-sensitive material for plate making that can be handled in an environment that can be called a bright room. As a method of making a light-sensitive material that can be handled in a bright room by lowering its sensitivity to visible light, a silver halide emulsion mainly containing silver chloride, a rhodium salt, an iridium salt,
A method using an emulsion to which inorganic and organic desensitizers such as pinacryptol yellow and phenosafranine are added is well known. 0.05 to 0.5 without chemical sensitization
A method of using a rhodium salt and / or an organic desensitizer in a fine grain silver chloride or fine grain silver chlorobromide emulsion having a size of μm is preferably used. Furthermore, in combination with these emulsions,
A method of incorporating a yellow dye or an ultraviolet absorbing dye into a light-sensitive material is used for the purpose of sensitivity adjustment and safelight safety.

On the other hand, the light-sensitive material used in the plate-collecting and reversing process has the following features:
There is a demand for what has a so-called ultra-high contrast photographic property, which has a high blackening density in which image areas and non-image areas are clearly distinguished. In particular, the halftone image and the line image original as the return original are overlapped and exposed (so-called character image formation is performed).
In this case, there is a demand for a light-sensitive material having good line drawing reproduction performance (extracted character quality).

As a method for imparting ultra-high contrast photographic characteristics to a light-sensitive material, a method of incorporating a vitrazine derivative or a tetrazolium compound into the light-sensitive material is known, and the above-mentioned inorganic and organic desensitizers and yellow. When the method of incorporating a dye or an ultraviolet absorbing dye into the light-sensitive material is combined, there may be a problem that the effect of the hydrazine derivative or the tetrazolium compound on the contrast enhancement is hindered or the good reproducibility of the line drawing is lost. It was

As an image system capable of obtaining ultra-high contrast photographic characteristics in a silver halide black and white photographic light-sensitive material for return,
JP-A-60-140338, JP-A-61-238049
No. 63-183438, No. 63-296034.
No. 61-198147, No. 61-198148.
No. 61-240235. However, the pH of the developer used in these inventions is 11 or more. A developer with a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage. Therefore, a silver halide photographic light-sensitive material containing a hydrazine derivative is developed with a developer having a lower pH to obtain a high contrast image. Is required.

However, when the pH of the developing solution is low, the effect of increasing the contrast of the hydrazine derivative is lowered, and a high contrast image cannot be obtained. Although attempts have been made to develop more active hydrazine derivatives and nucleation accelerators in order to promote higher contrast, the long-term storage stability of the light-sensitive material may be reduced in some cases.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a reversal silver halide photographic light-sensitive material which can be handled under bright safelight (substantially bright room) and has ultrahigh contrast photographic characteristics. To provide. A second object of the present invention is to provide a light-sensitive material which can be handled under a bright safelight (substantially in a bright room) and has good line drawing reproduction performance (extracted character quality). A third object of the present invention is to provide a light-sensitive material which has a super-hard tone photographic property even when processed with a low pH developer having a pH stable to 11 or less against air oxidation, and which has good extracted character quality. Especially.
A fourth object of the present invention is to provide a light-sensitive material having good long-term storage stability.

[0008]

These objects of the present invention are to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has the following general formula. A silver halide emulsion layer and / or a silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more containing 1 × 10 ⁻⁷ or more of cyanochrome complex ion represented by (I) per mol of silver halide; A hydrazine compound having at least one anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine near at least one hydrazine group in at least one of the other hydrophilic colloid layers, or the following general formula ( It was achieved by a silver halide photographic light-sensitive material characterized by containing at least one hydrazine compound represented by II). General formula (I) _{[Cr (CN) 6-n L} n ] in ^m- wherein, L is H ₂ O, represents OH, n represents 0 or 1, m represents 3 or 4. General formula (II)

[0009]

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In the formula, A ₀ represents a difluoromethyl group or a monofluoromethyl group, and R ₀ represents an aromatic group.
However, R ₀ contains a substituent containing an adsorption promoting group on silver halide.

The present invention will be described in detail below. In the present invention, silver halide grains are doped with a cyanochrome complex ion represented by the following formula (I). (I) [Cr (CN) _6-n L _n ] ^{m-In the} formula, L is H ₂ O or OH, n is 0 or 1, and m is 3 or 4. n is preferably 0. m is preferably 3.

The cyanochrome complex ion exists in an ionic form in an aqueous solution. For this reason, the counter cations of the complex ions are technically insignificant. As a counter cation,
Ions that are easily miscible with water and are suitable for the precipitation operation of the silver halide emulsion may be selected. Examples of counter cations include alkali metal ions (eg sodium ions,
Potassium ion, rubidium ion, cesium ion,
Lithium ion, etc.), ammonium ion, and alkylammonium ion. The alkyl ammonium ion is shown in the following formula. [R ₁ R ₂ R ₃ R ₄ N] ^{+ in the} formula,
R ₁ , R ₂ , R ₃ and R ₄ are lower alkyl groups each bonded to an N atom and having 6 or less carbon atoms.
Examples of the lower alkyl group include methyl group, ethyl group, propyl group, iso-propyl group and n-butyl group. R
It is preferred that ₁ , R ₂ , R ₃ and R ₄ are the same. Examples of preferable alkylammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n-butyl) ammonium ion.

