JPH09281624A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the occurrence of physical development fog even in the case of continuing development processing of a lot of the photosensitive materials by incorporating an N-containing heterocyclic compound having a mercapto group and an organo-polysiloxane compound. SOLUTION: This silver halide photographic sensitive material has hydrophilic colloidal layers including a silver halide emulsion layer on a support and contains at least one kind of N-containing heterocyclic compound having a mercapto group in the hydrophilic colloidal layers except the emulsion layer and at least one kind of organopolysiloxane compound in the emulsion layer or another hydrophilic colloidal layer. The N-containing heterocyclic compound is, preferably, embodied by a compound of formula I in which M is an H atom or a cation, and Z is a heterocyclic group having one or more nitrogen atoms. The organic polysiloxane compound is embodied by polyphenyl-siloxane, preferably, modified polysiloxanes, especially, by compounds represented by formula II in which R<11> is a divalent bonding group and R<12> is an H atom or a haydroxy group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material mainly used in the printing plate making industry and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the printing and plate making industry, colorization and complication of printed matter have been extremely advanced. Therefore, with the aim of shortening the work time as the number of printing points increases,
The demand for shortening the development processing time has increased, and when processing is performed using an automatic processor, the total processing time from when the leading edge of the film is inserted into the automatic processor to when it comes out of the drying zone is 90.
Processing within seconds has become common, and rapid processing within 60 seconds has also been performed. However, in the development processing by such an automatic developing machine, when a large amount of development processing is continuously performed, fogging due to physical development occurs at the leading edge or the trailing edge of the photosensitive material at the place of exiting the developing tank and entering the fixing tank. It has been a serious problem in terms of quality as a silver halide photographic light-sensitive material for printing plate making. As a method of suppressing these physical development fog, it is considered to use a compound generally known as an antifoggant for silver halide emulsions, but all of these compounds work to suppress physical development fog. is not. In addition, even those that act to suppress physical development fog,
It is necessary to use a large amount in order to suppress effectively,
The silver halide emulsion had a great influence on the photographic characteristics, especially on the sensitivity, and the sensitivity was lowered.

On the other hand, demands for improving the quality and stabilizing the quality of the silver halide photographic light-sensitive material for printing plate making, which is an intermediate medium for printing, are increasing year by year. It has been conventionally known to use various hydrazine compounds for the purpose of forming a high-contrast image in order to achieve higher quality of a silver halide photographic light-sensitive material. Addition of a hydrazine compound to a silver halide photographic emulsion or a developing solution is described in US Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine) and US Pat. No. 3,227,552. (Use of hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (containing β-monophenylhydrazide of aliphatic carboxylic acid as a stabilizer of silver halide sensitizer) , Ibid 2,41
No. 9,975, and "The Theory of Photog" by Mees.
Raphic process ”3rd edition (1966), page 281 etc.

[0004] Among them, in particular, US Patent No. 2,41
No. 9,975, when a hydrazine compound was added to a silver chlorobromide emulsion and development was performed with a developer having a high pH of 12.8, a gamma (γ) of more than 10 was obtained, and extremely hard photographic characteristics were obtained. Is listed. However, p
A strong alkaline developer having H close to 13 is easily oxidized by air, is unstable, and cannot withstand long-term storage or use. In contrast, US Pat. Nos. 4,168,977 and 4,22
4,401, 4,243,739, 4,26
9,929, 4,272,614, 4,32
According to the specification of 3,643 and the like, pH is 11.0 to 12.3.
Discloses a silver halide photographic light-sensitive material which gives extremely high-tone negative photographic characteristics by using the developer. In this new image forming system, only silver chlorobromide having a high silver chloride content can be used so far in order to obtain an extremely high contrast image, whereas silver iodobromide and silver iodochlorobromide can also be used. There is a feature called. Another feature of the conventional lith developer is that it can contain a large amount of a sulfite preservative, whereas it can contain a large amount of a sulfite preservative, so that it has relatively good storage stability.

The above-mentioned physical development fog has been a particularly serious problem in an extremely hard tone-sensitive photographic material containing these hydrazine compounds. That is, the compound considered to effectively act to suppress the physical development fog, significantly inhibits the contrast increasing effect of the hydrazine compound,
It has been difficult to achieve both suppression of physical development fog and high contrast.

Further, in the case of development processing using an automatic developing machine, it is necessary to replenish a fixed amount of a developing solution and a fixing solution proportional to the area of the light-sensitive material and to obtain stable photographic performance. It is common. Conventionally, to prevent fixing failure due to deterioration of fixing solution capacity, 400 per 1 m ²
Processing was performed while replenishing more than ml of fixer. However, in recent years, there has been an urgent need to reduce the amount of developing waste liquid as well as the amount of fixing waste liquid due to increasing concern about the environment.
1 m ^{2 of} a light-sensitive material containing the above hydrazine compound
When the continuous treatment is continued under the condition that the replenishing amount of the fixing solution is less than 300 ml, the pH of the fixing solution increases,
There is a problem that fog is more likely to occur due to the above-mentioned physical development, and under the condition of a small fixing replenishment amount of 300 ml or less per 1 m ² , physical development fog does not occur even if continuous processing is continued, and still hard photographic characteristics are obtained. There has been a demand for a treatment method that can be obtained.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material in which physical development fog does not occur even if a large amount of continuous development processing is performed without changing sensitivity and photographic characteristics. To provide the material.

Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material having a high contrast and a sufficient maximum density, and which does not cause physical development fog even when a large amount of continuous development processing is carried out. is there.

Thirdly, the object of the present invention is to maintain high photographic characteristics even when processing is performed while replenishing the fixing solution with an automatic processor at a rate of 300 ml or less per 1 m ² of the light-sensitive material. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material in which the occurrence of physical development fog is prevented.

[0010]

SUMMARY OF THE INVENTION The above objects of the present invention are to provide a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support. In the material, the hydrophilic colloid layer other than the emulsion layer contains at least one nitrogen-containing heterocyclic compound having a mercapto group, and the emulsion layer or another hydrophilic colloid layer contains at least one polysiloxane compound. And a silver halide photographic light-sensitive material.

The nitrogen-containing heterocyclic compound having a mercapto group will be described in detail. In the photosensitive material of the present invention,
As the nitrogen-containing heterocyclic compound having a mercapto group, the compound represented by the following general formula (1) is preferably used.

[0012]

Embedded image [In the general formula (1), M represents a hydrogen atom or a cation, and Z
Represents a heterocyclic residue containing at least one nitrogen atom, and the heterocyclic residue may be further condensed. ]

In the general formula (1), M represents a hydrogen atom or a cation (for example, an alkali metal ion or an ammonium ion), and the heterocyclic residue represented by Z may be further condensed. Specifically, imidazole, triazole, tetrazole, thiazole, oxazole, selenazole ring, benzimidazole, benzoxazole, benzothiazole, thiadiazole, oxadiazole, benzoselenazole, azaindene (for example, triazaindene, tetrazaindene, pentazine Den, etc.) and the like are preferable.

Further, these heterocyclic residue and condensed ring may be substituted with an appropriate substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, hydroxyethyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group), aryl group (eg, phenyl group, naphthyl group, etc.) ), A heterocyclic residue (such as a pyridine group), a halogen atom, a mercapto group, a cyano group, a carboxyl group, a sulfo group, a hydroxy group, an amino group, a nitro group, and an alkoxy group (such as a methoxy group).

Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to the following compounds.

[0016]

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[0017]

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In the light-sensitive material of the present invention, the nitrogen-containing heterocyclic compound having a mercapto group is contained in the hydrophilic colloid layer containing no silver halide emulsion. More preferably,
An adjacent layer of the silver halide emulsion layer, for example, an undercoat layer,
Alternatively, it may be contained in the protective layer. Since the content of the mercapto compound of the present invention in the layer varies depending on the characteristics of the silver halide emulsion used and the chemical structure of the compound,
A suitable content may vary over a wide range, but it is about 5 × 10 ^-5 to 1 × 1 per mol of silver in the silver halide emulsion.
A range of 0 ^-1 mol is practically useful, more preferably
The range of 4 × 10 ^{−4 to} 5 × 10 ⁻² mol is preferable.

The nitrogen-containing heterocyclic compound having a mercapto group of the present invention is generally known as a stabilizer for silver halide emulsions, and as described above, it does not impair the photographic characteristics such as sensitivity and tone. It may be contained in the silver halide emulsion layer. The content varies depending on the characteristics of the silver halide emulsion used and the chemical structure of the compound, but is preferably 2 × 10 ⁻³ mol or less per 1 mol of silver in the silver halide emulsion, and 8 × 10 ⁻⁴ per 1 mol of silver. It is more preferably not more than mol.

Next, the organic siloxane compound used in the light-sensitive material of the present invention will be described. Examples of the organic siloxane compound of the present invention include polyalkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane which are generally known, and JP-B-53. -292, Japanese Patent Sho 55-
49294, JP-A-60-140341, etc., organic polysiloxanes having an alkyl group having 5 or more carbon atoms, organic polysiloxanes having an alkoxy, hydroxy, hydrogen, carboxyl, amino, mercapto group in the side chain. A modified polysiloxane such as siloxane may be used, or a block copolymer having a siloxane unit or a graft copolymer having a siloxane unit as a side chain as disclosed in JP-A-60-191240 may be used.

Of these, modified polysiloxanes are preferable, and compounds represented by the following general formula (2) are particularly preferably used.

[0022]

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In the general formula (2), R ¹¹ represents a divalent linking group, R ¹² represents a hydrogen atom, a hydroxy group, a lower alkyl group,
Represents an alkoxyl group or the like, m and n each represent an integer of 1 to 20, p is an integer of 0 or 1 to 12, and q is 1 to 2
The integer of 0 and r represent the integer of 1-15. Specific examples of the compound represented by the general formula (2) are shown below. However, the present invention is not limited to the following compounds.

[0024]

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[0025]

[Chemical 6]

A part of the organosiloxane compound of the present invention can be generally obtained from Shin-Etsu Chemical Co., Ltd. and the like. For example, trade names Silicone Oil, KF-352, KF-3, marketed by Shin-Etsu Chemical Co., Ltd.
55, KF-615, KF-618, KF-851, X
-70-901 and so on.

The method for producing the organosiloxane compound of the present invention is as follows:
For example, EGRochou "Chemistry of the Silicone (Chapman & Hall 1951 edition)" pages 66-70, "Silicone processing and applications" (Kansai Plastics Research Group 1954) page 26, FGA
Stone and VAG Graham "Inorganic Polymers" (Academic Press 1962) 230-
Pp. 231 and 288 to 295, etc., and Japanese Patent Publications No. 35-10771 and 43-28694.
No. 45-14898, a method by addition reaction of olefins to siloxane containing SiH by a metal catalyst, or JP-B-36-22361.
It can be synthesized by applying the method of co-hydrolyzing each component organofluorosilane as described in the above publication.

The organosiloxane compound of the present invention may be contained in either the silver halide emulsion layer or the other hydrophilic colloid layer, but preferably in the hydrophilic colloid layer containing no silver halide emulsion. It is preferably contained. More preferably, it is contained in a layer adjacent to the silver halide emulsion layer, for example, an undercoat layer or a protective layer, and further preferably in the same hydrophilic colloid layer as the nitrogen-containing heterocyclic compound having a mercapto group. It is good to contain. The addition amount of the organosiloxane compound of the present invention is not particularly limited, but is preferably 0.0005 to ² g / m ² , more preferably 0.001 to 1 g / m ² , and particularly preferably 0.005 to 0.5 g / m ² . m ² . The addition method is to dissolve the siloxane compound in water, an organic solvent, a mixed solvent thereof or the like in advance and then add it to the hydrophilic colloid coating solution, or prepare it in the presence of an appropriate dispersant such as a surfactant. It can be added by a method such as addition as an aqueous dispersion.

A silver halide photographic light-sensitive material containing a hydrazine compound containing a compound having a mercapto group is disclosed in JP-A-60-153039 and 63-10.
3232 and the like, all of which are compounds having a mercapto group acting as an organic antifoggant. Further, JP-A-6-75319 discloses that a mercapto compound having a hydrophilic group is contained in a silver halide photographic light-sensitive material containing a hydrazine compound with silver chloride of 90 mol% or more and 0.2 μm or less. There is. This is to contain a mercapto compound having a hydrophilic group in the hydrophilic colloid layer on the side opposite to the emulsion layer to prevent silver stain in the developing solution. In addition, JP-A-6-75
No. 320 discloses a silver halide photographic light-sensitive material containing a hydrazine compound and containing a mercapto compound and a tetrazaindene compound in the emulsion layer. Even if treated with a developer whose activity has increased due to fatigue over time,
That is, stable photographic performance can be obtained.

However, when the mercapto compound is added to the emulsion layer in an amount effective for preventing physical development fog which is the object of the present invention, it adversely affects the photographic characteristics such as a decrease in sensitivity or hydrazine. In a silver halide photographic light-sensitive material containing a compound, the nucleating action of hydrazine is hindered, and sufficiently hard photographic characteristics cannot be obtained. Therefore, in order to obtain a similar antifoggant effect, a method of adding a mercapto compound to a hydrophilic colloid layer other than the emulsion layer is often used by those skilled in the art, but it is added to the hydrophilic colloid layer other than the emulsion layer. Then, the effect of preventing physical development fogging becomes weaker, and if the amount of addition is increased, there is a problem that the photographic characteristics and the nucleation action are also adversely affected.

On the other hand, the organosiloxane compound has been conventionally used in silver halide photographic light-sensitive materials for the purpose of improving the surface characteristics of photographic printing papers and photographic films such as stickiness, sticking resistance, scratch resistance and slipperiness. Has been used. JP-A-50-117414 and 60-14034
No. 1, No. 60-191240, No. 62-203152
No. 62-203155, JP-A-2-293843.
The details are described in the issue. The techniques described in these publications and the like are mainly applied to photographic films. In the present invention, in addition to the above effects, by using together with a mercapto compound, the organosiloxane compound does not adversely affect the photographic characteristics,
Alternatively, they have found that physical development fog can be prevented without impairing the nucleation action of hydrazine. The action of this organosiloxane compound is a novel effect which is not expected from the prior art.

The hydrazine compound used in the present invention will be described in detail. Examples of the hydrazine compound used in the present invention include U.S. Pat.
243,734, 4,272,614, 4,385,108, 4,269,929, 4,323,643, and JP-A-56-10624.
No. 4, No. 61-267759, No. 61-230145.
No. 62-270953, 62-178246.
No. 62-180361, No. 62-275247.
No. 63-253357, No. 63-265239.
And Japanese Patent Application Nos. 1-92356 and 1-99822, and the like, which can be used in the present invention, and are particularly represented by the following general formula (3). Preference is given to using hydrazine compounds.