The cyanochrome complex ion is added after being dissolved in water or a solvent mixed with a suitable organic solvent miscible with water (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.). can do.

The cyanochromium complex ion should be added directly to the reaction solution at the time of silver halide grain formation, or to an aqueous halide solution for forming silver halide grains or other solution to form grains. Preferably, When silver halide grains are doped with cyanochrome complex ions, they may be present uniformly inside the grains, and JP-A-4-208936 and 2-1.
As disclosed in JP-A No. 25245 and JP-A-3-188437, the particle surface layer may be doped with a higher concentration. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, the silver halide grains are physically aged by using silver halide fine grains doped with a cyanochrome complex ion. Alternatively, a cyanochrome complex ion may be introduced into the particle surface phase. It is also possible to combine the above methods. Preferably, the particle surface layer is highly doped. A method for doping a high concentration cyano metal complex ion with a particle surface layer is disclosed in JP-A-2-
125245, 3-188437 and 4-2.
It is described in each publication of No. 08936. Methods using silver halide fine particles doped with cyano metal complex ions are described in US Pat. Nos. 5,252,451 and 5,256,53.
No. 0 There is a description in each specification. The same can be applied to the cyanochrome complex ion of the present invention. Doping amount of cyanochrome complex ion is 1 × 10 ^-7 per mol of silver halide.
The molar ratio is preferably 1 × 10 ⁻² mol or less and more preferably 1 × 10 ⁻⁶ or more and 1 × 10 ⁻³ mol or less. The hydrogen ion concentration in the reaction solution when the cyanochrome complex ion is added is preferably pH 3 or higher.

Specific examples of the cyanochrome complex ion are shown below. (I-1) [Cr (CN) _6] ^3- (I-2) _{[Cr (CN) 5 (H 2} O) ] ^3- (I-3) [Cr (CN) ₅ (OH)] ⁴

The fact that the cyanochromium complex ion exhibits a photographic effect different from that of other cyanometal complexes can be estimated as follows. When light is absorbed by silver halide grains, photoelectrons and holes are generated. The lifetime of this excited photoelectron can be measured using microwave photoconduction. For example,
Emulsions doped with Group VIII hexacyano metal complexes such as iron, ruthenium, cobalt and iridium (JP-A-6-51
No. 423), the photoelectron lifetime is extended and a temporary shallow electron trap is generated. As is well known, when a shallow electron trap is generated, the probability that the electron contributes to latent image formation becomes high and the photographic sensitivity is improved.

On the other hand, even with the same cyano metal complex, in the case of the cyanochrome complex of the present invention, when the lifetime of excited electrons is similarly measured, it shows a remarkably short lifetime. Therefore, it is considered that the cyanochrome complex has a strong electron trapping ability. It is presumed that this is the cause of lowering the photographic sensitivity and increasing the contrast. As described above, the photographic effect of the cyanochrome complex is clearly different from that of the Group VIII hexacyano metal complex in terms of the physical properties of the doped particles.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide, silver chloroiodobromide or silver chloride in which 95 mol% or more, particularly 99 mol% or more, is composed of silver chloride. . If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.20.
μm or less. It is particularly preferably 0.08 to 0.16 μm. If the particle size exceeds 0.2μ, γ decreases and Dmax of the practical skill decreases. In the present invention, the reaction temperature is 5 as a mixing condition for adjusting the silver halide grains.
The silver potential is 70 mV or more, preferably 300 mV to 500 mV, or 5,6-cyclopentane-4-hydroxy-1,3 at 0 ° C. or lower, preferably 40 ° C. or lower, under a condition that the stirring speed is sufficiently high for uniform mixing. 80 mV in the presence of a stabilizer such as 1,3a, 7-tetrazaindene
Good results can be obtained by adjusting at ~ 120 mV. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodispersion means that at least 95% of the weight or the number of particles is ± 4 of the average particle size.
It is composed of particle groups having a size within 0%, more preferably within ± 20%. The silver halide grain of the present invention preferably has a regular crystal such as a cube, an octahedron and a tetradecahedron, and a cubic is particularly preferable.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples are US Pat.
48,060, British Patent No. 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a first tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. Since the silver halide emulsion of the present invention contains a cyano metal complex, chemical sensitization may be hindered. When chemical sensitization is performed, it is preferable to use a zinc compound in combination, as described in Japanese Patent Application No. 5-35605.

The hydrazine compound used in the present invention is
A hydrazine compound having an anionic group in the vicinity of a hydrazine group or at least one nonionic group having an intramolecular hydrogen bond with a hydrogen atom of hydrazine, or a hydrazine compound represented by the above general formula (II).

Further, the hydrazine compound having an anionic group near the hydrazine group and a nonionic group forming an intramolecular hydrogen bond with the hydrogen atom of hydrazine will be specifically described.

Examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group is formed by 2 to 5 atoms selected from at least one kind of carbon atom, nitrogen atom, oxygen atom and sulfur atom between the nitrogen atom close to the anionic group of hydrazine and the anionic group. Means that the binding chain is intervened. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and contains at least an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A group having one. As the nonionic group, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group,
Examples thereof include urethane group, ureido group, acyloxy group, and acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred.

Preferred nucleating agents used in the present invention are those represented by the following general formulas (III) to (V). General formula (III)

[0025]

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

[0027]

[Chemical 4]

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

[0029]

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

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

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

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

The alkyl group of R _3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkoxy group, and is, for example, methoxy, isopropoxy or benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ =
When 2, R ³ is preferably an amino group or an alkoxy group.

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

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

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

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

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

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler or may have an adsorption promoting group to silver halide. The diffusion resistant group has 8 to 30 carbon atoms, preferably 12 to 25 carbon atoms. The adsorption promoting group for silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide) and mercaptos (eg 5-
Mercaptotetrazole, 3-mercapto-1,2,4
-Triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole and other heterocyclic mercapto, alkylmercapto, arylmercapto) and 5- to 6-membered to form iminosilver Is a nitrogen-containing heterocycle (for example, benzotriazole). As those having a silver halide adsorption promoting group,
It also has a structure in which the adsorptive group is protected and the protecting group is removed during the development process to enhance the adsorptivity to silver halide.

In the general formulas (III) to (V), radicals from which hydrogen atoms of two compounds are removed may be bonded to each other to form a bis type. In the general formulas (III) to (V), the general formulas (III) and (IV) are preferable, and the general formula (III) is more preferable. Furthermore, the general formula (III)
To (V), the following general formulas (VI) to (V)
III) is more preferable, and general formula (VI) is the most preferable. General formula (VI)

[0042]

[Chemical 6]

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

[0044]

[Chemical 7]

(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (V), and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (IV). ) General formula (VIII)

[0046]

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

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

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

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The hydrazide compound represented by the following general formula (II) will be specifically described.

[0056]

[Chemical 15]

In the formula, A ₀ represents a difluoromethyl group or a monofluoromethyl group, and R ₀ represents an aromatic group. However, R ₀ contains a substituent containing an adsorption promoting group to silver halide. Among the compounds represented by the general formula (II), preferred compounds are represented by the following general formula (IX).

[0058]

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In the formula, A ₁ represents a difluoromethyl group or a monofluoromethyl group, R ₇ represents a divalent aromatic group, and X ₁ represents an adsorption promoting group on silver halide. R ₇₁ and R ₇₂ represent a divalent aliphatic group or an aromatic group, L ₁₁ and L ₁₂ represent a divalent linking group, and m ₂ and m ₃ each independently represent 0 or 1. General formula (I
Among the compounds represented by X), preferred compounds are represented by the following general formula (X).

[0060]

[Chemical 17]

In the formula, X ₁₁ , A ₁₁ , R ₈₁ , R ₈₂ , L ₂₁ and m ₂₁
And m ₃₁ are respectively X ₁ and A in the general formula (IX).
₁ , R ₇₁ , R ₇₂ , L ₁₂ , m _2, and m ₃ have the same meanings, Y ₇ represents a substituent, and n represents an integer of 0 to 4.
Next, the compound represented by formula (II) will be described in detail. The aromatic group represented by R ₀ in the general formula (II) is a monocyclic or bicyclic aryl group and an aromatic heterocyclic group. Specific examples thereof include a benzene ring, naphthalene ring, pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, furan ring, thiophene ring, thiazole ring and indole ring. A ₀ preferably contains a benzene ring, and particularly preferably a benzene ring. R ₀ may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, an acyl group, an oxycarbonyl group, a carbamoyl group, N-sulfonylcarbamoyl group, carboxyl group, substituted amino group, acylamino group, sulfonamide group, ureido group, urethane group, sulfonylureido group,
Alkylthio group, arylthio group, sulfonyl group, sulfamoyl group, acylsulfamoyl group, carbamoylsulfamoyl group, sulfo group, cyano group, halogen atom, phosphinyloxy group, phosphinylamino group, sulfamoylamino group , Oxamoylamino group and the like. These groups may be further substituted. Among these, a sulfonamide group, a ureido group, an acylamino group, a carbamoyl group, an alkoxy group, a substituted amino group, an alkyl group, a hydroxy group, a halogen atom, a carboxyl group and an oxycarbonyl group are preferable, and a sulfonamide group and a ureido group are particularly preferable. preferable. R ₀ has a substituent, but at least one substituent of R ₀ contains an adsorption promoting group on silver halide.