[0033]

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In the general formula (3), A ₁ and A ₂ are hydrogen atoms,
An alkylsulfonyl group and an arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group, or a phenylsulfonyl group substituted so that the sum of Hammett's σ p is -0.5 or more), an acyl group having 20 or less carbon atoms (Preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's σp is −0.5 or more), or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (as a substituent) Is, for example, a halogen atom, an ether group, a sulfonamide group, an amide group, a hydroxy group, a carboxy group, or a sulfo group, and A ₁ and A ₂ are most preferably hydrogen atoms. The aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group. R
_The aromatic group represented by ₁ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O, and S atoms, which may be a monocyclic ring, May form a condensed ring with an aromatic ring or a heterocyclic ring.
The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R ₁ may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted.
For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, Sulfinyl group,
A hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thyuronium group, an isothioureido group, and the like. When possible, these groups may be linked to each other to form a ring. Further, R ₁ may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy groups, alkylphenoxy groups and the like.

The divalent organic group represented by Y ₁ is a group represented by an aliphatic group or an aromatic group. As an aliphatic group,
A straight-chain, branched or cyclic alkylene group, an alkenylene group or an alkynylene group. The aromatic group is a monocyclic or bicyclic arylene group, and examples thereof include a phenylene group and a naphthylene group. Y ₁ is more preferably an arylene group, and particularly preferably a phenylene group. Y ₁ may have a substituent, and as the substituent, for example, those enumerated as the substituents of R ₁ can be applied.

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). When G ₁ is a carbonyl group, preferred among the groups represented by R ₂ are alkyl groups (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonyl group). Methyl group etc.), aralkyl group (eg 2-hydroxybenzyl group etc.), aryl group (eg phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 4-methanesulfonamidophenyl group, 2 -Hydroxymethylphenyl group), general formula (4) and the like. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. When G ₁ is an oxalyl group, R ₂
Preferred as such are an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-hydroxymethylphenoxy group, 4-chlorophenoxy group), amino A group (for example, a 3-hydroxypropylamino group, a 2,3-dihydroxypropylamino group, a 2-dimethylaminoethylamino group, a 3-diethylaminopropylamino group, etc.), a general formula (4), etc., and particularly an amino group is preferable. R ₁ and R ₂ may be those in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,355,105 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms As an example thereof, Japanese Patent Laid-Open No. 63-
29751 etc. are mentioned.

[0037]

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Q ⁺ in the general formula (4) is a group containing a cationic group having at least one quaternary nitrogen atom, and is a straight or branched hydrocarbon chain having 1 to 4 carbon atoms. bound to G ₁ through, some or all of the chain may form part of a heterocyclic ring having quaternary nitrogen atoms. Preferred examples of Q ⁺ include a trialkylammonioalkyl group, a pyridinium-1-ylalkyl group, a 1-alkylpyridinium-2-yl group, a 1-alkylpyridinium-3-yl group, and a 1-alkylpyridinium-4-yl group. Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and the substituents are preferably those exemplified as the substituent of R ₁ . Further, when these groups form a ring structure, they may be condensed with another ring. A ^- is a counter anion of Q ^+, Cl preferred examples ^-, Br -, ^{p-toluenesulfonate,} but like methyl sulfonate, having a sulfo group as a Q ⁺ substituents, inner salt Is not present when forming

Next, specific examples of the compound represented by the general formula (3) are shown below, but the present invention is not limited to the following compounds.

[0040]

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[0041]

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[0042]

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[0043]

[Chemical 12]

The hydrazine compound of the present invention is described in, for example, JP-A-61-213847, JP-A-62-178246 and JP-A-62-178246.
-180361, 62-260153, 63-25
3357, U.S. Pat. Nos. 4,684,604, and 3,
379,529, 4,377,634, 4,332,878, 4,937,160, and Japanese Patent Application No. 63-98803. Can be synthesized.

In the light-sensitive material of the present invention, the hydrazine compound is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers. Since the content of the hydrazine compound of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range. A range of about 5 × 10 ^-6 to 8 × 10 ^-2 mole per mole of silver in the silver emulsion is practically useful, more preferably a range of 5 × 10 ^-5 to 1 × 10 ^-2 mole. .

The silver halide emulsion used in the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, silver chloride and the like can be used. When silver bromide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less.

The form, crystal habit, size distribution, etc. of the silver halide grains used in the present invention are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable. It is preferable that 90% or more of all the particles have a particle diameter within the range of ± 10% of the average particle diameter. The preparation method of silver halide emulsion is forward mixing, reverse mixing,
Any of known methods such as simultaneous mixing may be used. It is preferable that the emulsion after physical ripening is desalted and then coated with necessary additives, but the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is:
Chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allyl isothiocyanate, cystine, and rhodanine, U.S. Pat. Nos. 1,574,944, 2,278,947, and 2,410,689, Sulfur-containing compounds as described in Nos. 2,440,206, 3,187,458, 3,415,649, 3,501,313 and the like can be used. Along with sulfur sensitization, US Pat. Nos. 2,448,060 and 2,540,086
Nos. 2,556,245 and 2,566,263 can be used in combination with a sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium or ruthenium. Further, a sensitization method using various gold compounds such as potassium chloroaurate and auric trichloride and a palladium compound such as palladium chloride can be used in combination.

The silver halide emulsion of the present invention can be spectrally sensitized with a dye known as a sensitizing dye in the photographic industry. These dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holo-holer cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes. These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The silver halide photographic light-sensitive material of the present invention comprises
In addition to the photosensitive emulsion layer, an overcoat layer, an intermediate layer, a back coat layer, an undercoat layer and other hydrophilic colloid layers can be provided. These layers can also contain a matting agent.

The binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the silver halide photographic light-sensitive material of the present invention is
It is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Sugar derivatives such as starch derivatives; various synthetic hydrophilicities such as polyvinyl alcohol, partial acetals of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, etc. Polymeric substances can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull.Soc.Sci.Phot.Japan, N
o.16, p.30 (1966), enzyme-treated gelatin may be used, and a hydrolyzate or enzyme-decomposed product of gelatin may also be used.

The silver halide photographic light-sensitive material of the present invention comprises
In order to obtain high-contrast photographic characteristics using a stable developer having a pH of less than 11.0, an amine derivative, an onium salt or the like is contained as a nucleation accelerator in a silver halide emulsion layer or another hydrophilic colloid layer. Can be done. Examples of the amine derivative include, for example, JP-A-60-140340,
No. 50829, No. 62-222241, No. 63-12
Compounds described in specifications such as No. 4045 and No. 63-286840 can be used. The onium salt is preferably an ammonium salt or a phosphonium salt.
Preferred examples of the ammonium salt are described in JP-A-62-2.
Compounds described in the specifications such as 50439 and 62-280733 can be used. Examples of preferred phosphonium salts are described in JP-A-61-16.
Compounds described in specifications such as Nos. 7939 and 62-280733 can be used.

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

[0054]

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[0055]

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[0056]

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[0057]

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In the light-sensitive material of the present invention, the nucleation accelerator is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers. Since the content of the nucleation accelerator in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range. About 6 × 10 ^-6 per mole of silver in the emulsion
A range of 6 × 10 ⁻² moles is practically useful, more preferably a range of 6 × 10 ⁻⁵ to 2 × 10 ⁻² moles.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-). 6-hydroxy-S-triazine, etc.) or the like can be used alone or in combination.

The photographic emulsion used in the present invention is an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing the image quality due to irradiation, halation, etc., the character removal performance and other performance required in the printing and plate making industry. Other hydrophilic colloid layers of can include filter dyes known to those skilled in the art.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement of slipperiness, an emulsion dispersion, an adhesion prevention and an improvement of photographic characteristics (for example, , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. Non-ionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surface active agent containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group, such as an alkylcarboxylic acid salt, an alkyl sulfuric acid ester, an alkyl phosphoric acid ester, etc. Agents; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium It can be used cationic surface active agents such as.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α A polymer having a monomer component of a combination of β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, and styrenesulfonic acid can be used.

For the photographic light-sensitive material used in the present invention, any support known in the art can be used. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as necessary.

In order to obtain photographic characteristics of ultrahigh contrast using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, the silver halide photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10.5-1
With the developer of 2.3, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably
Development inhibitors or antifoggants such as nitroindazoles or benzotriazoles). In addition, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a silver stain preventing agent for the film (for example, 2-mercaptobenzimidazoles), etc. May be included. Specific examples of these additives are Research Disclosure 17
No. 6, 17643, etc.

Further, in order to obtain ultrahigh contrast photographic characteristics, the developing solution is disclosed in JP-A-56-106244 and JP-A-61-2.
67759, 61-230145, 62-2116.
47, and the amine compounds described in JP-A Nos. 2-50150 and 2-208652 can also be added.
The representative ones are listed below.

A-1) Nn-butyldiethanolamine a-2) 3-diethylamino-1,2-propanediol a-3) 2-diethylamino-1-ethanol a-4) 2-diethylamino-1-butanol a -5) 3-Diethylamino-1-propanol a-6) Triethanolamine a-7) 3-Dipropylamino-1,2-propanediol a-8) 2-Dioctylamino-1-ethanol a-9) 3 -Amino-1,2-propanediol a-10) 1-diethylamino-2-propanol a-11) n-propyldiethanolamine a-12) 2-di-isopropylaminoethanol a-13) N, N-di-n -Butylethanolamine a-14) 2-methylamino-1-ethanol a-15) 3-dimethylamino-1,2-propanedi A-16) 4-dimethylamino-1-butanol a-17) 1-dimethylamino-2-butanol a-18) 1-dimethylamino-2-hexanol a-19) 5-dimethylamino-1-pen Tanol a-20) 6-Dimethylamino-1-hexanol a-21) 1-Dimethylamino-2-octanol a-22) 6-Dimethylamino-1,2-hexanediol It suffices, but generally 0.
An amount of 005 to 1.0 mol / l can be added.