The adsorption promoting group on silver halide is preferably a thioamide group, a mercapto group, a group having a disulfide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group is a divalent group represented by -CS-amino- and may be a part of the ring structure or may be an acyclic thioamide group.
Useful thioamide adsorption promoting groups are described, for example, in US Pat.
030,925, 4,031,127, 4,0
80,207, 4,245,037, 4,25
5,511, 4,266,013, and 4,2
76, 364, and "Research Disclosure", Volume 151, No. 15
162 (November 1976), and Vol. 176, No.
It can be selected from those disclosed in 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione and 4-thiazoline-2-thione group. Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like can be mentioned. It may be substituted. As the mercapto group, an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide group having a tautomer relationship with Are synonymous, and specific examples of this group are the same as those listed above).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group include 5- to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferable examples include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole and triazine.
These may be further substituted with appropriate substituents.
Preferred as the adsorption promoting group is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2
-Mercaptothiadiazole group, 3-mercapto-1,
2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group forming iminosilver (for example, , A benzotriazole group, a benzimidazole group, an indazole group, etc.). In the present invention, the adsorption promoting group includes its precursor. The precursor is an adsorption promoting group with a precursor group, which is released by the developing solution for the first time during development, and reacts with hydroxide ion or sulfite ion in the developing solution or with a developing agent. Disassembled as a trigger. Specifically, a carbamoyl group, a 1,3,3a, 7-tetrazainden-4-yl group, a lauryl group, an alkoxycarbonyl group, or 4
Examples thereof include a ureido group, a sulfonamide group, and a 4-substituted-2,5-dihydroxyphenyl group substituted with an amide group.

[0065] general formula R ₀ in (III), particularly preferred as adsorption accelerating group to silver halide includes in its substituent, a 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group , And a benzotriazole group, most preferably 3-mercapto-
1,2,4-triazole group and 5-mercaptotetrazole group.

Among the compounds represented by the general formula (II),
Preferred is represented by the general formula (IX),
This will be described in detail.

In the general formula (IX), R ₇₁ and R ₇₂ represent a divalent aliphatic group or aromatic group. What is a divalent aliphatic group?
A substituted or unsubstituted, straight-chain, branched or cyclic alkylene group, an alkenylene group, or an alkynylene group, and an aromatic group is a monocyclic or bicyclic arylene group. R
₇₁ and R ₇₂ are preferably an alkylene group or an arylene group, and most preferably R ₇₁ is a phenylene group and R ₇₂ is a phenylene group or an alkylene group. These may have the same substituent as described above for the substituent of R ₀ in the general formula (II). Examples of preferred substituents that R ₇₁ and R ₇₂ have include a halogen atom, an alkyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, an alkoxy group,
Aryloxy group, carbamoyloxy group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, sulfamoyl group, sulfonyl group, more preferably alkyl group, aryl group, carbamoyl group, alkoxy Group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group.

In the general formula (IX), the divalent linking group represented by L ₁₁ and L ₁₂ means --O--, --S--, --N ( _RN )-.
( _RN represents a hydrogen atom, an alkyl group, or an aryl group.), —CO—, —SO ₂ — and the like, or a group composed of a combination of these groups. The group consisting Here, specifically, -CON _(R N)
_{-, - SO 2 N (R} N) -, - COO -, - N (R N)
_{CON (R N) -, -} SO 2 N (R N) CO -, - SO
_{2 N (R N) CON (} R N) -, - N (R N) COCO
_{N (R N) -, -} N (R N) SO 2 N (R N) - is a group such as. In the general formula (IX), L ₁₁ is preferably -S
_{O 2 NH -, - NHCONH -} , - O -, - S -, - N
(R _N) - a and, most preferably -SO ₂ NH -, -
NHCONH-. L ₁₂ is preferably -CON
_{(R N) -, - SO} 2 NH -, - NHCONH -, - N
(R _N) CONH -, - it is COO-. Here L ₁₂ is -CON (R _N) - when referring to or _{-N (R N) CONH-, R} N is, as a substituted alkyl group, the general formula (IX)
May represent the group —R ₃ —X.

2 represented by R ₇ in the general formula (IX)
The valent aromatic group is preferably a monocyclic arylene group, and more preferably a phenylene group. When R ₇ represents a phenylene group, this may have a substituent. Examples of the substituent of the phenylene group include those described for the substituent that R ₀ of the general formula (II) may have, and preferably an alkyl group, an alkoxy group, a hydroxy group, an amino group and an alkylamino group. Group, acylamino group, sulfonamide group, ureido group, halogen atom, carboxyl group, sulfo group and the like, and the total number of carbon atoms of these groups is preferably 1 to 12, particularly preferably 1 to 8. When R ₇ represents a phenylene group,
It is particularly preferred that R ₇ represents an unsubstituted phenylene group.

In the general formula (IX), X ₇ represents an adsorption promoting group on silver halide, which is represented by R _{0 in the} general formula (II).
Are the same as those described for the adsorption-promoting group for silver halide contained in the at least one substituent, and their preferable ranges are also the same.

Of the compounds represented by the general formula (IX),
More preferable one is represented by the general formula (X). The substituent represented by Y ₇ in formula (X) means the compound represented by formula (IX)
The same as those described for the substituent which R ₇ may have in the above are mentioned, and the preferable range is also the same. n is preferably 0 or 1, and more preferably n is 0.

The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

[0081]

[Table 9]

The hydrazine compounds of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method, and then used.