In the present invention, a system may be adopted in which a developing agent is incorporated in the light-sensitive material and processing is performed with an alkaline activator solution. (Japanese Unexamined Patent Publication Nos. 57-129436, 57-129433, 57-129434, and 5)
7-129435, U.S. Pat. No. 4,323,643). The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

As the fixing solution used in the fixing process of the silver halide light-sensitive material of the present invention, those having a generally used composition can be used. The fixing solution is generally an aqueous solution consisting of a fixing agent and other components, and the pH is usually 3.8 to 3.8.
It is 5.8. As a fixing agent, sodium thiosulfate,
Potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds that form soluble stable silver complex salts and known as fixing agents can be used.

A water-soluble aluminum salt which acts as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

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

In fixing the silver halide light-sensitive material of the present invention, the replenishing amount of the fixing solution is 300 ml / m ^2.
The effect of the present invention is particularly exerted when the following is satisfied. In the light-sensitive material of the present invention, the replenishment is preferably performed according to the processed area of the light-sensitive material, but the replenishment depending on the blackening rate, the replenishment over time and the like may be combined. In these cases, in all the methods, the total replenishment amount is defined as a value obtained by dividing the total replenishment amount by the total area of the light-sensitive material processed during that period.

[0072] The silver halide light-sensitive material of the present invention is fixing replenishing amount is that good photographic performance can be obtained even when the processing of more than 300 ml / m ² is carried out, fixing replenishing amount is 300 ml / m ² Also in the following, good photographic performance is provided, and a particularly preferable replenishing amount is 100 to 300 ml / m ^2.
It is.

It is preferable to use an automatic processor for photographic processing. In the present invention, even if the total processing time from putting the light-sensitive material into the automatic developing machine until it comes out is set to 60 to 90 seconds, a super photographic negative gradation photographic characteristic can be sufficiently obtained.

[0074]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the description.

Example 1 <Preparation of emulsion> 5 g of sodium chloride in 600 ml of water,
An aqueous solution containing 40 g of gelatin was used at 40 ° C. to control the pAg to 8.5 by the double jet method, an aqueous solution of silver nitrate, a water-soluble iridium salt of 3.25 × 10 ⁻⁶ mol / mol Ag, and 1.8 × 10 ⁻⁷ mol / mol Ag. A halogen solution containing a water-soluble rhodium salt is mixed to prepare a silver chlorobromide (silver bromide 30 mol%) emulsion having an average particle size of 0.25 μm, which is 0.2 mol% with respect to 1 mol of silver. After adding the potassium iodide aqueous solution as described above, the precipitate was washed with water and redissolved. Sodium thiosulfate (2 mg) and chloroauric acid (4 mg) were added to this emulsion per mol of silver, and the mixture was heated at 55 ° C. for 60 minutes for chemical sensitization.
4-hydroxy-6-methyl-1,3,3 as stabilizer
150 mg of a, 7-tetrazaindene was added. To this emulsion, the compound of Chemical formula 17 as a sensitizing dye was added at 2.5 × 10 ⁻⁵ mol / mol Ag, and the compound of Chemical formula 18 as a surfactant was added, and further 2-hydroxy-4,6-dichloro-1,
Prepared by adding 3,5-triazine sodium salt. <Preparation of protective liquid> As a protective liquid, an aqueous gelatin solution was prepared 1
8 surfactants, matting agents, 2-hydroxy-4,6-
Prepared by adding dichloro-1,3,5-triazine sodium salt. <Preparation of undercoat liquid and intermediate liquid> As the undercoat liquid and intermediate liquid,
It was prepared by adding the surfactant of Chemical formula 18, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt, to an aqueous gelatin solution.

As shown in Table 1, a mercapto compound was added to each of the above-mentioned coating liquids in an amount of 3 × 10 ⁻³ mol / mol Ag and an organosiloxane compound was added in an amount of 20 mg / m ² to obtain the layer constitution shown in Table 1. On a polyethylene terephthalate film, the emulsion layer is 5 g / m ^{2 of} silver nitrate and 3 g / g of gelatin.
such that m ^2, the protective layer, a subbing layer, an intermediate layer of gelatin was coated so as to 1 g / m ^2.