The hydrazine compound of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × with ^respect to 1 mol of silver halide.
10 ⁻² mol is preferable, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferable, and 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferable. The hydrazine compound used in the present invention,
In addition to the above, RESEARCH DISCLOSURE Item 2351
6 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207,
4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4 , 560,638, 4,686,167, 4,912,016, 4,988,604, 4,994,365, 5,041,355, 5,104. , 769, British Patent No. 2,011,391
B, European Patent Nos. 217,310 and 301,799.
No. 356,898, JP-A-60-179734.
No. 61-170733 and No. 61-270744.
No. 62-178246 and No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-216544.
No. 5, No. 5-45761, No. 5-45762, No. 5-
No. 45763, No. 5-45764, No. 5-45765.
And those described in Japanese Patent Application No. 5-94925 can be used in combination.

The silver halide photographic light-sensitive material of the present invention preferably contains a nucleation accelerator in at least one of the emulsion layer and other hydrophilic colloid layers.

The nucleation accelerator preferably used in the present invention is a compound represented by the following general formulas (A), (B), (C) and (D).

[0086]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0088]

[Chemical 19]

In the formula, A represents an organic group for completing the heterocycle. B and D each represent a divalent group.
R ₁ and R ₂ each represent an alkyl group or an aryl group,
R ₃ and R ₄ represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt.

Details and compounds of the compounds of the general formulas (A) to (D) can be found in the description of Japanese Patent Application No. 6-250136 and the compound examples A201 to A262 therein. Many of the compounds represented by formula (A) are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

The compounds represented by the general formula (B), the general formula (C) and the general formula (D) can be synthesized by a generally well-known method (for example, Quart. Rev., 16, 163 (196).
It can be easily synthesized according to 2).

The addition amount of the compounds of the general formula (A), the general formula (B), the general formula (C) and the general formula (D) is not particularly limited, but it is 1 × 10 ⁻ per mol of silver halide. ⁵ to 2 × 10 ^-2 mol is preferably contained, especially 2 ×
The preferable addition amount is in the range of 10 ⁻⁵ to 1 × 10 ⁻² mol. The nucleation accelerator used particularly preferably in the present invention is a compound represented by the general formula (C).

When the compound of the general formula (A), the general formula (B), the general formula (C) or the general formula (D) is contained in the photographic light-sensitive material, it is dissolved in water as an aqueous solution. In the case of water-insoluble, as a solution of an organic solvent miscible with water such as alcohols (eg methanol, ethanol), esters (eg ethyl acetate), ketones (eg acetone), silver halide emulsion solution or hydrophilic It may be added to the colloid solution. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

When the above-mentioned hydrazine nucleating agent and nucleating accelerator are contained, it is necessary to suppress fog of the silver halide emulsion as much as possible. This is because fog is further increased by the hydrazine nucleating agent and the nucleation accelerator. Therefore, the silver halide grains of the present invention are
Or in the process of chemical sensitization, the following general formula (E),
It is preferable to add the thiosulfinic acid compounds represented by (F) and (G). This makes it possible to obtain an emulsion with low fog. (E) in _{R-SO 2 S-M (} F) R-SO 2 S-R 1 (G) R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is the same They may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas (E) to (G) may be polymers containing a divalent group derived from the structures represented by (E) to (G) as a repeating unit. For specific examples of the general formulas (E) to (G), see Japanese Patent Application No. 6-250.
Compound Examples (1-1) to (1-27) described in No. 136,
(2-1) to (2-20) and (3-1) to (3-9)
Can be mentioned.

Using the silver halide light-sensitive material of the present invention,
It is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in US Pat. No. 2,419,975 in order to obtain photographic characteristics having a safe light safety that can withstand ultra-high contrast and bright room applications. Instead, a stable developer can be used. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / liter or more of sulfite ion as a preservative, and a sufficiently high-contrast image can be obtained by a developer having a pH of 9.5 to 11.0.

There is no particular limitation on the development and fixing in the present invention, but it is preferable to use a dihydroxybenzene compound or reductone as a developing agent as a developing solution. Among these, a preferable developing solution in the case of using a dihydroxybenzene type developing agent has the following composition.
(1) 0.2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.06 mol / liter of 1-phenyl-3-pyrazolidone type or p-type
Aminophenol-based auxiliary developing agent, (3) 0.15-
It contains 1.2 mol / liter of free sulfite ion and (4) the compound represented by the general formula (H), and the concentration ratio of the compound represented by the general formula (H) and the dihydroxybenzene-based developing agent is 0.03. .About.0.12 and the pH is 9.0-11.
The developer is 0, and 9.5 to 10.7 is particularly preferable. General formula (H)

[0097]

Embedded image

In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = O or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.

Detailed description of the general formula (H) and specific compounds are described in Japanese Patent Application No. 5-282101.
Of these, ascorbic acid and erythorbic acid (stereoisomers) are preferable. The amount of the compound of the general formula (H) added is such that the concentration ratio of the compound represented by the general formula (H) / hydroquinone-based developing agent is the concentration of the compound represented by the general formula (H) of the dihydroxybenzene-based developing agent. The value divided by the concentration) is in the range of 0.03 to 0.12. A preferable concentration ratio is 0.03 to 0.10. A particularly preferable concentration ratio is 0.05 to 0.09.

Examples of the dihydroxybenzene type developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, but hydroquinone is particularly preferable. preferable. The concentration of the hydroquinone derivative in the developer is 0.2 to 0.75 mol / liter, preferably 0.2 to 0.5 mol / liter, particularly preferably 0.2 to 0.4 mol / liter. is there.

As the 1-phenyl-3-pyrazolidone derivative developing agent used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trilyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like are preferable, and 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are preferable.

The p-aminophenol-based developing agent used in the present invention includes N-methyl-p-aminophenol and p-aminophenol.
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / liter to 0.5 mol / liter, the latter of 0.0
It is preferably used in an amount of 6 mol / liter or less.

When the reductone is used as the developing agent, the compound of the above formula (H) is preferably used as the reductone, and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. In this case, the same auxiliary developing agent as the dihydroxybenzene type developing agent can be used, and a p-aminophenol type and / or 1-phenyl-3-pyrazolidone type auxiliary developing agent is preferable. When the compound of the general formula (H) is used as a developing agent, it is generally used in an amount of 5 × 10 ⁻³ to 1 mol, and particularly preferably 10 ^{−2 to} 0.5 mol per liter of the developing solution. It is a mole.

The preservative used in the developing solution preferred in the present invention is a free sulfite ion, and the form of addition to the developing solution includes sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like. The free sulfite ion concentration is 0.15 to 1.2 mol / liter,
It is preferably 0.3 to 1.0 mol / liter, and particularly preferably 0.3 to 0.8 mol / liter. The pH of the developer used in the developing treatment of the present invention is in the range of 9.0 to 11.0, preferably 9.5 to 10.7. Sodium hydroxide is used as the alkaline agent to set the pH.
It contains pH adjusters such as sodium carbonate, sodium triphosphate, potassium hydroxide, potassium carbonate, boric acid and the like.

In the developing solution used in the method of the present invention, a dialdehyde hardener or a bisulfite adduct thereof may be used. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. Examples include -n-butoxyglutaraldehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. Of these, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly prolonged. Specifically, it is 1 to 50 g, preferably 3 to 10 g per liter of the developing solution.

An antifoggant is used in the developer used in the method of the present invention, and examples thereof include indazole type, benzimidazole type and benztriazole type. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-
5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-thiadiazol-2-yl) thio] butane Sodium sulfonate, 5-amino-1,
3,4-thiadiazole-2-thiol and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

Further, various organic and inorganic chelating agents can be used in combination in the developing solution used in the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used.
As the organic carboxylic acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid,
Examples include tartar and the like, but the invention is not limited thereto.

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

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminotetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to the above, Research Disclosure 18170, JP-A-57-208554 and 54 -61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

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

In addition to the above composition, the developer used in the method of the present invention may optionally contain a buffering agent (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate), a solubilizing agent. (For example, polyethylene glycols,
These esters), pH adjusters (eg organic acids such as acetic acid), development accelerators (eg US Pat. No. 2,648,604).
No. 4, Japanese Patent Publication No. 4-9503, US Pat. No. 3,171,247.
Various pyridinium compounds and other cationic compounds described in No. 5, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, US Pat.
31832, 2950970, and 2577127.
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-9
509, Belgian Patent 682862, organic solvents described in U.S. Pat. No. 3,012,242, thioether compounds, etc., especially thioether compounds are preferable), and surfactants may be contained.

The development processing temperature and time are related to each other and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 400 ml or less, preferably 200 ml or less.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, Tyrone, It is an aqueous solution containing ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. The pH of the fixer is preferably 4.0 to 6.5,
Particularly preferably, it is in the range of 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
~ 45 ° C, fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, and particularly preferably 300 ml / m ² or less with respect to the processing amount of the light-sensitive material.

The light-sensitive material that has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
It is possible to eliminate the need for piping for the automatic processor. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-6-18350.
It is more preferable to provide a squeeze roller septic tank described in JP-A-2-287252. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or the whole of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with anti-vibration means according to the process by the method of the present invention is disclosed in JP-A-60-
As described in No. 235133, it can also be used for a processing liquid having a fixing ability which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when a small amount of water is used and / or to prevent the treatment agent component attached to the squeeze roller from being transferred to the treated film. Good. Further, to prevent contamination by dyes eluted from a light-sensitive material, JP-A-63-16
The dye adsorbent described in No. 3456 may be installed in the washing tank.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and as an example, there is JP-A-2-201357.
The baths containing the compounds described in JP-A No. 2-132435, JP-A No. 1-125255, and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material. In this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH buffers, hardeners, bactericides, fungicides, alkanolamines and surface active agents. As the water used for the agent, tap water, deionized water and halogen, ultraviolet germicidal lamps and various oxidizers (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, etc.).

The treatment liquid preferably used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147. On the other hand, in the case of reducing the replenishment amount, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area with the air in the processing tank. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971 and the like.
It is possible to preferably use those comprising four steps of fixing, washing with water and drying. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is powder, tablet, granule, powder, lump or paste, and the preferred form is JP-A-61-2599.
The form or tablet described in No. 21. The method for producing tablets is described in, for example, JP-A Nos. 51-61837 and 54-155.
038, 52-88025, British Patents 1,21
It can be produced by a general method described in No. 3,808,
Further, the granule treating agent is, for example, JP-A No. 2-109042,
2-109043, 3-39735 and 3-
It can be produced by a general method described in No. 39739 or the like. Furthermore, powder treating agents are disclosed in, for example, JP-A-54-133.
No. 332, British Patents 725,892 and 729,86.
No. 2 and German Patent No. 3,733,861 and the like, but can be produced by a general method.