[0077]

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[0078]

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The samples shown in Table 1 were exposed to xenon flash light through an interference filter of 670 nm and a sensitometric wedge, and then developed at a temperature of 35 ° C. by using a developing solution 1 having the following composition and a fixing solution having the following composition. Second development, fixing, washing with water and drying. For this processing, an automatic processor (Dainippon Screen Mfg. Co., Ltd., LD-221Q
T) was used. The sensitivity value was determined as the exposure amount required to obtain a transmission density of 3.0, and Table 1 shows the relative value when the sensitivity value of the sample (No 1) containing no mercapto compound and organosiloxane compound was 100. Indicated. The results are shown in Table 1.

Further, in order to test the physical development fog, a sample having a processing length of 61 cm was subjected to continuous development processing on 5 sheets by the above automatic developing machine without exposure. Visually check the physical development fog at the tip and end of the sample developed on the 5th sheet.
The grade was evaluated. 1 is the worst, 5 is the best, and 1 and 2 are severely fogged and practically unusable. No. 3 has some fog, but it is barely usable. Nos. 4 and 5 have almost no fog and are usable levels. The results are shown in Table 1.

<Developer 1> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA / 2Na 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzene imidazole-5-sulfonic acid 0.2 g 3- (5-Mercaptotetrazole) benzene sodium sulfonate 0.2 g N-n-butyl Diethanolamine 12.0 g Sodium toluenesulfonate 8.0 g Water is added and adjusted to pH 11.8 with 1 l potassium hydroxide.

<Fixer> Ammonium thiosulfate 124.0 g Sodium sulfite 22.0 g Sodium tartrate 2H ₂ O 5.0 g Na ₂ B ₂ O ₄ 8H ₂ O 15.3 g Aluminum sulphate 9.5 g Water was added 1 l Adjust to pH 4.7 with acetic acid.

[0083]

[Table 1]

From the results shown in Table 1, the photographic light-sensitive material of the present invention (Sample Nos. 3 to 8, 13) in which a mercapto compound and a siloxane compound were added to the protective layer, the intermediate layer or the undercoat layer.
It can be seen that the samples Nos. 17 to 17) suppress the physical development fog without significantly lowering the sensitivity as compared with the photographic light-sensitive materials of Comparative Examples (Nos. 1, 9, and 19) containing no mercapto compound. Further, in the photographic light-sensitive materials (No. 2, 10 to 12) in which the mercapto compound was added to the emulsion layer and the photographic light-sensitive material in which the siloxane compound of No. 18 was not contained, physical development fog was suppressed, but a large decrease in sensitivity was observed. To be Further, a photographic light-sensitive material containing a mercapto compound and a siloxane compound in the same hydrophilic colloid layer (No.
4, 6 to 8) are photographic light-sensitive materials (N
Compared with Nos. 3 and 7), the physical development fog did not increase, and the decrease in sensitivity was small.

Example 2 2 × 1 of the hydrazine compound of H-6 was added to the emulsion of Example 1.
Samples shown in Table 2 were prepared in the same manner as in Example 1 except that 0 ⁻⁴ mol / mol Ag was added. These samples were exposed and developed in the same manner as in Example 1, gamma was determined, and physical development fog was tested in the same manner as in Example 1. Gamma was measured at tan θ of a linear portion having an optical density of 1.0 to 2.5.
Table 2 shows the results.

[0086]

[Table 2]

From the results shown in Table 2, the photographic light-sensitive materials of the present invention (Sample Nos. 22 to 27 and 32-36) in which the mercapto compound and the siloxane compound were added to the protective layer were the photographic light-sensitive materials of Comparative Examples (containing no mercapto compound). No20,
28, 38), it is understood that a high-contrast image can be obtained while suppressing physical development fogging. Further, a photographic light-sensitive material (No. 21, 29
31 to 31) and the photographic light-sensitive material containing no No. 37 siloxane compound, although physical development fog is suppressed, hydrazine development is also greatly suppressed, and a high contrast image cannot be obtained. Further, the photographic light-sensitive material (No. 23, 25, 27) containing the mercapto compound and the siloxane compound in the same hydrophilic colloid layer has a physical development fog more than the photographic light-sensitive material (No. 22, 26) not containing in the same layer. It can be seen that a higher contrast image can be obtained without increasing the number.

Example 3 <Preparation of Emulsion> A chloride containing rhodium dichloride containing 6.4 × 10 ⁻⁶ mol / mol Ag in a cubic monodispersion having an average particle diameter of 0.13 μm by the pAg controlled double jet method. A silver emulsion was prepared, and 5-chlorobenzotriazole (1 × 10 ⁻³ mol / mol Ag) was added to the emulsion which was desalted, washed with water and redissolved by the flocculation method.
This is divided into 1 × 10 ⁻³ mol / mol Ag of the hydrazine compound shown in Table 3 and 2 × 10 ⁻³ mol / mol Ag of the nucleation accelerator shown in Table 3, and 2-hydroxy- It was prepared by adding 4,6-dichloro-1,3,5-triazine sodium salt and the surfactant of Chemical formula 18. <Preparation of protective liquid> As a protective liquid, 2 × 10 ⁻³ mol / mol Ag of a mercapto compound and 20 mg / m ^{2 of} an organic siloxane compound were added to an aqueous gelatin solution, and a surfactant, a matting agent and a hardener were added. In addition, it was prepared.

The coating solution prepared as described above was applied on a polyethylene terephthalate film, and the emulsion layer was made of silver nitrate.
The protective layer was coated such that the g / m ² and the gelatin were 3 g / m ^2, and the gelatin was 1 g / m ² .

The samples shown in Table 3 were exposed through a sensitometric wedge with a bright room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.), and then developed with Developer 2 having the following composition. The test was conducted in the same manner as in Example 2. Further, the same physical development fogging test as in Example 1 was performed. The results are shown in Table 3.

<Developer 2> 1-Phenyl-4-Hydroxymethyl-4-methyl-3-parasolidone 2.3 g Hydroquinone 85.0 g Sodium hydroxide 26.0 g Sodium carbonate 50.0 g Potassium sulfite 220.0 g Diethylenetriaminepentaacetic acid 9.1 g potassium bromide 12.5 g benzotriazole 0.6 g diethylene glycol 110.0 g water was added 1 l This concentrate was diluted to a ratio of 1 part concentrate to 2 parts water to give a pH of 10.5. Adjust the working strength developer.

[0092]

[Table 3]

From the results shown in Table 3, the photographic light-sensitive material of the present invention (Sample Nos. 39 to 46) in which the mercapto compound and the siloxane compound were added to the protective layer was the No. 47 mercapto even in the silver chloride emulsion in which physical development fogging was likely to occur. As compared with a comparative photographic light-sensitive material containing no compound or a siloxane compound and a comparative photographic light-sensitive material containing no No. 48 siloxane compound, physical development fogging was suppressed and p
It can be seen that a high-contrast image can be obtained even when processed with a developer having an H of less than 11.0.

Example 4 Using the emulsion prepared in Example 3, 1 × 10 ⁻³ mol / mol Ag of the hydrazine compound of H-9 and 2 × 10 ⁻³ mol of the nucleation accelerator of A-15 were used. / MolAg was added, and the mercapto compound and the comparative compound represented by Chemical formula 2 were added to the protective layer in an amount of 2 × 10 ^-3 mol / molAg and a siloxane compound of 20.
mg / m ^{2 was} added, a sample was prepared in the same manner as in Example 3, exposed and developed to determine gamma. Furthermore, an automatic processor (made by Dainippon Screen Mfg. Co., Ltd., LD-221Q
T), the developing solution is 300 ml / m ² , and the fixing solution is 5
While replenishing at a rate of 00, 300, 200 ml / m ² , a photosensitive material (blackening rate 50%) after exposure in an amount equivalent to 60 sheets per day in terms of size (20 × 24 inches) for one month After running, the sample prepared was subjected to the same physical development fog test as in Example 1 and evaluated. The developing solution used is the developing solution 2 used in Example 3, and the fixing solution is also Example 1
The fixer used in ~ 3 was used. The results are shown in Table 4.

[0095]

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[0096]

[Table 4]

From the results shown in Table 4, the photographic light-sensitive materials of the present invention (Sample Nos. 50 to 53) were compared with the photographic light-sensitive materials of Comparative Examples (No. 54 to 56) in which the comparative compound of Chemical formula 19 was added instead of the mercapto compound. Thus, it can be seen that a high-contrast image can be obtained even if processing is performed with a developer having a pH of less than 11.0 while suppressing physical development fogging. Furthermore, 300, 2
It can be seen that the physical development fog does not increase even when running with a fixing replenishing amount of 00 ml / m ² .

[0098]

INDUSTRIAL APPLICABILITY According to the present invention, a negative-working silver halide photographic light-sensitive material can be obtained which does not cause physical development fog even if a large amount of development is continuously carried out without impairing photographic characteristics such as sensitivity or tone. . Further, even when processing is performed while replenishing the fixing solution with an automatic processor at a rate of 300 ml or less per 1 m ² of the light-sensitive material, the halogen which can prevent physical development fog while maintaining photographic characteristics. A method of processing a silver halide photographic light-sensitive material is provided.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, in a hydrophilic colloid layer other than the emulsion layer. Containing at least one nitrogen-containing heterocyclic compound having a mercapto group, and at least one organosiloxane compound in the emulsion layer or other hydrophilic colloid layer. . 2. The halogenated compound according to claim 1, wherein the nitrogen-containing heterocyclic compound having at least one mercapto group and at least one organic siloxane compound are contained in the same hydrophilic colloid layer. Silver photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one hydrazine compound is contained in the emulsion layer or another hydrophilic colloid layer. 4. The fixing process of the silver halide photographic light-sensitive material according to claim 1, 2 or 3 while supplementing the replenishing amount of the fixing solution with an automatic developing machine at a ratio of 300 ml or less per 1 m ² of the light-sensitive material. A method for processing a silver halide photographic light-sensitive material, which is characterized.