The bulk density of the solid processing agent preferably used in the present invention is preferably 0.5 to 6.0 g / cm ³ , from the viewpoint of its solubility and the effect of the object of the present invention, and particularly, It is preferably 1.0 to 5.0 g / cm ³ .

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral sensitization described in JP-A Nos. 1-112235, 3-124560, 3-79928, 5-11389, and 4-330434. Pigment. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 7) Dye JP-A-2-103536, page 17, lower right column, line 1 to line 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 Dyes described in Kaihei 2-294638 and JP-A-63-296039. Further, solids described in WO88 / 04794, European Patent No. 456148, JP-A-5-11382, Japanese Patent Application No. 5-224717, Japanese Patent Application No. 6-117454, and the like. Disperse dye. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compounds Compounds represented by formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), JP-A-3-174143, pages 3 to 20 Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 11) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and European Patent No. 452,772. 13) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. Further, in Japanese Patent Publication No. 46-22507, Japanese Patent Publication No. 50-73625, US Pat. Nos. 34 88708, 3939130, 392 9482, and Japanese Patent Application No. 5-300182, or in the specification. Polymer latices having active methylene groups as described. 14) Organic desensitizers Compounds described in Japanese Patent Publication No. 3-76450, JP-A No. 63-64039, Japanese Patent Application No. 6-117454, etc. or the description thereof. 15) Amino group, ammoni JP-A-63-133145, page 8, line 5 to ammonium group, and nitrogen-containing, page 40, line 5. Compounds containing elementary heterocycles

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0121]

【Example】

Example 1 <Emulsion preparation> Emulsion A: pH containing sodium chloride kept at 40 ° C. and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate and sodium benzenethiosulfinate per mol of silver
Double jet of an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.5 × 10 ^-6 mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver in a 1.5% aqueous gelatin solution of 2.0%. According to the method, half of the silver amount of the final particles was simultaneously added at a potential of 95 mV for 3 minutes and 30 seconds to prepare 0.12 μm of core particles.
Then, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 4.5 × 10 ⁻⁶ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver were added in the same manner as above for 7 minutes to obtain an average particle size of 0.15μ
m silver chloride cubic grains were prepared. (Coefficient of variation 12%) After that, 4-hydroxy-6-methyl-1,3,3a,
1.5 × 10 ^{−3 of} 7-tetrazaindene per 1 mol of silver
Mole was added. Further, after this, the product is washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin is added. Compound- (a) and phenoxyethanol are added as preservatives per 1 mol of silver without chemical ripening. 50 mg, 4-hydroxy-6-methyl- as stabilizer
1,3,3a, 7-Tetrazaindene was added at 1.5 × 10 ⁻³ mol per mol of silver (as final particles, pH =
5.7, pAg = 7.5, Rh = 3.0 × 10 ⁻⁶ mol /
Ag mol).

Emulsion B; 1.5% gelatin aqueous solution having a pH of 6.5 and containing sodium chloride and sodium benzenethiosulfinate in an amount of 3 × 10 ^-5 mol per mol of sodium chloride and silver kept at 40 ° C. An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously added by a double jet method at a potential of 95 mV for 3 minutes and 30 seconds to halve the amount of silver of the final particles to adjust the particle size of the core to 0.12 μm. Then, 14.3 mol of silver nitrate aqueous solution and 1 mol of silver.
An aqueous sodium chloride solution containing 0 × 10 ⁻⁶ mol of K ₃ [Cr (CN) ₆ ] was added in the same manner as above for 7 minutes to prepare silver chloride cubic grains having an average grain size of 0.15 μm.
(Coefficient of variation: 12%) Other than that, the same preparation as in Emulsion A was carried out, and finally [Cr (CN) ₆ ] ^3- = 7 × 10 ^-6 mol /
It became particles containing Ag mol.

<Preparation of Emulsion Layer Coating Solution and Its Coating> Table 10
Emulsion The following compounds were added to the gelatin coating amount 0.9 g / m ² on the following support containing a subbing layer, a silver halide emulsion so that the amount of coated silver is 2.5 g / m ² as shown in The layers were applied. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² Nucleation accelerator 20 mg / m ² compound- (B) 10 mg / m ² compound- (c) 20 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² compound- ( d) (Hardener) 150 mg / m ² Furthermore, the hydrazine compounds of the present invention and comparative compounds are shown in Table 1.
It was added so that it was coated as 0.

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

<Preparation of Emulsion Protecting Lower Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.9 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound- (a) 5 mg / m ² compound- (e) 10 mg / m ² compound- (f ) 20 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.5 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8 g / m ² Amorphous silica matting agent 40 mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700 m ² / g) Amorphous silica matting agent 10 mg / M ² (average particle diameter 2.5μ, pore diameter 170Å, surface area 300m ² / g) N-perfluorooctanesulfonyl-N-propylglycine sympototadium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound -(A) 5 mg / m ² compound- (g) 20 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

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

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

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 2.22 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Dye [a] 140 〃 Dye [b] 140 〃 Dye [c] 40 〃 Dodecyl Sodium benzene sulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound- (h) 5 〃 N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

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

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

[0132]

[Chemical 21]

[0133]

[Chemical formula 22]

[0134]

[Chemical formula 23]

[0135]

[Chemical formula 24]

<Evaluation Method> (1) Evaluation of Photographic Properties The sample thus obtained was passed through an optical wedge to obtain a FPA-800FX printer manufactured by Fuji Photo Film Co., Ltd. (Lo
w mode), and exposed to Fuji Photo Film Co., Ltd. automatic processor FG-680AG and the following developer A at 38 ° C. for 20 seconds, fixed, washed with water and dried. The fixer used was the following fixer A. The following items were evaluated for these samples. 1) Sensitivity (S _1.5 ); logarithmic value of exposure amount giving a density of 1.5 (the smaller the value, the higher the sensitivity) 2) γ; (1.5-0.1) / {log (giving a density of 1.5) Exposure dose) -log (exposure dose that gives a density of 0.1)}

(2) Extracted character image quality In order to evaluate the extracted character image quality, Japanese Patent Publication No. 2-28,85
Document 6 of the structure shown in FIG. 1 of No. 6 "Transparent embedding base / film on which line image positive image is formed (line image original) / transparent embedding base / film on which halftone image is formed (mesh) Point original)), and then put the original and the emulsion surface of each sample in close contact with each other, expose them with an FPA-800FX (Low mode) printer in the same manner as in evaluation method (1), and use Fuji Processing was carried out at 38 ° C. for 20 seconds with an automatic processor FG-680AG manufactured by Photo Film Co., Ltd. and a developer A, fixing, washing with water and drying. The fixer used was fixer A. The exposure time of each sample was determined so that a halftone dot original portion having a halftone dot area ratio of 50% was imaged on each sample as halftone dots having a halftone dot area ratio of 50%. Here, the blank character image quality 5 is a character having a width of 30 μm when properly exposed such that 50% halftone dot area is 50% halftone dot area on the return light-sensitive material by using the original as shown in FIG. Is the image quality that is reproduced, and the image quality is very good. On the other hand, the extracted character image quality 1 is an unexplained extracted image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given. Rank is set.
A level of 3 or more is a practical level.

(3) Preservability ΔS _{1.5 The} sample was left under the condition of 45 ° C. and 70% for 20 days, then exposed through the optical wedge by the above-mentioned FPA-800FX (Low mode) printer, and developed in the same manner as above. It was fixed, washed with water and dried. The storability was evaluated by comparing this result with the sensitivity immediately after coating. As the sensitivity change, the change S of the logarithmic value (S _1.5 ) of the exposure amount giving a density of 1.5
_1.5 (immediately after coating) -S _1.5 (45 ° C., 70%, 20 days) evaluated. The larger this value is, the more sensitized the image is. <Developer A> Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4- Hydroxymethyl-4-methyl-1 phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole- Sodium 5-sulphonate 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide is added and water is added to 1 liter and the pH is adjusted to 10.5. 1 liter

<Fixer A> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 g Water was added to 1 liter 2 liters of water was added to 1 liter of the above fixing solution for use.

[0140]

[Table 10]

As can be seen from Table 10, the samples of the present invention are excellent in storability and have good image quality of extracted characters. Comparative compound-1 is extremely poor in storability, and comparative compound-2 cannot obtain sufficient activity by the treatment with developer A (pH = 10.5).

Example 2 A printer used was P-627 manufactured by Dainippon Screen.
FM, Mitsubishi Rayon Co., Ltd. between the light source and the sample at the time of exposure, Dialite P-100, 3 mm thick (transmittance of 393 nm is 50%, light of shorter wavelength side is absorbed, light of longer wavelength side is absorbed) Exposure was carried out by inserting a filter which transmits light), but the same results as in Example 1 were obtained (which means that the exposure was substantially carried out with light having a wavelength of 370 nm or more).

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
Cyanochrome complex ions represented by the following general formula (I) were added to the silver halide emulsion layer in an amount of 1 × 1 per mol of silver halide.
0 ^-7 comprise silver chloride content 95 mol% or more silver halide grains containing more, said silver halide emulsion layer and / or,
A hydrazine compound having at least one anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine near at least one hydrazine group in at least one of the other hydrophilic colloid layers, or the following general formula ( A silver halide photographic light-sensitive material containing at least one hydrazine compound represented by II). General formula (I) _{[Cr (CN) 6-n L} n ] in ^m- wherein, L is H ₂ O, represents OH, n represents 0 or 1, m represents 3 or 4. General formula (II): In the formula, A ₀ represents a difluoromethyl group or a monofluoromethyl group, and R ₀ represents an aromatic group. However, R ₀
Contains a substituent containing an adsorption promoting group for silver halide.